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CROSS REFERENCE TO RELATED APPLICATIONS
This patent application is a Utility application of pending Provisional Patent Application 60/232,461, titled “System for Estimating Thickness of Thin Subsurface Strata”, having a filing date of Sep. 13, 2000.
The subject matter of this patent application is related to U.S. patent application Ser. No. 09/498,012, titled “A System for Estimating Thickness of Thin Subsurface Strata”, having a filing date of Feb. 4, 2000.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention is related to seismic data processing. More specifically, the invention is related to a system for processing seismic data to more clearly delineate thin beds in the earth's subsurface.
2. Description of Related Art
A seismic survey is an attempt to map the subsurface of the earth by sending sound energy down into the ground and recording the reflected energy that returns from reflecting interfaces between rock layers below. On land, the source of the down-going sound energy is typically seismic vibrators or explosives. In marine environments the source is typically air guns. During a seismic survey, the energy source is moved across the earth's surface and a seismic energy signal is generated at successive locations. Each time a seismic energy signal is generated, the reflected energy is recorded at a large number of locations on the surface of the earth. In a two dimensional (2-D) seismic survey, the recording locations are generally laid out along a straight line, whereas in three-dimensional (3-D) surveys, the recording locations are distributed across the earth's surface in a grid pattern.
The seismic energy recorded at each recording location is typically referred to as a “trace”. The seismic energy recorded at a plurality of closely located recording locations will normally be combined to form a “stacked trace” and the term “traces” as used herein is intended to include stacked traces. Each trace comprises a recording of digital samples of the sound energy reflected back to the earth's surface from discontinuities in the subsurface where there is a change in acoustic impedance of the subsurface materials. The digital samples are typically acquired at time intervals between 0.001 seconds (1 millisecond) and 0.004 seconds (four milliseconds). The amount of seismic energy that is reflected from an interface depends on the acoustic impedance contrast between the rock stratum above the interface and the rock stratum below the interface. Acoustic impedance is the product of density, p, and velocity, v. The reflection coefficient, which is the ratio of amplitude of the reflected wave compared to the amplitude of the incident may be written:
reflection coefficient=(ρ 2 v 2 −ρ 1 v 1 )/(ρ 2 v 2 +ρ 1 v 1 ) (Eq. 1)
where,
ρ 2 =density of the lower layer ρ 1 =density of the upper layer v 1 =acoustic velocity of the lower layer, and v 2 =acoustic velocity of the upper layer.
Reflected energy that is recorded at the surface can be represented conceptually as the convolution of the seismic wavelet which is transmitted into the earth from a seismic source with a subsurface reflectivity function. This convolutional model attempts to explain the seismic signal recorded at the surface as the mathematical convolution of the downgoing source wavelet with a reflectivity function that represents the reflection coefficients at the interfaces between different rock layers in the subsurface. In terms of equations:
x ( t )= w ( t )* e ( t )+ n ( t ) (Eq. 2)
where,
x(t) is the recorded seismogram w(t) is the seismic source wavelet e(t) is the earth's reflectivity function n(t) is random ambient noise, and * represents mathematical convolution.
Seismic data that have been properly acquired and processed can provide a wealth of information to the explorationist. However, the resolution of seismic data is not fine enough to depict “thin” beds with clarity. Seismic resolution may be defined as the minimum separation between two seismic reflecting interfaces that can be recognized as separate interfaces on a seismic record. Where a stratum (or layer) in the earth's subsurface is not sufficiently thick, the returning reflection from the top and the bottom of the layer overlap, thereby blurring the image of the subsurface. However, even though there may be only a single composite reflection and the thickness of the layer cannot be directly observed, there is still information to be found within the recorded seismic data that may be used indirectly to estimate the actual thickness of the lithologic unit.
FIG. 1 shows a “pinch out” seismic model in which a wedge-shaped sand stratum within a shale zone gradually diminishes in thickness until it disappears at the left side of FIG. 1 . FIG. 2 is a set of mathematically generated synthetic seismic traces that illustrate the convolution of a seismic wavelet with the upper and lower interfaces of this wedge shaped stratum. At the right side of FIG. 2 , the seismic reflections from the upper boundary and the lower boundary of the wedge-shaped stratum are spatially separated enough so that the reflections do not overlap and the two interfaces are distinctly shown on the seismic trace. Moving to the left within FIGS. 1 and 2 , the individual reflections from the upper and lower surfaces of the wedge-shaped stratum begin to merge into a single composite reflection and eventually disappear as the thickness of the wedge goes to zero. However, the composite reflection still continues to change in character after the reflections from the upper and lower surfaces merge into a single composite reflection.
It has been disclosed in Widess, How thin is a thin bed?, Geophysics, December, 1973, vol. 38, p. 1176–1180, to use calibration curves which rely on the peak-to-trough amplitude of a composite reflected thin bed event, together with the peak-to-trough time separation, to provide an estimate of the approximate thickness of the thin layer. However, a necessary step in the calibration process is to establish a “tuning” amplitude for the thin bed event in question, which occurs at the layer thickness at which maximum constructive interference occurs between the reflections from the top and base of the unit. The success of this method is limited because of the need for careful seismic processing in order to establish the correct wavelet phase and to control the relative trace-to-trace seismic trace amplitudes.
Other methods for analyzing seismic data for the presence of thin beds involve converting the data to the frequency domain and analyzing the frequency domain data. For example, a method is disclosed in U.S. Pat. No. 5,870,691 which utilizes the discrete Fourier Transform to image and map the extent of thin beds and other lateral rock discontinuities in conventional 2-D and 3-D seismic data. The method is based on the observation that the reflection from a thin bed has a characteristic expression in the frequency domain that is indicative of the thickness of the bed. A homogeneous thin bed introduces a periodic sequence of notches into the amplitude spectrum of the composite reflection, which are spaced a distance apart that is inversely proportional to the temporal thickness of the thin bed. Accordingly, the thickness of the thin beds is determined by distance by which these notches are spaced apart.
A need continues to exist, however, for an improved method for extracting thin bed information from conventionally acquired seismic data. Frequently, a thin bed is a sand bed running through shale. Knowledge of the presence of sand beds and the bed thickness is very useful information because sand is a potential hydrocarbon reservoir.
It should be noted that the description of the invention which follows should not be construed as limiting the invention to the examples and preferred embodiments shown and described. Those skilled in the art to which this invention pertains will be able to devise variations of this invention within the scope of the appended claims.
SUMMARY OF THE INVENTION
A system is disclosed for processing a group of spatially related seismic data traces in which seismic data windows extending over selected portions of said group of spatially related seismic data traces are defined, and a transform is applied to the successively selected windows to convert the seismic data within the successively selected widows to the frequency domain thereby generating a frequency spectrum of the seismic data within said successively selected windows. Selected frequency spectra are then combined to generate an average of the selected frequency spectra, thereby generating averaged frequency spectra, and the averaged frequency spectra are utilized to generate data related to the location of thin beds in the earth's subsurface.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a “pinch out” seismic model in which a wedge-shaped stratum gradually diminishes in thickness.
FIG. 2 shows a set of mathematically generated synthetic seismic traces that illustrate the convolution of a seismic wavelet with the upper and lower interfaces of the wedge-shaped model of FIG. 1 .
FIGS. 3A , 3 B, 3 C and 3 D show various configurations for combining seismic traces in accordance with the invention.
FIGS. 4A , 4 B and 4 C show representations of seismic traces in the time domain and the frequency domain, and FIG. 4D shows an average of the frequency domain representations of FIGS. 4A , 4 B and 4 C.
FIG. 5A shows a flow diagram for a program useful in implementing an embodiment of the invention.
FIG. 5B shows another flow diagram for a program useful in implementing an embodiment of the invention.
FIG. 6 shows the form of the Welch window.
FIGS. 7A and 7B illustrate the results of use of the invention.
FIGS. 8A and 8B further illustrate the results of use of the invention.
While the invention will be described in connection with its preferred embodiments, it will be understood that the invention is not limited thereto, but shall include all alternatives, modifications, and equivalents within the scope of the appended claims.
DESCRIPTION OF PREFERRED EMBODIMENTS
The invention comprises a system for processing seismic data to detect the presence of thin beds. The data may be either two-dimensional (2-D) data gathered at a succession of data points along a line on the earth's surface, or the data may be three-dimensional (3-D) data gathered from seismic data points distributed, typically in a grid pattern, within an area of the earth's surface. A seismic signal that is transmitted into the earth for purposes of conducting a seismic survey will typically include substantial energy within a frequency range extending from as low as 5 Hz. up to at least 60 Hz. When this energy reaches a thin bed in the earth's subsurface, a portion of the incident energy will be reflected from the upper interface of the thin bed and from the lower interface of the bed. If the bed were thicker, the reflection from the upper interface and from the lower interface would appear separately in the resulting seismic data and it would be possible to determine the bed thickness with standard seismic data interpretation methods. For a thin bed, however, the signal reflections from the upper and lower interfaces will overlap.
Depending on the frequency of the incident seismic energy and the travel time of the seismic energy from the upper to the lower interface of a thin bed, and the acoustic velocities of the stratum above the thin bed and the stratum below the thin bed in relation to the acoustic velocity of the thin bed, the apparent amplitude of the reflected seismic energy will be enhanced or attenuated. The invention may be utilized for the analysis of seismic data to detect the presence of thin beds of sand between upper and lower strata of shale, such as illustrated in FIGS. 1 and 2 . The acoustic velocity of the sand stratum may be greater than or less than the acoustic velocity of the shale, depending on the region of the earth from which the data are gathered, but the acoustic velocity of both the upper and lower shale strata can be expected to be either greater than or less than the velocity of the sand stratum, so that maximum enhancement of the reflected seismic energy will occur when the distance between the upper and lower interfaces of the sand stratum is equal to a quarter wavelength of the dominant frequency of the incident seismic energy. The invention may also be utilized to detect thin beds of shale between sand layers, or thin beds of sand, shale, carbonates or other subsurface strata which may be sandwiched between strata of similar matter or between strata of dissimilar matter. In general, when the acoustic velocity within the thin bed is greater than the acoustic velocity in the stratum above and the stratum below the thin bed, or when the velocity in the thin bed is less than the acoustic velocity in the strata above and below the thin bed, maximum enhancement of the reflected seismic energy will occur when the time distance between the upper interface and the lower interface of the thin bed is one quarter wavelength. However, when the acoustic velocity within the thin bed is less than the acoustic velocity of the stratum above the thin bed but greater than the acoustic velocity of the stratum below the thin bed (or vice versa) maximum enhancement of the reflected seismic energy will occur when the distance between the upper and lower interfaces of the thin bed is equal to one half wavelength.
In practicing the present invention, seismic data traces are windowed, and these data windows are converted to the frequency domain. In one embodiment of the invention a discrete Fourier Transform is utilized for conversion of the seismic data to the frequency domain. In another embodiment, a transform having poles on the unit z-circle is utilized for conversion of the seismic data to the frequency domain. However, other transforms may be utilized for converting seismic data traces to the frequency domain. The frequency domain data are then analyzed for the presence of thin beds.
Calculation of a frequency domain transform of a time series results in a collection of transform coefficients that are complex data values of the form “A+Bi”, where “i” represents the “imaginary”number or the square root of a negative one. Further, it is well known that the expression A+Bi may be equivalently written as:
A+Bi=re iΘ (Eq. 3)
where,
r=|A+Bi|=√{square root over (A 2 +B 2 )}
and Θ = tan - 1 ( B A )
The quantity Θ is known as the phase angle (or just the “phase”) of the complex quantity A+Bi, the quantity “r” its magnitude, and the expression |A+Bi| is the mathematical notation for the magnitude of a complex valued quantity, also called the absolute value. A frequency spectrum is obtained from the transform coefficients by calculating the complex magnitude of each transform coefficient. The numerical size of each coefficient in the frequency spectrum is proportional to the strength of that frequency in the original data.
In accordance with the present invention a plurality of frequency spectra are combined, prior to generating a data display with these frequency spectra. The traces may be combined in various patterns. For example, the frequency spectrum from traces extending along a straight line, as depicted in FIG. 3A , may be combined, or a central trace may be combined with the frequency spectra of the four closest traces, as depicted in FIG. 3B ; or a central trace may be combined with the eight closest traces, as depicted in FIG. 3C ; or the frequency spectra of three traces positioned in the pattern of a right triangle, as depicted in FIG. 3D , may be combined. Patterns may also be selected to accentuate certain features of the subsurface such as a suspected fault.
The traces may also be weighted in various ways. For example, a center trace may be given a weight of 1.0 and the surrounding traces given a weight of 0.25. It will also be appreciated that the trace combinations may be formed in various ways. For example, the median value of the traces may be utilized, or the average (mean) value or other combinations.
FIGS. 4A , 4 B and 4 C each show a windowed segment of three seismic traces from adjacent locations. Each trace is shown in the time domain and in the frequency domain. The time domain traces in FIGS. 4A , 4 B and 4 C are designated by reference designations 10 a , 10 b and 10 c , respectively, and the frequency domain representations of these traces are designated by reference designations 12 a , 12 b and 12 c , respectively. The frequency domain representation shown in FIG. 4D and denoted by reference designation 12 d represents an average (mean) of the frequency representations designated by reference designations 12 a , 12 b and 12 c.
U.S. Pat. No. 5,870,691, which is incorporated herein by reference, discloses a process in which a discrete Fourier Transform, or a similar discrete linear unitary transformation, is utilized to image and map the extent of thin beds and other lateral rock discontinuities in conventional 2-D and 3-D seismic data. This process utilizes the observation that a thin bed introduces a periodic sequence of notches into the amplitude spectrum of a frequency domain transform of a seismic trace, which are spaced a distance apart that is inversely proportional to the temporal thickness of the thin bed. Accordingly, the thickness of the thin beds is determined by distance by which these notches are spaced apart. By applying the present invention to the process described in U.S. Pat. No. 5,870,691, and averaging the amplitude spectra of the frequency domain transform of a plurality of spatially related traces, the signal to noise ratio is substantially improved and, accordingly, the quality of the processed data is improved. The “average” may be the mean, the median, or other weighted average. In this embodiment of the invention the transform coefficients generated when the seismic data are transformed to the frequency domain may be multiplied by a scaling value to form a scaled tuning cube, where the scaling value is determined by selecting at least two transform coefficients corresponding to a same basis function, calculating a complex magnitude of all transform coefficients so selected, calculating an average value from all transform coefficient magnitudes so calculated and calculating a scaling value from the average value. The scaled tuning cube is then displayed.
In another embodiment of the invention, seismic data traces are windowed, these data windows are converted to the frequency domain, and the component of the resulting frequency spectrum having the greatest amplitude is estimated. Knowledge of this frequency, along with knowledge of the sonic velocity profile of the subsurface can be utilized to determine the presence of, and the thickness of, thin beds in the earth's subsurface. As discussed previously, the seismic signal recorded at the surface may be viewed as the mathematical convolution of the downgoing source wavelet with a reflectivity function that represents the reflection coefficients at the interfaces between different rock layers in the subsurface. If a long window is used, a lot of geology is averaged together, and for the purposes of performing the first embodiment of the present invention, the window should preferably be short to minimize geologic averaging.
In a preferred embodiment of the invention, an estimate of the frequency spectrum of the seismic data is generated by use of a transform having poles on the unit z-circle. Use of such a transform permits a shorter window to be utilized. In a preferred implementation the maximum entropy transform is utilized. The estimate of the frequency spectrum away from the peak frequency may be poor when a short time window is used, but in this embodiment of the invention, the objective is to identify just one amplitude peak in the frequency spectrum, rather than to precisely estimate the entire spectrum.
The maximum entropy method (MEM) equation for developing an approximation of the power spectrum, P(f), is as follows:
P ( f ) ≈ a 0 1 + ∑ M k = 1 a k z k 2 ( Eq . 4 )
where:
a 0 and a k are the coefficients M is the total number of samples in the data window k is the index for the summation, and z represents the Z transform.
Processes for computing the coefficients a 0 and a k are known to those of ordinary skill in the art. For example, one subroutine for computing these coefficients, listed in Numerical Recipes in C, Second Edition, by William H. Press et al., Cambridge University Press, Cambridge, England, 1992, on pages 568–569, is referred to therein as MEMCOF, and is incorporated herein by reference. However, other subroutines known to those of ordinary skill in the art may be used for this purpose. In the maximum entropy method, the coefficients which are determined in order to approximate the frequency spectrum are all in the denominator of the equation. Accordingly, the equation has poles, corresponding to infinite power spectral density, on the unit z-circle, i.e., at real frequencies in the Nyquist interval. Such poles can provide an accurate representation for underlying power spectra that have short, discrete “lines” or delta-functions.
In a preferred embodiment of the invention the peak frequency (i.e., the frequency in the frequency spectrum having the greatest power amplitude) is determined for each window of the averaged seismic data traces. In one embodiment of the invention, the kurtosis, the fourth moment of the spectrum, is then evaluated to determine how peaked the frequency distribution is for each data window. In one embodiment of the invention, only the data from those data windows for which the kurtosis exceeds a selected kurtosis value are utilized as output data.
In a particular implementation of the invention, either of three forms of output data may be selected. The first option (option one) is the amplitude of the spectrum at the peak frequency. The second option (option two) is the frequency at which the amplitude peak occurs, for example, 30 Hz. The third option (option three), provided a selected peakedness (i.e., kurtosis) threshold in the frequency spectrum is exceeded, is an estimate of the thickness of the thin bed.
The invention will normally be implemented in a digital computer. Computer instructions readable by a digital computer and defining the process of this invention will normally be stored on magnetic tape, a magnetic disk such as a CD-ROM, an optical disk, or an equivalent storage device and will instruct the computer to perform such process. A flow diagram for a program useful in implementing an embodiment of the invention is outlined in FIG. 5A . In a particular embodiment of the invention the following operational parameters may be used:
1. the output data option 2. the number of poles in the spectral estimate 3. the half-width (in milliseconds) of the spectral-estimation window 4. the minimum frequency of input data 5. the maximum frequency of the input data 6. The traces to be combined and any weighting to be applied to the traces 7. the frequency at which to begin the search for the peak frequency 8. velocity to use for the thickness estimation (in meters/second) 9. cutoff kurtosis for thickness estimation.
The first relevant issue in specifying the number of poles to be used in the spectral estimate and the half width of the spectral-estimation window is that the spectral resolution in Hz. will be approximately the reciprocal of the window length in seconds, so that as the window length is increased, spectral resolution is improved. The second point is that if the number of poles is close to the number of seismic data samples in the window then spurious peaks will be exhibited, and the quality of the image will be decreased. The third point is that the number of poles should be limited to a few times the number of sharp spectral features that are to be fit. Since only one spectral feature (one peak frequency) is desired, the number of poles may preferably be limited to 1, 2, 3 or 4 poles, however, useful results may be obtained with more than 4 poles. Accordingly, the number of data samples which are required will be controlled by the number of poles utilized, and the number of data samples required will determine the window length required.
The input data set could theoretically have data from zero frequency up to the Nyquist frequency (a typical Nyquist frequency is around 250 Hz.). However, most seismic data sets do not have significant very low frequency energy, that is, energy at less than 5 or 10 Hz., and most seismic data sets do not have significant energy above 60 Hz. Therefore, the calculations can be speeded up by limiting the calculations to between a specified minimum frequency cut-off, such as 5 or 10 Hz., and a maximum frequency cut-off, such as 60 Hz. If the user has advance knowledge of the likely value of the peak frequency, the calculation process can be speeded up by specifying the frequency at which to begin the search for the peak frequency.
The velocity to be used for the thickness estimation is usually known from well logs from the area from which the data were recorded. If such well logs are not available, velocity values determined from other subsurface regions having similar lithologies may be utilized. Test results suggest that a normalized kurtosis value of 0.5 is appropriate. However, based on user experience, different values for the kurtosis cutoff may be appropriate for different data sets.
Default operational parameters may be set up for the output data option, the number of poles in the spectral estimate, the half-width (in milliseconds) of the spectral-estimation window, the minimum frequency of input data, the maximum frequency of the input data, the number of traces to be averaged and any trace weighting, the velocity to use for the thickness estimation (in meters/second), and the cutoff kurtosis for thickness estimation. With reference to FIG. 5A these default values are inputted in step 20 .
In step 22 operational parameters for the specific set of seismic data being processed are inputted, which may include the parameters listed as parameters 1 – 9 , above.
In step 24 , the program obtains the data set parameters from the first seismic trace. These parameters may include the length of the trace, the sample time interval, the in-line and cross-line dimensions of the data set, the shot number, the length of vibrator sweep, static correction data, the date and time of day and the field identification.
In a particular implementation of the invention error checking is performed in step 26 to determine that the input values from step 24 are reasonable. For example, the sample interval, which is the amount of time between samples in the seismic trace, obviously cannot be zero or less than zero.
The next step, step 28 , is to precalculate a Welch window, which is applied to the window of seismic data before making the spectral estimate. Those of ordinary skill in the art will recognize from standard filter theory that the data in the selected window will need to be tapered, and precalculating a Welch window avoids the need to calculate the taper each time a trace is looped over. The form of the Welch window, which is well known to those of ordinary skill in the art is illustrated in FIG. 6 . Those of ordinary skill in the art will recognize that other patterns for tapering the data, other than the Welch window pattern, may be utilized.
In step 29 , the program initially obtains the first selected window of data from the first selected seismic trace. In a preferred embodiment, the program uses a first do loop to loop over the traces in the seismic data set and a second do loop to loop over successive data windows within each trace. Each time the program obtains the data from a selected window, it obtains the data samples within a time span of one-half the window length on each side of a selected center point. If the selected center point is from the beginning of the trace or the end of the trace, there may not be sufficient time span on either the upper or lower side of the center point for a full half-window, and if data for the full window is not available, then no spectral estimation is made. If there is enough time span on each side of the selected center point, the spectral estimate is performed. The window of data is copied into a work buffer, and it is verified that the data are not all zeros.
In step 30 , the first step of the maximum entropy routine is then performed, which is the calculation of the maximum-entropy coefficients. The routine utilized for computing the coefficients is sent to the work buffer into which the window of data samples has been copied, along with the length of the window (WIN) and the number of poles (N) to use in the maximum entropy spectral estimate. The coefficients for the maximum entropy spectral estimate are then returned from this calculation.
After the coefficients are calculated, the coefficients are used in step 32 to calculate the frequency spectrum by processes which are well known to those of ordinary skill in the art. One routine for performing this computation is the EVLEM routine shown on page 575 of Numerical Recipes in C , Second Edition, by William H. Press et al., Cambridge University Press, Cambridge, England, 1992, which page is incorporated herein by reference.
In step 33 , an average is then taken of the amplitude of the frequency spectra of a selected number of spatially associated traces to generate an “averaged” trace. The spectrum of this averaged trace is then evaluated to find the peak frequency in the spectrum of the averaged trace and the amplitude of the peak frequency.
Once the peak frequency is determined, the program outputs either of three data items for the output depending on which option is selected. Option one is the amplitude of the spectrum at the peak frequency. Option two is to provide the peak frequency as an output. Option three is an estimate of the thickness of the thin bed.
If output option 3 has been selected, the kurtosis of the spectrum is calculated in step 34 , and a determination is made in step 36 as to whether the kurtosis exceeds a preselected kurtosis value, and accordingly, indicates the presence of a thin bed.
If the spectrum is sufficiently peaked, and if the third output option is chosen, which is the option where the bed thickness is computed, then the thickness estimate is calculated in step 38 using the standard formula, known to those of ordinary skill in the art, for estimating a thickness at the tuning frequency. This formula is simply ¼ times the velocity divided by the frequency of the peak frequency (the tuning frequency).
The program will then loop over each successive window in the first selected seismic data trace and steps 29 , 30 , 32 , 33 , 34 , 36 and 38 of FIG. 5A are applied to the data samples within each selected window. After the second do loop has looped over each window of the first selected data trace, the first do loop will then loop over successive traces, and the second do loop will loop over each window in each successive traces in the same manner as for the first selected trace.
The flow diagram of FIG. 5A , and the foregoing discussion with reference to FIG. 5A , illustrate a particular embodiment of the invention in which kurtosis of the frequency spectra calculated in step 32 is determined, and the thickness of thin beds is calculated from the calculated frequency spectra which are sufficiently peaked.
It is also contemplated that the frequency spectra calculated in step 32 may be utilized to provide data regarding the presence of thin beds without performing steps 34 , 36 and 38 . The flow diagram of FIG. 5B illustrates this embodiment of the invention in which the output data may be in the form of either option 1 (the amplitude of the spectral peak) or option 2 (the frequency at which the amplitude peak occurs).
Output data, whether in the form of option 1, option 2 or option 3 are applied to a commercially available visualization software package to generate displays which may be viewed by an explorationist.
Improved results obtained from use of the invention are illustrated in FIGS. 7A and 7B , and in FIGS. 8A and 8B . FIGS. 7A and 8A represents data processed without use of spatial averaging according to the present invention. FIGS. 7B and 8B show the same data but with use of spatial averaging according to the invention. The white space in the figures represents higher amplitude signals related to tuning thickness. In FIGS. 7A and 7B the white space represents the locations and the frequencies at which tuning occurred. The improvement provided by the invention is illustrated in FIG. 7B by the absence of the artifact which is present in FIG. 7A . This artifact is indicated by arrow 40 pointing to the artifact in FIG. 7A and pointing to the location where the artifact was removed in FIG. 7B . FIGS. 8A and 8B are map (top) views, in which the white space represents locations where tuning is occurring. The improvement is evident because two layers of white space are shown more distinctly in FIG. 8B at the levels indicated by reference numerals 42 and 44 than in FIG. 8A .
While the invention has been described with reference to certain preferred embodiments, it is understood that the invention is applicable to any method for delineating a thin bed in which a seismic data trace is converted to the frequency domain, and features of the frequency domain traces are utilized to estimate the existence of or properties of the thin beds. Further, while the invention has been described and illustrated herein by reference to certain preferred embodiments in relation to the drawings attached hereto, various changes and further modifications, apart from those shown or suggested herein, may be made herein by those skilled in the art, without departing from the spirit of the invention, the scope of which is defined by the following claims. | A system is disclosed for processing a group of spatially related seismic data traces in which seismic data windows extending over selected portions of said group of spatially related seismic data traces are defined, and a transform is applied to the successively selected windows to convert the seismic data within the successively selected widows to the frequency domain thereby generating a frequency spectrum of the seismic data within said successively selected windows. Selected frequency spectra are then combined to generate an average of the selected frequency spectra, thereby generating averaged frequency spectra, ane the averaged frequency spectra are utilized to generate data related to the location of thin beds in the earth's subsurface. | 6 |
INTRODUCTION
[0001] This invention relates to toilets with improved flushing arrangements. There is increasing pressure to reduce usage of water, even in areas such as the UK which have relatively high rainfall. One area of interest for reducing water consumption is the flushing of toilets, but this must be balanced against requirements of hygiene.
[0002] All current flush toilets use water for two separate purposes, namely the removal of waste matter from the toilet pan and the provision of a seal against escapes of sewer gas into buildings. This second purpose determines the minimum volume of water required for any remotely conventional toilet to function. But much more water is currently used. This is because part of it is needed to impart sufficient kinetic energy to swimming waste matter to force it round the trap.
STATEMENTS OF INVENTION
[0003] According to the present invention, a toilet includes a pan, a trap which normally retains water as a gas seal, and an outlet; and the trap is arranged for movement, during flushing of the toilet, in a manner which causes said retained water to transfer by gravity to the outlet.
[0004] The trap, in some forms of the invention, is a rigid conduit arranged for rotary or pivotal movement. In other forms, the trap is constituted by a length of flexible hose. The hose may normally form a curve in which said water is retained and be straightened during flushing by relative movement between the pan and the outlet. The trap generally takes the form of a continuous conduit connecting the pan and the outlet and is designed to hold a body of water between flushes, which body acts as a gas seal.
[0005] The trap is preferably moved by means linked to the flushing mechanism of an associated cistern. Said flushing mechanism may be a conventional siphon or, more preferably, a bell mechanism of known type. Alternatively the flushing mechanism may comprise a flexible hose having a partial loop which is moved to initiate flushing. Preferably, the arrangement is such that the initiation of flushing causes cleaning water to be supplied to the pan before or while movement of the trap commences.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and, together with the description, serve to explain the objects, advantages, and principles of the invention.
[0007] [0007]FIG. 1 shows a vertical section of a slightly modified flush toilet.
[0008] [0008]FIG. 2 shows one embodiment of a link with the flushing mechanism.
[0009] [0009]FIG. 3 shows a toilet where a trap makes use of flexible hose.
[0010] [0010]FIG. 4 is a front view of the relevant parts of the flushing system.
[0011] [0011]FIG. 5 shows a main ring with a number of smaller rings which can rotate on the main ring.
[0012] [0012]FIG. 6 shows one embodiment of an attachment of a hose pipe to a cistern and an overflow, and an attachment to a toilet pan.
[0013] [0013]FIG. 7 illustrates a managed trap.
[0014] [0014]FIG. 8 illustrates an immobile trap management pipe relative to a toilet pan.
[0015] [0015]FIG. 9 shows a toilet where a trap makes use of a short section of a pipe.
[0016] [0016]FIG. 10 shows flanges which securely seal connection of a hose with a toilet pan.
DETAILED DESCRIPTION OF THE INVENTION
[0017] The embodiment shown in FIGS. 1 and 2 uses a mechanical trap in conjunction with an immobile toilet pan.
[0018] [0018]FIG. 1 shows a vertical section through relevant parts of a slightly modified flush toilet. The toilet pan 1 terminates more or less horizontally. There would actually be functional advantages in pointing downwards at a small angle (say 5°). It is linked to the trap management pipe 2 which empties into the pipe 3 leading to the drains. The seals 4 at both ends of the trap management pipe 2 allow said trap management pipe 2 to rotate slightly (45° will be sufficient) relative to the toilet pan I and the pipe 3 .
[0019] [0019]FIG. 2 shows one implementation of a possible link with the flushing mechanism. It represents a view, from the front, of all relevant components installed behind the toilet. The trap management pipe 2 is shown in a position 45% inclined against the vertical. This could be its normal position when the toilet is not in use. A user flushing the toilet would push down the lever 7 , which is hinged at point 11 . This pushes down the link 6 pressing the trap management pipe 2 to the floor. Once that has happened the water in the trap can flow to the drains without further impediments, carrying any waste matter with it. Once the lever 7 is released the spring 10 which is anchored to the floor or other parts of the whole mechanism, pulling on the lever 5 returns the trap management pipe 2 to its rest position.
[0020] Flushing can be achieved by an additional direct link from the lever 7 ; for example, the spindle of a conventional flushing mechanism could be linked to the lever at 11 . But preferably a spring 9 could operate a wire pull 8 to trigger the flush. A traditional type flushing bell would probably work better than a syphon, because the flush can be initiated faster as the bell does not need to be held in its trigger position as long as a syphon.
[0021] To preserve an acceptable appearance for the whole assembly the entire mechanism, apart from the lever 7 , would typically be enclosed in a box.
[0022] Instead of making the seals 4 watertight one could have a durable flexible hose pipe extending from the toilet pan 1 all the way through the bend in pipe 3 . The trap management pipe 2 would then merely guide the hose pipe through the positions required for its function.
[0023] [0023]FIG. 3 illustrates a toilet where the trap makes use of flexible hose which undergoes bending, rather than twisting, motion.
[0024] The toilet pan 1 is linked to the trap management hose 12 at the immobile seal 14 . The pan is held at the sides by sliding tracks 13 which allow it to be moved forward and upward in a frame (not shown), that is fixed to the floor. Preferably, the moving parts have an integrated back rest 18 . If any toilet lid is fitted this back rest 18 ensures that when the pan is moved in its frame the lid does not tilt further backwards, sliding down the front of the cistern and possible becoming trapped below it. To slide the toilet pan one would typically pull at one of the handles 15 . One such handle is preferably incorporated at the top of the backrest 18 in a position convenient for adult users. A second handle, for example below the front of the toilet pan, can be provided for children.
[0025] The pulling action straightens the trap management hose 12 and lifts the water trapped in the area of the seals 14 to a height from which it can flow to the drains without further impediment.
[0026] The balance between forward and upward motion of the toilet pan 1 is determined by the length of the hose 12 and the height to which the pan 1 must be lifted to achieve free flow water and waste.
[0027] Various mechanical means can be employed to ensure that the waste management pipe 12 is confined to shapes acceptable for the operation of the toilet. One of these methods could be prevention of sideways motion relative to the toilet by confinement between two vertical parallel plates (not shown).
[0028] As in the implementation described in FIGS. 1 and 2, this different design allows a direct mechanical link to the flushing mechanism. One such link is shown in FIG. 3. Again, a wire pull 8 is pulled via a spring 9 . The roller 17 , connected with a wall or the cistern, changes the direction of the pulling force. Alternatively, a Bowden cable could be used. In this implementation, as described in FIGS. 1 and 2, a flushing bell is preferable to a syphon.
[0029] Because the toilet pan moves relative to the cistern the water used in flushing has to travel through another hose pipe 17 , from which it enters the pan at 16 . The upper part of the pan can have the same shape as a conventional toilet, directing water to all parts of the pan.
[0030] Because a hose pipe 17 is used between the cistern and the toilet pan the method for flushing can be simplified. The wire pull 8 , spring 9 and roller 17 can be dispensed with, as can the flushing bell or syphon in the cistern. Instead, the flush can be controlled by the hose pipe 17 itself.
[0031] Details of one way of achieving this are shown in FIG. 4, which shows only the relevant parts of the total assembly from the front.
[0032] The cistern 19 does not contain mechanical devices for flushing at all. Instead, the hose pipe 17 is attached to the cistern at the bottom of the latter. There is always water in the hose pipe. But the section of the hose pipe closest to the cistern is normally held up beyond the height of the entrance to the overflow pipe 20 of the cistern 19 . In the implementation shown in FIG. 4 the hose pipe can move freely through the ring 21 which is shown more closely in FIG. 5 where one can see the main ring 21 with a number of smaller rings 29 rotating on it. Returning to FIG. 4, we see that the ring 21 is attached to a lever 22 which is hinged at point 25 . A spring 23 attached at point 24 normally holds up the lever and thus the hose pipe 17 . When the toilet pan is moved forward and upward the hose pipe 17 is pulled by the same action. This allows the cistern to be drained through the hose pipe. As in traditional flushing mechanisms the hose pipe acts as a syphon once enough water has passed its highest point.
[0033] Further rings like the ring 21 can be employed along the path of the hose pipe 17 to ensure smooth operation of the mechanism. To preserve an acceptable appearance of the whole assembly, substantially the whole flushing mechanism would typically be enclosed in a box.
[0034] In some parts of the world there may be regulatory objections to having a hosepipe linked to a self replenishing water vessel. Problems of possible leakage could be overcome with a slightly more elaborate design, such as the one shown in FIG. 6. Only the relevant parts are shown, namely the attachment of the hose pipe to the cistern and the overflow as well as the attachment to the toilet pan. No 19 again indicates the cistern itself with its overflow 20 . There are now two hose pipes, one within the other. The inner hose pipe 17 has the same function as in FIGS. 3 and 4. It is enclosed in an outer hose pipe 28 which is communicating with the overflow 20 through a short pipe 26 at its point of attachment to the cistern 19 either above (or as shown here) below the base of the cistern. The outer hose pipe 28 is divided from the cistern itself as well as the toilet pan. These blocked ends are marked with the number 27 in FIG. 6.
[0035] The foregoing are purely mechanical embodiments of the invention.
[0036] All of these could obviously be operated by electric motors. Electronic timing devices or mechanical systems (such as systems involving cams) can be used to optimise control of the flushing relative to the draining of the trap. Cisterns could then be dispensed with altogether and electrically controlled valves used to control the flushing. If an electric motor is used for controlling the trap the latter can be of a design not appropriate for any of the mechanical versions. One such managed trap is shown in FIG. 7.
[0037] As in FIG. 1 there is a toilet pan 1 ultimately draining into a pipe 3 . The waste management coil 30 is a pipe that can rotate freely in the seals 4 . Just as the version shown in FIGS. 1 and 2, it is beneficial if the path from the toilet pan to the pipe 3 is slightly downhill. To drain the trap, the waste management coil 30 is rotated around the common axis of the whole assembly. The water in the trap together with any waste matter is thereby removed on the principle of the endless screw. This makes it possible to maintain a seal against sewage gas at all times, provided the flushing of the toilet is controlled in such a way that new water is added at the time when the old water drains into the pipe 3 .
[0038] It is desirable that the toilet pan is cleaned before the trap is drained. All fully mechanical versions therefore incorporate devices that initiate flushing as soon as the user begins to drain the trap. To illustrate the principles of the various designs the mechanically most simple versions have been drawn. In all mechanical versions it would be preferable to have a slightly more complicated trigger mechanism. This is because in the simple versions shown the user does not just initiate the draining of the trap but has some control over its timing. When toilets are used by children, this involves the risk that they will not just pull levers or pans but hold them in the trigger position until the cistern is empty. In that case the seal against sewage gas is not reestablished.
[0039] Electrical operation does not involve this problem at all. It would even be possible to improve on the water saving effect by having two separate flushing programs. Regardless whether there is one flushing program or two, preferably the operation would begin by releasing enough water to clean the toilet pan. Depending on the design this would be followed or accompanied by draining the trap, which in turn would be followed (or accompanied in its last stage) by the release of more water to refill the trap. In an implementation with two flushing programs these would only differ in the first stage. Where nothing more than urine is to be removed, a very small quantity of water would initially be released for cleaning the pan. The other version could either release a predetermined larger quantity of water or, up to a predetermined maximum, as much water as the user requires (until the use r's trigger action stops).
[0040] [0040]FIG. 8 illustrates another embodiment, in this version the trap management pipe 31 is immobile relative to the toilet pan 1 . But it can slide into and out of the pipe 32 . The trap is drained by tipping out the toilet pan and its trap management pipe. This is done by tilting up the whole mechanism, including its frame 34 around the axis 33 . This slides the trap management pipe 31 into the pipe 32 against which it is sealed by the seal 35 in which it can slide freely.
[0041] The embodiment of FIG. 8 is described here for completeness. However, this embodiment is not preferred, and is in fact impracticable.
[0042] This is because hygiene dictates that the upper rim of a toilet pan should always be horizontal. Otherwise waste matter from the walls of the toilet pan can be tipped into the room as, in case of blocked pipes, can the entire contents. Moreover, as flushing has to begin as soon as one starts to tip up the toilet, water would rarely reach the upper part of the front of the toilet and could splash into the room from parts that have been raised higher than the rear of the toilet. Finally, children and physically weak people would find it unacceptably difficult to use such a toilet.
[0043] Referring now to FIGS. 9 and 10, there is described a further embodiment. FIG. 9 shows substantially the same type of toilet with sliding pan as FIG. 3. Again, pipe 3 leads to the drains. All parts of the toilet and its frame are unchanged, with a single exception at the bottom of the toilet pan. The toilet pan now terminates in a shorter section of pipe falling at a steeper angle.
[0044] Instead of managing the trap by a hose 12 there is now a short section of pipe 40 containing a permanently fixed solid object 36 that blocks the flow of water and waste matter from the toilet pan when the latter is in its rest position. The upper end of the pipe 40 and the lower end of the discharge pipe of the toilet pan are connected with an extensible hose 37 (made of rubber or some similarly elastic material), part of which is shown in greater detail in FIG. 10. The flanges 39 securely seal the connection of this hose 37 with the toilet pan 1 and the pipe 40 against water and sewer gas. The hose can expand and contract on the turtle neck principle in its section denoted with the number 38 .
[0045] When the toilet is not in use the hose 37 is in firm contact with the obstacle 36 , holding a small quantity of water in the toilet pan. When the toilet pan is pulled forward by one of its handles 15 a gap opens between the toilet pan's discharge pipe and the obstacle 36 , allowing water and waste matter to flow through the pipes 40 and 3 to the sewers. When the toilet pan slides back the seal is automatically re-established. As the tightness of the seal depends on close contact between the obstacle 36 and the lip of the hose 37 it would be advantageous if the part of the obstacle 36 in actual contact with the lip of the hose 37 would be spherical. Preferably, the relevant part of the obstacle should be hollow, so as to give it the required flexibility to secure a tight seal.
[0046] It would obviously be possible to depart from the design described above by having a fixed connection between a fixed toilet pan and the sewers and to achieve the effect described above by having a movable obstacle inside one of the pipes near the toilet pan. This, however, would have the disadvantage that complicated moving parts would be within that part of the whole toilet system that is open to the sewers and that has water and soil flowing through it, so that the mechanism would have a greater tendency to become clogged. Furthermore, it would then be necessary to provide additional seals against sewer gas escaping through the actuating mechanism.
[0047] In comparison with the other implementations of the invention described earlier the design shown in FIG. 9 has the advantage of saving much more water. This can be seen by comparing FIGS. 3 and 9. In FIG. 3 it is necessary to have water in the bottom of the toilet pan 1 as well as part of the hose 12 . In FIG. 9 only the bottom of the toilet pan needs to contain water. With appropriate dimensions the quantity of water consumed on each flush, besides that required to clean the toilet pan itself, can be reduced to significantly less than 1 liter With appropriate control over the flow of fresh water into the toilet pan this can be the only water loss when only urine is removed. Compared to some traditional toilets reductions in water consumption approaching 90% could thus be achieved.
[0048] The invention thus provides toilet arrangements which can operate in a satisfactory and hygienic manner with a low water consumption, since there is no requirement for flushing water to impart kinetic energy to floating waste.
[0049] Modifications and improvements may be made to the foregoing | A toilet comprises a pan, a trap which normally retains water as a gas seal, and an outlet. The trap is arranged for movement, during flushing of the toilet, in a manner which causes the retained water to transfer by gravity to the outlet. In one aspect, the trap comprises a length of flexible hose having a curved portion which retains water as the gas seal. | 4 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] Applicant hereby claims foreign priority benefits under U.S.C. §119 from German Patent Application No. 10 2008 024 670.0 filed on May 21, 2008, the contents of which are incorporated by reference herein.
FIELD OF THE INVENTION
[0002] The invention concerns a method of mounting a cylinder arrangement of a hermetically enclosed refrigerant compressor arrangement in a carrier arrangement, in which the cylinder arrangement is inserted in the carrier arrangement, aligned in relation to a crank shaft and connected to the carrier arrangement.
BACKGROUND OF THE INVENTION
[0003] Further, the invention concerns a hermetically enclosed refrigerant compressor arrangement with a crank shaft and a cylinder arrangement, in which a piston is arranged that is connected to the crank shaft via a connecting rod, the cylinder arrangement being supported on a carrier.
[0004] Such a hermetically enclosed refrigerant compressor arrangement is, for example, known from U.S. Pat. No. 6,095,768, EP 0 524 552 A1 or U.S. Pat. No. 7,244,109 B2.
[0005] Hermetically enclosed refrigerant compressors are used in many domestic and industrial refrigeration appliances, for example, refrigerators, refrigerating chests, freezers, top opening freezers or refrigerating cabinets. They are manufactured in large numbers and must thus be regarded as mass products, which should be manufactured in the most cost effective way possible.
[0006] In order to simplify the manufacturing, the cylinder arrangements are, in the cases mentioned above, arranged on a carrier, which is made to be relatively stable, and which is connected to the stator of the drive motor. Thus, it is no longer required to make the cylinder arrangement and the bearing for the rotor of the drive motor in one piece.
[0007] Such an embodiment has the disadvantage that it is difficult to mount the cylinder arrangement of the refrigerant compressor arrangement with the exact alignment. It is desired to position the cylinder arrangement so that the axis of the cylinder arrangement extends exactly at right angles to the axis of the crank shaft. If this is not the case, this may cause cocking of the piston in the cylinder during operation, which would cause increased wear. A cocked cylinder also requires more energy during operation, which has a negative influence on the efficiency.
SUMMARY OF THE INVENTION
[0008] The invention is based on the task of ensuring a good efficiency of a refrigerant compressor arrangement.
[0009] With a method as mentioned in the introduction, this task is solved in that, before inserting the cylinder arrangement, the carrier arrangement is deformed by means of a calibration cylinder, until the calibration cylinder has a predetermined alignment, after which the calibration cylinder is removed and replaced by the cylinder arrangement in the carrier arrangement.
[0010] With this embodiment, a carrier arrangement (or short: a carrier) can be used, which has been pre-manufactured with a relatively poor accuracy. The accuracy of the manufacturing of the accommodation, in which finally the cylinder arrangement is inserted, will only be achieved by the use of the calibration cylinder. At least with regard to the diameter, the calibration cylinder has outer dimensions, which correspond to those of the cylinder arrangement. Otherwise, the calibration cylinder only has to be so stable that it can deform the carrier. Usually, in this connection, it is endeavoured to avoid a deformation of the calibration cylinder. When the calibration cylinder is acted upon by a sufficient force, it can deform the carrier. This deformation is controlled by the force applied, so that the axis of the calibration cylinder preferably crosses the axis of the crank shaft, or, if the cylinder is laterally offset in relation to the crank shaft axis, a parallel to the crank shaft axis. When, then, the calibration cylinder is removed from the carrier, the accommodation has a geometry, into which the cylinder arrangement fits exactly, so that also the axis of the cylinder arrangement crosses the crank shaft axis or a line that extends in parallel to the crank shaft axis. In any case, the cylinder arrangement can then be mounted so that its axis crosses the crank shaft axis or a parallel thereto under a right angle.
[0011] Preferably, a carrier arrangement is used with projections extending in the direction of the cylinder arrangement, and the projections are deformed. If only the projections must be deformed, a smaller force is required, than would be required for the deformation of the whole carrier arrangement. Accordingly, the deformation of the carrier arrangement can be made with a better accuracy. The risk that during the deformation of the carrier arrangement other parts of the carrier arrangement outside the projections are deformed in an undesired manner is relatively small. This means that the deformation of the carrier arrangement can be concentrated on an area, where the deformation is desired.
[0012] It is preferred that at least two rows of projections are used, projections being farther away from the crank shaft being higher than projections, which are closer to the crank shaft. With this embodiment, it is achieved that during insertion the calibration cylinder initially has an inclination in relation to the alignment, which it must finally assume. This inclination is pre-specified by the different heights of the projections. Thus, it is also specified, where a force must be applied in order to deform the projections. The calibration cylinder is then tilted from its inclined position to the desired position; the force applied deforming the higher projections more than the lower projections. This is a simple and fast way of achieving the desired deformation of the carrier arrangement.
[0013] It is preferred that in the area of the higher projections a press force is applied on the calibration cylinder. When the press force is applied in the area of the higher projections, it is applied, where it can immediately be active. It must be assumed that with this method, mainly the higher projections are deformed. This keeps the deformation work small.
[0014] It is preferred that two rows are provided, each row having two projections. This means that a total of four projections is provided, of which two are higher than the other two. Four projections provide a sufficiently stable support for the cylinder arrangement to be mounted.
[0015] Preferably, before connecting the cylinder arrangement to the carrier arrangement, the cylinder arrangement is displaced on the carrier arrangement in a direction perpendicular to the crank shaft axis, until a dead space inside the cylinder arrangement has reached a predetermined minimum value. After the deformation, the deformed projections or the deformation zone of the carrier arrangement as a whole are formed so that during a displacement along the axis of the cylinder arrangement, that is, perpendicular to the crank shaft axis, a change of the angle between the cylinder axis and the crank shaft axis will not occur. This can be utilised to displace the cylinder towards or away from the crank shaft, until the dead space occurring in the upper dead point of the piston has reached its minimum value. The smaller the dead space is, the better is the efficiency of the refrigerant compressor arrangement.
[0016] Preferably, a calibration cylinder is used, whose one front side extends perpendicular to its axis, and that in at least two positions a distance of the front side to the crank shaft axis, or a line parallel to that, is determined, the carrier arrangement being deformed, until the distances are equal. The two positions are offset in relation to each other in parallel to the crank shaft axis. As long as the calibration cylinder is inclined, the two positions have different distances to the crank shaft axis or a line parallel thereto. Not until one front side of the calibration cylinder is vertical, the distances are the same. In this case, however, the axis of the calibration cylinder extends perpendicular to the crank shaft axis or a line parallel thereto.
[0017] Preferably, the parallel line used is a line on the circumference of a crank pin, which is connected to the crank shaft. This is particularly advantageous, if the axis of the cylinder arrangement and the crank shaft axis do not cross, but the cylinder arrangement is laterally offset in relation to the crank shaft. Then, the crank pin can be turned to the desired position, and measuring can be performed.
[0018] It is also advantageous, if a carrier arrangement is used, which comprises a carrier element and a reinforcement element, the reinforcement element being deformed. The use of a reinforcement element makes it possible to reduce the mass of the carrier arrangement. The carrier element can be dimensioned with a view to the fixing on the stator and the reinforcement element can be dimensioned with a view to the fixing of the cylinder arrangement. Accordingly material only has to be provided, where it is required for the corresponding application purpose. Additionally, the use of two elements, which are joined, can provide acoustic advantages, as, for example, the intrinsic frequency of the joined carrier arrangement is displaced from the audible area, and vibrations are damped. The carrier element and the reinforcement element can, for example, be made as shaped metal sheet parts, which can be manufactured with the required accuracy in a cost effective manner. In order to achieve the ultimate accuracy of the alignment of the axis of the cylinder arrangement to the crank shaft axis, the reinforcement element is deformed.
[0019] Preferably, the cylinder arrangement and the carrier arrangement are joined by means of a cold-formed joint. The cold-formed joint can, for example, be achieved by toxing or clinching. Thus, auxiliary joining parts can be saved. Deformations caused by a thermal load can be avoided. Thus, the accuracy of the alignment is not influenced by the joining process.
[0020] With a refrigerant compressor arrangement as mentioned in the introduction, the task is solved in that the carrier arrangement has at least one deformed deformation zone.
[0021] When the cylinder arrangement is mounted, the deformation zone has previously been deformed by the calibration cylinder. Thus, in the deformation zone it can be determined, if such a deformation has taken place. The deformation of the deformation zone causes that the axis of the cylinder arrangement and the crank shaft axis or a line parallel thereto cross each other under a right angle. Thus, the piston can be guided in the cylinder without risking a cocking, which keeps the wear and the energy consumption during operation small.
[0022] Preferably, the deformation zone has several projections directed towards the cylinder arrangement, at least one of these projections being deformed. During the deformation, the height of the deformed projection is reduced, so that the axis of the cylinder arrangement gets the desired alignment, namely at right angles to the crank shaft axis or a line parallel thereto.
[0023] It is also advantageous, if a projection far away from the crank shaft is more deformed than a projection next to the crank shaft. With a carrier arrangement, whose deformation zone comprises more or less deformed projections, the projections would, before the deformation, have different heights. Accordingly, the calibration cylinder can be inserted in the deformation zone with a certain inclination, and this inclination can then be removed by an external force application, so that the axis of the cylinder arrangement gets the desired alignment.
[0024] Preferably, the carrier arrangement has a carrier element mounted on a motor and a reinforcement element connected to the cylinder arrangement, the deformation zone being located in the reinforcement element. As mentioned above, the carrier arrangement can then be made with a relatively small mass. The carrier element can be dimensioned for the mounting on the motor. The reinforcement element, however, is dimensioned for accommodating the cylinder arrangement. Accordingly, material will only be provided, where it is required for the individual purposes. With an assembled carrier arrangement, the resonant frequency can under certain circumstances be displaced into a non-audible range.
[0025] In the following, the invention is described on the basis of a preferred embodiment in connection with the drawings, showing:
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] FIG. 1 is a schematic, partial section through a refrigerant compressor arrangement,
[0027] FIG. 2 is a perspective view of a reinforcement element, and
[0028] FIG. 3 is a view according to FIG. 1 with a calibration cylinder.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0029] A refrigerant compressor arrangement 1 has a motor 2 with a stator 3 and a rotor 4 , having between them an air gap 29 . The rotor 4 is unrotatably connected to a rotor shaft 5 (also called “crank shaft), having at its lower end an oil pump and at its upper end a crank pin 7 . For reasons of clarity, a casing usually surrounding the refrigerant compressor arrangement 1 is not shown.
[0030] Via a connecting rod 8 , the crank pin 7 is connected to a piston 9 , which reciprocates in a cylinder 10 . The cylinder 10 is arranged in a mounting sleeve 11 . The cylinder 10 and the mounting sleeve 11 form a cylinder arrangement 12 , which also comprises a cylinder head 13 , which is only schematically shown.
[0031] A connection between the cylinder arrangement 12 and the motor 2 is realised via a carrier, in the present case comprising a carrier element 14 and a reinforcement element 15 .
[0032] The carrier element 14 has four flanges 16 , which rest with a bearing surface 17 on a front side of the stator 3 . Flaps 18 being angled in relation to the bearing surface 17 , ensure that the carrier element 14 is undisplaceably held on the stator 3 . The flanges 16 can then be welded onto or otherwise connected to the stator 3 .
[0033] The carrier element 14 has a cable entry opening 19 , through which an electrical supply cable 20 for the motor 2 is guided.
[0034] As shown in FIG. 2 , the reinforcement element 15 forms a pan 21 . In this pan 21 , oil gathers that is pumped upwards by the oil pump during operation and sprayed inside a case, not shown in detail, in which the refrigerant compressor arrangement 1 is located. Through an oil passage 22 , this oil can get into a gap 23 between the carrier element 14 and the reinforcement element 15 , from where it can flow off. This gap 23 is kept open by a spacer 24 , which is formed on the carrier element 14 .
[0035] The carrier element 14 and the reinforcement element 15 are made as formed sheet metal parts, that is, they are made during one or more working steps by means of punching and bending sheet metal plates. The sheet metal plate used for the carrier element 14 is thinner than the one used for the reinforcement element 15 .
[0036] The reinforcement element 15 forms a bearing shell 25 for a calotte ring 26 , in which the rotor shaft 5 is supported. The calotte ring 26 has a circumferential surface that forms a part of a spherical surface. The bearing shell 25 has an inner surface, which also forms a part of a spherical surface. The spherical surface of the calotte ring 26 has a somewhat smaller radius than the spherical surface of the bearing shell 25 . The calotte ring 26 is held in the bearing shell 25 by a clamp 27 . The clamp 27 prevents the calotte ring 26 from moving out of the bearing shell 25 . However, it permits a certain tilting movability of the calotte ring 26 in relation to the reinforcement element 15 .
[0037] As can particularly be seen from FIG. 2 , the reinforcement element 25 has a trough shaped accommodation 30 for the mounting sleeve 11 . Fixing surfaces 31 , 32 are located next to the accommodation 30 . The mounting sleeve 11 comprises flanges bent out from its surface. When the mounting sleeve 11 has not yet been connected to the reinforcement element 15 , these flanges can enclose an obtuse angle. When the mounting sleeve 11 is inserted in the accommodation 30 and pressed into the accommodation 30 with a certain force, the flanges align in parallel to the fixing surfaces 31 , 32 . In this state, the flanges can be connected to the fixing surfaces 31 , 32 by means of toxing or clinching. Before connecting the flanges to the fixing surfaces 31 , 32 , the mounting sleeve 11 with the cylinder 10 inside can be displaced in the axial direction within certain limits, so that in this manner a dead space can be set, which will at the end still remain at the upper dead point of the piston 9 . This dead space should be kept as small as possible.
[0038] The reinforcement element 15 has four projections 36 - 39 , which are located in the accommodation 30 . These projections 36 - 39 are directed towards the cylinder arrangement 12 , when the cylinder arrangement 12 is mounted in the reinforcement element 15 , as shown in FIG. 1 .
[0039] In the “raw state”, that is, after manufacturing the reinforcement element 15 and before mounting the cylinder arrangement 12 , the projections 36 , 37 , which are arranged next to the rotor shaft 5 , have a smaller height than the projections 38 , 39 , which are located farther away from the rotor shaft 5 . All in all, four projections 36 - 39 , which are arranged in two rows, will be sufficient to support the cylinder arrangement 12 with the required reliability and accuracy in the accommodation 30 , when eventually the cylinder arrangement 12 can be connected to the fixing surfaces 31 , 32 .
[0040] In order to provide the desired alignment of the cylinder arrangement 12 in the reinforcement element 15 , a calibration cylinder is used, as shown in FIG. 3 . The same elements as in FIGS. 1 and 2 are provided with the same reference numbers. In order to simplify the explanation, the projections 36 , 38 are arranged in the section level. As can be seen from FIG. 2 , however, they are actually located a small distance away from the section level in the circumferential direction.
[0041] As mentioned above, the projections 38 , 39 are higher than the projections 36 , 37 . This means that, when the calibration cylinder 40 is inserted in the accommodation 30 , it will tilt, as can be seen from FIG. 3 . In other words, it has an inclination.
[0042] The calibration cylinder 40 has a front side 41 , which extends perpendicularly to its axis 42 . Accordingly, as long as the reinforcement element 15 with its projections 36 - 39 has not yet been deformed, a first distance 43 between the front side 41 and the circumferential surface of the crank pin 7 is larger than a distance 44 between the front side 41 of the calibration cylinder 40 and the circumferential surface of the crank pin 7 at the same circumferential position. This circumferential surface 45 of the crank pin 7 extends in parallel to the axis 6 of the rotor shaft 5 .
[0043] The calibration cylinder 40 is now loaded with a force 46 (symbolized by an arrow). In relation to the axial direction of the calibration cylinder 40 , this force 46 is applied in the area of the projections 38 , 39 . With a correspondingly large force, these projections 38 , 39 are deformed. At any rate they are more heavily deformed than the other projections 36 , 37 .
[0044] This deformation of the projections 38 , 39 reduces the inclination of the axis 42 of the calibration cylinder 40 , until it coincides with a straight line 47 that encloses a right angle 48 with the axis 6 of the motor shaft. When the cylinder arrangement is somewhat laterally offset, the straight line 47 can also enclose a right angle with a parallel to the axis 6 of the rotor shaft 5 .
[0045] The alignment of the calibration cylinder 40 can easily be monitored in that the distances 43 , 44 are currently compared to each other. As soon as these distances have become the same, the axis 42 of the calibration cylinder 40 extends with the desired alignment, that is, together with the axis 6 of the rotor shaft 5 , or a parallel to that, it encloses a right angle 48 .
[0046] When now the calibration cylinder 40 is replaced by the cylinder arrangement 12 , also the cylinder arrangement 12 has the desired alignment to the axis 6 of the crankshaft 5 , as the cylinder arrangement 12 and the calibration cylinder 40 have the same outer dimensions.
[0047] Then the cylinder arrangement 12 can be displaced towards or away from the crank pin 7 , until a dead space formed by the piston 9 and the cylinder 10 as well as the cylinder head 13 has reached a minimum value.
[0048] While the present invention has been illustrated and described with respect to a particular embodiment thereof, it should be appreciated by those of ordinary skill in the art that various modifications to this invention may be made without departing from the spirit and scope of the present invention. | The invention concerns a method of mounting a cylinder arrangement of a hermetically enclosed refrigerant compressor arrangement in a carrier arrangement ( 14, 15 ), in which the cylinder arrangement is inserted in the carrier arrangement ( 14, 15 ), aligned in relation to a crank shaft ( 5 ) and connected to the carrier arrangement ( 14, 15 ). It is endeavoured to ensure a good efficiency of the refrigerant compressor arrangement. For this purpose the carrier arrangement is deformed, before inserting the cylinder arrangement, by means of a calibration cylinder ( 40 ), until the calibration cylinder ( 40 ) has a predetermined alignment, after which the calibration cylinder ( 40 ) is removed and replaced by the cylinder arrangement in the carrier arrangement ( 14, 15 ). | 8 |
FIELD OF INVENTION
The subject matter disclosed herein relates generally to the field of electrical power generating systems.
DESCRIPTION OF RELATED ART
Vehicles, such as military hybrid vehicles or aircraft, may include electric power generating systems (EPGS) that utilize a synchronous generator to power a DC load in the vehicle. The synchronous generator may comprise a permanent magnet (PM) or wound field (WF) generator. A voltage ripple on the direct current (DC) bus exists after rectification of the generator output. To reduce the DC bus voltage ripple to levels that are appropriate to meet specification requirements for the DC load, a relatively large DC bus capacitor may be required in the EPGS, adding weight and size to the EPGS. The DC bus capacitor is sized based on the ripple frequency, and may need to be significantly increased when the generator operates at a relatively low speed. Another approach to reduce DC bus voltage ripple includes increasing the frequency bandwidth of an active rectifier that rectifies the generator output; however, this approach may increase system noise.
BRIEF SUMMARY
According to one aspect of the invention, a method of startup of an electric start electrical power generating system (EPGS), the EPGS comprising a generator configured to power a direct current (DC) load via a DC bus includes: disconnecting the DC load from the DC bus; connecting a battery to a boost converter, the boost converter being connected to the generator; powering the generator using the battery via the boost converter; when the generator reaches a minimum speed, disconnecting the battery from the boost converter; deactivating the boost converter; and activating a synchronous active filter, the synchronous active filter being connected to the DC bus; bringing up a voltage on the DC bus by the generator; and when the voltage on the DC bus reaches a predetermined level, connecting the DC load to the DC bus.
According to another aspect of the invention, an electrical power generating system (EPGS) includes a generator connected to a direct current (DC) bus; a boost converter connected to the generator; a battery, the battery configured to power the generator during startup via the boost converter, wherein when the generator reaches a minimum speed, the battery is configured to be disconnected from the boost converter; and a synchronous active filter (SAF), the SAF being connected to the DC bus; wherein when a voltage on the DC bus is brought up to a predetermined level by the generator, the generator is configured to power a DC load, the boost converter is configured to be deactivated, and the SAF is configured to be activated.
Other aspects, features, and techniques of the invention will become more apparent from the following description taken in conjunction with the drawings.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
Referring now to the drawings wherein like elements are numbered alike in the several FIGURES:
FIG. 1 illustrates an embodiment of an EPGS with a WF generator comprising a reconfigurable power converter configured as a boost converter during start mode.
FIG. 2 illustrates an embodiment of the EPGS with a WF generator comprising a reconfigurable power converter configured as a synchronous active filter during generate mode.
FIG. 3 illustrates an embodiment of an EPGS with a WF generator comprising a buck-boost converter and a synchronous active filter.
FIG. 4 illustrates a detailed view of an embodiment of a synchronous active filter.
FIG. 5 illustrates an embodiment of an EPGS with a PM generator comprising a reconfigurable power converter.
FIG. 6 illustrates an embodiment of a method of operating an EPGS comprising a boost converter and a synchronous active filter.
DETAILED DESCRIPTION
Embodiments of systems and methods for an EPGS with a boost converter and a synchronous active filter (SAF) are provided, with exemplary embodiments being discussed below in detail. A boost converter is a DC-DC power converter that has an output voltage that is greater than its input voltage. The boost converter may be connected to a battery that powers a generator via the boost converter and start inverter during startup. The generator is operated as a motor in the startup to convert electrical power supplied by a start inverter into motive power, which is provided to the prime mover to bring it up to self-sustaining speed. In the case of a WF generator, AC power is provided to the armature windings of the main portion of the WF generator and to AC exciter field windings, so that the motive power may be developed. This may be accomplished by using two separate inverters. During generate mode, the DC bus is connected to a DC load, and the power converter is reconfigured as an SAF. The SAF acts to reduce DC bus voltage ripple on the DC bus during generate mode. Reduction in DC bus voltage ripple allows for reduction in size of the DC bus capacitor. In some embodiments, the boost converter may comprise a buck/boost converter, which may output a voltage that is either higher or lower than the input voltage. In some embodiments, the boost converter and the SAF may be embodied in a reconfigurable power converter.
FIG. 1 illustrates an embodiment of an electric start EPGS 100 comprising a reconfigurable power converter 113 and a WF generator 101 . Reconfigurable power converter 113 may function as a boost converter during startup, and as an SAF during normal operation. The WF synchronous generator 101 generates AC power through the rotation of rotating portion 103 , which comprises an exciter armature winding 104 , rotating rectifier 105 , and main field winding 106 . Rotating portion 103 rotates in proximity to exciter field winding 102 and main armature winding 107 . Exciter field winding 102 is connected to exciter inverter 108 , and main armature winding 107 is connected to start inverter 110 . Exciter inverter 108 and start inverter 110 are both on high voltage DC (HVDC) bus 109 . Battery 112 is connected to reconfigurable power converter 113 via switches 111 a - b . DC bus capacitor 116 is connected across reconfigurable power converter 113 , and DC load 115 is connected across reconfigurable power converter 113 via switches 114 a - b.
Reconfigurable power converter 113 is configured as a three-phase interleave boost converter during startup. During startup, the DC load 115 is disconnected from the HVDC bus 109 by opening switches 114 a - b , and switches 111 a - b are closed, connecting battery 112 to the reconfigurable power converter 113 . Then the reconfigurable power converter 113 increases the voltage on the HVDC bus 109 using power from battery 112 , increasing the voltage to exciter inverter 108 and start inverter 110 . Exciter inverter 108 provides AC constant frequency (about 400 Hz in some embodiments) power from HVDC system bus 109 to the three-phase exciter field windings 102 , and start inverter 110 provides variable voltage variable frequency (VVVF) power from HVDC bus 109 to the main armature windings 107 . Then, upon achieving generate mode speed (about 800 rpm in some embodiments) by WF synchronous generator 101 , the battery 112 is disconnected from the reconfigurable power converter 113 by opening switches 111 a - b , and the reconfigurable power converter 113 is reconfigured as an SAF for normal operation of EPGS 100 . Also, after startup is completed, the exciter inverter 108 is reconfigured as DC exciter by disabling one of the phase legs, and all switches comprising start inverter 110 are turned-off, reconfiguring start inverter 110 into a 6-pulse rectifier.
FIG. 2 illustrates an embodiment of an EPGS 200 comprising a WF generator 201 and a reconfigurable power converter 213 during generate mode. Reconfigurable power converter 213 may function as a boost converter during startup and as an SAF during normal operation. Start mode is not supported in the embodiment of FIG. 2 . The EPGS 200 of FIG. 2 also includes a 6 -pulse rectifier 210 and DC exciter inverter 208 . The WF synchronous generator 201 generates AC power through the rotation of rotating portion 203 , which comprises an exciter armature winding 204 , rotating rectifier 205 , and main field winding 206 . Rotating portion 203 rotates in proximity to exciter field winding 202 and main armature winding 207 . Exciter field winding 202 is connected to DC exciter inverter 208 , and main armature winding 207 is connected to rectifier 210 . DC exciter inverter 208 and rectifier 210 are both on HVDC bus 209 .
To enable power generation, the battery 212 provides a DC voltage to the DC exciter inverter 208 that controls the DC exciter current in response to the voltage on DC bus 209 . During this time, the DC load 215 is disconnected from the DC bus 209 by opening switches 214 a - b , and switches 211 a - b are closed. When the DC bus voltage exceeds the battery voltage, the battery 212 is disconnected from the DC bus 209 by opening switches 211 a - b . The DC exciter inverter 208 gradually increases DC exciter field current to provide soft start of the voltage on HVDC bus 209 to its specified value (about 270 Vdc-800 Vdc in some embodiments). When the voltage on HVDC bus 209 reaches the specified value, a power quality monitor (not depicted) may detect that DC power at no-load on HVDC bus 209 is within specification levels for DC load 215 . At this point, reconfigurable power converter 213 is reconfigured from a boost converter to an SAF, and the DC load 215 is connected to the HVDC bus 209 by closing switches 214 a - b . DC exciter inverter 208 controls the DC exciter current to achieve gradual increase of the voltage on DC bus 209 , which is commonly referred as a soft start of the DC bus voltage. The DC exciter inverter 208 powers exciter field winding 202 . Rectifier 210 may comprise a 6-pulse rectifier in some embodiments. Reconfigurable power converter 213 acts to reduce the ripple on HVDC bus 209 during generate mode by acting as an SAF.
FIG.3 illustrates another embodiment of an EPGS 300 comprising a buck/boost converter and an SAF during generate mode. Start mode is not supported in the embodiment shown in FIG. 3 . EPGS 300 comprises a WF synchronous generator 301 comprising a rotating portion 303 , which comprises an exciter armature winding 304 , rotating rectifier 305 , and main field winding 306 , exciter field winding 302 , main armature winding 307 . Exciter field winding 302 is connected to DC exciter 308 , and main field winding 306 is connected to rectifier 310 . Battery 312 is connected to exciter inverter 308 via buck/boost converter 317 and switches 311 a - b . DC load 315 connected to HVDC bus 309 via switches 318 a - b . At low generator speed, the battery 312 is connected to buck/boost converter 317 by closing switches 311 a - b , switch 314 is opened, and switches 318 a-b are opened to disconnect DC load 315 from HVDC bus 309 . The buck/boost converter 317 raises the voltage on HVDC bus 309 available to exciter inverter 308 to accommodate for any residual load on the bus, or, in the case when the voltage on HVDC bus 309 is relatively high (above 200 Vdc), the buck/boost converter 317 may reduce the voltage available to exciter inverter 308 to a level appropriate to avoid exciter inverter operation with a very low duty cycle. When generate mode speed (about 800 rpm in some embodiments) is achieved by WF synchronous generator 301 , battery 312 is disconnected by opening switches 311 a - b , and the SAF 313 is enabled to reduce the ripple on HVDC bus 309 during generate mode. The DC exciter 308 gradually increases exciter field current to achieve soft start of the voltage on HVDC bus 309 to its specified value (about 270 Vdc-800 Vdc in some embodiments). Then, a power quality monitor may detect that DC power at no-load on HVDC bus 309 is within the specification levels for DC load 315 . At this point, the DC load 315 is connected to the bus by closing switches 318 a - b , and switch 314 is also closed. The voltage applied to the DC exciter inverter 308 is controlled by operating the buck/boost converter 313 in buck mode during operation.
FIG.4 illustrates a detailed view of an embodiment of a synchronous active filter (SAF) 414 for an EPGS in generate mode, which may comprise either of SAFs embodied in reconfigurable power converters 113 or 213 , or SAF 313 . SAF 414 may exhibit a single phase topology. Synchronous active filter 414 comprises capacitor 415 , inductor 416 , and switches 418 a - b connected in series. The gate drive 413 of switches 418 a - b is controlled using data from current sensor 417 . Main armature winding 401 (which may comprise any of main armature windings 107 , 207 , or 307 ) and voltage sensor 402 are connected via a phase locked loop 403 to the multiplier 404 . The multiplier 404 provides synchronization frequency to the synchronous compensators 405 , 406 , and 407 by multiplying signal from the phase locked loop 403 by 6 . This synchronization frequency is the dominant frequency of the voltage ripple on DC bus after 6 -pulse rectification of the generator voltage. Synchronous compensators also receive input from voltage sensor 420 , which is connected across HVDC bus 421 and DC bus capacitor 419 (which may comprise any of HVDC buses 209 or 309 , and DC bus capacitors 216 or 316 , respectively). The outputs of synchronous compensators 406 and 407 are added by adder 408 , and the output of adder 408 is added to the output of synchronous compensator 405 by adder 409 . The output of adder 409 after a limit function becomes a current reference (I_ref) to the current loop that comprises current feedback signal (I fdbk) from the current sensor 417 , error summer 410 and amplifier 411 . Pulse width modulator 412 converts controlled voltage out the amplifier 411 output to modulate SAF 414 power switches 418 a and 418 b via gate drive 413 . Synchronous compensator 405 is tuned to cancel or reduce the dominant frequency of the DC bus voltage ripple, while synchronous compensators 406 and 407 are tuned to cancel or reduce the 2 nd and 4 th harmonics of the DC bus voltage ripple respectively. Synchronous active filter 414 modulates the DC bus in response to the current reference I_ref to cancel or reduce the voltage ripple on DC bus which is the product of 6-pulse rectification of the generator voltages.
FIG. 5 illustrates an embodiment of an EPGS 500 with a permanent magnet (PM) generator 502 , start inverter/active rectifier 505 and reconfigurable power converter 509 . Reconfigurable power converter 509 may function as a boost converter during startup, and as an SAF during normal operation. PM generator 502 is powered by prime mover 501 , which maybe any portion of a vehicle that moves in a manner appropriate to be harnessed for power generation. During startup, reconfigurable power converter 509 is configured as a boost converter, and start inverter/active rectifier 505 acts as a start inverter. During startup, battery 506 is connected to boost converter 505 by closing switches 507 a-b, and DC load 511 is disconnected from HVDC bus 504 by opening switches 510 a - b . Battery 506 then powers armature winding 503 during startup via reconfigurable power converter 509 and start inverter 505 . When generate mode speed is reached by PM generator 502 , battery 506 is disconnected by opening switches 507 a - b , reconfigurable power converter 509 is reconfigured to act as an SAF, and start inverter/active rectifier 505 is reconfigured to act as an active rectifier 505 . Voltage on HVDC bus 504 is then brought up to an appropriate level DC load 511 , and a power quality monitor may detect that DC power at no-load is within the specification levels. At this point, the DC load 511 is connected to the bus by closing switches 510 a - b . Power is then transferred from armature winding 503 of PM generator 502 to active rectifier 505 , which powers DC load 511 via to HVDC bus 504 and SAF 509 . The SAF portion of buck/boost converter/SAF 509 helps to reduce the necessary size ofthe DC bus capacitor 508 by reducing ripple on HVDC bus 504 , without increasing the frequency bandwidth of the active rectifier 505 during generate mode.
FIG. 6 illustrates an embodiment of a method 600 of operating an EPGS comprising a boost converter/SAF. Method 600 may be implemented in any of EPGSs 100 , 200 , 300 , or 500 . In block 601 , a battery is connected to a generator of the EPGS via the boost converter in start mode. In block 602 , the generator reaches a predetermined generate speed using the power from the boost converter and battery. In block 603 , the battery is disconnected from the boost converter, the boost converter is deactivated, and the SAF is activated. In embodiments in which the boost converter comprises a buck/boost converter (for example, FIG. 3 ), deactivating the boost converter may comprise operating the buck/boost converter in buck mode. In block 604 , the voltage on the HVDC bus reaches an appropriate level for the DC load. In block 605 , the DC load is connected to the HVDC bus via the SAF in generate mode. The boost converter functions to increase voltage to power start inverter during startup, and the SAF functions to reduce the ripple that is experienced by the DC load during generate mode.
The technical effects and benefits of exemplary embodiments include reduction of weight and size of DC bus capacitance due to introduction of an SAF that reduces voltage ripple experienced by a DC load connected to an HVDC bus of an EPGS. A reconfigurable power converter, which may be configured as a boost converter or an SAF, allows reduction of power electronic components by utilizing multiple functions via software configuration of a three-phase interleave power converter.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. While the description of the present invention has been presented for purposes of illustration and description, it is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications, variations, alterations, substitutions, or equivalent arrangement not hereto described will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the invention. Additionally, while various embodiment of the invention have been described, it is to be understood that aspects of the invention may include only some of the described embodiments. Accordingly, the invention is not to be seen as limited by the foregoing description, but is only limited by the scope of the appended claims. | A method of startup of an electric start electrical power generating system (EPGS) is provided. The EPGS includes a generator configured to power a direct current (DC) load via a DC bus. The method includes: disconnecting the DC load from the DC bus; connecting a battery to a boost converter, the boost converter being connected to the generator; powering the generator using the battery via the boost converter; when the generator reaches a minimum speed: disconnecting the battery from the boost converter; deactivating the boost converter; and activating a synchronous active filter, the synchronous active filter being connected to the DC bus; bringing up a voltage on the DC bus by the generator; and when the voltage on the DC bus reaches a predetermined level, connecting the DC load to the DC bus. | 8 |
This is a continuation of application Ser. No. 07/762,626, filed on Sep. 19, 1992, now U.S. Pat. No. 5,250,250.
FIELD OF THE INVENTION
The present invention relates to a process for forming landscaping objects, such as hollow rocks useful in landscaping for residences and businesses.
BACKGROUND OF THE INVENTION
Landscape rocks and boulders have long been used as in landscaping to provide a natural effect and to highlight certain areas. To use actual boulders, it is necessary to find suitably shaped boulders, transport them to the location to be used and then dig the ground around the boulder such that it rests within tile ground at a suitable height. This process is obviously time consuming and burdensome. A variety of alternatives to natural boulders have been developed.
Contemporary landscape architects utilize artificial boulders, which are actually hollowed out boulder liners or shells, having a bottom portion cut off to fit flush on the ground. Such liners are typically formed of concrete which is formed from a mold. The mold, in turn, is formed from an actual boulder which has been selected for its size, shape and design characteristics. By varying the composition or surface treatment of the boulder liner, different colors or surface characteristics can be obtained.
Though contemporary landscape boulder liners have significant functional and economic advantages over actual boulders, the current processes for forming such landscape boulders suffer significant shortcomings which impede both production rate and the quality of the resulting landscape boulders. The quality of such landscape boulders may be measured by how closely the surface of the landscape boulder reflects the surface details of the actual boulder used in the formation process.
Contemporary processes for forming landscape boulders typically use fiberglass molds made by forming a latex skin on the surface of the actual boulder, and then constructing the fiberglass mold around the latex skin. Cement is pumped or hand troweled into the inverted fiberglass mold and allowed to set. The only force acting on the cement is its own weight. By the action of gravity, the cement generally moves downward toward the bottom of the mold, i.e., representing the upper portion of the landscape boulder when the process is complete. Consequently, the resulting product typically does not assume all surface characteristics of the mold. This deficiency is particularly significant in the upper and side portions of the inverted landscape boulder. In order to remedy the deficiencies of the product formed by such processes, it is typically necessary to apply additional cement by hand to the lower outside portions of the completed landscape boulder, resulting in the addition of non-repeating detail which is only vaguely reminiscent of the initial boulder. As will be evident from the above description, such contemporary processes have significant deficiencies with respect to both the quality of the resulting product and the production rate. The present invention addresses these and other deficiencies in the prior art as set forth below.
SUMMARY OF THE INVENTION
A process for forming an artificial rock is disclosed. The process comprises forming an outer mold having an outer surface and inner surface, the inner surface defining the size, shape and detail of the artificial rock to be formed. An inner mold is formed to be receivable within the outer mold. The inner mold and outer mold are secured in place relative to each other to define a space therebetween. Molding material is poured into the space between the inner mold and outer mold. The molding material is allowed to harden to form an artificial rock within the space. The molds are then separated leaving the artificial rock.
The void between the inner mold and outer mold defines the thickness of the resulting landscape boulder, which can be regulated by varying the size of the inner mold, and the clearance between the inner and outer molds.
In the presently preferred embodiment, the inner mold is made by forming a hard liner on the outer mold and carving a body of foam into a mold insert. The mold insert may further be provided with a plurality of holes into which the molding material may flow. Molding material is poured into the space between the hard liner and mold insert, attaching to the mold insert. Upon hardening of the molding material, the molds are separated and the hard liner may be discarded. The inner mold is then complete.
The outer mold may be formed by a variety of different processes. In the presently preferred embodiment, an outer mold is formed by building a dam about a actual boulder to a height defined by a molding line. The dam is filled with molding material and allowed to harden to form the shape of the outer mold.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view of the apparatus used to form a mold in accordance with the present invention;
FIG. 2 is a top view of the apparatus used to form a mold in accordance with the present invention;
FIG. 3 is a side view illustrating the outer and inner molds.
FIG. 4 is a top view illustrating the outer and inner molds.
FIG. 5 is an enlarged view of a portion of FIG. 3.
FIG. 6 is an enlarged view of a portion of FIG. 3, wherein the hard liner has been removed to provide space for the cement mixture.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The detailed description set forth below in connection with the appended drawings is intended as a description of the presently preferred embodiment of the invention, and is not intended to represent the only form in which the present invention may be implemented or utilized. The description sets forth the functions and sequence of steps of constructing a landscape boulder in connection with the illustrated embodiments. It is understood, however, that the same or equivalent process steps may be accomplished by different embodiments and that objects other than landscape boulders may be replicated in accordance with the disclosed process. Such equivalent process steps and process products are also intended to be encompassed within the spirit and scope of the invention.
The first step in the formation of landscape objects is the selection of a rock or other object suitable for molding. Not all objects can be molded. Rocks with deep impressions or angled undercuts may pose significant problems upon removal of the casting. Rocks with minimal undercuts are selected and a molding line is determine prior to set up. The molding line is an imaginary plane which passes through the rock eliminating that portion of the rock which may be unsuitable for molding due to unacceptable undercuts and/or impressions.
As illustrated at FIGS. 1 and 2, once an appropriate rock 11 is selected, the rock 11 is placed upon a support platform 13. The support platform 13 supports the rock 11 and set-up material in a level position. The platform is preferably constructed for mobility, incorporating mounting wheels or being constructed to allow forklift use.
After the platform 13 is constructed, the rock 11 is centered on the platform with the molding line level. The molding line 17 is typically above the platform. A frame 19 is then constructed around the rock and fastened down to the platform. The depth of the frame 19 is defined by the distance between the molding line 17 and the upper surface of the support platform 13. The length and width of the frame are preferably formed to be adequate to allow 5 or 6 inches between the inside of the frame 19 and the surface of the rock 11. The void 21 between the frame 19 and the rock 11 is filled with sand and packed firm to within 1-2 inches of the molding line 17. This 1-2 inches is a formed concrete base 23, troweled smooth and level, and allowed to dry. The concrete base 23 and rock 11 are preferably both sealed with an appropriate sealer, such as shellac, and coated with a mold release agent.
The next step in the formation of the mold is to put a sheet metal dam in place. In the presently preferred embodiment, sheet metal of 26 gauge is cut to a width that exceeds the dimension between the molding line and the pour line. The length exceeds the circumference of the rock with an allowance of at least 1-2 inches between the rock 11 and the dam wall. The sheet metal dam 25 is carefully bent around the rock 11 allowing 1-2 inches for molding material. The overlap of the sheet metal may be joined with duct tape on both sides. With the sheet metal dam 25 in place, a ring of cement grout 27 is applied to the outside bottom edge with a grouting bag. The purpose of cement grout 27 is to hold the sheet metal in place and to seal the joint between the sheet metal dam 25 and the concrete base 23. When the grout is dry, a release agent is applied to the inside surface of the sheet metal.
The next step is .the placement of the alignment fasteners. Alignment fasteners 29 are later used to hold down and properly align the inner mold with respect to the outer mold. In the presently preferred embodiment, the alignment fasteners 29 are steel dowels with female threads embedded in the surface of the outer mold. The placement of the alignment fasteners 29 is significant in that they are preferably positioned to equalize the upwards stress on the outer mold, uniformly distributing the stress of holding down the inner mold.
With the alignment fasteners in position, molding material is then poured into place. In the presently preferred embodiment, the molding material used is a polyurethane compound, two component system. However, various types of molding material may be used within the scope of the invention. When mixed together, the molding material cures at room temperature to an elastomer with shore "A" hardness of 40-60. When the molding material has dried, the resulting mold, i.e., outer mold 31, is removed from the rock and placed upright with the impression facing up.
Referring to FIGS. 3 and 4, the next step in the process is the formation of a hard liner 37 on the inside surface of the outer mold 31. As described below, once the mold is complete, it will function to reproduce products which are substantially replicas of the hard liner 37. To form the hard liner, cement or other similar materials is hand trolled on the inner surface of the outer mold. The thickness of the mixture depends upon the size of the rock to be produced and the strength desired, typically between 3/4 and 3 inches thick. The inside surface of the hard liner 37 is typically formed to have a smooth bowl shape. A sealer and release agent are then applied to the exposed surface of the hard liner as described above.
Next, a foam insert is then placed within the outer mold. The insert 39 is formed of a rigid polyurethane foam, carved and shaped to substantially fill the space of the hard liner, leaving approximately 1/2 to 1 inch of space between the rigid foam and the hard liner on all sides. The space remaining between the hard liner 37 and foam insert is filled with liquid molding material 40, as described below. 1/2 to 1 inch holes 41 are preferably drilled through the foam in all directions, particularly where the alignment brackets touch the foam. This procedure prevents the hardened molding material from pulling away from the foam insert during mold separation.
Alignment brackets 33 are used to hold down and properly align the foam insert 39 to the outer mold. The alignment brackets may be formed of wood, metals or plastic and is formed to be of size and strength sufficient to hold the inner mold without bowing under stress created by buoyancy during the casting process. The brackets 33 are centered over the alignment fasteners 29, with holes marked and drilled for an anchor bolt. The brackets are preferably marked and cut to fit the outside edge of the outer mold. With the brackets 33 in place, the center of each bracket is identified and marked. At each mark, a hole is drilled to attach a 3/8 or 1/2 inch eyebolt 35. The eyebolt is used to pull up on when separating the inner mold from the casting.
Molding material 40, such as polyurethane, is then poured into the space between the hard liner and the foam insert. Once half poured, the buoyancy of the foam insert upon the molding material will typically urge the foam upwards against the alignment brackets. The foam insert may then be manually manipulated in order to provide circumferential clearance between the foam insert and the hard liner. The pouring is then completed. When the molding material 40 is dried, the foam insert incased in molding material now attached thereto, is separated from the hard liner. The hardened molding material 40 and foam insert 39 collectively become the inner mold. The hard liner may then be separated from the outer mold and discarded or may be used as a landscape boulder.
In the production of landscape boulders as shown at FIG. 6, the outer and inner molds are again mated and the cement mixture is poured into the intermediate space 42 previously occupied by the hard liner. After the cement mixture hardens, the outer and inner molds are separated, leaving a landscape boulder. This process is then repeated to make additional landscape boulders.
The use of the inner mold to form the landscape boulder substantially equalizes and provides a means to effectively regulate the thickness of the landscape boulder around its entire surface area. Though variations in such thickness may occur as a consequence of the irregularity of the desired surface, the landscape boulder may be formed so that all portions of the landscape boulder have a minimum thickness without requiring an excess of cement mixture or other molding material. Moreover, the use of the inner mold provides a further advantage that the cement mixture is urged against the side walls of the mold to a greater degree than that resulting from contemporary process of simply pumping or shooting casting material into the mold. As a consequence, products formed in accordance with the present invention can obtain significantly greater detail on a repeatable basis, substantially eliminating the need for any hand troweling of the product after it is withdrawn from the mold. Consequently, the production rate that can be achieved by use of the present inventive process is significantly greater than that achieved by contemporary processes.
As will be apparent to those of ordinary skill in the art, the present invention has application beyond merely the reproduction of landscape boulders. Other types of landscape objects, such as objects for decorating pools or buildings may be reproduced in accordance with the same process as described above. Accordingly, the present invention is not intended to be limited to the particular types of objects being reproduced.
As will further be apparent to those of ordinary skill in the art, the process may be modified or supplemented to provide various types, of surface coloring or detail. For example, a more granular surface may be provided by spray application of commercially available surface finish products. Coloring finishes may also be applied in accordance with techniques well-known in the art to those of ordinary skill in the art.
It should also be recognized that various aspects of the present invention may be implemented in conjunction with inner and/or outer molds formed in accordance with different methods or construction. Accordingly, the description of the presently preferred embodiments of the overall process, described above, are not intended to be limiting of the particular combination of process steps which constitute the present invention. | A process for forming an artificial rock is disclosed. The process includes forming an outer mold having an outer surface and inner surface, the inner surface defining the size, shape and detail of the artificial rock to be formed. An inner mold is formed to be receivable within the outer mold. The inner mold and outer mold are secured in place relative to each other to define a space therebetween. Molding material is poured into the space between the inner mold and outer mold. The molding material is allowed to harden to form an artificial rock within the space. The molds are then separated leaving the artificial rock. | 1 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention is related to an objective protector and to a microscope observation method.
[0003] This application is based on Japanese Patent Application No. 2005-171209, the content of which is incorporated herein by reference.
[0004] 2. Description of Related Art
[0005] Various configurations of objective lenses for microscopes have been proposed in the related art (for example, see Japanese Unexamined Patent Application Publication No. 2005-31425).
[0006] These objective lenses in the related art are configured such that a plurality of lenses are arranged inside a substantially cylindrical lens barrel. By constructing the lens barrel with a comparatively large diameter and a thick wall, it has high stiffness and can firmly hold a plurality of lenses. Because only a cover glass at the tip is disposed close to the exterior of the sample to be observed, it is possible to keep the outer diameter thereof quite large.
[0007] However, in the case of microscope apparatuses for carrying out in-vivo examination of living organisms, it is necessary to insert the tip of the objective lens inside the living organism to carry out observation. In other words, a great burden is placed on the living organism if the degree of invasiveness is high. Therefore, from the viewpoint of observing living organisms with minimal invasiveness, it is necessary to design objective lenses having small-diameter tips.
[0008] On the other hand, it is also necessary, in the case of microscope apparatuses for in-vivo examination of living organism such as those described above, to place the tip of the objective lens in contact with the living organism to carry out observation. Therefore, in order to prevent contamination, such as bacteria, or dust from adhering to the tip of the objective lens, it is absolutely essential to clean, disinfect, or sterilize it after use.
[0009] However, performing such cleaning, disinfecting, or sterilizing after each use is cumbersome. In addition, if the tip of the objective lens has a small-diameter, there is a risk of deformation of the small-diameter tip during cleaning or the like due to the external force applied, particularly because the rigidity against external forces from the lens barrel is reduced.
BRIEF SUMMARY OF THE INVENTION
[0010] The present invention has been conceived in light of the circumstances described above, and an object thereof is to provide an objective protector and a microscope observation method which can reduce or remove the need to clean an objective lens, thus simplifying the observation procedure, which can prevent bacteria or contamination from adhering to the objective lens, and which can protect the objective lens from external force that would be exerted during cleaning.
[0011] In order to realize the object described above, the present invention provides the following solutions.
[0012] A first aspect of the present invention is an objective protector comprising an optically transparent covering configured to cover at least an end surface of an objective lens; and an attaching mechanism configured to attach the covering to the objective lens.
[0013] According to the above-described aspect, the covering is attached to at least the end surface of the objective lens by the action of the attaching mechanism. Because the covering is formed of an optically transparent material, light enters and emerges via the end surface of the objective lens without being disrupted. In addition, because at least the end surface of the objective lens is prevented from directly making contact with the specimen, such as a living organism, by the covering, it is possible to prevent the objective lens from being contaminated by bacteria, dirt, or the like. Also, merely by removing the covering after observation, it is possible to eliminate the need for disinfecting the objective lens.
[0014] In the aspect of the invention described above, the covering may include a cover member that is brought into close contact with the end surface of the objective lens.
[0015] By doing so, the end surface of the objective lens can be protected from bacteria, contamination, or the like by the cover member, and it is possible to allow light from the specimen to enter the objective lens without any losses.
[0016] In the aspect of the invention described above, the covering may include a membrane member that is brought into close contact with the end surface of the objective lens and that is made from a plastic material selected from the group consisting of polyethylene, polyvinylidene chloride, polystyrene, polypropylene, and polycarbonate.
[0017] With this configuration, it is possible to deform the membrane member so that it follows the shape of the end surface of the objective lens, thus making it easier to bring into close contact therewith. Therefore, it is possible to efficiently prevent bacteria and contamination from adhering to at least the end surface of the objective lens, without changing the optical characteristics at the tip of the objective lens. In addition, by using a relative large membrane, it is possible to easily protect a large portion of the objective lens, not just the end surface thereof.
[0018] In the aspect of the invention described above, a circumferential groove may be formed in an outer circumferential surface of the objective lens, and the attaching mechanism may include a constricting member made from a ring-shaped elastic body configured to engage with the circumferential groove to pinch the membrane member between the constricting member and the outer circumferential surface of the objective lens.
[0019] With this configuration, the membrane member is disposed as to cover the outer circumferential surface of the objective lens, and the constricting member is engaged with the circumferential groove from the outer side thereof. Doing so allows the membrane member of the objective lens to be easily secured to the outer circumferential surface of the objective lens by means of the elastic force of the constricting member.
[0020] In the aspect of the invention described above, the attaching mechanism may include a ring-shaped member secured to the outer circumferential surface of the objective lens; and a ring-shaped constricting member configured to engage with the ring-shaped member to pinch the membrane member between the constricting member and the ring-shaped member.
[0021] Therefore, the membrane member can be easily secured to the outer circumferential surface of the objective lens even if the objective lens has a small diameter or if it is difficult to form a circumferential groove in the outer circumferential surface thereof due to its thin structure.
[0022] The aspect of the invention described above may further comprise a tension-applying mechanism configured to apply tension to the membrane member so that the membrane member is brought into close contact with the end surface of the objective lens.
[0023] With this configuration, it is possible to bring the membrane member into close contact with the end surface of the objective lens simply by applying tension to the membrane member by the action of the tension-applying mechanism. Therefore, it is possible to effectively protect the end surface of the objective lens without changing the optical characteristics at the tip of the objective lens.
[0024] A second aspect of the present invention is an objective protector comprising an optically transparent covering configured to cover at least an end surface of a fiber bundle, which is disposed at the tip of an objective lens; and an attaching mechanism configured to attach the covering to the fiber bundle.
[0025] According to the above-described aspect, the covering is attached to at least the end surface of the fiber bundle by the attaching mechanism. Because the covering member is formed of an optically transparent material, light can enter and exit via the end surface of the fiber bundle without being disturbed. In addition, because at least the end surface of the fiber bundle is prevented from coming into direct contact with the specimen, such as a living organism, by the covering, it is possible to prevent the tip of the fiber bundle from becoming contaminated by bacteria, dirt, or the like. Moreover, simply by removing the covering after observation, it is possible to eliminate the need to disinfect the fiber bundle.
[0026] A third aspect of the present invention is a microscope observation method comprising covering an objective lens provided in a microscope with a membrane member made of an optically transparent plastic material selected from the group consisting of polyethylene, polyvinylidene chloride, polystyrene, polypropylene, and polycarbonate; and carrying out observation with the membrane member being in close contact with an end surface of the objective lens.
[0027] According to the above-described aspect, because the objective lens is covered with the membrane member, it is possible to prevent bacteria or contamination from adhering to the objective lens, even when the objective lens is brought into contact with the specimen or inserted inside the specimen. Therefore, it is possible to eliminate the need to clean the objective lens after observation. In such a case, by bringing the membrane member into close contact with the end surface of the objective lens, it is possible to carry out observation with no effect on the optical characteristics.
[0028] The present invention provides an advantage in that it can reduce or remove the need to clean the objective lens, prevent bacteria or contamination from adhering to the objective lens, and protect the objective lens from external force which would be exerted thereon during cleaning.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0029] FIG. 1 is a plan view showing an objective protector according to a first embodiment of the present invention.
[0030] FIG. 2 is a partially magnified view showing the relationship between a small-diameter tip and a covering, when the objective protector in FIG. 1 is attached.
[0031] FIG. 3 is a plan view showing an objective protector according to a second embodiment of the present invention.
[0032] FIG. 4 is a longitudinal sectional view showing an objective protector according to a third embodiment of the present invention.
[0033] FIG. 5 is a longitudinal sectional view showing a modification of the objective protector in FIG. 4 .
[0034] FIG. 6 is a longitudinal sectional view showing a modification of the covering.
[0035] FIG. 7 is a plan view showing a modification of the objective protector when attached only to a small-diameter tip.
[0036] FIG. 8 is a schematic diagram showing an objective protector according to a fourth embodiment of the present invention.
[0037] FIG. 9 is a perspective view showing an attaching mechanism of the objective protector in FIG. 8 .
[0038] FIG. 10 is a longitudinal sectional view showing a modification of a structure for attaching a fiber bundle.
DETAILED DESCRIPTION OF THE INVENTION
[0039] An objective protector 1 according to a first embodiment of present invention will be described below with reference to FIGS. 1 and 2 .
[0040] As shown in FIG. 1 , the objective protector 1 of this embodiment protects an objective lens 4 which has a small-diameter tip 2 at the front end thereof and the rear end of which is attached to a microscope main body 3 .
[0041] This objective protector 1 includes an optically transparent covering 6 , which covers at least an end surface 5 of the objective lens 4 , and an attaching mechanism 7 for attaching the covering 6 to the objective lens 4 .
[0042] The covering 6 is formed of a membrane member made from an optically transparent plastic material, for example, polyethylene, polyvinylidene chloride, polystyrene, polypropylene, or polycarbonate. The thickness of the covering 6 is, for example, from several micrometers to several hundred micrometers.
[0043] The attaching mechanism 7 is formed, for example, of a circumferential groove 8 , which is formed around the entire circumference of the outer circumferential surface of a large-diameter portion 4 a of the objective lens 4 , and an O-ring constricting member 9 which can engage with the circumferential groove 8 .
[0044] A microscope observation method using the objective protector 1 according to this embodiment, having such a configuration, will be described below.
[0045] As shown in FIG. 1 , to attach the objective protector 1 according to this embodiment to the objective lens 4 , first the part from the small-diameter tip 2 of the objective lens 4 to the large-diameter portion 4 a at the top thereof is covered with the covering 6 . Next, the constricting member 9 , which is stretched open larger than the outer diameter of the large-diameter portion 4 a , is placed on the large diameter portion 4 a from above the covering 6 . Then, by releasing the constricting member 9 at the position of the circumferential groove 8 formed in the large-diameter portion 4 a , the covering 6 is pinched between the constricting member 9 and the large-diameter portion 4 a by the elastic restoring force of the constricting member 9 , and the constricting member 9 engages with the circumferential groove 8 , the covering 6 being disposed therebetween. Accordingly, the constricting member 9 is prevented from moving in the axial direction, and the covering 6 is securely held on the outer circumferential surface of the objective lens 4 by the frictional force between the constricting member 9 and the circumferential groove 8 .
[0046] As shown in FIG. 2 , by applying tension to the covering 6 when the covering 6 is secured by the constricting member 9 , it is possible to bring the covering 6 into close contact with the front surface of a front lens 4 b disposed at the end surface 5 of the objective lens 4 . Because the covering 6 has a thickness of several micrometers to several hundred micrometers, bringing it into close contact with the front surface 4 b of the objective lens 4 forms a flat surface that follows the shape of the front surface. Therefore, light passing therethrough does not experience refraction or the like.
[0047] In this state, the tip of the objective lens 4 is brought into contact with a specimen (not shown in the drawing) or is inserted inside a specimen, and observation is carried out. By doing so, because the end surface 5 and the outer circumferential surface of the objective lens 4 are covered by the covering 6 , as described above, the specimen can be prevented from coming into direct contact with the front surface of the objective lens 4 . Therefore, it is possible to prevent problems such as the front surface of the objective lens 4 becoming contaminated by contact with the specimen, or bacteria and the like contained in the specimen becoming adhered to the objective lens 4 . In addition, because the covering 6 has no effect on the light passing through the objective lens 4 , as described above, it is possible to acquire a clear image.
[0048] After observation, it is possible to remove the used covering 6 to which the specimen has adhered simply by removing the constricting member 9 and taking off the covering 6 from the outer surface of the objective lens 4 . Cleaning, disinfecting, sterilizing and so forth of the objective lens 4 can thus be eliminated. Therefore, it is possible to omit the procedures for removing the objective lens 4 from the microscope main body 3 and attaching it again, which allows the preparation procedure for observation to be simplified. In addition, it is possible to prevent an external force being applied to the outer surface of the objective lens 4 during these procedures, which can prevent parts that are susceptible to external force, especially the small-diameter tip 2 , from being damaged.
[0049] Next, an objective protector 10 according to a second embodiment of the present invention will be described below with reference to FIG. 3 .
[0050] In the description of this embodiment, parts having the same configuration as those of the objective protector 1 according to the first embodiment described above are assigned the same reference numerals, and a description thereof is omitted.
[0051] The difference between the objective protector 10 according to this embodiment and the objective protector 1 according to the first embodiment is an attaching mechanism 11 .
[0052] As shown in FIG. 3 , the attaching mechanism 11 in this embodiment includes a ring-shaped member 12 disposed so as to fit with a large-diameter portion 4 a of an objective lens 4 . The ring-shaped member 12 may be attached to the objective lens 4 with a bonding agent, or it may be removably secured to the objective lens 4 by means of a push screw (not shown).
[0053] A circumferential groove 8 is formed in the outer circumferential surface of the ring-shaped member 12 around the entire circumference thereof, and a constricting member 9 is engaged therewith to pinch the covering 6 therebetween.
[0054] This embodiment affords similar advantages to those of the first embodiment. Namely, it is possible to prevent bacteria or contamination from adhering to the outer circumferential surface of the objective lens 4 . In addition, cleaning, disinfecting, and sterilizing procedures, as well as various procedures associated therewith, can be omitted, and the objective lens 4 can be protected. Furthermore, because the circumferential groove 8 is formed in the ring-shaped member 12 which is fitted to the outer circumferential surface of the objective lens 4 , it is not necessary to form the circumferential groove 8 in the objective lens 4 itself. Therefore, it is possible to attach the covering 6 even to an objective lens 4 which has no circumferential groove 8 . By providing the circumferential groove 8 in the ring-shaped member 12 , this embodiment can be employed even in cases where there is no space for providing the circumferential groove 8 in the thickness direction of the lens barrel of the objective lens 4 .
[0055] Next, an objective protector 20 according to a third embodiment of the present invention will be described below with reference to FIG. 4 .
[0056] The objective protector 20 according to this embodiment differs from the objective protector 10 according to the second embodiment in the structure of a ring-shaped member 21 attached to an objective lens 4 .
[0057] In this embodiment, the ring-shaped member 21 includes a first ring-shaped member 22 which is secured to the outer surface of a large-diameter portion 4 a of the objective lens 4 ; a second ring-shaped member 23 having a tapered female-threaded portion 23 a which is engaged with a tapered male-threaded portion 22 a provided on the outer surface of the first ring-shaped member 22 ; and a third ring-shaped member 24 which is attached to the bottom surface of the second-ring-shaped member 23 in such a manner that it can be moved relative thereto in the circumferential direction.
[0058] The first ring-shaped member 22 includes a slotted portion 22 b which is axially cut at one place in the circumferential direction. Therefore, by increasing and decreasing the width of the slotted portion 22 b , it is possible to increase and decrease the inner diameter.
[0059] An outer circumferential portion of the covering 6 is secured in the third ring-shaped member 24 .
[0060] The operation of the objective protector 23 according to this embodiment, having such a configuration, will be described below.
[0061] To attach the objective protector 20 according to this embodiment to the objective lens 4 , the slotted portion 22 b in the first ring-shaped member 22 is opened to increase the inner diameter and is fitted to the large-diameter portion 4 a of the objective lens 4 . Then, once the axial position of the first ring-shaped member 22 has been aligned at an appropriate position, the tapered female-threaded portion 23 a of the second ring-shaped member 23 is engaged with the tapered male-threaded portion 22 a on the outer surface of the first ring-shaped member 22 .
[0062] When the second ring-shaped member 23 is rotated about the axis of the objective lens 4 , the second ring-shaped member 23 moves in the axial direction relative to the first ring-shaped member 22 due to the engagement of the tapered male-threaded portion 22 a and the tapered female-threaded portion 23 a . Accordingly, the first ring-shaped member 22 is constricted inwards in the radial direction as the engagement proceeds and eventually becomes tightly secured to the objective lens 4 by substantially increasing the friction between itself and the outer circumferential surface of the large-diameter portion 4 a . On the other hand, the second ring-shaped member 23 gradually moves towards the microscope main body 3 relative to the first ring-shaped member 22 .
[0063] Because the third ring-shaped member 24 is attached so as to be capable of rotating relative to the second ring-shaped member 23 , it does not rotate even though the second-ring-shaped member 23 rotates. When the second ring-shaped member 23 moves in the axial direction relative to the first ring-shaped member 22 , the third ring-shaped member 24 also moves axially together with the second ring-shaped member 23 . As a result, by pulling back the covering 6 , which is secured to the third ring-shaped member 24 , in the axial direction, tension is applied to the covering 6 , and the covering 6 is brought into close contact with the front surface of the front lens 4 b disposed at the end surface 5 in the objective lens 4 .
[0064] Therefore, according to this embodiment, the covering 6 can be attached to the objective lens 4 simply by rotating the second ring-shaped member 23 about the axis of the objective lens 4 , and the covering 6 can be brought into close contact with the front surface of the front lens 4 b.
[0065] As shown in FIG. 5 , by forming a circumferential groove 8 in the outer surface of the second ring-shaped member 23 , it is possible to secure a second covering 25 (drape), for covering parts on the microscope main body 3 side, in the circumferential groove 8 in the second ring-shaped member 23 using a constricting member 9 . In such a case, it is possible to protect the entire microscope, including not only the objective lens 4 but also the microscope main body 3 , from damage or to prevent bacteria adhering thereto.
[0066] Although a membrane member is employed as the covering 6 in the embodiments described above, as shown in FIG. 6 , it is also possible to dispose a cover member 26 , made from optically transparent glass or plastic, at a position where it touches the end surface 5 of the objective lens 4 . By doing so, it is possible to easily set the distance between the specimen A and the end surface 5 of the objective lens 4 to match the working distance of the objective lens 4 . In this case, it is possible to secure the cover member 26 to the objective lens 4 with wire or the like, without employing a membrane member.
[0067] The objective protectors 1 , 10 , and 20 are secured to the large-diameter portion 4 a of the objective lens 4 in the embodiments described above; instead of this, however, an objective protector may be secured to a small-diameter tip 2 of the objective lens 4 , as shown in FIG. 7 . With this configuration, the covering 6 can be disposed around the outer surface of the small-diameter tip 2 without spreading out into the periphery of the small-diameter tip 2 . Therefore, it is possible to ensure that the covering 6 does not act as an obstruction when inserting the objective lens 4 into a small incision made in the specimen.
[0068] Next, an objective protector 30 according to a fourth embodiment of the present invention will be described below with reference to FIGS. 8 and 9 .
[0069] As shown in FIG. 8 , the objective protector 30 according to this embodiment protects at least an end surface 35 b of a fiber bundle 35 , whose tip is disposed in the vicinity of a focal point of an objective lens 34 , using a bracket 33 which is secured to a base 32 of a microscope 31 . The objective protector 30 includes a covering 6 formed of a membrane member, and an attaching mechanism 36 which secures the covering 6 to the end of the fiber bundle 35 .
[0070] As shown in FIG. 9 , the attaching mechanism 36 is provided with, for example, a through-hole 37 through which the fiber bundle 35 passes and includes a sleeve 37 whose outer surface is tapered and an engaging ring 38 which is fitted to the outer surface of the sleeve 37 . A collar 37 b is formed at one end of the sleeve 37 , and a slotted portion 37 c which extends in the axial direction from the central position in the longitudinal direction is formed at the other end thereof. When the engaging ring 38 is fitted to the sleeve 37 , the engaging ring 38 presses the tapered outer surface 37 d inwards in the radial direction, whereupon the slotted portion 37 c is reduced in size, and by doing so, the sleeve 37 is secured such that it squeezes the outer surface of the fiber bundle 35 .
[0071] Because a circumferential groove is formed at the outer circumferential surface of the attaching mechanism 36 by the collar 37 b of the sleeve 37 and the engaging ring 38 , when the sleeve 37 is secured to the outer surface of the fiber bundle 35 by fitting the engaging ring 38 to the sleeve 37 , it is possible to attach the covering 6 to the end of the fiber bundle 35 by positioning an O-ring constricting member 9 so as to pinch the covering 6 .
[0072] Reference numeral 39 in FIG. 8 is a light source such as a halogen lamp, reference numeral 40 is an eyepiece lens, and reference numeral 41 is a dichroic mirror.
[0073] With this embodiment, the end of the fiber bundle 35 , which is placed in contact with or inserted into the sample, is protected by the objective protector 30 . Therefore, procedures for cleaning, disinfecting, or sterilizing the fiber bundle 35 after observation are not necessary, and it is thus possible to simplify the preparation procedure for observation.
[0074] Although an example has been given in which the fiber bundle 35 is secured to the base 32 of the microscope 31 with the bracket 33 , instead of this, it is also possible to directly secure the fiber bundle 35 to the objective lens 34 using a bracket 42 , as shown in FIG. 10 . | The present invention reduces or removes the need to clean an objective lens, thus simplifying the observation procedure, prevents bacteria or contamination from adhering to the objective lens, and protects the objective lens from external force that would be exerted during cleaning. The invention includes an optically transparent covering configured to cover at least an end surface of an objective lens; and an attaching mechanism configured to attach the covering to the objective lens. | 6 |
TECHNICAL FIELD
The present invention relates to an inflator, and particularly to an inflator for use in inflating an inflatable vehicle occupant protection device.
BACKGROUND OF THE INVENTION
A conventional inflator for inflating an inflatable vehicle occupant protection device includes a container having a storage chamber. Inflation fluid under pressure is stored in the storage chamber. An igniter assembly is associated with the container and is actuatable for heating the inflation fluid in the storage chamber to increase the fluid pressure in the storage chamber. The increased fluid pressure ruptures a burst disk. The ruptured burst disk defines an outlet opening through which the inflation fluid flows.
U.S. Pat. No. 5,529,333 describes an inflator for inflating an air bag that includes a container that defines a storage chamber. The container has an opening that leads to the storage chamber. A plug member is received in the opening of the container and closes the opening of the container. Two passages extend through the plug member. A first passage through the plug member enables inflation fluid to flow from the storage chamber toward an air bag. A wall portion of the plug member closes the first passage. The wall portion of the plug member includes a break away center. An actuator is actuatable for opening the break away center of the wall portion of the plug member to form an outlet opening through which inflation fluid flows. A second passage through the plug member is provided for filling the storage chamber with inflation fluid. A ball is located in the second passage for preventing inflation fluid from flowing out of the storage chamber of the container through the second passage of the plug member.
SUMMARY OF THE INVENTION
The present invention relates to an inflator comprising structure defining a chamber. First and second passages extend through the structure to the chamber. A burst disk closes the first passage. The inflator also comprises a fill valve assembly having a valve housing and a valve member. The valve housing is received in the second passage and defines a fill passage. A fluid is stored under pressure in the chamber. An igniter is actuatable for opening the burst disk for enabling fluid to flow out of the chamber through the first passage. The valve member enables flow of the fluid through the fill passage of the valve housing into the chamber and prevents flow out of the chamber through the fill passage.
According to another aspect, the present invention relates to an inflator comprising structure defining a chamber. First and second passages extend through the structure to the chamber. A fluid is stored under pressure in the chamber. A device closes the first passage and is actuatable for enabling fluid to flow out of the chamber through the first passage. The inflator also comprises a fill valve having a valve housing, a valve member, and a plug member. The valve housing is received in the second passage and defines a fill passage. The valve member enables flow of the fluid through the fill passage of the valve housing into the chamber and prevents flow out of the chamber through the fill passage. The plug member seals the fill passage of the valve housing after the fluid is introduced into the chamber through the fill passage. The plug member is spaced away from the valve member outward of the chamber.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing and other features of the present invention will become apparent to those skilled in the art to which the present invention relates upon reading the following description with reference to the accompanying drawings, in which:
FIG. 1 illustrates a vehicle safety system including an inflator constructed in accordance with the present invention;
FIG. 2 is a cross-section of the inflator of FIG. 1 in a non-actuated condition;
FIG. 3 is an enlarged view of a portion of FIG. 2 ;
FIG. 4 is a partially exploded view of the portion of the inflator shown in FIG. 3 ;
FIG. 5 is a cross-section of the inflator of FIG. 1 in an actuated condition; and
FIG. 6 is an enlarged view of a portion of an inflator constructed in accordance with a second embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 illustrates a vehicle safety system 10 including the inflator 12 constructed in accordance with the present invention. The inflator 12 of the present invention is for use in inflating an inflatable vehicle occupant protection device of the vehicle safety system 10 . The inflatable vehicle occupant protection device of FIG. 1 is an inflatable curtain 14 . Alternatively, the inflatable vehicle occupant protection device may include an inflatable air bag, an inflatable seat belt, an inflatable knee bolster, an inflatable headliner, or a knee bolster operated by an inflatable air bag.
The inflatable curtain 14 of FIG. 1 is in a deflated condition and is stored within a housing 16 . The inflatable curtain 14 , in the deflated condition, and the housing 16 have an elongated configuration and are mounted to a vehicle 18 in a location adjacent both the side structure of the vehicle and a roof 20 of the vehicle. The side structure of the vehicle 18 includes an A-pillar 22 , a B-pillar 24 , a C-pillar 26 , and side windows 28 and 30 . FIG. 1 shows four brackets 32 securing the housing 16 and the inflatable curtain 14 to the side structure of the vehicle 18 .
In the illustrated embodiment, a fill tube 34 connects the inflator 12 of the present invention to the inflatable curtain 14 . The inflator 12 is in fluid communication with the inflatable curtain 14 through the fill tube 34 . Upon actuation of the inflator 12 , inflation fluid flows through the fill tube 34 and into the inflatable curtain 14 . In response to receiving the inflation fluid, the inflatable curtain 14 deploys from the deflated condition to an inflated condition to cover portions of the side structure of the vehicle, such as side windows 28 and 30 .
As shown in FIG. 2 , the inflator 12 includes a tubular metal body portion 40 . The body portion 40 includes cylindrical inner and outer surfaces 42 and 44 , respectively. The inner and outer surfaces 42 and 44 are centered on a longitudinal axis A. The body portion 40 of the inflator 12 also has opposite first and second open ends 46 and 48 , respectively.
An igniter endcap 50 closes the first open end 46 of the body portion 40 . The igniter endcap 50 includes an annular, radially extending peripheral portion 52 . An outer diameter of the peripheral portion 52 of the igniter endcap 50 is approximately equal to a diameter of the outer surface 44 of the body portion 40 . The peripheral portion 52 of the igniter endcap 50 is affixed to the body portion 40 at the first open end 46 . The peripheral portion 52 of the igniter endcap 50 may be welded to or crimped to the body portion 40 at the first open end 46 . FIG. 2 shows the peripheral portion 52 of the igniter endcap 50 welded to the body portion 40 at the first open end 46 .
The igniter endcap 50 also includes an axially protruding central portion 54 . The central portion 54 includes first and second annular, axially extending portions 56 and 58 , respectively. The first annular, axially extending portion 56 is disposed adjacent to the peripheral portion 52 and has a diameter that is greater than a diameter of the second annular, axially extending portion 58 . A tapered portion 60 connects the first and second annular, axially extending portions 56 and 58 . A central flange 62 extends radially inwardly from an end of the second annular, axially extending portion 58 opposite the tapered portion 60 . A radially inner surface 64 of the central flange 62 defines a passage 66 through the igniter endcap 50 .
An igniter 70 is secured to the igniter endcap 50 . The igniter 70 includes a portion 72 containing a pyrotechnic material (not shown) and a resistive wire (not shown) for igniting the pyrotechnic material. The igniter 70 also includes leads 74 for connecting the resistive wire of the igniter to electronic circuitry 76 ( FIG. 1 ) of a vehicle safety system 10 . The electronic circuitry 76 includes a sensor 78 for sensing a deployment condition for which inflation of the inflatable curtain 14 is desired. When a deployment condition is sensed, the igniter 70 receives an actuation signal through the leads 74 . The igniter 70 is responsive to the actuation signal for actuating the inflator 12 to provide inflation fluid to the inflatable curtain 14 .
An isolation disk 80 is affixed to the central flange 62 of the igniter endcap 50 on a side opposite to the igniter 70 . The isolation disk 80 closes and seals the passage 66 through the igniter endcap 50 . Preferably, the isolation disk 80 is welded to the central flange 62 of the igniter endcap 50 .
The inflator 12 also includes a diffuser endcap 82 . The diffuser endcap 82 closes the second open end 48 of the body portion 40 of the inflator 12 . The diffuser endcap 82 includes a tubular end portion 84 . The tubular end portion 84 includes inner and outer surfaces 86 and 88 , respectively. The outer surface 88 of the tubular end portion 84 of the diffuser endcap 82 has a diameter that is equal to the diameter of the outer surface 44 of the body portion 40 . An annular end surface 90 of the tubular end portion 84 connects the inner and outer surfaces 86 and 88 . A passage 92 ( FIG. 4 ) extends radially through the tubular end portion 84 of the diffuser endcap 82 . As shown in FIG. 4 , the passage 92 defines an opening 94 on the outer surface 88 of the diffuser endcap 82 and an opening 96 on the inner surface 86 of the diffuser endcap.
An annular wall portion 100 of the diffuser endcap 82 extends radially inwardly from the tubular end portion 84 at an end of the tubular end portion opposite end surface 90 . The annular wall portion 100 includes inner and outer surfaces 102 and 104 , respectively, and terminates at a cylindrical end surface 106 . The inner surface 102 of the annular wall portion 100 joins with and extends perpendicular to the inner surface 86 of the tubular end portion 84 of the diffuser endcap 82 . The outer surface 104 of the annular wall portion 100 joins with and extends perpendicular to the outer surface 88 of the tubular end portion 84 of the diffuser endcap 82 .
A tubular discharge portion 110 of the diffuser endcap 82 extends axially away from the annular wall portion 100 . The tubular discharge portion 110 includes cylindrical inner and outer surfaces 112 and 114 , respectively. The inner surface 112 of the tubular discharge portion 110 extends axially from the cylindrical end surface 106 of the annular wall portion 100 . The outer surface 114 of the tubular discharge portion 110 joins with and extends perpendicular to the outer surface 104 of the annular wall portion 100 . The inner surface 112 of the tubular discharge portion 110 and the cylindrical end surface 106 of the annular wall portion 100 collectively define a passage 116 through which inflation fluid flows. Inflation fluid flows axially, i.e., in a direction that is parallel to the longitudinal axis A of the body portion 40 of the inflator 12 , from the tubular discharge portion 110 of the diffuser endcap 82 of FIGS. 2–4 .
A metal burst disk 120 closes the passage 116 of the diffuser endcap 82 . The burst disk 120 has a domed central portion 122 and a radially outwardly extending flange portion 124 that is affixed to the inner surface 102 of the annular wall portion 100 of the diffuser endcap 82 . Preferably, the burst disk 120 is welded to the annular wall portion 100 . When the flange portion 124 of the burst disk 120 is affixed to the inner surface 102 of the annular wall portion 100 , the domed central portion 122 of the burst disk 120 is located in the passage 116 . The burst disk 120 is designed to rupture when subjected to a predetermined differential pressure. In a preferred embodiment, the burst disk 120 is designed to rupture when exposed to a differential pressure of approximately 12,000 pounds per square inch (psi). When the burst disk 120 ruptures, an outlet opening 126 ( FIG. 5 ) is formed in the burst disk 120 .
The body portion 40 , the igniter endcap 50 , and the diffuser endcap 82 collectively define a chamber 130 . The chamber 130 extends axially along the longitudinal axis A between the igniter endcap 50 and the diffuser endcap 82 . The inner surface 42 of the body portion 40 and the inner surface 86 of the tubular end portion 84 of the diffuser endcap 82 define a radial outer boundary of the chamber 130 .
The inflator 12 also includes a fill valve assembly 140 through which the chamber 130 is filled. Details of the fill valve assembly 140 are described with reference to FIGS. 3 and 4 . The fill valve assembly 140 includes a valve housing 142 and a valve member 144 . The valve housing 142 has a main body portion 146 , an outer portion 148 , and an inner portion 150 . The main body portion 146 of the valve housing 142 is located between the outer and inner portions 148 and 150 . The main body portion 146 of the valve housing 142 includes a cylindrical outer surface 152 . A fill passage 154 extends through the main body portion 146 . As shown in FIG. 4 , the fill passage 154 includes a large diameter portion 156 , a tapered portion 158 , and a smaller diameter portion 160 . The large diameter portion 156 of the fill passage 154 is located nearest the outer portion 148 of the valve housing 142 . The tapered portion 158 of the fill passage 154 is located nearest the inner portion 150 of the valve housing 142 . The smaller diameter portion 160 is located between the large diameter portion 156 and the tapered portion 158 of the fill passage 154 .
The outer portion 148 of the valve housing 142 is the widest part of the valve housing. The outer portion 148 includes a tapered shoulder portion 162 and a tubular outer portion 164 . The tapered shoulder portion 162 extends radially outwardly of the main body portion 146 of the valve housing 142 as it extends axially away from the main body portion. The tapered shoulder portion 162 includes outer and inner surfaces 166 and 168 ( FIG. 4 ), respectively. The outer surface 166 joins with the cylindrical outer surface 152 of the main body portion 146 . The inner surface 168 of the tapered shoulder portion 162 leads to the large diameter portion 156 of the fill passage 154 . The tubular outer portion 164 extends axially away from the tapered shoulder portion 162 in a direction opposite to the main body portion 146 . The tubular outer portion 164 includes an outer surface 170 ( FIG. 4 ) having a diameter approximately twice the diameter of the cylindrical outer surface 152 of the main body portion 146 . An inner diameter of the tubular outer portion 164 defines a mouth 172 that leads to the fill passage 154 of the valve housing 142 .
The inner portion 150 of the valve housing 142 is generally tubular and terminates at an end surface 174 ( FIG. 4 ). The inner portion 150 includes cylindrical outer and inner surfaces 176 and 178 ( FIG. 4 ), respectively. The outer surface 176 of the inner portion 150 of the valve housing 142 is coaxial with and has a diameter that is equal to the cylindrical outer surface 152 of the main body portion 146 . The inner surface 178 of the inner portion 150 defines a chamber 180 . The inner portion 150 of the valve housing 142 includes four cutouts 182 , one of which is shown in full in FIG. 4 . The cutouts 182 are located adjacent to the end surface 174 of the inner portion 150 . The four cutouts 182 separate four finger portions 184 of the inner portion 150 of the valve housing 142 . FIG. 4 shows two of the four finger portions 184 .
The valve member 144 of the fill valve assembly 140 is a check ball. The check ball 144 is formed from an elastomer. Preferably, the check ball 144 is made from either VITON elastomer (trademark of E.I. DuPont de Nemours & Co.) or a synthetic rubber made from the polymerization of butadiene and sodium. The check ball 144 is placed in the chamber 180 of the inner portion 150 of the valve housing 142 . The four finger portions 184 of the inner portion 150 of the valve housing 142 are bent inwardly toward one another to the positions shown in FIG. 3 so as to form a cage for retaining the check ball 144 in the chamber 180 . The cutouts 182 between the finger portions 184 enable fluid flow into and out of the chamber 180 .
The fill valve assembly 140 is inserted into the passage 92 in the diffuser endcap 82 until the outer surface 166 of the tapered shoulder portion 162 engages the outer surface 88 of the tubular end portion 84 of the diffuser endcap 82 . The valve housing 142 is then affixed to the diffuser endcap 82 . Preferably, the tapered shoulder portion 162 of the outer portion 148 of the valve housing 142 is welded to the tubular end portion 84 of the diffuser endcap 82 . When affixed to the diffuser endcap 82 , the inner portion 150 of the valve housing 142 and the check ball 144 are located in the chamber 130 .
A combustible gas mixture 186 ( FIG. 2 ) is stored in the chamber 130 . The combustible gas mixture 186 preferably includes an inert gas, hydrogen, and oxygen or an inert gas, hydrogen and air. The inert gas may be argon, nitrogen, or any suitable inert gas. Trace amounts of helium may be added to the combustible gas mixture 186 to aid in leak detection. The combustible gas mixture 186 is stored under pressure in the chamber 130 of the inflator 12 . Preferably, the pressure of the stored combustible gas mixture 186 in the chamber 130 of the inflator 12 is 6,000 to 7,000 pounds per square inch (psi).
When the fill valve assembly 140 is oriented as shown in FIG. 3 and there is no difference between the air pressure in the chamber 130 and atmospheric pressure, gravity acts on the check ball 144 and the check ball lies on the bent finger portions 184 of the valve housing 142 . To fill the chamber 130 of the inflator 12 with the combustible gas mixture 186 , a filling tube (not shown) of a filling device (not shown) is inserted into the mouth 172 of the outer portion 148 of the valve housing 142 . The combustible gas mixture 186 flows through the fill passage 154 of the valve housing 142 of the fill valve assembly 140 and into the chamber 180 of the inner portion 150 of the valve housing 142 of the fill valve assembly 140 . The combustible gas mixture 186 then flows through the cutouts 182 into the chamber 130 of the inflator 12 .
As the pressure of the combustible gas mixture 186 stored in the chamber 130 of the inflator 12 increases, the gas pressure in the chamber 130 tends to force the check ball 144 upwardly, as viewed in FIG. 3 , toward the main body portion 146 of the valve housing 142 to close the fill passage 154 . The flow of the combustible gas mixture 186 through the fill passage 154 toward the chamber 130 moves the check ball 144 away from the main body portion 146 and enables flow into the chamber 130 . When the flow of the combustible gas mixture 186 through the fill passage 154 toward the chamber 130 ceases, the check ball 144 moves upwardly, as viewed in FIG. 3 , into the tapered portion 158 of the fill passage 154 and seats against the main body portion 146 of the valve housing 142 to close the fill passage. The check ball 144 forms a seal against the main body portion 146 of the valve housing 142 to prevent the escape of the stored combustible gas mixture 186 from the chamber 130 through the fill passage 154 .
When the filling tube (not shown) of the filling device (not shown) is removed from the mouth 172 of the tubular outer portion 164 of the outer portion 148 of the valve housing 142 , any of the combustible gas mixture 186 that is present in the fill passage 154 of the valve housing 142 dissipates into the atmosphere. Alternatively, the fill passage 154 may be aspirated to remove any of the combustible gas mixture 186 that is present in the fill passage. A metal seal plug 188 is then secured to the valve housing 142 to close and seal the large diameter portion 156 of the fill passage 154 . The metal seal plug 188 , prior to being secured to the valve housing 142 , is a spherical ball, as shown in FIG. 4 . The metal seal plug 188 may have a shape other than spherical.
To secure the metal seal plug 188 to the valve housing 142 , the inflator 12 is oriented so that the outer portion 148 of the valve housing 142 is located above the check ball 144 , as is shown in FIG. 3 . The metal seal plug 188 is placed in the mouth 172 of the outer portion 148 of the valve housing 142 and gravity causes the metal seal plug 188 to rest on the inner surface 168 of the tapered shoulder portion 162 of the outer portion 148 . The metal seal plug 188 is then heated until a portion of the metal seal plug melts. Since the inner surface 168 of the tapered shoulder portion 162 leads to the large diameter portion 156 of the fill passage 154 , the melted portion of the metal seal plug 188 flows along the inner surface 168 and into the large diameter portion 156 of the fill passage 154 . When the heat is removed from the metal seal plug 188 , the metal seal plug 188 bonds to the valve housing 142 to close and seal the fill passage 154 . A portion of the metal seal plug 188 is located within and closes the large diameter portion 156 of the fill passage 154 and a portion of the metal seal plug is located outside of the fill passage and abuts the inner surface 168 .
The fill passage 154 spaces the metal seal plug 188 away from the check ball 144 and thus, away from the combustible gas mixture 186 in the chamber 130 . The spacing of the metal seal plug 188 away from the chamber 130 and the seal of the check ball 144 over the fill passage 154 enable the metal seal plug to be safely heated without igniting the combustible gas mixture 186 .
When the igniter 70 of the inflator 12 receives the actuation signal from the electronic circuitry 76 of the vehicle safety system 10 , the igniter 70 is actuated. Combustion products, including a shock wave, from actuation of the igniter 70 travel through the passage 66 in the igniter endcap 50 , rupture the isolation disk 80 , and enter the chamber 130 . The combustion products heat and ignite the combustible gas mixture 186 that is stored under pressure within the chamber 130 . The resulting combustion of the combustible gas mixture 186 produces inflation fluid, which is further heated by the combustion of the combustible gas mixture. The heating and ignition of the combustible gas mixture 186 increases the pressure within the chamber 130 . When the predetermined differential pressure across the burst disk 120 is reached, the burst disk 120 is ruptured and the outlet opening 126 is formed through the ruptured burst disk. Inflation fluid passes through the outlet opening 126 , through the passage 116 in the diffuser endcap 82 , and into the fill tube 34 for inflating the inflatable curtain 14 . FIG. 5 illustrates an actuated inflator 12 including an actuated igniter 70 , a ruptured isolation disk 80 , and a ruptured burst disk 120 . The metal seal plug 188 and the check ball 144 of the fill valve assembly 140 prevent inflation fluid from passing through the fill passage 154 of the valve housing 142 .
FIG. 6 is an enlarged view of a portion of an inflator 12 ′ constructed in accordance with a second embodiment of the present invention. Structures of FIG. 6 that are the same as or similar to structures of FIG. 3 are numbered using the same reference numbers.
The diffuser endcap 82 illustrated in FIG. 6 provides a radial discharge of inflation fluid from the inflator 12 ′. A tubular discharge portion 210 of the diffuser endcap 82 extends axially away from an annular wall portion 100 of the diffuser endcap. The tubular discharge portion 210 includes cylindrical inner and outer surfaces 212 and 214 , respectively. The inner surface 212 of the tubular discharge portion 210 extends from the cylindrical end surface 106 of the annular wall portion 100 . The outer surface 214 of the tubular discharge portion 210 joins with and extends perpendicular to the outer surface 104 of the annular wall portion 100 . A radially extending wall 216 closes an end of the tubular discharge portion 210 opposite the annular wall portion 100 . The radially extending wall 216 includes inner and outer surfaces 218 and 220 , respectively. The inner surface 212 of the tubular discharge portion 210 and the inner surface 218 of the radially extending wall 216 collectively form a discharge chamber 222 . Passage 116 leads from the chamber 130 into the discharge chamber 222 .
A plurality of flow openings 224 extends radially through the tubular discharge portion 210 . FIG. 6 illustrates two flow openings 224 . The flow openings 224 provide for radial flow of inflation fluid out of the inflator 12 ′. The inflator 12 ′ of FIG. 6 operates in substantially the same manner as the inflator 12 of FIG. 3 for providing inflation fluid to an inflatable vehicle occupant protection device. The fill valve assembly 140 of FIG. 6 is identical to the fill valve assembly 140 described above with reference to FIGS. 2–5 .
From the above description of the invention, those skilled in the art will perceive improvements, changes and modifications. For example, the passage 92 for receiving the fill valve assembly 140 may be located on the body portion 40 of the inflator 12 , 12 ′ or on the annular wall portion 100 of the diffuser endcap 82 . Also, the inflator 12 may store a non-combustible gas under pressure. The inflator 12 may be connected to the inflatable vehicle occupant protection system in any manner, which may include eliminating the fill tube 34 of FIG. 1 . Such improvements, changes and modifications within the skill of the art are intended to be covered by the appended claims. | An inflator ( 12 ) includes structure ( 40, 50, 82 ) defining a chamber ( 130 ). First and second passages ( 92 and 116 ) extend through the structure ( 40, 50, 82 ). A burst disk ( 120 ) closes the first passage ( 116 ). A valve housing ( 142 ) is received in the second passage ( 92 ) and defines a fill passage ( 154 ). A fluid ( 186 ) is stored under pressure in the chamber ( 130 ). An igniter ( 70 ) is actuatable for opening the burst disk ( 120 ) for enabling the fluid ( 186 ) to flow out of the chamber ( 130 ) through the first passage ( 116 ). A valve member ( 144 ) enables flow of the fluid ( 186 ) through the fill passage ( 154 ) of the valve housing ( 142 ) into the chamber ( 130 ) and prevents flow out of the chamber ( 130 ) through the fill passage ( 154 ). | 1 |
The United States Government has rights in this invention pursuant to Contract No. W-31-109-ENG-38 between the U.S. Department of Energy and the University of Chicago.
The invention is concerned generally with a method of modifying a surface region of high temperature iron alloys, such as Fe--Cr alloys. More particularly, the invention is directed to a method of protection against corrosive atmospheres by modifying the surface of an Fe--Cr alloy by forming a silicide based coating on the Fe--Cr surface.
Protection against corrosion of structural iron based alloys is of fundamental importance in high temperature materials applications. Typically, corrosion protection is obtained by formation of a chromium oxide scale which acts as a diffusion barrier between the corrosive environment and the iron based alloy. Unfortunately, conventional protective coatings are subject to erosion and spallation under high temperature corrosive atmospheric use. Such iron based alloys have been the subject of substantial unsuccessful research to determine compositions resistant to formation of such unstable coatings.
It is therefore an object of the invention to provide an improved article and method of manufacture of iron based alloys.
It is another object of the invention to provide a novel article and method of manufacture of a protective coating on iron based alloys.
It is a further object of the invention to provide an improved article and method of manufacture of a protective silicide based coating on iron-chromium alloys.
It is still another object of the invention to provide a novel article and method of manufacture of a protective amorphous silicon containing coating on an iron based alloy.
It is yet a further object of the invention to provide an improved article and method of manufacture of a protective silicon (nitrogen and/or chromium) compound coating on an iron based alloy.
It is also an object of the invention to provide a novel article and method of manufacture of an iron-chromium alloy doped with cerium, yttrium or lanthanum with the surface coated with a silicide layer diffused into the alloy surface.
It is an additional object of the invention to provide an improved article and method of manufacture of a silicon containing (or silicide), corrosion protection coating which passivates line and point defects near the surface of an iron based alloy.
Other objects, features and advantages of the present invention will be readily apparent from the following description of the preferred embodiments thereof, taken in conjunction with the accompanying drawings described below wherein like elements have like numerals throughout the several views.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrate a schematic of a microstructural cross section near the surface of an iron based alloy undergoing ion diffusion;
FIG. 2 illustrates another schematic of a microstructural cross section near the surface of an iron based alloy with grain boundary phases containing yttria;
FIG. 3 illustrates a chemical vapor deposition apparatus used to apply silicon based coatings to the surface of iron based alloys;
FIG. 4A illustrates the weight change arising from corrosion for selected iron based alloys oxidized in a pO 2 atmosphere of 10 -4 atm, at 1000° C. over a 0-40 hour time period; FIG. 4B is a similar plot as FIG. 4A but for a different alloy set oxidized in air at 1000° C. over a 30-day time period; FIG. 4C illustrates weight change arising from corrosion for selected iron based alloys sulfided at 700° C. over a 50-hour time period; FIG. 4D illustrates the same tests of FIG. 4C but extended to 35 days; and FIG. 4E shows the relationship between log pS 2 versus 1/T for 498 ppm H 2 S/H 2 , Cr/CrS and Fe/FeS;
FIG. 5A illustrates grain size variation in iron based alloys during oxidation; and FIG. 5B illustrates a comparison of grain size variation in iron based alloys annealed at 1000° C. over time;
FIG. 6 illustrates sample weight gain for the chemical vapor deposition process for Fe--25Cr--0.3Y and Fe--25Cr--0.3 Ce; and
FIG. 7A illustrates a microstructure of an iron based alloy with silicide diffused into the dark gray areas in and around surface defects, fissures and microcracks; and FIG. 7B shows a magnified portion of the right side of the microstructure of FIG. 7A.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
A system 10 for practicing a preferred form of the method of the invention is shown generally in FIG. 3. As shown in FIG. 1 an iron based alloy 12 can undergo corrosion to form an oxide layer 14 which grows by cation diffusion 16 and/or anion diffusion 18 out of, or into, respectively, the iron based alloy 12. In addition to growth and spallation of the oxide layer 14 due to lack of adhesion, the high temperatures of operation (such as, 700°-1000° C.) applied to the iron based alloy 12, can cause enlargement of the size of grains 20 (see FIG. 5A), which also contributes to spallation of the oxide layer 14. This unwanted grain growth can be substantially eliminated by including selected reactive elements, such as Y (0.1-3 wt.%), Ce (0.3-1.0 wt.%), or other such elements like lanthanum as small additions to the iron based alloy 12. Without limiting the scope of any invention which may be claimed herein, it is believed the reactive elements form phases 22 of intermetallic compounds, oxides or stabilized voids at various grain boundary sites as shown in FIG. 2 (the vertically cross hatched phased are, for example, a Fe--Cr--Y phase, the horizontally cross hatched phases are, for example, yttrium oxide and the open circle is a void region). These reactive element containing phases 22 act to stabilize the grain boundaries, prevent any substantial grain growth as can be noted by considering FIG. 5B, and inhibit outward cation diffusion to the surface of the alloy 12.
In order to form an oxide layer 24 (see FIG. 2), which is stable (good adhesion and grows slowly) at high temperatures in a corrosive atmosphere, the system 10 shown in FIG. 3 is used to deposit a silicon containing (preferably a silicide, i.e., a silicon compound) composition on the iron based alloy 12. In a preferred method a chemical vapor deposition source 25 is disposed near iron based alloy samples 26 within a chamber 28 positioned in a furnace 30. In this system 10 the vapor deposition source 25 is heated to cause emission of vapors 32 which can be, for example, a powder mixture of NaF--Si--SiO 2 , a silane gas source, or other conventional sources which will produce a silicon containing layer on the surface of the alloy samples 26. In a preferred embodiment, the silicide layer can include silicon and oxygen and/or nitrogen and/or chromium. Preferably, the silicon containing layer is roughly 1-2 microns in thickness. The furnace 30 can be used to perform a post anneal and/or to maintain the alloy samples 26 at an elevated temperature (typically, 700°-1200° C.). Such thermal treatments, preferably maintaining elevated temperature during silicide deposition, enable the deposited silicon containing layer to diffuse into the alloy samples 26 and also fill or compensate selected defects, such as dislocations, cracks, voids, atomistic point defects and the like.
In the most preferred embodiment the resulting silicide coated form of the alloy samples 26 were next exposed to an ammonia (NH 3 ) vapor 32 input from ammonia supply 34. Other suitable sources for treating the silicon containing coating can be various nitrogen containing gases, such as NH 4 OH, NH 4 ions or SiN 2 . The ammonia vapor 32 reacts with the silicon containing coating to form a resulting preferred silicon/oxygen/nitrogen coating 36 on the oxide layer 24 (see FIG. 2). In other forms of the invention, the coating 36 is generally a silicon containing layer having at least a partially amorphous structure. These silicide layers, silicon containing layers, and amorphous silicon containing layers are stable under corrosive atmospheres, such as oxidizing or sulfiding atmospheres, and fill defects, such as cracks, voids and other surface defects. If uncompensated, such defects can act as conduits for cation and/or anion diffusion which act to thicken the oxide layer 24 (or sulfide layer if the alloy 12 is exposed to a corrosive sulfur atmosphere).
Comparison of examples of corrosion protection between iron based alloys with and without the silicon containing protective layer are shown in FIG. 4. Tests were performed in a thermogravimetric microbalance. In FIGS. 4A and 4B are comparisons of iron based alloys oxidized at 1000° C. As can be noted, the alloys coated with the silicon containing layer were much more stable than the unprotected alloys, including even the iron based alloys having reactive element additions of cerium and yttrium. In FIGS. 4C and 4D are shown data from iron based alloys protected with the silicon containing protective layer and exposed to a sulfiding corrosive atmosphere (498 ppm H 2 S/H 2 gas mixture and see FIG. 4E re partial pressure versus 1/T). The protected alloys are again much more stable than the unprotected alloys.
In other forms of the invention a silicon/oxygen/nitrogen and/or chromium layer can be obtained by ion beam deposition of silicon followed by, or preferably accompanied by, introducing ammonia to react with the ion beam deposited silicon to form the silicon and oxygen and/or nitrogen and/or chromium layer. Table I summarizes the resulting properties of ion beam deposited (IBAD) layers and chemical vapor deposition (CVD) layers as measured by X-ray diffraction, Auger spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy. This layer is then treated by annealing at high temperatures during deposition to enable diffusion and compensation to take place as described hereinbefore. The resulting layer has good adhesion to the alloy 12 but does not slow down the oxide layer thickening as well as the chemical vapor deposition process. However, the protective layer does provide protection superior to iron based alloys having no protection.
TABLE I______________________________________FE--25Cr--Re (Re = 1 & 0.3 Y and Ce)IBADNo Heat After Heat CVDTreatment Treatment Annealing______________________________________XRD Amorphous Cr.sub.2 O.sub.3 Cr.sub.2 O.sub.3 Fe--Cr-Silicides Fe--Cr-SilicidesAuger Si, N, OXPS Si, N, OSEM Good Adhesion Good Adhesion Good Adhesion______________________________________
The following nonlimiting example illustrates various exemplary methods of manufacture of articles.
EXAMPLE
A coating of silicon containing material on an iron-chromium alloy was obtained by chemical vapor deposition using a powder mixture of NaF--Si--SiO 2 . Initially, a 10 gram mixture of NaF--Si--SiO 2 was made having a weight ratio of NaF/Si/SiO 2 =2/1/7. The mixture was ground in a mortar and pestle to refine the powder size. About 2.5 grams of mixed powder was loaded into a high purity alumina boat and then moved into the middle of a quartz chamber (OD-1.5 inch, one end closed and 4 feet long). Coupon samples (0.5 inch ×0.5 inch and 0.05 inches in thickness) of Fe--25Cr--0.3(Y and/or Ce) were placed into the chamber. A liquid ammonia (NH 3 ) container was attached to the chamber. About 1/4 by volume of the chamber was filled with a gas phase of ammonia preceded by filling with high purity Argon gas. The quartz chamber was evacuated with a rotary vacuum pump 50 sitown in FIG. 3. Care was taken not to disturb the powder with slow vacuum pumping at the beginning, and the evacuation process required only several minutes. The furnace was then heated to about 1000° C. over a period of 25 minutes from room temperature. The rotary pump was stopped after 30 minutes heating. About 8 hours later, the ammonia containing chamber was opened slowly and left open for about 2 hours, and the stopcock was closed. The temperature was maintained for several hours, and then the furnace power was turned off. FIG. 6 shows the sample weight gain versus position for the chemical vapor deposition process for Fe--25Cr--0.3Y and Fe--25Cr--0.3Ce. After each run, samples were examined by SEM and by electron energy-dispersive, Auger and X-ray photoelectron spectroscopies. Investigations by SEM, TEM and energy-dispersive spectroscopy, show that the silicon diffused and reacted near the surface of the Fe--25Cr--0.3Y alloy. Silicon has also diffused into and around surface defects, fissures, and micro cracks that are normally the chemically active sites where corrosion begins on the surface of an alloy (see FIG. 7). This sample was polished to remove the silicon containing material from smooth areas of the alloy surface.
While preferred embodiments of the invention have been shown and described, it will be clear to those skilled in the an that various changes and modifications can be made without departing from the invention in its broader aspects as set forth in the claims provided hereinafter. | A method and article of manufacture of a coated iron based alloy. The method includes providing an iron based alloy substrate, depositing a silicon containing layer on the alloy surface while maintaining the alloy at a temperature of about 700° C.-1200° C. to diffuse silicon into the alloy surface and exposing the alloy surface to an ammonia atmosphere to form a silicon/oxygen/nitrogen containing protective layer on the iron based alloy. | 2 |
BACKGROUND OF THE INVENTION
With the advent of sophisticated electronic circuitry, high speed solid state devices, optical techniques, and related hardware, the problem of high labor costs in the production of high quality, high volume industrial parts has begun to be solved. Robots utilizing these sophisticated devices and computing tools have been finding rapidly increasing use in many industries where highly repetitive tedious operations can justify the relatively high expense. Although very sophisticated by standards for robots of only a decade or two ago, industrial robots are still in their infancy in their ability to perform fairly complicated and complex operations. Where only visual orientation is necessary, sophisticated optical devices, such as vidicon tubes, laser scanners, and the like, have provided practical and excellent abilities for robots to solve maneuvering and space oriented problems.
However, state-of-the-art industrial robots are severly deficient in tactile sensing means. No satisfactory, simple, efficient, low-cost means have yet been devised to serve the purpose of the human hand in its ability to provide information relating to object shape, grasping force, slipping motion, etc.
The medical profession, similarly to highly automated industries, has also made great progress in providing useful protheses to replace missing or disabled body parts for human patients. Such protheses utilize strong light weight materials, small energy conservative motors, ingenious mechanicals and life-like plastics to achieve use and function unknown until recent decades. However, one area where a great deal of progress remains to be made, is in sensor mechanisms to replace or mimic an appendage, e.g., the human hand and foot as it relates to tactile sensing of position, pressure, slippage, etc. As yet no satisfactory prosthesis that can sense the above requirements has been devised, at least in a small, compact, simple form.
Many manipulative operations require actions that depend upon a sensing of pressure; a sensing of pressure in relation to an area, i.e., pressure distribution over a predetermined area; a sensing of the presence or absence of pressure over a predetermined area; the sensing of the variations in the strength of pressure in the entire area wherein pressure is being exerted; and the presence or absence of slip in relation to a pressure point or pressure area. All of the above-mentioned and other physical qualities, with attendant feedback systems, have been admirably addressed and solved by the human hand.
From the standpoint of robotics and medical prostheses, a "human hand-like" apparatus would be an extremely important and vital apparatus essential to the advancement of the art.
BRIEF DESCRIPTION OF THE INVENTION
The present invention relates to tactile sensors for use both in industry and in medicine; or wherever there is a need for tactile sensing devices. The invention tactile sensor is quite simple in concept and implementation, but extremely versatile in its range of applications.
More specifically the sensor comprises an element that has the property of conducting or "piping" electomagnetic radiation, especially in the visible or near visible, i.e., ultra-violet and/or infra-red light through its interior volume wherein the "piped" light is internally reflected to pass continually through the interior of the light conducting element. As used herein the term "light" shall include visible, ultra-violet and infra-red radiations. A second element comprising a resilient or pressure transferring material, e.g., an elastomer or rubber-like material, is positioned adjacent to at least a portion of the exterior surface of the light conducting element.
If the resilient element, or a portion thereof, is forced against the surface of the light conducting element, the internal reflection characteristics of the light conducting element are altered at the point, or areas of contact. This compression of the resilient element against the light conducting element may occur when an object of some sort is placed upon the sensor, or when the sensor is moved against an object, or when an object is grasped by a mechanical device of which the sensor is a part.
If any event, when the resilient element is forced against, or bears up against a portion of the light conducting element's surface, the light reflection characteristics are altered, and a portion of the light passing therethrough will be reflected at such an angle that is passes out through an opposing surface rather than continuing to be "piped" as it would under normal circumstances. Any light thereby passing out of the light conducting element is then detected by a suitable means, e.g. an electronic optical sensor suitable for detecting and/or recording the light signal, whether in the visible, ultra-violet or infra-red ranges, as may be appropriate. The signal detected will be indicative of the shape and size of the area where the resilient element is pressed against the light conducting element's surface.
The information received from the optical sensor can then be electronically processed to provide a picture of the area on a video screen, or it may be utilized to operate or regulate electro-mechanical servo devices to control the movement of a grasping device in response to the information obtained from the tactile sensor i.e., to provide "feed back" for controlling the operation of the device. In fact, the tactile sensor would normally be an integral part of the grasping device.
In some embodiments of the sensor as described hereinafter, the light conducting and resilient elements may be combined into a single element. In such embodiments, a second transparent contact element is provided to afford contact with the combined resilient light conducting element.
A large number of modifications may be made to the basic sensor as outlined above to adapt it for use in a broad range of applications. Some of these modifications and adaptations will be discussed below.
It is an object of the invention to provide tactile sensing devices.
It is another object of the invention to provide tactile sensing devices for use in industrial robots.
It is another object of the invention to provide tactile sensing devices for use in medical prosthetics.
It is still another object of the invention to provide tactile sensing devices that include a light conducting element, a resilient element for contacting the light conducting element, and electronic light sensing means for optically determining the contact area between said light conducting element and said resilient element.
It is yet another object of the invention to provide tactile sensors that display a video image of the area where an object contacts said sensor.
It is still another object of the invention to provide tactile sensors that yield electronic signals or information that can be utilized to control the motion of a robotic device.
Other objects and advantages of the invention will be apparent upon review of the following specification, the drawings, and the claims appended hereto.
BRIEF DESCRIPTION OF THE DRAWINGS
In the accompanying drawings:
FIG. 1 is a schematic view of a tactile sensor illustrating the principles upon which the invention operates.
FIG. 2 is a cutaway perspective view of a sensor device of the invention.
FIG. 3 is a schematic illustration of the appearance of a contact area as viewed through the sensor device.
FIG. 4 is a schematic view of an embodiment of the sensor in operation with an object in contact therewith.
FIG. 5 is a schematic illustration of the appearance of the sensor contact area produced by the object in FIG. 4.
FIG. 6 is a schematic view of an embodiment of the sensor in operation with a different object in contact therewith.
FIG. 7 is a schematic illustration of the appearance of the sensor contact area produced by the object in FIG. 6.
FIG. 8 is an exploded view of an embodiment of the sensor.
FIG. 9 is a schematic view of yet another embodiment of the sensor.
FIG. 10 is a schematic view of still another embodiment of the sensor.
FIG. 11 is a schematic view of another embodiment.
FIG. 12 is a schematic view of a sensor utilizing the embodiment of FIG. 11.
FIG. 13 is a cut-away perspective view of a sensor especially adapted to detect and display shear forces applied to the sensor surface.
FIG. 14 is a schematic view of a variation in the sensor device wherein light conducting and resiliency are combined in a single element.
DETAILED DESCRIPTION OF THE INVENTION
The invention comprises tactile sensing devices wherein an object grasped or held will produce a detectable image that directly reflects the object's pressure and pressure pattern upon the device. The image is detected by suitable video camera elements and then transmitted for further processing to give direction to a robotic mechanism. This invention is only concerned with the sensor and not with the processing of the data and its use in directing robotic mechanisms which can be accomplished by means well known in the art.
As used herein "tactile sensing" or "tactile sensor" refers to the touching or grasping of any object and the device or instrumentality that makes the touching or grasping available as visual information that can be further processed for controlling touching or grasping devices. The tactile sensor replicates visually much of the same information that is revealed when an object is touched or grasped by a human hand.
The basic elements of the tactile sensor device include a light conducting element, a resilient element adjacent and co-extensive the light conducting element, and a light detecting and imaging device adapted to view the light conducting element and the resilient element from a position where any contact between the two elements can be detected.
The basic elements of the tactile sensor and its principle of operation may be understood by reference to FIG. 1 of the drawing. Specifically, the tactile sensor 11 comprises a light conducting element 12 which has an edge thereof illuminated by a light source 13. Light source 13 is only shown schematically, but it may be simply natural light, or more usually a suitable incandescent or fluorescent lamp.
Light conducting element 12 may be of any suitable configuration as will be more fully described hereafter, but for the purposes of illustration may be of a sheetlike shape. Positioned adjacent one surface 16 of the sheetlike light conducting element is a resilient element 14. When contacted by an object (see for instance, FIGS. 4 and 6), a portion of the resilient element 14 will be pressed against surface 16 as shown at area 17.
Positioned adjacent the opposite surface 18 of element 12 is a light detecting and imaging device 19 (shown schematically in FIG. 1 as an eye).
Light conducting element 12 may be fabricated from any number of transparent or semi-transparent materials that have the ability to confine light within their volumes. Materials such as organic polymers like the acrylates or methacrylates, or glass fibers utilized in fiber optics, are several illustrations of suitable materials. These materials have the property of reflecting any internal light from their surfaces whereby the light is confined or piped within the volume of the light conducting material. In any event, element 12 is fabricated from some such light conducting or piping material.
Where desirable in some applications of the sensor, contrast at the contact areas between the light conducting element and the resilient element can be enhanced by fabricating the light conducting element from plastic materials having dye, especially fluorescent dye, impregnated therein. Such dye impregnated plastic will provide greater uniformity of illumination throughout its volume. Fluorescent dye impregnated sheet material is commercially available and may comprise methyl methacrylate impregnated with a fluorescein or fluorescein-type dye. Such dye impregnated plastic sheet is readily excited by visible light. Most of the light emitted by the excited dye molecules is trapped within the confines of the sheet and will produce lighted areas of good contrast when the resilient element is pressed against it as described herein. This means of enhancing the illumination provides particularly uniform lighting over a large area of the light conducting element.
Resilient element 14 may be fabricated from any resilient, deformable material. Any elastomer, rubberlike, or skinlike material is suitable. Silicone rubbers, natural rubbers, or synthetic rubbers, or soft resilient organic polymers, such as polyethylene or polyurethane serve this purpose quite well. The prime requirements for such resilient elements are compressiblity, resiliency, toughness, and preferably, a light color such as white or yellow, to maximize the reflection of light from contact area 17.
Resilient element 14 essentially forms a "skin" covering one surface of the light conducting element 12. However as hereinafter described the resilient element 14 is not normally in contact with light conducting element 12; or if normally in contact, then only at pre-selected limited areas as will be hereafter explained.
Light detecting and imaging device 19 may be any device that is capable of viewing a light image and recording or transmitting the same for further processing or use. Normally for the purpose herein the smaller and more compact the device is, the better. One solid state electro-optical device that is useful for the present purpose is known as the "OpticRAM" produced by Micron Technology, Inc., of Boise, Id. The active element of the OpticRAM is a silicon dynamic random-access memory (RAM) chip of small dimensions perhaps 7/16 inch by 3/16 inch by 1/64 inch. Its protective package, usually fitted with a transparent cover, measures approximately 3/4 inch by 3/8 inch by 3/16 inch. It is composed of 65,536 individual image sensing elements or pixels. The pixels are organized into two rectangular arrays of 128×256 pixels each. Each array is separated by an optical dead zone of about 25 elements in width. The arrays are covered by an optically clear window and a number of electrical connectors on the back permit connection with a computer and video display. Any light image viewed by the OpticRAM generates a digital representation thereof. This digitized representation is transmitted via suitabale software into a computer and from thence to a display on a video screen. Any other similar electro-optical imaging device such as a charge-coupled imager may be used as the light detecting and imaging device 19.
In operation, and as schematically shown in FIG. 1, the light rays 21 from light source 13 enter an edge of light conducting element 12. The rays 21 are normally channelled through element 12 by internal reflection from surfaces 16 and 18. However, those rays reflected at the resilient element contact area 17 have their reflection angles altered whereby at least a portion thereof emerge from surface 18 and impinge upon detecting and imaging device 19. Thus device 19 can detect an area, or areas, wherein resilient element 14 is in contact with light conducting element 12.
It will be understood that the Figures are schematic illustrations. Variations in illuminating the light conducting element are contemplated. Thus the light source 13 can be located at a position normal to the general plane of element 21, and if the external edge is beveled and silvered, light from the source 21 can be directed into the interior.
FIG. 3 schematically illustrates the type of image produced by the above described effect. As seen by device 19, the area of contact 17a will appear as a bright area in contrast to the uncontacted area of element 12. The bright area of contact 17a is indicative of the shape of a pressure area exerted by any object resting upon or grasped by the tactile sensor. For instance, as illustrated in FIGS. 4 and 5, a round object 22 will produce a round contact area 17b; whereas an angular object 23 as shown in FIG. 6 will produce an angular contact area 17c as shown in FIG. 7.
It will also be apparent that due to the resilient nature of element 14, the harder an object is pressed against the sensor 11, the larger will be the characteristic light area viewed by image detecting device 19; and vice-versa.
Additionally, it will also be apparent that light areas 17a, b, c, will define the exact position in which the object is contacting the sensor; that is, as the object moves about on the resilient element, the position of light area 17a, b, c, will move in correspondence thereto.
Slippage of a grasped object is also detected by the sensor. If an object begins to slip across the viewed area, light of contact area 17 will begin to change position and move across the viewed area or its representation on a display screen. This will warn that the object is slipping and suitable measures can be taken to tighten the grasp of the electro-mechanical mechanism in which the sensor is being used.
Heretofore the most simple embodiment of the tactile sensor has been described. Upon further consideration; it will be apparent that the resilient element 14, unless restrained, may randomly contact the light conducting element 12 even in the absence of external pressure. This is possible in view of the resilient nature of element 14, its own weight and elasticity. Random contact of the light conducting element 12 is to be avoided since such contact may give rise to spurious or false contact areas. The production of such spurious or false signals is avoided by introducing a spacer between the resilient element 14 and light conducting element 12; or by building an effective spacer means directly into the resilient element 14 or light conducting element 12.
More specifically and as shown in FIG. 8, a tactile sensor 24 comprises a light conducting element 26 and a resilient element 27, like those previously described. Interposed between the two elements in a thin spacer 28. Spacer 28 is provided with a plurality of holes or apertures 29 arrayed over the entire surface thereof. Spacer 28 is fabricated from any dimensionally stable, thin sheet material such as paper, metal, plastic or the like. Spacer 28 is quite thin relative to the thickness of elements 26 and 27, being of the order of perhaps 2-5 mils. The surface of spacer 28 adjacent light conducting element 26 is non-sticky and preferably has a very finely pebbled or fibrous texture (as in paper) so that contact with element 26 is minimized and does not result in a light generating area.
Since spacer 28 is interposed between light conducting element 26 and resilient element 27, no contact between the two elements can occur unless pressure is brought to bear against resilient element 27. If an object is forced upwards against resilient element 27, those portions overlying holes 29 will be forced therethrough and into contact with element 26. Where such contact occurs light generating areas will develop. Should the pressure be released, the resilient material will withdraw from the surface of element 26 and holes 29. Therefore, spacer 28 removes the possiblity of spurious signals being generated between the two elements, 26 and 27. Spacer 28 also permits use of a plane sheet of resilient material rather than a contoured sheet as would be necessary in the embodiment illustrated in FIG. 10, below.
As illustrated in FIG. 9, the spacer may take many forms. In FIG. 9, the spacer 28a is punched out to form a grid-like structure wherein the grid serves to separate light conducting element 26a from resilient element 27a. Spacer 28a in FIG. 9 performs the same function as does Spacer 28 in FIG. 8. With further reference to FIG. 9, it should be noted that the tactile sensor can be formed into a curved surface. Such curved surface can simulate the curved grasping surfaces of a human finger, or any other desired curved grasping surface. Any such curved tactile sensor will still remain operationally functional so long as suitable means such as spacer 28 or 28a, are provided to separate the light carrying and resilient elements.
FIG. 2 is a perspective cutaway view of an assembled tactile sensor unit. As shown therein light detecting and imaging device 19 is placed closely adjacent the back surface of light conducting element 12. Connectors lead from device 19 to a computer (not shown). A spacer 28, as previously described, is placed against the opposite surface of element 12 and serves to separate resilient element 14 therefrom. Apertures or holes 29 are arrayed in spacer 28 to permit resilient element 14 to press against light conducting element 12 when an object (not shown) bears against any area of resilient element 14.
FIG. 10 illustrates another embodiment of the tactile sensor. In this embodiment, the sensor 29 comprises a light conducting element 31 identical with those previously described. A resilient element 32 is also provided, however it differs from the resilient elements previously described in that a plurality of bumps or projections 33 are integrally formed on the surface 34 and facing the light conducting element. Bumps 33 may be in any form suitable for spacing the surface 34 a slight distance away from the adjacent surface of element 31 when the two element are brought into contact.
The points at which bumps 33 contact element 31 will produce a regular pattern of small light areas as previously described, however the major portion of surface 34 will remain out of contact. If, however, an object is placed upon, or is grasped by the tactile sensor, a number of the bumps corresponding to the pressure areas will be compressed allowing the contiguous portions of surface 34 to contact light conducting element 31. As previously described, such pressure contact areas will produce light areas corresponding to the pressure areas. Larger light areas will then be visible to the light detecting and imaging device (not shown) positioned above element 31.
Thus the embodiment shown in FIG. 10 is capable of yielding the same type of information as the embodiments of FIGS. 8 and 9, without the necessity of a separate spacer interposed between the light conducting element and resilient element.
With respect to the embodiment of FIG. 10, it will be apparent that the lower surface 35 of light conducting element 31 may be provided with protruding bumps, while the upper surface 34 of resilient element 32 may be smooth, i.e., the configurations of light conducting element 31 and resilient element 32 are reversed. The advantage of such an arrangement in this embodiment may be economical. Specifically, with use, the resilient element 32, being the exterior member of the sensor, will tend to receive greater wear from contact with external objects. It may become abraded, torn etc., necessitating replacement. In such event, a simple planar sheet of resilient material will be much less expensive than a contoured resilient sheet. Therefore the cost of replacement will be less.
It will be apparent that a large number of modifications may be made to the tactile sensor as previously described to ensure the separation of the resilient element from the light conducting element in the unloaded mode. FIGS. 2, 8, 9, and 10 illustrate several methods of ensuring separation, however, variations thereof are contemplated as being part of this invention.
The sensors of the invention are also capable of the detection and display of forces (shear) applied tangentially to the surface of the resilient element. For instance, with reference to FIG. 10, a shear force applied to the lower surface of resilient element 32 will cause the points of contact with light conducting element 31 to be translated in the direction of the force. This movement of the contact points in a transverse direction can be detected by the imaging device. In addition, the contact areas will be oval in configuration rather than circular as would be the case when force is applied normally to the surface of element 32. The long axis of any such oval contact areas will be parallel to the direction in which the transverse force is applied to element 32.
FIG. 13 illustrates an embodiment of the sensor especially adapted to detect shear forces. As shown therein a light conducting element 51 overlies a resilient element 52. Resilient element 52 includes a plurality of recesses or cells 53 which may be generally rectangular or square in the plane parallel to the sensor. Each recess 53 includes a rounded nipple or projection 54 centered within the recess, and extending upwardly from the recess bottom to a height co-extensive with, or slightly higher than the upper surface 56 of resilient element 52. The upper surface 56 of element 52 is affixed, by means of an adhesive to the under surface of light conducting element 51. However the tips of nipples 54, although in contact with element 51, are not adhered thereto, but are free to move across the undersurface.
Application of transverse force on the underside of resilient element 52 will cause the contact areas 57 between the tips of nipples 54 and the light conducting element 51 to move relative to the contact areas 58 between the upper surface of resilient element 52 and light conducting element 51. Thus any transverse force applied to the resilient element will be detectable from observing the movement of areas 57 relative to the fixed areas 58.
It will be appreciated that in some applications it is useful to provide open viewing areas through the sensor light conducting element and resilient element. That is, portions of the sensor elements may be removed so that the light detecting element has at least a portion of its view umimpeded by the light conducting element and resilient element. In such open areas the light sensitive pixels of the light sensitive element will be available for conventionally viewing objects which are being gripped, or are to be gripped by the robotic device. Thus the robotic device can be used in a simple viewing mode concurrently with the tactile sensing elements.
The tactile sensors can also be provided in a flexible form for use, for instance, as a "glove" covering a mechanical "hand" prosthesis; or as a sensor "glove" adapted to fit over a hand that has been nerve damaged.
FIG. 11 schematically illustrates in brief detail a flexible embodiment of the tactile sensor. As illustrated therein a plurality of light conducting fibers 36 (like those utilized in light fiber optics) comprise the light conducting element previously described. The light conducting fibers are arrayed side by side in a flat sheet 37 which may be as wide and as long as desired. A light source 38 illuminates the fibers at one end thereof. The other ends of the fibers may be silvered to reflect the light back in the direction of the source. A light detecting and imaging device 39 (depicted schematically as an eye) is positioned at the light entry end of the fibers to observe the light reflected back from the silvered ends.
A resilient element or "skin" 41 is positioned across the fiber array 37 such that when depressed by a grasped object, at least a portion of the resilient element will press against the fiber array. The contact area with the fibers alters the reflection characteristics of the fibers and the reflected light signal is thereby altered to indicate to the light detecting device 39 that a portion of the resilient element 41 is pressed against the fiber array 37.
It will be appreciated that the fibers 36 and the array 37 thereof are quite flexible and may be bent or folded into desired configurations. The flexible tactile sensor is suited for application to a hand prosthesis where the flexible sensors can be arranged to provide tactile information in the fingers of a glove-like covering for an electro-mechanical hand or nerve damaged human hand.
FIG. 12 illustrates the manner in which a plurality of flexible sensors can provide tactile information at various positions over a grasping prosthetic surface. As shown therein, a number of light fiber arrays 42 are encased in a flexible enclosure 43. Enclosure 43 may be any suitable flexible material such as silicone rubber, rubber-like polymers, etc.
A number of openings 44 are provided at predetermined positions over the surface of enclosure 43. These openings expose a respective array of the light fibers 42. In the event the light fibers are clad with a light reflective or protective coating, said coating is removed where the fibers are exposed at openings 44.
A flexible skin 46 of resilient plastic is provided to cover the enclosure 43 and overlie openings 44. If an object grasped by the prosthesis underlies one of the openings 44, a portion of skin 46 will be forced through the corresponding opening and against the exposed fiber array. Contact of the skin against the array will alter the reflected light signal passing through the array and light detecting device 39 will reveal that the skin 46 has been forced against the array at a particular point over the surface of the prothesis. Thus it can be determined at exactly what point, or points, over the prosthesis surface, contact is being made with a grasped object. By such an arrangement, the tactile sensors of the present invention can simulate the nerve endings and tactile information of a human hand, for instance.
In the embodiments of the tactile sensor heretofore discussed, a relatively rigid element is utilized as the light conducting member, and a resilient element is utilized as the outer tactile contact. It is possible however to combine the light conducting function into the outer resilient element and utilize a transparent backing or contact member to define tactile contact areas. This variation of the tactile sensor will be apparent from a review of FIG. 14 of the drawing.
As illustrated in FIG. 14, a light source 61 illuminates a resilient and light conducting element 62. Element 62 is of an essentially sheet-like configuration. It is preferably fabricated from a clear, transparent rubbery material such as silicone polymers, or silicone methacrylate co-polymers. Such materials have resilient rubbery properties but also effectively transmit light therethrough.
Light rays 63 pass into element 62 from the light source 61 and are internally reflected throughout the volume thereof. A second contact element 64 is positional adjacent to and coextensively with element 62. Contact element 64 is provided with a plurality of bumps or protuberances 66 on the surface thereof immediately adjacent element 62. The protuberances 66 serve to position the main portion of element 64 at a slight distance from element 62.
Any points of contact 67 between element 62 and element 64 will interrupt the internal reflection of light within element 62 and permit a portion thereof to pass into contact element 64. Any of such light passing into contact element 64 at an angle normal to the upper surface 68 thereof will pass through and be detected by a light detecting device 69 (herein schematically denoted by an eye).
It will be readily apparent that a force applied normally to resilient element 62 will force portions thereof between protuberances 66 up against contact element 64 to thereby increase the area wherein light is transmitted through contact element 64 to detector 69.
Other applications and arrangements the tactile sensors of the invention will become readily apparent to those having need of tactile information in robotic devices. All such variations and applications are intended to be encompassed by this disclosure. | A tactile sensing device for use in robotics and medical prosthetics includes a transparent sheet-like element and a second resilient sheet-like element positioned adjacent the first transparent element. A light detection and imaging means is positioned to observe the interface between the two elements. A light source is provided to illuminate the interior of one of the two elements. Any object pressing against the resilient element deforms the same into contact with the transparent element. Areas of contact caused by the pressing object produce a lighted area that can be detected by the light detecting means. The output from the light detecting means may be processed by a computer and an image of the contact area produced by the pressing object can be displayed on a monitor or processed to operate an electro-mechanical control. | 6 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation-in-part of U.S. patent application Ser. No. 13/731,109, entitled “MULTIPLE FUEL COMBUSTION SYSTEM AND METHOD,” filed Dec. 30, 2012 (docket number 2651-008-03), which claims priority benefit from U.S. Provisional Patent Application No. 61/616,223, entitled “MULTIPLE FUEL COMBUSTION SYSTEM AND METHOD,” filed Mar. 27, 2012 (docket number 2651-008-02); and is a continuation-in-part of U.S. patent application Ser. No. 14/203,539, entitled “ELECTRICALLY-DRIVEN CLASSIFICATION OF COMBUSTION PARTICLES,” filed Mar. 10, 2014 (docket number 2651-006-03), which claims priority benefit from U.S. Provisional Patent Application No. 61/775,482, entitled “ELECTRICALLY-DRIVEN CLASSIFICATION OF COMBUSTION PARTICLES,” filed Mar. 8, 2013 (docket number 2651-006-02); each of which, to the extent not inconsistent with the disclosure herein, are incorporated by reference.
SUMMARY
[0002] According to an embodiment, electro-dynamic and/or electrostatic fields may be applied to a co-fired combustion system to enhance combustion property(ies). In an example system, a bench-top scale model selectively introduced an AC field across a simulated tire-derived fuel (TDF) (a cut up bicycle inner-tube) held in a crucible over a propane pre-mixed flame. Without the electric field, the simulated TDF smoked profusely. With the electric field turned on, there was not any visible soot (although instrumentation detected a low level of soot). A cause and effect relationship was established by repeatedly turning on and turning off the electric fields. There was no observable hysteresis effect—switch on=no visible soot, switch off=visible soot.
[0003] According to an embodiment, a co-fired combustion apparatus may include a first fuel-introduction body defining a portion of a first combustion region. This may correspond to the premix nozzle and a flame region, for example. The first combustion region may be configured to combust a first fuel (e.g., propane) in a first combustion reaction. The apparatus may also include a second fuel-introduction body defining at least a portion of second combustion region. For example, the second fuel-introduction body may include the crucible described above. The second combustion region may be configured to combust a second fuel in a second combustion reaction. The first combustion reaction may be operable to sustain the second combustion reaction. For example, the simulated TDF was not readily ignited until heated by the propane flame. An electrode assembly associated with the second combustion region may be operable to be driven to or held at one or more first voltages. In the example above, the electrode assembly included the metallic crucible itself. A grounded 4-inch stack that was located approximately axial to the crucible may be envisioned as providing an image charge that varied to solve a field equation driven by the AC waveform.
[0004] Accordingly to another embodiment, a method of co-fired combustion may include maintaining the first combustion reaction by combusting the first fuel at the first combustion region. In other words, the propane combustion reaction C 3 H 8 +50 2 →3C0 2 +4H 2 O may be a self-sustaining exothermic reaction. The first combustion region may have a portion thereof defined by the first fuel-introducing body. The method may further include maintaining a second combustion reaction by combusting a second fuel at a second combustion region having a portion defined by a second fuel-introducing body. The second combustion may be sustained by the first combustion reaction. According to embodiments, the method includes applying at least one first electrical potential (which may include a time-varying electrical potential) proximate the second combustion region.
[0005] According to an embodiment, a combustion system may include a combustion volume configured to support a combustion reaction with a fuel and oxidant, and produce a flame and a main flow of a flue gas including entrained exhaust particles. The combustion system may further include at least one shaped electrode acting as a corona electrode, configured to generate a corona discharge, resulting in an ionic flow. The ionic flow may charge some of the entrained exhaust particles of the flue gas. The combustion system may further include a high voltage power supply (HVPS) configured to apply voltage to the at least one shaped electrode.
[0006] According to an embodiment, the charged exhaust particles may further be attracted to a collector plate, which may be may be formed as a single segment, or it may include a plurality of mechanically coupled segments.
[0007] According to another embodiment, the charged exhaust particles may be drawn into a director conduit for recirculation back into the combustion volume. The director conduit may further include a fan, impeller or vacuum means for facilitating the transfer of the particles.
[0008] According to yet another embodiment, the combustion system may include both a collector plate and a director conduit. Additionally, the combustion system may include a combustion control system, configured to monitor and control electric field necessary for generation of the corona discharge, via a programmable controller operatively coupled to one or more sensors placed inside the combustion volume, and to at the at least one shaped electrode.
[0009] According to an embodiment, a method for operating a combustion system includes outputting a first fuel and a first oxidant, supporting a first combustion reaction with the first fuel and first oxidant, and supporting a second combustion reaction of the heated second fuel to the produce a flue gas including entrained particles. The method also includes providing an electrical charge to the second combustion reaction, wherein the electrical charge is carried by the entrained particles, supporting a first field electrode adjacent to a main flow of the flue gas, applying a first voltage to the first field electrode, and electrostatically attracting the entrained particles toward the first field electrode to remove at least a portion of the entrained particles from a main flow of the flue gas.
[0010] According to an embodiment, a co-fired combustion apparatus, includes a first fuel-introduction body configured to provide a first fuel to a first combustion reaction and a second fuel-introduction body configured to provide a second fuel to a second combustion reaction, wherein the second combustion reaction emits an exhaust flow having a plurality of combustion particle classifications and wherein the first fuel introduction body is positioned relative to the second fuel introduction body to cause the first combustion reaction to at least intermittently provide heat to the second combustion reaction. The apparatus further includes an electrode assembly associated with the second fuel introduction body or a second combustion volume to which the second fuel introduction body provides the second fuel, the electrode assembly being configured to be driven to or maintained at one or more first voltages selected to provide an electric field to the second combustion volume, a charge source configured to supply electrical charges into the exhaust flow, a high voltage power supply (HVPS) configured to apply an electrical potential having a first polarity to the charge source and a collector plate including an electrical conductor coupled to receive an electrical potential having a second polarity from a node operatively coupled to the HVPS, the collector plate disposed above and a distal to the second combustion reaction and arranged to cause at least one combustion particle classification to flow to a collection location and to cause at least one different combustion particle classification to flow to one or more locations different from the collection location.
BRIEF DESCRIPTION OF THE FIGURES
[0011] FIG. 1 is a diagram of a co-fired combustion apparatus, according to an embodiment.
[0012] FIG. 2 is a diagram of a co-fired combustion apparatus, according to an embodiment.
[0013] FIG. 3 is a flow chart of a co-fired combustion method, according to an embodiment.
[0014] FIGS. 4-27 are thermographic images captured during a heat-exchange experiment wherein a voltage was applied to and removed over time from a crucible supporting a combustion, according to embodiments.
[0015] FIG. 28 depicts an embodiment of a combustion system employing a corona discharge structure and a collector plate, according to an embodiment.
[0016] FIG. 29 shows an embodiment of a combustion system employing a corona discharge structure and a director conduit, according to an embodiment.
[0017] FIG. 30 illustrates an embodiment of combustion system employing a corona discharge structure, a director conduit and a collector plate, according to an embodiment.
[0018] FIG. 31 shows a block diagram of a combustion control system, according to an embodiment.
[0019] FIG. 32 is a flow chart of a method for reducing the size and/or amount of exhaust particles entrained within a flue gas leaving a combustion system, according to an embodiment.
DETAILED DESCRIPTION
[0020] In the following detailed description, reference is made to the accompanying drawings, which form a part hereof. In the drawings, similar symbols typically identify similar components, unless context dictates otherwise. The illustrative embodiments described in the detailed description, drawings, and claims are not meant to be limiting. Other embodiments may be utilized, and other changes may be made, without departing from the spirit or scope of the subject matter presented here.
[0021] FIG. 1 is a diagram of a co-fired combustion apparatus 100 , according to an embodiment. The apparatus 100 may include a first fuel-introduction body 105 defining a portion of first combustion region 110 . The first combustion region 110 may be configured to combust a first fuel (not shown) in a first combustion reaction 115 . In an embodiment, the first fuel-introduction body 105 may be supported in a housing 120 by a first fuel-introduction-body support 125 . The first fuel may be provided by a first fuel supply 130 . The first fuel may be substantially liquid or gaseous. For example, the first fuel may include at least one of natural gas, propane, oil, or coal. In an embodiment, the first fuel-introduction body 105 may include a burner assembly that is configured to support a flame.
[0022] A second fuel-introduction body 135 may define a portion of a second combustion region 140 . The second combustion region 140 may be configured to combust a second fuel 145 in a second combustion reaction 150 . In an embodiment, the second fuel-introduction body 135 may include a crucible assembly, which may be operable to hold the second fuel 145 . Alternatively, the second fuel-introduction body 135 may include a grate, a screen, a fluidized bed support, or another apparatus configured to introduce, contain and/or hold the second fuel 145 proximate the second combustion region 140 . The second fuel-introduction body 135 may be supported in the housing 120 by a second fuel-introduction-body support 155 . In an embodiment, the second fuel 145 may be substantially solid under standard conditions. The second fuel 145 may melt, melt and vaporize, sublime, and/or be dried responsive to heating from the first combustion reaction 115 . In an embodiment, the second fuel 145 may include one or more of rubber, wood, glycerin, an industrial waste stream, a post-consumer waste stream, an industrial by-product, garbage, hazardous waste, human waste, animal waste, animal carcasses, forestry residue, batteries, tires, waste plant material, or landfill waste. In an embodiment, the second fuel 145 may be fluidized to form at least a portion of a fluidized bed.
[0023] In an embodiment, the first combustion reaction 115 may sustain the second combustion reaction 150 . For example, the first combustion reaction 115 may generate heat which initiates or supports the second combustion reaction 150 . Accordingly, in an embodiment, the first fuel-introduction body 105 may be positioned at a distance proximate to the second fuel-introduction body 135 so that the first combustion reaction 115 may support the second combustion reaction 150 . In an embodiment, a portion of the apparatus 100 may be enclosed within a flue, stack, or pipe configured to convey at least a portion of a combustion product stream generated by the first and/or second combustion reactions 115 , 150 .
[0024] According to an embodiment, the first combustion region 110 may be substantially separated from the second combustion region 140 . According to another embodiment, the first combustion region 110 may extend to overlap or occupy the entirety of the second combustion region 140 . According to an embodiment, the first combustion reaction 115 may provide ignition for the second combustion reaction 150 .
[0025] An electrode assembly 160 associated with the second combustion region 140 may be operable to be driven to or held at one or more first voltages such as a constant (DC) voltage, a modulated voltage, an alternating polarity (AC) voltage, or a modulated voltage with a DC voltage offset. In an embodiment, the electrode assembly 160 may include at least a portion of one or more of the second fuel-introduction body 135 , the second fuel-introduction-body support 155 , the housing 120 , or an electrode (not shown) separate from the second fuel-introduction body 135 , the second fuel-introduction body support 155 , and the housing 120 . In an embodiment, any of the second fuel-introduction body 135 , the second fuel-introduction-body support 155 , the housing 120 , or a separate electrode assembly 160 may each be configured to be driven to or held at one or more voltage(s), which may or may not be the same voltage. For example, the housing 120 may be held at a ground voltage and the second fuel-introduction-body support 155 may be held at or driven to positive and/or negative voltages. In an embodiment, the housing 120 may rest on a grounding plate 180 , which may ground the housing 120 .
[0026] It was found that the smoke reduction was most pronounced when the first voltage included a high voltage greater than +1000 volts and/or less than −1000 volts. For example, in experiments, the voltage was an AC waveform with amplitude of +/−10 kilovolts. Other high voltages may be used according to preferences of the system designer and/or operating engineer.
[0027] The electrode assembly 160 may be configured to be driven to or held at a voltage produced by a voltage source including a power supply 165 . The power supply 165 may be operatively coupled to controller 170 , which is configured to drive or control the electrode assembly 160 . In some embodiments, the electrode assembly 160 may include one or more electrodes positioned proximate to the second combustion region 140 , which may or may not directly contact the second fuel-introduction body 135 or the second fuel 145 . Such electrodes may be positioned in any desirable arrangement or configuration. In an embodiment, a portion of the first fuel-introduction body 105 , a portion of the first fuel-introduction-body support 125 , or a portion of an electrode (not shown) proximate to the first combustion region 110 may be configured to be held at one or more second voltage(s).
[0028] The apparatus 100 may optionally include one or more sensor(s) 175 operable to sense one or more conditions of the apparatus 100 , components thereof, and/or the second fuel 145 combustion reaction 150 . For example, a sensor 175 may sense heat, voltage, fluid flow, fluid turbulence, humidity, particulate matter, or one or more compounds or species. In an embodiment, the sensor 175 may be used to sense the condition or state of a combustion product stream generated by the second combustion reaction 150 . A sensed state or condition of the combustion product stream generated by the second combustion reaction 150 may be used by a feedback controller 170 to modify or modulate the one or more voltages and/or waveforms that the electrode assembly 160 is held at or driven to.
[0029] For example, as further discussed herein, driving or holding the electrode assembly 160 at one or more voltages may affect the second combustion reaction 150 . Driving or holding the electrode assembly 160 at one or more voltages may modify the efficiency, rate, thermal output, or turbulence, of the second combustion reaction 150 . The sensor(s) 175 may be operable to detect such effects.
[0030] It was found that applying an electric field proximate to a combustion reaction may be used to improve the efficiency of the combustion reaction. The improvement in efficiency may include a reduction in undesirable combustion products such as unburned fuel, oxides of sulfur (SO X ), oxides of nitrogen (NO X ), hydrocarbons, and other species. Additionally, the improvement in efficiency may include an increase in thermal energy generated by the combustion reaction per the amount of fuel. In addition to being less harmful to the environment, supporting a cleaner combustion reaction may result in lower operating expense. Discharge of certain combustion pollutants may require the purchase of emission-permits for an amount of pollutant discharge. Reducing pollutant discharge in a given reaction may therefore allow a business to obtain fewer emission-permits and/or output more heat at a reduced cost. Additionally or alternatively, less fuel may be consumed to generate an equivalent amount of energy.
[0031] Increased efficiency of a combustion reaction may occur via one or more mechanisms. For example, applying an electric field proximate to a combustion reaction may increase the number of collisions between reactants, which may increase the reaction rate. In one example, applying an electric field proximate to a combustion reaction may increase the collision energy of reactants and therefore increase the rate of reaction. In another example, applying an electric field proximate to a combustion reaction may provide a self-catalysis effect for various desirable reactions and may reduce the reaction activation energy by urging reactants to come together in a correct reaction orientation. In a further example, applying an electric field proximate to a combustion reaction may increase the turbulence of a reaction and thereby increase the mixture or introduction rate of reactants (e.g., increased mixing of oxygen with fuel), which may promote a more efficient or complete combustion reaction (e.g., where reactants combust to produce a greater proportion of desired reaction products, fewer unreacted reactants and undesired products or by-products of the combustion reaction will be emitted).
[0032] FIG. 2 is a diagram of a co-fired combustion apparatus 200 , according to an embodiment. The apparatus 200 may include a first fuel-introduction body 105 defining a portion of first combustion region 110 . The first combustion region 110 may be configured to combust a first fuel from a first fuel supply 130 in a first combustion reaction 115 . In an embodiment, the first fuel-introduction body 105 may be supported in a housing 120 by a first fuel-introduction-body support 125 .
[0033] The apparatus 200 may also include a second fuel-introduction body 135 defining a portion of a second combustion region 140 . The second combustion region 140 may be configured to combust a second fuel (not shown) in a second combustion reaction (not shown). In an embodiment, the second fuel-introduction body 135 may include a crucible assembly, which may be configured to hold the second fuel. Alternatively, the second fuel-introduction body 135 may include a grate, a screen, a fluidized bed support, or another apparatus configured to introduce and/or contain or hold the second fuel proximate the second combustion region 140 . The apparatus may also include a stoker 210 , configured to introduce the second fuel to the fuel-introduction body 135 .
[0034] For example, in an embodiment, the second fuel may include timber waste products, and the stoker 210 may be configured to convey timber waste products into the fuel-introduction body 135 so that sufficient second fuel is present to sustain a relatively constant combustion fuel volume within the second fuel-introduction body 135 . For example, as the second fuel is consumed, additional second fuel may be introduced by the stoker 210 so that the second combustion reaction may continue. Optionally, the second fuel-introduction body 135 may include a containment body 160 B configured to prevent entrainment of unburned second fuel particles in flue gas exiting through the top of the body 120 .
[0035] In another embodiment, the second fuel may include black liquor, such as a residue from a sulfite pulp mill. The stoker 210 may be configured to convey liquid or semi-solid black liquor to the second combustion region 140 .
[0036] Optionally, the burner 200 may include a heat recovery system including one or more heat transfer surfaces such as water tube boiler tubes to convert heat output by the second (not shown) and/or first combustion reaction 115 to heated water or steam. According to an embodiment, the application of electrical energy to at least the second combustion reaction (not shown) may reduce tendency for combustion byproducts or entrained materials to be deposited on heat transfer surfaces. This may allow a longer operating duration between service shut-downs to clean heat transfer surfaces.
[0037] A first and second electrode assembly 160 A, 160 B associated with the second combustion region 140 may be operable to be driven to or held at one or more voltages using a substantially constant (DC) voltage, a modulated voltage, an alternating polarity (AC) voltage, or a modulated voltage with DC voltage offset. The first electrode 160 A assembly may be configured to be driven to or held at one or more first voltages. The second electrode 160 B assembly may be configured to be driven to or held at one or more second voltages. In an embodiment, the first and second one or more voltages may be the same. The first and second electrode assemblies 160 A, 160 B may be electrically isolated from a portion of the housing 120 via respective insulators and/or air gaps 220 A, 220 B. In an embodiment, the first and second electrode assembly 160 A, 160 B may be held or driven to a first and second voltage respectively, and the housing 120 may be held at or driven to a third voltage. For example, the housing 120 may be held at ground potential via a grounding plate 180 .
[0038] The first and second electrode assembly 160 A, 160 B may each be configured to be driven to or held at a voltage produced by a voltage source including a power supply 165 . The power supply 165 may be operatively coupled to controller 170 , which may be configured to control the output voltage, current, and/or waveform(s) output by the power supply 165 to the first and/or second electrode assemblies 160 A, 160 B.
[0039] The apparatus 200 may optionally include a first and/or second sensor 170 A, 1706 operable to sense one or more conditions of the apparatus 200 or components thereof. For example, the first sensor 170 A may be associated with the first electrode assembly 160 A, and the second sensor 170 B may be associated with the second electrode assembly 160 B.
[0040] FIG. 3 is a flow chart showing a method 300 for operating a co-fired combustion system, according to an embodiment. The method 300 begins in block 310 where a first combustion is maintained at a first combustion region by combusting a first fuel. For example, referring to FIGS. 1 and 2 , the first combustion 115 may be maintained at the first fuel-introduction body 105 in the first combustion region 110 . The first fuel may be a relatively free-burning fuel such as a hydrocarbon gas, a hydrocarbon liquid, or coal. The first fuel should be chosen to have a flame temperature that is sufficiently high to support and/or ignite combustion of the second fuel.
[0041] The method 300 continues in block 320 , where a second combustion reaction is sustained by heat and/or ignition from the first combustion reaction. The second combustion reaction may be maintained at a second combustion region by combusting the second fuel. For example referring to FIGS. 1 and 2 , the second combustion reaction 150 may be sustained by the first combustion reaction 115 , at the second fuel-introduction body 135 in the second combustion region 140 . According to an embodiment, heat from the first combustion reaction may dry, volatilized, and/or raise a vapor pressure of the second fuel sufficiently to allow the second fuel to burn. Additionally or alternatively, the first combustion region may overlap with or contain the second combustion region. The first combustion reaction may provide ignition and/or maintain combustion of the second fuel.
[0042] The method 300 continues in block 330 where a first potential or sequence of potentials is applied to a first electrode operatively coupled to the second combustion region. For example, referring to FIG. 1 a first potential or sequence of potentials may be applied to the electrode assembly 160 proximate to the second combustion region 140 . Referring to FIG. 2 , a first potential may be applied to the first electrode assembly 160 A proximate to the second combustion region 140 . According to an embodiment, the first potential or sequence of potentials may include a substantially constant (DC) voltage, a modulated voltage, an alternating polarity (AC) voltage, or a modulated voltage with DC voltage offset.
[0043] The method 300 continues in block 340 , where a second electrical potential or sequence of potentials is applied to a second electrode operatively coupled to the second combustion region. For example, referring to FIG. 1 a second potential may be applied to the housing 120 proximate to the second combustion region 140 . Referring to FIG. 2 , a second potential may be applied to the second electrode assembly 160 B proximate to the second combustion region 140 .
[0044] The electrical potentials applied in steps 330 and 340 may be selected to cause an increase in reaction rate and/or an increase in the reaction extent reached by the second combustion reaction. According to an embodiment, the first electrical potential or sequence of potentials may include a time-varying high voltage. The high voltage may be greater than 1000 volts and/or less than −1000 volts. According to an embodiment, the high voltage may include a polarity-changing waveform with an amplitude of +/1 10,000 volts or greater. The waveform may be a periodic waveform having a frequency of between 50 and 300 Hertz, for example. In another example, the waveform may be a periodic waveform having a frequency of between 300 and 1000 Hertz. According to an embodiment, the second electrical potential may be a substantially constant (DC) ground potential.
[0045] The method is shown looping from step 340 back to step 310 . In a real embodiment, the steps 310 , 320 , 330 , and 340 are generally performed simultaneously and continuously while the second fuel is being burned (after start-up and before shut-down).
EXAMPLE
[0046] Referring to FIG. 1 , a burner assembly 105 was disposed within a cylindrical housing 120 , defining a first combustion region 110 . The burner assembly 105 was operatively connected to a propane gas supply (first fuel supply 130 ), which was used to sustain a propane flame on the burner assembly 105 in a first combustion 115 . The housing 120 was approximately 3 inches in diameter and approximately 1 foot tall. The burner assembly 105 was substantially cylindrical having a diameter of approximately ¾ inch, and a height of approximately 1 inch.
[0047] A crucible 135 having a diameter of approximately ¾ inch was positioned within the housing 120 above the propane first combustion 115 . The crucible 135 held a mass of rubber pieces (second fuel 145 ), which were obtained by cutting pieces from a bicycle inner-tube. The propane first combustion 115 caused the rubber pieces to ignite, thus generating a second combustion 150 . The second combustion 150 of the rubber pieces generated a combustion product stream (not shown), which visually presented as black smoke. The housing 120 was used to contain and direct the combustion product stream, and rested on a grounding plate 180 , which held the housing 120 at a ground voltage.
[0048] A modulated voltage of 10 kV was then applied to the crucible 135 at a frequency of 300-1000 Hz. The smoke generated by the combustion of the rubber pieces changed from a black smoke to no visible smoke. This indicated that the combustion product stream included fewer particulates. The voltage was removed from the crucible 135 and the combustion product stream again presented as black smoke. The voltage was again applied to the crucible 135 and the combustion product stream again presented as a lighter or substantially no visible smoke.
[0049] In a first particulate-residue trial, a first volume of rubber pieces was burned in the crucible 135 and a first paper filter was positioned on the top end of the housing 120 to collect particulate matter in the combustion product stream. A voltage was not applied to the crucible 135 .
[0050] In a second particulate-residue trial, a second volume of rubber pieces (having substantially the same mass as the first volume of the first trial) was burned in the crucible 135 and a second paper filter was positioned on the top end of the housing 120 to collect particulate matter. A modulated voltage of 10 kV was then applied to the crucible 135 at a frequency of 300-1000 Hz.
[0051] The first and second filter papers were compared, and the first filter paper exhibited a substantial layer of black particulate matter. The second filter paper on exhibited a light discoloration of the paper, but did not have a layer of particulate matter. This result further indicated that the application of the voltage created a substantial reduction in particulate matter in the combustion product stream of the combusting rubber pieces.
[0052] In a first heat-exchange trial, a first volume of rubber pieces was burned in the crucible 135 and thermographic images of the combustion were recorded over time using a Fluke Ti20 Thermal Analyzer at a perspective substantially the same as the perspective of FIG. 1 . A propane fuel volume of 0.4 actual cubic feet per hour (acfh) was supplied to the burner assembly 105 during the trial. A voltage was not applied to the crucible 135 .
[0053] In a second heat-exchange trial, a second volume of rubber pieces (having substantially the same mass as the first volume of the first trial) was burned in the crucible 135 and thermographic images of the combustion were recorded over time using a Fluke Ti20 Thermal Analyzer at a perspective substantially the same as the perspective of FIG. 1 . A propane fuel volume of 0.2 actual cubic feet per hour (acfh) was supplied to the burner assembly 105 during the trial (i.e., half of the fuel compared to the first trial). A modulated voltage of 10 kV was then applied to the crucible 135 at a frequency of 300-1000 Hz.
[0054] The thermographic images of the first and second heat-exchange trial were compared over time. At 15 seconds, both burners registered approximately 130° F. At 45 seconds the first heat-exchange trial continued to register 130° F.; the second heat-exchange trial burner (with 50% fuel) registered approximately 186° F. These trials indicated that even with 50% fuel volume, application of a voltage to the crucible 135 generated a higher combustion temperature.
[0055] In a third heat-exchange trial, a volume of rubber pieces was burned in the crucible 135 and thermographic images of the combustion were recorded over time using a Fluke Ti20 Thermal Analyzer at a perspective substantially the same as the perspective of FIG. 1 . Over time, a modulated voltage of 10 kv was then applied to the crucible 135 at a frequency of 300 Hz for a period of time; the voltage was removed for a period of time; a modulated voltage of 10 kv was then applied to the crucible 135 at a frequency of 1000 Hz for a period of time; and the voltage was removed for a period of time. The application and removal of these voltages was repeated six times. An image was captured at the end of each period.
[0056] FIGS. 4-27 depict the thermographic images captured during the heat-exchange trial from a time of 9:27:16 until 10:52:16 and show that application of a voltage to the crucible 135 generated a higher combustion temperature.
[0057] Schlieren photography was used to visualize the flow of the combustion product stream generated by the combustion of rubber pieces within the crucible 135 . When no voltage was applied to the crucible 135 , the flow of the combustion product stream appeared to be laminar flow; however, when a modulated voltage of 10 kV was then applied to the crucible 135 at a frequency of 300-1000 Hz, the combustion product stream appeared to have turbulent flow. In other words, the combustion product stream behaved according to a low Reynolds number, laminar flow regime when no voltage was applied, and exhibited a high amount of turbulence evocative of a high Reynolds number when a voltage was applied, even though mass flow rates were nearly identical.
[0058] With reference to FIGS. 1-3 , According to an embodiment, a co-fired combustion apparatus 100 may include a first fuel-introduction body 105 configured to provide a first fuel (not shown) to a first combustion reaction 115 , and a second fuel-introduction body 135 configured to provide a second fuel 145 to a second combustion reaction 150 . The first fuel introduction body 105 may be positioned relative to the second fuel introduction body 135 to cause the first combustion reaction 115 to at least intermittently provide heat to the second combustion reaction 150 . The co-fired combustion apparatus 100 may further include an electrode assembly 160 associated with the second fuel introduction body 135 or a second combustion volume to which the second fuel introduction body 135 provides the second fuel 145 . The electrode assembly 160 may be configured to be driven to or maintained at one or more first voltages selected to provide an electric field to the second combustion volume. The electrode assembly 160 may include one or more electrodes proximate or within the second combustion region 140 . Additionally, it may include the second fuel-introduction body 135 .
[0059] A portion of the apparatus may be enclosed within a housing 120 . The portion of the housing 120 may be operable to be driven to or held at one or more second voltages. In an embodiment, the electrode assembly 160 may include a portion of the housing 120 . Additionally or alternatively, the electrode assembly 160 may include the second fuel-introduction body 135 . The second fuel-introduction body 135 may include a crucible assembly configured to support the second fuel 145 . In an embodiment, the electrode assembly 160 may include the crucible assembly.
[0060] According to an embodiment, the first fuel-introduction body 105 may include a burner assembly. Additionally, the first fuel-introduction body 105 may be operable to be driven to or held at one or more second voltages. The electrode assembly 160 associated with the second combustion region 140 may be operable to increase combustion efficiency of the second combustion when the electrode assembly 160 is driven to or held at the one or more first voltages. The second combustion may produce a combustion product stream having a flow, wherein the electrode assembly 160 associated with the second combustion region 140 may be operable to generate a combustion product stream flow having turbulent flow when the electrode assembly 160 is driven to or held at the one or more first voltages.
[0061] According to an embodiment of a co-fired combustion apparatus, the first fuel may be substantially liquid or gaseous, whereas the second fuel 145 may be substantially solid. For example, the first fuel may include at least one of natural gas, propane, butane, coal, or oil. The second fuel 145 may include one or more of rubber, wood, glycerin, an industrial waste stream, a post-consumer waste stream, an industrial by-product, garbage, hazardous waste, human waste, animal waste, animal carcasses, forestry residue, batteries, tires, waste plant material, or landfill waste. Additionally, the second fuel 145 may form a portion of a fluidized bed.
[0062] In an embodiment, a co-fired combustion apparatus may include a stoker 210 configured to introduce the second fuel 145 to the second combustion region 140 .
[0063] In an embodiment, a portion of the co-fired apparatus may be enclosed within a flue, stack, or pipe configured to convey a combustion product stream generated by at least the second combustion.
[0064] In an embodiment, the co-fired combustion apparatus may further include a first burner assembly configured to support the first combustion, and a burner support configured to support the first burner assembly in a housing 120 .
[0065] According to an embodiment, a method of co-fired combustion may include step maintaining a first combustion by combusting a first fuel at a first combustion region having a portion defined by a first fuel-introducing body, step maintaining a second combustion by combusting a second fuel at a second combustion region having a portion defined by a second fuel-introducing body, the second combustion sustained by the first combustion, and step applying at least one first electrical potential proximate to the second combustion region. The method of co-fired combustion may further include step applying at least one second electrical potential proximate to the first combustion region. Additionally or alternatively, the method may also include applying at least one second electrical potential at another location proximate to the second combustion region.
[0066] In an embodiment, the method of co-fired combustion may include conveying a combustion product stream generated by at least the second combustion through a flue, stack or pipe.
[0067] According to an embodiment of the method of co-fired combustion, an electrode assembly may be operable to apply the at least one first electrical potential. The electrode assembly may include one or more electrodes proximate to the second combustion region. The electrode assembly associated with the second combustion region may be operable to increase combustion efficiency of the second combustion when the electrode assembly applies the one or more first electrical potential, compared to not applying the one or more first electrical potential.
[0068] According to an embodiment of the method of co-fired combustion, the second combustion may produce a combustion product stream including particulates. The electrode assembly associated with the second combustion region may be operable to increase combustion of the particulates in the combustion product stream when the electrode assembly applies the one or more first electrical potential. The second combustion may produce a combustion product stream having a flow, wherein applying the first electrical potential proximate to the second combustion region may be operable to generate a combustion product stream flow having greater turbulence than another flow having substantially equal Reynolds number with no electrical potential applied.
[0069] Additionally, the second fuel may be introduced to the second combustion region with a stoker. In an embodiment, the first fuel may be substantially liquid or gaseous, and the second fuel may be substantially solid. Additionally or alternatively, the second fuel may include one or more of rubber, wood, glycerin, an industrial waste stream, a post-consumer waste stream, an industrial by-product, garbage, hazardous waste, human waste, animal waste, animal carcasses, forestry residue, batteries, tires, waste plant material, or landfill waste material. The first fuel may include natural gas, propane, butane, coal or oil.
[0070] As used herein, the following terms may have the following definitions:
[0071] “corona discharge” may refer to an electrical discharge, either positive or negative, produced by the ionization of a fluid surrounding an electrically energized conductor.
[0072] “ionic wind” may refer to a stream of ions generated from a tip electrode by a strong electric field exceeding a corona discharge voltage gradient and that may be used to charge exhaust combustion particles.
[0073] FIG. 28 depicts an embodiment of a combustion system 2100 employing a corona discharge device using at least two sharp shaped electrodes 2106 , i.e., electrodes that taper to a sharp tip directed outward toward the combustion exhaust gases 2103 and a collector plate 2102 , according to an embodiment. Suitable materials for the collector plate 2102 may include conductive materials such as iron, steel (such as stainless steel), copper, silver or aluminum or alloys of each of these metals provided that the preponderant constituent of the alloy consists of iron, steel, copper, silver or aluminum. Combustion itself may be provided for though a variety of fuels such as solid, liquid and gas hydrocarbon fuels together with various oxidizers, the most common being ambient air. Other fuel and oxidizer combinations are also possible.
[0074] In order to accomplish a simultaneous charging and collection of exhaust particles 2104 , electrodes 2106 may be placed at either side of a combustion volume 2108 above flame 2101 , and charged with a sufficiently high voltage to generate a corona discharge. Voltage may be applied to electrodes 2106 by a high voltage power source (HVPS) 2110 .
[0075] In order to generate a corona discharge one or both electrodes 2106 is configured to taper to a sharp tip, which can produce a projection of ions near the end of this tip when excited by voltages above a minimum ionization limit. Corona discharge is a process by which a current flows from one electrode 2106 with a high voltage potential into a zone of neutral atmospheric gas molecules such as is present in the combustion exhaust gases 2103 adjacent to the tips of electrodes 2106 . These neutral molecules can be ionized to create a region of plasma around electrode 2106 . Ions generated in this manner may eventually pass charge to nearby areas of lower voltage potential, such as at collector plate 2102 , or they can recombine to again form neutral gas molecules.
[0076] When the voltage potential gradient, or electric field, is large enough at a point in the area where a corona discharge is established, neutral air molecules may be ionized and the area may become conductive. The air around a sharp shaped electrode 2106 may include a much higher voltage potential gradient than elsewhere in the area of neutral air molecules. As such, air near electrodes 2106 may become ionized, while air in more distant areas may not. When the air near the tips of sharp shaped electrodes 2106 becomes conductive, it may have the effect of increasing the apparent size of the conductor. Since the new conductive region may be less sharp, the ionization may not extend past this local area. Outside this area of ionization and conductivity, positively charged air molecules may move in the direction of an oppositely charged object such as collector plate 2102 , where they may be neutralized and/or collected.
[0077] The movement of these ions generated by a corona discharge, therefore, may form an ionic wind 2114 . When exhaust particles 2104 pass through ionic wind 2114 , ions may be attached to some or all of exhaust particles 2104 such that particles 2104 become positively charged to provide charged particles 2112 .
[0078] When the geometry and voltage potential gradient applied to a first conductor increase such that the ionized area continues to grow until it can reach another conductor at a lower potential, a low resistance conductive path between the two conductors may be formed, resulting in an electric arc.
[0079] Corona discharge, therefore, may be generally formed at the highly curved regions on electrodes 2106 , such as, for example, at sharp corners, projecting points, edges of metal surfaces, or small diameter wires. This high curvature may cause a high voltage potential gradient at these locations on electrodes 2106 so that the surrounding air breaks down to form a plasma. The electrodes 2106 are preferably driven to a voltage sufficiently high to eject ions, but sufficiently low to avoid causing dielectric breakdown and associated plasma formation. The corona discharge may be either positively or negatively charged depending on the polarity of the voltage applied to electrodes 2106 . If electrodes 2106 are positive with respect to collector plate 2102 , the corona discharge will be positive and vice versa. Typically charges of either sign are deposited on molecules and/or directly onto larger particulates. Charges deposited onto molecules tend to transfer to larger particles (e.g. onto particles including carbon chains with a relatively large number of carbon atoms). Particles including carbon chains essentially constitute unburned fuel. It is desirable to recycle carbon into the combustion reaction to achieve more complete combustion.
[0080] Moreover, charges tend to collect on metals and metal-containing particulates including mercury, arsenic, and/or selenium. According to embodiments, structures and functions disclosed herein are arranged to remove metal cations from flue gas.
[0081] In some embodiments, ions in ionic wind 2114 can have a constant positive polarity. Positively charged particles 2112 may be attracted by collector plate 2102 which may be negatively charged. Particles 2104 which are larger may obtain more charge due to a larger area exposed to receive more positive ions, for example. Charged particles 2112 sized between about 0.1 μm and about 10 μm may be more easily attracted and collected by collector plate 2102 , while charged particles 2112 with size smaller than about 0.1 μm can exit combustion system 2100 without being attracted by collector plate 2102 . Re-entrainment of charged particles 2112 larger than 10 μm into combustion volume 2108 or disposal within a suitable storage component of combustion system 2100 (not shown) may reduce exhaust emissions, including but not limited to soot and unburned fuel that may be contained within particles 2104 .
[0082] In other embodiments, ions in ionic wind 2114 can have a negative polarity.
[0083] In still other embodiments, charging the combustion reaction can be omitted. A collector plate 2102 or director conduit 202 (see FIG. 29 ) can attract charged particles such as metal cations from the flue gas.
[0084] Other charging methods can, for example, include utilizing fluxes of x-rays or laser beams, radiation material enrichment-like processes, and various electrical discharge processes. The application of an electric field by a corona discharge generated by an application of high voltage at electrodes 2106 may be controlled by a combustion control system.
[0085] According to another embodiment, the collector plate 2102 may include an electrical conductor coupled to receive a second polarity electrical potential from a node (not shown) operatively coupled to the HVPS 2110 . The collector plate 2102 may be disposed above and away from the combustion volume 2108 distal to the flame 2101 , arranged to cause at least one particle classification to flow to a collection location and to cause at least one different particle classification to flow to one or more locations different from the collection location. The main particle flow may typically be aerodynamic. The differentiation between the collected particles and uncollected particles may be based at least partly on the response of a characteristic charge-to-mass ratio (Q/m) of the collected particles.
[0086] In yet another embodiment, a director conduit may be configured to receive the flow of the selected particle classification at a first collection location and to convey the flow of at the least one particle classification to an output location. The output location may be selected to cause the output flow of the selected particle classification to flow back toward the flame 2101 . For example, unburned fuel particles may be relatively heavy, and have a tendency to carry positive charges on their surface. According to yet another embodiment, the described system can recycle the unburned fuel to the flame 2101 . For example, this can allow higher flow rates than could normally be sustained with high combustion efficiency.
[0087] FIG. 29 shows an embodiment of a combustion system 2200 employing a corona discharge device, as described in FIG. 28 , and the director conduit 2202 . Particles 2104 charged by ionic wind 2114 generated by a corona discharge created by the application of a high voltage to electrodes 2106 , provide charged particles 2112 , in an embodiment. Charged particles 2112 may exit combustion volume 2108 and may be attracted to director conduit 202 which may be polarized or grounded such that director conduit 202 may be negatively charged with respect to positively charged particles 2112 . A fan or impeller 204 may be placed inside director conduit 202 to provide additional dragging force to attract charged particles 2112 back into combustion volume 2108 where charged particles 2112 may be re-burned or disposed of into a suitable storage location (not shown) in combustion system 2200 . As described in FIG. 28 , larger particles 2104 may obtain more charge than smaller particles 2104 , therefore, particles 2104 of a size raging from about 0.1 μm to about 10 μm may be more easily attracted to director conduit 2202 . After re-burning, charged particles 2112 may be consumed or may be agglomerated to a size larger than about 0.1 μm, and thus may exit combustion system 2200 without being attracted by director conduit 2202 . Fan or impeller 2204 may generate a vacuum pressure selected to reduce sedimentation of charged particles 2112 in director conduit 2202 . Suitable materials for director conduit 2202 may include a variety of insulated and/or dielectric materials such as elastomeric foam, fiberglass, ceramics, refractory brick, alumina, quartz, fused glass, silica, VYCOR™, and the like.
[0088] In still another embodiment, FIG. 30 illustrates a combustion system 2300 employing a corona discharge device and a collector plate 2102 , as described in FIG. 28 , and a director conduit 202 , as described in FIG. 29 . Particles 2104 may again be charged by ionic wind 2114 generated by a corona discharge created by the application of a high voltage to electrodes 2106 to provide charge particles 2112 . The charged particles 2112 may exit combustion volume 2108 and may be attracted to director conduit 2202 which may be polarized or grounded such that director conduit 2202 may be negatively charged with respect to positively charged particles 2112 . As before, director conduit 2202 may include an inlet port disposed above the combustion volume, an outlet port disposed adjacent to the flame, a tubular body between the inlet and outlet ports. Fan or impeller 2204 may be placed inside director conduit 202 to provide additional dragging force to draw charged particles 2112 back into combustion volume 2108 where charged particles 2112 may be re-burned. Fan or impeller 2204 may also generate a vacuum pressure which may reduce sedimentation of charged particles 2112 in director conduit 2202 . Suitable materials for director conduit 2202 may again include insulated and dielectric materials such as elastomeric foam, fiberglass, ceramics, refractory brick, alumina, quartz, fused glass, silica, VYCOR™, and the like.
[0089] Finally, particles 2104 in exhaust gases that are recirculated trough flame 2101 and re-burned may be charged again during another cycle of corona discharge application and may be collected by collector plate 2102 for later disposal according to established methods for exhaust gas emissions.
[0090] FIG. 31 is a block diagram of combustion control system 2400 that may be integrated in combustion systems 2100 , 2200 , and 2300 , according to an embodiment. Programmable controller 2402 may determine and control the necessary electric field for the generation of a corona discharge from HVPS 2110 to apply suitable voltages to electrodes 2106 based on information received from sensors 2404 . Sensors 2404 may be placed inside combustion volume 2108 to send feedback to programmable controller 2402 to determine the voltage potential gradient required to establish the corona discharge. Combustion control system 2400 may include a plurality of sensors 2404 such as combustion sensors, temperature sensors, spectroscopic and opacity sensors, and the like. The sensors 2404 may also detect combustion parameters such as, for example, a fuel particle flow rate, stack gas temperature, stack gas optical density, combustion volume temperature and pressure, luminosity and levels of acoustic emissions, combustion volume ionization, ionization near one or more electrodes 2106 , combustion volume maintenance lockout, and electrical fault, amongst others. The information (sensor output data) provided by the plurality of sensors 2404 may be typically in the form of continuous, discrete voltage output data (e.g., ±5V, ±12V) several times a second which is compared against predetermined (preprogrammed) values, in real time, within programmable controller 402 .
[0091] FIG. 32 is a flow chart of a method 2500 for reducing the size and number of particles entrained within an exhaust flow leaving a combustion system, according to an embodiment. The method 2500 includes step 2502 , a first electrical potential is applied to one or more shaped electrodes positioned above a flame within a combustion volume and adjacent to an exhaust flow including a plurality of burned and unburned particles leaving the combustion volume. The one or more shaped electrodes may be tapered to a sharp tip directed into the exhaust flow. The applied electrical potential may generate a corona discharged proximate to the sharp tip of each of the one or more shaped electrodes. The corona discharge may generate an ionic wind passing through the exhaust flow. A portion of the plurality of burned and unburned particles may acquire an electric charge having a first polarity.
[0092] In step 2504 an electrically conductive collector plate is provided. The collector plate may be disposed above and away from the combustion volume distal to the flame.
[0093] In step 2506 , a second electrical potential is applied to the electrically conductive collector plate. The second electrical potential may have a polarity opposite that of the first polarity, wherein some fraction of the plurality of the charged particles may be collected at a surface of the collector plate.
[0094] In step 2508 , a “flow” or director conduit is provided. The director conduit may include an inlet port disposed above the combustion volume, an outlet port disposed adjacent to the flame, a tubular body between the inlet and outlet ports, and a fan, impeller or vacuum means for drawing some portion of the exhaust flows through the tubular body thereby redirecting some portion of the burned and unburned particles not captured by the collector plate back into the combustion volume.
[0095] According to an embodiment, a combustion system 2100 may include a combustion volume 2108 configured to support a flow stream including a mixture of fuel and oxidizer ignited within the combustion volume 2108 to generate a flame 2101 and an exhaust flow 2103 having a plurality of combustion particle classifications; and a charge source configured to supply electrical charges into the exhaust flow. Additionally, it may include a high voltage power supply (HVPS) 2110 configured to apply an electrical potential having a first polarity to the charge source; and a collector plate 2102 including an electrical conductor coupled to receive an electrical potential having a second polarity from a node operatively coupled to the HVPS 2110 .
[0096] The collector plate 2102 may be disposed above and away from the combustion volume 2108 distal to the flame 2101 and arranged to cause at least one combustion particle classification to flow to a collection location and to cause at least one different combustion particle classification to flow to one or more locations different from the collection location. The charge source may include one or more shaped electrodes 2106 .
[0097] In an embodiment, the one or more shaped electrodes 2106 may be positioned within the combustion volume 2108 above and to a side of the flame 2101 and adjacent to the exhaust flow 2103 . Additionally, the one or more shaped electrodes 2106 may be tapered to a sharp tip directed into the exhaust flow 2103 . In an embodiment, the one or more shaped electrodes 2106 may generate a corona discharge proximate to the sharp tip. The corona discharge may, in turn, generate an ionic wind 2114 passing through the exhaust flow 2103 . The ionic wind 2114 may be partly responsible for causing the at least one combustion particle classification to flow to the collection location. The corona discharge may be selected to cause a charge to attach to all or most of the plurality of combustion particle classifications.
[0098] In an embodiment, the collector plate 2102 may include an electrically conductive surface proximate to the exhaust flow 2103 . The electrically conductive surface may include a metal, such as iron, steel, copper, silver or aluminum, or alloys of each, wherein the preponderant constituent of the alloy consists of iron, steel, copper, silver or aluminum.
[0099] According to an embodiment, the combustion system may further include a director conduit 2202 configured to receive the flow of the at least one combustion particle classification at the collection location and to convey the flow of at the least one combustion particle classification to an output location. The director conduit 2202 may include an inlet port disposed above the combustion volume 2108 proximate the collection location, an outlet port disposed adjacent the combustion volume 2108 proximate the flame 2101 , and a hollow body connecting the inlet and outlet ports. The director conduit 2202 may further include a fan, impeller or vacuum means 2204 to provide an additional dragging force on the first combustion particle classification through the hollow connecting body from the inlet port to the outlet port. The output location may be selected to cause the flow of the at least one combustion particle classification to flow toward the flame 2101 . The director conduit 2202 may include a dielectric or insulator material, such as elastomeric foam, fiberglass, ceramics, refractory brick, alumina, quartz, fused glass, silica, VYCOR™, and combination thereof.
[0100] According to an embodiment, a combustion system 2200 may include a combustion volume 2108 configured to support a flow stream including a mixture of fuel and oxidizer ignited within the combustion volume 2108 to generate a flame 2101 and an exhaust flow 2103 having a plurality of combustion particle classifications; and a charge source configured to supply electrical charges into the exhaust flow. The combustion system may further include a high voltage power supply (HVPS) 2110 configured to apply an electrical potential having a first polarity to the charge source, and a director conduit 2202 configured to receive a flow of at least some portion of the plurality of combustion particle classifications at a collection location and convey the flow of at the least some portion of the plurality of combustion particle classifications to an output location.
[0101] The charge source may include one or more shaped electrodes 2106 , which may be positioned above and to a side of the flame 2101 and adjacent to the exhaust flow 2103 . The one or more shaped electrodes 2106 are tapered to a sharp tip directed into the exhaust flow 2103 . The one or more shaped electrodes 2106 may be configured to generate a corona discharge proximate to the sharp tip. The corona discharge may, in turn, generate an ionic wind 2114 passing through the exhaust flow 2103 . The ionic wind 2114 may be partly responsible for causing at least some portion of the plurality of combustion particle classifications to flow to the collection location. The corona discharge may be selected to cause a charge to attach on to all or most of the plurality of combustion particle classifications.
[0102] According to an embodiment, the director conduit 2202 may include an inlet port disposed above the combustion volume 2108 proximate the collection location, an outlet port disposed adjacent the combustion volume 2108 proximate the flame 2101 , and a hollow body connecting the inlet and outlet ports. The director conduit 2202 may further include a fan, impeller or vacuum means 2204 to provide an additional dragging force on the first combustion particle classification through the hollow connecting body from the inlet port to the outlet port. In an embodiment, the output location may be selected to cause the flow of the at least one combustion particle classification to flow toward the flame 2101 . The director conduit 2202 may include a dielectric or insulator material, such as elastomeric foam, fiberglass, ceramics, refractory brick, alumina, quartz, fused glass, silica, VYCOR™, and combination thereof.
[0103] According to an embodiment, a combustion system may further include one or more sensors 2404 in electrical communication with a programmable controller 2402 . The one or more sensors 2404 may each provide a plurality of time-sequenced sensor inputs to the programmable controller. The programmable controller may be configured to change the electrical potential applied by the HVPS 2110 to the one or more shaped electrodes 2106 from time-to-time based on a comparison of the plurality of time-sequenced sensor inputs received by the programmable controller 2402 against a set of one or more predetermined values preprogrammed onto the programmable controller 2402 .
[0104] According to an embodiment, a method for reducing the size and number of particles entrained within an exhaust flow leaving a combustion system may include applying a first electrical potential to one or more shaped electrodes positioned above a flame within a combustion volume and adjacent to the exhaust flow an exhaust flow including a plurality of burned and unburned particles leaving the combustion volume. A corona discharge may be generated proximate to the shaped electrodes, thereby providing an ionic wind including a plurality of electric charges passing through the exhaust flow. In an embodiment, at least some of the electric charge having a first polarity may be deposited onto at least a portion of the plurality of burned and unburned particles thereby providing a plurality of charged particles.
[0105] According to an embodiment, an electrically conductive collector plate may be provided. The collector plate may be disposed above and away from the combustion volume distal to the flame.
[0106] According to an embodiment, a second electrical potential may be applied to the electrically conductive collector plate, the second electrical potential having a polarity which is opposite that of the first polarity, wherein at least a fraction of the plurality of charged particles is collected at a surface of the collector plate.
[0107] According to an embodiment, generating a corona discharge proximate to the shaped electrodes may include providing shaped electrodes that are tapered to a sharp tip. Generating a corona discharge proximate to the shaped electrodes may further include generating a high voltage potential proximate to the sharp tip. The ionic wind may be partly responsible for causing the fraction of the plurality of the charged particles to flow to the surface of the collector plate. The collector plate may include an electrically conductive surface proximate to the exhaust flow. In an embodiment, the electrically conductive surface may include a metal, such as iron, steel, copper, silver or aluminum, or alloys of each, wherein the preponderant constituent of the alloy consists of iron, steel, copper, silver or aluminum.
[0108] According to an embodiment, the method further include providing a director conduit configured to receive a flow of some portion of the plurality of burned and unburned particles at an input location and to convey the flow to an output location. The director conduit may include an inlet port disposed above the combustion volume proximate the input location disposed away from the collection plate, an outlet port disposed adjacent the combustion volume proximate the flame, and a hollow body connecting the inlet and outlet ports. The director conduit may further include a fan, impeller or vacuum means to provide an additional dragging force on at least some of the plurality of burned and unburned particles through the hollow connecting body from the inlet port to the outlet port. The output location may be selected to cause the flow of the at least some of the plurality of burned and unburned particles to flow toward the flame. In an embodiment, the director conduit may include a dielectric or insulator material, such as elastomeric foam, fiberglass, ceramics, refractory brick, alumina, quartz, fused glass, silica, VYCOR™, and combination thereof.
[0109] According to an embodiment, the method may further include providing a director conduit having an inlet port disposed above the combustion volume, an outlet port disposed adjacent to the flame, a tubular body between the inlet and outlet ports, and a fan, impeller or vacuum means for drawing some portion of the exhaust flows through the tubular body thereby redirecting some portion of the burned and unburned particles not captured by the collector plate back into the combustion volume. The method may further include providing one or more sensors in electrical communication with a programmable controller. The one or more sensors may each be providing a plurality of time-sequenced sensor inputs to the programmable controller. The programmable controller may change the electrical potential applied by the HVPS to the one or more shaped electrodes from time-to-time based on a comparison of the plurality of time-sequenced sensor inputs received by the programmable controller against a set of one or more predetermined values preprogrammed onto the programmable controller.
[0110] The various systems, apparatuses, burners, devices, processes, and methods disclosed in FIGS. 1-32 can be combined to provide other embodiments. As an example, the combustion apparatuses 100 and 200 of FIG. 1 and FIG. 2 can implement the electrodes 2106 , the collector 2102 , and the voltage source 2110 and other components of FIGS. 28-31 in order to remove collect, trap, draw away, and/or remove portions of an exhaust or flue gas from the combustion reaction 150 and/or the combustion reaction 115 . For example, the electrodes 2106 , can be positioned above the second combustion reaction 150 of FIG. 1 in order to inject charged particles into an exhaust stream or flue gas stream. The collector 2102 can be positioned above and lateral from the combustion reaction 150 and can act as a field electrode to attract exhaust or flue gas particles. The conduit 2202 can also be positioned to act as a field electrode to attract exhaust particles from the second combustion reaction 150 .
[0111] With reference to FIGS. 1-3, 28-32 , according to an embodiment, a method for operating a combustion system, includes outputting a first fuel and a first oxidant, supporting a first combustion reaction 115 with the first fuel and first oxidant, supporting a second combustion reaction 150 of the heated second fuel to the produce a flue gas including entrained particles. The method further includes providing an electrical charge to the second combustion reaction 150 , wherein the electrical charge is carried by the entrained particles, supporting a first field electrode, such as the collector 102 , adjacent to a main flow of the flue gas and applying a first voltage to the first field electrode. The method also includes electrostatically attracting the entrained particles toward the first field electrode to remove at least a portion of the entrained particles from a main flow of the flue gas.
[0112] According to an embodiment the first voltage is opposite in polarity to the electrical charge provided to the second combustion reaction 150 . According to an embodiment, providing the electrical charge to the second combustion reaction 150 includes applying a voltage to a grate 135 supporting the second fuel 145 and transferring charges from the grate 135 to the second fuel 145 . According to an embodiment, the grate includes a crucible. According to an embodiment, providing the electrical charge to the second combustion reaction 150 includes operating an ionizer, for example including electrodes 106 , to apply charges to the first combustion reaction 150 . According to an embodiment, the method includes outputting a second oxidant proximal to the second fuel. According to an embodiment providing the electrical charge to the second combustion reaction includes operating an ionizer 2106 to apply charges to the second oxidant. According to an embodiment, the method includes
[0113] According to an embodiment the method includes providing a second field electrode, for example the director conduit 2202 , disposed in juxtaposition to the first field electrode and applying a second voltage different than the first voltage to the second field electrode to form an electric field between the first and second field electrodes. According to an embodiment, the first field electrode includes a plurality of conductors disposed across the main flow of the flue gas and wherein the second field electrode includes a plurality of conductors interlineated with the first electrode plurality of conductors.
[0114] According to an embodiment, the second voltage is opposite in polarity to the first voltage. According to an embodiment, the method includes providing a secondary flue gas flow different than the first flue gas flow adjacent to the first field electrode, and entraining the electrostatically attracted particles in the secondary flue gas flow. The method can further include directing the secondary flue gas flow and entrained electrostatically attracted particles toward the first or second combustion reaction 115 , 150 . Removing the entrained electrostatically attracted particles from the secondary flue gas flow can include filtering the secondary flue gas flow.
[0115] With reference to FIGS. 1-3, 28-32 a co-fired combustion apparatus includes a first fuel-introduction body 105 configured to provide a first fuel to a first combustion reaction 115 and a second fuel-introduction body 135 configured to provide a second fuel to a second combustion reaction 150 , wherein the second combustion reaction emits an exhaust flow having a plurality of combustion particle classifications and wherein the first fuel introduction body 105 is positioned relative to the second fuel introduction body 135 to cause the first combustion reaction to at least intermittently provide heat to the second combustion reaction 150 . The apparatus further includes an electrode assembly 160 associated with the second fuel introduction body 135 or a second combustion volume to which the second fuel introduction body 135 provides the second fuel, the electrode assembly 160 being configured to be driven to or maintained at one or more first voltages selected to provide an electric field to the second combustion volume. The apparatus further includes a charge source, for example electrodes 2106 , configured to supply electrical charges into the exhaust flow and a high voltage power supply 2110 (HVPS) configured to apply an electrical potential having a first polarity to the charge source. The apparatus further includes a collector plate 2102 including an electrical conductor coupled to receive an electrical potential having a second polarity from a node operatively coupled to the HVPS, the collector plate 102 disposed above and a distal to the second combustion reaction 150 and arranged to cause at least one combustion particle classification to flow to a collection location and to cause at least one different combustion particle classification to flow to one or more locations different from the collection location.
[0116] According to an embodiment, the electrode assembly includes one or more electrodes proximate or within the second combustion region. According to an embodiment, the electrode assembly 160 includes the second fuel-introduction body 145 .
[0117] According to an embodiment, a portion of the apparatus is enclosed within a housing 120 . According to an embodiment, a portion of the housing 120 is operable to be driven to or held at one or more second voltages. According to an embodiment, the electrode assembly 160 includes a portion of the housing 120 .
[0118] According to an embodiment, the second fuel-introduction body 135 includes a crucible assembly configured to support the second fuel. The electrode assembly 160 may include the crucible assembly.
[0119] According to an embodiment, the first fuel-introduction body 105 includes a burner assembly. The first fuel-introduction body 105 may be configured to be driven to or held at one or more second voltages.
[0120] According to an embodiment, the electrode assembly 160 associated with the second combustion region is operable to increase combustion efficiency of the second combustion reaction 150 when the electrode assembly 160 is driven to or held at the one or more first voltages.
[0121] According to an embodiment, the second combustion reaction 150 produces a combustion product stream having a flow and the electrode assembly associated with the second combustion region is operable to generate a combustion product stream flow having turbulent flow when the electrode assembly 160 is driven to or held at the one or more first voltages.
[0122] According to an embodiment, the first fuel is substantially liquid or gaseous. According to an embodiment, the second fuel is substantially solid. According to an embodiment, the second fuel forms a portion of a fluidized bed.
[0123] According to an embodiment, the apparatus includes a stoker configured to introduce the second fuel to the second combustion region.
[0124] According to an embodiment, a portion of the apparatus is enclosed within a flue, stack, or pipe configured to convey a combustion product stream generated by at least the second combustion.
[0125] According to an embodiment, the first fuel includes at least one of natural gas, propane, butane, coal, or oil. According to an embodiment, the second fuel includes one or more of rubber, wood, glycerin, an industrial waste stream, a post-consumer waste stream, an industrial by-product, garbage, hazardous waste, human waste, animal waste, animal carcasses, forestry residue, batteries, tires, waste plant material, or landfill waste.
[0126] According to an embodiment, the co-fired combustion apparatus further includes a first burner assembly configured to support the first combustion and a burner support configured to support the first burner assembly in a housing.
[0127] According to an embodiment, the charge source includes one or more shaped electrodes 2106 . According to an embodiment, the one or more shaped electrodes 2106 are positioned within the combustion volume above and to a side of the second combustion reaction 150 and adjacent to the exhaust flow. According to an embodiment, the one or more shaped electrodes 106 are tapered to a sharp tip directed into the exhaust flow. The one or more shaped electrodes may generate a corona discharge proximate to the sharp tip. The corona discharge may generate an ionic wind 2114 passing through the exhaust flow.
[0128] According to an embodiment, the ionic wind 2114 is partly responsible for causing the at least one combustion particle classification to flow to the collection location 2102 . According to an embodiment, the corona discharge is selected to cause a charge to attach to all or most of the plurality of combustion particle classifications.
[0129] According to an embodiment, the collector plate 2102 includes an electrically conductive surface proximate to the exhaust flow. The electrically conductive surface may include a metal. According to an embodiment, the metal is iron, steel, copper, silver or aluminum, or alloys of each, wherein the preponderant constituent of the alloy consists of iron, steel, copper, silver or aluminum.
[0130] According to an embodiment, the co-fired apparatus includes a director conduit 2202 configured to receive the flow of the at least one combustion particle classification at the collection location and to convey the flow of at the least one combustion particle classification to an output location. The director conduit 2202 may include an inlet port disposed above the combustion volume proximate the collection location, an outlet port disposed adjacent the combustion volume proximate the flame, and a hollow body connecting the inlet and outlet ports.
[0131] According to an embodiment, the director conduit 2202 further includes a fan 2204 , impeller or vacuum means to provide an additional dragging force on the first combustion particle classification through the hollow connecting body from the inlet port to the outlet port. According to an embodiment, the output location is selected to cause the flow of the at least one combustion particle classification to flow toward the flame. The director conduit 2202 includes a dielectric or insulator material. According to an embodiment, the dielectric or insulator material is selected from the list consisting of elastomeric foam, fiberglass, ceramics, refractory brick, alumina, quartz, fused glass, silica, VYCOR™, and combination thereof.
[0132] Finally, while various aspects and embodiments have been disclosed herein, other aspects and embodiments are contemplated. The various aspects and embodiments disclosed herein are for purposes of illustration and are not intended to be limiting, with the true scope and spirit being indicated by the following claims.
[0133] While various aspects and embodiments have been disclosed herein, other aspects and embodiments are contemplated. The various aspects and embodiments disclosed herein are for purposes of illustration and are not intended to be limiting, with the true scope and spirit being indicated by the claims. | According to embodiments, a co-fired or multiple fuel combustion system is configured to apply an electric field to a combustion region corresponding to a second fuel that normally suffers from poor combustion and/or high sooting. Application of an AC voltage to the combustion region was found to increase the extent of combustion and significantly reduce soot evolved from the second fuel. | 5 |
BACKGROUND
[0001] The present invention relates to the field of semiconductor device manufacturing. In particular, it relates to a method of etching silicon wafer, and to apparatus and solution used in or by the method.
[0002] State of art semiconductor device manufacturing technologies include, for example, deposition and etching techniques that are most commonly used to add material to or remove material from certain areas of a functional device structure, or a portion thereof, in a process of forming that device, be that material metallic, semiconductor, dielectric, or insulating material. For example, among the various etching techniques, processes using certain types of chemical solutions are widely used. In particular such processes, known as wet etching process or WETS, may be used in thinning semiconductor wafers in a three-dimensional (3-D) semiconductor device integration process.
[0003] Nevertheless, currently available WETS processes commonly used in thinning semiconductor wafers have individually their own shortfalls. For example, some wet etching processes may employ special chemical solutions including, for example, tetramethylammonium hydroxide (TMAH) solution, potassium hydroxide (KOH) solution, and ethylene diamine and pyrocatechol (EDP) solution but these processes generally have the property of anisotropic etching. In other words, their etch profiles depend on wafer crystallographic orientation i.e. (111), (110), etc., which as a result do not suit for wafer scale silicon removal.
[0004] On the other hand, some other wet etching processes that rely on a mixture solutions of for example HF-HNO3-H2504, although being able to provide isotropic etch with high etch rate, have no doping selectivity and thus cannot provide adequate etch stop mechanism that may be required in order to control the etching process. In the meantime, although there are some other traditional wet etching processes but they generally have very low etch rate.
SUMMARY
[0005] Embodiments of the present invention provides an apparatus that includes a solution bath of a seasoned solution, the seasoned solution containing a mixture of hydrofluoric acid, nitric acid, and acetic acid; and one or more silicon wafers being suspended in a position above the solution bath, wherein at least a portion of the mixture having been used in thinning the one or more silicon wafers.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] The invention will be understood and appreciated more fully from the following detailed description of preferred embodiments, taken in conjunction with the accompanying drawings of which:
[0007] FIG. 1 is a demonstrative illustration of a method of wafer etching and an apparatus used therein having a solution re-circulation mechanism according to an embodiment of the present invention;
[0008] FIG. 2 is a sample experimental chart illustrating rapid etch rate change using solution re-circulation according to an embodiment of the present invention;
[0009] FIGS. 3A-3C are demonstrative illustrations of cross-sectional views of a wafer subjecting to a wafer thinning process according to an embodiment of the present invention; and
[0010] FIG. 4 is a simplified flow-chart illustration of applying a solution re-circulation mechanism in a wafer etching process, according to an embodiment of the present invention.
[0011] It will be appreciated that for the purpose of simplicity and clarity of illustration, elements in the drawings have not necessarily been drawn to scale. For example, dimensions of some of the elements may be exaggerated relative to other elements for clarity purpose.
DETAILED DESCRIPTION
[0012] In the following detailed description, numerous specific details are set forth in order to provide a thorough understanding of various embodiments of the invention. However, it is to be understood that embodiments of the invention may be practiced without these specific details.
[0013] In the interest of not obscuring presentation of essences and/or embodiments of the invention, in the following detailed description, some processing steps and/or operations that are known in the art may have been combined together for presentation and/or for illustration purpose and in some instances may have not been described in detail. In other instances, some processing steps and/or operations that are known in the art may not be described at all. In addition, some well-known device processing techniques may have not been described in detail and, in some instances, may be referred to other published articles, patents, and/or patent applications for reference in order not to obscure description of essences and/or embodiments of the invention. It is to be understood that the following descriptions have rather focused on distinctive features and/or elements of various embodiments of the invention.
[0014] FIG. 1 is a demonstrative illustration of a method of semiconductor wafer etching as well as an apparatus used therein that has a solution re-circulation mechanism according to an embodiment of the present invention. More specifically, the apparatus may include at least a solution bath 110 , at the bottom of which there may be a solution re-circulation port 113 and a drain port 119 . During the use of solution bath 110 in etching/thinning semiconductor wafers, drain port 119 may be closed. Solutions collected by solution bath 110 after being used in the thinning of wafers (thus sometimes being referred to as waste solution or used solution) may be channeled 132 via re-circulation port 113 into a chemical cabinet 115 through an input port 114 of the chemical cabinet 115 . Coming out of an output port 116 of the chemical cabinet 115 , the solutions, possibly with newly added chemicals from chemical cabinet 115 , may be re-applied to the semiconductor wafers, such as wafers 121 , 122 , 123 , and 124 that are inside solution bath 110 undergoing the thinning process. In some embodiment, new chemicals are periodically added in order to sustain a stable etch rate on silicon. As an example, the new chemical may simply be a fresh solution of what was originally in bath 110 , which is then mixed with the used solution to maintain stable etch rate. When being added, the newly added fresh solution may be, for example, 10 to 20 vol. % of the total solution in solution bath 110 .
[0015] According to an embodiment, during a wafer thinning process chemical solutions (such as one with hydrofluoric acid, nitric acid, and acetic acid known as HNA solution) may be re-circulated through ports 113 , 114 , 116 and chemical cabinet 115 to be re-applied to semiconductor wafers 121 , 122 , 123 , and 124 through for example a spray nozzle 111 or any other solution outlet port. More specifically, as being demonstratively illustrated in FIG. 1 , in an embodiment solution 131 coming out of nozzle 111 may be applied to a spinning platform 112 . Spinning platform 112 may subsequently through its spinning motion spray or distribute solution 131 , referred to herein as seasoned solution 131 after solution re-circulation, onto surrounding semiconductor wafers such as wafers 121 , 122 , 123 , and 124 as being illustrated in FIG. 1 . Other solution spraying or applying mechanism may be used as well.
[0016] In an embodiment, semiconductor wafers 121 , 122 , 123 , and 124 may be held to suspend in air or certain regulated or controlled environment such that solutions being applied to them may drip away from the wafers and into underneath solution bath 110 and re-collected by re-circulation port 113 .
[0017] According to an embodiment, it is unexpectedly discovered that seasoned HNA solution 131 may contain a high level of concentration of nitride-oxide, NOx (for example NO or NO2), provided uniquely by the wafer thinning process, which helps etch heavily doped semiconductor wafers and in particular heavily boron (B) doped silicon wafers. For example, after starting an etching process with solution re-circulation mechanism, when it reaches to about 10% of volume in the solution mixture coming from re-circulation, it has been observed that etch rate of heavily doped silicon wafer may reach a steady level of approximate 5 μm/min, with the wafer under thinning having a boron doped level of approximate 1×1019 atoms/cm3. This etch rate is confirmed to be more than 6 times faster than the about 0.8 μm/min etch rate being commonly observed in non-circulation (therefore non-seasoned) HNA solution.
[0018] FIG. 2 is an exemplary sample experimental chart illustrating rapid etch rate increase with an HNA solution bath using solution re-circulation mechanism according to an embodiment of the present invention. In the chart illustrated in FIG. 2 , x-axis denotes seasoning time of the HNA solution bath, expressed in minute. In other word, x-axis represents the time lapsed when HNA solution starts to be sprayed or applied onto heavily boron doped silicon wafers while in the meantime waste solution (or used solution) is being collected by solution bath 110 through re-circulation port 113 ( FIG. 1 ) and re-applied to the silicon wafers. Y-axis denotes silicon wafer etch rate expressed in micrometer (μm) per minute. It is to be noted that the silicon wafer etch rate is only measured on one side of the wafer since the other side is not conditioned, such as heavily boron doped, to be etched.
[0019] In the chart shown in FIG. 2 , it is clearly observed that the etch rate of silicon wafer increases dramatically within the initial approximate 5 minutes, starting at around 0.8 μm/min, which is the typical etch rate of silicon wafers in a non-seasoned HNA bath, to around 5 μm/min when the solution bath may be considered as being fully seasoned, that is, having at least 10 vol. % of re-circulated solution of the total solution volume in the solution bath. In other words, after approximately 5 minutes, the solution bath may be conditioned to become having sufficiently high level of NOx that in turn aids the etching of wafers that are heavily doped by p-type dopants such as boron. After approximately 5 minutes the etching rate, in the illustrated chart of experiment, tapers down slightly and eventually settles at around a steady level of about 4.2-4.3 μm/min. This tapering may partially be due to the solution in solution bath reaching equilibrium and is considered to be mainly caused by slight lag in reaching uniform mixture through solution recirculation. In a 3-D semiconductor device integration process, the etching or thinning process trims down the thickness of silicon wafer to a level that is desirable for the integration.
[0020] FIGS. 3A-3C are demonstrative illustrations of cross-sectional views of a semiconductor wafer being subjected to a wafer thinning process according to an embodiment of the present invention. For example, in a 3-D integration process of manufacturing semiconductor devices, embodiments of present invention may be applied in removing a handler substrate. More specifically as being illustrated demonstratively in FIG. 3A , during manufacturing, a first device layer 312 may be formed on a first substrate 311 , and a second device layer 314 may be formed on a second substrate 316 . Here, the second substrate 316 may be known as a handler substrate and may be heavily doped with boron (B) 320 . Device layer 314 may be formed on top of second substrate 316 or handler substrate via a lightly doped layer 315 . Lightly doped layer 315 may be, for example, epitaxially grown on top of second substrate 316 . In FIG. 3A , the second device layer 314 may be illustrated upside-down and be bonded together with the first device layer 312 through a bonding layer 313 , which may be for example activated silicon oxide, silicon nitride, metal oxide hybrid bonding layer, polymeric adhesive materials, etc.
[0021] In an embodiment, the heavily doped handler substrate 316 may be doped with a dopant level of at least 1×1019 atoms/cm3, compared with the lightly doped layer 315 which may typically be doped at between about 1×1015 cm−3 and 1×1016 atoms/cm3 in dopant level. In other words, dopant level in handler substrate 316 may be at least 1000 times higher than that in layer 315 . In a 3-D integration process, handler substrate 316 may be removed after integration. In removing handler substrate 316 , according to an embodiment of present invention, a significant portion of handler substrate 316 may first be removed through a grinding or polishing process, which may rapidly reduce the thickness of handler substrate 316 to close to, for example, 10˜12 μm. With a portion of handler substrate 316 (10˜12 μm) still remaining on top of lightly doped layer 315 , seasoned HNA solution may be applied or sprayed onto substrate 316 , as being illustrated in FIG. 3B , which etches and removes the remaining portion of substrate 316 . This wet etch process may slow down dramatically to stop at lightly doped layer 315 by virtue of the dopant level in layer 315 . For example, layer 315 may be a p-type dopant (such as boron) doped silicon epitaxial layer with a dopant concentration level around approximately 1×1015 to 1×1016 atoms/cm3, as being illustrated in FIG. 3C .
[0022] According to an embodiment, seasoned HNA solution may be prepared by first creating a mixture of chemical solution having HF: HNO3: CH3COOH in a ratio of approximate 1:3:5 in weight, although embodiment of present invention is not limited in this aspect and certain variation of the ratio of chemical components are acceptable and within the spirits of present invention. For example, ratio variation of above chemicals may range as follows: HF 1: HNO3 3˜6: CH3COOH 3˜5 with HF being as a reference set at 1. It should be noted that other concentration variations outside the suggested range may be used as well, depending upon what the etch rate is desirable. In an embodiment, it is observed that etching and removing of a 12 μm thick substrate 316 took about 2.5 minutes, which is to be compared with the approximate 15 minutes that would otherwise be needed when a conventional, unseasoned HNA solution is used as the best-known method (BKM) process. For clarification, the 2.5 minutes does not include any additional time for wafer handling and rinsing.
[0023] FIG. 4 is a simplified flow-chart illustration of a method of creating a seasoned solution using re-circulation mechanism and applying the seasoned solution in a wafer thinning process, according to an embodiment of present invention. More specifically, an embodiment of a method of present invention may include steps of first creating a HNA solution bath at step 411 , by mixing hydrofluoric acid, nitric acid, and acetic acid in a pre-determined mix ratio such as a ratio of about 1:3:5, although slightly higher or lower content (within for example 5% relative to others) of each acid are fully contemplated by present embodiment as well. In each of the mixing chemical solutions, water is an integral part and concentration of the chemicals may be, for example, HF 49 wt. %, nitric acid 70 wt. % and acetic acid 98 wt. % respectively. After the creation of the solution additional water may be added depending on the intended application, although not necessarily needed, with the effect of dilution where adding water generally will lower the etch rate. Next at step 412 , the prepared mixture of chemical solution may be applied, such as through a spray-on process, onto heavily doped (such as heavily boron doped) silicon wafers and in particular to the side (or sides) of the silicon wafers that are boron doped for the purpose of etching and/or thinning thereof. Solution coming off these wafers, known as waste solution or used solution, may then be collected at step 413 by using for example a solution bath, and subsequently re-circulated back to be applied to the wafers and re-collected by the solution bath at step 414 to create seasoned bath solution. After a certain number of re-circulation, the solution may become seasoned solution to contain a desired level of NOx (such as NO or NO2), that is discovered to be advantageous to the etching of wafers, and the seasoned solution may be re-used and re-applied to the silicon wafer for further thinning the substrate at step 415 . In the seasoned solution, the level of NOx may be proportional to the concentration of HNO3 and in approximate 1:1-2 molar ratio. Once most of the heavily doped portions of silicon is etched away and underneath lightly doped (less than 1×1015 atoms/cm3) portion of wafer is exposed, the etching rate may significantly slow down to close to zero at which point the wafer thinning process may be considered as accomplished, at step 416 .
[0024] While certain features of the invention have been illustrated and described herein, many modifications, substitutions, changes, and equivalents will now occur to those of ordinary skill in the art. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and changes as fall within the spirit of the invention. | An apparatus that includes a solution bath of a seasoned solution, the seasoned solution containing a mixture of hydrofluoric acid, nitric acid, and acetic acid; and one or more silicon wafers being suspended in a position above the solution bath, wherein at least a portion of the mixture having been used in thinning the one or more silicon wafers. | 7 |
BACKGROUND OF THE INVENTION
This invention is particularly useful for controlling plants and processes of various kinds, where some regularly occurring disturbance affects the output of the plant or process. As the ordinary worker in the field of controls will readily recognize the invention described herein as application to any field of control technology from heating, ventilation and air conditioning systems to chemical processing plants, navigational systems, and so on.
A method is described which provides, in the preferred embodiment, using a model based predictive control framework to improve regulatory performance, particularly those processes that are subject to periodic or cyclic disturbances.
Such examples might include temperature disturbances affecting distillation columns (in oil refineries) due to ambient temperature variations over the course of a day (solar cycle), continuous grinding mills subject to feed disturbances near feed-bin changeover times, etc.
Perhaps the primary benefit to using a model that predicts disturbances in feeding this information into the control loop is that processes which are controlled in this way can perform more closely to their constraints. Using the example of a continuous grinding mill, the neural network would be trained on plant data indicating that (using this example) required power consumption to the grinders occurs each time a new ore car is unloaded into the process. Based on the grinding rate, or the size of the ore car, or some other criteria known to the plant operator, a neural net can be trained to expect the occurrence in the change in power requirement for the grinder.
There are many other examples which could be cited for using inventions of this type to improve the performance of the process under control and increase yield by allowing operation of the plant close to the equipment constraints.
Model-based predictive control (MPC) techniques have gained widespread acceptance in the process industry over the past decade due to their ability to achieve multi variable control objectives in the presence of dead time, process constraints and modeling uncertainties. A good review of various MPC algorithms can be found in "Model Predictive Control: Theory and Practice--A Survey", Automatica 23 (3), (1989), Garcia, Pret, & Morari. In general, these algorithms can be considered optimal control techniques which compute control moves as a solution to an optimization problem to minimize an error subject to constraints, either user imposed or system imposed.
In general, an MPC algorithm can be described with reference to the multivariable process. For example, one modeled by the equations:
x=f(x,u) (1a)
y=g(x,u) (1b),
wherein x is the state variable vector, u is the manipulated variable vector and y is the output variable vector.
There are two broad steps: a prediction step and an optimization step. In the prediction step, at every time step (k), the model is used to predict the plant output over a number of future intervals. This is called the prediction horizon. This prediction is corrected by adding the difference in the outputs from the plant and the model to the predicted output. The predicted output is then subtracted from the desired output trajectory over the prediction horizon to give the predicted error. In the optimization step, the minimization of the predicted error subject to the constraint(s) is performed (usually by a least squares minimization, although other techniques may be used) with the computer control moves being the decision variables. Constraints are specified as direct bounds on the decision variables (called manipulated variable constraints) or as constraint equations, usually based on the process model (output constraints). The first computed control move is implemented on the plant and model, then the steps are repeated for the next time step k. It is within the contemplation of the invention that one or all constraint variables of the one or all constraints are predicted.
It is important to know that in the above procedure, feedback information is utilized. At each and every time step this is used again and again to correct the predictions. However, in conventional MPC schemes it is assumed that the current measured disturbance remains constant over the entire prediction horizon because there is no process information in the future. This is called a constant additive disturbance assumption. It is well known that conventional MPC is a special case of the linear quadratic formulation. Looking at the MPC in a linear quadratic framework, the constant additive disturbance assumption suggests that all disturbances effecting the process are random steps that effect each output independently. In many, if not most, applications, this adversely effects the regulatory performance of a standard MPC controller. To counter this linear quadratic formulation, researchers have used a Kalman filter design to obtain estimates of the states and hence the predicted outputs. A review of known methods for dealing with this is provided in the reference "Model Predictive Control: State of the Art" CPC IV-Proceedings of the 4th International Conference on Chemical Process Control, Padre Island, Tex., pp. 271-296 (1991), Ricker.
A combination of an MPC controller with the neural network as explained in this invention provides for a substantial improvement in overall controller design. It may be referred to herein as a Hybrid controller which may include other controller types besides the MPC), or a Hybrid MPC controller.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram of a hybrid predictive/nominal control loop, including the processing plant in accord with the preferred embodiment of the invention.
FIGS. 2 and 3 are graphs of disturbance prediction of the trajectory of y compared to the trajectory of y built into the nominal controller, preferably the MPC type, all in accord with the preferred embodiments of the invention.
FIG. 4 is a graph of the output and load variable trajectories for the conventional MPC and the Hybrid predictive/MPC controllers.
FIG. 5 is a graph of the manipulated variable trajectory for the Hybrid and MPC controllers corresponding to FIG. 4 in time.
SUMMARY OF THE INVENTION
This invention provides for a controller for controlling a process which has an output signal which controls the process through an actuator that's associated therewith. The controller also receives as input a signal representative of the plant or process output.
In a minimum configuration, the invention requires a nominal controller which in the preferred embodiment is an MPC controller that generates an output which can be used for the controller output signal but which output is only used by the process in the absence of predicted disturbances to the process.
The controller also has a disturbance mode controller unit which determines whether a disturbance model output should supplement a nominal controller output to generate a controller output signal to the plant. Of course, a disturbance predictor unit in the preferred embodiment having a trained neural network, understands the likelihood of expected disturbances or disturbance patterns and produces output calculated to adjust the process to setpoint as the disturbance occurs.
The disturbance mode controller unit employs the signal from the disturbance predictor unit as well as the plant or process output signal in a comparative manner. By making a comparison over a selected period of time the disturbance controller unit determines whether or not a disturbance is actually occurring and, if one is not occurring, returns control to the nominal controller for the plant.
Variations of the invention include the use of an on/off output from the disturbance model in the neural network, or several disturbance models, each of which have an output to the disturbance mode controller unit which uses the difference between the plant output signal and the predictive information from the various disturbance models to determine which of them, if any, to use to supplement the nominal controller output.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring first to FIG. 1, a control loop having a hybrid predictive/nominal controller therein is indicated by the numeral 10. In the preferred embodiment the nominal controller is in box 20 and is of the MPC variety and the predictive controller (DMCU 14) is a neural network trained on the inputs and outputs in the loop 10 and a disturbance model relevant to the plant or process 2. The plant or process 2 can be anything controlled by a controller, as would be well understood by those of ordinary skill in this art.
The output of the plant appears on line 3 which, in the vernacular of the industry, is considered a signal representative of its output, also and more commonly known generally as "y". ("y" can be an output variable or a set of output variables. In one case, where only the disturbance affected variable is affected, no part of the y output is sent to the nominal controller. In most complex controlled systems, other output variables will exist that will influence the nominal controller. See the Air Conditioner example in the Detailed Description for more detail about "y".) This indicator of plant or process output is fed to the disturbance processor 19 as well as the controller box 20. The output of the nominal controller is on line 6. The disturbance processor 14 is preferably a neural network trained to understand either with reference to time 15 or some other periodicity indicator, when and to what extent the disturbance is expected to occur. If the periodicity of the disturbance is related to y then y may be the only input necessary for the DMCU 14 (Disturbance Mode Controller Unit). The output of the DMCU 14 appears on line 5.
There are several different ways in which this control by the DMCU can be achieved. In a preferred embodiment, the predictive model or neural network looks at the plant output y and compares it with the expected plant output occurring prior to the event of an oncoming disturbance. Based on the input(u)/output(y) data used to train the neural net, its output (which will appear on line 5) can be used to predict one or more affected control variables or one or more constraint variables, each represented in its own controller within the main controller block 20. Another preferred embodiment can also use the input of an external event, such as that of the movement of time, here illustrated as input from clock block 15.
A short discussion of constraint and control variables is in order here. A constraint variable is one on which the limits of machine performance lie. For example, a fan can only turn at a range of revolutions per minute, and is constrained beyond that range. A feed pipe can only allow a certain volume of fuel to pass through it in a given amount of time and is thus constrained by a flow rate variable. A control variable is one which the controller can affect, such as the size of the opening of a valve, for example, or the directly related rate of flow through an associated pipe. Thus a constraint variable may also be affected by a control variable.
The output of the trained neural net 5(or other predictive model if one other than a neural net is used) simulates the disturbance affecting the process over the prediction horizon at each time step. This output 5 may take any form compatible with the form of the controller box 20. Ordinarily in the preferred embodiment the output is the prediction vector profile of the constraint variable based on the disturbance model the DMCU was trained on (or based on the disturbance model and computational iterations if a computational DMCU is used rather than a neural net). If the predicted disturbance does not materialize, the neural network will respond to that fact because the output y will not be as predicted. When the dissonance with the trained in model becomes apparent to the neural net, it will remove the expected disturbance profile from its output, and if properly trained, can also remove the effects of its error, by compensating output. In a computational DMCU, a monitor will need to be established that checks the output y for some predetermined time to determine whether the disturbance predicted by the iterative model has occurred, and some other model for corrective action could also be added on the nonoccurrence of a predicted disturbance.
In the real-world application of this to a control situation, say to an air conditioning system, the DCMU would be programmed or trained to expect the occurrence of substantial and increasing heat load during the day, and subsequent decreasing heatload as the sun headed for the horizon in the west. If the day is very overcast, the predicted disturbance will not develop and the DMCU will notice this, since the output of the air conditioned space will not show the expected rise in temperature for the no control move situation (or, of course, the flat or decreasing temperature level of the conditioned space with the addition of the disturbance predicted control response situation).
This example is a case where the only output "y" may be temperature of the space. Where this is the case, using FIG. 1, line 4 should not provide any information to the nominal controller. However if the nominal controller were to account for humidity, the "y" output of the space representing humidity (which, let us assume, is not related to the predicted disturbance that the DMCU accounts for) is connected as input to the Nominal Controller but this humidity signal does not, in this example, get sent to the DMCU.
An alternative preferred embodiment would send either a "I predict a disturbance" signal or, in the alternative, a "no disturbance is predicted" signal on line 5. In implementation this would be a logical 0 or logical 1. In such an implementation, the disturbance and non-disturbance responses would have to be programmed or trained into the nominal controller 20, in which case it would not look like a standard MPC controller, rather it would be able to send out an appropriate u for the case where a disturbance exists or where one does not, in response to the DMCU input from line 5. Numerous similar variants can easily be constructed by one of ordinary skill in the art once the basic idea of supplementing a standard controller with the predicted output y expected from a predicted disturbance. In other words, it is believed to be an incorporated invention to place a model of the effect of a potential disturbance into the controller block 20, and have the DMCU merely predict its occurrence. The function of an external clock like that in block 15 in FIG. 1 could be to provide an additional input besides the output y from the plant for such systems to predict the coming of a disturbance.
Training for neural networks to accomplish these tasks is not difficult but should be done, preferably in simulation representative of the situation into which one wishes to place the inventive controller. Background literature that demonstrates that this is within the competence of those of ordinary skill includes "Neural Networks--A Tutorial for the Power Industry," Proceedings of the American Power Conference, 1990, Mathur and Samad, and the literature cited therein.
FIGS. 2-5 describe the profiles or trajectories of the relevant variables on the occurrence of a disturbance. Referring first to FIG. 2, the disturbance D occurs at time=k, the origin of the graph 40. This graph 40 is of the prediction of the output u from the controller in the loop. The dotted line 43 shows no response to the predicted disturbance at time k because it has not yet affected the output y from the plant or process. This line 43 represents the prediction the conventional MPC would produce at time k. By allowing the conventional controller to employ the y predicted by the predictive DMCU, the output u will follow line 41. The actual variance from setpoint is described by line 42.
In FIG. 3, the same graph moves to (or is redrawn with the origin at) time k+2. The disturbance is noticed by the conventional MPC (without a DMCU, as in the prior art MPC). Thus it's response is shown as line 44, anticipating a control move with a model error e2. The model error of e1 at time k+2 for the MPC configured with a predictive DMCU in accord with this invention is in addition to the error e2, allowing the model corrected by the neural net disturbance predictor to bring the process or plant to setpoint 7 in a more timely manner, assuming the occurrence of the actual disturbance is close to the predicted one.
FIG. 4 shows the output and load profiles in graph 45. The hybrid MPC (in accord with the invention) produces the plant output profile of line 49, because it knows (predicts because of its training or model) the coming occurrence of the increasing load line 46. The conventional MPC will produce a plant output profile of line 48 because it takes it until the disturbance has occurred to respond. Thus it can easily be seen that the disturbance response (known as disturbance rejection) is for most situations better for the inventive hybrid MPC than for the conventional MPC when the predicted disturbance to the load occurs.
In FIG. 5 the graph 47 again demonstrates the relative efficiencies of the hybrid MPC and the conventional, although this time with respect to controller output u. line 51 represents the u output for the hybrid MPC in accord with the invention and the line 51 represents the u output of the conventional MPC, in response to the load change profile in FIG. 4, line 46. FIGS. 4 and 5 are both drawn on the same time scale.
The invention thus described is taken as limited only by the following claims. | A control loop for controlling a process or plant which controls the process or plant via an actuator. The control loop receives from the process or plant a signal representative of the process or plant output. The loop includes a nominal controller that generates a control signal for the actuator which is used only in the absence of a predicted disturbance to the process or plant signal from a disturbance mode controller unit having a neural network conditioned for predicting and indicating a disturbance. | 8 |
BACKGROUND OF THE INVENTION
[0001] Tadalafil (compound of formula I), having the (6R,12aR)-configuration,
[0000]
[0000] is a selective inhibitor of cGMP specific Type V phosphodiesterase (PDE5) and it is used for treatment of erectile dysfunction (Clalis®). The pharmacological activity of Tadalafil is specifically attributable to (6R,12aR)-enantiomer and many syntheses have been developed to prepare the enantiomerically pure compound. Since Tadalafil possesses at C(12a)-atom R-configuration, corresponding to configuration of D-tryptophan, all published syntheses have been using exclusively the significantly more expensive D-tryptophan as the starting material (U.S. Pat. No. 6,140,329, U.S. Pat. No. 6,127,542, Synlett 2004, 8, 1428, OPPI Briefs 2005, 37, No. 1, Tetrahedron Asymmetry 2008, 19, 435-442, ibid. 2009, 20, 2090, ibid. 2009, 20, 430, Synth. Commun. 2008, 38, 4265 and Europ. J. Org. Chem. 2010, 1711.
[0002] No synthesis of Tadalafil has ever been reported using either L- or rac.-tryptophan which are less expensive: L-tryptophan is less expensive because its industrial production is based on the fermentation of indole and serine using either wild-type or genetically modified bacteria. This conversion is catalyzed by the enzyme tryptophan synthase which cannot produce D-tryptophan. For the synthesis of Tadalafil the required, more expensive D-tryptophan has to be manufactured by a resolution of rac.-tryptophan prepared by chemical method. For cost efficient manufacture of Tadalafil there is a clear need for a new process in which the less expensive either L- or racemic tryptophan could be used.
SUMMARY OF THE INVENTION
[0003] The present invention discloses a novel efficient process for the manufacture of enantiomerically pure Tadalafil from less expensive and readily available either L- or rac.-tryptophan as shown in Scheme 1:
[0000]
[0004] It has been unexpectedly found that the compound of formula II, which is an important intermediate in the synthesis of Tadalafil, having (1R,3R)-configuration can be efficiently prepared from inexpensive rac.- or L-tryptophan in high yield and high optical purity. Treatment of rac.- or L-tryptophan with piperonal of formula VI in the presence of suitable chiral acid (H—X) provides initially compound of formula IV which undergoes readily acid catalyzed epimerization at the carbon atom bearing the nitrogen function. If an appropriate solvent is used, in which the HX salt of compound of formula III is only limited soluble, crystallization induced asymmetric transformation converts finally all material of formula IV into the enantiomerically pure compound of formula III which undergoes stereo specific cyclization to enantiomerically pure intermediate of formula II. As shown in Tetrahedron Asymmetry 2008, 19, 435-442, this intermediate of formula II can be converted into Tadalafil in 2 steps.
DETAILED DESCRIPTION OF THE INVENTION
[0005] The present invention claims a process (Scheme 1) for preparation of a compound of formula II, having (1R,3R)-configuration as given in the formula II,
[0000]
wherein R 1 represents hydrogen, alkyl, aryl, alkylaryl, arylalkyl, preferably hydrogen, methyl, ethyl and benzyl,
from either L- or rac.-tryptophan of general formula V,
[0000]
wherein R 1 is the same as defined for compound of formula II,
by reacting with a compound of formula VI,
[0000]
[0000] providing in situ compound of formula IV,
[0000]
wherein R 1 is the same as defined for compound of formula II,
which after addition of a suitable chiral acid H—X, preferably in stoichiometric amount, undergoes in suitable solvent under elevated temperature crystallization induced asymmetric transformation providing stereoselectivly enantiomerically pure compound of formula III,
[0000]
wherein R 1 is the same as defined for compound of formula II and HX is a suitable chiral acid,
which spontaneously stereo selectively cyclizes to enantiomerically pure HX salt of the compound of formula II, which is collected from the precipitate and converted into an enantiomerically pure compound of formula II by treatment with suitable organic or inorganic base or using an ion-exchange resin.
[0010] Depending on the choice of starting material the compound of formula V can be present in the form as enantiomerically pure compound as (L)-tryptophan or as racemic tryptophan or as a mixture containing variable amount of both enantiomers.
[0011] As a resulting agent any chiral acid, as commonly used for resolution of nitrogen containing compounds, can be used. Preferably acids as (1R or 1S)-10-camphorsulfonic acid or (D or L)-tartaric acid or (D or L)-dibenzoyl tartaric acid, (1R or 1S)-3-bromocamphor-8-sulfonic acid, (+ or −)-1,1′-binaphtyl-2,2′-diyl-hydrogenphosphate itself or in a mixture with another aliphatic or aromatic carboxylic acid, preferably glacial acetic acid, can be used.
[0012] The chiral acid can be used in the amount of about 0.5 to 2 equivalents, preferably in stoichiometric amount.
[0013] The best results have been achieved specifically with (1R or 1S)-10-camphorsulfonic acid in a suitable solvent in which the compound of formula II is only limited soluble as e.g. acetonitrile, nitromethane, lower alcohols, preferably isopropanol, n-butanol, n-pentanol, THF, chlorinated hydrocarbons, preferably CHCl3, dichloroethylene, or dimethoxyethane. Also aromatic solvents as benzene, toluene, xylene or halogenated derivatives thereof, preferably toluene, can be used.
[0014] The reaction temperature for formation of the compound of formulas II, III and IV and for crystallization induced asymmetric transformation can be in the range of −10° C. until boiling temperature of the used solvent. Preferably reflux temperature in solvents as nitromethane or acetonitrile has been used.
[0015] A recrystallization from an appropriate solvent may further be useful to increase the diastereomeric excess (% ee) of the crystalline diastereomeric salt of formula II.
[0016] A small addition of lower alkyl carboxylic acids, as preferably acetic acid (up to one equivalent) or even addition of water can significantly promote the crystallization of the salt and increase the ee value.
[0017] In the further embodiment of the invention reaction of either L- or rac.-tryptophan of general formula V,
[0000]
wherein R 1 represents hydrogen, alkyl, aryl, alkylaryl, arylalkyl, preferably hydrogen, methyl, ethyl and benzyl,
with a compound of formula VI,
[0000]
[0000] in the presence of a suitable chiral acid H—X, preferably in stoichiometric amount, under elevated temperature in a suitable solvent, followed by crystallization of the said mixture, collection of the desired diastereomeric salt from the precipitate and treatment of the salt with suitable organic or inorganic base, provides also the enantiomerically pure compound of formula II, having specifically the (1R,3R)-configuration.
[0019] In another embodiment of the invention a compound of general formula II, having the (1R,3R)-configuration as given in formula,
[0000]
wherein R 1 represents hydrogen, alkyl, aryl, alkylaryl, arylalkyl, preferably hydrogen, methyl, ethyl and benzyl,
can be also prepared from a compound of formula II, having any possible configuration at C(1)- and C(3)-chiral atoms, in the form as an enantiomerically pure compound or as a racemate or as a mixture of diastereomers,
[0000]
[0021] by adding a suitable chiral acid HX, preferably in stoichiometric amount, followed in a suitable solvent at elevated temperature crystallization induced asymmetric transformation, collection of the desired diastereomeric salt of compound of formula II from the precipitate and converting the salt into an enantiomerically pure compound of formula II by treatment with suitable organic or inorganic base or using an ion-exchange resin.
[0022] As a chiral acid preferably (1R or 1S)-10-camphorsulfonic acid or (1R or 1S)-3-bromocamphor-8-sulfonic acid in stoichiometric amount can be used. The reaction can be carried out preferably in boiling solvents as acetonitrile or nitromethane where the HX salt of the compound of formula II, having (1R,3R)-configuration, has only limited solubility. Under these conditions the starting material containing the compound of formula II, either in a form as enantiomerically pure compound or as racemate or diastereomeric mixture, undergoes crystallization induced asymmetric transformation providing enantiomerically pure HX salt of the compound of formula II, having specifically only (1R,3R)-configuration. This process is possible because at elevated temperature the chiral centers at C(1)- and C(3)-atoms in compound of formula II can be epimerized via its open structure intermediates of formulas IIc and IId as shown in Scheme 2. If an appropriate solvent is used, in which the HX salt of the compound of formula II, having (1R,3R)-configuration, is only limited soluble, crystallization induced asymmetric transformation converts finally all material into the enantiomerically pure compound of formula II specifically with (1R,3R)-configuration.
[0023] In addition dependent on a solvent a catalytic amount, preferably 5-10 mol.-%, of compound of formula VI can be beneficial for the asymmetric transformation.
[0000]
[0024] When referring to compounds described in the present invention, it is understood that references are also being made to salts thereof, preferably as H—X salts, wherein H—X is a suitable chiral acid.
[0025] In this invention a characteristic of protective group R 1 is that it can be removed readily (without the occurrence of undesired secondary reactions) for example by solvolysis, reduction, or alternatively under physiological conditions (as e.g. enzymatic cleavage or formation). Different protective group can be selected so that they can be removed selectively at different stages of the synthesis while other protective groups remain intact. The corresponding alternatives can be selected readily by a person skilled in the art from those given in the standard reference works mentioned in literature (as e.g. Mc Omie “Protective Groups in Organic Chemistry” or Green et al. “Protective Groups in Organic Synthesis”) or in the description or in the claims or the Examples.
[0026] For the purpose of this disclosure, a compound is considered to be “enantiomerically pure” if the content of one isomer is higher than 95%, preferably 99%.
[0027] The example are provided to illustrate particular aspects of the disclosure and do not limit the scope of the present invention as defined by the claims.
EXAMPLES
[0028] Determination of optical purity was carried out with HPLC using chiral columns as Chiralcel OJ-H, Chiralpak AS-H or Chiralpak AD-H from Daicel Chem. Ind. In some cases the optical purity was also determined with NMR-Spectroscopy using chiral Eu-shift reagent. If not mentioned otherwise, all evaporations are performed under reduced pressure, preferably between 5-50 Torr, in some case even under high vacuum. The structure of final products, intermediates and starting materials is confirmed by standard analytical methods, e.g. spectroscopic characteristics as MS or NMR or IR. Abbreviations used are those conventional in the art.
Preparation of (1R,3R)-1-(3,4-methylenedioxyphenyl)-2,3,4,9-tetrahydro-9H-pyrido[3,4-b]indole-3-carboxylic methyl ester (IIa) from L-tryptophan methyl ester (Va)
[0029]
Example 1
[0030] To a solution of piperonal (VI, 165 g), dissolved in dried acetonitrile (900 ml), under good stirring in inert atmosphere L-tryptophan methyl ester (Va, 220 g) and oven dried magnesium sulfate (500 g) were slowly added that the temperature stayed below 25° C. After complete addition the reaction slurry was stirred at rt over night, then filtered and the filter cake washed twice with acetonitrile (2×100 ml). To the filtrate (1R)-10-camphorsulfonic acid (232 g), dissolved in acetonitrile (400 ml), was slowly added, the mixture then seeded with crystals of the enantiomerically pure CSA-salt of compound (IIIa, 20 g), the slurry stirred over night and then heated under reflux for ca. 5 hrs (the reaction progress of the cyclization step was monitored by TLC). After slow cooling to 0° C. another portion of seeding crystals of the enantiomerically pure CSA-salt of the title compound (IIa, 20 g) was added and the slurry stirred over night. The precipitate was then collected by filtration, washed twice with cold acetonitrile (2×100 ml) and dried under vacuum to provide CSA salt of the title compound (IIa): 533 g (91.5% yield, 98% ee).
[0031] Crude CSA salt of IIa (533 g) was added upon an aqueous saturated NaHCO 3 solution (3000 ml) and methylenechloride (2000 ml) and shaken vigorously. The organic phase was separated, the aqueous phase washed twice with methylenechloride (2×300 ml), the combined organic phases dried over magnesium sulfate (100 g), filtered and the filtrate evaporated under reduced pressure to provide the title compound IIa: 301 g (86% yield, 98% ee).
[0032] For analytical purposes small sample of the crude product was purified by column chromatography on silica gel (eluens:hexane/ethyl acetate=8:1): Anal. calculated for C 20 H 18 N 2 O 4 : C, 68.56; H, 5.18; O N, 8.00; O 18.20. Found: C, 68.50; H, 5.22; N, 7.91; O 18.31. The analytical data of HCl salt of the title compound (IIa) was identical with analytical data as reported in Tetrahedron Asymmetry 2008, 19, 435-442.
Preparation of (1R,3R)-1-(3,4-methylenedioxyphenyl)-2,3,4,9-tetrahydro-9H-pyrido[3,4-b]indole-3-carboxylic methyl ester (IIa) from L- or rac.-tryptophan methyl ester (Va or Vb)
[0033]
Example 2
[0034] To a solution of piperonal (VI, 165 g), dissolved in dried acetonitrile (1000 ml), under good stirring in inert atmosphere rac.-tryptophan methyl ester (Vb, 220 g) and (1R)-10-camphorsulfonic acid (232 g) were slowly added that the reaction temperature stayed below 25° C. After complete addition the slurry was seeded with crystals of the enantiomerically pure CSA-salt of the title compound (IIa, 20 g), then stirred at rt over night, and afterwards heated under reflux for ca. 5 hrs (the reaction progress of the cyclization was monitored by TLC). After slow cooling to 0° C. second portion of seeding crystals (IIa) was added and the slurry stirred over night at 0° C. The precipitate was collected by filtration, washed twice with cold acetonitrile (2×100 ml) and dried under vacuum to provide CSA salt of the title compound (IIa): 501 g (86% yield, 97% ee).
Example 3
[0035] To a solution of piperonal (VI, 175 g), dissolved in nitromethane (1100 ml), under good stirring in inert atmosphere rac.-tryptophan methyl ester (Vb, 220 g) and (1R)-10-camphorsulfonic acid (230 g), were slowly added that the temperature stayed below 30° C. After complete addition the slurry was seeded with crystals of the enantiomerically pure CSA-salt of the title compound (IIa, 20 g) and heated under reflux for ca. 5 hrs (the reaction progress of cyclization was monitored by TLC). After slow cooling to rt a second portion of seeding crystals (IIa) was added and the slurry stirred at 0° C. over night. The precipitate was collected by filtration, washed twice with cold nitromethane (2×100 ml) and dried under vacuum to provide CSA salt of the title compound (IIa) as pail yellow solid: 523 g (90% yield, 98.5% ee).
Crystallization Induced Asymmetric Transformation Compound of Formula IIb into (1R,3R)-1-(3,4-methylenedioxyphenyl)-2,3,4,9-tetrahydro-9H-pyrido[3,4-b]indole-3-carboxylic methyl ester (IIa)
[0036]
Example 4
[0037] Under good stirring in inert atmosphere to a slurry of compound (IIb, 580 g) as a mixture of diastereomers in nitromethane (1100 ml), (1R)-10-camphorsulfonic acid (230 g) and piperonal (VI, 5 g) were added. The slurry was seeded with crystals of the enantiomerically pure CSA-salt of the title compound (IIa, 10 g) and then heated under reflux for ca. 8 hrs. After cooling to rt a second portion of seeding crystals (IIa) was added and the slurry stirred at 0° C. over night. The precipitate was collected by filtration, washed twice with cold nitromethane (2×100 ml) and dried under vacuum to provide CSA salt of the title compound (IIa) as pail yellow solid: 540 g (92% yield, 96% ee). | The present invention relates to a novel manufacturing process of pharmaceutically active compound of formula I, having (6R,12aR)-configuration, used for treatment of erectile dysfunction. Starting from racemic or L-tryptophan the invention describes preparation of an enantiomerically pure intermediate of formula II which is a known precursor in the synthesis of Tadalafil (formula I). | 2 |
CROSS REFERENCES TO RELATED APPLICATIONS
[0001] This application is a continuation of international patent application PCT/EP2009/003144, filed on Apr. 30, 2009 designating the U.S., which international patent application has been published in English language and claims priority from German patent application 10 2008 023 826.0, filed on May 8, 2008. The entire contents of these priority applications are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to a method for generating a glass ceramic composite structure.
[0003] A method for producing a composite structure consisting of a zero-expansion material, and a method for producing the same, are known from WO 2006/034775 A1.
[0004] That publication describes different components, consisting of a zero-expansion material, for example of a LAS glass ceramic, that are bonded together by at least one adhesive layer. Any disadvantages are to be kept as small as possible by keeping the adhesive layer used as thin as possible. However, such a bond of course does not stand high temperatures and in addition has relatively low stability. Also, the advantageous properties of the zero-expansion materials are influenced detrimentally.
[0005] DE 198 21 679 A1 discloses a method for joining fiber-reinforced glass or glass ceramic materials to other materials, such as ceramic materials, where the glass or glass ceramic materials and the other materials are pressed together at a boundary surface between the two materials at high temperatures to form a heat fusion joint. The hot-pressing operation is intended to improve the joint.
[0006] A disadvantage of that method is seen in the relatively high expense connected with the hot-pressing operation. Further, pressing can be realized only with difficulty in the case of large components. Finally, the strength of the joint so produced is limited.
[0007] According to JP 63319230 a bonding material used for joining components made from glass or glass ceramics consists of a mixture of glass powder having a low softening point and a glass powder having a higher softening point, and the powder mixture serves as a joining partner between the components which is subsequently solidified by sintering and subjected to a crystallization treatment.
[0008] This process is relatively expensive, and still does not yield a high-strength joint due to the sintering process.
[0009] According to JP 2005061747 a plurality of components made from glass that are to be bonded together, are softened in a furnace and fused so that they are bonded one to the other. The structure so obtained is then heat-treated and crystallized.
[0010] Similarly, US 2005/0014008 A1 provides that a plurality of components made from glass that are to be bonded together, are initially joined by welding in their green glass condition and are then ceramized.
[0011] In order to do so, the edges of the two components must be heated up to a temperature far above the softening point, and this purposefully at the same time and homogeneously over their full length, in order to ensure that a strong bond is achieved when the two edges are pressed together. This is extremely difficult, especially in the case of long joining edges. In addition, there is only little time (in the order of seconds) available to complete the joining operation before the undesirable ceramization process of the green glass components begins.
[0012] For joining glass ceramics, there have also been known cementation processes of the type described, for example, by U.S. Pat. No. 3,715,196.
[0013] In that case, the strength of the bond depends on the adherence of the cement and its mechanical properties. And there is no real zero-expansion cement that would be capable of bonding together two glass ceramic materials with zero-expansion characteristics. Moreover, such a bond as a rule does not stand the high thermal stresses which normally would be tolerated by glass ceramic materials.
SUMMARY OF THE INVENTION
[0014] Accordingly, it is a first object of the present invention to disclose a method for generating a glass ceramic composite structure having high-strength and durable bonding of the individual components.
[0015] It is a second object of the present invention to disclose a method for generating a glass ceramic composite structure having a high degree of hermetic tightness of the bond between the components.
[0016] It is a third object of the present invention to disclose a method for generating a glass ceramic composite structure wherein the bond is highly temperature resistant.
[0017] It is a fourth object of the present invention to disclose a method for generating a glass ceramic composite structure wherein the composite structure produced has essentially the same material properties which a monolithic component would have.
[0018] These and other objects of the invention are achieved by a method for joining components made from glass based materials, wherein a first and at least a second component, with an intermediate layer of a joining solder placed between them, are assembled to form a raw composite structure, where the joining solder has a radiation absorption capacity higher than the components to be joined, and wherein the raw composite structure is irradiated with radiation energy at least in the area of the joining solder until the joining solder has softened sufficiently to bond together the components and the joining solder to produce a composite structure, wherein the components and the joining solder are made from glasses that can be transformed by heat treatment into glass ceramics, and wherein the composite structure is formed from the base glass components and the glass joining solder into a glassy composite structure and is ceramized thereafter.
[0019] The invention is further achieved by a composite structure comprising at least one first and one second component, made from glass ceramics, preferably from LAS glass ceramics, that are bonded one with the other via a joining solder consisting of a glass ceramic, the joining solder having a higher radiation absorption capacity than the first and the second components.
[0020] The invention thereby allows a high-strength and durable bond to be achieved in a simple way between a plurality of components made from glass or glass ceramics, where the properties of the bond produced largely correspond to the properties of the different components, so that high overall strength is achieved and the thermal coefficient of expansion is not impaired, especially when zero-expansion materials are used, for example.
[0021] Further, it is possible to achieve a high-temperature resistant bond, largely designed for a maximum application temperature corresponding to the maximum application temperature of the components that have been bonded together.
[0022] Since according to the invention the components to be bonded as well as the joining solder are used in its green glass condition to obtain a composite structure which is ceramized thereafter, any cracking can be avoided which would evolve, if one or more of the components would be ceramized before joining.
[0023] As the bond produced using a joining solder is obtained by application of radiation energy and local softening and/or fusing of the joining solder, the method so realized is very efficient and energy-saving. Due to the higher radiation absorption capacity of the joining solder, compared with the radiation absorption capacity of the components to be bonded together, softening of the components to be bonded together during softening or fusing of the joining solder can be avoided. As a result, high-strength and dimensionally stable composite structures can be produced.
[0024] Further, the method generally is also suited for bonding together larger components.
[0025] Finally, according to the invention an efficient bonding between glass ceramic components is made possible. The composite structure may have the same properties that have the individual components have.
[0026] E.g. the components to be bonded may consist of a zero-expansion material such as Zerodur® (a LAS glass ceramic produced by Schott AG, Germany). In this application a zero-expansion material is regarded as a material having a CTE (coefficient of thermal expansion) which is close to zero (smaller than ±0·10 −6 /K) in the application range of, for example, 0° C. to 50° C. More specifically, CTE is smaller than ±0.5·10 −6 /K ist, in particular smaller than ±0.1·10 −6 /K ist, in particular smaller than ±0.05·10 −6 /K ist, more particularly smaller than ±0.02·10 −6 /K ist. Also the composite ceramic structure may have essentially the same CTE.
[0027] The invention is applicable to any kind of glass ceramics, also to other known zero-expansion LAS glass ceramics such as CERAN®, Clearceram® and ROBAX® (all produced by Schott AG, Germany). Also MAS (magnesium aluminosilicate) glass ceramics may be of interest.
[0028] According to another embodiment of the invention, the joining solder has a higher radiation absorption capacity at least in the UV range, in the visible light range, in the IR range, or in the microwave range. Accordingly, irradiation can be effected using UV radiation, visible light, IR radiation, microwave radiation or laser radiation.
[0029] Advantageously, the joining solder is placed between the components to be bonded together in the form of a thin plate or a thin bar.
[0030] According to another embodiment of the invention, the joining solder used is a glass that absorbs in the infrared range, preferably a LAS glass ceramic containing components that absorb in the IR range (essentially coloring constituents), used in its green glass condition.
[0031] The absorbing components may be selected, individually or in combination, from the group comprised of Co, Fe, Mn, Ni, Cr, Sn, Ti, Zn, V, Nb, Au, Ag, Cu, Mo, Rh, Dy, Pr, Nd, Ce, Eu, Tm, Er, and Yb.
[0032] Preferably, the joining solder used is one that has a cumulative content of absorbing constituents of at least 0.1% by weight, preferably at least 0.2% by weight, more preferably at least 0.3% by weight, most preferably at least 0.4% by weight. Preferably, the maximum may be 5% by weight, or 2% by weight, or 1% by weight.
[0033] It is possible in this way to obtain an infrared absorption capacity of the joining solder sufficiently high to ensure that during heating-up of the composite structure using infrared radiation only the joining solder will be softened to bond together the components, while the components to be bonded together will not soften and not be altered essentially with respect to their dimensions.
[0034] For producing the infrared energy, an IR heater unit is used according to an advantageous further development of the invention.
[0035] The heater unit may be a heater unit with IR heating elements that produce a radiation temperature of 1500 K, preferably at least 2000 K, more preferably at least 2700 K, most preferably at least 3000 K, as is generally known from U.S. Pat. No. 7,000,430 B1 or U.S. Pat. No. 7,017,370 B1.
[0036] By using a heater unit with specified radiator temperature it is possible to produce short-wave infrared radiation to which the joining solder will couple especially efficiently to ensure quick heating-up of the joining solder, within the shortest possible period of time, whereas the components to be bonded together will not be excessively heated up so that dimensional alteration due to softening will be avoided.
[0037] The components to be joined may, for example, consist of a LAS (lithium aluminosilicate) glass ceramic that comprises a base glass having the following components (in wt.-% on oxide basis):
[0000] Li 2 O 2-5 Al 2 O 3 18-28 SiO 2 50-70,
wherein the joining solder comprises (in wt.-%):
[0000]
Li 2 O
2-5
Al 2 O 3
18-28
SiO 2
50-70
absorbing componets
0.1-5.
[0038] More specifically, the components may consist of a base glass comprising the following components (in wt.-% on oxide basis):
[0000]
SiO 2
50-70
Al 2 O 3
18-28
Li 2 O
2-5
Na 2 O
0-3
K 2 O
0-3
MgO
0-3
CaO
0-3
SrO
0-3
BaO
0-4
ZnO
0-3
TiO 2
0-6
ZrO 2
0-4
SnO 2
0-2
ΣTiO 2 + ZrO 2 + SnO 2
2.5-6
P 2 O 5
0-8
F
0-1
B 2 O 3
0-2
refining agents
0-2.
[0039] The refining agents such as be As 2 O 3 , Sb 2 O 3 , SnO2, may usually be present in amounts of at least 0.1 wt-%.
[0040] The joining solder may preferably comprise the same base glass to which further 0.1 to 2 wt.-% of coloring oxides are added.
[0041] According to an advantageous further development of the invention, the components are pre-heated preferably to a temperature above the glass transformation temperature T g before the raw composite structure is irradiated.
[0042] When larger components are to be joined it is possible in this way to avoid any disadvantageous effects due to thermal stresses that may result when the joining solder is heated up locally by irradiation energy.
[0043] Especially when larger components are to be bonded together, thermal stresses can be reduced in this way.
[0044] The method according to the invention is also suited for the production of structures of a more complex nature, composed from a plurality of individual components by a series of successive steps.
[0045] For example, a first composite structure, produced by irradiation from at least one first and at least one second component and an intermediate layer of joining solder, may be joined via an intermediate layer of joining solder with another component to form another raw composite structure, whereafter the joining solder may be irradiated until it has sufficiently softened to bond the components together.
[0046] It is easily possible in this way to produce even complex components for forming three-dimensional structures. These may be glass ceramic baking ovens, mirror bases, fireplace shields, architectural paneling, etc.
[0047] According to an advantageous further development of the invention, the first composite structure is initially pre-heated to a temperature above T g before the joining solder with at least one further component is irradiated with infrared energy.
[0048] One avoids in this way stresses that may occur especially in larger components.
[0049] It is understood that the features of the invention mentioned above and those yet to be explained below can be used not only in the respective combination indicated, but also in other combinations or in isolation, without leaving the scope of the invention.
[0050] Ceramization is always effected after bonding of the joining solder. So the components and the joining solder are used in its green glass condition and are ceramized only after the bonding process.
[0051] A typical heating cycle to effect bonding, for an LAS base glass, for example, would be:
[0052] pre-heating to a pre-heating temperature of at least 600° C.;
[0053] heating the joining solder by IR radiation within less than 1 minute, preferably within a maximum of 30 seconds, to a bonding temperature of the joining solder, preferably to 1100° C. to 1350° C.;
[0054] holding at the bonding temperature up to a maximum of 120 seconds, preferably for 5 to 60 seconds, to effect bonding of the composite structure; and
[0055] cooling thereafter.
[0056] Preferably, the composite structure is cooled to a temperature below ceramization temperature within less than 10 minutes, preferably is cooled below 750° C. within 1 to 5 minutes.
[0057] Thereafter a typical ceramization cycle may be started. This may involve, for example, heating the composite structure to a nucleation temperature of 750° C., holding for 1 hour, heating to 900° C. holding for 1 hour and cooling to room temperature thereafter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0058] Further features and advantages of the invention will be apparent from the description that follows of certain preferred embodiments, with reference to the drawing. In the drawings
[0059] FIG. 1 shows an IR heater unit in which two components that are to be bonded together, and an intermediate layer of a joining solder can be irradiated with infrared energy;
[0060] FIG. 2 shows a roller-type heating furnace for pre-heating two components to be bonded together, followed by an IR heating station for subsequently bonding the preheated components with the intermediate layer of a joining solder using infrared energy; and
[0061] FIGS. 3-16 show different applications of the method according to the invention for different glass ceramic components, joined in each case by a joining solder.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0062] FIG. 1 shows, by way of a diagrammatic representation, an infrared heater unit (IR heater unit) 10 in which two components 16 , 18 , made from glass or glass ceramics, with an intermediate layer of a joining solder 20 in the form of a thin glass plate, can be bonded together.
[0063] The IR heater unit 10 may be an IR heater unit of the kind known from U.S. Pat. No. 7,000,430 B1 or U.S. Pat. No. 7,017,370 B1, both of which are integrated herein in full by reference.
[0064] The heaters used may be quartz radiators, for example, which have a color temperature of 3000 K and a radiation maximum in the range of approximately 960 nm. The greatest part of the emitted radiation is in the range of between 500 and 5000 nm.
[0065] The components to be bonded together, for example two plates 16 , 18 made from a LAS glass ceramic, are loaded into the interior 14 of the IR heater unit 10 preferably in green glass condition together with an intermediate layer of a joining solder 20 in the form of a thin plate. The joining solder 20 may for example also consist of a LAS glass ceramic material containing highly absorbing constituents whereby high infrared absorption is achieved.
[0066] The raw composite structure so formed is then irradiated with the infrared energy emitted by the quartz radiators 22 of the IR unit until the joining solder 20 has softened sufficiently to bond the two components 16 , 18 together. The two components 16 , 18 are fused at their boundary surfaces to the joining solder 20 , the latter having been heated up to a higher temperature, so that the effect of gravity leads to a substance bond.
[0067] Heating up may be carried out within a short period of time of, for example, 30 seconds and may be followed by a cooling-down phase caused by switching off the heater elements or by a well-directed cooling-down process, in order to reduce stresses.
[0068] Preferably, the components 16 , 18 to be joined and the joining solder 20 are used in green glass condition, and the composite structure so produced is subsequently ceramized, for example in a roller conveyor furnace.
[0069] Especially when larger components are to be bonded together, the method which will be described hereafter with reference to FIG. 2 may be an obvious choice.
[0070] In that case, the components 16 , 18 to be bonded together can be heated up in a furnace 30 , for example a roller conveyor furnace, to a temperature clearly higher than the glass transformation temperature T g , and can then be heated up locally, substantially in the area of the joining solder 20 , by an IR heater unit 22 in an IR heating station 32 until the joining solder 20 has softened sufficiently to bond the components 16 , 18 together.
[0071] Heating up the components 16 , 18 in this way is recommendable in order to avoid high stresses that may result when the joining solder 20 is heated up locally.
[0072] Due to the poor thermal conductivity of glass, initial heating-up to a temperature clearly above T g , for example to 750° C., will be sufficient to avoid excessively high stresses during the subsequent bonding operation using infrared energy.
[0073] If necessary, the IR heating station 32 may be additionally enclosed by a conventional furnace to generally guarantee more uniform heating-up and to keep the components at a temperature above T g during the bonding operation.
[0074] The invention is further suited for producing three-dimensional components for complex structures, also by a plurality of successive steps.
[0075] Different applications will be briefly described hereafter with reference to FIGS. 3 to 16 .
[0076] A composite structure 24 b according to FIG. 3 , or 24 c according to FIG. 4 , comprises for example a first component 16 and a second component 18 made from glass ceramics of different coloring, that are to be bonded together using a joining solder 20 .
[0077] According to FIG. 5 , a composite structure 24 d comprises a first component in the form of a glass ceramic plate on which a second glass ceramic component 18 of circular shape and a third component 19 of hexagonal shape are placed using respective intermediate layers of a joining solder 20 .
[0078] According to FIG. 6 , a composite structure 24 e comprises a first component 16 made from glass ceramics and a second component 18 made from glass ceramics, that are bonded together in the way of a frame via an intermediate layer of a joining solder 20 .
[0079] According to FIGS. 7 to 10 , a composite structure 24 f in the form of a panel is formed from a first glass ceramic component 16 with a structured bottom surface and a second component 18 with a smooth bottom surface, with an intermediate layer of a joining solder 20 , and/or a composite structure 24 g in the form of a panel is formed comprising two glass ceramic components 16 , 18 with smooth bottom surfaces, but different thicknesses, and/or a composite structure 24 h in the form of a channel is formed from three glass ceramic components 16 , 18 , 19 with smooth bottom surfaces but different thicknesses, and/or a composite structure 24 i in the form of a tray is formed from three glass ceramic components 16 , 18 , 19 with smooth bottom surfaces, in each case with an intermediate layer of a joining solder 20 .
[0080] FIG. 11 shows a composite structure 24 j in the form of a web, FIG. 12 shows a composite structure 24 k in the form of a pot holder. A first component 16 has the form of a glass ceramic plate on which two circular plates 18 , 19 are placed via intermediate layers of a joining solder 20 .
[0081] FIG. 13 shows a closed composite structure 24 l consisting of components 16 , 18 , 19 , 21 which, together with the respective intermediate layers of a joining solder 20 , supplement each other so as to form together a structure of square or rectangular cross-section. Production is effected in a plurality of successive steps. A first raw composite structure and a second raw composite structure are formed from the components 16 , 18 and the intermediate layer of joining solder 20 and from the components 19 , 21 and the intermediate layer of joining solder 20 , respectively. The two raw composite structures, with the intermediate layers of joining solder 20 , are then bonded together to form the composite structure 24 l . The overall composite structure may, for example, be a tube for a glass ceramic baking oven or a closed fireplace insert made from glass ceramics.
[0082] FIG. 14 shows another application with a composite structure 24 m of closed rectangular form made from a U-shaped component 16 and a plate-shaped component 18 with an intermediate layer of a joining solder.
[0083] FIGS. 15 and 16 show composite structures 24 n or 24 o in cylinder form or in semi-cylinder form, respectively, with attached flat marginal portions 18 , 19 .
[0084] Preferably, the components to be bonded together are bonded under the effect of gravity.
Example 1
[0085] The components to be bonded consist of two rectangular plates of Robax®, a LAS glass ceramic material sold by Schott AG under Ref. No. 8721. The joining solder used is a highly IR absorbing glass ceramic material which is sold by Schott AG under the name Ceran-Color® under Ref. No. 8557. The components to be bonded together, in the form of plates measuring 250×150 mm, with an intermediate layer of joining solder consisting of Ceran-Color® in the form of a plate of 1 mm thickness, were placed in an IR heater unit one above the other and were then heated up for a period of 40 seconds. Ceran-Color® is a LAS glass ceramic material containing Co, Fe Mn and Ni in concentrations of between 0.1 and 0.3% by weight, respectively, which means that the total content of coloring constituents is between 0.4 and 1.2% by weight.
[0086] After having cooled down, the two components are joined to a composite structure via a substance bond produced by the joining solder.
[0087] Both the components to be bonded together and the joining solder were used in green glass condition, and the composite structure produced was subsequently ceramized by a suitable temperature treatment, e.g. heating to 750° C., holding for 1 hour, heating to 900° C., holding for 1 hour and cooling to room temperature. The composite structure so produced may be used, for example, as a fireplace shield.
Example 2
[0088] Two components that were to be bonded together, made from Clertrans®, a material sold by Schott AG under Ref. No. 8724, were joined using CeranColor® as a joining solder under otherwise identical conditions as in Example 1.
Example 3
[0089] Two components made from Suprema® LAS glass ceramic, a material sold by Schott AG under Ref. No. 8701, were bonded together using an intermediate layer of a joining solder consisting of Ceran-Hightrans®, a material sold by Schott AG under Ref. No. 8575, under otherwise identical conditions as in Example 1. CeranHightrans® is an LAS glass ceramic material containing vanadium as a coloring constituent in a proportion of between 0.4 and 1.2% by weight. The composite structure so produced may be employed especially for ceramic hobs. | A method for making glass ceramic composite structures, wherein a first and at least a second glass component, with an intermediate layer of a joining solder consisting of glass placed between them, are assembled to form a raw composite structure, wherein the joining solder has a radiation absorption capacity higher than the components to be joined, and wherein the raw composite structure is irradiated with energy, for example IR energy, at least in the area of the joining solder until the joining solder has softened sufficiently to bond together the components and the joining solder to produce a composite glassy structure. Thereafter a ceramization treatment is performed. | 2 |
REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. provisional patent application Ser. No. 60/678,309, filed May 6, 2005 and entitled “Portable Ballistic Shelter System”, and is a continuation-in-part of U.S. application Ser. No. 11/429,700, filed May 8, 2006, and entitled “Portable Ballistic Shelter System and Device”, the disclosures of which are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to shelters, and more particularly to portable armor provided in connection with portable shelters such as tents and soft-sided shelters, so as to provide shelters capable of withstanding various types of ammunition and fragmentation and thereby protect the occupants within.
BACKGROUND OF THE INVENTION
[0003] Temporary Shelters such as tents can be provided with one or more layers of material forming the outer boundaries or walls of the structure. Such layers are generally penetrable by common ammunition and fragmentation or shrapnel. While such weaknesses are of little concern to a recreational camper, they become of grave concern to those engaged in activities within tents that are positioned in military zones and other hostile areas. Such tent or shelter deployments must necessarily he close to the hostile activities in order to provide individuals such as troops with proper medical attention, decontamination facilities, and the like; however, the standard shelter wall structure provides little to no protection to the shelter occupants.
SUMMARY OF THE INVENTION
[0004] The present invention provides a portable, lightweight ballistic panel as part of a shelter capable of withstanding penetration by ammunition and fragmentation, so that the occupants of the shelter remain safe and unharmed. In one embodiment of the invention, wail segments or panels of ballistic material are provided so as to hang from an interior or exterior frame member of the shelter. The wall segments or panels can be formed with ballistic inserts and seams to permanently retain the inserts. In one embodiment, the seams can be formed by welding, in another embodiment, the present invention provides a frame independent of the shelter frame to which the panels can be secured. The panels can be provided such that they fold up into portable and manageable units.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] FIG. 1 is a top right perspective view of a sample shelter structure in which the present invention can be deployed, with one end wall broken away.
[0006] FIG. 2 is a top right perspective view of the shelter of FIG. 1 , with portions of the roof cut away to show interior features.
[0007] FIG. 3 is a right front perspective view of a series of adjoining tent structures in which the present invention can be deployed.
[0008] FIG. 4 shows a right side view of a portion of a wall structure in accordance with the present invention.
[0009] FIG. 5 shows a front view of an interior wall as outfitted in accordance with one embodiment of the present invention.
[0010] FIG. 6 shows a front view of an interior wall as outfitted in accordance with another embodiment of the present invention.
[0011] FIG. 7 is a schematic view of a wall attachment incorporating a seam in accordance with one embodiment of the present invention.
[0012] FIGS. 8 and 9 show schematic cross-sectional views of a wall attachment in accordance with different embodiments of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0013] As shown in FIGS. 1 and 2 , temporary shelters 12 such as tents can be provided with one or more layers of material forming the outer boundaries or walls 14 of the structure. In some cases, material also is provided to form a floor 16 covering the otherwise exposed ground within the tent or structure. Doors 15 and windows 17 are frequently provided as well. In some shelter systems, an outer layer or cover fabric 18 is employed along with an inner layer or liner fabric 20 to provide substantial protection from the elements as well as different physical invasive species (e.g., insects, chemical or biological weapons, etc.). These fabrics are portable and may be joined together in series to form a longer structure or complex, as shown at 30 in FIG. 3 . Further, some shelters are provided with external or internal stabilizing frames 22 to facilitate the shelter build-out and strengthen the shelter frame.
[0014] FIG. 4 is a right side view of a portion of a wall structure in accordance with the present invention. As shown in FIG. 4 , a wall 14 and window 17 are provided along with internal framework 22 . A ballistic panel 25 can be suspended from the framework 22 such as by a hook member 26 secured to the framework and looped through an opening in the panel. The opening can be reinforced by a grommet 27 , for example. In one embodiment of the invention, the hook members 26 can he slidably mounted to the framework so as to enable a customized fitting of the ballistic paneling. For example, if a portion of a shelter were barricaded behind a military vehicle or other large object, there may be no need for ballistic paneling for that portion, as any ammunition, fragmentation or other would-be penetrating element would need to first go through the vehicle before it reached the tent. In such examples, ballistic paneling may only be required for the remaining portion of the shelter not protected by the outside object (e.g., vehicle), in which case the hook members can be moved along the framework and positioned such that the paneling secured to the hook members appropriately covers the unprotected areas of the shelter. As further shown in FIG. 4 , it will be appreciated that lighting 28 and other necessary internal objects can be positioned within the tent inside of the wall structure provided in accordance with the present invention to safely allow lighting or other functions within the tent, while not being exposed to projectiles, The hook members can optionally be clasp members, such as C-shaped metal clasps biased in the closed position and having a hinged portion which allows a user to open the otherwise closed clasp to receive a loop, grommet or eyelet, for example. In one embodiment of the invention, peg members are integrally formed with the frame or tent wall for receiving the loop, grommet or eyelet.
[0015] In one embodiment, a secondary frame separate and apart from the primary frame can be erected inside of the primary frame to provide a surface for mounting the panels or wall members. The secondary frame can be dimensioned so as to extend to the edges of the interior of the shelter generally defined by the wall members and somewhat defined by the primary frame where applicable.
[0016] FIG. 5 shows a front view of the interior wall of a shelter as provided in accordance with one embodiment of the present invention. As shown therein, one or more wall blankets, attachments or panels 25 are positioned and secured in place along the wall member 14 of the shelter 12 in accordance with one aspect of the present invention. Each panel can be rigid or non-rigid and can be formed using soft or hard armor material to withstand bullets, small arms fire, personnel ammunitions, fragmentation from explosions, or other known forms of penetrating and potentially lethal objects (hereinafter “projectiles”). In one embodiment, the panel includes an outer shell of heavy-duty nylon which can contain a ballistic insert packet made of plies of appropriate ballistic material, woven or non-woven. The insert packet in this embodiment can be any ultra high molecular weight polyethylene based fiber having an appropriately high strength to weight ratio and an appropriately low specific gravity so as to meet threat level standards. Spectra™ and Dyneema™ materials may be employed in one embodiment, as well as aramid materials such as Kevlar™ and Twaron™, for example. The insert packet can also be made of a para-aramid fiber a woven or non-woven form that possesses high tensile strength, cut and flame resistance and high chemical resistance. It will be appreciated that the outer shell can be provided of various types of materials depending upon the particular deployment requirements (e.g., waterproof, fire retardant, etc.).
[0017] FIG. 7 illustrates an embodiment of the wall attachment 25 of the present invention with a seam 55 along the outer perimeter 51 thereof, In one embodiment of the present invention, the seam 55 acts to seal two plies of an outer shell material of the wall attachment around the insert packet so as to encapsulate it therein. The seam can be provided by sewing, or in one embodiment of the present invention, the seam is provided by welding using an impulse welder, for example. As illustrated in FIG. 8 , for example, the outer shell 50 can be welded with the insert packet 52 between the plies 54 , 56 of the outer shell and forming part of the seam 55 , such that the outer shell 50 and the insert packet 52 are joined together. The insert packet 52 resides in a pocket or opening 53 created between the outer plies 54 , 56 of the outer shell of the wall attachment. In this embodiment of the present invention, the insert packet is not only encapsulated within the outer shell, but is also held in place along its external perimeter, to thereby prevent shifting, sliding, sinking, sagging and/or other undesirable movement within the outer shell. Such movement of the insert packet is undesirable because it can reduce the anti-ballistic coverage of the present invention. In a further embodiment of the present invention, as shown in FIG. 9 , the welding of the seam 55 of the outer shell 50 can also include the welding of an external strip of material 58 (e.g., fabric) that can be provided with attachment mechanisms (not shown), such as hook or loop fasteners, grommets, hooks, clasps, or similar articles. These attachment mechanisms can be used to attach one panel to another and are provided or secured on the material 58 in accordance with known methods in the art. Thus, as part of the present invention, a single welded seam 55 can join the outer plies 54 , 56 of the outer shell 50 , the ballistic insert packet 52 and the attachment mechanism strip 58 , In one embodiment of the present invention, the ballistic panel 52 is sewn to a heat seal fabric not shown) before being welded to the outer shell plies.
[0018] As further shown in FIG. 5 , the arrangement of panels can also accommodate entry and exit components of the existing tent or structure, and can further accommodate windows or other openings in the tent or structure. Thus, for example, if there is a door 15 in a doorway or entryway provided as part of the existing shelter, the panels can be arranged such that two adjacent panels overlie one another at or around the entry way, as shown by arrow 35 . In such embodiment, a person desiring to enter or leave the tent can pull back or push away one of the panels and slip through the entry way. Each panel member can have the specific dimension of approximately 88 inches by approximately 110 inches, although the precise dimensions will depend upon the shelter type and the implementation involved in the deployment. In this way, the shelter of the present invention can be utilized as if the ballistics were not in the shelter. While any windows 17 will be covered in the preferred embodiment of the invention, the windows can still be opened if necessary to allow ventilation.
[0019] As further shown in FIG. 5 , wall panel 14 can be provided with attachment means such as grommets or eyelets 27 integrally formed into the panel such that the grommets can be placed over and around hooks 26 or similar items provided on a tent frame or external frame so as to depend downwardly and outwardly therefrom. The tent frame (whether as part of the existing tent or as provided separately) can be provided with a cable secured thereto for receiving the hook members. In one embodiment of the present invention, the hooks are held stationary by the cable member. In another embodiment, the hooks are slidable back and forth along a horizontal cable secured to the frame in such a way that the hooks can be easily moved to the location most accessible to the panel grommets.
[0020] Alternatively, the wall panel members can be secured to the shelter or shelter frame using attachment means such as a hook and loop connector, a zipper or a snap member, for example. In the embodiment incorporating a zipper, a first zipper edge or taper can be provided on the wall panel member and a second zipper edge or taper can be provided on the shelter wall or frame. Because of the non-rigid nature of the wall panel, once it is secured to the tent frame, it is collapsible along the provided wall of the tent or shelter, in the sense that the panel rests alongside the wail and does not extend obtrusively therefrom, as shown in FIG. 4 , for example.
[0021] In one embodiment of the invention, the panel can be provided with side attachment elements for securing to a separate panel in side-by-side format such that little or no space exists between the respective sides of the panels. Such arrangement can be through attachment mechanisms similar to that described for securing a panel to a structure frame as noted above. In one embodiment of the present invention, panels are placed and secured side by side with an overlap of for example, four to six inches. In one embodiment, adjacent panels are integrally formed as a single unit. In another embodiment, the adjacent panels are integrally formed with a permanent hinge type member or are sewn or otherwise attached so as to allow either the front faces or the back faces of the panels to be mated upon hinging to assist in ease of transport, as well as breakdown and setup of the wall structure. The overlap formation can limit the ability of a projectile penetrating the seam of the two panels.
[0022] The present invention can also accommodate corners within tents or structures. A corner element may be configured to adhere or otherwise attach to the wall panel elements so as to protect any corners that may not otherwise be sealed using the panels described above. Such a corner member may be smaller in width, but of the same length so as to provide a full length barrier to any projectile that might otherwise be capable of penetrating a corner where two adjacent panels are not sufficiently overlapping. The corner member can also be provided with attachment means such as those described above for securely mating with appropriate receiving means of the tent or structure frame. In one embodiment, the side wall non-rigid panel can be bent and attached to the end panel to create sufficient overlap and protection.
[0023] FIG. 6 shows a front view of the interior wall of a shelter as provided in accordance with another embodiment of the present invention. As shown in FIG. 6 , a securing pole member 44 made of metal, plastic or other suitable material can be secured to a top portion of the panel members 25 such as by straps or other suitable means on the exterior of the panels, or by folding over a top portion of the panel member and stitching a seam substantially horizontally along the panel member so as to form an opening through which the pole member can be threaded. The pole member 44 can act as an anchoring point for securing straps, cords or other drawstring-type members 41 which can be used to raise and lower the panel members up and down the wall 14 . The straps 41 can be nylon or other suitable material and can he secured at one end to a top shelter frame member 23 and at the other end to the pole member 44 , in one embodiment of the present invention, the straps 41 are secured at a first end by hook and loop-type fasteners (or similar fasteners as described) to the pole member 44 of a corresponding panel 25 , and then positioned around an upper, substantially horizontal frame member 23 with the other end of the strap being secured to the pole member 44 or the panel member 25 itself using hook and loop type fasteners or similar fasteners. In this way, one end of the strap members 41 can be disconnected from the pole or panel member so that the user can pull the strap member and thereby the panel member can be moved further up or down the shelter wall. As such, the present invention allows for adjusting the height of the ballistic panel member(s) on the wall,
[0024] In the embodiment shown in FIG. 6 , an overlap panel member 42 is provided in between two panel members 25 around a door opening 15 , and the overlap panel member 42 is not provided with a pole member or straps secured thereto. Rather, overlap panel member can be secured to the panel members 25 by sewing, hook and loop fastener or similar fastening means. In one embodiment of the present invention, overlap panel member is sewn to a first panel member, and then connected via hook and loop fastener to a second panel member adjacent the first panel member. In this way, the hook and loop-type fastener can be easily detached while the sewn connection of the overlap panel to the first panel member restricts the detachability. Thus, the overlap panel member can possibly pivot around the sewn seam as a door would pivot, thereby allowing a user easier entry and exit through a door 15 in the structure.
[0025] The invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the claims of the application rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. | A portable, lightweight ballistic panel integrated with a shelter is capable of withstanding penetration by ammunition and fragmentation, so that the occupants of the shelter remain safe and unharmed. In one embodiment of the invention, wall segments or panels of ballistic material are provided so as to hang from an interior or exterior frame member of the shelter. In another embodiment, the present invention provides a frame independent of the shelter frame to which the panels can be secured. The panels can be provided such that they fold up into portable and manageable units. In one embodiment of the invention, wall panels are provided with a welded seam that binds plies of the outer shell of the wall attachment with an inner ballistic-resistant material. | 4 |
BACKGROUND OF THE INVENTION
The present invention relates to a device for transmitting yarn monitoring signals to the control circuit of a spinning station of an open-end spinning machine for determining actuation and deactuation of a sliver feeding device.
In open-end spinning machines, a yarn monitor determines whether a yarn spun by the spinning station is drawn off or whether the travel path of the yarn has been interrupted. If the yarn monitor determines that the spinning of the yarn has stopped, then the feeding of sliver at the spinning station is interrupted. However, problems in the circuit of a yarn monitor can cause the feeding device for the sliver to continue operation although a yarn break has occurred. Such an error can remain unnoticed for a rather long time if the sliver is removed via the suction conduit connected to the spinning chamber due to the prevailing spinning vacuum applied. However, there is also the possibility that the fibers collect in the spinning chamber and clog it. There is the further danger, especially in high-speed rotor spinning machines, that the fibers become heated and ultimately burn on account of the frictional heat.
German Patent Publication DE-OS 25 43 324 teaches an electric circuit arrangement for a yarn-break detecting element for textile machines, especially for fine spinning machines without spindles. A mechanical yarn feeler is utilized as a yarn-break detecting element. The attempt has already been made with the circuit disclosed in this publication to reduce the susceptibility to trouble of the control circuit, especially as concerns the possible failure of a transistor. The circuit therefore does not contain any transistors. However, the circuit is nevertheless not trouble-free since the contacts can remain stuck in the switch which is magnetically actuated upon a yarn break, as a result of which a signal flow indicating the presence of the traveling yarn path nevertheless remains preserved.
In electronic yarn monitors, a yarn traveling in a measuring slot of the yarn monitor generates a yarn traveling signal as the output of the sensor monitoring the yarn. This yarn traveling signal is transformed via switching amplifiers and fed as a direct-current signal to the control circuit of the spinning station. Upon failure of the yarn traveling signal, the drawing-in of the sliver is stopped.
FIG. 1 shows a simplified view of a block circuit diagram of the circuit of an electronic yarn monitor, explained in detail further below, as currently used in textile machines. A defect in an electronic component in the circuit of the yarn monitor or in the receiver itself, produced for example by an error in the voltage supply of the yarn monitor or by the sudden discharge of static electricity produced by the running yarn in the measuring slot, can cause the control circuit to fail to receive a yarn traveling signal at the spinning station or to constantly receive a yarn run signal even though no yarn is being spun any more, which is considerably more dangerous in its effect. If, for example, a short circuit between an emitter and a collector, i.e., a so-called transalloying, arises in the circuit transistor for the yarn traveling signal, the transistor can no longer be switched. The voltage signal then constantly assumes the value indicating continued traveling of the yarn, as a result of which fibers continue to be fed to the spinning station with the consequences indicated. Therefore, it must be absolutely assured that the infeed of fibers into the spinning chamber ceases if the yarn travel path is interrupted.
SUMMARY OF THE INVENTION
It is accordingly an object of the present invention to secure an open-end spinning station against problems and component errors in the transmitting of the signals by a yarn monitor to the control circuit of the spinning station so that the infeed of fibers is reliably avoided upon an interruption of the spinning process.
This object is basically achieved in a device for transmitting yarn monitoring signals to the control circuit of a spinning station of an open-end spinning machine for determining actuation and deactuation of a sliver feeding device, by providing a receiver for contactless receiving a yarn signal representing traveling movement of a yarn being spun and for producing an output signal based on the yarn signal, and an oscillator which is actuable according to the receiver output signal and is connected to the control circuit of the spinning station. An integrated circuit is connected between the receiver and the oscillator for generating and maintaining an actuating signal to the oscillator for generating oscillations thereby, and an alternating-voltage coupling is connected between the oscillator and the control circuit of the spinning station for transmitting only an alternating voltage.
If the yarn monitor is damaged, for example by an error in the supply voltage or the sudden discharge of static electricity, the design of the device in accordance with the present invention causes the oscillator integrated into the circuit to cease to generate any alternating voltage. Even if there would still be a direct voltage at the output of the yarn monitor or oscillator, a signal interruption would be present as a result of the subsequently actuated alternating voltage coupling on the control circuit of the spinning station so that the drive of the sliver feeding device would be immediately stopped. The danger of fire caused by overfeeding the rotor can be avoided in this manner.
The oscillator and the circuit for generating and maintaining its actuated signal can be housed with semiconductor circuits on commonly utilized substrate surfaces or chip surfaces. A fourfold operational amplifier can be utilized in this connection, for example, having two stabilized feedback inverse-coupled operational amplifiers for generating the actuated signal, i.e., for the signal evaluation of the receiver, and for the generation of oscillations in the oscillator. As a result, the common damage e.g. upon a voltage discharge is connected to the reliable sequence of the failure of the production of alternating voltage by the oscillator.
An especially simple form of alternating voltage coupling is constituted by a capacitor. Alternatively, for example, a transformer could be used.
In the present invention, even the use of an alternating voltage switching amplifier for the output of the oscillator does not involve the danger that a transalloying of the switching amplifier will result in maintaining the actuated signal for the fiber infeed since the alternating voltage coupling does not transmit the direct voltage signal which is then produced.
Since the control circuit is usually controlled by direct voltage signals, a rectifier should be connected in advance of the input of the control circuit due to the arriving alternating voltage signal.
In order to distinguish a yarn standing in the yarn monitor from a traveling yarn, it is advantageous to connect an alternating voltage coupling between the receiver of the yarn monitor and oscillator so that only the noise caused by the traveling yarn is transmitted. The use of an electric filter in the circuit for actuating and deactuating the oscillator can be necessary, particularly if noise sources are present in the area of the yarn monitor which generate a noise signal in the yarn monitor independently of the yarn, such as gas discharge lamps by way of example. Moreover, it is advantageous to set a threshold value for the noise signal at a level which is exceeded only if the yarn is actually moving in the measuring slot.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram showing a conventional circuit for signal formation and signal transfer in a yarn monitor utilized in an open-end spinning machine.
FIG. 2 is a similar block circuit diagram representing a control circuit in accordance with the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the accompanying drawings and initially to FIG. 1, a block circuit diagram is shown representing a known conventional form of yarn monitor, designated as a whole by 1. In this exemplary embodiment, the yarn monitor basically consists of an optical yarn sensor as well as the electronic components required for signal amplification and evaluation. The yarn monitor can also be equipped with a capacitive sensor. The yarn monitor can be completely installed in and removed from the spinning station. A light transmitter 2, e.g. an infrared transmitting diode, is arranged in the yarn monitor 1, and is connected to current supply 3 of yarn monitor 1. Transmitting diode 2 emits a constant infrared light flux 4 which is directed onto receiver 5. Yarn 7 to be checked travels within light flux 4 through measuring slot 6. The movement of yarn 7 and its cross section, which is constantly changing over its length, cause a shadowing of receiver 5 with a constantly changing intensity.
Receiver 5 consists of a phototransistor which is connected to a circuit 8 for signal amplification and evaluation. In the case that yarn is absent from or standing stationary in measuring slot 6, e.g. after a yarn break, the shadowing of phototransistor 5 does not change in intensity, so that a direct current flows. In circuit 8, a capacitor is connected after the transistor and forms a barrier for a direct current signal. When the yarn is traveling, a yarn noise signal is produced as a voltage with constantly changing amplitude. Circuit 8 for signal amplification and evaluation transmits a signal when the yarn is running. A customary supply direct voltage, e.g. 24 volts, is actuated with this yarn running signal via switching amplifier 9, which may be a transistor amplifier. This direct voltage signal G is applied to control circuit 11 of a spinning station via lead 10. Disturbances, e.g., noise, can also occur in the area of lead 10, e.g. by damage or defective contacts at the connection positions, such as may be caused by contact corrosion.
Coupling 12 of the sliver supply is maintained in an actuated state by control circuit 11 due to the presence of direct voltage signal G. Coupling 12 is opened only upon the absence of signal G. In the embodiment depicted, a magnetic coupling is used for coupling the feeding roller to its drive. The sliver is fed into the spinning station with the feeding roller.
It will be understood from the above that, whenever a disturbance occurs which maintains a current flux or flow in lead 10, e.g. upon a transalloying of the transistor of switching amplifier 9, the coupling can not be opened and, as a result, the fiber infeed can not be interrupted.
Direct voltage signal G in lead 10 is also used in control circuit 11 to determine production data, e.g. to determine the spooled-up yarn length, which in turn is used to deactuate the sliver supply when the length of spun yarn attains a pre-set value. The linking of the yarn traveling signal to other data is indicated by arrow 13. A signal which is then present can likewise be delivered to coupling 12 in order to interrupt the supply of sliver, if necessary. Furthermore, the lifting of the cross-wound bobbin off of the winding roller can be initiated with the signal.
FIG. 2 is a block circuit diagram of the control circuit in accordance with the present invention. In this embodiment, the yarn monitor also consists of a replaceable structural unit 1' comprising the electronic components necessary for signal amplification and evaluation, and particularly has in common with the yarn monitor of FIG. 1 a light transmitter 2' and a receiver 5'. A capacitive sensor can also be provided. The monitoring of traveling yarn 7' in measuring slot 6' also takes place in this embodiment by the evaluation of infrared light flux 4' which is directed at receiver 5' and is attenuated by yarn 7'.
The evaluation of the signals of receiver 5' and the transmission of the yarn traveling signal to the control circuit of the spinning station takes place with a circuit comprised as follows. Circuit 15 for signal amplification and evaluation is connected with receiver 5' and generates the yarn traveling signal. Circuit 15 comprises an electric filter which filters out interfering frequencies of external noise sources which may simulate a yarn noise signal in the case of a standing or absent yarn through a frequency course similar to the yarn traveling signal. Possible noise sources are e.g. gas discharge lamps. The filtering out of the interfering frequencies assures that only the actual yarn noise signal is evaluated.
Moreover, a threshold switch is integrated in circuit 15 for signal amplification and evaluation which switch makes possible the transmission of a yarn traveling signal only if the yarn noise signal has exceeded a certain threshold, i.e., a noise level at or above which the yarn is moving at a sufficient speed to indicate that normal drawing off of the yarn during a spinning procedure is occurring and thereby justifies an infeed of sliver.
As in the circuit of FIG. 1, the circuit of the present invention operates in the case of an absent or standing yarn to block or prevent the direct current signal of receiver 5' by means of an alternating voltage coupling, e.g. by a capacitor, in signal amplification and evaluation circuit 15.
Oscillator 16 is an essential component of the circuit of the yarn monitor in the present invention. Oscillator 16 should only generate an alternating voltage if a signal is present from signal amplification and evaluation circuit 15 indicating that the yarn is running. The oscillator is followed in the present exemplary embodiment by alternating-voltage switching amplifier 17 which switches a supply voltage, e.g., of 24 volts, via lead 18 to control circuit 19 of the spinning station. A switching amplifier is always advantageous if the signals must be transmitted over leads extending any considerable spatial distance. The output signal of alternating-voltage switching amplifier 17 controlled by the oscillator is alternating-voltage signal W.
This alternating-voltage signal W is supplied to alternating-voltage coupling 20 which is connected in advance of control circuit 19 of the spinning station S of open-end spinning machine M and which is also essential for the invention. Alternating-voltage coupling 20 may consist of a capacitor or transformer. If, for example, an error in alternating-voltage amplifier 17 would result in a direct-voltage signal, the input signal on control circuit 19 would be interrupted since the direct-voltage signal can not pass alternating-voltage coupling 20. A direct-voltage signal therefore has the same effect as a signal that the yarn is absent or stationary.
As a result of the possible appearance of errors in components connected in advance of oscillator 16, it is possible that a voltage may be presented to the oscillator which mimics a yarn traveling signal although no yarn is present or running. In such an instance, oscillator 16 would continue to supply an alternating-voltage signal as a yarn traveling signal. In order to prevent this occurrence, however, the present invention is designed as a precaution that, in the case of damage occurring to or the destruction of a component in advance of oscillator 16, the oscillator is also damaged such that it either supplies no signal or only a direct-voltage signal. In both instances, this would result in an interruption of the yarn traveling signal and thereby would result in a separation of the coupling on the feeding roller so that the feeding of sliver would be stopped.
If the oscillator and the signal amplification and evaluation circuit which generates the yarn traveling signal are housed on a common substrate surface or chip surface, damage in one component will entail the damaging of all circuits on the substrate. In the present exemplary embodiment, receiver 5', signal amplification and evaluation circuit 15 which generates the yarn traveling signal, oscillator 16 and alternating-voltage switching amplifier 17 are supported on common substrate surface 21 indicated by the dotted frame in FIG. 2. In the present exemplary embodiment, two stabilized-feedback operational amplifiers of fourfold operational amplifier 22 serve for the signal evaluation of receiver 5' and to generate the yarn traveling signal as an actuation signal to oscillator 16 and two other stabilized-feedback operational amplifiers of the fourfold operational amplifier serve to generate oscillations in oscillator 16. A voltage discharge or other form of damage results in a destruction of fourfold operational amplifier 22 and therewith in a reliable failure of the generation of alternating voltage by oscillator 16. Even if a direct voltage is still present beyond oscillator 16 it is not transmitted through alternating-voltage coupling 20.
The design of the circuit of the yarn monitor in accordance with the present invention assures that in the case of any conceivable damage to the circuit no signal reaches control circuit 19 of the spinning station which would make possible an inadmissible feeding of sliver.
Since only a direct voltage can be used in control circuit 19 of the spinning station in the present exemplary embodiment, rectifier 23 is connected in after alternating-voltage coupling 20. As a result thereof a direct-voltage input signal is delivered to control circuit 19 of the spinning station. Coupling 24 is coupled to the sliver feeding roller R via control circuit 19 in accordance with the exemplary embodiment of FIG. 1 only when the yarn is running. If the feeding roller is driven by a single drive, not shown, the yarn traveling signal can also act on the circuit of such drive.
As in the circuit of FIG. 1, the yarn traveling signal produced by the control circuit of the present invention according to FIG. 2 can also be used to determine production data or be linked to other signals, as indicated by arrow 25. The signal which is then produced can also act on the coupling at the feeding roller, e.g. when the winding bobbin has reached its a predetermined fullness.
It will therefore be readily understood by those persons skilled in the art that the present invention is susceptible of broad utility and application. Many embodiments and adaptations of the present invention other than those herein described, as well as many variations, modifications and equivalent arrangements, will be apparent from or reasonably suggested by the present invention and the foregoing description thereof, without departing from the substance or scope of the present invention. Accordingly, while the present invention has been described herein in detail in relation to its preferred embodiment, it is to be understood that this disclosure is only illustrative and exemplary of the present invention and is made merely for purposes of providing a full and enabling disclosure of the invention. The foregoing disclosure is not intended or to be construed to limit the present invention or otherwise to exclude any such other embodiments, adaptations, variations, modifications and equivalent arrangements, the present invention being limited only by the claims appended hereto and the equivalents thereof. | A device for transmitting yarn monitor signals to the control circuit of an open-end spinning station for determining whether a yarn spun by the spinning station is being drawn off or whether the yarn travel has been interrupted so that, in case of a yarn break, the infeed of the sliver into the spinning station is interrupted. Defects in electronic components in the circuit of the yarn monitor or in the sensor can result in a continuous yarn traveling signal to the control circuit of the spinning station despite a yarn break. The present invention therefore provides a receiver (5') for contactless receiving the yarn signal of the monitor and an oscillator (16) which can be actuated and deactuated based on the receiver output signal. An integrated circuit (22) is connected between the receiver and the oscillator (16) for generating and maintaining an actuating signal to the oscillator for generating oscillations thereby, and an alternating-voltage coupling (20) is connected between the oscillator and the control circuit of the spinning station for transmitting only an alternating voltage. | 3 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates, in general, to stockings and hosiery and, more particularly, to a stocking that is releasably and removably attachable to footwear, such as thong-style sandals, commonly known as “flip-flops”.
[0003] 2. General Background of the Invention
[0004] While they have been in existence for quite some time, flip-flop sandals have become increasingly popular in recent years. While flip-flops are traditionally worn during the summer months and in warmer weather, there are many who, for purposes of comfort, fashion, or both, prefer to wear summer in cooler weather and, indeed, year round.
[0005] Accordingly, there are those who may benefit from wearing flip-flops in combination with stockings and hosiery, both for warmth, and for fashion. While flip-flops may potentially work with conventional hosiery, such as socks, there are many who do not find such a combination aesthetically pleasing.
BRIEF SUMMARY OF THE INVENTION
[0006] The present invention comprises hosiery, such as stockings, that are releasably and removably attachable to footwear such as flip-flops, and/or which serve to secure footwear such as flip-flops adjacent the foot while the flip-flop is being worn. The stockings may be of a length sufficient to completely cover the calf, extending further over the knee and at least a portion of the thigh, serving as a leg warmer. Alternatively, the stocking may extend any desired height above the ankle but terminate below the knee, serving as a sock.
[0007] In one embodiment of the present invention, the stocking includes a generally cylindrical leg covering region, and an instep covering front flap extending a bottom front edge of the leg covering region. Each distal corner of the front flap includes a cooperating fastening element. In operation, the stocking is worn first, with leg covering region, depending upon its length, surrounding at least the ankle and lower leg of the wearer. Next, the flip-flop is worn in the conventional manner, with the toes slid underneath the strap members or arms of the V-strap of the flop-flop, and with the apex of the V-strap positioned between the big and second toes of the wearer. Next, the opposing corners of the instep covering front flap are drawn forward, between the foot and the arms of the V-strap. Each opposing corner is then wrapped over the top of its associate V-strap arm, and brought towards the other corner of the flap. Finally, the cooperating fastening elements are brought together and affixed to each other. In this manner, The V-strap and, in turn, the remainder of the flip-flop, are secured to the stocking and, in turn, are secured in place adjacent the wearer's foot, while, at the same time, leaving a significant portion of the toes exposed and in view.
[0008] In this embodiment, the cooperating fastening elements may comprise, for example, a button and buttonhole. Alternatively, the cooperating fastening elements may comprise male and female portions of a snap fastener. Other types of cooperating fastener element combinations contemplated by the present invention involve hook-and-loop type fasteners, laces that can be tied together, a button in combination with a looped string or cord, and a pair of mating hooked members.
[0009] In another embodiment of the present invention, a substantially tubular leg covering region is again provided. In this embodiment, the instep covering front flap takes on the form of a tapering partial foot covering region, having a loop of string, cord, or an elastic material at the tapered distal end. In operation, the stocking is again worn first, with leg covering region, depending upon its length, surrounding at least the ankle and lower leg of the wearer. Next, the flip-flop is again worn in the convention manner, with the toes slid underneath the strap members or arms of the V-strap of the flip-flop, and with the apex of the V-strap positioned between the big and second toes of the wearer. Next, the loop at the distal end of the partial foot covering region is stretched over the top of the V-strap, and over and around one of the wearer's toes, such as the second or third toe, where the loop remains in place. Inasmuch as a portion of the V-strap is thus sandwiched between the wearer's foot and the partial foot covering region, this, in turn, serves to secure the flip-flop in place adjacent the wearer's foot, while, at the same time, leaving a significant portion of the toes exposed and in view.
[0010] In a variation of this second embodiment, a cooperating fastening element, such as a button, is provided proximate the attachment point of the looped material to the distal end of the instep covering front flap. In operation, the loop is passed underneath one of the arms of the V-strap, wrapped around the strap back towards the leg, and placed around the button, thus securing the loop to the button. Moreover, it is also contemplated that a plurality of such loops may be provided, with at least one loop being passed underneath and back around each of the separate arms or strap members of the V-strap. Each loop may be secured to its own button attached to the instep covering front flap. Alternatively, all of the loops may be secured to the same, central button. Moreover, as in the first described embodiment, a variety of cooperating fastening members, other than loops and buttons, may alternatively be used. Such cooperating fastening members may comprise, for example, cooperating hook-and-loop tape segments, male and female snap members, eyelets and hooks, buttons and buttonholes, etc.
[0011] One potential benefit of this releasable attachment of the flip-flop adjacent the foot by means of the present invention is that the requirement to repetitively curl the toes while walking, in order to maintain the flip-flop in attachment to the foot, is lessened or eliminated. Flip-flop wearers tend to grip the shoe with their toes while walking, forcing them to take shorter steps. This modification in gait may potentially produce muscle imbalances and improper joint mechanics. It is believed that the additional support provided by the attachment of the flip-flop to a stocking may lessen the modifications made to the gait by the wearer, and thus reduce the risk of associated injuries.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0012] FIG. 1 is a top plan view of a conventional thong-style sandal or flip-flop;
[0013] FIG. 2 is an elevated side perspective view of a first embodiment of a stocking according to the present invention, and showing, in particular, the stocking attached to a flip-flop while being worn about the leg and foot;
[0014] FIG. 3 is a top plan view of the front panel of the stocking of FIG. 2 ;
[0015] FIG. 4 is a to plan view of the rear panel of the stocking of FIG. 2 ;
[0016] FIG. 5 is a top plan view of the back heel panel of the stocking of FIG. 2 ;
[0017] FIG. 6 is a top plan view of the bottom heel panel of the stocking of FIG. 2 ;
[0018] FIG. 7 is an elevated side perspective view of a second embodiment of a stocking according to the present invention, and showing, in particular, the stocking attached to a flip-flop while being worn about the leg and foot;
[0019] FIG. 8 is an elevated side view of the stocking of FIG. 7 ;
[0020] FIG. 9 is a top plan view of the bottom strap portion of the stocking of FIG. 7 ; and
[0021] FIG. 10 is an elevated front view of the stocking of FIG. 7 .
DETAILED DESCRIPTION OF THE INVENTION
[0022] While the present invention is susceptible of embodiment in many different forms, there is shown in the drawings and will herein be described in detail, several specific embodiments, with the understanding that the present disclosure is intended as an exemplification of the principles of the present invention and is not intended to limit the invention to the embodiments illustrated.
[0023] As shown in FIG. 1 , conventional flip-flop 10 includes exposed sole 11 having top surface 12 , and V-strap 15 . V-strap 15 includes first strap member or arm 16 , and second strap member or arm 17 . Both strap members 16 and 17 are joined together at apex 18 , where V-strap 15 attaches to top surface 12 of sole 11 , typically via a cylindrical stem. Distal ends of strap members 16 and 17 may likewise attach to top surface 12 of sole 11 , as shown in FIG. 1 . Alternatively, distal ends of strap members may attach to sole 11 along opposing side edges of sole 11 . In another embodiment of a conventional sandal, a single, relatively wide strap is disposed transversely across the upper toe or lower instep region of the foot.
[0024] A first embodiment of the present stocking, that is releasably and removably attachable to at least a portion of a flip-flop, is shown in FIGS. 2-6 as comprising stocking 30 having front panel 40 , rear panel 80 , back heel portion 90 , and bottom heel portion 100 . Referring to FIG. 3 , front panel 40 includes top edge 41 , bottom edge 42 , first side edge 43 , and second side edge 44 . A slightly tapered upper portion of front panel 40 forms a part of generally cylindrical leg covering region 50 . A somewhat more tapered lower portion of front panel 40 forms instep covering front flap 60 , having first distal corner 61 and second distal corner 62 . Button 70 is sewn or otherwise attached to an inner, reverse side of front flap 60 proximate second corner 62 , and forms a first fastening element associated with stocking 30 . Buttonhole 71 is disposed through a portion of front flap 60 proximate first corner 61 , and thus forms a second fastening element associated with stocking 30 .
[0025] Referring to FIG. 4 , rear panel 80 is substantially rectangular, with slightly tapered side edges, and comprises top edge 81 , bottom edge 82 , first side edge 83 , and second side edge 84 . Rear panel 80 is sewn or otherwise attached to front panel 40 , with top edges 41 and 81 aligned to form substantially circular top opening 31 of leg covering region 50 , with a first longitudinal seam running proximate first side edge 43 and second side edge 84 , and with a second longitudinal seam running proximate second side edge 44 and first side edge 83 , thus forming a substantially cylindrical leg covering region 50 . Alternatively, substantially cylindrical leg covering 50 may be formed in a continuous, seamless manner. Moreover, zero, one, or two seams may be employed proximate substantially circular top opening 31 .
[0026] Referring to FIG. 5 , back heel panel 90 is substantially semicircular in configuration, and includes base edge 91 and semicircular edge 92 . As shown in FIG. 2 , back heel panel may optionally be attached for additional strength and reinforcement proximate the heel portion of stocking 30 , by stitching or otherwise attaching back heel panel to rear panel 80 , with base edge 91 of back heel panel 90 substantially aligned with bottom edge 82 of rear panel 80 .
[0027] Referring to FIG. 6 , bottom heel panel 100 is substantially semielliptical in configuration, and includes base edge 101 and semielliptical edge 102 . If desired, in order to provide additional bottom heel coverage and additional securing of a portion stocking 30 in place proximate the heel of the wearer. Heel panel 100 may be stitched or otherwise attached to rear panel 80 , with semielliptical edge 102 substantially aligned with bottom edge 82 of rear panel 80 .
[0028] Referring to FIG. 2 , in operation, stocking 30 is first worn, by drawing top opening 31 over foot 21 , beyond instep 24 thereof, past ankle 25 and adjacent leg 20 , until leg covering region 50 surrounds leg 20 , and instep covering front flap 60 extends over the top of foot 21 , from instep 24 towards the toes, including big toe 22 and second toe 23 . Next, foot 21 is inserted into flip-flop 10 , with the toes slid underneath first strap member 16 and second strap member 17 of V-strap 15 , such that toes 22 and 23 are disposed on opposing sides of apex 18 of V-strap 15 . Next, bottom edge 42 of instep covering front flap 60 is drawn towards the toes and underneath V-strap 15 , with second corner 62 drawn forward adjacent the foot and underneath first strap member 16 , and first corner 61 drawn forward adjacent the foot and underneath second strap member 17 . Next, a generally triangular portion of front flap 60 proximate first corner 61 is folded back over the top surface of second strap member 17 , exposing first fastening element, or button 70 , proximate instep 24 of foot 21 . Similarly, another generally triangular portion of front flap 60 proximate second corner 62 is folded back over the top surface of first strap member 16 , such that second fastening element, or buttonhole 71 , engages button 70 , with button 70 being inserted through buttonhole 71 to secure second corner 62 to first corner 61 . This, in turn, secures flip-flop 10 , generally, to stocking 30 , thus securing flip-flop 10 in position with foot 21 inserted therein. Undoing the foregoing steps in the reverse order serves to unattach flip-flop 10 from stocking 30 . In this manner, stocking 30 is thus releasably attachable to and detachable from flip-flop 10 .
[0029] Another embodiment of the present invention is shown in FIGS. 7-10 as comprising stocking 200 , having generally cylindrical leg covering region 210 , having a top opening at top edge 211 thereof. Partial foot covering region 220 extends forward from a bottom portion of leg covering region 210 , and includes instep covering front flap 220 . When stocking 200 is worn, the underside of the foot is generally left exposed, with the exception of the region covered by the transverse attachment, by sewing or other means of attachment, of elastic bottom strap 240 across opposing sides of instep covering flap 230 . Optional heel cutout 227 is disposed proximate the junction of leg covering region 210 and partial foot covering region 220 , if an exposed heel is desired. Alternatively, a heel panel, or a heel extension of either leg covering region 210 or partial foot covering region 220 may be provided to cover the heel.
[0030] As best seen in FIG. 10 , partial foot covering region 220 includes proximal portion 221 , instep covering front flap 230 , and tapered edges 222 , terminating at apex 223 . A first fastening element, in the form of loop 250 , is sewn or otherwise attached to front flap 230 proximate apex 223 . A second fastening element, in the form of button 251 , is sewn or otherwise attached to front flap 230 , again proximate apex 223 .
[0031] Referring to FIG. 7 , stocking 200 is first worn, by drawing the top opening at top edge 211 over foot 21 , beyond instep 24 thereof, past ankle 25 and adjacent leg 20 , until leg covering region 210 surrounds leg 20 , and instep covering front flap 230 extends over the top of foot 21 , from instep 24 towards the toes, including big toe 22 and second toe 23 . Next, foot 21 is inserted into flip-flop 10 , with the toes slid underneath first strap member 16 and second strap member 17 of V-strap 15 , such that toes 22 and 23 are disposed on opposing sides of apex 18 of V-strap 15 . Next, first fastening element or loop 250 is drawn forward, underneath either first strap member 16 or second strap member 17 of V-strap 15 , proximate apex 18 . Next, loop 250 is wrapped around, back over the top of either first strap member 16 or second strap member 17 , and is secured about second fastening element or button 251 . This, in turn, secures flip-flop 10 , generally, to stocking 200 , thus securing flip-flop 10 in position with foot 21 inserted therein. Undoing the foregoing steps in the reverse order serves to unattach flip-flop 10 from stocking 200 . In this manner, stocking 200 is thus releasably attachable to and detachable from flip-flop 10 .
[0032] Various means of attachment to flip-flop 10 , other than an elastic loop and button, may be employed in variation of this embodiment of the invention. For example, a length of material, having a buttonhole proximate a distal end, may instead be attached to apex 223 , wrapped around a portion of V-strap 15 , and attached to button 251 . Hook-and-loop type fastening elements may alternatively be disposed at the distal end of such a strip of material, and in place of button 251 . Male and female portions of a snap fastener may likewise be disposed at the distal end of such a strip of material, and in place of button 251 . A hook may be disposed proximate apex 251 in place of a fastener, to engage and secure loop 250 . Moreover, a plurality of any of the foregoing fastening elements may be employed, with at least one pair of such fasteners associated with each opposing tapered edge 222 of front flap 230 . In this manner, loops or lengths of material may alternatively be simultaneously wrapped around both strap member 16 and strap member 17 of V-strap 15 , thereby providing more balanced, enhanced securement, as compared to a single point of attachment.
[0033] Moreover, a variation of the embodiment of FIGS. 7-10 is also contemplated, wherein second fastening element or button 251 is omitted. In this embodiment, loop 250 is instead extended over V-strap 15 and is placed so as to encircle one of the toes, such as second toe 23 . Moreover, a sufficient length of loop 250 may be provided, or loop 250 may be of a material of sufficient elasticity, so as to permit loop 250 to be wrapped one or more times completely around either first strap member 16 or second strap member 17 , prior to attachment to one of the toes. This attachment of a distal end of instep covering front flap 230 over V-strap 15 and to one of the toes of the foot likewise serves to maintain flip-flop 10 in attachment to the foot. As in the previously discussed embodiments, a plurality of such loops 250 may be provided, for attachment to multiple toes, and/or for wrapping about both strap members of V-strap 15 , providing enhanced securement of flip-flop 10 in place while being worn.
[0034] In the embodiments illustrated in FIGS. 2-10 , the stocking of the present invention is in the form of a leg warmer, extending up the leg approximately sixteen to eighteen inches, as measured from the bottom of the foot. Alternatively, the length of the stocking may be shortened to mid-calf, or to just above the ankle, in the configuration of a sock. Moreover, the general circumference and lengths of the stocking may be varied to accommodate various sized wearers, such as by matching established sock or shoe sizes.
[0035] The stockings of the present invention may be woven or knit from a variety of natural or synthetic materials, such as cotton, wool, polyester, nylon, Spandex®, or natural/synthetic blends. It is desirable that at least the portion of the stocking that partially covers the foot be sufficiently stretchable or elastic in nature to facilitate attachment of the stocking to the flip-flop while the stocking is being worn.
[0036] Many modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced other than as specifically described. Various modifications, changes and variations may be made in the arrangement, operation and details of construction of the invention disclosed herein without departing from the spirit and scope of the invention. The present disclosure is intended to exemplify and not limit the invention. | Hosiery, such as stockings, are releasably and removably attachable to footwear such as flip-flop type sandals, and/or serve to secure a flip-flop adjacent the foot while the flip-flop is being worn. An instep covering front flap is provided, covering portions of the top of the foot while leaving toes exposed. The stockings include cooperating fastening elements configured to secure the stocking to the V-strap portion of the flip-flop. | 0 |
This is a continuation of application Ser. No. 08/072,499, filed Jun. 4, 1993. Now abandoned.
BACKGROUND OF THE INVENTION
The invention relates generally to the copying of a master.
More particularly, the invention relates to the copying of a transparency on photosensitive material where the latter is exposed to light of the primary colors blue, green and red.
For photographs having individual areas with large brightness differentials, the copies are often overexposed in the light regions and underexposed in the dark regions. As a result, details and fine structures are poorly visible or completely invisible on the copies.
The German patent 28 20 965 discloses a copying apparatus having a liquid crystal display between the light source and the film. A black-and-white negative mask of an exposure to be reproduced is formed on this display by means of an electric control mechanism. When the copy paper is now exposed using light which has passed through the mask and the exposure, a desired density compression is achieved. However, it has been found that color errors are present in the copies.
SUMMARY OF THE INVENTION
It is an object of the invention to provide a copying apparatus which enables copy quality to be improved.
Another object of the invention is to provide a masking arrangement which allows color errors in copies to be reduced or eliminated.
An additional object of the invention is to provide a copying method which makes it possible to improve copy quality.
A further object of the invention is to provide a copying method which permits color errors in copies to be reduced or eliminated.
The preceding objects, as well as others which will become apparent as the description proceeds, are achieved by the invention.
One aspect of the invention resides in an apparatus for copying a master, particularly a transparent master. The apparatus comprises a first holder or first positioning means for positioning the master at a first location, and a second holder or second positioning means for positioning copy material, e.g., photographic copy paper, at a second location. The copy material, which may be photosensitive, has respective sensitivity maxima in a plurality of preselected colors. The apparatus further comprises means for forming an image of the master on the copy material when the master is positioned at the first location and the copy material is positioned at the second location. The forming means includes a unit for exposing the master to illumination of the preselected colors and this unit comprises a plurality of zones each having an independently variable intensity. The apparatus additionally comprises means for changing the intensities of the zones in such a manner that, in the spectral ranges corresponding to the neighborhoods of the sensitivity maxima, the intensity of each zone changes by approximately the same factor.
The zones of the exposing or illuminating unit may be considered to function as a mask.
The preselected colors are preferably the primary colors blue, green and red. The apparatus can be designed so that, at least on occasion, the copy material is exposed to these three primary colors simultaneously. The changing means may be arranged to produce approximately equal changes in average intensity over the spectral ranges of 420 nm to 490 nm, 500 nm to 560 nm and 670 nm to 730 nm.
The apparatus of the invention makes it possible to eliminate the dependence of the coloring of a copy on the degree of masking. The "color neutrality" of the illuminating unit does not mean that the copy light has no coloring. Rather, the coloring does not change in spite of the fact that the intensity or brightness varies from zone to zone. The coloring of the copy light is the same for different degrees of masking. This does not refer to the visible color range but to the wavelength ranges corresponding to the color sensitivity of the copy material. A change in coloring with different degrees of masking is referred to as color distortion of the mask.
As just indicated, the color neutrality of the mask should be in the wavelength ranges where the copy material has its most significant sensitivity instead of in the visible spectrum. Differences exist particularly in the red color range. While the sensitivity maximum of photographic paper normally lies at a wavelength of more than 700 nm, the eye has a very low sensitivity at this wavelength.
In accordance with one embodiment of the invention, the illuminating unit consists solely of an LED matrix. The individual LEDs can be controlled independently of one another so that the so that the source of illumination itself also serves as a mask.
According to another embodiment of the invention, the illuminating unit includes a conventional source of illumination, e.g., a lamp, filter arrangement and reflector shaft, as well as an LCD or liquid crystal matrix.
When using either an LED matrix or an LCD, it can be desirable to prevent the individual zones from being visible on the copy. This can be accomplished by projecting the zones unsharply onto the copy material and/or by interposing a matte or ground glass smoothing element between the illuminating unit and the master. The boundaries between the zones are then invisible on the copy.
If the gray values of the individual or localized zones of an LCD are to be changed directly, it is preferred to use a matrix of individual cells or zones collectively referred to as modulating elements. By precise incorporation of coloring matter in these liquid crystals, a change in intensity which is practically neutral as regards color can be achieved.
Both for an LED matrix and an LCD, having a matriy of cells it is of particular advantage for each individual zone to have its own control line. The cells can then be directly controlled individually by means of an electronic control unit.
An a.c. voltage source can be provided to regulate the intensities of the individual zones. A discrete amplifier is required for each zone to regulate the a.c. voltage.
If the illuminating unit is to have a high resolution with approximately 1,000 to 2,000 zones, an integrated circuit of the type normally used to control TFT displays can be employed. However, such a component cannot produce the high voltages necessary for high illumination intensities and correspondingly short exposure times. Hence, it may be more effective to use a pulsating d.c. voltage source. The change in intensity of the elements is achieved by a change in the effective value of the voltage. By way of example, the effective value can be changed by influencing the waveform of the voltage or by regulating the number of transmitted pulses. This can be accomplished by assigning a change-over switch to each element which can selectively connect the element to a d.c. voltage source and a reference potential. A common change-over switch is provided for all of the zones and allows the d.c. voltage source or the reference potential to be connected to all of the elements simultaneously. If the common change-over switch is switched at a frequency in the kHz range, e.g., at a frequency of 1 to 100 kHz, an individual element can be activated when the associated individual change-over switch is set in a sense opposite to the common change-over switch. When the common change-over switch is set in the same sense as the change-over switch for an individual element, the respective element is deactivated. The intensity of a element can be regulated by causing the associated change-over switch to be set in a sense opposite to the common change-over switch a certain number of times during a predetermined period, and by causing the associated change-over switch to be set in the same sense as the common change-over switch a certain number of times during this period. The effective value of the voltage can be controlled through the sizes of transmitted pulse packets.
The switching frequency of the common change-over switch should be kept as low as possible in order that a LCD, for example, may be supplied with a high voltage (corresponding to a high transparency) in spite of high resistance in the line between the voltage source and the element. A certain inconsistency exists here since, on the other hand, a high frequency is necessary to be able to generate enough different transparency levels or steps. This is due, in particular, to the nonlinear voltage-transparency curves of present LCDs. In a preferred embodiment of the invention, therefore, the switching frequency of the common change-over switch is periodically changed. Each period begins with a high frequency and ends with a low frequency. Consequently, the pulse width increases during a period. The voltage can likewise be varied within a period. This makes it possible to generate a voltage profile which, in each period, has only as many pulses as required transparency stages and is nevertheless very well matched to the nonlinear transparency curves of the LCDs.
For a large number of individual zones, the common change- over switch can be constructed discretely while the change-over switches assigned to the individual elements can be formed by one or more conventional integrated circuits. When the elements are in the form of a matrix or display, it is advantageous to mount the integrated circuit or circuits directly on the matrix so as to avoid long conducting paths and a large number of control lines between the matrix and an electronic control unit for the same.
Another way of achieving a neutral change, as regards color, for the elements of the illuminating unit is by means of a bright/dark transition. To this end, the individual elements can be divided into subzones each of which can be switched between two states or conditions, namely, a "bright" state and a "dark" state. A subzone which has been switched to the "dark" condition transmits practically no illumination of wavelengths classified as significant. For each zone, different gray stages can be obtained without color distortion by changing the combination of active and inactive subzones. It is preferred here to use ferroelectric liquid crystals.
Ferroelectric liquid crystals have a bistable character. This means that each subzone or cell need be operated on only once before a copying procedure in order to bring it into the required state. It maintains this state until it is operated on again. Simple control of a matrix or display of the zones is made possible by virtue of this bistable character.
In order that the individual zones may have sufficiently fine gradations in intensity, it is preferred for each element to have six different subzones. When the subzones of a given element are dimensioned such that the sum of the areas of a first combination of subzones does not equal the area of any single subzone nor the sum of the areas of a second combination of subzones, an intensity gradation with sixty-four individual steps or levels can be achieved with six different subzones per element. For a uniform gradation, the areas of the six subzones should be in the ratio of 1:2:4:8:16:32. This ratio can be appropriately changed if, for instance, a finer gradation is required at high intensity than at low intensity, or vice versa.
If a smaller number of subzones per element is desired, the number of intensity levels can be increased by means of a timing circuit. If, for example, there are to be only two subzones per element so that only four intensity levels would normally be available, the number of levels can be increased via a control unit which makes it possible to once again switch states during the exposure in a copying procedure.
Another aspect of the invention resides in a method of copying a master, particularly a transparent master, on copy material. The copy material, which may be photosensitive, has respective sensitivity maxima in a plurality of preselected colors. The method comprises the step of positioning the master and the copy material in predetermined relationship to a unit for exposing the master to illumination of the preselected colors so as to form an image of the master on the copy material. The exposing or illuminating unit includes a plurality of elements each having an independently variable intensity, and the method further comprises the step of adjusting the intensities of the elements in such a manner that, in the spectral ranges corresponding to the neighborhoods of the sensitivity maxima, the intensity of each zone changes by approximately the same factor.
The copy material may, for instance, be constituted by photographic paper.
The preselected colors may be the primary colors blue, green and red, and the adjusting step may include producing approximately equal changes in average intensity over the spectral ranges of 420 nm to 490 nm, 500 m to 560 nm and 670 nm to 730 nm. The method can additionally comprise the step of forming an image of the master on the copy material, and the forming step may involve exposing the copy material at one time to blue, green and red illumination coming from the master. It is possible to carry out at least part of the adjusting step during the forming step.
The positioning step may include locating the copy material in a predetermined plane, and the method can then further comprise the step of unsharply projecting the elements onto such plane.
The adjusting step may involve applying either an a.c. voltage or voltage pulses to the elements. The operation of applying voltage pulses to the element can include generating a varying number of voltage pulses per unit of time, generating a set of voltage pulses having different pulse widths and/or generating a set of voltage pulses having different amplitudes. When a set of voltage pulses with different pulse widths is generated, the pulse width of successive pulses of the set may increase progressively.
The adjusting step can also involve applying voltage of variable effective value and substantially constant peak value to the elements.
The method may additionally comprise the step of monitoring the intensities of the elements. The positioning step can include locating the master and the copy material in an optical path for projection of an image of the master onto the copy material, and the monitoring step can be performed outside of this path. It is also possible for the monitoring step to involve a sensing of the illumination coming from the elements. At least part of the adjusting step may here be performed in automatic response to the sensed illumination.
The adjusting step may comprise switching subzones of at least one of the elements between a bright state and a dark state. The adjusting step may further comprise changing the number or combination of subzones having the bright state.
The novel features which are considered as characteristic of the invention are set forth in particular in the appended claims. The improved copying method, as well as the construction and mode of operation of the improved copying apparatus, together with additional features and advantages thereof, will, however, be best understood upon perusal of the following detailed description of certain specific embodiments when read in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 schematically illustrates a copying apparatus in accordance with the invention;
FIG. 2 is first embodiment of an enlarged, fragmentary plan view of an LCD which can constitute part of an illuminating unit for a copying apparatus according to the invention;
FIGS. 3a and 3b show one embodiment of a switching arrangement for the LCD of FIG. 2;
FIG. 4 shows another embodiment of the switching arrangement;
FIGS. 5a and 5b illustrates a transparency-voltage curve for the LCD of FIG. 2 as well as sequences of voltage pulses for obtaining different transparencies on the curve;
FIGS. 6a and 6b show an arrangement for monitoring the transparency of the LCD of FIG. 2; and
FIG. 7 illustrates another embodiment of an LCD which can constitute part of an illuminating unit for a copying apparatus in accordance with the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows an apparatus according to the invention for copying or printing a master 9 on copy material 13. The master 9 is here assumed to be a transparent exposure or frame of a negative film 8 while the copy material 13 is assumed to be a photosensitive material such as photographic paper.
The copying apparatus or copier includes an illuminating or exposing unit 1 which serves to illuminate the master 9 and to expose the copy material 13. The illuminating unit 1 includes a light source 2, a mixing tube 3, a diffusing disc 4, an LCD 5, and a matte or ground glass smoothing disc 6. The LCD 5, which may also be considered a matrix of individual cells, can be replaced by an LED matrix. This allows the light source 2, the mixing tube 3 and the diffusing disc 4 to be eliminated. The light emitted by the illuminating unit 1 includes the wavelength ranges corresponding to the primary colors blue, green and red, and the copy material 13 is, at least on occasion, exposed to radiation in all of these wavelength ranges simultaneously.
A support or platen 7 is provided for the film 8 and defines a support plane for the same. Similarly, a support or platen 12 is provided for the copy material 13 and holds the latter flat in a predetermined plane during exposure. An objective 10 functions to project an image of the master 9 onto the copy material 13.
The illuminating unit 1, objective 10 and platens 7, 12 at least in part constitute a copying or printing station of the copying apparatus.
The film 8 is transported along a predetermined path in order to bring different frames into register with the illuminating unit 1. Upstream of the copying station is a non-illustrated scanning station in which the frames of the film 8 are scanned to generate density values. The density values obtained in this manner are sent to a computer 11 where they are transformed into control values representing an unsharp mask. The control values are used to regulate the LCD 5 which serves as a mask. Control lines 43 connect the computer 11 to the LCD 5.
LCDs have been found to be especially well-suited for masking. Thus, the gray value or transparency of these LCDs is voltage-dependent. Moreover, they are highly stable as regards temperature and their transparency as well as color neutrality depend to only a small degree on the viewing angle. However, to employ a guest-host LCD having these advantages, individual control of each cell is desirable.
An enlarged, fragmentary view of a first embodiment of an LCD or matrix of cells is shown in FIG. 2. The individual cells are identified by the reference numeral 20, and each cell 20 has its own control line 30 for incoming signals. The cells 20 are mounted on a conducting board 23 which functions as a common output for all of the cells 20. A control line 32 common to all of the cells 20 is connected to the board 23. The control lines 30 extend between the individual cells 20 in the form of conductor bundles 24. To reduce the number of lines per bundle, the control lines 30 to the left and right of the center 25 of the LCD are bundled separately.
To avoid galvanic processes in the individual cells 20, these should be subjected to an a.c. voltage. The transparency of the cells 20 can then be regulated by the effective value of the a.c. voltage. However, since it can be extremely expensive to amplify the a.c. voltage in the same manner for each individual cell 20 of the matrix, it is preferred to use voltage pulses. The effective voltage can then be controlled via the number of voltage pulses transmitted to the cells 20.
A particularly simple embodiment of a circuit for generating voltage pulses is illustrated in FIGS. 3a and 3b. The individual control line 30 for a cell 20 is connected to a change-over switch 33 which can connect the cell 20 to either a d.c. voltage supply 31 as shown by an unbroken line or a reference potential 34 as shown by a broken line. The common control line 32 for all of the cells 20 is connected to a change-over switch 35 which is likewise common to all of the cells 20. Again, the change-over switch 35 can connect the cells 20 to either the d.c. voltage supply 31 as shown by a broken line or the reference potential 34 as shown by an unbroken line. The switches 33, 35 are switched back-and-forth between their broken line and unbroken line positions at a predetermined frequency, e.g., 40 kHz. A square-wave d.c. voltage A is thus generated in the individual control lines 30 while a square-wave voltage B is generated in the common control line 32.
FIG. 3a illustrates the switching arrangement in a condition in which the square-wave voltages A, B yield a resultant voltage C in the form of a train of voltage pulses which are applied to the cells 20. In contrast, FIG. 3b illustrates the switching arrangement in a condition in which the square-wave voltages A, B yield a steady resultant voltage C so that the cells 20 are not subjected to voltage pulses. The voltages C applied to the cells 20 are due to the voltage reversal occurring upon each switching operation.
Assuming, for each cell 20, that a transparency gradation of approximately 50 density levels or steps is adequate for masking and that the respective cell 20 behaves linearly, a control period corresponding to 50 individual pulses is established. Regulation of the effective voltage, and thus the density level of a cell 20, then occurs through the number of transmitted pulses per control period. Only the individual change-over switches 33 need be controlled for this purpose whereas the common change-over switch 35 switches continuously at a predetermined frequency.
Referring to FIG. 4, a matrix or display of individual cells 20 is identified by the reference numeral 40. The common change-over switch 35 is constructed discretely and, as before, switches the common control line 32 to either the voltage supply 31 or the reference potential 34. Each of the cells 20 is again provided with its own change-over switch, and the individual switches are here contained in integrated circuits 41 which are connected to the voltage supply 31 and the reference potential 34. The individual switches of the integrated circuits 41 are connected to the control lines 30 of the corresponding cells 20 via respective outputs 42 of the integrated circuits 41. The matrix 40 is connected to the computer 11 of FIG. 1 by means of the control lines 43.
If the integrated circuits 41 are mounted on their own printed circuit boards, each output 42 of the integrated circuits 41 must be contacted with the matrix 40 via a respective flexible connecting element. It is therefore preferred for the integrated circuits to be mounted directly on the matrix 40. Only a small number of control lines, which serve to connect the matrix 40 to the computer 11, are then required.
FIG. 5a shows a nonlinear transparency curve for a guest-host cell. In order to attain the uniformly spaced transparency levels or steps T1, T2, T3, T4, the cell must be subjected to the voltages V1, V2, V3, V4, respectively. The requisite voltage V1, V2, V3 or V4 is obtained by transmitting only a specified number of voltage pulses to the cell during each control period 47. In the example of FIG. 5a, every control period 47 must correspond to at least 15 voltage pulses in order to achieve an approximately uniform gradation with four transparency levels. It will be observed that the voltage V3 cannot be obtained with a whole number of voltage pulses so that a higher pulse frequency would be required for a more precise gradation.
FIG. 5b shows a preferred sequence of voltage pulses for achieving the transparency levels T1, T2, T3, T4. Here, both the pulse width and amplitude are varied during each control period 47. This makes it possible to match practically any transparency curve even though the number of pulses is no higher than the number of transparency levels. For each transparency level T1, T2, T3, T4, the illustration shows the instant within the control period 47 at which no further pulses need be transmitted to the cell in order to achieve the respective transparency level T1, T2, T3 or T4.
FIGS. 6a and 6b show an arrangement which can be used in the copying apparatus of FIG. 1 to monitor the density of the LCD 5. The monitoring arrangement includes a test pixel 5a which is mounted on the LCD 5 outside of the projected cross section of the mixing tube 3 but within the sphere of illumination of the light source 2. The test pixel 5a is surrounded by a shield so that a photosensor 48 above it detects only light which has passed through the test pixel 5a. The transmittance of the test pixel 5a is regulated in the same manner and by the same control unit as the transmittances of the masking cells located within the projected cross section of the mixing tube 3. By continuously illuminating the test pixel 5a with light from the light source 2, the transmittance of the pixel 5a can be checked via the photosensor 48. If the measurements fall outside of a predetermined range, the apparatus can generate an appropriate warning signal for an operator.
At greater time intervals, it is further possible to check the uniformity of the transmittances of the masking cells. To this end, the photosensor can be mounted on a device which is shiftable in two mutually perpendicular directions. The device successively travels by all of the masking cells of the LCD 5 and, for each cell, measures the intensity value which is generated by the photosensor 48 and represents the transmittance of the cell. When the intensity values lie outside a preselected range, the voltage in the control circuit can be adjusted automatically. This allows precise adjustment of the LCD 5 to be achieved. Thus, the uniformity of the transmittances of the masking cells can be checked at predetermined time intervals, for example, and reestablished if deviations occur.
FIG. 7 illustrates a second embodiment of an LCD in which a ferroelectric LCD or matrix is used for masking. The matrix is divided into a large number of individual or localized zones 50 of which only one is shown in FIG. 7, and each zone 50 is again divided into individually controllable subzones. The zone 50 of FIG. 7 contains six subzones a,b,c,d,e,f. Prior to a copying procedure, the subzones a,b,c,d,e,f are operated on once, e.g., by the computer 11 of FIG. 1, so as to place each subzone a,b,c,d,e,f in a state of either maximum transparency or minimum transparency. The matrix of zones are preferably powered and controlled by the known method of multiplexing.
The subzones a,b,c,d,e,f have different sizes and are designed such that the sum of the areas of a first combination of individual subzones a,b,c,d,e,f does not equal the area of any single subzone a,b,c,d,e,f or the sum of the areas of a second combination of individual subzones a,b,c,d,e,f. The possible combinations of the individual subzones a,b,c,d,e,f allow the zone 50 to assume sixty-four different transparency levels. When the areas of the subzones a,b,c,d,e,f are in the ratio of 1:2:4:8:16:32, a uniform gradation between adjacent transparency levels can be achieved.
If additional transparency levels are required, time may be used as an additional variable. However, it is then necessary to perform one or more switching operations during a copying procedure. Just one switching operation during a copying procedure permits the number of transparency levels to be doubled to one-hundred and twenty-eight. Should a lesser number of transparency levels be adequate, the number of subzones per zone can be reduced accordingly.
Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic and specific aspects of our contribution to the art and, therefore, such adaptations should and are intended to be comprehended within the meaning and range of equivalence of the appended claims. | A transparency to be reproduced is positioned in register with copy material having respective sensitivity maxima in the blue, green and red wavelength ranges of the spectrum. An illuminating unit for exposing the copy material includes an array of cells such as an LCD. The density of each cell can be varied individually to thereby change the illumination intensity, and the densities are adjustable in such a manner that, in the spectral ranges corresponding to the neighborhoods of the sensitivity maxima, the density of each cell changes by approximately the same factor. | 6 |
FIELD OF THE INVENTION
[0001] The present invention relates to automobile engine peripheral devices, and more particularly to an on-line cleaning system and control method for carbon deposit in engine intake valve and combustion chamber.
BACKGROUND ART
[0002] Because of oil quality problems, road traffic conditions and environments and poor driving habits, automobiles, after traveling several thousand kilometers, will produce carbon deposit and colloid in the intake valve and combustion chamber in the engine fuel system, especially GDI engines produce carbon deposit and colloid in the intake valve and combustion chamber more seriously.
[0003] The carbon deposit and colloid in the engine intake valve and combustion chamber are major factors that result in engine performance degradation, insufficient power, increased fuel consumption and super-standard emission, and have always plagued the automobile manufacturers and users.
[0004] There're two conventional methods for cleaning the carbon deposit and colloid in the intake valve and combustion chamber: one is periodically adding fuel additive to the fuel tank and cleaning the carbon deposit and colloid in the above-mentioned parts, such a manner is inconvenient for the automobile users; the other one is professional cleaning made to the above-mentioned parts with devices in automobile maintenance stations, the major problem with this manner is the long cleaning period and the high cost. The actual situation is that the carbon deposit and colloid in the intake valve and combustion chamber are not often cleaned for many automobiles, so that the fuel is wasted and the environment is contaminated.
[0005] In recent years, governments including China, especially the United States and European countries, are putting more and more emphasis on the environmental pollution problem caused by automobiles and are all improving automotive emission standards, causing large automotive manufacturing companies around the world to improve and perfect the conventional automobile engines and launch novel engines, such novel engines employ GDI+TURBO techniques, GDI is an in-cylinder direct injection technique, which allows more complete combustion of the fuel, enhances fuel economy and reduces exhaust emissions, TURBO is a turbocharging technique, which allows the engine to have a minimized volume and save materials and to be more powerful.
[0006] However, there's a great conflict between fuel quality requirements of novel engines and present situation of fuel quality, leading to appearance of more serious carbon deposit in intake valves and combustion chambers of novel engines, especially the carbon deposit in intake valves limits the exertion of advanced performance of novel engines, which can not desirably improve power, save fuels and reduce emissions.
[0007] Meanwhile, since the fuel injection nozzle is directly mounted in the combustion chamber for the GDI engine, and conventional methods which add cleaning agents to the fuel tank have been unable to clean the carbon deposit in the intake valve; the TURBO technique results in a high temperature of the engine lubricating oil, the crankcase oil exhaust gas is more liable to form drum-type carbon deposit on the intake valve lever, which severely affects the intake effect, affects the air-fuel ratio, and even leads to the occurrence of pushed valve phenomenons.
[0008] It has been a pressing problem to clean the carbon deposit and colloid in the GDI engine intake valve and combustion chamber and sufficiently exert the engine performance
SUMMARY OF THE INVENTION
[0009] The object of the present invention is to provide an on-line cleaning system and control method for carbon deposit in engine intake valve and combustion chamber, a closed-loop control is formed by the system and the engine electronic control system, and this cleaning system can be automatically started up after the automobile travels a certain kilometers, achieving frequent cleaning of the carbon deposit in the intake valve and the combustion chamber.
[0010] In order to achieve the above objects, the technical solutions of the present invention are:
[0011] An on-line cleaning system for carbon deposit in engine intake valve and combustion chamber, this system is one system that can clean the carbon deposit in intake valve and combustion chamber while the automobile is driving, comprising a cleaning agent tank, a cleaning agent inlet line and a control circuit, the cleaning agent tank is filled with intake valve cleaning agents, the control circuit comprises a cleaning work procedure which controls turn-on and turn-off of the cleaning agent inlet line; wherein, the control circuit is provided with a cleaning start-up circuit, the cleaning agent tank is disposed on a frame within the automobile engine hood, one end of the cleaning agent inlet line is connected to the cleaning agent tank, the other end of the cleaning agent inlet line is connected to an engine vacuum pipeline which is a vacuum pipeline in communication with the automobile engine intake valve, a control signal at the automobile engine operating state is connected with the start-up circuit in the control circuit.
[0012] The solutions are further: the cleaning agent inlet line from the engine vacuum pipeline to the cleaning agent tank is sequentially connected with a vacuum pressure sensor and an electromagnetic flow controller, respectively; the control circuit is provided with a vacuum pressure measuring interface and an electromagnetic flow control interface, the electrical output signal of the vacuum pressure sensor is connected to the vacuum pressure measuring interface, and the electromagnetic flow control interface is connected with the electrical signal control input of the electromagnetic flow controller.
[0013] The solutions are further: the vacuum pipeline in communication with the automobile engine intake valve is the vacuum pipeline disposed in a pipeline between a throttle and an engine intake manifold.
[0014] The solutions are further: the control signal is a push-button switch signal and the start-up circuit is a signal trigger, when the push-button switch is pressed as the engine runs, the signal trigger triggers the control circuit into the cleaning work procedure.
[0015] The solutions are further: the control signal is a mileage count signal of the automobile, the start-up circuit is a mileage count controller provided with a preset mileage register and a mileage counter in numerical comparison with the mileage register, the mileage count signal is connected to the count input of the mileage counter, when the mileage value of the mileage counter reaches a preset value of the preset mileage register, the output of the mileage count controller triggers the control circuit into the cleaning work procedure.
[0016] A control method based on an on-line cleaning system for carbon deposit in engine intake valve and combustion chamber is a control method which can clean the carbon deposit in intake valve and combustion chamber while the automobile is driving, the system comprises a cleaning agent tank, a cleaning agent inlet line and a control circuit, one end of the cleaning agent inlet line is connected to the cleaning agent tank, the other end of the cleaning agent inlet line is connected to an engine vacuum pipeline which is a vacuum pipeline disposed in a pipeline between a throttle and an engine intake manifold, the control circuit comprises a cleaning work procedure which controls turn-on and turn-off of the cleaning agent inlet line; the control circuit is provided with a cleaning start-up circuit comprising a preset mileage register and a mileage counter in numerical comparison with the mileage register, an automobile driving mileage count signal is connected to the mileage counter; steps of the control method are:
[0017] a. Inputting a preset mileage number into the preset mileage register, the preset mileage number is such a mileage that cleaning the carbon deposit in intake valve and combustion chamber is required after the travelling distance of the automobile has reached the mileage;
[0018] b. Starting up the automobile engine;
[0019] c. Reading the mileage data in the mileage counter, and comparing the mileage data with the preset mileage number;
[0020] d. Starting up the cleaning work procedure and zero clearing the mileage counter when the mileage data is equal to the preset mileage number, and returning to step c when the mileage data is smaller than the preset mileage number;
[0021] The cleaning work procedure is: at the engine operating state, when the vacuum pressure value is in the range between 75 kPa and 20 kPa, inputting the cleaning agent with a flow of 5-13.5 g/min into the cleaning agent inlet pipe to clean the engine intake valve and combustion chamber; the cleaning time is 15-25 mins.
[0022] The solutions are further: the preset mileage number is 2000 km.
[0023] The solutions are further: the cleaning work procedure is: at the engine operating state, when the vacuum pressure value is in the range between 50 kPa and 40 kPa, inputting the cleaning agent with a flow of 6±0.3 g/min into the cleaning agent inlet pipe to clean the engine intake valve and the combustion chamber, the cleaning time is 20 mins.
[0024] The method is further: dividing the pressures in the vacuum pressure value range into a plurality of pressure zones, setting different cleaning agent introduction times for each pressure zone seperately, the ranges of the different introduction times are between 10 microseconds and 18.2 microseconds, and the total inhalation amount of the cleaning agent during the set overall introduction time is between 5 g/min and 13.5 g/min
[0025] The present invention has the following advantages compared to the prior art:
[0026] 1. The on-line cleaning of carbon deposit in engine intake valve and combustion chamber is achieved without changing the existing basic design of the automobile, and the control method is simple and practical.
[0027] 2. A closed-loop automatic control of the cleaning agent inflow amount and the vacuum pressure is achieved; the cleaning quality of the engine intake valve and the combustion chamber is guaranteed, the engine knocking accident is avoided, the maximum efficacy of the novel engine is exerted, and the environmental performance of the engine emission is improved.
[0028] Hereinafter, the present invention will be described in detail with reference to the accompanying drawings and embodiments.
BRIEF DESCRIPTION OF THE DRAWINGS
[0029] FIG. 1 is a schematic view of the structure of the present invention;
[0030] FIG. 2 is a schematic view of the electronic control principle of the present invention;
[0031] FIG. 3 is a table illustrating the relationship between the flow control time values and the vacuum pressure values according to the present invention;
[0032] FIG. 4 is a table illustrating the relationship between the flow control values actually measured and the vacuum pressure values according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Embodiment 1:
[0033] An embodiment of an on-line cleaning system for carbon deposit in engine intake valve and combustion chamber, this system is a one system that can clean the carbon deposit in intake valve and combustion chamber while the automobile is driving, comprising a cleaning agent tank 1 , a cleaning agent inlet line 2 and a control circuit 3 , the cleaning agent tank is filled with intake valve cleaning agents, the control circuit comprises a cleaning work procedure which controls turn-on and turn-off of the cleaning agent inlet line; wherein, the control circuit is provided with a cleaning start-up circuit 3 - 1 , the cleaning agent tank is disposed on a frame within the automobile engine hood, one end of the cleaning agent inlet line is connected to the cleaning agent tank, the other end of the cleaning agent inlet line is connected to an vacuum pipeline of the engine 4 which is a vacuum pipeline in communication with the automobile engine intake valve, a control signal 5 at the automobile engine operating state is connected with the start-up circuit in the control circuit.
[0034] In the embodiment: the cleaning agent inlet line from the engine vacuum pipeline to the cleaning agent tank is sequentially connected with a vacuum pressure sensor 7 and an electromagnetic flow controller 8 , respectively; the control circuit is provided with a vacuum pressure measuring interface 3 - 1 and an electromagnetic flow control interface 3 - 2 , the electrical output signal of the vacuum pressure sensor is connected to the vacuum pressure measuring interface, and the electromagnetic flow control interface is connected with the electrical signal control input of the electromagnetic flow controller. In the embodiment, the vacuum pressure sensor connects to the cleaning agent inlet line through one tee-junction 2 - 1 provided in the cleaning agent inlet line. The vacuum pressure sensor in the embodiment is a commercially available vacuum pressure sensor whose model is AT80 series, and the model of the vacuum pressure sensor used in this embodiment is AT8013; the electromagnetic flow controller is an automobile electronically controlled fuel injection nozzle whose model is STN99, and the electronically controlled fuel injection nozzle is concatenated in the cleaning agent inlet line.
[0035] In the embodiment: as shown in FIG. 1 , the vacuum pipeline in communication with the automobile engine intake valve is the vacuum pipeline 5 disposed in a pipeline between a throttle 6 and an engine intake manifold 4 - 1 . Often, one vacuum pipeline interface is provided here and a line is connected in the automobile. One tee-junction 9 is added at this interface in this embodiment, and in the case it is guaranteed that the original line is unobstructed, the cleaning agent inlet line is connected-in by the provided tee-junction, and the cleaning agents are inhaled to clean the carbon deposit in the inlet valve and the combustion chamber taking advantage of the vacuum pressure of this line at the automobile engine operating state .
[0036] There may be mutiple schemes for the control circuit in the above embodiment, the control circuit in this embodiment comprises a single chip 3 - 4 which contains a modulatable pulse width/pulse frequency output port (PWM) and a plurality of data input/output ports (D 0 -D 7 ,P 1 -P 3 ), and a liquid crystal display 3 - 5 , a parameter setting key 3 - 6 , a vacuum pressure measuring interface 3 - 2 and an electromagnetic flow control interface 3 - 3 are disposed around the single chip; wherein the liquid crystal display is connected to the data output port of the single chip through the liquid crystal display driver 3 - 7 , the parameter setting keys is connected to the data output port of the single chip, the vacuum pressure measurement interface is the data input port of the single chip, and the electrical flow control interface is the modulatable pulse width/pulse frequency output port.
[0037] The single chip described in the embodiment is a commercially available 8-bit single chip with a memory, and what is used in this embodiment is an 8-bit single chip with a 24 K flash memory whose model is STC125624, the liquid crystal display driver is of a commercially available model HT1621, and the electromagnetic flow control interface includes the modulatable pulse width/pulse frequency output port and a bipolar transistor drive 3 - 8 connected with the modulatable pulse width/pulse frequency output port of the single chip.
[0038] There are two schemes for the start-up system operation in the embodiment:
[0039] The first is: the control signal is a push-button switch signal and the start-up circuit is a signal trigger, when the push-button switch is pressed as the engine runs, the signal trigger triggers the control circuit into the cleaning work procedure. This scheme is to manually control the cleaning operation of the system based on the engine conditions.
[0040] The second is: the control signal is a mileage count signal of the automobile, the start-up circuit is a mileage count controller provided with a preset mileage register and a mileage counter in numerical comparison with the mileage register, the mileage count signal is connected to the count input of the mileage counter, when the mileage value of the mileage counter reaches a preset value of the preset mileage register, the output of the mileage count controller triggers the control circuit into the cleaning work procedure. This scheme is an automatic cleaning scheme through inputting a mileage number into the preset mileage register, and the automobile would automatically start up the system when the automobile runs to the set mileage. In this embodiment, the mileage count controller is provided in the single chip described above, and the mileage count signal is connected to the I/O port of the single chip.
Embodiment 2:
[0041] A control method for on-line cleaning of the carbon deposit in the engine intake valve and combustion chamber, this embodiment is based on the control method of the on-line cleaning system for the carbon deposit in the engine intake valve and combustion chamber in embodiment 1 and is a control method for cleaning the carbon deposit in the intake valve and combustion chamber while the automobile is driving; for understanding of the part in this embodiment which is identical to that in embodiment 1, please refer to the content disclosed in embodiment 1, and the content disclosed in embodiment 1 should also be considered as the content of this embodiment, and description thereof will not be repeated herein.
[0042] The system described in this embodiment is the system of the second scheme for starting up the system operation in embodiment 1, comprising a cleaning agent tank, a cleaning agent inlet line and a control circuit, one end of the cleaning agent inlet line is connected to the cleaning agent tank, the other end of the cleaning agent inlet line is connected to an engine vacuum pipeline which is a vacuum pipeline disposed in a pipeline between a throttle and an engine intake manifold, the control circuit comprises a cleaning work procedure which controls turn-on and turn-off of the cleaning agent inlet line; the control circuit is provided with a cleaning start-up circuit comprising a preset mileage register and a mileage counter in numerical comparison with the mileage register, an automobile driving mileage count signal is connected to the mileage counter; steps of the control method are:
[0043] a. Inputting a preset mileage number into the preset mileage register, the preset mileage number is such a mileage that cleaning the carbon deposit in intake valve and combustion chamber is required after the travelling distance of the automobile has reached the mileage;
[0044] b. Starting up the automobile engine;
[0045] c. Reading the mileage data in the mileage counter, and comparing the mileage data with the preset mileage number;
[0046] d. Starting up the cleaning work procedure and zero clearing the mileage counter when the mileage data is equal to the preset mileage number, and returning to step c when the mileage data is smaller than the preset mileage number;
[0047] The cleaning work procedure is: at the engine operating state, when the vacuum pressure value is in the range between 75 kPa and 20 kPa, inputting the cleaning agent with a flow of 5-13.5 g/min into the cleaning agent inlet pipe to clean the engine intake valve and combustion chamber; the cleaning time is 15-25 mins.
[0048] In the embodiment, the preferred data about the preset mileage is: the preset mileage number is 2000 km.
[0049] In the embodiment, the rest of preferred datum are: the cleaning work procedure is: at the engine operating state, when the vacuum pressure value is in the range between 50 kPa and 40 kPa, inputting the cleaning agent with a flow of 6±0.3 g/min into the cleaning agent inlet pipe to clean the engine intake valve and the combustion chamber, the cleaning time is 20 mins.
[0050] Wherein, the method is further: the manner for inputting the cleaning agents into the cleaning agent inlet line is dividing the pressures in the vacuum pressure value range into a plurality of pressure zones, setting different cleaning agent introduction times for each pressure zone seperately, the ranges of the different introduction times are between 10 microseconds and 18.2 microseconds, and the total inhalation amount of the cleaning agent during the set overall introduction time is between 5 g/min and 13.5 g/min
[0051] In the embodiment, the vacuum pressure signal is transferred into a voltage signal and sent to the cleaning agent flow control circuit by the vacuum pressure sensor; the relationship between the vacuum pressure (P) and voltage (V) is: V=0.053 P-0.56 (this relationship is well known, the unit of the pressure P is kPa and that of the voltage is volt);
[0052] In the embodiment, the turn-on flow of the electromagnetic flow controller is determined by the turn-on time of the electromagnetic valve.
[0053] The range between the maximum pressure value and the minimum pressure value of the vacuum pressure is divided into a plurality of pressure zones, and a plurality of turn-on times for the electromagnetic flow controllers corresponding to the plurality of pressure zones are set.
[0054] The number of the pressure zones is one of 5, 6, 7, 8 and 9, and the more zones divided into, the more accurate the control will be.
[0055] The table of the relationship between the turn-on time and the vacuum pressure of the electromagnetic flow controller which is an electronically controlled fuel injection nozzle whose model is STN99 in this embodiment is as shown in FIG. 3 .
[0056] In the embodiment, the maximum pressure value of the vacuum pressure is 75 Kpa, and the minimum pressure value of the vacuum pressure is 20 KPa.
[0057] The vacuum pressures of intake lines will be different for different automobile engines; the vacuum pressures of intake lines will also be different for different engine rotational speeds ; all these factors will affect the flow of the cleaning agents inhaled by the engine, so 9 sub-pressure ranges are contained in the pressure value range between 75 kPa vacuum pressure and 20 kPa vacuum pressure, and the 9 sub-pressure ranges are 75 kPa to 61 kPa, 61 kPa to 56 kPa, 56 kPa to 51 kPa, 51 kPa to 46 kPa, 46 kPa to 41 kPa, 41 kPa to 36 kPa, 36 kPa to 31 kPa, 31 kPa to 26 kPa and 26 kPa to 21 kPa, respectively; the turn-on time of the electromagnetic flow controller set corresponding to the range of 75 kPa to 61 kPa is 18.2 milliseconds; the turn-on time of the electromagnetic flow controller set corresponding to the range of 61 kPa to 56 kPa is 17.2 milliseconds; the turn-on time of the electromagnetic flow controller set corresponding to the range of 56 kPa to 51 kPa is 16.4 milliseconds; the turn-on time of the electromagnetic flow controller set corresponding to the range of 51 kPa to 46 kPa is 14.7 milliseconds; the turn-on time of the electromagnetic flow controller set corresponding to the range of 46 kPa to 41 kPa is 14 milliseconds; the turn-on time of the electromagnetic flow controller set corresponding to the range of 41 kPa to 36 kPa is 13.4 milliseconds; the turn-on time of the electromagnetic flow controller set corresponding to the range of 36 kPa to 31 kPa is 12.4 milliseconds; the turn-on time of the electromagnetic flow controller set corresponding to the range of 31 kPa to 26 kPa is 11 milliseconds; the turn-on time of the electromagnetic flow controller set corresponding to the range of 26 kPa to 21 kPa is 10 milliseconds.
[0058] FIG. 4 is an actual measurement table of the cleaning agent flow corresponding to a specific point in the 9 ranges. The voltage values in the table are obtained according to the relational expression between the vacuum pressure (P) and the voltage (V), which are also actually measured voltage values.
[0059] The specific operation process is: the electromagnetic flow controller is turned off when the voltage signal (Vm) measured by the vacuum sensor is greater than 3.4 volts; when the voltage signal (Vm) measured by the vacuum sensor is greater than 2.67 volts and smaller than 3.4 volts, the turn-on time (T) of the electromagnetic flow controller is 18.2 milliseconds, and the corresponding actually measured flow (L) is 13.6 g/min; extending the analogy, when the voltage signal (Vm) measured by the vacuum sensor is smaller than 0.55 volts, the electromagnetic flow controller is turned off. | The present invention discloses an on-line cleaning system and control method for carbon deposit in engine intake valve and combustion chamber comprising a cleaning agent tank, a cleaning agent inlet line and a control circuit, the control circuit comprises a cleaning work procedure, and is provided with a cleaning start-up circuit, the cleaning agent tank is disposed on a frame within the automobile engine hood, one end of the cleaning agent inlet line is connected to the cleaning agent tank, the other end of the cleaning agent inlet line is connected to an engine vacuum pipeline which is a vacuum pipeline in communication with the automobile engine intake valve, a control signal at the automobile engine operating state is connected with the start-up circuit in the control circuit. The on-line cleaning of the carbon deposit in engine intake valve and combustion chamber is achieved without changing the existing automobile basic design, and the control method is simple and practical. A closed-loop automatic control of the cleaning agent inflow amount and the vacuum pressure is achieved; the cleaning process is safe and reliable, and the environmental performance of the engine emission is improved. | 5 |
FIELD OF THE INVENTION
This invention relates generally to fluid handling and, more particularly, to analysis of samples of fluid drawn from process flow lines as found in, for example, electrical power generating and petrochemical manufacturing plants.
BACKGROUND OF THE INVENTION
"Process sampling" (as it is often referred to) is widely used for analyzing characteristics of liquids present in particular flow lines of process equipment. For example, the manufacturer of a pharmaceutical compound may want to test a characteristic of such compound (or of an ingredient thereof) for purity or concentration.
As other examples, water is used in power generation and in the manufacture of electronic products. Those who are carrying out such processes often wish to measure the presence of, e.g., silica, sodium and/or dissolved oxygen in the water or measure water turbidity.
For most applications, process sampling is carried out while the process is ongoing and while fluid is actually moving in the fluid flow line. And it is often desirable to draw samples of a particular fluid from several different locations in the process equipment. A common way of doing so is to mount a sampling nozzle at each such location (and such locations may be quite far apart from one another) and pipe fluid from the nozzles to a centralized sampling and analysis location where the sampling valves are located. Such valves are operated in some sort of coherent sequence.
The fluid samples drawn from such sampling valves are directed to a fluid analyzer. Such an analyzer is a device configured to provide information about one or more sample parameters, e.g., pH or dissolved oxygen content. Because fluid analyzers are relatively expensive, the practice is to use a single analyzer to provide information about fluid taken from each of several different locations in process equipment. Since samples are taken from any particular location at periodic intervals (rather than continuously), samples are taken from several locations in sequence and are routed to the analyzer in the same sequence.
A control device is often used to operate the several sampling valves. Such device, a programmable logic controller, a timer relay, a computer or the like, may be "programmed" to operate each of several sampling valves according to some coherent sampling strategy, often involving some sort of sequential valve operation.
While arrangements like those described above are generally satisfactory for their intended purpose, they tend to be characterized by certain disadvantages. One disadvantage is that mounting an individual sampling valve at each of several sampling locations is cumbersome and expensive in both labor and material. And if a single analyzer is used for several widely-spaced sampling valves, the volume of the "dead" fluid between a sampling valve outlet port and the analyzer may be very substantial. (Of course, the analyzer cannot be mounted adjacent to all of the separate, widely-spaced valves.) Dead fluid volume is an important concern and can have a direct bearing on the accuracy with which the analyzer provides information about the sample.
These factors suggest the use of a multi-port valve and, in fact, one type of multi-port fluid sampling valve is shown in technical literature titled "Whitey `T2` Series Valves" and bearing the name "Swagelok Co." However, configurations of the depicted valve appear to have certain deficiencies. One is that it relies upon one or more O-rings for sealing at critical locations such as between the inlet and outlet ports. And other O-rings are used as sliding seals. It is thought that O-rings can prove unreliable, particularly in the presence of fluid contaminants and/or when used as dynamic seals.
Another apparent deficiency is that the inlet and outlet ports and passages are arranged so that inlet pressure is in a direction tending to lift the O-ring sealing between the inlet and outlet ports. Sealing is solely by spring pressure which must be sufficiently high to overcome this "liftoff" tendency and assure a good seal.
The apparent need for high spring force probably accounts for the fact that the Whitey valves are pneumatically operated. It seems at least possible that spring pressure must be so high that a pneumatic actuator is required to operate the valve. Compressed air or other compressed gas is not often available at sampling locations or, if provided, is expensive to install. And, often, a device known as an "I-to-P" valve is needed and the current cost of such a valve is on the order of $100 each. (The I-to-P valve derives its name from the fact that it converts an electrical current signal, I, into a pressure signal, P.)
Other valves are shown in the patent literature. For example, U.S. Pat. No. 3,747,623 (Greenwood et al.) depicts a fluid flow control manifold with solenoid operated valves. Such manifold uses what are shown as looped tubes, one each for inlet and exhaust. Each valve has a pair of inlet ports connected together and a pair of outlet ports connected together. The solenoid controls two valves in tandem, one of which closes when the other opens.
That is to say, no valve is capable of operation by itself and no valve is capable of porting flow from a single inlet port to an outlet port. And the external tubing includes 90° bends which may contribute to fluid "dead legs" and, at the least, contributes to pressure drop along the tubing. Thus, neither the valves nor the manifold are suitable for sampling from individual lines.
U.S. Pat. No. 5,259,416 (Kunz et al.) depicts individually operable valves, each sealing against a flat-faced truncated-cone-shaped valve seat. The Kunz et al. valve has a common inlet and separate outlets. Actuation of either valve directs flow from the common inlet to only one of the outlets. Fluid flows from both outlets only if both valves are actuated.
U.S. Pat. No. 4,611,631 (Kosugi et al.) involves a poppet-type changeover valve with three passages and a closure member movable to seal against one or the other of two seats. While the patent does not so state, it appears from the arrangement of the closure member and the seats that port 2c is the inlet and ports 2b and 2d are outlet ports. The valve closure member shifts between two positions, either of which connects the assumed inlet to one of the assumed outlet ports. There is no opportunity to simultaneously flow fluid to both outlet ports.
U.S. Pat. No. 3,357,232 (Lauer) shows an analyzing apparatus which uses three ball-type, pneumatically-shifted shuttle valves to control flow. The user selects from one of two sample streams by introducing inert gas into port 5 or port 9. Either of two outlet pipes (e.g., pipes 11', 12'), are selected by introducing inert gas into port 14. But irrespective of the outlet pipe selected, all of the sampled fluid flows to a common gas analyzer. The legs 16, 21 do not carry fluid simultaneously and like the external tubing depicted in the Greenwood et al. patent, such legs have 90° bends.
An improved manifolded sampling valve which resolves some of the deficiencies of prior art valves would be an important advance in the art.
OBJECTS OF THE INVENTION
It is an object of the invention to provide an improved manifolded sampling valve assembly overcoming some of the problems and shortcomings of the prior art.
Another object of the invention is to provide an improved manifolded sampling valve assembly which maintains a continuous sample flow stream through such assembly.
Another object of the invention is to provide an improved manifolded sampling valve assembly which reduces the volume of "dead" fluid within such assembly and the volume of fluid in a common outlet passage.
Another object of the invention is to provide an improved manifolded sampling valve assembly in which wetted surfaces downstream of a valve are "swept" by flowing fluid whenever such valve is opened.
Another object of the invention is to provide an improved manifolded sampling valve assembly which reduces the volume of "dead" fluid between the valve assembly and an analyzer.
Yet another object of the invention is to provide an improved manifolded sampling valve assembly which is free of O-ring seals between the inlet and outlet ports.
Another object of the invention is to provide an improved manifolded sampling valve assembly which is free of pneumatic actuators.
Still another object of the invention is to provide an improved manifolded sampling valve assembly constructed so that inlet pressure tends to urge the valve sealing surface in a "valve-closed" direction.
Another object of the invention is to provide an improved manifolded sampling valve assembly having parallel-path exterior tubing free of sharp bends which may cause fluid "dead legs."
Yet another object of the invention is to provide an improved manifolded sampling valve assembly which maintains sampling flow velocities which helps prevent "settling" of fluid or fluid contaminants.
How these and other objects are accomplished will become more apparent from the following descriptions and from the drawing.
SUMMARY OF THE INVENTION
The invention is an improvement in a valve assembly for controlling flow of fluid and is particularly useful for periodic sampling of fluid streams of the type described above. The assembly has a valve block with at least two inlet passages, each connected to a different point in the equipment. The valve block also has an outlet passage connected to a fluid analyzer and a separate flow control valve for connecting each inlet passage to the outlet passage.
In the improvement, each valve has a primary valving surface and each of the two inlet passages is selectively placed in flow communication with the outlet passage by positioning the corresponding primary valving surface. The assembly includes provisions for parallel flow from the outlet passage to the analyzer.
Specifically, the outlet passage has first and second ends which are coupled in flow communication with one another by a curvilinear tube. A curvilinear tube is one having bends therein in which the bending radius (or radii) are several times greater than the diameter of the tube. The absence of sharp bends, e.g., 90° bends, and the provision of redundant, parallel flow paths for each inlet passage helps decrease pressure drop in the assembly and also helps prevent "dead legs," vagrant small quantities of accumulated fluid in the assembly.
The tube includes a connector about midway between the tube ends and such connector is in flow communication with a fluid analyzing device. In that way, the analyzing device is shared between (or among) the sample streams connected to the inlet passages and its available analytical time is more fully utilized.
In another aspect of the invention, the block of the new assembly includes at least two intermediate flow passages, e.g., first and second flow passages, each of which is in flow communication with the outlet passage. Each inlet flow passage and its corresponding intermediate flow passage can be selectively connected to the outlet passage (and thence to the analyzer) by operating the appropriate valve.
In a highly preferred embodiment, fluid flow in the first intermediate passage is in a first direction and fluid flow in the second intermediate passage is in a second direction. Preferably, such directions are about 180° from one another and the intermediate flow passages are coaxial. Further, the flow control valves are solenoid-actuated and the valves move in opposite directions when actuated. In that respect, the orientation of the valves to one another resembles a two-cylinder "flat opposed" internal combustion engine.
In another aspect of the invention, the assembly includes a separate drain passage for each inlet passage. Each such inlet passage contains pressurized fluid which is diverted to a drain passage when the valve is closed and which is routed to the outlet passage when the valve is open.
The primary valving surface abuts a valve face when the valve is closed and the pressurized fluid urges the valving surface toward the valve face when the valve is closed. This is a desirable feature since the greater the fluid pressure, the more tightly the valving surface is urged toward the valve face. Leakage is thus reduced or eliminated.
And the new valve assembly is not limited to individually sampling only two or four process streams. The new assembly conveniently facilitates "ganged" arrangements for sampling more than four process streams. In such an arrangement, there is a first valve block having two (most preferably, four) inlet passages and two (most preferably, four) intermediate flow passages. The assembly has plural flow control valves, each valve selectively placing a separate inlet passage in flow communication with a separate intermediate flow passage and thence with the outlet passage of that valve block.
The assembly also has a second valve block having its own, i.e., second, outlet passage. Each of the outlet passages in the first block and the second block has a first end and a second end. In ganged arrangement, the second end of the first outlet passage and the first end of the second outlet passage are connected together by tubing.
As in the first valve block, the second valve block has (a) two inlet passages, (b) two intermediate flow passages, and (c) a pair of flow control valves. Each valve selectively places a separate inlet passage in the second valve block in flow communication with a separate intermediate flow passage in the second valve block. In the two-block ganged arrangement, the first end of the first outlet passage and the second end of the second outlet passage are connected together by a curvilinear tube. In the manner of the "one-block" assembly, the curvilinear tube has ends and includes a connector in flow communication with a fluid analyzing device.
Further details of the invention are set forth in the following detailed description and in the drawing.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a representative view of how the new sampling valve assembly may be used to sample "streams" of liquid in a process plant.
FIG. 2 is a schematic circuit diagram of the manifolded sampling valve assembly.
FIG. 3 is a front elevation view of the valve assembly. Parts are shown in cross-section and other parts are broken away.
FIG. 4 is an elevation view, somewhat enlarged, of a portion of the valve assembly of FIG. 3. Parts are shown in cross-section, surfaces of parts are shown in dashed outline and other parts are omitted for clarity.
FIG. 5 is a cross-section elevation view of a portion of the valve block used in the assembly. Parts are broken away.
FIG. 6 is an isometric view, greatly enlarged, of a solenoid valve plunger of the type used in the valve assembly.
FIG. 7 is a front elevation view of two "ganged" valve assemblies.
FIG. 8 is a top plan view of the valve block used in the assembly and taken along the viewing plane 8--8 of FIG. 4. Certain surfaces are shown in dashed outline.
FIG. 9 is a cross-sectional elevation view of the valve block of FIG. 8 taken along the viewing plane 9--9 thereof. Certain surfaces are shown in dashed outline.
FIG. 10 is a cross-sectional elevation view of the valve block of FIG. 8 taken along the viewing plane 10--10 thereof. Certain surfaces are shown in dashed outline.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Before describing details of the new manifolded sampling valve assembly 10, it will be helpful to gain a better appreciation of a way in which such assembly 10 may be used. In this specification, reference is made to liquid sampling but it is to be understood that the new assembly 10 may be adapted for gas sampling, as well.
Referring to FIG. 1, a process plant 11 (such as for generating power, manufacturing a petrochemical product or the like) has a number of liquid flow lines 13 from which samples of liquid are taken at various sampling points 15. Liquid samples flow along the lines 13 to the assembly 10.
A control device 17 (e.g., timer relay, programmable logic controller) operates the assembly 10 in a way that liquid from each of the lines 13 is directed in some usually-predetermined sequence to an externally-connected tube 19. In turn, the tube 19 has a connector 21 attached to an analyzer 23 through which the liquid flows. The analyzer 23 provides information about some characteristic, e.g., mineral content, turbidity or the like, of the liquid.
It is to be appreciated that it is desirable to perform "sample conditioning" before the sampled fluid is brought to the assembly 10. Such conditioning, as particularly espoused by Sentry Equipment Corp. of Oconomowoc, Wis., U.S.A., involves reducing fluid temperature and pressure and maintaining fluid flow rate before a sample is taken.
Referring now to FIG. 2, the circuit diagram for the new valve assembly 10 will be described by identifying symbolic portions thereof, e.g., ports, passages and the like, using the same numerals used to identify the corresponding aspects of the actual valve assembly 10 described in connection with other FIGURES. The assembly 10 has a valve block 25 in which is formed a plurality of separate inlet passages 27 and a plurality of intermediate flow passages 29. There is also a plurality of drain passages 31 and as described in more detail below, each inlet passage 27 functions in association with a particular flow passage 29 and a particular drain passage 31. For example, the inlet passage 27a functions only in association with the flow passage 29a and the drain passage 31a.
(It is to be appreciated that the term "drain" in the phrase "drain passage" does not necessarily imply that the fluid is discarded. The phrase "bypass passage" is equally apt for passages 31.)
The intermediate flow passages 29 are in flow communication with a common outlet passage 33 having a first end 35 and a second end 37. The ends 35, 37 are coupled in flow communication with one another by the curvilinear tube 19 having the connector 21 in flow communication with the analyzer 23.
The assembly 10 also has a plurality of two position solenoid-actuated valves 39. Each such valve 39 is used to direct liquid from a particular inlet passage 27 to either a particular intermediate flow passage 29 and thence to the outlet passage 33 or, when the valve 39 is de-energized, to a particular drain passage 31.
In FIG. 2, the lefthand valve 39 is energized and open so that liquid flows from the inlet passage 27a through the passage 29a to the common outlet passage 33 and thence to the analyzer 23. The drain passage 31a is blocked. In use, only a single valve 39 is open at a particular time.
In the field of sampling valves, much has been made of "double-block-and-bleed" valves, i.e., valves which have a bypass line (the "bleed") and two redundant valve closures in series between an inlet passage and the valve per se. Any of the valves 39 in the assembly 10 can be configured as a double-block-and-bleed valve by adding a three-way valve 40 ahead of an inlet passage 27.
The valve 40 is preferably solenoid operated and in one position permits fluid to flow to passage 27 and blocks drain passage 42. In the other position, passage 27 is blocked and fluid flows to passage 42 which may be "teed" to passage 31.
Referring now to FIGS. 3, 4 and 5, the assembly 10 includes the valve block 25 (shown in cross-section) into which is fitted plural solenoid-actuated valves 39. Each valve 39 has a coil housing 41 and a solenoid plunger 43 which moves away from the block 25 when the associated coil is energized.
When the coil is de-energized, the plunger 43 is urged toward the block 25 by a compression spring 45 and by the fact that the pressure in the inlet passage 27 is greater than that in the intermediate flow passages 29. To put it another way, the pressure "drop" across the plunger 43 is in a direction to urge such plunger 43 toward the block 25 to more tightly seal the passage 29. Connection boxes 47 are provided to connect electrical wiring to the coils.
The block 25 has plural inlet passages 27 and in the depiction of FIG. 4, such passages 27 extend in a direction perpendicular to the plane of the drawing sheet. Each such passage 27 communicates with a separate annular cavity 49 in the block 25 and in the depiction of FIG. 4, the passage 27 opens into the cavity 49 at a location behind the solenoid valve plunger 43. Thus, the passages 27 are shown in dashed outline.
Referring to FIGS. 4 and 6, each of a plurality of intermediate flow passages 29 (four in the depicted block 25; one such passage 29 corresponding to each inlet passage 27) is in continuous flow communication with an outlet passage 33 described in more detail below. It is to be appreciated that these passages 29 shown in FIG. 5 and to the left in FIG. 4 are coaxial with one another and that fluid flowing in such passages 29 flows toward the outlet passage 33. That is, such fluid flow is in two directions about 180° from one another. The two opposed passages 29 to the right in FIG. 4 are similarly arranged and fluid flows through them in the same way.
The intermediate flow passages 29 are extremely short, have very small contained volume and are formed in truncated-cone-shaped "bosses" 51. Each boss 51 has a smooth, substantially flat valve face 53. When a solenoid coil is de-energized, an elastomer disk on the primary valving surface 55 of the plunger 43 contacts the face 53 and prevents fluid from flowing through that intermediate flow passage 29. Conversely, when a coil is energized, its plunger surface 55 is spaced from the corresponding face 53 and fluid can flow through that corresponding passage 29.
The valve block 25 has an outlet passage 33 which extends the length of the block 25 and is terminated at the first (left) and second (right) passage ends 35 and 37, respectively, by threaded ports 57. The ends 35, 37 are coupled in flow communication with one another by the curvilinear tube 19. Such tube 19 is free of "angle-like" bends, i.e., bends such as would be defined by two straight lengths of tube intersecting at an angle. The tube has a "T" connector 21 about midway between the ends 35, 37 and the connector 21 is attached to the fluid analyzer 23.
There are also plural drain passages 31, one for each inlet passage 27 and each cavity 49. In the depictions of FIGS. 3 and 4, the drain passages 31 for the two upper cavities 49 extend upward while those for the two lower cavities 49 extend downward. As shown in FIG. 6, the solenoid plunger 43 includes a pair of longitudinal grooves 59 which communicate between a particular cavity 49 and the drain passage 31 associated with such cavity 49. When a solenoid coil is deenergized and its plunger 43 abuts the associated valve face 53, fluid flowing in the inlet passage 27 flows along the grooves 59 and to and through the drain passage 31. When the coil is energized, the drain passage 31 is closed by an elastomer disc 56 at the top of the plunger 43. Such disc 56 defines a secondary valving surface 58. With the drain passage 31 closed, fluid is forced to flow to an intermediate flow passage 29 and thence to the outlet passage 33.
From the foregoing and from an inspection of FIGS. 3 and 5, it is to be appreciated that any fluid flowing in any intermediate passage (as symbolized by the arrow 63) flows through the outlet passage 33 in two opposite directions as symbolized by the arrows 65. Both directions are away from that particular intermediate passage 29. It is also to be appreciated that as symbolized by the arrows 67, such fluid flows to the connector 21 along both legs 69 of the tube 19. Thus, there are parallel flow paths between each intermediate passage 29 and the connector 21.
An advantage of the new valve assembly 10 is that it can be "ganged" very easily with other assemblies 10. FIG. 7 shows such an arrangement. In that arrangement, there are first and second valve blocks 25a and 25b, respectively. Each such block 25a, 25b has its own outlet passage 33a, 33b as described above. And each such passage 33 has a first end 35 and a second end 37.
In the ganged arrangement, the second end 37 of the first outlet passage 33a and the first end 35 of the second outlet passage 33b are connected together by tubing 71. And the first end 35 of the first outlet passage 33a and the second end 37 of the second outlet passage 33b are connected together by a curvilinear tube 19 similar to that shown in FIG. 3.
FIGS. 8, 9 and 10 show structural details of the valve block 25 including the relative locations of the inlet passages 27, the annular cavities 49, the intermediate flow passages 29 and the outlet passage 33. The tapped holes 73 accept fasteners holding the solenoid valves 39 and the block 25 to one another.
While the principles of the invention have been shown and described in connection with specific embodiments, it is to be understood clearly that such embodiments are exemplary and are not limiting. | The improved valve assembly controls flow of fluid in "stream sampling" applications. The assembly valve block has at least two inlet passages, an outlet passage and a separate flow control valve for connecting each inlet passage to the outlet passage. Each valve has a single primary valving surface and each of the two inlet passages is selectively placed in flow communication with the outlet passage by positioning one of the primary valving surfaces. Actuation of each valve places the corresponding inlet passage in flow communication with an outlet passage common to all inlet passages. Both ends of the outlet passage are connected together by a "smooth bend" curvilinear tube attached to a fluid analyzer. The assembly can be operated by a control device for "programmed" stream sampling. | 5 |
BACKGROUND OF INVENTION
[0001] The present invention relates generally to vehicle doors and more particularly to the glass attachment for a movable window in a vehicle door.
[0002] Automotive vehicles typically include movable window glass in some or all of the vehicle side windows. For vehicle doors with movable window glass, the interiors of the doors include two separate assemblies. A first assembly, a glass run channel assembly, is mounted adjacent to the front and rear edges of the door. The run channel assembly directs the window glass in the fore-aft and inboard-outboard directions. A second assembly, a window regulator assembly, is spaced from the channel assembly more toward the middle of the door. The window regulator assembly is used to move the window glass up and down. The window regulator assembly typically includes a pair of guide rails, upon which sliders are mounted and guided. Typically, these two assemblies can be installed separately, with the window glass thereafter slid into the run channel assemblies and secured to the sliders in some way.
[0003] The window glass has been secured to the sliders in various ways, including mounting a regulator carrier plate to slide along the guide rails and bolting this plate to clips bonded on the window glass. Another attachment method includes using a clamping mechanism with an elastomeric insulator that is squeezed against the window glass, with the clamping mechanism being attached to the window regulator. Still others have employed a combination slider and carrier with a screw or bolt driven into a plastic clip that is snapped into a hole in the glass. All of these approaches generally have drawbacks in that they require more assembly time and/or cost more than is desirable.
[0004] A convenient way to assemble a window glass to a window regulator assembly may be particularly desirable for vehicle doors having movable window glass where the glass run channel assembly and the window regulator assembly are combined into a single assembly. Some have proposed combining the glass run channels and the window regulator assembly into one subassembly. However, the proposed solutions, while combining these components, tend to make installation of the window glass and connection to the window regulator more difficult. Consequently, for these types of configurations, while they have some advantages over conventional separate assemblies, they also have the potential to make assembling the window glass into this assembly more cumbersome and difficult—thus negating some of the advantage in combining the assemblies in the first place.
SUMMARY OF INVENTION
[0005] An embodiment contemplates a glass clip and carrier assembly for use in supporting a movable window glass in a vehicle door. The assembly may comprise a glass clip and a carrier. The glass clip may include a glass support flange engageable with the window glass, a clip body extending from the glass support flange, and a pair of cam engagement arms extending from the clip body, each of the cam engagement arms including a cam engagement flange extending therefrom to define a channel. The carrier may include a carrier body operatively engageable with a first cable set, and a pair of camming guide shoulders extending from the carrier body and slidably received in the channel, the camming guide shoulders extending farther from the carrier body at a first end adjacent to the glass support flanges and tapering toward the carrier body as the camming guide shoulders extend away from the first end, whereby the carrier body is pulled closer to the clip body as the camming guide shoulders are slid further into the channel.
[0006] An embodiment contemplates a window glass support assembly for use in supporting a movable window glass in a vehicle door. The assembly may comprise a glass clip, a carrier, a first cable set and a second cable set. The glass clip may include a glass support flange engageable with the window glass, a clip body extending from the glass support flange, and a pair of engagement arms extending from the clip body, each of the engagement arms including an engagement flange extending therefrom to define a channel. The carrier may include a carrier body having a pair of guide shoulders extending from the carrier body and slidably received in the channel, a first cable groove recessed in the carrier body and including a first end extending in a generally horizontal direction and a second end extending in a generally vertical direction, and a second cable groove recessed in the carrier body and including a first end and a second end. The first cable set may be mounted in the first cable groove and supporting the carrier, and the second cable set may be mounted in the second cable groove and supporting the carrier.
[0007] An embodiment contemplates a method of assembling a movable window glass into a vehicle door comprising the steps of: affixing a glass clip under a bottom edge of the window glass; supporting a carrier in a location in the vehicle door by securing the carrier to a first cable set and a second cable set; sliding the glass clip and the window glass into the vehicle door; sliding a first end of a pair of camming guide shoulders of the carrier into a channel in the glass clip, with the first end of the camming guide shoulders extending a first distance from a carrier body and tapering toward a second end that is a second distance from the carrier body, the second distance being less than the first distance; sliding the camming guide shoulders into the channel, thereby camming the carrier body closer to a clip body against a bias of the first cable set and the second cable set; and securing the glass clip to the carrier.
[0008] An advantage of an embodiment is the ability to attach a floating carrier to a glass clip, secured to the window glass prior to installation, during glass installation with a snap-in type of connection. This may be particularly useful in vehicle door applications where glass run channels and window regulators have been integrated into a single assembly.
[0009] An advantage of an embodiment is reduced assembly time, reduced cost, and potential for reduced material costs with a relatively simple and quick snap-in place installation, versus conventional attachment methods and assemblies.
BRIEF DESCRIPTION OF DRAWINGS
[0010] FIG. 1 is a side elevation view looking inboard at a portion of a vehicle door.
[0011] FIG. 2 is a side elevation view looking inboard at a window glass, glass clips and carriers.
[0012] FIG. 3 is a side elevation view looking outboard at a portion of the window glass and a forward glass clip and forward carrier.
[0013] FIG. 4 is a perspective view of a portion of the window glass, forward glass clip and forward carrier.
[0014] FIG. 5 is a partially schematic, side elevation view looking inboard at a portion of the window glass, forward glass clip and forward carrier, prior to assembly of the glass clip to the carrier, and a portion of a forward integrated channel/regulator.
[0015] FIG. 6 is a perspective view of a portion of the forward integrated channel/regulator, and a portion of the forward glass clip as it is beginning to be assembled to the forward carrier.
[0016] FIG. 7 is a view similar to FIG. 6 , but illustrating the forward glass clip being partially assembled onto the forward carrier.
[0017] FIG. 8 is a view similar to FIG. 6 , but illustrating the forward glass clip fully assembled onto the forward carrier.
DETAILED DESCRIPTION
[0018] Referring now to FIG. 1 , a portion of a vehicle door 10 , having a door inner panel 12 , is illustrated. The door inner panel 12 includes structure forming a window frame 14 that defines a window opening 16 , the bottom edge 17 of which is generally referred to as a beltline, and other structure forming a lower door portion 18 that defines an access hole 20 . The access hole 20 allows various components and sub-assemblies, such as a latch/window regulator module 24 , to be assembled into the door 10 .
[0019] The latch/window regulator module 24 is mounted to the door inner panel 12 . The latch/window regulator module 24 includes a door latch assembly 26 mounted to a rear integrated channel/regulator 28 , a forward integrated channel/regulator 30 , and a window regulator cable assembly 32 . The window regulator cable assembly 32 is mounted to and extends between the rear and forward integrated channel/regulators 28 , 30 .
[0020] The forward integrated channel/regulator 30 may include a forward glass run channel 34 that extends from and may be integral with a forward window regulator guide rail 36 . The forward glass run channel 34 may extend somewhat above the beltline 17 . A top front pulley 38 and a bottom front pulley 40 may mount to the forward guide rail 36 . A motor flange 42 may extend from the forward integrated channel/regulator 30 and provide support for a motor 44 and cable drum 45 . Upper and lower mounting flanges 46 , 48 , respectively, may provide locations for securing the forward integrated channel/regulator 30 to the door inner panel 12 .
[0021] The term integral, as used herein, means that the particular elements are formed as a single monolithic piece rather than being formed separately and later assembled and secured together.
[0022] The rear integrated channel/regulator 28 may include a rear below belt glass run channel 50 that extends from and may be integral with a rear window regulator guide rail 52 . A top rear pulley 54 and a bottom rear pulley 56 may mount to the guide rail 52 . Also, a rear/lower door mounting flange 68 may extend from the rear integrated channel/regulator 28 and provide a location for securing the channel/regulator 28 to the door inner panel 12 .
[0023] FIG. 2 illustrates window glass 22 having an outboard surface 23 , and inboard surface 25 (shown in FIG. 3 ), a bottom edge 27 , a forward edge 29 , and a rear edge 31 . The window glass 22 is sized and shaped to fit into the door 10 ( FIG. 1 ) and slide up an down to selectively cover the window opening 16 ( FIG. 1 ). A forward glass clip 58 is mounted to the bottom edge 27 adjacent to the forward edge 29 of the glass 22 , and a rear glass clip 60 is mounted to the bottom edge 27 adjacent to the rear edge 31 of the glass 22 . A forward carrier 62 mounts to the forward glass clip 58 (discussed in more detail below) and a rear carrier 64 mounts to the rear glass clip 60 .
[0024] FIGS. 3-5 illustrate the forward glass clip 58 and forward carrier 62 in more detail. Since the rear glass clip 60 and rear carrier 64 are preferably mirror images of the forward glass clip 58 and forward carrier 62 , they are not shown in greater detail herein.
[0025] The forward glass clip 58 includes a main body 65 from which a pair of glass support flanges 66 extend. One each of the glass support flanges 66 is bonded to the outboard surface 23 and the inboard surface 25 , respectively, of the glass 22 . Alternatively, the glass support flanges 66 may be attached to the glass by a different method—for example being pressed-on, bolted-on via a through-hole in the glass, and snapped-on with a feature engaging a hole in the glass. The main body 65 also includes a catch hole 70 , within which is mounted a cantilevered catch member 72 . Extending from the catch member 72 , adjacent to a free end 74 , is a catch lip 76 . A pair of cam engagement arms 78 extend from the main body 65 , each including a cam engagement flange 80 . The cam engagement arms 78 and cam engagement flanges 80 define a channel 82 within which the forward carrier 62 is received.
[0026] The forward carrier 62 includes a carrier body 84 from which a pair of cam guide shoulders 86 extend. The cam guide shoulders 86 extend farther from the carrier body 84 near an upper end 88 and taper toward the carrier body 84 near a lower end 90 . The cam guide shoulders 86 are also spaced apart so they can slide in and be retained by the channel 82 of the forward glass clip 58 . The carrier body 84 has a catch opening 92 that aligns with the free end 74 of the cantilevered catch member 72 , allowing the catch lip 76 to engage an edge of the catch opening 92 when the forward carrier 62 is fully assembled to the forward glass clip 58 . A cable retention flange 94 extends generally horizontally from the carrier body 84 and includes a ferrule pocket 96 and a cable take-up spring pocket 98 . The term “generally horizontal”, as used herein, means that the element extends in a direction that is horizontal or within about plus or minus thirty degrees from horizontal—as opposed to something that extends in a more vertical direction. Since the window glass 22 is raised and lowered generally vertically, a component extending generally horizontally would be oriented about normal to the direction of window movement. Generally vertically means that a component extends or moves vertically or within about plus or minus thirty degrees of vertical.
[0027] A first cable groove 100 and a second cable groove 102 are recessed in the carrier body 84 (best seen in FIG. 5 ). The first cable groove 100 is oriented generally horizontally at a first end adjacent to the cable take-up spring pocket 98 and curves upward about ninety degrees toward a second end that is oriented generally vertically. The second cable groove 102 is oriented generally horizontally at a first end adjacent to the ferrule pocket 96 and curves downward about ninety degrees toward a second end that is oriented generally vertically.
[0028] FIG. 5 shows portions of a first cable set 104 and a second cable set 106 , both being part of the window regulator cable assembly 32 . The first cable set 104 includes a first cable take-up spring 108 (shown schematically) attached at a first end, which is oriented generally horizontally in the cable take-up spring pocket 98 . The first cable set 104 extends through the first cable groove 100 , where it is redirected to a generally vertical orientation, around the top front pulley 38 , where it is redirected to the cable drum 45 (shown in FIG. 1 ). From the cable drum 45 , the first cable set 104 is directed down around the bottom rear pulley 56 (only the pulley, not the cable, shown in FIG. 1 ), where it is redirected up to a second end (not shown) at the rear carrier 64 (only the carrier, not the cable, shown in FIG. 2 ). The second end of the first cable set 104 is preferably attached to the rear carrier 64 the same way that a first end of the second cable set 106 is attached to the forward carrier 62 , discussed below.
[0029] The second cable set 106 includes a ferrule 110 , attached at a first end, that is mounted and retained in the ferrule pocket 96 . The second cable set 106 extends through the second cable groove 102 where it is redirected to a generally vertical orientation, around the bottom front pulley 40 (only the pulley, not the cable, shown in FIG. 1 ), where it is redirected to the top rear pulley 54 (only the pulley, not the cable, shown in FIG. 1 ), and around the top rear pulley 54 , where it is again redirected to the rear carrier 64 (only the carrier, not the cable, shown in FIG. 2 ) A second end of the second cable set 106 is preferably attached to the rear carrier 64 the same way that the first end of the first cable set 104 is attached (i.e., extending through a groove and attaching to a second cable take-up spring (not shown)).
[0030] Referring to FIGS. 1-5 , pre-assembled components of the latch/window regulator module 24 , then, may be inserted through the access hole 20 and secured to the door inner panel 12 , rather than assembling the components after insertion into the door 10 . The rear integrated channel/regulator 28 allows for pre-assembly of some components before assembly into the door 10 . The forward integrated channel/regulator 30 also allows for pre-assembly of some components before assembly into the door 10 . For example, the motor 44 and cable drum 45 may be mounted to the forward integrated channel/regulator 30 before installation. Also, the window regulator cable assembly 32 may be pre-assembled to the latch/window regulator module 24 , with the forward and rear carrier 62 , 64 and first and second cable sets 104 , 106 pre-assembled before insertion of latch/window regulator module 24 into the door 10 . All of these pre-assembled components of the latch/window regulator module 24 , then, may be inserted through the access hole 20 and secured to the door inner panel 12 . Consequently, far less of the assembly work for a vehicle assembler needs to be accomplished within the door itself. With these pre-assembled components mounted in the door, the window glass 22 , having the forward and rear glass clips 58 , 60 already attached, may be assembled into the door 10 .
[0031] FIGS. 6-8 illustrate the installation of the glass clips 58 , 60 , and hence the window glass 22 (shown in FIGS. 2-5 ) onto the carriers 62 , 64 (only the forward glass clip 58 and forward carrier 62 shown). The rear glass clip 60 and rear carrier 64 (shown in FIG. 2 ) preferably install in the same way and so are not shown separately. The first and second cable sets 104 , 106 are not shown in these views, but would be installed and support the carriers 62 , 64 prior to installation of the window glass clips 58 , 60 (shown in FIG. 2 ). Initially, prior to the installation of the window glass 22 , the first and second cable sets 104 , 106 hold the forward and rear carriers 62 , 64 in surface contact with the forward and rear window regulator guide rails 36 , 52 , a shipping position. It is the cable sets 104 , 106 themselves that position the carriers 62 , 64 —so they are free floating. That is, unlike conventional window regulator guide rails where the carrier plates are secured to and slide along a vertically extending flange (thus the motion being defined by the flange), these carriers are secured to and guided by the cable sets 104 , 106 .
[0032] In FIG. 6 , as the window glass 22 (see FIG. 2 ) is inserted, the forward glass clip 58 is held outboard off of the surface of the forward window regulator guide rail 36 by a spacer 112 , aligning the channel 82 with the cam guide shoulders 86 at the upper end of the forward carrier 62 . The cam guide shoulders 86 , extending out farther from the carrier body 84 , allow for the alignment, even though the forward carrier 62 is off to one side of the forward glass run channel 34 against the forward window regulator guide rail 36 . As seen in FIG. 7 , the forward carrier 62 is moved upward into the forward glass clip 58 . As this occurs, the cam guide shoulders slide farther into the channel 82 , causing the forward carrier 62 to be pulled outboard off of the forward window regulator guide rail 36 toward the center of the forward glass run channel 34 . The forward carrier 62 is moved upward farther until the forward glass clip 58 is fully seated on the forward carrier 62 and the forward carrier 62 is cammed further into the middle of the forward glass run channel 34 , as seen in FIG. 8 . At this point, the free end 74 of the cantilevered catch member 72 (shown in FIG. 3 ) overlaps with the catch opening 92 ( FIG. 3 ) such that the catch lip 76 ( FIG. 3 ) snaps over and engages an edge of the catch opening 92 . The forward glass clip 58 and forward carrier 62 are now secured together. The self-locating of the carrier 62 relative to the glass clip 58 as they initially contact each other and then cam into the use position, as well as the snap-securing of the glass clip 58 to the carrier 62 , in particular, allow for this type of assembly. This arrangement is particularly advantageous when the glass run channels are integral with the guide rails in the latch/window regulator module 24 .
[0033] Once installed, the latch/window regulator module 24 , employing the rear and forward integrated channel regulators 28 , 30 , both guides the window glass 22 and controls its up and down motion. The rear and forward integrated channel/regulators 28 , 30 guide the window glass 22 both inboard/outboard as well as fore/aft. The pulleys 38 , 40 , 54 , 56 cooperate with the window regulator cable assembly 32 to guide the cable sets 104 , 106 , while the motor 44 and cable drum 45 control the up and down movement of the window glass 22 .
[0034] While certain embodiments of the present invention have been described in detail, those familiar with the art to which this invention relates will recognize various alternative designs and embodiments for practicing the invention as defined by the following claims. | The present invention concerns a glass attachment and method of assembly for a movable vehicle window, particularly in a vehicle door. A pair of glass clips are attached to a window glass, and a pair of carriers are mounted and retained in a door by cable sets. A snap-in installation is performed by sliding camming guide shoulders on the carriers into channels formed by cam engagement flanges on the glass clips. As the camming action takes place, the carriers are lifted into use positions and catches on the glass clips engage catch openings on the carriers to secure the components together. Grooves in the carriers direct the cable sets, the ends of which are retained in the carriers by ferrules and cable take-up springs. | 1 |
FIELD
[0001] This disclosure relates to an exhaust gas aftertreatment system and a doser system used with the aftertreatment system to inject a dosing agent into exhaust gas in the aftertreatment system.
BACKGROUND
[0002] The use of an aftertreatment system to treat exhaust gas before the exhaust gas is exhausted to atmosphere is known. One known aftertreatment system uses a diesel oxidation catalyst (DOC) device that is intended to react with the exhaust gas to convert nitric oxide to nitrogen dioxide. In the case of diesel exhaust, a diesel particulate filter (DPF) can also be provided downstream of the DOC to physically remove soot or particulate matter from the exhaust flow.
[0003] When exhaust gas temperatures are sufficiently high, soot is continually removed from the DPF by oxidation of the soot. When the exhaust gas temperature is not sufficiently high, active regeneration is used. In the case of diesel engine exhaust, one form of active regeneration occurs by injecting fuel into the exhaust gas upstream of the DOC. The resulting chemical reaction between the fuel and the DOC raises the exhaust gas temperature high enough to oxidize the soot in the DPF.
[0004] A doser system that includes a doser injector is used to inject the fuel into the exhaust gas. Deterioration of the doser injector can occur over its lifetime, for example due to doser tip carboning or a reduction of doser stroke. It is currently believed by the inventors that doser deterioration is the most frequent mode of failure in aftertreatment systems. A known doser monitoring method that attempts to determine the efficiency of the doser injector senses the temperature difference across the DOC. However, the effectiveness of this method is decreased by deterioration of the DOC which cannot be independently monitored.
SUMMARY
[0005] A real time doser efficiency monitoring method is described that measures the average instant pressure difference within one duty cycle of the doser injector. The disclosed method results in improved doser efficiency monitoring. The disclosed method can be implemented in a number of areas. For example, in a diesel truck application, the doser efficiency can be monitored accurately, for example within 5% error, all the time, no matter whether the truck is in a transient or steady state.
[0006] In one embodiment, a method of monitoring the efficiency of a doser injector that is configured and arranged to inject a dosing agent into exhaust gas comprises determining the average instant pressure difference of the dosing agent at a dosing agent shut-off valve assembly within a duty cycle of the doser injector. The doser injector is preferably pulse-width modulation controlled.
[0007] In another embodiment, a method of monitoring the efficiency of a doser injector that is configured and arranged to inject a dosing agent into exhaust gas comprises, in a single duty cycle of the doser injector, measuring a pressure of the dosing agent when the doser injector is off and measuring a pressure of the dosing agent when the doser injector is on, each pressure measurement occurring at a dosing agent shut-off valve assembly. The difference between the dosing agent pressure when the doser injector is off and the dosing agent pressure when the doser injector is on is then determined and used to calculate the average instant pressure difference.
[0008] The method can be implemented by a doser system that comprises a doser injector that is configured and arranged to inject a dosing agent into exhaust gas, a dosing agent supply line connected to the doser injector, and a dosing agent shut-off valve assembly connected to the supply line that is configured and arranged to control the flow of the dosing agent in the supply line and to the doser injector. The valve assembly includes a pressure sensor for detecting dosing agent pressure in the valve assembly. A controller monitors the efficiency of the doser injector, with the controller determining the average instant pressure difference of the dosing agent at the dosing agent shut-off valve assembly within a duty cycle of the doser injector.
[0009] The dosing agent can be fuel, for example diesel fuel, alcohols, urea, ammonia, natural gas, and other agents suitable for use in aftertreatment of exhaust gases.
[0010] The disclosed method can complete monitoring within fraction of seconds, which works well even during transient engine operations and dosing. The disclosed method also has increased accuracy. The average instant pressure difference is the maximum pressure drop so it has a better signal-to-noise ratio. The disclosed method is also independent of the performance, e.g. degradation, of individual aftertreatment components as is the current temperature based efficiency monitoring method. Further, the disclosed method is independent of the dosing command.
[0011] The disclosed method permits compliance with the on-board diagnostics requirement for the year 2010, which requires independent monitoring for each aftertreatment component. In addition, the higher efficiency achieved by the disclosed method reduces the injection of excess fuel, called hydrocarbon slip, thereby avoiding violation of hydrocarbon emission regulations. Further, the occurrence of false detected “bad” dosers is reduced, thereby reducing warranty costs of doser replacement.
DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 illustrates an exemplary doser system that can implement the real time doser efficiency monitoring method.
[0013] FIG. 2 illustrates the shut-off valve assembly.
[0014] FIG. 3 is detailed view of the portion in box 3 of FIG. 2 illustrating the trim orifice in the shut-off valve assembly.
[0015] FIG. 4 depicts a pressure reading over one cycle period of the doser injector.
[0016] FIG. 5 is a graph of the dosing agent pressure versus time at different dosing rates.
[0017] FIG. 6 is a graph of the doser efficiency versus instant pressure difference for 6 doser injectors with differing deterioration levels.
[0018] FIG. 7 is a graph of dosing agent pressure and dosing rate versus time.
DETAILED DESCRIPTION
[0019] With reference to FIG. 1 , a doser system 10 for an exhaust gas aftertreatment system is illustrated. For sake of convenience in describing the unique concepts, this description will describe the doser system 10 as being a hydrocarbon doser system for a diesel fuel engine that injects diesel fuel into exhaust gas from the engine. However, it is to be realized that the unique concepts described herein can be applied to other doser systems that inject other types of dosing agents.
[0020] The basic configuration and operation of the doser system 10 and aftertreatment system are well known to persons of ordinary skill in the art. The doser system 10 includes a doser injector 12 that is connected to an exhaust gas connection tube 14 connected to the exhaust from an engine (not illustrated). As part of the aftertreatment system, exhaust gases in the connection tube 14 flow to a diesel oxidation catalyst (DOC) device that is intended to react with the exhaust gas to convert nitric oxide to nitrogen dioxide. A diesel particulate filter (DPF) is provided downstream of the DOC to remove soot or particulate matter from the exhaust flow.
[0021] The doser injector 12 is configured and arranged to inject a dosing agent, which in this exemplary embodiment is diesel fuel, into the exhaust gas in the tube 14 to increase the temperature of the DOC. The fuel is supplied via a fuel supply line 16 . A shut-off valve assembly 18 is connected to the supply line 16 and is configured and arranged to control the flow of fuel in the supply line 16 and to the doser injector 12 .
[0022] Details of the shut-off valve assembly 18 are illustrated in FIGS. 2 and 3 . The assembly 18 includes a fuel inlet port 20 , a fuel outlet port 22 connected to the supply line 16 , and a drain port 24 . A pressure sensor 26 connected to the valve assembly 18 senses fuel pressure in the assembly 18 . A trim orifice 28 is provided to keep the fuel pressure in the assembly 18 more stable. The construction and operation of the valve assembly 18 illustrated in FIGS. 2 and 3 are conventional.
[0023] Returning to FIG. 1 , a controller 30 is connected to the pressure sensor 26 and receives pressure readings therefrom. The controller 30 monitors the efficiency of the doser injector 12 by determining the average instant pressure difference of the fuel at the shut-off valve assembly 18 within one duty cycle of the doser injector which is pulse-width modulation (PWM) controlled. The controller 30 , which can be an electronic control module (ECM), can also control the aftertreatment system. The doser injector 12 is controlled by a separate PWM controller 32 .
[0024] The fuel dosing rate is controlled by the duty cycle of the PWM controller. FIG. 4 shows one cycle period T of doser pressure, with P off and P on being the fuel pressure measured by the pressure sensor 26 when the doser injector is turned off and on, respectively. All references to pressure herein and the pressures shown in FIGS. 5-7 are the fuel pressure measured by the pressure sensor 26 in the valve assembly 18 . P avg is the average pressure when the doser injects fuel at that duty cycle, calculated as follows:
[0000]
P
avg
=
P
on
·
T
on
+
P
off
·
(
T
-
T
on
)
T
=
P
on
·
R
D
C
+
P
off
·
(
1
-
R
DC
)
where
R
DC
=
T
on
T
Radio
of
duty
cycle
(
Eq
.
1
)
[0025] The average pressure difference, ΔP avg , can be calculated as follows:
[0000]
Δ
P
avg
=
P
off
-
P
avg
=
P
off
-
P
on
·
R
DC
-
P
off
·
(
1
-
R
DC
)
=
(
P
off
-
P
on
)
·
R
DC
=
Δ
P
ins
·
R
DC
(
Eq
.
2
)
[0026] The average instant pressure difference, ΔP ins , is the average pressure difference by a factor of duty cycle. The average instant pressure difference is substantially independent of dosing rate. This is evident from FIG. 5 which depicts a graph of dosing agent pressure versus time at different dosing rates. From FIG. 5 , it can be seen that the instant pressure difference (i.e. the difference between the maximum pressure P off and the minimum pressure P on ) remains substantially constant even with dosing rate changes.
[0027] FIG. 6 is a graph of the doser efficiency versus average instant pressure difference for 6 doser injectors with differing deterioration levels. From this graph, it can be determined that under the conditions set forth (e.g. at a supply pressure of about 1200 kPa) in the graph, a 10 kPa variation in instant pressure difference means approximately a 3.1% doser efficiency error. It is believed by the inventors that this level of accuracy is not achievable by doser efficiency monitoring methods in existence at the time of filing this application.
[0028] FIG. 7 is a graph depicting pressure measurements when the fuel dose rate changes from about 1.4 g/s to about 0.8 g/s within 2.2 seconds at a supply pressure of about 1950 kPa. The graph plots the individual instant pressure readings 40 versus time, the average pressure 42 versus time, the average instant pressure 44 versus time, and the dose rate 46 versus time.
[0029] First, looking at the average instant pressure difference method described herein, relying upon the average instant pressure difference within a single duty cycle eliminates duty cycle error. In addition, the average instant pressure difference method relies upon a relatively large range of instant pressure difference, shown in FIG. 7 as about 256 kPa, over the single duty cycle. This helps to minimize the impact of pressure variations on the doser efficiency. From FIG. 7 , the average instant pressure 44 while the doser is off holds relatively steady at about 1950 kPa, which is the assumed supply pressure. The variation in instant pressure difference while the doser injector is on varies by about 10 kPa. Assuming that the doser used in FIG. 7 is a 100% efficient doser, and assuming that a 100% efficiency doser at 1950 kPa supply pressure has an instant pressure difference of 256 kPa, then the doser efficiency error can be determined by taking the variation in instant pressure difference, 10 kPa, and dividing it by the pressure difference range of 256 kPa. The doser efficiency error for the average instant pressure difference method is thus about 4.1%.
[0030] In contrast, looking at the instant pressure 40 and the average pressure 42 , one doser efficiency monitoring method in existence at the time of filing this application relies upon the average pressure 42 to determine doser efficiency. In the average pressure difference method, the dynamic range of the average pressure difference is the dynamic range of the pressure difference multiplied by a factor of duty cycle. In FIG. 7 , the duty cycle is about 0.15 seconds. The dynamic range of the average pressure difference (i.e. the maximum average pressure minus the minimum average pressure) is about 38.5 kPa. This is a much smaller range than the average instant pressure difference method which means that pressure variations have a much greater impact on the doser efficiency. Relying on the same assumptions in the preceding paragraph, and assuming that the variation in instant pressure difference while the doser injector is on varies by about 10 kPa as above, the doser efficiency error of the average pressure difference method is 10 kPa divided by 38.5 kPa, or about 27.5%. If one factors in duty cycle error, that error becomes even larger.
[0031] Although the average instant pressure difference method has been described with respect to diesel fuel as the dosing agent, the concepts described herein can be applied to other dosing agents. For example, the dosing agent can be one or more of other types of fuels including hydrocarbon fuels, or other dosing agents such as alcohols, urea, ammonia, and natural gas.
[0032] The monitoring method described herein can be implemented in a number of different ways. For example, the monitoring method can be implemented by software residing in an aftertreatment system controller, for example in the controller 30 . Alternatively, the monitoring method can be implemented by hardware such as electronic circuitry at or near the pressure sensor 26 .
[0033] The concepts described herein may be embodied in other forms without departing from its spirit or characteristics. The described embodiments are to be considered in all respects only as illustrative and not restrictive. The scope of the invention is therefore, indicated by the appended claims rather than by the foregoing description. All changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope. | A real time doser efficiency monitoring method is described that measures the average instant pressure difference within one duty cycle of the doser injector. The disclosed method results in improved doser efficiency monitoring. The disclosed method can be implemented in a number of areas. For example, in a diesel truck application, the doser efficiency can be monitored accurately, for example within 5% error, all the time, no matter whether the truck is in a transient or steady state. | 5 |
CROSS-REFERENCE TO RELATED APPLICATIONS
The present application is a continuation in part of U.S. patent application Ser. No. 07/172,762 filed Mar. 28, 1988, now U.S. Pat. No. 4,858,412.
FIELD OF THE INVENTION
This invention relates to an apparatus for attaching an elastomeric roofing membrane to the top surface of a roof, and more particularly to an apparatus which is capable of securing a roofing membrane without penetrating the same. Included with the apparatus is a unique fastening system to attach the apparatus to the roof.
BACKGROUND OF THE INVENTION
The traditional method used to protect roofs from rain and other forms of inclement weather was to lay down several layers of material, normally felt soaked with bitumen, thereby building up a waterproof membrane. This method has several problems, two of which are that the process is very long, and it is also susceptible to contamination by rainwater or other foreign materials. Furthermore, the bitumen must be heated to the point where it gives off noxious odors.
In recent years, alternate systems using elastomeric membranes have become increasingly popular. A suitable elastomeric membrane is laid over the top surface of the roof itself or, more preferably, an insulation board. A variety of methods for fastening the elastomeric membrane to the surface of the roof have also been developed. One method is to spread an adhesive over the entire surface of the roof before laying down the membrane. This process is very labor-intensive and requires the installers to be exposed to adhesives that give off noxious fumes.
Alternatively, the membrane can be fastened to the roof mechanically. Several devices have been developed which require that a nail or screw be allowed to penetrate the membrane. This can lead to rips and tears in the membrane, especially as the membrane expands and contracts in response to changes in the ambient temperature. These breaches in the integrity of the membrane in turn can lead to water leakage and eventual damage to the underlying roof.
A variety of other devices have also been developed which are capable of securing a membrane to the upper surface of a roof without penetrating the membrane. The applicant believes that the following references are illustrative of the non-penetrating anchoring systems which have been patented. Included in the following list of references are patents related to screw guns. These are included for being related to, but not disclosing the applicant's fastener system.
______________________________________U.S. Pat. No. Patentee______________________________________4,519,175 Resan4,617,771 Tomaszewski4,624,092 Baginski4,631,887 Francovitch4,658,558 Verble3,960,191 Murray3,973,605 DeCaro4,236,555 Dewey4,246,939 Boegel4,361,997 DeCaro4,397,412 Dewey4,638,532 Yang et al4,657,167 Mays______________________________________
U.S. Pat. No. 4,519,175 issued to Resan discloses a three-piece fastening apparatus wherein the roofing membrane is laid over the bottom piece and then a second tined piece is clipped over the membrane and the protruding boss of the bottom piece. The top piece of the device is then screwed onto the second piece thereby locking the device together and securing the membrane.
U.S. Pat. No. 4,617,771 issued to Tomaszewski discloses a three-piece fastening system which snaps together. The device includes an elastic ring which provides tension when a top piece is snapped into the bottom piece.
U.S. Pat. No. 4,624,092 issued to Baginski discloses a two-piece fastening system which snaps together. The bottom piece of the device serves as the male element; the membrane is laid over the bottom piece, and a collar is snapped over the top of the bottom piece. This device, however, allows the area of the membrane directly over the bottom piece to be exposed to the atmosphere.
U.S. Pat. No. 4,631,887 issued to Francovitch discloses a three-piece fastening system which snaps together. In the use of this device, a second piece is inserted inside of the bottom piece which helps maintain the tension produced when the top, or cap piece is snapped over the membrane and the protruding boss of the bottom piece.
U.S. Pat. No. 4,638,532 issued to Yang et al discloses an anchoring plate with a hinged retainer for securing a membrane to a roof surface. The membrane is held between the anchor plate and the retainer without penetration.
U.S. Pat. No. 4,658,558 issued to Verble discloses a two-piece fastening system which snaps together. In this device, the bottom piece serves as the female piece. The bottom piece is attached to the top surface of the roof, the membrane is laid out, and the top piece is snapped into the bottom piece, thereby locking the device together and securing the membrane.
U.S. Pat. No. 3,960,191 issued to Murray discloses a driving attachment for a portable power screwdriver capable of automatically feeding fasteners to the nosepiece.
U.S. Pat. No. 3,973,605 issued to DeCaro discloses a driving tool for threaded fasteners with a washer installed on the fastener shank. Fasteners are loaded manually into the tool and guided for straight insert into the workpiece.
U.S. Pat. No. 4,236,555 issued to Dewey discloses a screw gun for driving screws up to twelve inches long from a standing position, the tool having adjustments to accomodate screws of various lengths.
U.S. Pat. No. 4,246,939 issued to Boegel discloses a screw driving apparatus for driving screws with large washers over three inches in diameter, the driver designed for use on flat roofs to retain insulation.
U.S. Pat. No. 4,361,997 issued to DeCaro discloses a fastening screw with two sets of threads. The screw is used to fasten down a plate.
U.S. Pat. No. 4,397,412 issued to Dewey discloses a screw gun for long fasteners for attaching thick insulating boards to roofs, the screw gun having provision for preventing nails being loaded backwards.
U.S. Pat. No. 4,657,167 issued to Mays discloses a fastening machine for roof and deck coverings which includes a supply magazine.
Many of these devices are capable of securing an elastomeric membrane to the upper surface of a roof without penetrating the membrane; however, there are several limitations and suboptimizations inherent in these devices and the prior art in general.
First and foremost, the way in which previously-disclosed devices generate the restraining force necessary to secure the membrane to to roof creates problems. For example, devices which screw together, such as the device disclosed by Resan in U.S. Pat. No. 4,519,175, carry with them the danger that the device will be over-tightened, thereby straining or even ripping the membrane. Alternatively, devices which screw together may be under-tightened, allowing the top, or cap piece of the device to work its way loose.
Devices which utilize the thickness of the membrane itself to generate the majority of the restraining force used to hold the device together and, hence, anchor the membrane to the roof have other problems associated with their use. Devices such as those disclosed by Verble in U.S. Pat. No. 4,658,558 and Francovitch in U.S. Pat. No. 4,631,887, in essence, call for the installer to provide the wedging force necessary to either push a cap over a protruding boss as in the case of Francovitch, or to push a plug into a housing as in the case of Verble. These types of devices can stretch and fatigue the membrane, increasing the risk that a rip will form which will allow water to pass through the membrane and damage the underlying roof structure. Furthermore, fastening devices which employ the thickness of the membrane itself to supply the majority of the tensional force necessary to keep the device locked together have very little margin for error. For example, the calender seams formed where two sheets of the roofing membrane are joined together are often too thick to fit into these types of devices. This can lead to either the necessity for careful pre-planning of the placement of the devices, or wastage of those bottom pieces which are installed too near a calender seam. Also, devices of this type that utilize base plates which are basically circular may give rise to a large number of irregularly-distributed wrinkles which gives the impression of a slovenly installation.
A second major problem with the devices disclosed by the existing patents is the difficulty of servicing these devices. After an elastomeric membrane has been installed on a roof, it may become necessary to inspect the membrane for a variety of reasons; for example, when a water leak is discovered inside the underlying structure. With the previously-patented fasteners it is almost impossible to disassemble the fastening system without damaging both the device and the membrane.
The Yang et al reference has an anchor device and hinged retainer, but lacks an insert member to maintain a tight grip on the membrane. The Yang et al patent also uses a normal screw which is separate from the anchor plate, unlike the present invention.
Of the cited screw gun systems only Boegel and Mays show applying screws to any sort of rectangular plate or washer, the screws and plates starting out as separate. In the two devices cited above the screw has to be driven into the plate or washer by the screwgun. The DeCaro device shows a screw with an attached washer, but it is quite small and is not for the same purpose as the large plate disclosed by the applicant. The screw and anchoring plate of the applicant's device come as one unit from the start.
SUMMARY OF THE INVENTION
Accordingly, it is among the objects of this invention to remedy the foregoing disadvantages by providing an improved non-penetrating anchoring system wherein the device itself supplies the majority of the locking force necessary to keep the device interlocked and the elastomeric roofing membrane stable.
A second object of the present invention is to provide a non-penetrating anchoring system which can be serviced easily and without damage to either the device or the elastomeric membrane.
A further object of the present invention is to provide a non-penetrating anchoring system which cannot be either over- or under-tightened.
A further object of the present invention is to provide a non-penetrating anchoring system which can accommodate a variety of different types of elastomeric membranes as well as the calender seams formed where two sheets of elastomeric membrane are joined.
A further object of the present invention is to provide an economical system for attaching an elastomeric roofing membrane to an existing structure without the use of special tools or extensive modification of the existing structure.
A further object of the invention is to provide a unique fastening system for attaching a membrane anchoring system to the roof.
These and other objects and advantages will become more apparent from the following detailed description taken in conjunction with the illustrative drawing figures, and the novel features thereof will be defined in the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an exploded view of the present invention showing the relative positioning of the anchoring plate, spacing insert and insert wedge components thereof;
FIG. 2 is a perspective view showing the constituent components of the present invention assembled, and in the process of securing an elastomeric membrane; and
FIG. 3 is an elevational view of the present invention in cross section showing the spacing insert being inserted within the anchoring plate.
FIG. 4 is an elevational view of the present invention in cross section showing the anchor plate with special fastener.
FIG. 5 is a perspective view showing the driving mechanism.
FIGS. 6 and 7 are an exploded view of an alternate embodiment of the present invention showing the relative positioning of the various components including the anchor plate, retainer and retainer wedge.
FIG. 8 is an elevational view of the present invention in cross section showing the alternate embodiment assembled together.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawings wherein like numbers refer to like elements throughout, the anchoring system 10 includes, in general, an anchoring plate 20, a spacing insert 40, an insert wedge 60, fastening means 70 and a driving mechanism 80.
The anchoring plate 20 is rigid and, as is best shown in FIG. 1, includes a planar bottom 21 which can include cutouts (not shown) to reduce the total weight of the device. The anchoring plate 20 is rectangular in shape, having two shorter sides 22 and 22' and two longer sides 23 and 23'. Two sidewalls 24 and 24' are disposed along the two longer sides 23 and 23' of the anchoring plate 20. The sidewalls 24 and 24' each have a horizontal lip 25 which extends inwardly over the top planar surface 26 of anchoring plate 20.
The anchoring plate 20 is provided with a plurality of apertures 27 to facilitate securing the anchoring plate 20 to the top surface of a roof (for example, by a screw or other fastening means 70; in FIG. 1, three apertures 27 are shown, but clearly a different number of apertures could be utilized). As shown in FIG. 3, the apertures 27 are counterbored to allow the fastening means 70 to be tightened down to the point where the heads of the screws are beneath the top planar surface 26 of the anchoring plate 20, thereby assuring that the membrane 90 will not be abraded by the tops of the fastening means 70.
The anchoring plate 20 also includes a plurality of triangular braces 28 which are mounted perpendicularly to, and outside of, each of the sidewalls 24 and 24' (in FIG. 1, five triangular braces 28 are shown, but clearly a different number of braces could be utilized). The triangular braces 28 are mounted on the anchoring plate 20 in such a way that a first side 29 runs along the top surface 26 of the anchoring plate 20, and a second side 30 runs along the height of the sidewalls 24 and 24'. These two sides 29 and 30 of the triangular braces 28 are by definition perpendicular to each other. Hence, the hypotenuse 31 of each triangular brace 28 runs from the outside edge of one of the longer sides 23 and 23' of the anchoring plate 20 to the top outside edge of the sidewalls 24 and 24'; in other words, to the point where the sidewalls 24 and 24' intersect with the horizontal lip 25.
The second component of the anchoring system 10 is a spacing insert 40. The spacing insert 40 has a planar bottom surface 41 and top surface 42. Like the anchoring plate 20, the spacing insert 40 is rectangular in shape, having two longer sides 43 and 43' and two shorter sides 44 and 44'. A pair of vertical flanges 45 and 45' are disposed parallel to the longer sides 43 and 43' of the spacing insert 40. The flanges 45 and 45' are positioned near, but not at, the outer edges of the spacing insert 40.
Each of the flanges 45 and 45' has a lip 46 mounted on its top. The lip 46 is parallel to the planar top surface 42 of the spacing inset 40 and extends both inwardly and outwardly from the flanges 45 and 45'. The exterior portion of each lip 46 extends out beyond the edge of the two longer sides 43 and 43' of the spacing insert 40, and when considered in conjunction with the exterior face of the flanges 45 and 45' and the portion of the top surface 42 of the spacing insert 40 outside of the flanges 45 and 45', forms a C-shaped notch 47 and 47'.
The portion of the lips 46 which extends inwardly from the flanges 45 and 45', when taken in conjunction with the portion of the planar top surface 42 of the spacing insert 40 which is disposed between the two flanges 45 and 45', forms a substantially rectangular-shaped cavity 48 into which the insert wedge 60 is inserted, to conform to the configuration of the flanges 45 and 45' of the spacing insert 40 and thereby provide sufficient rigidity to the device, thus providing an anchoring system 10 capable of securely fastening an elastomeric membrane 90 to the top surface of a roof.
The spacing insert 40 also includes a hinge 49 which is disposed parallel to, and midway between, the flanges 45 and 45'. In the preferred embodiment, as is best shown in FIG. 1, the hinge 49 is a groove which runs from one of the shorter sides 44 of the spacing insert 40 to the other short side 44. As is best shown in FIG. 3, this hinge 49 provides a line of flexure along which the spacing insert 40 can be flexed to aid in inserting the spacing insert 40 within the anchoring plate 20.
The third major component of the present anchoring system 10 is an insert wedge 60. The insert wedge 60, like the spacing insert 40 and anchoring plate 20, is preferably formed of substantially rigid plastic. The insert wedge 60 has a planar bottom member 61 which can be inserted within the substantially rectangular-shaped cavity 48 of the spacing insert 40, as will be more fully described hereinafter.
Finally, the anchoring system 10 utilizes appropriate fastening means 70, shown in FIG. 4, to secure the anchoring plate 20 to the upper surface of the roof. It comprises an elongated screw 71 with threads 72,73 at either end. The bottom threads 72 being greater in area along the screw 71 length. Lower screwthreads 72 serve to hold the anchor plate 20 to the roof while screwthreads 73 serve to anchor the screw 71 to the anchor plate 20. Screwhead 74 mates with the end 89 of a screwdriver 85.
Driving mechanism 80, shown in FIG. 5, used to drive screw 71 comprises a rectangular base 81 with side flanges 81a and notches 81b that fit over the anchor plate 20 to retain and stabilize the driving mechanism 80 and the anchor plate 20 while driving the screw 71. Notches 81b would fit over braces 28 to secure the position of the plate. Concentric housing tubes 82 and 83 containing the driver 85 could be spring biased. The tubes would be pushed together to expose the driver in order to drive in screw 71. A power tool would engage the driver head to rotate the driver 85 and the engaged screw 71. The screw is driven in completely until screwhead 74 is in the countersunk aperture 27. Of course, conventional screws 70 could also be used as shown in FIG. 3 instead of the special fastener described above.
A second embodiment of the anchoring system 110 is shown in FIGS. 6 and 7. It consists of anchoring plate 120 with top surface 126 and bottom surface 121. Mounted on the top surface 126 is a straight ridge 124 that extends between the short sides 122,122' of the anchoring plate 120 and in the middle between longer sides 123,123'. Ridge 124 is flat on top and has a plurality of apertures 127 disposed along its length. These apertures extend vertically downward to the planar bottom 121 as before to accept fasteners 70. Counterbores are also provided to prevent damaging the membrane 90. Extending outward away from the ridge 124 and parallel to the anchor plate 120 are flanges 125,125'. The space formed between the flanges 125,125' and the anchor plate 120 will serve to accept the retainer 140.
Retainer 140 serves to cover the membrane 90 over anchor plate 120. It consists of a flat plate with top surface 142 and bottom surface 141. A hinge 149 extends down the middle of longer sides 143,143' as before. Mounted on the longer sides 143,143' perpendicular to the top surface 142 are flanges 145,145'. These extend on both sides of the retainer plate. On the bottom side of the flanges 145,145' are lips 146,146', forming cavities 147,147', which face inward parallel to the bottom surface 141. These lips 146,146' are disposed in the notches formed between the flanges 125,125' and the anchor plate top surface 126. The top side of the flanges 145,145' have lips 146,146' that form a cavity 148 to accept insert wedge 160 as shown in FIG. 8.
As before an insert wedge 160 is slid into the cavity 148 to maintain the whole device under tension. This allows for a tight fit for membrane 90 so that it does not loosen.
OPERATION
The first step in assembling and utilizing the present anchoring system 10 (disregarding those steps necessary to prepare the upper surface of a roof for installation) is to fasten the anchoring plate 20 to the surface of a roof. As is shown in FIG. 3, this can be done by inserting screws 71 through the apertures 27 in the top surface 26 of the anchoring plate 20. It is important that the screw 71 be fully tightened down in order that the membrane 90 not be abraded by the screwhead 74. As is best seen in FIG. 3, the apertures 27 are formed in such a way that the screwhead 74 can be counterbored beneath the top surface of the anchoring plate 20.
The next step in utilizing the anchoring system 10 of the present invention is to spread the elastomeric membrane over the upper surface of the roof and, hence, the anchoring plates 20. As will be more fully discussed hereinafter, the thickness of the membrane at those places where it overlays the anchoring plate 20 determines the way in which the spacing insert 40 is positioned within the anchoring plate 20. For example, at the calender seams formed where adjacent rolls of elastomeric membrane are jointed together, the effective thickness of the membrane will be twice as great as in places where anchoring plates 20 have been positioned beneath the middle of a sheet of the membrane 90. Furthermore, in some situations, for example, in high-wear installations, it may be desirable to utilize a heavier-than-normal membrane (for example, 60 mils instead of the normal 45 mil membrane).
For example, the relative positioning seen between the anchoring plate 20 and spacing insert 40 in FIG. 3, i.e., with the lips 46 above the upper planar surface 41 of the spacing insert 40, would be utilized to secure relatively thicker portions of the membrane 90 (e.g., calender seams in thin membranes which are normally 90 mils thick, or thicker membranes which are normally 60 mils thick). This configuration is used in this context because the lips 46 attached to the tops of the flanges 45 and 45' extend outwardly (i.e., away from the central hinge 49) further than the two longer sides 43 and 43' of the spacing insert 40.
The relative positioning shown in FIG. 2, on the other hand (i.e., with the lips 46 of the flanges 45 and 45' positioned below the top planar surface 41 of the spacing insert 40) is utilized where a relatively thinner section of membrane 90 has been positioned over the anchoring plate 20 (e.g., a single thickness of membrane, which usually has a thickness of approximately 45 mils). Since the two longer sides 43 and 43' of the spacing insert 40 do not extend outwardly as far as the lips 46 mounted at the ends of the flanges 45 and 45', the configuration shown in FIG. 2, wherein the lips 46 are inserted beneath the horizontal lips 25 of the anchoring plate 20, exerts more pressure on the elastomeric membrane and, hence, generates more retaining force than the configuration shown in FIG. 3, wherein the two longer sides 43 and 43' of the spacing insert 40 are inserted beneath the horizontal lips 25,25' of the anchoring plate 20.
In either configuration, the insertion of the spacing insert 40 within the anchoring plate 20 is made possible by the hinging action of the spacing insert 40. The hinging action of the spacing insert 40 is in turn made possible by the central hinge 49 of the spacing insert 40. In FIG. 3, the hinge 49 is shown as a groove within the top planar surface 42 of the spacing insert 40, running from one of the two shorter sides 44 and 44' to the other, but as will be appreciated by those skilled in the relevant art, other mechanisms could be employed.
Once the spacing insert has been snapped into place by applying pressure along the hinge 49, as is shown in FIG. 3, the horizontal lips 25 of the anchoring plate 20 will fit within the C-shaped notches 47 and 47' formed as part of the spacing insert 40 by the portion of the lips 46 extending outwardly from the flanges 45 and 45', taken in conjunction with the outer face of the flanges 45 and 45', and the portion of the top planar surface 42 of the spacing insert 40 outside of the flanges 45 and 45', in a tongue-and-groove fashion which is capable of reliably securing and immobilizing the elastomeric membrane 90 within the anchoring plate 20.
In either configuration, that is, when the substantially rectangular-shaped cavity 48 of the spacing insert 40 is pointed either upwardly or downwardly, the final step in utilizing the present anchoring system 10 is to to insert the insert wedge 60 within the substantially rectangular-shaped cavity 48 of the spacing insert 40 and thereby interlock the components of the anchoring system 10 in a secure fashion. The insert wedge 60, therefore, is inserted into the substantially rectangular-shaped cavity 48 in such a way that the bottom member 61 of the insert wedge 60 becomes positioned between the bottom of the flanges 45 and 45' and the top planar surface 42 of the spacing insert 40, as is seen in FIG. 2. The orientation of spacing insert 40 within the anchoring plate 20 depends upon the configuration--that is, with the flanges 45 and 45' pointing up (as shown in FIG. 3, as is used with thicker portions of the membrane 90); the insert wedge 60 is positioned in the same basic fashion (i.e., with the bottom member 61 inserted between the flanges 45 and 45' and the top planar surface 42 of the spacing insert 40).
The insertion of the insert wedge 60 within the substantially rectangular-shaped cavity 48 of the insert wedge 40 is facilitated by a lip 62 disposed perpendicularly to the bottom member 61. The lip 62 can be, for example, hit by a mallet or kicked gently by a worker's boot in order to drive the insert wedge 60 into the rectangular-shaped cavity 48 of the spacing insert 40.
The operation of the second embodiment 110 is similar in fashion to that of anchor system 10. The main difference being that the retainer 140 is not inserted, but is now placed on the outside of anchor plate ridge 124. Membrane 90 would be over the ridge 124 and under the retainer bottom surface 141. Lips 146,146' and flanges 125,125' serve grip the membrane 90 and keep it in position without shifting. As before, fastening means 70 is first applied to secure the anchor plate 120 to the roof before membrane 90 is placed over and the retainer 140 placed further on top of the membrane 90.
A similar driving mechanism 80 can be used to drive screw 71 into anchor plate 120. The side flanges 81a would have to be longer in order to accomodate the height of the central ridge 124.
The process of disassembling the present anchoring system 10 or 110, as may become desirable in order to inspect or repair the membrane 90, is similarly easy to accomplish and is begun by using a mallet to drive the insert wedge 60 out of the rectangular-shaped cavity 48 of the spacing insert 40.
The foregoing description of the preferred embodiment of the present invention is to be considered as illustrative only. Furthermore, since numerous modifications and variations will readily occur to those skilled in the relevant art, it is not desired to limit the scope of the present invention to the exact construction and operation shown and described and, accordingly, all suitable modifications and equivalents which fall within the scope of the claims may be resorted to. | An anchoring system for securing an elastomeric membrane to the upper surface of a roof has a rigid anchoring plate which has a planar bottom surface, apertures to facilitate securing the anchoring plate to the roof, and a pair of raised reinforced sidewalls to aid in interlocking the device. A spacing insert is provided which employs a pair of flanges, a pair of horizontal lips, and a central hinge to snap into the anchoring plate after the membrane has been laid out over the anchoring plates. A planar wedge is also provided which includes a lip to facilitate inserting the wedge into, and withdrawing the wedge from, the spacing insert. A special fastening device is provided to secure the anchoring system to the roof surface. When the components of the present anchoring system are fitted together, an elastomeric membrane may be substantially immobilized. The structure of the device is also easily disassembleable, as may become necessary in order to inspect or service the elastomeric membrane. | 4 |
BACKGROUND OF THE INVENTION
[0001] In the recent years, extensive efforts are being made to develop novel ways for drug delivery to the affected tissues and body organs. To cause little tenacity and minimal side effects; It is necessary to deliver the biologically active agents to the target tissues in an optimal amount during the required period of time. In this regard, delivery of anti-cancer agents as inject able/implantable devices in cancerous tissues has attracted much attention to divert them away from the other organs and tissues in which toxicity arises especially considering the huge burden of side effects caused by these agents.
[0002] Biodegradable polymers play a major role as carriers in drug delivery systems since the mid-1970s. As these polymers degrade in the body to small molecular weight compounds that are either metabolized or excreted, they obviate the need for removal of the carrier after the device is exhausted.
[0003] Therefore, it would be advantageous to have an improved process if insertion.
[0004] Accordingly, the present invention discloses a method for fabricating an array of unsaturated, aliphatic, biocompatible and biodegradable polyesters with photo curing capability which upon mixing with an active ingredient will provide an inject able liquid or putty-like material. The composition can be injected via a customary syringe and needle and be photo cured in situ using visible light irradiation. Changing in the network cross-linking, molecular weight of the linear polymeric precursors and their chemical structures can control delivery rate of the active ingredient from the device.
FIELD OF THE INVENTION
[0005] The present invention relates to the synthesis of novel unsaturated polyester macromers, which are clear in color, biodegradable, biocompatible and tunable in properties. The prepared compositions based on these materials can be used as injectable drug delivery devices upon compounding, injection to the desired site and visible light irradiation.
BACKGROUND OF THE ART
[0006] Using in situ forming devices as injectable/implantable drug delivery systems has attracted much attention due to several potential advantages over conventional prefabricated ones. These advantages include the possibility of using the initial materials as liquids or moldable putties and forming them easily in complex shapes which upon the subsequent reaction, a solid implant of exactly the required dimensions will be shaped without need to any invasive surgical process for implantation. Some reactions may be used to transform a liquid polymeric sol to a solid/semisolid gel including application of thermoplastic pastes, polymer precipitation from solution, ion-mediated gelation or chemical cross-linking. Administration of these devices via injection through a customary syringe and needle will also reduce the invasiveness of insertion process of traditional implants. Using biodegradable and biocompatible polymers in this construct; there will be no need for a removal procedure to be performed surgically after the effective period of drug delivery. Finally, localized or systemic drug delivery can be achieved for prolonged periods of time, typically ranging from one to several months.
[0007] Thermoplastic pastes are polymeric compositions, which their melt are injected into the body and form a semi-solid depot upon cooling to body temperature. The polymers used in this way should melt at temperatures near to the physiologic one i.e. 37° C. also low melt viscosity so, flow easily when pushed or stretched by a load, usually at elevated temperatures. Polymers of low molecular weights and glass transition temperatures are the best candidates to meet these requirements and provide a facile inject ability however; melting points ranging from 25 to 65° C., and intrinsic viscosities of 0.05 to 0.8 dl/g (at 25° C.) are reported for these devices which are far from the prerequisites hence, high temperature at the time of injection will be observed.
[0008] Polymer precipitation from solution is also reported to produce an injectable drug delivery depot. Precipitation can be induced by solvent-removal; a change in the temperature or pH, which can be described as solvent-removal precipitation and thermally, induced sol-gel transition, respectively. These devices are comprised of, for example; a water insoluble biodegradable polymer dissolved in a water miscible, physiologically compatible solvent. Upon injection into the aqueous environment of human body, the solvent diffuses into the surrounding aqueous environment while water diffuses into the polymer matrix. Since the polymer is water insoluble, it precipitates upon contact with the water and results in a solid polymeric implant. The most critical property for a solvent to be used in this system is their capabilities to form hydrogen bonding with water. Many drug candidates have been examined using this system including gonadotrophins, Chlorhexidine, doxycycline, naproxen and theophylline. Although sustained release was achieved and some commercial products were introduced in the market in this way but high initial burst release, relatively rapid release rates, and use of controversial solvents are the case with them yet. Many polymers including acrylamide-based ones and amphiphilic copolymers also undergo abrupt changes in solubility in response to changes in the environmental temperature. This physical characteristic has been employed to form drug depots by using polymer systems, which undergo a sol-gel transition upon injection into the body. Acrylamide-based polymers are not generally suitable for injectable/implantable devices due to their inherent toxicity
[0009] Organogels are composed of water-insoluble amphiphilic lipids, which swell in water and form various types of lyotropic liquid crystals. The nature of the liquid crystalline phase formed depends on the structural properties of the lipid, temperature, nature of the drug incorporated, and the amount of water in the system. They are promising injectable delivery systems for lipophilic compounds. Stability of oils and purity of waxes which are used in their composition along with very broad phase transition with temperature are the common problems in this way. Lacks of toxicity data and phase separation that can easily reduce the potency of some drugs are common problems.
[0010] Unfortunately, most of the methodologies which have been used to provide such devices achieved limited success to control the gelation kinetics and hence the properties of the resulting materials. However, strict controlling of the crosslink density in the strategies based on free radical reaction (initiated by heat, redox, or photo irradiation mechanisms) will provide the readily adjustable network properties including permeability, degradation, water uptake, or mechanical properties.
[0011] Thermoses macromers can flow and be molded when initially constituted hence will provide the required flow for injectability. Soon after crosslinking reaction initiated by heat or redox initiation systems, they will irreversibly turn to solid bodies. In the most cases, crosslinking reaction means the formation of covalent bonds between neighboring polymer chains, which ends to a macromolecular network. Irreversibility of these bonds provides long life to the device i.e. high thermal and mechanical stability. The advantage of using this system is its facile syringeability. And there are some disadvantages like unacceptable level of heat released during the reaction, and burst in drug release and toxicity of un-reacted monomers.
[0012] Photocrosslinked gels are another type of in situ crosslinked systems who provide many advantages over chemically initiated thermoset systems. These include rapid polymerization rates in physiological temperatures, achieving complex shaped with exactly the required dimensions. In this approach, prepolymers, mostly based on polyanhydrides are introduced to the desired site via simple injection and photocured in situ with fiber optic cables. Numerous medical applications may benefit from such compositions e.g. in dentistry ceramic filled dimethacrylate monomers are photo polymerized with blue light to produce tooth colored restorations in situ as an alternative to mercury amalgam fillings. Some prior art presented some of the first works using degradable polymers that were photocured in vivo to prevent post-operative adhesions. Second, the adhesion of the polymer to surrounding tissue is generally significantly improved because of intimate contact of the polymer with the tissue during formation and the resulting mechanical interlocking that can arise from surface microroughness. Third, the invasiveness of some surgical techniques is minimized as liquid solutions are easily introduced through needle injections and can be photocured with fiber optic cables using arthroscopic techniques.
[0013] Most of the reports on photo crosslinkable macromers are devoted to acrylate-based monomers, which are generally well recognized as unsafe materials. There are few unsaturated moieties available as alternatives to acrylate-based monomers such as fumarate and itaconate monomers. Some macromers reported based on fumarate macromers are polyethylene glycol fumarate, polypropylene fumarate and poly(ε-caprolactone fumarate). Degradation products resulted from these copolyesters is completely biocompatible and will be metabolized in Krebs's cycle. The photoinitiated crosslinking of unsaturated macromers by visible light to produce three-dimensional polymeric networks seems interesting due to its rapid and effective nature. In this way, the initiation time of the reaction will be easily controlled and can be carried out at lower temperatures with minimal heat generation. Using visible light in the photocuring of transparent, unsaturated, and liquid or putty-like materials, thick layers (in much more depth) could be cured rapidly due to tendency of the corresponding photoinitiators, for example, camphorquinone, to quickly photobleach. This is why this method has found more versatile applications than UV or gamma ray curing. In this way, due to the very mild reaction conditions, the polymerization can be carried out in direct contact with drugs, cells, and tissues.
[0014] In addition to the advantages mentioned before, these systems have some problems like shrinkage and brittleness of the polymer due to high degree of crosslinking.
[0015] One of the major problems facing cancer chemotherapy is the achievement of the required therapeutic concentration of the drug at the tumor site for a desired period of time without causing undesirables effects on the organs while circulating in the body. The vascular system of tumors is highly disorganized and unpredictable both in its structure and in function. This disorganization serves as a major barrier in the delivery of drugs to solid tumors. High viscosity of blood in the tumor significantly hinders drug delivery to poorly perfused regions of tumor mass. Another factor that poses a problem to drug delivery in solid tumors is the abnormally high pressure in the interstitial matrix of the tumor that retards the passage of molecules across the vessel walls and into the interstitial matrix. Oral administration of the non-steroidal anti-estrogen like Tamoxifen is the treatment of choice for the patients with all stages of estrogen receptor (ER) positive breast cancer. Despite being quite effective, tamoxifen can have harmful long term side effects such as the development of endometrial cancer, or an acquired Tamoxifen resistance leading to further tumor progression. To overcome these undesirable side effects, one could encapsulate Tamoxifen in stealth PEGylated nanoparticles.
[0016] Microparticulate drug delivery systems are considered and accepted as a reliable means to deliver the drug to the target site with specificity, if modified, and to maintain the desired concentration at the site of interest without outward effects. Sehra et al. prepared biodegradable microspheres of PLGA 65:35 by o/w emulsification solvent evaporation method, and they synthesized different batches of varying concentration of drug, polymer, polyvinyl alcohol and solvent. They demonstrated that concentration of polymer, drug and stabilizer affects the part size, encapsulation efficiency and drug release rate.
[0017] Oral administration of the non-steroidal anti-estrogen like Tamoxifen is the treatment of choice for the patients with all stages of estrogen receptor (ER) positive breast cancer. Tamoxifen citrate, a non steroidal antiestrogen has potential applications in treatment of breast cancer. This drug is slightly soluble in water.
[0018] Tamoxifen, an antiestrogen, is widely used as an adjuvant in the treatment of breast cancer. Tamoxifen has undergone clinical trials in Europe, as well as in the United State and Canada, to evaluate its preventive effect on breast cancer in women at high risk. Recently, TAM has been used to treat other cancers, such as liver, brain and pancreas. It has been reported that TAM and its active metabolite 4-hydroxytamoxifen exert anti-oxidative effects in vitro.
SUMMARY OF THE INVENTION
[0019] The principal object of the present invention is to provide a method for controlled delivery of a predetermined amount of a drug wherein said method comprises;
[0020] Combining a macromer with a predetermined amount of a drug, and a plurality of initiators, and obtaining a first composition,
[0021] Applying a crosslinking procedure to said first composition, wherein said drug is unaffected by said crosslinking; and
[0022] Obtaining a second composition, wherein said second composition controls said delivery of said predetermined amount of said drug.
[0023] Yet another object of the present invention is to provide macromer which comprises of unsaturated aliphatic polyesters, wherein said unsaturated aliphatic polyesters are a result of a polyesterification reaction catalyzed by a catalyst between a diol, wherein said diol comprises polyethyelene glycol, polycaprolactone diol, and polyhexamethylene carbonate diol and an acyl halide wherein said acyl halide comprises of fumaryl chloride and itaconyl chloride.
[0024] Yet another object of the present invention is to provide catalyst, which comprises of epoxy containing compounds wherein said compounds comprise propylene oxide, and 1,2-butylene oxide.
[0025] Yet another object of the present invention is to provide macromer, which is a white clear macromer.
[0026] Yet another object of the present invention is to provide macromer which is crosslinked by visible light initiation, wherein said visible light initiation characterized with duration and intensity of said visible light irradiation.
[0027] Yet another object of the present invention is to provide macromer which is crosslinked by thermal initiation, wherein said thermal initiation characterized with duration of crosslinking, temperature of crosslinking and concentration of said thermal initiation.
[0028] Yet another object of the present invention is to provide macromer which is crosslinked by redox initiation, wherein said redox initiation characterized with duration of crosslinking, and concentration of said redox initiation.
[0029] Yet another object of the present invention is to provide a method in which said controlled delivery of said predetermined amount of said drug is based on intensity and duration of said visible light irradiation.
[0030] Yet another object of the present invention is to provide a method in which said controlled delivery of said predetermined amount of said drug is based on said duration of crosslinking, said temperature of crosslinking and said concentration of said thermal initiation.
[0031] Yet another object of the present invention is to provide a method in which said controlled delivery of said predetermined amount of said drug is based on said duration of crosslinking, and said concentration of said redox initiation.
[0032] Yet another object of the present invention is to provide a composition for controlling duration and amount of delivery of a predetermined amount of a drug, wherein said composition comprises:
[0033] A first composition comprising a macromer, a predetermined amount of a drug, and a plurality of initiators, wherein said macromer is subject to a crosslinking procedure, thereby obtaining a second composition, wherein said second composition controls said duration and amount of delivery of said predetermined amount of said drug.
[0034] Yet another object of the present invention is to provide a composition for controlling duration and amount of delivery of a predetermined amount of a drug wherein said macromer comprises of unsaturated aliphatic polyesters, wherein said unsaturated aliphatic polyesters are a result of a polyesterification reaction catalyzed by a catalyst between a diol, wherein said diol comprises polyethylene glycol, polycaprolactone diol, and polyhexamethylene carbonate diol and an acyl halide wherein said acyl halide comprises of fumaryl chloride and itaconyl chloride.
[0035] Yet another object of the present invention is to provide a composition in which catalyst comprises of epoxy containing compounds wherein said compounds comprises propylene oxide, and 1,2-butylene oxide.
[0036] Yet another object of the present invention is to provide a composition in which macromer is a white clear macromer.
[0037] Yet another object of the present invention is to provide a composition in which macromer is crosslinked by visible light initiation, wherein said visible light initiation characterized with duration and intensity of said visible light irradiation.
[0038] Yet another object of the present invention is to provide a composition in which macromer is crosslinked by thermal initiation, wherein said thermal initiation characterized with duration of crosslinking, temperature of crosslinking and concentration of said thermal initiation.
[0039] Yet another object of the present invention is to provide a composition in which macromer is crosslinked by redox initiation, wherein said redox initiation characterized with duration of crosslinking, and concentration of said redox initiation.
[0040] Yet another object of the present invention is to provide a composition in which controlled delivery of said predetermined amount of said drug is based on intensity and duration of said visible light irradiation.
[0041] Yet another object of the present invention is to provide a composition in which controlled delivery of said predetermined amount of said drug is based on said duration of crosslinking, said temperature of crosslinking and said concentration of said thermal initiation.
[0042] Yet another object of the present invention is to provide a composition in which controlled delivery of said predetermined amount of said drug is based on said duration of crosslinking, and said concentration of said redox initiation.
[0043] This present invention comprises synthesis of biodegradable, biocompatible, unsaturated polyesters based on different diols including polyethylene glycol, poly (ε-caprolactone diol) and poly(hexamethylene carbonate diol) and diacids comprising fumaric acid and itaconic acid. Polyesters were synthesized via reaction of precursor diol with acyl halide derivative of diacid in the presence of propylene oxide as a catalyst and proton scavenger. The resulting polymers were completely white clear materials suitable for photo crosslinking.
[0044] Injectable polymeric compositions based on an unsaturated polyester e.g. poly (ethylene glycol) fumarate (PEGF), poly (ε-caprolactone fumarate), poly (hexamethylene carbonate fumarate) or their corresponding itaconate derivatives were crosslinked using N-vinyl pyrrolidone (NVP) as a reactive diluent also crosslinking agent, N, N dimethyl p-toluidine (DMPT) as an accelerator and a photo initiator such as comphorquinone (CQ). Samples were photo cured after adding the corresponding amount of active ingredient i.e. tamoxifen citrate to the above composition.
[0045] The present invention includes a new method in which a macromer that is injectable, biodegradable can be in situ photo crosslinked by using visible light source and makes networks, which are useful for biomedical application. To achieve these objectives, optically transparent and biodegradable macromers based on polyethylene glycol, poly (ε-caprolactone diol) and poly (hexamethylene carbonate diol), and diacids comprising fumaric acid and itaconic acid were synthesized using propylene oxide as a different proton scavenger to enhance in situ photocrosslinking capability. The macromers in different compositions were then photocrosslinked for 300 sec in the presence of a visible light initiator/accelerator couple and also a reactive diluent.
[0046] In this invention includes some methods in order to characterize crosslinked networks, there are applied some studies e.g., determination of the degree of conversion, measurement of the shrinkage strain and initial shrinkage strain rates and equilibrium swelling and sol fraction study and also some dynamic mechanical analysis of the resulting networks. The macromer may also be advantageous for in situ visible photo curing because they are colorless. This reaction may be useful for other applications. Further, the reaction can be influenced by a factor such as diol molecular weight. Fabrication of networks using visible light photo crosslinking is also described. Application of these networks in drug delivery was also described.
BRIEF DESCRIPTION OF DRAWINGS
[0047] FIG. 1 is a schematic representation of macromer synthesis pathway and subsequent photo crosslinking in the presence of NVP for PEGF as an example;
[0048] FIG. 2 shows FTIR spectra of PEG 1 kDa and PEGF obtained from different initial molecular weights of precursor diols;
[0049] FIG. 3 shows 1HNMR spectra of the PEG 1 kDa, PEGF 0.4 and 1 kDa in CDCl3;
[0050] FIG. 4 shows Shrinkage strain of PEGF 1 kDa based specimens with different contents of NVP during photo crosslinking;
[0051] FIG. 5 shows Shrinkage strain of PEGF 0.4 kDa based specimens with different contents of NVP during photo crosslinking;
[0052] FIG. 6 shows comparison of the shrinkage strain rates of PEGF 0.4 kDa with different contents of NVP during photo crosslinking;
[0053] FIG. 7 shows correlation between shrinkage strain and NVP-fraction of the hydrogels (n=3);
[0054] FIG. 8 shows degree of conversion for PEGF 0.4 and 1 kDa based formulations with different NVP contents (n=3);
[0055] FIG. 9 shows NVP content dependence of the Mc values for PEGF 0.4 and 1 kDa swollen in water (20° C.);
[0056] FIG. 10 shows cell Culture test, L929 fibroblast cells growing neighboring to crosslinked networks, (X=400); and
[0057] FIGS. 11A-11G illustrate in vitro release profiles of TMX released from different formulations of PEGF 0.4 KDa (n=4). L stands for drug loading (% w/w) and D stands for disk thickness (mm).
DETAILED DESCRIPTION OF THE INVENTION
Materials and Methods
[0058] Materials
[0059] Polyethylene glycol (Mw=0.4 and 1 kDa), poly (ε-caprolactone diol) (Mw=0.63, 1.2 and 2 kDa) and poly (hexamethylene carbonate diol) (Mw=0.83 and 2 kDa), N-vinyl-2-pyrrolidone (NVP), camphorquinone (CQ), calcium hydride, fumaryl chloride (FuCl), itaconyl chloride (ItCl) and propylene oxide (PO) were all purchased from Aldrich (Milwaukee, Minn., USA). N, N-Dimethyl-p-toluidine (DMPT), sodium hydroxide (NaOH) and methylene chloride (DCM) were obtained from Merck (Germany). FuCl was purified by distillation at 161° C. under ambient pressure. Anhydrous DCM was obtained by distillation under reflux condition for 1 hour in the presence of calcium hydride. NVP was also distilled under reduced pressure (30 mmHg). Tamoxifen citrate (TMX) was a kind gift from Iran Hormon Co. (Iran). Other solvents and reagents were of the reagent grade and used without further purification.
[0060] Synthesis of Macromers
[0061] As shown in FIG. 1 for PEGF macromers (as an example) were synthesized according to the procedure which is depicted in FIG. 1 . Typically, 0.03 mole of diol i.e. PEG diol was dissolved in 100 mL of anhydrous DCM in a three necked 250 mL reaction flask equipped with reflux condenser and magnetic stirrer. PO was added to the mixture in a 2:1 molar ratio. The purified diacid i.e. FuCl or ItCl (0.995:1 molar ratio to diol) was dissolved in 50 mL of the same solvent and added dropwise in one hour to the stirred reaction flask at −2° C. under nitrogen atmosphere. The reaction temperature was then raised to the room temperature and run overnight. Upon completion of the reaction, the product was washed several times with 0.1N sodium hydroxide (NaOH) to remove the resulted byproducts such as chlorinated propanols. The macromer was then obtained by rotovaporation, dried at 25° C. in vacuum for 24 hours. Then, which was reserved at −15° C. until further applications.
[0062] Photo Polymerization of Macromers
[0063] Macromers were crosslinked by visible light in the presence of CQ and DMPT as photo initiator system ( FIG. 1 ). Typically, 0.3 mg of macromer was dissolved in 1 μL of DMPT (26 mg) containing NVP and the equivalent of CQ (1:1 w/w to DMPT) was mixed thoroughly in this solution according to a 2 level factorial design. The factors were comprised of the initial diol molecular weights (e.g. 0.4 & 1 kDa for PEG diol) and the reactive diluent percentage (8 & 12%). The reported measurements for the experimental design are represented as means±standard deviation. The mixture was then cast in molds with a definite geometry (cylindrical shape with 8 mm diameter and 1 mm height) and cured for 300 seconds using a blue light source with an irradiance of circa 450 mW/cm2 (Optilux 501, USA) to prepare the specimens.
[0064] Macromers Characterizations
[0065] FTIR spectra (4000-400 cm-1) were obtained on a Bruker, Equinox 55 spectrophotometer at 4 cm-1 resolution and 32 scans. The specimens were analyzed on KBr disks at room temperature. 1HNMR spectra were recorded in CDCl3 at 25° C. (Bruker Ultrashield® 400 MHz, Germany) and chemical shifts were recorded in ppm.
[0066] Gel permeation chromatography (GPC) was accomplished using a GPC instrument (Shimadzu, CR4AX, GC15A, Japan). Polystyrene of known molecular weights were used as the calibration standards. THF was used as the mobile phase eluting at a flow rate of 1.0 mL/min. A 100 μL sample of 0.1 mg/mL solution of the macromer in THF, which was filtered through a 0.22 μm filter prior to use, was injected for all measurements.
[0067] Thermal Analysis
[0068] Melting point (Tm), glass transition temperature (Tg) and crystallinity of the samples were evaluated using a TA instrument 920 differential scanning calorimeter (DSC) under nitrogen gas flow rate of 100 mL/min measured at a heating rate of 10° C./min via heating from −80° C. to 100° C. First, the specimens were heated from −80 to 100° C. at heating rate of 10° C./min, and then quenched rapidly to −80° C. The glass transition temperature, Tg, was taken as a midpoint of the heat capacity change. Tm and heat of fusion (ΔHm) were determined from the maximum endothermic peaks position and integrating of endothermic area.
[0069] Polymerization Shrinkage Strain and Shrinkage Strain Rate Measurement
[0070] The bounded disk technique was used to measure the shrinkage of light cured samples. Briefly, the specimen to be cured was placed at the center of a brass ring (with square cross section) adhesively bonded to a rigid glass plate and the top edge of the ring and the disk specimen were covered by a flexible diaphragm e.g. a microscope lamella. A centrally aligned LVDT displacement transducer was positioned in contact with the center of the cover slip. The light source was beneath the rigid glass plate and upon initiation of reaction the cover slip deflected due to polymerization shrinkage and LVDT transducer which was connected to the signal conditioning unit, microcomputer transient recorder and data logging system, monitored the deflection of cover slip over time. The total shrinkage strain of the sample was assessed for 400 seconds after starting the light irradiation, at which time the contraction had plateau-out.
[0071] Measurement of Conversion
[0072] To determine the degree of conversion (DC), the specimens were placed between two polyethylene films and pressed to form a very thin film. FTIR absorbance spectra of the samples were recorded before and after curing reaction. DC % was determined from the ratio of absorbance intensities of aliphatic C═C (peak at 1645 cm-1) against the internal references (peaks at 724, 1463 cm-1) before and after curing of the specimen. The degree of conversion was then calculated as follows (eq. (1)):
[0000]
DC
%
=
(
1
-
(
1645
cm
-
1
Reference
Peak
cm
-
1
)
peak
area
after
curing
(
1645
cm
-
1
Reference
Peak
cm
-
1
)
peak
area
before
curing
)
×
100
(
1
)
[0073] Equilibrium Swelling and Sol Fraction Study
[0074] The equilibrium swelling of the photocrosslinked networks was investigated by a gravimetric method. All of samples were molded as previously described and weighed in dry state, Wi. Then the disks were placed in 50 mL of deionized distilled water (DDW) until equilibrium and weighed again, Ws. The swollen gels were dried overnight at reduced pressure, and then weighed, Wd. Swelling data were used to calculate the equilibrium swelling ratio and sol fraction percent for each formulation using the following formulas (eqs. (2,3):
[0000]
Ratio
=
W
s
-
W
d
W
d
(
2
)
Sol
fraction
%
=
W
i
-
W
d
W
i
×
100
(
3
)
[0075] DMA
[0076] The rheological measurements were carried out using a Paar-Physica oscillatory rheometer (MCR300, Germany) at 20° C. with parallel plate geometry (plate diameter of 8 mm, gap of 1-1.5 mm). The tests were accomplished at 20° C. in order to avoid water evaporation during the experiment. The strains used were chosen to be in the linear viscoelastic (LVE) range, where G′ and G″ are independent of the strain amplitude. LVE range was determined for the photo crosslinked gels in the swollen state in water. The specimen was placed between the parallel plates of the rheometer and a strain sweep test (ω=1 rad/s) was conducted. The test conditions for the frequency sweeps were selected to confirm that the test is really carried out in the LVE range (shear strain of 0.2%). Then a frequency sweep was performed and a graph of G′ and G″ versus frequency were achieved in a range of 0.1-100 Hz at constant temperature at 20° C.
[0077] Biocompatibility Assay
[0078] Cell culture was performed on photocrosslinked samples using L929 fibroblast cells of mice as a test model. The cells were maintained in growth medium RPMI-1640 supplemented with 100 IU/mL of penicillin, 100 μg/mL of streptomycin and 10% fetal calf serum. A routine subculture was used to maintain the cell line. The cells were incubated in a humidified atmosphere of 5% CO2 at 37° C. After one week incubation the monolayer was harvested by tripsinization. The samples were sterilized in an autoclave and placed in a multiple tissue culture polystyrene plate with 5 mL of cell suspension and then maintained in incubator for 48 hours. One sample was kept as a negative control. After incubation the samples were taken away from the incubator and examined for morphology and cell growth.
[0079] In vitro Drug Release
[0080] The resulting macromer was dried at 25° C. in vacuum oven for 24 hours and stored at −15° C. until further use. macromer was crosslinked by visible light in the presence of CQ and DMPT as photo initiator system. The CQ/amine photo initiator system for generation of radicals is widely used for the curing of dental restoration materials. First, Appropriate amount of the macromer was mixed with TMX (1 or 2% wt % macromer as drug loading) so the homogeneous material was obtained and then DMT and the corresponding amount of CQ (1:1 w/w to DMT) dissolved in NVP (12% wt total) and was added to the macromer mixture. The specimens (cylindrical shape with 8 mm diameter and 1 or 2 or 3 mm height) were cured for 300 seconds using a blue light source with intensity of 450 mW/cm2 (Optilux 501, USA).
[0081] The release profile of TMX from different geometries with different loading were determined in 10 mL PBS solution pH 7.4 containing 30% v/v Isopropanol providing sink conditions in a thermostatic bath system at 37° C. Samples were withdrawn at given time intervals and replaced with fresh buffer solution maintained at the same temperature. Samples was then analyzed for TMX concentration with UV-VIS spectrophotometer (UV1650PC, Shimadzu, Japan) using an analytically validated method (r2>>0.99) at 277 nm.
Results
[0082] As shown in FIG. 2 , the FTIR spectra of PEGF 0.4 and 1 KDa are presented as an example. Asymmetrical C-O-C stretching band at 1100 cm −1 , C═C stretching at 1645 cm −1 , carbonyl stretching at 1720 cm-1, strong methylene absorption at 2871 cm-1, methylene scissoring and asymmetric bending at 1455 cm-1 and hydroxyl absorption at 3442 cm-1 are evident and can be found. The absorption bands presented at 950 and 858 cm-1 positioned in the FTIR spectra are characteristic of the crystalline phase of PEG.
[0083] As shown in FIG. 2 , 1HNMR spectra of the synthesized PEGF macromers are shown as an example. The chemical shifts with peak positions at 3.63, 4.33, 2.7 and 6.8 ppm are due to the protons of PEG main ethylene (b), methylene groups adjacent to the fumarate groups (c), the hydroxyl group of PEG (d) and hydrogens of the fumarate group (a), respectively. Since the chemical shift of the fumarate hydrogens is below 7.0 ppm, the steric configuration of the fumarate functional groups in the copolymer should be in the cis position. The presence of chemical shift at 6.8 ppm clearly reveals that fumarate groups are incorporated in PEG.
[0084] According to the GPC results; no significant effect on number-average molecular weight (Mn) of the resulted PEGF macromers were observed with increasing PEG diol molecular weights (from 0.4 to 1 kDa). This is in contrast to what observed with weight-average molecular weight (Mw) of the macromers which implies a larger polydispersity index (PDI). Table 1 indicates Mn, Mw and PDI for these macromers. In comparison with PEG diol of 1 kDa, 0.4 kDa, PEG diols of 0.4 kDa have more reactive hydroxyl end groups since the larger PEG random coil exerts more steric hindrance, so Mn and Mw of PEGF 0.4 kDa increase considerably. For that reason, our results clearly prove that the hydroxyl groups of low molecular weight PEGs are also more accessible to fumaryl chloride during the oligomerization ( FIG. 2 and Table 1).
[0000]
TABLE 1
Sample
Mn
Mw
PDI
PEG 0.4 kDa
380
420
1.10
PEGF 0.4 kDa
3050
5800
1.90
PEG 1 kDa
930
1190
1.27
PEGF 1 kDa
3440
8380
2.43
[0085] Crosslinking characteristics in terms of maximum shrinkage strain (and strain rate), ultimate shrinkage strain and time at maximum shrinkage strain rate are reported in Table 2. Maximal shrinkage strain for PEGF 1 kDa samples are lower than the corresponding 0.4 kDa samples due to the fewer number of double bonds (nearly 3 times), and hence the ultimate shrinkage strain will be smaller in turn.
[0086] FIGS. 4 and 5 show the shrinkage strains of PEGFs 0.4 and 1 kDa with different NVP contents. The results indicate that the total shrinkage strain was increased with increasing NVP content due to further conversion of weak intramolecular Van der Waals forces to the strong covalent single bonds during the crosslinking reaction. By increasing in molecular weight of the PEGF macromers or decreasing NVP content, viscosity of the mixture is also increased which in turns affects the photocrosslinking reaction via limiting the diffusion of free radicals. This phenomenon would decrease the maximum observed shrinkage strain rate and increase the time at which maximum shrinkage strain rate are observed at the set point of the mixture. As the viscosity increases, the limited diffusion of radicals may interfere with the termination step of the crosslinking reaction by bimolecular coupling. Therefore, this may be another reason for low shrinkage strain observed in PEGF 1 kDa specimens ( FIG. 5 ).
[0087] As shown in FIG. 6 , as the shrinkage is the consequence of the polymerization reactions, it should follow the polymerization reaction model. Shrinkage strain rate, which is related to polymerization rate, is an important factor affecting the biomechanics and marginal integrity of the crosslinked polymer cured to form a biomedical device. FIG. 6 depicts the shrinkage strain rate behavior of PEGFs 0.4 kDa which shows that the ultimate shrinkage strain rate being dependent on the NVP content. The time at which the maximum shrinkage strain rate is reached is also shown by tεm. As illustrated in Table 2, there is a significant difference between the tεm of PEGFs 0.4 and 1 kDa with different NVP contents. Increasing in the NVP content will decrease the time at which the shrinkage strain rate reaches its maximum due to the more accessible crosslinking agent also lower viscosity of the mixture. As a consequence, the species with more NVP content have higher shrinkage strain rates and faster crosslinking reactions at the early times.
[0000]
TABLE 2
Max.
Ultimate
Max.
Time at
shrinkage
shrinkage
shrinkage strain
max. shrinkage
Samples
strain (%)
strain (%)
rate (%/s)
strain rate (s)
PEGF 0.4
2.06 ± 0.01
2.64
0.025 ± 0.001
40 ± 6.50
kDa - 5% NVP
PEGF 0.4
2.95 ± 0.07
3.45
0.038 ± 0.004
35 ± 2.50
kDa - 8% NVP
PEGF 0.4
3.92 ± 0.06
4.32
0.058 ± 0.003
30 ± 3.10
kDa - 12% NVP
PEGF 0.4
6.14 ± 0.11
6.37
0.085 ± 0.006
25 ± 1.90
kDa - 25% NVP
PEGF 1
0.72 ± 0.001
1.24
0.01 ± 0.00
80 ± 6.70
kDa - 5% NVP
PEGF 1
1.45 ± 0.06
2.05
0.09 ± 0.00
50 ± 5.20
kDa - 8% NVP
PEGF 1
1.75 ± 0.08
2.14
0.13 ± 0.00
40 ± 3.20
kDa - 12% NVP
[0088] FIG. 7 denoted a linear correlation (R2>>0.95) between NVP content and shrinkage strain. The slope of shrinkage strain of PEGF 0.4 kDa and the intercept of linear plot of PEGF 0.4 kDa are more than PEGF 1 kDa. The shrinkage strain percentages are increased more in PEGF 0.4 kDa upon light irradiation due to the higher amount of double bonds present also its lower viscosity in comparison to the PEGF 1 kDa. This will cause NVP molecules to be more mobile and place speedily among the chains to make a crosslinked networks.
[0089] The increase in molecular weight of PEG increases viscosity of PEGFs as well as decreases the reactivity. The time and the conversion at which the maximum strain rate was acquired decreased with an increase in the molecular weight of PEGFs. The very high viscosity of PEGF hinders the mobility of growing macroradicals and monomers and causes the maximum rate appearing at longer times. However, there is some increase in PEGFs viscosities due to increasing in PEGs molecular weights but the number of double bonds strongly influences the curing conversion of PEGF 0.4 and 1 kDa in contrast to NVP content ( FIGS. 6 , 8 ).
[0090] As mentioned before, the increase in NVP content results in an increasing in degree of conversion which means enough double bonds for NVP as a crosslinker to be placed among them and result in the corresponding network. As shown in FIG. 8 the decrease in conversion of PEGF 0.4 kDa and PEGF 1 kDa with the same NVP contents shows no considerable changes in 8% and 12% NVP content (p<0.05). The outcomes of the amount of double bonds also viscosities which are related to PEGF and PEG molecular weight itself play a determinant role in this phenomenon. Adding the reactive diluent i.e. NVP to the base macromer improves the chain mobility which enhances the reactivity of the components in turn, hence it is expected that the higher proportion of NVP, the greater the degree of conversion of the compositions. The present findings coincided with the expectations. FIG. 8 depicts degree of conversion for the crosslinked PEGF macromers containing diverse NVP contents.
[0091] To derive Mc from DMA, G′ was measured and static shear modulus (G) was then assumed by extrapolation of the rheogram to the zero frequency. The time scale for the indentation experiment was about 10 seconds in each measurement. Actually, we extrapolated oscillation graphs to 0.1 Hz. Moreover, we linearized these data by plotting G′ against log frequency. Extrapolated values of G′ were estimated to concentrations, respectively. Molecular weights between crosslinks (Mc) of the photocrosslinked gels were calculated using DMA, it means the G′ can be converted into crosslinking density (ρx) from rubber elasticity theory (eqs. (4, 5, 6)) [39, 40]:
[0000]
v
2
,
s
=
V
d
V
s
=
W
d
ρ
p
W
d
ρ
p
+
[
W
s
-
W
d
ρ
o
]
(
4
)
G
′
=
2
ρ
x
RTv
2
,
s
(
1
/
3
)
(
5
)
ρ
x
=
1
vMc
(
6
)
[0092] here ρx is the crosslink density (moles of crosslinks per unit volume), R is the gas constant (8.314 JK-1Mol-1), T is the temperature (293 K), Mc is the average molecular weight between crosslinks, v2,s is the polymer fraction at equilibrium swelling and v is the partial specific volume of PEGF and Vd, Vs, Ws, Wd ρp and ρo are dry polymer volume (cm3), swollen polymer volume (cm3), swollen polymer weight (g), dry polymer weight (g), polymer density, solvent density (water) (g/cm3), respectively (Table 3).
[0000]
TABLE 3
Swelling
Sol
% NVP
Ratio ± SD
Fraction ± SD
PEGF 0.4 kDa
5
1.46 ± 0.10
25.92 ± 4.43
8
1.09 ± 0.12
18.65 ± 2.91
12
0.98 ± 0.09
15.22 ± 2.26
PEGF 1 kDa
5
0.61 ± 0.008
7.00 ± 0.41
8
0.52 ± 0.01
7.20 ± 0.97
12
0.52 ± 0.02
10.18 ± 1.27
[0093] The elastic behavior of the samples prevails over its viscous behavior and the swollen gel exhibits mechanical rigidity. The increase in NVP content causes a decrease in Mc also rigidity of the PEGF gels. It seems that ( FIG. 9 ), as the content of NVP is increased; the swelling ratio is decreased because the network tends to vary to a denser one.
[0094] Cellular biocompatibility as determined by cell culture showed very good agreement with the results obtained from control samples. The solid photocrosslinked networks and their precursor uncured macromers were not toxic towards the cells at all. FIG. 10 depicts the morphology of L929 fibroblast cells cultured on photocrosslinked samples. As can be seen in this picture fibroblast cells could be considered completely flattened and well spread and elongating and expanding their filopedia.
[0095] As shown in FIG. 6 , In vitro profiles release of tamoxifen citrate from PEGF 0.4K are seen as an example. The rapid burst effect is very much delayed when different loading technique is used for tamoxifen citrate. Based on the above finding, it observed that 1% drug loading and 2 mm shows optimum release characteristics. The release rate of tamoxifen citrate from PEGF 0.4K could be properly controlled for 8 h.
[0096] The macromers have potential to be used as in-situ forming injectable hydrogels systems. In vitro profiles release of tamoxifen citrate from PEGF 0.4K show the rapid burst effect is very much delayed when different loading technique is used for tamoxifen citrate. Appropriate variation in the proportions of drug and depth of matrix can lead to product with the desired controlled-release
CONCLUSION
[0097] Unsaturated macromers were synthesized from diacids e.g. fumaryl chloride and diols e.g. polyethylene glycol in the presence of propylene glycol as a new proton scavenger and characterized as an injectable biomaterial. NVP was used as a crosslinking/reactive diluent agent to increase final double bond conversion and to reduce the composition viscosity hence, improving injectabiliy. The results showed that photocrosslinking was facilitated at higher NVP contents and shrinkage strain rate of PEGF/NVP mixtures followed the same pattern of polymerization reaction of multifunctional monomers showing auto-acceleration and auto-deceleration patterns. Total shrinkage strain of mixture was increased by increasing amount of NVP from 5% to 20% and increasing molecular weight. Mc was determined with ball indentation DMA which indicated an increasing crosslink density of networks and decreasing Mc upon an increase in the NVP content of the compositions. Cell biocompatibility evaluation of PEGF/NVP copolymers by general fibroblast cell culture showed that these materials are biocompatible and the solid photocrosslinked networks were not toxic towards the cells at all. Unsaturated macromers can be used as precursors to prepare polymeric networks and scaffolds with controlled hydrophilicity, swelling and mechanical properties for applications in drug release and tissue engineering. The macromers have potential to be used as in-situ forming injectable hydrogels systems.
[0098] The description of the embodiment set forth above is intended to be illustrative rather than exhaustive of the present invention. It should be appreciated that those of ordinary skill in the art may make certain modifications, additions or changes to the described embodiment without departing from the spirit and scope of this invention as claimed hereinafter. | Disclosed is a method for making a composition which comprises of an array of unsaturated, aliphatic, biocompatible and biodegradable polyesters with photo curing capability which upon mixing with an active ingredient will provide an inject able liquid or putty-like material. The composition can be injected via a customary syringe and needle and be photocured in situ using visible light irradiation. Changing in the network crosslinking, molecular weight of the linear polymeric precursors and their chemical structures can control delivery rate of the active ingredient from the device. | 0 |
FIELD OF THE INVENTION
[0001] The present invention relates to a system and method for verifying the integrity of the condition and operation of a pipetter device for manipulating fluid samples in test tubes. More particularly, the present invention relates to a system and method for an automated pipetter device that makes use of pressure transducers to detect the presence and integrity of filtered pipette tips on the nozzle of the device, and to sense liquid levels in test tubes from which the pipetter device draws fluid samples.
BACKGROUND OF THE INVENTION
[0002] A variety of molecular biology methodologies, such as nucleic acid sequencing, direct detection of particular nucleic acids sequences by nucleic acid hybridization, and nucleic acid sequence amplification techniques, require that the nucleic acids (DNA or RNA) be separated from the remaining cellular and non-cellular sample components. This process generally includes the steps of collecting a sample containing the cells of interest in a sample tube. The sample is then treated with heat or heat plus reagent, which causes the cells to rupture and release the nucleic acids (DNA or RNA) into the solution in the tube. Alternatively, the sample tube is placed in a centrifuge and spun down to separate the cells from other sample components. The resulting pellet is then re-suspended with an appropriate buffer and lysed as described above. The lysed solution containing free nucleic acids is removed from the sample tube by a pipette or any suitable instrument. The solution is then transferred to other tubes or microtiter wells containing reagents necessary for the desired downstream application. One such application, the amplification and detection of specific nucleic acid sequences, requires the addition of priming sequences, fluorescein probes, enzymes, and other reagents. The nucleic acids are then detected in an apparatus such as the BDProbeTec® ET system, manufactured by Becton, Dickinson and Company and described in U.S. Pat. No. 6,043,880 to Andrews et al., the entire contents of which is incorporated herein by reference.
[0003] In order to properly control a pipetter device to draw fluid from a sample container such as a test tube, it is necessary to know the level of the sample fluid in the tube so the pipette can be lowered to the appropriate depth. It is also necessary to detect whether the pipette tip has been properly connected to the pipetter device. Prior methods to detect the level of a fluid in a container include the use of electrical conductivity detection. This method requires the use of electrically conductive pipette tips connected to a sensitive amplifier which detects small changes in the electrical capacitance of the pipette tip when it comes in contact with an ionic fluid. Pipette tip detection in this known system is achieved by touching the end of the conductive pipette tip to a grounded conductor. Drawbacks of this approach include the higher cost of conductive pipette tips, and that the method only works effectively with ionic fluids. In other words, if the fluid is non-conductive, it will not provide a suitable electrical path to complete the circuit between the conductors in the pipette tip.
[0004] A system and method for the measurement of the level of fluid in a pipette tube has been described in U.S. Pat. No. 4,780,833, issued to Atake, the contents of which are herein incorporated by reference. Atake's system and method involves applying suction to the liquid to be measured, maintaining liquid in a micro-pipette tube or tubes, and providing the tubes with a storage portion having a large inner diameter and a slender tubular portion with a smaller diameter. A pressure gauge is included for measuring potential head in the tube or tubes. Knowing the measured hydraulic head in the pipette tube and the specific gravity of the liquid, the amount of fluid contained in the pipette tube can be ascertained.
[0005] Devices used in molecular biology methodologies can incorporate the pipette device mentioned above, with robotics, to provide precisely controlled movements to safely and carefully move sample biological fluids from one container to another. Typically, these robotic devices are capable of coupling to one or more of the aforementioned pipette tips, and employ an air pump or other suitable pressurization device to draw the sample biological fluid into the pipette tips. However, these robotic systems presently have no suitable mechanism to determine whether any of the pipette tips are defective or have been properly acquired by the robot.
[0006] Therefore, there exists a need for an improved system and method for determining the level of a fluid sample in a container. Also, there exists a need for a system and method for determining when a defective pipette tip has been acquired by a robotic device which is used in the fluid sample transfer process.
SUMMARY OF THE INVENTION
[0007] It is therefore an object of the invention to provide a system and method that effectively determines when a pipette tip has come into contact with a fluid sample in a container, to thus determine the level of fluid sample in the container, without the use of a specialized equipment, or restricted to applications in which only specific types of fluid samples can be used.
[0008] It is therefore an additional object of the invention to use existing pipette technology to determine the condition of a pipette tip has been acquired by a robotic device performing a sample transfer, so that prior to insertion pipette tip into the fluid sample, it can be discarded if it is defective, thereby preventing waste of the sample or unacceptable handling of the sample.
[0009] These and other objects of the invention are substantially achieved by providing a method for determination of a pipette tip's condition, comprising the steps of measuring pressure in a nozzle, acquiring a pipette tip with the nozzle, determining whether said pressure in the nozzle changes upon acquisition of the pipette tip, and ascertaining the condition of the acquired pipette tip based on the change in air pressure.
[0010] Still another object of the invention is substantially achieved by providing another method for determination of a pipette tip's condition, comprising, measuring pressure in a nozzle, acquiring a pipette tip with the nozzle, determining a maximum air pressure in the nozzle upon acquisition of the pipette tip and ascertaining the acquired pipette tip's condition based on the rate of change in air pressure after the maximum air pressure was reached.
[0011] A further object of the invention is substantially achieved by providing a method for discarding a non-defective pipette tip, comprising controlling an ejection assembly to engage said pipette tip from said nozzle, creating an air flow in said nozzle, determining whether said air flow causes a change in pressure in said nozzle and if said determining determines that substantially no pressure change has occurred ascertaining that the non-defective pipette tip has not been discarded.
[0012] A system for determination of a pipette tip's condition, is provided comprising an air pump in communication with a nozzle, and a pressure transducer, adapted to measure a change in air pressure in the nozzle as the pipette tip is acquired by the nozzle.
[0013] An additional system is provided according to the present invention for discarding a non-defective pipette tip, comprising an air pump with a nozzle, a pressure transducer, adapted to measure a change in air pressure in the nozzle as the pipette tip is acquired by the nozzle, and an ejection assembly adapted to eject a non-defective pipette tip.
[0014] Another method according to the present invention is provided for detecting a level of liquid in a container using a pipette tip, comprising moving the pipette tip toward the liquid in the container without aspirating through said pipette tip while detecting for a change in air pressure in said pipette tip, and ascertaining that the pipette tip has entered the fluid holding container when said change in air pressure is detected.
[0015] Lastly, another system according to the present invention is provided for detecting a level of fluid in a container using a pipette tip, comprising an air pump in communication with a nozzle, and a pressure transducer, adapted to measure a change in air pressure in the nozzle as the pipette tip is inserted onto the fluid holding container.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] The novel features and advantages of the invention will be best understood by reference to the detailed description of the specific embodiments which follows, when read in conjunction with the accompanying drawings, in which:
[0017] [0017]FIG. 1 illustrates a typical implementation of a robotic pipetting system for manipulating fluid samples which employs a system and method according to an embodiment of the present invention;
[0018] [0018]FIG. 2 is a conceptual block diagram illustrating a cross sectional view of a pipetter device and pipette tip employed in the system shown in FIG. 1;
[0019] [0019]FIG. 3 illustrates a frontal view of an industrial application of the pipetter device;
[0020] [0020]FIG. 4 illustrates a right side view of the pipetter device;
[0021] [0021]FIG. 5 illustrates a bottom perspective view of the pipetter device;
[0022] [0022]FIG. 6 illustrates a front perspective view of the pipetter device;
[0023] [0023]FIG. 7 illustrates a conceptual block diagram of a controller board assembly used with the system shown in FIG. 1;
[0024] [0024]FIG. 8 illustrates a graph depicting an example of air pressure versus time during pipette tip acquisition, for a non-defective pipette tip;
[0025] [0025]FIG. 9 illustrates a graph depicting an example of air pressure versus time during pipette tip acquisition, and its subsequent ejection, for a defective pipette tip;
[0026] [0026]FIG. 10 illustrates a graph depicting an example of air pressure versus time during ejection of a non-defective pipette tip;
[0027] [0027]FIG. 11 illustrates a graph depicting an example of air pressure versus time during insertion of a pipette tip into a fluid sample;
[0028] [0028]FIG. 12 illustrates a flow diagram of an example of a first method according to an embodiment of the invention; and
[0029] [0029]FIG. 13 illustrates a flow diagram of an example of a second method according to another embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0030] The various features of the invention will now be described with reference to the figures, in which like parts are identified with the same reference characters.
[0031] [0031]FIGS. 1 and 2 illustrate a typical implementation of a robotic pipetting system pipetter device and pipette tip, for manipulating fluid samples which employs a system and method according to an embodiment of the invention. Pipetter device 200 , attached to the end of a robotic arm 102 , can acquire disposable pipette tips 202 from a holder onto the pipetter device nozzle 204 .
[0032] The disposable pipette tips 202 are used to transfer biological (fluid) samples 218 from one container 216 in a diagnostic process to another. Each fluid sample 218 transfer requires a new pipette tip 202 to prevent cross contamination between fluid samples 218 . Additionally, each pipette tip 202 contains a filter 206 that prevents the fluid sample 218 from contaminating the nozzle 204 of the pipetter device 200 . As shown in FIG. 2, the pipetter device 200 employs a pressurization apparatus such as air pump 210 , with piston 210 A. The interior portion of air pump 210 is an air pump chamber 214 and is in communication with pressure transducer 208 , which measures the air pressure within the cavity formed within air pump 210 nozzle 204 of pipetter device 200 and pipette tip 202 . Shown also in FIG. 2 are originating position 212 and overdrive position 224 , which conveys the extent of travel of piston 210 within air pump 210 . These features will be discussed in detail below.
[0033] FIGS. 3 - 6 illustrate various views of an industrial application of the pipetter device 200 and pipette tip 202 shown in FIGS. 1 and 2. FIG. 3 illustrates a frontal view. In FIG. 3, motor 302 is shown connected to lead screw 304 . Lead screw 304 is, in turn, also connected to piston drive bar 306 . Piston drive bar 306 is connected to actuating bars 310 A and 310 B, and both actuating bars 310 A, 310 B are connected to ejection bar 312 . Springs 310 A (left side) and 310 B (right side) act upon body part 314 to resist downward motion of piston drive bar 306 , and actuating bars 310 A, 310 B and ejection bar 312 . However, springs 308 A, 308 B are chiefly intended to assist in returning the aforementioned components to their resting position. The combination of motor 302 , lead screw 304 , piston drive bar 306 , springs 308 A, 308 B, actuating bars 310 A, B and ejection bar 312 , comprise the tip ejection assembly.
[0034] The tip ejection assembly is designed to facilitate easy insertion of pipette tips 202 into nozzles 204 , yet provide a reliable means and manner for proper ejection of used and/or defective pipette tips 202 . Ejection bar 312 performs the physical ejection of pipette tips 202 . Ejection bar 312 has a plurality of holes; each hole allowing nozzle 204 to pass through it, so that it might be received into a pipette tip 202 . However, pipette tip 202 cannot pass through ejection bar 312 , because at the very bottom of pipette tip 202 , there is a flange 203 having a dimension larger than the body of pipette tip 202 and larger than the diameter of the holes in ejection bar 312 . Additionally, there are pipette tip adapters 316 , with upper adapter flange 318 A and lower adapter flange 318 B. Upper adapter flange 318 A and lower adapter flange 318 B mate with pipette tip 202 , providing a two-point seal that inn turn provides an air-tight interface between pipetter device 200 and pipette tip 202 .
[0035] To eject pipette tips 202 , motor 302 turns lead screw 304 , which in turn forces piston drive bar 306 down. As piston drive bar 306 moves down, it forces actuating bars 310 A, 310 B down. This movement causes ejection bar 312 to move down, until ejection bar 312 encounter flanges 203 of pipette tips 202 . Flange 203 and ejection bar 312 come in contact and as ejection bar 312 continues its downward movement, it ejects pipette tips 202 from its mated connection with nozzle 204 . Then, motor 302 reverses and all the components of the tip ejection assembly move in the opposite direction. Springs 308 A, 308 B, which were compressed by the downward motion now decompress and assist in forcing the entire ejection assembly to its resting position. FIGS. 4 - 6 show different views of pipetter device 200 and pipette tip 202 . FIG. 4 is a right side view; FIG. 5 is a bottom-perspective view; and FIG. 6 is a front-perspective view.
[0036] [0036]FIG. 7 illustrates a conceptual block diagram of a controller board assembly used with the system shown in FIG. 1. It is well known in the art that a robotic arm 102 may be controlled by a controller board 726 that is part of controller assembly 700 . Controller board 726 may contain processor 716 and memory 718 that stores executable software (system software) 722 that controls operation of robotic arm 102 , and pipetter device 200 .
[0037] In general, controller assembly 700 will be designed to be able to control numerous robotic arms 102 . The number of robotic arms 102 able to be controlled by a single controller board is dependent upon several factors, including, but not limited to, the processing capability of processor 716 on the controller board, data acquisition rates, amount of memory, difficulty of tasks the robotic arms must perform, and how much data must be acquired about environmental conditions or the manufacturing process itself.
[0038] As further shown in FIG. 7, a typical controller assembly includes controller board 726 , data and control cables 704 A-C and 706 that can be coupled to display 724 , motor 702 (that can control movement of piston 210 A), pressure transducer 208 and robotic arm 102 . Data and control cables 704 A-C might also be one continuous cable in some particular applications. As discussed above, controller board 726 includes memory 718 , which contains system software 722 , and can be connected by internal bus 724 to processor 716 . Processor 716 can be connected to network card 720 , by a second internal bus 726 , which can transfer collected data to and from network computer 730 . Processor 716 can communicate with analog-to-digital converter (ADC) 714 and input/output devices (I/O) 708 A by internal bus 724 . I/O 708 B is a different type of interface. Because it receives analog signals, these often require special cabling and coupling techniques to prevent the coupling of noise onto the signal. I/O 708 B are often separated from purely digital signals for these reasons. The received analog signal from I/O 708 B is first processed by AMP/filter 714 , which may contain an amplifier, filter, or even a level shifter, depending on the nature of the analog signal and ADC 712 .
[0039] Controller assembly 700 , used in conjunction with an embodiment of the invention, is shown having a single ADC 712 and amplifier circuit 714 . In general, the amplifier 714 might also include a filter, which might be necessary depending on the nature of the analog signal received by controller board 726 . Controller board 726 communicates with robotic arm 102 via control/data bus 704 B. Control bus 704 A transmits control data from processor 716 to robotic arm 102 , and receives data from robotic arm 102 , which is reported to processor 716 . In this manner, motion control data is given to robotic arm 102 , and motion data that reports the movement of robotic arm 102 is fed back to processor 716 , providing a means for checking the movement and positioning of robotic arm 102 . Such data can include relative and absolute position in three axes (x, y and z), and relative and absolute velocity, acceleration and even angular velocities and acceleration measurements in the three axes.
[0040] Controller assembly 700 communicates in a similar fashion with motor 302 . Control/data bus 704 A transmits control data to motor 302 , which controls the movement of piston 210 A of air pump 210 . Pressure transducer 208 outputs an analog pressure transducer (APT) signal 732 , transmitted on analog signal line 706 , which is connected to I/O 708 B on controller board 726 . For use in biotech and pharmaceutical industries, pressure transducer 208 is capable of detecting pressure with a resolution of 0.5 psi. After being received on I/O 708 B, APT signal 732 is input to AMP/filter 714 , which then outputs conditioned APT signal 734 to ADC 712 . ADC 712 converts conditioned APT signal 734 to a digital word, which can be processed by processor 716 . In this manner, processor 716 ascertains the air pressure in pipetter device 200 , and the methods of the invention including determining the volume of liquid in pipette device 200 , determining whether or not pipette tip 202 has entered fluid sample 218 , and determining whether or not a defective pipette tip 202 has been acquired by the robotic arm, and if not defective, when it has been discarded.
[0041] [0041]FIG. 8 illustrates a graph depicting an example of air pressure versus time during pipette tip acquisition, for a non-defective pipette tip. During pipette tip 202 acquisition, robotic arm 102 moves pipetter device 200 to a holder that contains one or more pipette tips 202 (time T 0 in FIG. 8). Robotic arm 102 then positions nozzle 204 of the pipetter device 200 over a pipette tip 202 and pushes the nozzle 204 into pipette tip receptacle 202 A (time T 1 in FIG. 8). As nozzle 204 is pushed into the pipette tip 202 , air is forced through the filter 206 . This occurs between T 1 and T 2 in FIG. 8. Referring back to FIG. 2, air would flow through nozzle 204 , filter 206 and out opening 220 of pipette tip 202 . Because filter 206 restricts airflow, a momentary increase in air pressure is produced. In describing the embodiments of the invention, the convention used is that any increase in air pressure recorded by pressure transducer 208 is shown as a positive value (above the x axis). This is the situation when air enters pipette tip 202 . If air is released, or a vacuum created, air pressure is shown decreasing or becoming a negative value.
[0042] Pressure transducer 208 mounted between the nozzle 204 and air pump 210 detects this momentary increase in air pressure and allows system software 722 to identify that a non defective pipette tip 202 has been acquired, and that filter 206 is in pipette tip 202 .
[0043] At time T 2 , the air pressure measured by transducer 208 has reached a maximum, and begins to decay from time T 2 to T 3 . During the period of time from T 2 to T 3 , filter 206 allows the air pressure to decrease to 0 . This occurs because filter 206 is porous. The periods T 1 to T 2 , and T 2 to T 3 are dependent upon the type of filter 206 (i.e. what materials and manufacturing method used), and how fast nozzle 204 is inserted into pipette tip 202 (for the T 1 to T 2 period). In some applications, it is necessary for the air pressure to return to 0. Note that for a defective pipette tip 202 , which was completely blocked, i.e., little or no porosity in filter 206 , the air pressure versus time diagram would look similar to that of FIG. 8. The chief difference would be that the time it would take for air to escape from pipette tip 202 , through filter 206 (if at all possible), would be much longer. This is shown in FIG. 8 as the dashed lines in FIG. 8. Note that the dashed line of FIG. 8 eventually does return to zero at time T 3′ . As such, it may be possible to differentiate between a non-defective pipette tip 202 and a defective pipette tip 202 due to a completely or partially blocked filter 206 , by way of examining the rate of decay of the air pressure versus time, after a maximum air pressure had been reached after insertion of pipette tip 202 . Although this may have to be done on a trial basis, such a method can ensure the detection of defective pipette tips 202 due to blocked filters 206 .
[0044] If an increase in air pressure is not detected between T 1 and T 2 , system software 722 will instruct robotic arm 102 to reject pipette tip 202 and acquire a new pipette 202 tip from the next location. Ejection of a defective pipette tip 202 is discussed in detail with respect to FIG. 9.
[0045] [0045]FIG. 9 illustrates a graph depicting an example of air pressure versus time during pipette tip acquisition, and its subsequent ejection, for a defective pipette tip. At time T 0 in FIG. 9, robotic arm 102 is moving to acquire pipette tip 202 . At time T 1 , pipette tip 202 is acquired, and the nozzle is inserted in the period of time defined between T 1 and T 2 . As previously discussed, if a non-defective pipette tip 202 was acquired, there would be a positive change in air pressure measured by pressure transducer 208 . However, in this instance, pipette tip 202 is defective, and system software 722 notes that no change in air pressure has occurred. Therefore, from time T 2 to T 3 , robotic arm 102 moves pipette device 200 to a position in which defective pipette tip 202 can be discarded.
[0046] In rejecting pipette tip 202 , robotic arm 102 moves from pipette tip 202 acquisition location, to an area where used or defective pipette tips 202 can be discarded, usually a waste container. This occurs from time T 2 to time T 3 . Pipette tips 202 are ejected from pipetter device 200 by over-driving the air pump 210 piston 210 A to overdrive position 224 in air pump chamber 214 , which engages the tip ejector assembly, and ejects defective pipette tips 202 into a waste container. The process by which this occurs was described above in detail with respect to FIGS. 3 - 7 . Because pipette tip 202 is defective (i.e. no filter 206 ). There will be no change in air pressure, even though piston 210 A has moved to overdrive position 224 . All the air simply escapes through the unrestricted opening 220 of pipette tip 202 .
[0047] As piston 210 A then moves to its originating position, which occurs at time T 4 , the air pressure will not change. This is because there is no restriction to the flow of air within pipetter device 200 . After rejecting defective pipette tip 202 , robotic arm 102 can move pipetter device 200 to its starting position, or to a position to acquire a new pipette tip 202 . While robotic arm is moving pipetter device 200 , piston 210 A is recovering from its overdrive operation.
[0048] [0048]FIG. 10 illustrates a graph depicting an example of air pressure versus time during ejection of a non-defective pipette tip. In FIG. 10, it is assumed a non-defective tip has already been acquired, and may have been used, but that in any case, it is desirable to eject it, and to acquire a new pipette tip 202 for a new use.
[0049] At time T 1 , in FIG. 10, motor 302 is beginning to move piston 210 A to overdrive position 224 . This action also caused lead screw 304 to engage the tip ejection assembly, which ultimately causes ejection bar 312 to force the non-defective pipette tip(s) 202 off nozzle(s) 204 . Because these are non-defective pipette tips 202 , filter 206 will restrict air being forced out of air pump chamber 214 , and air pressure will rise. Pressure transducer 208 measures this air pressure rise and this information is communicated to controller board 726 , and ultimately processor 716 .
[0050] At time T 2 , the tip ejection assembly has moved to a position where ejection bar 312 should force pipette tip 202 away from nozzle 204 . Between time T 2 and T 3 there will be a sudden decrease in air pressure, and the measured air pressure should, for a proper ejection, drop to a reading of, or about, zero. In general the ejection period could be sudden, but it might also be gradual; however, in a proper ejection of a non-defective pipette tip 202 the decrease in air pressure from T 2 to T 3 will be very quick. Therefore, at some short time later T 4 , a subsequent air pressure reading should indicate at, or about, zero, indicating no significant air pressure measured by pressure transducer 208 .
[0051] If, however, at time T 4 , there is still a significant air pressure reading, this might indicate the ejection of pipette tip 202 was not successfully accomplished. The measured air pressure would then be indicated by the dashed lines in FIG. 10. Processor 716 recognizes that the air pressure should have returned to zero by the time T 4 , or even T 5 , but it has not. Therefore, it will attempt the tip ejection process again. As in the case of a non-defective pipette tip 202 acquisition, discussed in reference to FIG. 8, air pressure will eventually begin to reduce because of the porous nature of filter 206 . This is shown in the drop of pressure at T 5 . From time T 5 to T 6 piston 210 A returns to its originating position 212 , and causes the air pressure to return to, or about, zero. At some time later T 7 , the ejection process will begin again. Measured air pressure will rise, and at time T 8 the ejection assembly will again have moved to the position where ejection should have occurred.
[0052] Thus, by measuring the air pressure through pressure transducer 208 , processor 716 can quickly determine whether non-defective pipetting tip 202 was properly ejected, and if not, re-active the tip ejection procedure.
[0053] [0053]FIG. 11 illustrates a graph depicting an example of air pressure versus time during insertion of a pipette tip into a fluid sample. During the transfer of fluid samples 218 there is a need to limit the depth pipette tip 202 is submerged into container 216 to prevent overflowing and to minimize fluid build-up on the outer surface of pipette tip 202 . This is accomplished by monitoring the pressure within pipette tip 202 as it is submerged into fluid sample 218 to ascertain when pipette tip 202 insertion has occurred.
[0054] The presence of fluids 218 in a container 216 is determined by measurement of the signal generated by pressure transducer 208 . Even a short insertion, e.g. several millimeters, of pipette tip 202 into fluid sample 218 , will cause a pressure change, readily ascertainable by pressure transducer 208 and system software 722 .
[0055] However, the insertion of pipette tip 202 into fluid 218 by several millimeters to achieve reliable results may not be, under some circumstances, advantageous. Sometimes there is very little fluid to be spared, or, the fluid needs to be transferred as rapidly as possible. Therefore, and alternative method for ascertaining when pipette tip 202 insertion has occurred is to move pipette tip 202 through the air-to-liquid interface 222 while pump 210 is aspirating. In this manner, an adequate signal is achieved when opening 220 of pipette tip 202 initially penetrates fluid 218 . This approach allows detection of lower volumes of fluid 218 in small containers 216 . Detection of volumes as small as a milliliter are possible because pipette tip 202 needs only penetrate the air-to-liquid interface 222 a very small amount.
[0056] Referring to FIG. 11, prior to insertion of pipette tip 202 into fluid sample 218 , robotic arm 102 moves pipetter device 200 into position during the period of time from T 0 to T 1 . From time T 1 to T 2 , pipette tip 202 is moved into fluid sample 218 . As pipette tip 202 is submerged into the fluid, fluid sample 218 compresses the air inside of pipette tip 202 . This compression registers as pressure reading P 1 . After a predetermined pressure is reached, P 1 , system software 722 commands robotic arm 102 to stop moving pipette tip 202 further into container 216 . This occurs at time T 2 . Pipetter device 200 then aspirates fluid sample 218 into opening 220 of pipette tip 202 , which is submerged in fluid sample 218 . This occurs from time T 2 to T 3 , and the pressure changes from P 1 to P 2 . P 2 is negative because air pump 210 is creating a vacuum to draw fluid sample 218 into pipette tip 202 . As fluid is drawn into pipette tip 202 , robotic arm 102 moves pipette tip 202 downward into container 216 at a speed based on the rate of aspiration and the diameter of the container 216 .
[0057] The volume of fluid aspirated into the pipette tip can be verified using pressure transducer 208 . For example, U.S. Pat. No. 4,780,833, the contents of which are incorporated herein by reference, describes a system and method for determining the volume of a liquid sample drawn into a similar pipetter device 200 , by measuring the head pressure above the fluid column with knowledge of the fluid's specific gravity.
[0058] At time T 3 aspiration of pipette tip 202 is stopped. The measured air pressure settles from P 2 to P 3 . P 3 is the air pressure that corresponds directly to the volume of liquid in pipette tip 202 . P 2 is the air pressure equal to the volume of aspirated fluid plus the friction force of the aspirated fluid sample 218 A to pipette tip 202 (inner wall surface) interface, due to surface tension. As the fluid is drawn up, it resists movement through friction; that friction is caused by, or directly proportional to, the surface tension of the fluid. When aspiration ceases, so does movement of the fluid and the friction due to the fluid's surface tension. Thus, at time T 4 , the measured air pressure is equivalent to the weight of aspirated fluid sample 218 A, and through use of its specific gravity (which is known, a priori), the fluid's volume is likewise known.
[0059] From time T 4 to T 5 , robotic arm 102 , at the command of system software 322 , moves pipette device 200 to another location where another container, 216 A, might be located to dispense the aspirated fluid into. At time T 5 , piston 210 A begins pumping the aspirated fluid out, and at time T 6 the desired amount of fluid has been expelled. The resultant pressure, P 4 or P 4 might still be negative (i.e., in the case that only a small amount of aspirated fluid was pumped out, and there is still a negative pressure retaining the fluid) or positive (i.e., in the case that all or nearly all of the fluid pumped out, requiring greater “pumping” force).
[0060] [0060]FIG. 12 illustrates a flow diagram of a first method according to an embodiment of the invention. The flow diagram illustrated in FIG. 12 shows the steps in a method for detecting defective pipette tips, as discussed above. The method begins with step 1202 , in which pressure transducer 208 measures a first air pressure, which is recorded by processor 716 . In step 1204 , robotic arm 102 moves pipetter device 200 such that nozzle 204 may be inserted over pipette tip receptacle 202 A of pipette tip 202 . In step 1206 , a second air pressure is measured and recorded, soon after the pipette tip 202 has been inserted over nozzle 204 . Processor 716 then compares the first air pressure to the second air pressure: If the second air pressure is greater than the first air pressure, then a non-defective pipette tip 202 has been acquired by robotic arm 102 , and it may be used for acquiring fluids (yes path 1210 from decision box 1208 ).
[0061] If however, the first and second air pressure are substantially the same, i.e., there has been no change in air pressure in the acquisition of pipette tip 202 by robotic arm 102 , then processor 716 determines that a defective pipette tip 202 has been acquired, and can discard it, using the ejection process discussed in reference with FIG. 9 (no path 1212 from decision box 1208 ).
[0062] [0062]FIG. 13 illustrates a flow diagram of a second method according to another embodiment of the invention. The flow diagram illustrated in FIG. 13 shows the steps in a method for determining whether a non-defective pipette tip has been ejected, as discussed above. The method according to FIG. 13 begins with step 1302 . In step 1302 , air pressure is measured continuously by pressure transducer 208 , and recorded by processor 716 . Then, in step 1304 , processor 716 decides to eject the non-defective pipette tip 202 , and causes robotic arm to engage the tip ejection assembly. Engaging the tip ejection assembly means that motor 302 begins to overdrive air pump 210 , and turn lead screw 304 , etc., as described with reference to FIGS. 3 - 6 . As the piston bar reaches its overdrive position 224 , processor 716 again monitors the measured air pressure: At this point, the tip ejection assembly should have forced pipette tip(s) 202 off nozzle(s) 204 . Therefore, in step 1308 , processor 716 compares the air pressure just before piston bar 210 reached overdrive position 224 , and the air pressure just after piston bar reached overdrive position 224 , to determine whether a substantial and sudden decrease in air pressure has occurred. This decrease in air pressure would be caused by air being suddenly released when pipette tip 202 was forcibly ejected from nozzle 204 , and the pressurized air in air pump chamber 214 and pipette tip receptacle 202 A was released into the atmosphere. If there was a sudden and substantial decrease in the measured air pressures, then pipette tip 202 was properly ejected (yes path 1310 from decision box 1308 ).
[0063] If however, there was no sudden and substantial decrease in the air pressure between the time just before piston bar 210 reached overdrive position 224 , and the air pressure just after piston bar reached overdrive position 224 , the processor 716 determines that pipette tip 202 was not properly ejected (no path 1712 from decision box 1708 ). It will cause piston bar 210 to return to an intermediate position (i.e., between its originating position and overdrive position) and begin the process of ejecting pipette tip 202 again (i.e., it returns to step 1304 ). It may do this several times before pipette tip 202 is properly ejected.
[0064] The embodiments described above are merely given as examples and it should be understood that the invention is not limited thereto. It is of course possible to embody the invention in specific forms other than those described without departing from the spirit and scope of the invention. Further modifications and improvements, which retain the basic underlying principles disclosed and claimed herein, are within the spirit and scope of this invention. | A system and method for determining when a defective or non-defective pipette tip has been acquired by a robotic device performing a sample transfer, prior to the insertion of the defective pipette tip into the fluid sample, thereby preventing waste of the sample or unacceptable handling of the sample. Furthermore, the system and method can effectively eject pipette tips, and in some circumstances, determine whether the ejection of the pipette tip was successful. | 1 |
[0001] This application claims benefit of Ser. No. 201131327, filed 29 Jul. 2011 in Spain and which application is incorporated herein by reference. To the extent appropriate, a claim of priority is made to the above disclosed application.
FIELD OF THE INVENTION
[0002] The present invention relates to a drive system for driving moving walkways, and more specifically for driving moving walkways used for transporting people and goods and which are formed by an endless band of pallets which move on side guides.
[0003] Conventional moving walkways for the indicated purpose are made up of a set of pallets which move on guides, which pallets are secured and fitted on a structure supporting the weight of the components and users. The walkways are further provided with a glass or opaque balustrade which is also secured to the same support structure and on which a handrail moves at the same speed as the pallets.
BACKGROUND OF THE INVENTION
[0004] Conventional systems for transporting passengers/goods such as moving walkways include a chain of conveyor pallets which move in a track for the purpose of providing a continuous movement along a specific path. The conveyor pallets are connected to said chain track which moves as a result of a drive system. The drive system normally consists of a chain of conveyor plates, cogged wheels, a shaft and an electric geared motor. The electric motor drives the shaft to which there are integrally attached cogged wheels, which transmit the movement to the links of the chain of conveyor pallets. The conveyor pallets move in the same manner as said chain. The drive system is located at one of the ends of the moving walkway whereas the elements responsible for tensing the system are normally located at the opposite end. The turnover of the conveyor pallets which travel the entire moving walkway in the lower part completing the return trip occurs at these end areas of the moving walkway.
[0005] A series of new designs aiming to reduce the maximum machine height has emerged in recent years; the conventional drive system must therefore be modified.
[0006] There are several solutions which were chosen according to the walkway concept being used. One of these solutions is described in WO 05042392 from Kone Corporation, according to which the drive system is at least partially located inside the balustrade which is made possible by means of using a flat motor. The drive thus occurs by means of a series of belts or chains which finally drive the chain of pallets which has a short pitch to enable turning over in the small available space, but it otherwise works as a conventional walkway chain.
[0007] U.S. Pat. No. 7,341,139 also from Kone Corporation describes the drive of a handrail and its attachment to the pallets drive and motor system. U.S. Pat. No. 7,353,932 from Kone Corporation describes the arrangement of a band of pallets and the possible simultaneous use of two drive motors.
[0008] ThyssenKrupp's Spanish patent 200601651 describes a compact walkway based on the concept of a band formed by pallets having a pitch shorter than the conventional ones. This walkway comprises a drive system moving the pallets of a moving walkway through drive chains which directly engage the lower part of the drive link chains. The drive chain has separate drive rollers which are made of deformable and elastic materials. The links of the drive chains are connected to one another by attachment shafts and have teeth and jaws in the lower part to engage the drive chain and the rollers.
[0009] ThyssenKrupp's Spanish patent with application number 2009311290 proposes a drive system for driving chainless escalators and moving walkways by means of using a set of roller wheels integral with shafts assembled between the departing and returning sections of the band of steps or pallets and engaging either the steps or pallets directly through engaging formations of said steps or pallets on their inner surface or similar formations present in a chain integral with the band of pallets or steps.
[0010] All these applications have the drawback of the limitation of power which can be transmitted by the drives to the band of steps or pallets due to the small available space in comparison with conventional drives, hindering the use of several transmission elements and the suitable reinforcement thereof.
[0011] These limitations in terms of power transmitted restrict the maximum distance which can “be provided” with these systems in both directions of movement. Another drawback of having the drive unit at only one end is that for very long horizontal walkways it is necessary to apply in the case of “down” direction (drive unit in the upper head) an excessive force from the tensing station located in the head opposite the drive unit in order to prevent the appearance of areas with excessive negative stresses in the chain/band of pallets. This is so because in that direction the drive pushes the band of pallets and all the load thereon and does not pull it as occurs in the “up” direction.
SUMMARY OF THE INVENTION
[0012] The present invention relates to a drive system for driving moving walkways of the type initially described which entails a modification in the conventional concept for driving moving walkways.
[0013] The object of the invention is to provide a traction scheme based on using several drive units for the purpose of overcoming the problems described above. A drive unit will particularly be used at each end of the walkway, the drive units are controlled such that they work cooperatively.
[0014] The drive system of the invention comprises a drive unit arranged at each end of the walkway, control means for controlling each drive unit and overall control means for controlling the set of drive units of the drive system.
[0015] The drive units can each include one or more motors and controlling the motors of the drive units so that they work cooperatively, i.e., sharing the total load/power of the system between them is necessary in order to assure a correct operation of the drive system. The motors of the drive units arranged at both ends of the walkway will thus together provide the power necessary for driving said walkway.
[0016] The control means for controlling each drive unit will directly control the motor or motors of said drive unit for providing the torque and speed required at all times.
[0017] In turn, the overall control means will include a control and/or supervision algorithm, responsible for executing the coordination strategy between the motors of the drive units and issuing the necessary commands to the control means for controlling each drive unit.
[0018] The control means for controlling the motor or motors of each drive unit can comprise a frequency variator for alternating current motors with a closed loop vector control algorithm. The frequency variator can include an input rectifier, responsible for generating the direct voltage for a bus, from where a DC-AC inverter powering the motor or motors of the corresponding drive unit is powered.
[0019] The drive units arranged on either side of the walkway will work together cooperatively with a master-slave load sharing algorithm, the drive unit acting as master providing a fixed amount of torque greater than 50%, and the unit acting as slave providing the rest. The master-slave load sharing algorithm can be dependent on or independent of the direction of rotation.
[0020] The master drive unit can be controlled in speed and the slave drive unit in torque tracking mode for tracking the torque set point corresponding to the torque exerted at all times by the master drive unit, set for respecting the percentages of load/torque sharing established between both units. The master and slave drive units can also be controlled in speed, both speed set points being the same and the slave drive unit having a torque limit which will correspond to the torque exerted by the master drive unit at all times, set for respecting the percentages of load/torque sharing established between both units.
[0021] The master unit can be formed by the drive unit furthest from the passenger entrance, therefore being dependent on the direction of movement. This master unit must provide most of the power required by the system, the other motor being a mere assisting slave.
[0022] Different coordination strategies can be used, for example the motor placed in the passenger exit area for this direction of movement can be the master, providing the walkway with most of the power required, the other motor being limited to assisting it. Another possible embodiment would be setting the upper head motor of the walkway as the master of the system, providing as in the case above most of the power required for both directions of movement. The motor located in the lower head would always be limited to providing the additional power required by the system according to its load state.
[0023] The overall control means for controlling the entire traction system will be responsible for executing this motor coordination strategy, issuing the necessary commands to the control means for controlling said motors. The control means are responsible for directly controlling the motors so that they provide the torque and the speed required at all times. A possible embodiment of this device is that of a frequency variator for alternating current motors by means of PWM based on an architecture of AC/DC rectification, DC Bus and a DC/AC converter with a PWM output and control, although other embodiments are possible.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] An embodiment of the drive system of the invention is shown in the attached drawings:
[0025] FIG. 1 shows a schematic view of a conventional walkway with 2 drive units.
[0026] FIG. 2 shows a diagram of the control and actuation means of the drive system of the invention.
[0027] FIG. 3 a shows the stress distribution in a walkway with a drive unit in the up direction.
[0028] FIG. 3 b shows the stress distribution in a walkway with a drive unit in the downward direction.
[0029] FIG. 4 a shows the stress distribution in a walkway with two drive units in the up direction and master dependent on the direction of rotation.
[0030] FIG. 4 b shows the stress distribution in a walkway with two drive units in the down direction and master dependent on the direction of rotation.
[0031] FIG. 5 a shows the stress distribution in a walkway with two drive units in the up direction and master in the upper head.
[0032] FIG. 5 b shows the stress distribution in a walkway with two drive units in the down direction and master in the upper head.
[0033] FIG. 6 shows the traction system diagram of the band of pallets.
DETAILED DESCRIPTION
[0034] FIG. 1 schematically shows the different components of the drive system of the invention which include a drive system 1 of the band of pallets and at each end of the walkway a drive unit made up of one or more motors 2 - 2 ′, control means 3 - 3 ′ for controlling the motors 2 - 2 ′, and overall control means 4 for controlling the system.
[0035] A preferred not exclusive embodiment of the drive system for driving the band of pallets 1 is that described in ES 2342532 from the same applicants consisting of, as shown in FIG. 6 , a series of wheels 5 with rollers 5 ′. The wheels 5 are arranged on shafts 6 perpendicular to the direction of movement of the band of pallets 1 . The shafts 6 are driven by the motor/motors by means of a series of transmissions, for example by gears. The power is transmitted to the band of pallets 1 by means of engaging the rollers 6 in the engaging formations 7 of the pallets.
[0036] The control means 3 - 3 ′ for controlling the motors can preferably consist of, although not exclusively, a frequency variator for alternating current motors with a closed loop vector control algorithm, the block diagram of which corresponds to that indicated in FIG. 2 with the references 3 - 3 ′: it contains an input rectifier 8 - 8 ′ which generates the direct voltage for a DC BUS 9 - 9 ′ from where the DC-AC inverter 10 - 10 ′ powering the motor 2 - 2 ′ is powered.
[0037] The control means 3 - 3 ′ for controlling the motor must be capable of controlling the motor 2 - 2 ′ for tracking the speed and/or position and/or torque set points indicated by the overall control means of the system as well as providing it with several state variables such as torque exerted by the motor, speed of rotation, etc. . . To that end, it may need information from other external sensors such as motor speed and/or position measuring sensors (encoders), sensors for current flowing through the motor phases, torquemeters, etc. . .
[0038] A preferred embodiment of a motor coordination algorithm consists of defining a master motor which will always be on the side furthest from the passenger entrance, therefore it is dependent on the direction of movement. This master must provide most of the power required by the system the other motor being a mere assisting slave.
[0039] In the preferred embodiment, the overall control and supervision means of the system send commands to the control means for controlling the motors so that the master provides a fixed amount of torque, for example 60%, and the slave provides the rest, for example 40%.
[0040] To perform this, the overall control means of the system sends commands to the control means for controlling the master motor so that it maintains a constant speed in the selected direction of movement, which will be that of the band of pallets. At the same time it sends the current torque value of the master to the slave motor control system. This motor will be controlled in torque mode, i.e., its control means will attempt to make the motor reach the torque set point by not actively controlling its speed.
[0041] This embodiment of the mechanism for transferring load from the master to the slave can work in the following manner: Initially the master motor sets the speed of the system which requires an initial_P_M torque, this value is transferred by the overall control means of the system to the slave. An infinitesimal instant later the slave, and therefore the rest of the system, is accelerated above the nominal speed of the master for the purpose of reaching the initial_P_M torque, the control means for controlling the master responded by reducing its torque to attempt to keep the initial speed of the system constant. This new torque value of the master is transferred again to the slave such that after several iterations of this process a torque equilibrium is reached between the two motors according to the torque sharing percentage established (for example 60% master, 40% slave) and the nominal speed also being maintained.
[0042] To maximally reduce the small speed oscillations of the system during load sharing it is necessary that the different control means are efficiently interconnected in terms of reliability, precision and speed. This will assure a quick transfer of the operation variables of each motor such as torque exerted, speed, etc. . . to the control means and these can thus send the suitable commands.
[0043] A possible embodiment would be by means of using analogue signals in the form of 4-20 mA current loop allowing greater speed, precision and is suitable for large transmission distances of hundreds of metres.
[0044] At the same time as the motor coordination algorithm is executed the control means must control that the state of the system is correct, for example in case of an unjustified over-torque in one of the motors the system has to be taken to a safe position. Another situation to control would be the failure of one of the motors or of its control system.
[0045] The preferred architecture for implementing overall control means of the system would be that depicted in FIG. 2 , with reference 11 , being made up of:
One or several CPUs 12 which will execute the control algorithms. One or several external signal input modules 13 such as for example the order of movement, direction of forward or reverse movement, nominal speed, etc. . . One or several external signal output modules 14 such as state of the system/failure, current speed, current torque exerted, etc. . . One or several output modules 15 - 15 ′ per motor control means present, usually two: control means 3 for controlling the upper head motor and control means 3 ′ for controlling the lower head. These will process the set point signals sent to these systems such as for example torque to be exerted, speed to be maintained, etc. . . One or several input modules 16 - 16 ′ per motor control means present, usually two: control means for controlling the upper head motor and control means for controlling the lower head. These will process the state signal of these systems such as for example the torque exerted, current speed, etc. . .
[0051] Having described the above a stress distribution corresponding to FIGS. 4 a and 4 b (preferred embodiment with a floating master) or to FIGS. 5 a and 5 b (embodiment with a fixed master independent of the direction of rotation) where how the maximum stress levels are lower than those obtained with a single and fixed drive system can be seen ( FIGS. 3 a and 3 b ), is to be achieved. | A drive system for driving moving walkways, includes a drive unit ( 2 - 2′ ) arranged at each end of the walkway ( 1 ), a controller ( 3 - 3′ ) for controlling each drive unit and overall control ( 4 ) for controlling the set of drive units ( 3 - 3′ ). | 8 |
FIELD OF THE INVENTION
[0001] The present invention relates to magnetic nanoparticles, and in particular to magnetic nanoparticles having immobilised ligands and their use in studying the interaction of these ligands with other species. The present invention further relates to applications of the nanoparticles, for example for screening, diagnosis and therapy.
BACKGROUND OF THE INVENTION
[0002] The development of methodologies to produce nanoparticles with bio-responsive properties has opened the way for producing useful tools for molecular diagnostics, therapeutics and biotechnology [1]. Metal, semiconductor and magnetic colloidal nanoparticles are presently under intensive study for potential applications [2].
[0003] Nanoparticles containing paramagnetic materials such as iron oxide have been made which exhibit unusually strong magnetic properties under external magnetic fields. These magnetic nanoparticles can be used in many biomedical applications, including cell separation, in vivo cell and tissue labelling, contrast enhancement in magnetic resonance imaging, tumour targeting, hyperthermia therapies and drug delivery.
[0004] For such applications, the nanoparticles should preferably be small enough to avoid provoking an immune response and to be taken up by cells, where necessary. It is also useful if the size of the particles can be controlled as the particles should be of approximately the same size so they display the same magnetic properties. The particles should also preferably be chemically stable, so they are not broken down by the body.
[0005] In is also preferred that magnetic nanoparticles for use in biomedicine are soluble, especially in water, in order that they may be stored and administered effectively. Ideally, such particles would be stable in solution and would not aggregate, either when stored before use or in the body. Magnetic nanoparticles tend to clump together in solution because they attract each other. If this happened in the body it could impede blood flow and potentially be dangerous; in colloidal solution it would make the colloid difficult to use.
[0006] Previously, commercially available iron oxide particles have been used in cell sorting and separation [3]. Monodisperse magnetic nanoparticles of Fe/Pt [4], Co and Co/Fe [5], Fe [6], and iron oxides [7] have recently been synthesised by solution chemistry for materials applications [8]. Iron oxide nanoparticles coated with cross-linked dextran to prevent clumping have also been described, see for example WO 03/005029.
[0007] Ideally, the magnetic nanoparticles are made of elemental magnetic metal rather than metal oxide, as elemental metal is a better enhancer of magnetic imaging. However, such nanoparticles are often chemically unstable, as the metal may oxidise. One possibility for increasing the chemical stability of magnetic nanoparticles is to synthesise them from a magnetic metal with a passive metal to stabilise the magnetic metal.
[0008] US 2002/0068187 discloses surfactant protected gold-iron core-shell nanoparticles synthesised by means of reverse micelles. However, this method is complex, requiring three synthesis steps. The multi-layered composition of the resulting particles also increases the lower size limit for the particles, which can be a disadvantage if very small particles are required [14].
[0009] U.S. Pat. No. 6,254,662 discloses use of FePt and CoPt alloy nanoparticles to form nanocrystalline thin films on a solid surface, for use in making ultra-high density recording media. Other uses of the films are mentioned in the patent, including use as magnetic bias films and magnetic tips for magnetic force microscopy, but biomedical applications are not envisaged.
[0010] For many of the applications described above, it is necessary to link the nanoparticles to biologically active molecules such as ligands that bind to intracellular or extracellular molecules. Such ligands may for example be carbohydrate, nucleic acid or protein.
[0011] U.S. Pat. No. 6,514,481 discloses iron oxide nanoparticles coated with a silica shell, where the shell is linked to a targeting molecule such as a peptide via a spacer molecule. WO 02/098364 and WO 01/19405 disclose magnetic metal oxide nanoparticles coated with dextran and functionalised with peptides and oligonucleotides. Similar strategies have been used to prepare nanoparticles for intracellular labelling [9] and as nanosensors.[10]. All these methods are time-consuming multi-step methods requiring that the nanoparticles be coated with dextran or silica, the coated nanoparticles be functionalised so they will bind the ligand, and finally that the ligand be bound to the nanoparticles.
[0012] WO 03/073444 discloses superparamagnetic nanoparticles having a cores formed from Au and Fe metal atoms in a ratio of at least 3:7. The application says that ligands can be linked to the core via a sulphide group and that the nanoparticles are used for forming nanoelectronic devices. The cores of the nanoparticles have diameters in the range of 5 nm to 50 nm.
[0013] WO 02/093140 discloses magnetic nanowires which comprise one or more segments and functional groups or ligands associated with a at least one of said segments. The nanowires have a diameter in the range of about 10-300 nm and a length from 10 nm to tens of microns. The segments of the nanowires may be formed from materials such as gold, silver, platinum, copper, iron and cobalt in pure or alloyed form and the functional groups may be atoms or groups of atoms that are capable of further chemical reactivity such as reacting with a ligand to attach the ligand to the wire, or to bind a target molecule. Although a range of possible ways of associating the ligands and the nanowires are proposed, the examples rely on the ionic interaction between ligands containing carboxylic acid groups and the nanowire.
[0014] U.S. Pat. No. 6,531,304 discloses a nanoscale colloid formed from metal alloys which is reacted and non-covalently binds a polysaccharide or sugar “modifier”.
[0015] WO 02/32404 discloses water soluble nano-tools for studying carbohydrate mediated interactions [11], [12]. These tools are gold glyconanoparticles and cadmium sulphide glyco-nanodots incorporating carbohydrate antigens. These water soluble gold and semiconductor nanodots are stable for months in physiological solutions and present exceptionally small core sizes. They are resistant to glycosidases and do not present cytotoxicity. They are also useful platforms for basic studies of carbohydrate interactions [13] and are tools for biotechnological and biomedical applications. However, these nanoparticles are not magnetic.
[0016] There is therefore a continuing need in the art for stable magnetic nanoparticles which are bound to ligands to make them suitable for biomedical uses, which can be synthesised to a desired size, and which can be produced by a simple, reliable synthesis method.
SUMMARY OF THE INVENTION
[0017] Broadly, the present invention provides materials and methods for producing magnetic nanoparticles that are particularly suitable for use in biomedical applications. In particular, the present invention provides magnetic nanoparticles which are employed as a substrate for immobilising a plurality of ligands, where the ligands are covalently linked to the core of the nanoparticle. The ligands may comprise carbohydrate groups, peptides, protein domains, nucleic acid segments or fluorescent groups. These nanoparticles can then be used to study ligand mediated interactions, e.g. with other carbohydrates, proteins or nucleic acids, and as therapeutics and diagnostic reagents. In some embodiments, the particles have the further advantage that they are soluble, e.g. in water and a range of organic solvents, and can be used in a variety of homogeneous application formats.
[0018] The inventors have now developed magnetic nanoparticles with size in the nanometre scale which form stable colloidal aqueous solutions (ferrofluids). The methods described herein constitute a simple and versatile approach by which neoglycoconjugates of significant carbohydrates are covalently linked to gold/iron clusters as a method for tailoring stable, water-soluble, magnetic glyconanoparticles with globular shapes and highly polyvalent carbohydrate surfaces. The methodology also allows the attachment of many other molecules directly to the nanocluster.
[0019] Accordingly, in a first aspect, the present invention provides a particle comprising a magnetic core, such as a metallic core, linked to a plurality of ligands. The ligands may comprise carbohydrate groups, peptides, protein domains, nucleic acid segments or other biological macromolecules. The ligands may additionally or alternatively comprise fluorescent groups.
[0020] Preferably, where the magnetic core comprises passive metal atoms and magnetic metal atoms, and the ratio of passive metal atoms to magnetic metal atoms in the core is between about 5:0.1 and about 2:5. More preferably, the ratio is between about 5:0.1 and about 5:1.
[0021] As used herein, the term “passive metal” refers to metals which do not show magnetic properties and are chemically stable to oxidation.
[0022] The passive metals of the invention may be diamagnetic. “Diamagnetic” refers to materials with all paired electrons which thus have no permanent net magnetic moment per atom. “Magnetic” materials have some unpaired electrons and are positively susceptible to external magnetic fields—that is, the external magnetic field induces the electrons to line up with the applied field, so the magnetic moments of the electrons are aligned.
[0023] Magnetic materials may be paramagnetic, superparamagnetic or ferromagnetic. Paramagnetic materials are not very susceptible to external magnetic fields and do not retain their magnetic properties when the external magnetic field is removed. Ferromagnetic materials are highly susceptible to external magnetic fields and contain magnetic domains even when no external magnetic field is present, because neighbouring atoms cooperate so their electron spins are parallel. External magnetic fields align the magnetic moments of neighbouring domains, magnifying the magnetic affect. Very small particles of materials that normally have ferromagnetic properties are not ferromagnetic, as the cooperative effect does not occur in particles of 300 nm or less so the material has no permanent magnetism. However, the particles are still very susceptible to external magnetic fields and have strong paramagnetic properties, and are known as superparamagnetic. Preferably, the nanoparticles of the invention are superparamagnetic.
[0024] In one embodiment, the nanoparticle consists of a core comprising passive metal atoms and magnetic metal atoms, which core is covalently linked to a plurality of ligands. Preferably, the ratio of passive metal atoms to magnetic metal atoms in the core is between about 5:0.1 and about 2:5. More preferably, the ratio is between about 5:0.1 and about 5:1.
[0025] In a further aspect, the present invention provides compositions comprising populations of one or more of the above defined particles. In some embodiments, the populations of nanoparticles may have different densities of the same or different ligands attached to the core.
[0026] In a further aspect, the present invention provides the above defined particles for use in a method of medical treatment.
[0027] In a further aspect, the present invention provides the use of the above defined particles for the preparation of a medicament for the treatment of a condition ameliorated by the administration of the ligand. By way of example, this may occur as the ligand blocks a carbohydrate mediated interaction that would otherwise tend to lead to a pathology.
[0028] In this embodiment, the present invention has advantages over prior art approaches for treating conditions involving carbohydrate mediated interactions. As described above, typically the interactions are polyvalent whereas the agent used to treat the interactions are often only capable of modulating one or a few of these interactions. This has the result that it is difficult to deliver an agent to the site of the interaction which is capable of reliably modulating the interaction for the desired therapeutic effect. In contrast to this problem, the present invention provides agents having a plurality of ligands for modulating the carbohydrate mediated interactions, potentially overcoming the difficulty in modulating the polyvalent interactions.
[0029] In preferred embodiments, the mean diameter of the core, preferably the metallic core, is between 0.5 and 100 nm, more preferably between 1 and 50 nm, more preferably between 1 and 20 nm. More preferably, the mean diameter of the core is below 5 nm, more preferably below 2.5 nm, and still more preferably below 2 nm. The mean diameter can be measured using techniques well known in the art such as transmission electron microscopy.
[0030] The core material can be a metal (e.g. Au, or another passive, metal atom) or may be formed of more than one type of atom. Preferably, the core material is a composite or an alloy of a passive metal and a magnetic metal. Preferred passive metals are Au, Ag, Pt or Cu and preferred magnetic metals are Fe and Co, with the most preferred composite being Au/Fe. Other composites or alloys may also be used. Nanoparticle cores may also be formed from alloys including Au/Fe, Au/Cu, Au/Gd, Au/Zn, Au/Fe/Cu, Au/Fe/Gd and Au/Fe/Cu/Gd, and may be used in the present invention. Preferred core materials are Au and Fe, with the most preferred material being Au. The cores of the nanoparticles preferably comprise between 100 and 500 atoms (e.g. gold atoms), more preferably between about 20 and 500 atoms, and still more preferably between about 50 and 500 atoms, to provide core diameters in the nanometre range. A further preferred example of nanoparticles of the present invention have cores formed from Au atoms and Gd, e.g. Gd III, e.g. having a mean diameter less than 10 nm, more preferably less than 5 nm and most preferably about 2.5 nm. Preferred particles of this type comprise between about 1-20% Gd atoms and 99 to 80% Au atoms, and more preferably between about 1-10% Gd and 99 to 90% Au, based on the ratio of the ratio of respective metal atoms present in the core of the nanoparticle.
[0031] For some applications, core materials are doped or labelled with one or more atoms that are NMR active, allowing the nanoparticles to be detected using NMR, both in vitro and in vivo. Examples of NMR active atoms include Mn +2 , Gd +3 , Eu +2 , Cu +2 , V +2 , Co +2 , Ni +2 , Fe +2 , Fe +3 and lanthanides +3 , or the quantum dots described elsewhere in this application.
[0032] Nanoparticle cores comprising semiconductor atoms can be detected as nanometre scale semiconductor crystals are capable of acting as quantum dots, that is they can absorb light thereby exciting electrons in the materials to higher-energy levels, subsequently releasing photons of light at frequencies characteristic of the material. An example of a semiconductor core material is cadmium selenide, cadmium sulphide, cadmium tellurium. Also included are the zinc compounds such as zinc sulphide.
[0033] In some embodiments, the nanoparticle of the present invention or ligand(s) may comprise a detectable label. The label may be an element of the core of the nanoparticle or the ligand. The label may be detectable because of an intrinsic property of that element of the nanoparticle or by being linked, conjugated or associated with a further moiety that is detectable. Preferred examples of labels include a label which is a fluorescent group, a radionuclide, a magnetic label or a dye. Fluorescent groups include fluorescein, rhodamine or tetramethyl rhodamine, Texas-Red, Cy3, Cy5, etc., and may be detected by excitation of the fluorescent label and detection of the emitted light using Raman scattering spectroscopy (Y. C. Cao, R. Jin, C. A. Mirkin, Science 2002, 297:1536-1539).
[0034] In some embodiments, the nanoparticles may comprise a radionuclide for use in detecting the nanoparticle using the radioactivity emitted by the radionuclide, e.g. by using PET or SPECT, or for therapy, i.e. for killing target cells. Examples of radionuclides commonly used in the art that could be readily adapted for use in the present invention include 99m Tc, which exists in a variety of oxidation states although the most stable is TcO 4− ; 32 P or 33 P; 57 Co; 59 Fe; 67 Cu which is often used as Cu 2+ salts; 67 Ga which is commonly used a Ga 3+ salt, e.g. gallium citrate; 68 Ge; 82 Sr; 99 Mo; 103 Pd; 111 In which is generally used as In 3+ salts; 125 I or 131 I which is generally used as sodium-iodide; 137 Cs; 153 Gd; 153 Sm; 158 Au; 186 Re; 201 Tl generally used as a Tl + salt such as thallium chloride; 39 Y 3+ ; 71 Lu 3+ ; and 24 Cr 2+ . The general use of radionuclides as labels and tracers is well known in the art and could readily be adapted by the skilled person for use in the aspects of the present invention. The radionuclides may be employed most easily by doping the cores of the nanoparticles or including them as labels present as part of ligands immobilised on the nanoparticles.
[0035] Previously described magnetic nanoparticles for biological applications are almost always made from a magnetic metal oxide, usually iron oxide (magnetite). Nanoparticles comprising Fe and Au have been made, as described above, but have not been used for biological applications or bound to biologically active molecules. These nanoparticles are synthesised as a “nano-onion” comprising a gold core surrounded by an iron shell which is coated with gold to prevent oxidation. The nanoparticles described herein, which have a heterogeneous core comprising both gold and iron atoms, are an improvement over the previously described particles because they can be synthesised in a single simple step, rather than requiring multiple synthesis steps to form the different shells of the nano-onion.
[0036] The nanoparticles and the results of their interactions can be detected using a number of techniques well known in the art. These can range from detecting the aggregation that results when the nanoparticles bind to another species, e.g. by simple visual inspection or by using light scattering (transmittance of a solution containing the nanoparticles), to using sophisticated techniques such as transmission electron microscopy (TEM) or atomic force microscopy (AFM) to visualise the nanoparticles. A further method of detecting metal particles is to employ plasmon resonance, that is the excitation of electrons at the surface of a metal, usually caused by optical radiation. The phenomenon of surface plasmon resonance (SPR) exists at the interface of a metal (such as Ag or Au) and a dielectric material such as air or water. As changes in SPR occur as analytes bind to the ligand immobilised on the surface of a nanoparticle changing the refractive index of the interface. A further advantage of SPR is that it can be used to monitor real time interactions. As mentioned above, if the nanoparticles includes or is doped with atoms which are NMR active then this technique can be used to detect the particles, both in vitro or in vivo, using techniques well known in the art. Nanoparticles can also be detected as described in [18], using a system based on quantitative signal amplification using the nanoparticle-promoted reduction of silver (I) and using a flatbed scanner as a reader. Fluorescence spectroscopy can be used if the nanoparticles include ligands combining carbohydrate groups and fluorescent probes. Also, isotopic labelling of the carbohydrate can be used to facilitate their detection.
[0037] The ligand linked to the core may comprise one or more carbohydrate (saccharide) groups, e.g. comprising a polysaccharide, an oligosaccharide or a single saccharide group. The ligand may be also be a glycanoconjugate such as a glycolipid or a glycoprotein. In addition to the carbohydrate group, the ligand may additionally comprise one or more of a peptide group, a protein domain, a nucleic acid molecule (e.g. a DNA segment, a single or double stranded nucleic acid molecule, a single or double stranded RNA molecule, a RNA molecule having from 17 to 30 ribonucleotides, e.g. a siRNA or miRNA ligand) and/or a fluorescent probe.
[0038] In another embodiment, the ligand may be a peptide or a protein. These may be peptides which binds to receptors on a cell, or they may be antibodies, or therapeutic proteins.
[0039] In a further embodiment, the ligand may be a nucleic acid molecule. The nucleic acid may be an oligonucleotide probe that binds to a sequence within the cell. Alternatively, the nucleic acid may comprise an encoding gene sequence for delivery to a cell.
[0040] The particles may have more than one species of ligand immobilised thereon, e.g. 2, 3, 4, 5, 10, 20 or 100 different ligands. Alternatively or additionally a plurality of different types of particles can be employed together. Ligands with multiple attachment sites may be linked to a plurality of nanoparticle cores, e.g. 2, 3, or 4 particles. An example of this would be nanoparticle cores linked to the ends of polypeptides or nucleic acid molecules.
[0041] In preferred embodiments, the mean number of ligands linked to an individual metallic core of the particle is at least 20 ligands, more preferably at least 50 ligands, and most preferably 60 ligands.
[0042] Preferably, the ligands are attached covalently to the core of the particles. Protocols for carrying this out are known in the art, although the work described herein is the first report of the reactions being used to covalently bond ligands to the core of the particle.
[0043] This may be carried out by reacting ligands with reductive end groups with gold and iron under reducing conditions. A preferred method of producing the particles employs thiol derivatised carbohydrate moieties to couple the ligands to particles. Thus, in one aspect, the present invention provides a method of preparing the above defined particles, e.g. having a core comprising gold or gold and iron, which core is covalently linked to a plurality of ligands, the method comprising:
(a) synthesizing a sulphide derivative of the ligand; and (b) reacting the sulphide derivatised ligand with HAuCl 4 (tetrachloroauric acid), and optionally with a ferric salt where iron atoms are present in the core, in the presence of reducing agent to produce the particles. A preferred iron salt is FeCl 3 .
[0046] In some embodiments, the ligand is derivatised with a linker. Preferably, the linker is a disulphide linker, for example a mixed disulphide linker. The linker may further comprise in the chain ethylene groups, peptide or amino acid groups, polynucleotide or nucleotide groups.
[0047] An exemplary linker group is represented by the general formula HO—(CH 2 ) n —S—S—(CH 2 ) m —OH, wherein n and m are independently integers between 1 and 5. The ligand can conveniently be linked to the spacer via a suitable group, and in the case of the preferred mixed disulphide linkers via one of the linkers terminal hydroxyl groups. When the nanoparticles are synthesized, the —S—S— of the linker splits to form two thio linkers that can each covalently attach to the core of the nanoparticle via a —S— group. Thus, in a preferred embodiment, the ligand is derivatised as a protected disulphide. Conveniently, the disulphide protected ligand in methanol or water can be added to an aqueous solution of tetrachloroauric acid. A preferred reducing agent is sodium borohydride. Other preferred features of the method are described in the examples below.
[0048] The present invention provides a way of presenting a spherical array of ligands having advantages over other types of array proposed in the prior art. In particular, the nanoparticles are soluble in most organic solvents and especially water. This can be used in their purification and importantly means that they can be used in solution for presenting the ligand immobilised on the surface of the particle. The fact that the nanoparticles are soluble has the advantage of presenting the ligands in a natural conformation. For therapeutic applications, the nanoparticles are non-toxic, soluble and stable under physiological conditions.
[0049] Magnetic nanoparticles in solution form magnetic colloids known as ferrofluids. Ferrofluids have the fluid properties of a liquid and the magnetic properties of a solid. They have a range of applications, as described below. The main problem encountered with ferrofluids known in the art is their lack of stability: because the magnetic particles attract each other, they will agglomerate after a certain time. Previously used methods of preventing agglomeration include coating the particles with surfactants, crosslinking polymers or polysaccharides. If the nanoparticle is to be bound to a ligand or targeting molecule, a further synthesis step is required.
[0050] The particles of the present invention are highly soluble in water and are thus ideal for making ferrofluids. Moreover, the resulting ferrofluids are extremely stable and can be kept for many months without aggregating. Ferrofluids of the invention have been kept for a year with no sign of aggregation. The methods of the present invention allow magnetic nanoparticles that are stable and already bound to functional ligands to be synthesised in a single reaction, rather than requiring the particles first to be coated and then bound to ligands.
[0051] Stability may be assessed by eye—a colloidal solution remains transparent in the absence of agglomeration, but becomes opaque once it starts to agglomerate. Alternatively, the presence of flocculation may be determined by transmission electron micrography (TEM), or by comparing the proton NMR spectra of the particles in deuteron water with those of freshly prepared nanoparticles. Preferably, the magnetic particles will show no sign of agglomeration for at least a year after preparation.
[0052] In the method described herein, the formation of the core and the covalent linking of the ligand is a simultaneous process, so that the presence of the neoglycoconjugate controls the shape and size of the nanoclusters. The glyconanoparticles prepared in this way have a core of less than 2 nm diameter, which is smaller than any of the magnetic nanoparticles known in the art. Superparamagnetic behaviour is shown at all temperatures and superconducting quantum interference device (SQUID) measurements indicate also the existence of a ferromagnetic component at room temperature. This anomalous magnetic property may be of importance for imaging and cell separations.
[0053] The following examples of application for the magnetic nanoparticles and ferrofluids are provided by way of illustration and not limitation to support the wide applicability of the technologies described herein.
[0054] In one aspect of the invention, the magnetic properties of the nanoparticles of the invention are exploited in cell separation techniques which eliminate the need for columns or centrifugation. This permits a highly pure population of cells to be obtained quickly and easily. In one embodiment, the nanoparticles may be linked to ligands which specifically bind a receptor on the cell of interest. The nanoparticles may then be added to a cell suspension and the particle-bound cells separated from the rest of the suspension by application of a magnetic field.
[0055] This is a highly sensitive as well as efficient method which can be used in many applications, for example in diagnosis of tumours by testing body fluids for the presence of tumour cells. The sensitivity of the technique is a great advantage in this respect.
[0056] In a further aspect, the present invention provides a method of determining whether an interaction with a ligand occurs, the method comprising contacting one or more species of ligand-bound nanoparticles with a candidate binding partner and determining whether binding takes place.
[0057] In a further aspect, the present invention provides a method of screening for substances capable of binding to a ligand, the method comprising:
contacting nanoparticles as defined herein having a core comprising a passive metal or passive metal and a magnetic metal, which core is covalently linked to a plurality of the ligands, with one or more candidate compounds; and detecting whether the candidate compounds binds to the ligand.
[0060] Preferably, the ratio of passive metal atoms to magnetic metal atoms in the core is between about 5:0.1 and about 2:5. More preferably, the ratio is between about 5:0.1 and about 5:1.
[0061] In a further aspect, the present invention provides a method of determining the presence in a sample of a substance capable of binding to a ligand, the method comprising contacting the sample with nanoparticles linked to the ligand and determining whether binding takes place. The method may be used to determine the presence or amount of one or more analytes in a sample, e.g. for use in assisting the diagnosis of a disease state associated with the presence of the analyte. The presence of analytes may be signalled by the formation of analyte-nanoparticle aggregates, the presence of which can be detected by measuring the relaxation properties of the fluid in the sample. A change in the relaxation properties indicates the presence of aggregates and hence target molecules.
[0062] Where the ligand is a carbohydrate, a range of different carbohydrate mediated interactions are known in the art and could be studied or modulated using the nanoparticles disclosed herein. These include leukocyte-endothelial cell adhesion, carbohydrate-antibody interactions, carbohydrate-protein bacterial and viral infection, immunological recognition of tumour cells, tumour cells-endothelial cells (e.g. to study metastasis) and foreign tissue and cell recognition.
[0063] In another aspect, the magnetic nanoparticles and ferrofluids of the invention can be used to treat cancer. Magnetic nanoparticles may be used for hyperthermic treatment of tumours, in which magnetic nanoparticles are injected into tumours and subjected to a high frequency AC or DC magnetic field. Alternatively, near IR light may be used. The heat thus generated by the relaxation magnetic energy of the magnetic material kills the tumour tissue around the particles. In one embodiment of the present invention, tumour cells may be specifically targeted by incorporating tumour-specific antigens into the nanoparticles. This allows tumours not easily reached by injection to be targeted by the therapeutic particles, and avoids killing of normal healthy cells.
[0064] For a given excitation frequency, there exists an optimum nanoparticle size that yields a maximum specific absorption rate (SAR) and thus most efficient heating. This technique thus requires magnetic nanoparticles with a narrow core size distribution, to maximise the efficiency of the therapy and minimise the amount of ferrofluid to be administered. The magnetic nanoparticles of the invention are thus particularly well suited to this application, as the synthesis method enables the size of the nanoparticles to be closely controlled.
[0065] In another embodiment, the nanoparticles may be linked to therapeutically active substances such as antibodies or tumour-killing drugs. The magnetic properties of the nanoparticles can also be used to target tumours, by using a magnetic field to guide the nanoparticles to the tumour cells. However, use of magnetic field alone to direct nanoparticles to tumour cells is not always feasible or accurate, so the present invention provides an advantage by enabling the nanoparticles to be specifically directed to tumour cells via tumour-specific ligands. This may enable less drug to be used and reduce the chance of side effects, as the drug is directed only to the cells where it is needed and not to healthy cells.
[0066] In a further aspect, the magnetic nanoparticles of the invention may be used to improve the quality of magnetic resonance imaging (MRI). MRI does not always provide enough contrast to enable structures such as tumours to be efficiently viewed, but the images obtained can be enhanced by using magnetic nanoparticles as contrast media. The enhanced sensitivity thus obtained enables tumours to be detected while still very small and permits detection of tumours at a very early stage when there is more chance of successful treatment.
[0067] Detection of tumour cells in this way can also be combined with hyperthermia: once the tumour cells are identified, laser or near IR light may de directed to the tumour site to kill the cells.
[0068] Moreover, at present, the lungs cannot be imaged by MRI scanning. Positron emission tomography (PET) can image the lungs, but cannot be used for patients requiring regular scans such as asthma and emphysema patients due to the hazards of repeated exposure to radiation. Recent work has shown that hyperpolarised gas MRI can be applied to diseases such as asthma as the magnetisation of these gases is sufficient enough for an image of an entire lung to be taken in the few seconds it takes a patient to inhale, hold their breath and exhale. The capacity to take images as a patient inhales and exhales can also produce dynamic images as the patient breathes in and out using MRI. The magnetised glyconanoparticles, and in particular those containing gadolinium, can be produced as small as 0.8 nm. Particles this small can effectively be considered “a magnetised gas” and therefore may be usable for lung imaging in a far more convenient setting than the use of hyperpolarised gases.
[0069] The ligand-bound particles of the present invention can be delivered specifically to tumour cells so even tumour cells which have moved away from the original tumour site may be targeted for therapy.
[0070] Embodiments of the present invention which have a core comprising elemental magnetic metal are particularly well suited to imaging applications, as elemental metal is a more efficient enhancer of imaging then metal oxide. The presence of a passive metal in the core is advantageous as it inhibits oxidation of the magnetic metal. The passive metal also increases the biocompatibility of the nanoparticles and permits the core to be bound to ligands, which in addition to their biological uses further protect the magnetic metal from oxidation and reduce the likelihood of agglomeration.
[0071] Another advantage of the nanoparticles of the present invention is their exceptionally small size, which makes them more likely to be taken up by cells even when linked to targeting or therapeutic molecules.
[0072] In a further aspect, the magnetic nanoparticles of the invention may be used to replace radioactive materials used as tracers for drug delivery. Use of magnetic particles instead of radioactive materials permits drug delivery to be assessed by measuring magnetic variations, eliminating potential harm from radiation.
[0073] In general, it has been a difficult problem in the art to detect or modulate, carbohydrate-mediated interactions since the binding of carbohydrates to other species such as proteins or other carbohydrates is very weak and tends to be polyvalent. Thus, for detection the binding is weak and for modulating interaction, monovalent agents have only had a limited success in disrupting polyvalent carbohydrate based interactions.
[0074] In embodiments of the invention relating to carbohydrate-carbohydrate interactions, two types of interaction can be identified. In homophilic interactions, identical carbohydrates interact with one another and could be detected by steadily increasing the concentration of particles having a single species of ligands immobilised on their surface until aggregation occurs. This may be detected by light scattering or electronic effects. Heterophilic interactions can be detected by mixing together two or more different nanoparticles and determining the aggregation state of the particles.
[0075] Thus, the present invention provides a versatile platform for studying and modulating carbohydrate-mediated interactions. For example, the particles could be used to detect anti-carbohydrate antibodies, detecting the binding of antibody to the ligands on the particle via light scattering to pick up aggregation of the particles, or electric field effects, such as surface plasmon resonance, which would be modified when the metal atoms in the particles cluster together.
[0076] The invention thus provides a method of determining whether a carbohydrate mediated interaction occurs, the method comprising contacting one or more species suspected to interact via a carbohydrate mediated interaction with the nanoparticles of the invention, and determining whether the nanoparticles modulate the carbohydrate mediated interaction.
[0077] The invention also provides a method of disrupting ah interaction between a carbohydrate and a binding partner, the method comprising contacting the carbohydrate and the binding partner with the nanoparticles of the invention, wherein the nanoparticles comprise a carbohydrate group capable of disrupting the interaction of the carbohydrate and the binding partner.
[0078] In a further aspect, nanoparticles in which the ligand is an antigen can be administered as a vaccine, e.g. ballistically, using a delivery gun to accelerate their transdermal passage through the outer layer of the epidermis. The nanoparticles can then be taken up, e.g. by dendritic cells, which mature as they migrate through the lymphatic system, resulting in modulation of the immune response and vaccination against the antigen.
[0079] Nanoparticles in which the ligand is nucleic acid encoding an antigen may also be administered as a vaccine. Nanoparticles are particularly well suited to such applications because nucleic acid vaccines must enter individual cells to be effective, so it is important that particles small enough to penetrate the cell membrane without damaging the cells be used.
[0080] Vaccine delivery guns known in the art power delivery by use of compressed air or gas, usually helium gas. This can be painful and causes weals on the skin. The magnetic nanoparticles of the invention could be used in an alternative delivery system whereby the power for delivering the particles is provided by application of a magnetic field. Reversal of the magnetic field would result in rapid acceleration of the nanoparticles, sufficient to propel them through the outer epidermal layer. This would reduce pain and weal formation resulting from the use of compressed gas.
[0081] In a further application, it is known that cell surface carbohydrates act as ligands for viral or bacterial receptors (called adhesins) and that binding of the carbohydrates to the receptors is an event required during infection. Synthetic carbohydrates, e.g. glycoconjugates, that are capable of modulating these interactions can be immobilised in the nanoparticles of the invention and used as reagents to study these interactions and as therapeutics to prevent viral or bacterial infection.
[0082] In a further application, the present invention may be useful in the modulation of immune response, e.g. following transplantation. As the immunological recognition of tissue begins with carbohydrate mediated interactions between surface carbohydrates present on transplanted tissue and the components of the host's immune system such as antibodies, so this can be targeted to ameliorate immune reactions that result from this interaction. By way of example the carbohydrate Galα1-3Galβ1-4GlnAc (the “αGal” epitope) has been implicated as an important antigenic epitope involved in the rejection of transplanted tissue. Thus, modulation of the interaction of the αGal epitope and the immune system may be a therapeutic target for the nanoparticles described herein.
[0083] An alternative approach may be useful in the treatment of cancer as many tumour associated antigens or tumour autocrine factors are carbohydrate based. In this event, the nanoparticles could be provided as vaccines to prime the immune system to produce antibodies which are capable of attacking tumour cells presenting the carbohydrates on their surface. In this regard, it is known that many tumour cells possess aberrant glycosylation patterns which may enable the immune response stimulated by nanoparticles to be directed specifically to tumour cells as opposed to normal, healthy cells. The nanoparticles can also be used to inhibit metastasis in cancer, e.g. through the migration of tumour cells through the endothelial cells.
[0084] Non-invasive detection of clinically occult lymph-node metastases in prostate cancer has already been demonstrated by using lymphotrophic superparamagnetic nanoparticles in conjunction with MRI. Listed below are examples of glyconanoparticles that may have increased affinity or specificity for metastases.
[0000]
Le x -GNP
Le y -GNP
STn-GNP
Globo-H-GNP
Gg 3 -GNP
Gluco-GNP
Malto-GNP
Lacto-GNP
Man-GNP
[0085] In addition to other ligands that might be present such as glyconanoparticles, hormones such as estrogen, DHEA, etc, can also be attached to the nanoparticles and solubilised. These may have use in the detection of cancers such as breast. Peptides can also be attached to nanoparticles that localise to specific receptors such as cell surface oncogene coded receptors. Lipids, in particular those binding to the toll receptors, can also be attached. Chemical ligands such as methylene blue can be attached to the glyconanoparticles that may be of use in the detection of melanoma metastasis. Finally, siRNA nanoparticles can be made which, after uptake into the cell, could image the expression of oncogene or viral-specific mRNA.
[0086] In a further aspect, the nanoparticles can be used as carriers to raise antibodies capable of specifically binding the ligand. This is particularly advantageous where the ligand is a carbohydrate, as it can be a challenging problem in the art to raise antibodies against carbohydrates-containing moieties as they are often small and do not cause strong immune responses.
[0087] In a further aspect, carbohydrates can be attached to nanocrystals of cadmium selenide to provide quantum dots, which can then be guided to the required cellular structure by nanoparticles. Other anions such as sulphide may be used in addition to selenide. Quantum dots have potential uses in biological imaging, in both electronic and optical devices, quantum computers and the screening of candidate drugs.
[0088] In a further aspect, the present invention includes the use of the nanoparticles defined herein for the assessment of myocardial salvage, i.e. the amount of heart tissue remaining viable after a heart attack. At present this is predominantly monitored by scintigraphic techniques (e.g. SPECT)—using compounds such as sestamibi or tetrofosmin, which can be taken up by cells, in conjugation with radionuclides such as technetium. The uptake of the radioactive tracers is proportional to regional blood flow and thus gives an indication of the degree of myocardial salvage—the greater the uptake, the greater the myocardial salvage.
[0089] Compounds such as sestamibi or tetrofosmin work because they are lipophilic cationic complexes that passively diffuse across cell membranes. The functionalised ligands of such complexes can easily be incorporated as surface ligands during the self-assembly of magnetised nanoparticles. A wide variety of other novel chemical ligands can be attached to the nanoparticles to make them freely diffusible.
[0090] The nanoparticles described herein may be self-assembled in the presence of derivatives of sestamibi, tetrofosmin or other compounds which permit diffusion into cells. The resulting nanoparticles may then be used to allow myocardial salvage to be monitored by magnetic imaging, without the need for radioactivity. Magnetic resonance imaging may be used to detect the nanoparticles; as for radioactive tracers, uptake of nanoparticles will be proportional to regional blood flow. The scintigraphic tracers most commonly used at present are 99 mTc-sestamibi and 99m-tetrofosmin (Recent Advances in 99Tc Radiopharmaceutiocals—Annals of Nuclear Medicine 16:79-93 (2003); Contributions of Nuclear Cardiology to Diagnosis and Prognosis of Patients with Coronary Artery Disease—Circulation 2000: 101:1465-1478). In a preferred aspect, the nanoparticles of the invention are conjugated to sestamibi and used for magnetic imaging. In this way, nanoparticles may be used to substitute for 99 mTc to monitor myocardial salvage.
[0091] In a further application, the magnetic nanoparticles disclosed herein may be used in the production of magnetic recording media.
[0092] Embodiments of the present invention will now be described by way of example and not limitation with reference to the accompanying figures.
BRIEF DESCRIPTION OF THE FIGURES
[0093] FIG. 1 shows the Zero-Field Cooling (ZFC, bold symbols) and the Field Cooling (FC, empty symbols) curves for lacto-AuFe glyconanoparticles (a) and the malto-AuFe glyconanoparticles (b).
[0094] FIG. 2 shows transmission electron micrographs (left) and core size distribution histograms (right) for the lacto-AuFe glyconanoparticles (A) and the malto-AuFe glyconanoparticles (B).
[0095] FIG. 3 depicts schematically the synthesis the magnetic glyconanoparticles.
[0096] FIG. 4 shows a) The neoglycoconjugate 1 used for the preparation of the malto-Au glyconanoparticles and the corresponding TEM micrograph and histogram; b) the 1 H-NMR in D 2 O and DMSO-d 6 of the of the malto-Au nanoparticles.
[0097] FIG. 5 shows HRTEM of malto-Au glyconanoparticles showing the fcc structure.
[0098] FIG. 6 shows hysteresis loops corresponding to 1.5 nm gold-thiol protected of malto-Au glyconanoparticles at 5 K. The magnetization is given in emu per gram of gold, i.e., no contribution of the magnetization coming from ligand is assumed.
[0099] FIG. 7 show changes in the T 1 (A) and T 2 (B) values of malto-Au glyconanoparticles with increasing Gd (III) concentration.
[0100] FIG. 8 show changes in the r 1 (A) and r 2 (B) values of malto-Au glyconanoparticles with increasing Gd(III) concentration.
DETAILED DESCRIPTION
Pharmaceutical Compositions
[0101] The nanoparticles described herein or their derivatives can be formulated in pharmaceutical compositions, and administered to patients in a variety of forms. Thus, the nanoparticles may be used as a medicament for tumour targeting and hyperthermic therapies, for in vivo cell and tissue labelling, or as contrast enhancement media in magnetic resonance imaging.
[0102] Pharmaceutical compositions for oral administration may be in tablet, capsule, powder or liquid form. A tablet may include a solid carrier such as gelatin or an adjuvant or an inert diluent. Liquid pharmaceutical compositions generally include a liquid carrier such as water, petroleum, animal or vegetable oils, mineral oil or synthetic oil. Physiological saline solution, or glycols such as ethylene glycol, propylene glycol or polyethylene glycol may be included. Such compositions and preparations generally contain at least 0.1 wt % of the compound.
[0103] Parenteral administration includes administration by the following routes: intravenous, cutaneous or subcutaneous, nasal, intramuscular, intraocular, transepithelial, intraperitoneal and topical (including dermal, ocular, rectal, nasal, inhalation and aerosol), and rectal systemic routes. For intravenous, cutaneous or subcutaneous injection, or injection at the site of affliction, the active ingredient will be in the form of a parenterally acceptable aqueous solution which is pyrogen-free and has suitable pH, isotonicity and stability. Those of relevant skill in the art are well able to prepare suitable solutions using, for example, solutions of the compounds or a derivative thereof, e.g. in physiological saline, a dispersion prepared with glycerol, liquid polyethylene glycol or oils.
[0104] In addition to one or more of the compounds, optionally in combination with other active ingredient, the compositions can comprise one or more of a pharmaceutically acceptable excipient, carrier, buffer, stabiliser, isotonicizing agent, preservative or anti-oxidant or other materials well known to those skilled in the art. Such materials should be non-toxic and should not interfere with the efficacy of the active ingredient. The precise nature of the carrier or other material may depend on the route of administration, e.g. orally or parenterally.
[0105] Liquid pharmaceutical compositions are typically formulated to have a pH between about 3.0 and 9.0, more preferably between about 4.5 and 8.5 and still more preferably between about 5.0 and 8.0. The pH of a composition can be maintained by the use of a buffer such as acetate, citrate, phosphate, succinate, Tris or histidine, typically employed in the range from about 1 mM to 50 mM. The pH of compositions can otherwise be adjusted by using physiologically acceptable acids or bases.
[0106] Preservatives are generally included in pharmaceutical compositions to retard microbial growth, extending the shelf life of the compositions and allowing multiple use packaging. Examples of preservatives include phenol, meta-cresol, benzyl alcohol, para-hydroxybenzoic acid and its esters, methyl paraben, propyl paraben, benzalkonium chloride and benzethonium chloride. Preservatives are typically employed in the range of about 0.1 to 1.0% (w/v).
[0107] Preferably, the pharmaceutically compositions are given to an individual in a “prophylactically effective amount” or a “therapeutically effective amount” (as the case may be, although prophylaxis may be considered therapy), this being sufficient to show benefit to the individual. Typically, this will be to cause a therapeutically useful activity providing benefit to the individual. The actual amount of the compounds administered, and rate and time-course of administration, will depend on the nature and severity of the condition being treated. Prescription of treatment, e.g. decisions on dosage etc, is within the responsibility of general practitioners and other medical doctors, and typically takes account of the disorder to be treated, the condition of the individual patient, the site of delivery, the method of administration and other factors known to practitioners. Examples of the techniques and protocols mentioned above can be found in Remington's Pharmaceutical Sciences, Mack Publishing Company, Easton, Pa., 19th Edition, 1995, Handbook of Pharmaceutical Additives, 2nd Edition (eds. M. Ash and I. Ash), 2001 (Synapse Information Resources, Inc., Endicott, N.Y., USA), and Handbook of Pharmaceutical Excipients, 2nd edition, 1994. By way of example, and the compositions are preferably administered to patients in dosages of between about 0.01 and 100 mg of active compound per kg of body weight, and more preferably between about 0.5 and 10 mg/kg of body weight.
Antibodies
[0108] The nanoparticles may be used as carriers for raising antibody responses against the ligands linked to the core particles. These antibodies can be modified using techniques which are standard in the art. Antibodies similar to those exemplified for the first time here can also be produced using the teaching herein in conjunction with known methods. These methods of producing antibodies include immunising a mammal (e.g. mouse, rat, rabbit, horse, goat, sheep or monkey) with the nanoparticle(s). Antibodies may be obtained from immunised animals using any of a variety of techniques known in the art, and screened, preferably using binding of antibody to antigen of interest. Isolation of antibodies and/or antibody-producing cells from an animal may be accompanied by a step of sacrificing the animal.
[0109] As an alternative or supplement to immunising a mammal with a nanoparticle, an antibody specific for the ligand and/or nanoparticle may be obtained from a recombinantly produced library of expressed immunoglobulin variable domains, e.g. using lambda bacteriophage or filamentous bacteriophage which display functional immunoglobulin binding domains on their surfaces; for instance see WO92/01047. The library may be naive, that is constructed from sequences obtained from an organism which has not been immunised with any of the nanoparticles, or may be one constructed using sequences obtained from an organism which has been exposed to the antigen of interest.
[0110] The term “monoclonal antibody” refers to an antibody obtained from a substantially homogenous population of antibodies, i.e. the individual antibodies comprising the population are identical apart from possible naturally occurring mutations that may be present in minor amounts. Monoclonal antibodies can be produced by the method first described by Kohler and Milstein, Nature, 256:495, 1975 or may be made by recombinant methods, see Cabilly et al, U.S. Pat. No. 4,816,567, or Mage and Lamoyi in Monoclonal Antibody Production Techniques and Applications, pages 79-97, Marcel Dekker Inc, New York, 1987.
[0111] In the hybridoma method, a mouse or other appropriate host animal is immunised with the antigen by subcutaneous, intraperitoneal, or intramuscular routes to elicit lymphocytes that produce or are capable of producing antibodies that will specifically bind to the nanoparticles used for immunisation. Alternatively, lymphocytes may be immunised in vitro. Lymphocytes then are fused with myeloma cells using a suitable fusing agent, such as polyethylene glycol, to form a hybridoma cell, see Goding, Monoclonal Antibodies: Principles and Practice, pp. 59-103 (Academic Press, 1986).
[0112] The hybridoma cells thus prepared can be seeded and grown in a suitable culture medium that preferably contains one or more substances that inhibit the growth or survival of the unfused, parental myeloma cells. For example, if the parental myeloma cells lack the enzyme hypoxanthine guanine phosphoribosyl transferase (HGPRT or HPRT), the culture medium for the hybridomas typically will include hypoxanthine, aminopterin, and thymidine (HAT medium), which substances prevent the growth of HGPRT-deficient cells.
[0113] Preferred myeloma cells are those that fuse efficiently, support stable high level expression of antibody by the selected antibody producing cells, and are sensitive to a medium such as HAT medium.
[0114] Culture medium in which hybridoma cells are growing is assayed for production of monoclonal antibodies directed against the nanoparticles/ligands. Preferably, the binding specificity is determined by enzyme-linked immunoabsorbance assay (ELISA). The monoclonal antibodies of the invention are those that specifically bind to the nanoparticles/ligands.
[0115] In a preferred embodiment of the invention, the monoclonal antibody will have an affinity which is greater than micromolar or greater affinity (i.e. an affinity greater than 10 −6 mol) as determined, for example, by Scatchard analysis, see Munson & Pollard, Anal. Biochem., 107:220, 1980.
[0116] After hybridoma cells are identified that produce neutralising antibodies of the desired specificity and affinity, the clones can be subcloned by limiting dilution procedures and grown by standard methods. Suitable culture media for this purpose include Dulbecco's Modified Eagle's Medium or RPM1-1640 medium. In addition, the hybridoma cells may be grown in vivo as ascites tumours in an animal.
[0117] The monoclonal antibodies secreted by the subclones are suitably separated from the culture medium, ascites fluid, or serum by conventional immunoglobulin purification procedures such as, for example, protein A-Sepharose, hydroxylapatite chromatography, gel electrophoresis, dialysis, or affinity chromatography.
[0118] Nucleic acid encoding the monoclonal antibodies of the invention is readily isolated and sequenced using procedures well known in the art, e.g. by using oligonucleotide probes that are capable of binding specifically to genes encoding the heavy and light chains of murine antibodies. The hybridoma cells of the invention are a preferred source of nucleic acid encoding the antibodies or fragments thereof. Once isolated, the nucleic acid is ligated into expression or cloning vectors, which are then transfected into host cells, which can be cultured so that the monoclonal antibodies are produced in the recombinant host cell culture.
[0119] Hybridomas capable of producing antibody with desired binding characteristics are within the scope of the present invention, as are host cells containing nucleic acid encoding antibodies (including antibody fragments) and capable of their expression. The invention also provides methods of production of the antibodies including growing a cell capable of producing the antibody under conditions in which the antibody is produced, and preferably secreted.
[0120] Antibodies according to the present invention may be modified in a number of ways. Indeed the term “antibody” should-be construed as covering any binding substance having a binding domain with the required specificity. Thus, the invention covers antibody fragments, derivatives, functional equivalents and homologues of antibodies, including synthetic molecules and molecules whose shape mimics that of an antibody enabling it to bind an antigen or epitope, here a carbohydrate ligand as defined herein.
[0121] Examples of antibody fragments, capable of binding an antigen or other binding partner, are the Fab fragment consisting of the VL, VH, Cl and CH1 domains; the Fd fragment consisting of the VH and CH1 domains; the Fv fragment consisting of the VL and VH domains of a single arm of an antibody; the dAb fragment which consists of a VH domain; isolated CDR regions and F(ab′) 2 fragments, a bivalent fragment including two Fab fragments linked by a disulphide bridge at the hinge region. Single chain Fv fragments are also included.
[0122] A hybridoma producing a monoclonal antibody according to the present invention may be subject to genetic mutation or other changes. It will further be understood by those skilled in the art that a monoclonal antibody can be subjected to the techniques of recombinant DNA technology to produce other antibodies, humanised antibodies or chimeric molecules which retain the specificity of the original antibody. Such techniques may involve introducing DNA encoding the immunoglobulin variable region, or the complementarity determining regions (CDRs), of an antibody to the constant regions, or constant regions plus framework regions, of a different immunoglobulin. See, for instance, EP 0 184 187 A, GB 2 188 638 A or EP 0 239 400 A. Cloning and expression of chimeric antibodies are described in EP 0 120 694 A and EP 0 125 023 A.
EXPERIMENTAL SECTION
Example 1
Au—Fe Nanoparticles
[0123] A method of synthesising magnetic glyconanoparticles covalently bound to ligands was devised. By way of example, thiol derivatised neoglycoconjugates 1 and 2 of two significant oligosaccharides, the non-antigenic disaccharide maltose (Glcα(1→4)Glcβ1-OR) and the antigenic lactose (Galβ(1→4)Galβ1-OR), were prepared to functionalise in situ magnetic nanoparticles ( FIG. 3 , scheme 1). The synthesis of the disulfides 1 and 2 was carried out by glycosidation of the conveniently protected maltose and lactose derivatives with 11-acetylthio-undecanol and 11-acetylthio-3,6,9-trioxa-undecanol, respectively.[12] Both linkers have been used to test the influence of their hydrophobic or hydrophilic nature in the properties of the whole material. Compounds 1 and 2 were isolated as disulfide forms, and used in this form for the preparation of gold-iron protected glyconanoparticles. The water-soluble glyconanoparticles 1-AuFe (malto-AuFe) and 2-AuFe (lacto-AuFe) were obtained in methanol/water mixtures using one-pot synthesis. FeCl 3 and HAuCl 4 in a ratio 1:4 were reduced with NaBH 4 in the presence of disulphides 1 or 2. The protection of the metal core with the neoglycoconjugate monolayers results in highly stable and bio-functional nanoclusters. They have been purified by means of centrifugal filtering and characterised by 1 H-NMR, UV-vis, ICP, TEM, EDX and SQUID.
[0124] Iron analysis of the particle, carried out by means of inductively coupled plasma-atomic emission spectrometry (ICP), indicated 0.27% and 2.81% iron content for 1-AuFe and for 2-AuFe, respectively. These data correspond to an average Au:Fe ratio of 5:0.1 and 5:1 respectively. FIG. 1 shows Zero-Field Cooling and Field Cooling magnetisation curves obtained for the lacto-AuFe (A) and malto-AuFe (B) nanoparticles by means of Superconducting Quantum Interference Device (SQUID) between 5 k and 300 k in a field of 500 Oe. From the magnetic measurements it is inferred that both a superparamagnetic and ferromagnetic behaviour are present between 5 k and 300 k. SQUID measurements confirm the superparamagnetic character of the glyconanoparticles which have a blocking temperature (T B ) below 5K ( FIG. 1 ), which would be expected for a magnetic nanoparticle of 2 nm diameter. The superparamagnetic component is clearly observed from a) the partial fitting of the experimental thermal dependence of magnetisation to the Curie-Weiss law; b) the partial dependence of the hysteresis loop on the ration between the applied field and the temperature (H/T); and c) the difference between ZFC and FC curves.
[0125] FIG. 2 shown transmission electron micrographs (left) and core-size distribution histograms (right) for the lacto-AuFe (A) and malto-AuFe (B) nanoparticles. Each black dot corresponds to a single particle. The dots are regularly separated by the ligands (neoglycoconjugate) attached to the core and they form ordered monolayers. The TEM was recorded at a 200 kV electron beam energy on a Philips CM200 microscope.
[0126] In the case of the 2-AuFe sample (lacto-AuFe), the glyconanoparticles are dispersed, spherical and homogeneous. The mean diameter of the gold/iron cluster was evaluated to be 2 nm. A few isolated particles with a size of about 10 nm have been found in some regions of the grid, but these particles have not been included in the histogram. In the case of the sample 1-AuFe (malto-AuFe), the glyconanoparticle presents a bimodal particle size distribution, as indicated by the corresponding histogram ( FIG. 2B ). Particles with a mean diameter of the gold/iron cluster about 2.5 nm and less than 1.5 nm have been found. Worthy of note is the spontaneous formation of aligned chains in extended regions of the grid, indicating an additional magnetostatic force ( FIG. 2B ). This behaviour could be attributed to dipole-dipole magnetic forces or quantum tunneling among the nanoparticles. The aligned arrangement was not observed in the micrographs obtained for the 2-AuFe nanodots, although a high ordered monolayer is observed.
Preparation
MaltoC 11 SauFe:
[0127] A solution of FeCl 3 (2 mg; 0.013 mmol; 0.25 equiv) in water (0.5 mL) was added to a solution of disulfide 1 (80 mg; 0.075 mmol; 3 equiv.) in MeOH (11.5 mL) followed by the addition of a solution of HauCl 4 (17 mg; 0.05 mmol; 1 equiv) in water (2 ml). NaBH 4 1 M (52 mg; 1.38 mmol; 27.5 equiv) was then added in small portions with rapid stirring. The black suspension formed was stirred for an additional 2 h and the solvent removed under vacuum. The glyconanoparticles are insoluble in MeOH but soluble in water.
LactoEG 4 SauFe:
[0128] A solution of FeCl 3 (1 mg; 0.0065 mmol; 0.25 equiv) in water (0.25 mL) was added to a solution of disulfide 2 (70 mg; 0.07 mmol; 5.5 equiv.) in MeOH (12 mL) followed by the addition of a solution of HAuCl 4 (8 mg; 0.025 mmol; 1 equiv) in water (1 mL). NaBH 4 1 M (26 mg; 0.69 mmol; 27.5 equiv) was then added in small portions with rapid stirring. The black suspension formed was stirred for an additional 2 h and the solvent removed under-vacuum. The glyconanoparticles are insoluble in MeOH but soluble in water.
Purification:
[0129] Purification was performed by centrifugal filtration. The crude product was dissolved in water (˜15 mL) NANOpure and the solution was loaded into a centrifugal filter device (CENTRIPLUS YM30, MICROCON, MWCO=30000), and subjected to centrifugation (3000×g, 40 min). The dark glyconanoparticle residue was washed with MeOH and water and the process repeated several times until the starting material could no longer be detected by thin layer chromatography (TLC). The residue was dissolved in water and centrifuged several times to eliminate insoluble materials. The clear solution was lyophilised and the products obtained were free of salts and starting material (absence of signals from disulfide and Na + ions in 1 H and 23 Na NMR spectroscopy).
Characterization:
[0130] TEM examination of the samples was carried out at 200 KV (Philips CM200 microscope). A single drop (20 μL) of the aqueous solutions of the Au/Fe glyconanoparticles were placed onto a copper grid coated with a carbon film. The grid was left to dry in air for several hours at room temperature. Particle size distributions of the Au/Fe clusters were evaluated from several micrographs using an automatic image analyser. EDX analysis was performed with a Philips DX4 equipment attached to the microscope. ICP analysis was performed by Agriquem S. L. following PEC-009 protocol. UV spectra were obtained by a UV/vis Perkin Elmer Lambda 12 spectrophotometer. 1 H-NMR spectra were acquired on Bruker DRX-500 spectrometers and chemical shifts are given in ppm (δ) relative to D 2 O.
1-AuFe:
[0131] TEM: average diameter of metallic core, 1.5 and 2.5 nm.
[0132] ICP: 0.27% Fe
[0133] UV (H 2 O): λ=500 nm, surface plasmon resonance 1 H-NMR (500 MHz, D 2 O) δ: 5.32 (s, 1H, H-1′), 4.37 (s, 1H, H-1), 4.00-3.30 (m, 13H), 2.70 (s, 2H, CH 2 S), 1.85-1.20 (m, 17H)
2-AuFe:
[0134] TEM: average diameter of metallic core, 2 nm.
[0135] ICP: 2.81% Fe
[0136] UV (H 2 O): λ=500 nm, surface plasmon resonance 1 H-NMR (500 MHz, D 2 O) δ: 4.49 (brd, 1H, H-1′), 4.40 (brs, 1H, H-1) 4.10-3.30 (m, 23H), 2.92 (m, 0.5H).
Example 2
Magnetic Au Nanoparticles
[0137] Water soluble gold glyconanoparticles (GNPs) stabilized with self-assembled monolayers (SAMs) of different carbohydrate molecules were prepared by the chemical reduction of a metal salt precursor in aqueous solution in the presence of an excess of thiol derivatised neoglycoconjugates. The preparation sample procedure used as a starting point the Penadés et al [11] [19] that produces gold GNPs in which the metal cluster has been at same time protected and functionalised with the organic molecule. The formation of Au—S covalent bonds isolate the metal cluster preventing its growth (core diameter≈2 nm) and confer on the nanoclusters exceptional stability in solution.
[0138] In this example, we report on the experimental observation of magnetic hysteresis up to room temperature in gold glyconanoparticles with average diameters of 1.4 and 1.5 nm. By increasing the ratio of thiol:gold in the Penadés procedure, GNPs sample with diameter of less than 1.5 nm can be obtained. This is illustrated by the preparation and the magnetic properties of Au-GNPs obtained using the maltose neoglycoconjugate 1 as thiol linker species ( FIG. 4 ).
[0000] Preparation of Gold Glyconanoparticles malto-Au:
[0139] An aqueous solution of tetrachloroauric acid (HAuCl4, 0.018 mmol) and an excess of disulfide neoglycoconjugate 1 (0.2 mmol) was reduced with sodium borohydride (NaBH4, 22 equiv) at room temperature. A brown suspension was immediately formed. The suspension was shaken for about two hours, then the solvent was removed and the glyconanoparticles (GNPs) were purified by washing with water and centrifugal filtering (CENTRIPLUS, Mr 30000, 1 h, 3000×g). The residue in the filter was dissolved in water and lyophilized. The GNPs were characterised by transmission electron microscopy (TEM), and 1 HNMR and UV-visible spectroscopy, induced coupling plasma (ICP) and elemental analysis. TEM: average diameter and; number of Au atoms, 1.5 nm and 79, respectively. UV-VIS (H 2 O): λ=520 nm. ICP: 28% Au. Elemental analysis calculated for (C 23 H 43 O 11 S) n Au n (n=79): C, 38.18; H, 5.98; S, 4.40; Au, 27.18. Found: C, 39.5; H, 6.07; Au, 28.0.
[0140] FIG. 4 shows in a) the synthetic scheme for the malto-Au GNPs and the corresponding TEM micrographs for the malto-Au GNPs and the corresponding particle size distribution histograms for the samples; and in b) the 1 HNMR spectra in D 2 O and in DMSO-d 6 are also shown. The malto-Au GNPs present, in all the cases, narrow particle size distribution with an average size of 1.5 nm or less. High resolution electron micrograph (HRTEM) indicating the fcc structure of the thiol protected malto-Au GNPs is show in FIG. 5 .
[0141] Superconducting Quantum Interference Devise (SQUID) magnetometry indicated ferromagnetic behaviour even up to room temperature. Hysteresis loop measured at 5K exhibits a coercive field of 120 Oe. The blocking temperature, obtained from the thermal dependence of coercivity, was found to be 395 K that corresponds to an effective anisotropy constant of 10 meV/atom which is similar to that observed in a single Co atom onto platinum (III) surface [20]. The magnetisation did not conform to the Curie-Weiss law, but showed a much slower T-dependence. An atomic magnetic moment of around 0.003 μ B per Au atom was derived from low T magnetic measurements.
[0142] FIG. 6 show the hysteresis loops measured at 5K for gold thiol capped malto-Au GNPs. It is evident from FIG. 5 the magnetization process of thiol protected glyconanoparticles exhibit similar behaviour as typical ferromagnetic materials describing a hysteresis loops even at room temperature. In addition, it was observed that the samples are not saturated at any temperature. Remanence values around half of the magnetisation value at 1 T are measured, which implies that atoms as well as GNPs hold a permanent magnetic moment and that the gold GNPs system consists of an assembly of magnetic moments randomly distributed in orientation.
[0143] One can argue whether the observed behaviour is due to the presence of ferromagnetic impurities. Inductive Coupled Plasma (ICP) analysis indicated that the amount of Fe impurities (0.007% wt.) in the malto-Au is very low to account for the obtained magnetization values. In spite of that analysis, samples of malto-Au Fe GNPs containing 0.2% wt of iron have been prepared to characterized the influence of Fe on the magnetic behavior. FIG. 6 shows the hysteresis loops measured at 5 K for both set of GNPs. It is clear that the presence of increased amounts of iron (ferromagnetic impurities) in the malto-AuFe nanoparticles reduces the ferromagnetic behaviour at this temperature, whereas the hysteresis loop still remains for malto-Au samples. As the GNPs are dispersed, inter-particle interactions can only be of magnetostatic nature. The average distance between gold core is determined by the length of two consecutive molecules of the maltose neoglycoconjugate 1 (6 nm). As the permanent magnetic moment of each particle is very low, the magnetic field acting on a GNP by a single neighbour GNP is lower than 10 Oe. Therefore, the influence of the stray fields can be neglected.
[0144] Since bulk Au is diamagnetic, the ferromagnetic behaviour may be due to the combination of both size and bonding effects [21]. The discrete electronic energy structure [22], the presence of stacking faults [23], as well as the extremely high percentage (≧80%) of surface atoms [24], covalently bonded to S, may be the possible causes of the onset of ferromagnetism.
[0145] In conclusion, it has been shown ( FIG. 6 ) that very small thiol protected gold glyconanoparticles exhibit a localized permanent magnetism in contrast to the metallic diamagnetism characteristic of other non-thiol protected gold nanoparticles or bulk gold. This observation point out that the thiol-gold bonding induces in gold glyconanoparticles permanent magnetic moments probably associated with the extra d-holes localized near to the Au bonds. This suggest the technological application of the nanoparticles of the present invention for magnetic recording. Furthermore, the water solubility and the biological label of these GNPs amplify enormously their application in the biological field.
Example 3
Au—Gd(III) Nanoparticles
[0146] Gold glyconanoparticle (GNPs) may be complexed to Gd(III) and other lanthanides to give new contrast agent. The neoglycoconjugate ligands present in the GNPs (60 to 100 molecules) are the chelating moiety.
[0000] Preparation of lactoEG 4 -Au(Gd) Glyconanoparticles:
[0147] To a solution of the corresponding gold glyconanoparticle (20.0 mg) in water (1 mL) a solution of GdCl 3 . (0.5 M, 1.08 mL) was added. The mixture was stirred in the absence of light during 20 h. The solution was filtered by centrifugation (MICROCON YM30, 13000 rpm, 8 min). The residue was washed (8×0.5 mL, methanol/water, 1/3). The nanoparticles were dissolved in water and lyophilized to give 17.5 mg of dark violet nanoparticles. TEM: average diameter 2.5 nm. EDX: Gd 6.8%; Au 33:2% atomic.
Determination of Relaxivities:
[0148] 1 H NMR relaxation times T 1 and T 2 (37° C., pH 7.2) of the water protons in aqueous solution were measured at 1.5 Tesla in a Brucker Minispec NMR spectrometer. T 1 values were determined by the inversion-recovery method and the T 2 values were determined by the Carr-Purcell-Maiboom-Gill sequence. Solutions of the lacto-Au(Gd) nanoparticles at five different concentration (0.01, 0.1, 1, 10, 100 μg/mL) were prepared in Hepes buffer with 150 mM of NaCl. The relaxivities were calculated from the differences in longitudinal and transversal relaxation rates (1/T 1(2) ) of the water protons in the presence and absence of the glyconanoparticles, and the concentration of Gd(III) expressed in mM. FIGS. 7 and 8 show the results.
[0149] In conclusion, in the examples shown herein, the inventors have developed a simple methodology to prepare water-soluble, superparamagnetic nanoparticles covalently linked to antigenic oligosaccharides. The methodology can be extended to the preparation of hybrid nanoparticles incorporating carbohydrates and other molecules. Carbohydrate-receptor interactions can direct the magnetic glyconanoparticles to target cells and tissues allowing their selective labelling. This demonstrates that this type of polyvalent magnetic glyconanoparticles complements the scarcely available bioactive magnetic nanoparticles.[9] [10] [17] Accordingly, the easy preparation and purification, their small core size and their stability and solubility in physiologically conditions of nanoparticles of the present invention convert these tools in potential candidates for diagnostic, tumour targeting [15], hyperthermia [16], and magnetic resonance imaging [17] applications.
REFERENCES
[0150] The references mentioned herein are all expressly incorporated by reference.
[1] Niemeyer, C. M. Angew. Chem. Int. Ed. 2001, 40, 4128-4158. [2] Bergemann, C.; Müller-Schulte, D.; Oster, J.; Brassard, L.; Lübbe, A. S. J. Magn. Magn. Mater. 1999, 194, 45. [3] Whitesides, G. M.; Kazlauskas R. J.; Josephson L. Trends Biotechnol. 1983, 1, 144-148. [4] Sun, S.; Murray, C. B.; Weller, D.; Folks, L.; Moser, A. Science 2000, 287, 1989. [5] a) Shafi, K. V. P. M.; Gedanken, A.; Prozorov, R. Adv. Mater. 1998, 10, 590-593. b) Fried, T.; Shemer, G.; Markovich, G. Adv. Mater. 2001, 13, 1158-1161. c) Moumen, N.; Veillet, P.; Pileni, M. P. J. Magn. Magn. Mater. 1995, 149, 67-71. [6] Park, S.-J.; Kim, S.; Lee, S.; Khim, Z. G.; Char, K.; Hyeon, T. J. Am. Chem. Soc. 2000, 122, 8581-8282. [7] a) Suslick, K. S.; Fang, M.; Hyeon, T. J. Am. Chem. Soc. 1996, 118, 11960-11961. b) Sun, S.; Zeng H. J. Am. Chem. Soc 2002, 124, 8204-8205. c) Guo, Q.; Teng, X.; Rahman, S.; Yang, H. J. Am. Chem. Soc. 2003, 125, 630-631. [8] Sun, S.; Anders, S.; Hamann H. F.; Thiele, J.-U.; Baglin, J. E. E.; Thomson, T.; Fullerton, E. E.; Murray, C. B.; Terris, B. D. J. Am. Chem. Soc. 2002, 124, 2884-2885. [9] a) Josephson, L.; Tung, C.-H.; Moore, A.; Weissleder, R. Bioconjugate Chem. 1999, 10, 186-191. b) Lewin, M.; Carlesso, N.; Tung, C.-H.; Tang, X.-W; Cory, D.; Scadden, D. T.; Weissleder, R. Nat. Biotechnol. 2000, 18, 410-414. [10] Josephson, L.; Pérez, J. M.; Weissleder, R. Angew. Chem. Int. Ed. 2001, 40, 3204-3206. [11] de la Fuente, J. M.; Barrientos, A. G.; Rojas, T. C.; Rojo, J.; Cañada, J.; Fernández, A.; Penadés, S. Angew. Chem. Int. Ed. 2001, 40, 2257-2261. [12] Barrientos, A. G.; de la Fuente, J. M.; Rojas, T. C.; Fernández, A.; Penadés, S. Chem. Eur. J. 2002, 9, 1909-2001. [13] Hernáiz, M. J.; de la Fuente, J. M.; Barrientos, A. G.; Penadés, S. Angew. Chem. Int. Ed. 2002, 41, 1554-1557. [14] Zhou, W. L.; Carpenter, E. E.; Lin, J.; Kumbhar, A.; Sims, J.; O'Connor, C. J. Eur. Phys. J. D. 2001, 16, 289-292. [15] Mykhaylyk O.; Cherchenko A.; Ilkin A.; Dudchenko N.; Ruditsa V.; Novoseletz M.; Zozulya Y. J. Magn. Magn. Mater. 2001, 225, 241-247. [16] Jordan, A.; Scholz, R.; Wust, P.; Fähling, H.; Felix, R. J. Magn. Magn. Mater. 1999, 201, 413-419. [17] Josephson, L.; Kircher M. F.; Mahmood, U.; Tang, Y.; Weissleder R. Bioconjugate Chem. 2002, 13, 554-560. [18] Taton et al, Science 2000 289:1757-1760. [19] Barrientos A. G. et al., Chem. Eur. J. 9, 2003, 1909-1921. [20] Gambardela, P. et al, Giant Magnetic Anisotropy of Single Cobalt Atoms and Nanoparticles, Science, 2003, 300, 1130-1133. [21] Di Felice, R., Selloni, A., Molinari, E., J. Phys. Chem. B., 2003, 107, 1151-1156. [22] D. Davidovic and M. Tinkham, Phys. Rev. Lett., 1999, 83 (8), 1644-1647. [23] Vitos, L., Johansson, B., Phys. Rev. B., 2000, 62 (18), R11957. [24] Villás, I. M. L., Chàtelain, A., de Heer, W. A., Science, 1994, 265, 1682-1684. | Materials and methods for making small magnetic particles, e.g., clusters of metal atoms, which can be employed as a substrate for immobilizing a plurality of ligands. Also disclosed are uses of these magnetic nanoparticles as therapeutic and diagnostic reagents, and in the study of ligand-mediated interactions. | 0 |
BACKGROUND OF INVENTION
This invention relates to automatic garage door opening apparatus and more particularly to a mounting assembly for the safety sensors mounted on either side of the door opening adjacent the bottom thereof.
Effective Jan. 1, 1993 all electric garage door openers installed must be equipped with a safety device that will reverse a closing door if an obstruction is present in the last six inches of the door's travel. These safety devices have generally taken the form of infrared transmitter and receiving cells being installed on either side of the door opening at the bottom of the opening. The sensors have usually been mounted on a metal bracket that extends from the frame into the garage past the door track so as to give a clear transmission path across the door opening. The sensors have thus been subject to frequent impact with people, vehicles and other objects that knock the units out of alignment and even break them requiring replacement of the entire unit.
In addition the sensors being mounted in the open near the floor are subject to collecting all sorts of dust, dirt, insects and other debris which greatly reduces the sensitivity of the sensors and eventually may cause the door opener not to function necessitating frequent cleaning to ensure reliable operation.
OBJECTS AND SUMMARY OF THE INVENTION
Accordingly it is an object of the present invention to provide an improved mounting system for garage door opener safety sensors.
It is another object of the present invention to provide a mounting assembly for safety sensors for garage door openers which protects the sensors from both contamination and direct physical damage.
It is yet another object of the present invention to provide a mounting assembly for garage door safety sensors that not only protects the sensors but also protects people walking by them from injury by accidental contact therewith.
It is a further object of the present invention to provide a garage door safety sensor mounting assembly that will maintain alignment of the sensors even though the sensor housing is impacted with a substantial but non destructive force.
It is a still further object of the present invention to provide a garage door safety sensor mounting assembly in which the shroud assembly may be used as a gage to position the base member at the federally mandated height position by placing the shroud assembly on the floor and installing fasteners through the base member holes to secure the base member to the wall.
These and other and further objects are achieved in one embodiment in which a base member has an adjustable mounting pedestal for a sensor generally in the center of the base and a protective shroud with optical ports, completely enclosing the sensor and mounting pedestal, fixed to the outer periphery of the base member. The space between the shroud and sensor is chosen to provide omnidirectional clearance about the sensor from impact blows to the shroud short of actual destruction of the assembly. The shroud also effectively seals out dust and insects normally encountered in a garage setting.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevation, partially broken away, of the mounting assembly according to the present invention;
FIG. 2 is an end elevation of the assembly of FIG. 1 showing the shroud in minimum height position;
FIG. 3 is a top plan view of the base member of the assembly of FIG. 1;
FIG. 4 is an end elevation of the base member partially broken away to show the location of the sensor mounting stud;
FIG. 5 is a sectional view of the sensor mounting stud showing the gimbal mounting of the sensor, and;
FIG. 6, is a perspective view showing the shroud assembly in use as an height gage.
DESCRIPTION OF PREFERRED EMBODIMENT
Referring now to FIG. 1 the safety sensor assembly 10 has a base member 12, an outer shroud 14, a mounting pedestal or stud assembly 16 and a sensor head 18. The base member 12 has a flat base plate portion 20, upon which is formed an outer tubular sleeve 22 and an inner tubular sleeve 24. The sleeves 22 and 24 are mounted perpendicular to the base plate 20 and have a vertical length sufficient to permit the outer shroud 14 to be adjusted up and down (compare positions in FIGS. 1 and 2) to accommodate various sensor 18 heights at time of installation. Typically a sleeve length of about three inches has been found satisfactory. Outer sleeve 22 also has a pair of slots 26 formed in opposite ends as may best be seen in FIGS. 2 and 3. Holes 28 are formed in the ends of shroud 14 adjacent the bottom through which screws 30 are inserted into slots 26. The size of the slots and screws are chosen so that the screws will be self tapping in forming threads in the slots and just long enough to fill the slot and block entrance of insects and other dirt into the inner part of the assembly.
Base plate 20 has a series of holes 32 formed about the periphery to permit easy mounting of the assembly on the usual wall and/or door frame surrounding a garage door opening. A clearance hole 34 may be provided for the usual electrical wires connecting the sensor 18 to the rest of the door control system.
Inner sleeve 24 is positioned at the center of the outer sleeve 22 and forms a receptacle for the mounting stud 16. Stud 16 is a tubular sleeve 40 with a concave upper surface 42, and a partially slit lower end 44. A spherically faced nut 54 is positioned on the upper end of threaded bolt 48 which is inserted through sensor 18 and tubular sleeve 40 into tapered plug 46. Plug 46 is secured to the end 50 of bolt 48 by pin 58. The sensor 18 housing is provided with a recess 53 on the upper side and a convex boss 55 on the lower surface. As bolt 48 is retracted from nut 54 by rotation of head 52 plug 46 is tightened into the slit end 44 of tubular sleeve 40 which expands and secures stud 16 in position in inner sleeve 24 of base 12. Spherically sided hex nut 54 positioned on the upper threaded portion of bolt 48 cooperates with recess 53 in the sensor 18 housing and together with boss 55 and convex surface 42 in stud 16 permits sensor 18 limited gimbal action relative to stud 16 to properly align the sensor on one side of the door opening with the sensor on the other side. A locking washer 64 is provided between surfaces 55 and 42 in the stud assembly 16. Once aligned the sensor and stud are locked in position by retracting bolt 48 to secure the stud 16 assembly in inner sleeve 24 of the base member 12.
The outer shroud 14 has two transparent lenses 60 and 62 positioned in the surface thereof. Lens 60 is positioned in the end of the shroud 14 to permit the sensor 18 to send and receive infrared beams to a companion assembly on the opposite side of a door opening. The lens 62 is provided in the top of shroud 14 to permit observation of the usual LED bulb on the top of the sensor 18 which is used to indicate proper operation of the safety sensors when activated.
As may be seen from FIGS. 1 and 2 the shroud 14 may be adjusted vertically relative to base member 12 to accommodate variable sensor height and size requirements while at the same time maintaining a tight seal about the base outer sleeve 22 to keep the sensor free of insects, dirt, and other debris. Shroud 14 is formed with well rounded corners and edges not only to conform to the base inner sleeve but also to help in deflecting accidental impact to the assembly. Also it must be noted the shroud is sized considerably larger than the sensor 18 so that accidental striking of the shroud will normally not hit the sensor so that the proper alignment of the sensors is not disturbed.
Referring now to FIG. 6 the outer shroud 14 is shown being used as a gage to position the base member 12 at the required height from the floor 68 when it is mounted on the door frame 66. In a preferred embodiment of the invention the shroud width is chosen so as to provide the federally required spacing of the beam above the floor across the door opening. The juxtaposition of the sensor assembly 10 to the door track 70 is also shown.
While there are given above certain specific examples of this invention and its application in practical use, it should be understood that they are not intended to be exhaustive or to be limiting of the invention. On the contrary, these illustrations and explanations herein are given in order to acquaint others skilled in the art with this invention and the principles thereof and a suitable manner of its application in practical use, so that others skilled in the art may be enabled to modify the invention and to adapt and apply it in numerous forms each as may be best suited to the requirement of a particular use. | A mounting assembly for safety sensors for automatic garage door openers is shown in which the sensor is gimbal mounted in a insect and dust proof shroud on a mounting stud. The stud and shroud are adjustable in height. The shroud has transparent lenses for sensor and status information and provides protection against external impact to the sensor as well as improved safety for users of the device. | 4 |
FIELD OF THE INVENTION
The present invention relates to a pressure control device. More particularly the invention relates to a compact pressure control device for use in a subsea lubricator stack.
BACKGROUND OF THE INVENTION
When developing subsea oil and gas wells there are stringent demands to the control and containment of the well during all aspects of the work, be it drilling, production or later intervention. The needs for control of well pressure have lead to requirements for safe barriers in the well and/or above ground, both during production and during intervention work.
During the lifetime of the well various types of work may be carried out to enhance production or to measure conditions in the well. Well intervention may be difficult, as existing barriers have to be removed to gain entry into the well. There are in most countries strict rules regarding the size and number of barriers needed to keep control of the well during intervention. To gain access to a living well a blowout preventer, containing a number of valves, must be connected to the well before the well barriers can be opened. In addition, a number of pressure containment devices ensure control over the well during the work.
One of the methods for gaining entry into a live well is by using a lubricator. This employs a tool attached to the end of a wire or cable and inserted into the well. This equipment includes means whereby grease can be injected under pressure to seal around and lubricate the wire or cable during rising or lowering of the tool, hence the name lubricator.
Lubricators are in use both on surface and on subsea wells. U.S. Pat. No. 4,993,492 shows an example of a surface lubricator, while U.S. Pat. No. 3,638,722 and International Patent Application no. WO 0125593 shows examples of subsea lubricators. In for example WO 0125593 there is shown a subsea lubricator consisting of the afore-mentioned blowout preventer, called a Lower Intervention Package (LIP), a tool housing (or lubricator pipe), and a pressure control head which includes a grease injector assembly. When lowering a tool into the well using this equipment, the wire or cable is inserted through the pressure control head and the tool attached to the end of the wire. Then the whole assembly is lowered to the seabed and the tool guided into the tool housing while the LIP valves and Christmas tree valves are closed. Then the grease injector is closed around the wire above the tool. The LIP valves and Christmas tree master valve can now be opened so that the tool can be lowered into the well.
The tool housing must be of a length capable of holding the full length of the tool, and this can be up to 30 meters. The whole lubricator assembly may be up to 50 meters long.
To ensure a greater degree of safety, an additional blow out preventer is mounted on top of the tool housing. One common type of blow out preventer includes a shear/blind ram in combination with one or two wireline rams. The shear ram is used to cut the wire or cable in an emergency. As described in U.S. Pat. No. 4,938,2909, the wireline ram(s) are designed to grip and hold the wire and include facilities for grease injection. The main disadvantage with these is their large size and weight. The weight, mounted on top of up to a 30 meters column, exerts a large bending moment on the lubricator and necessitates a stronger (and therefore heavier) tool housing and connectors.
A stuffing box is also normally included in a lubricator assembly above the grease injector. The stuffing box is intended to grip and hold the wire or cable in the event of gas leaking past the grease injector. Examples of known stuffing boxes are shown in UK Patent No. GB 2,214,954 and U.S. Pat. No. 2,943,682. In Pat. No. U.S. Pat. No. 5,863,022, a stripper/packer having a split bonnet is shown. The packer also serves as a blowout preventer. The packer can be axially activated to achieve a radial sealing, and the function of the packer is similar to a stuffing box. The present invention can be used together with a packer of this type.
To reduce some of the the weight the lubricator described in WO 0125593 uses only a shear/blind ram in conjunction with a second high pressure stuffing box with grease injection, the stuffing box being a replacement for the wireline ram. However, a stuffing box in this position will have well pressure acting on the lower surface of its rubber cylinder, thereby adding to the forces keeping the rubber in compression. There are also higher frictional forces. This makes it difficult to control the stuffing box properly. One consequence has been that it has proved difficult to reopen the stuffing box, forcing the operator to cut the wire and retrieve the whole lubricator to the surface. This can be a costly operation.
In U.S. Pat. No. 6,394,460, a one-piece ram element block for wireline blowout preventers is shown. The ram element block is a part of a BOP housing having a generally vertically oriented bore for a wireline. The BOP housing defines a pair of opposed ram element bores wherein linearly movable ram elements are located. Here, high pressure grease is injected into the flow passage between the upper and lower ram elements, thereby effecting a proper wireline seal when the rams are actuated to their closed positions. The ram elements are not located in separate bores and can not be independently controlled.
An object of the present invention is therefore to produce a pressure containment device in place of the stuffing box which can be positively and exactly balanced and will give a better control over the gripping forces than existing stuffing boxes. As the shear/blind ram function is also built into the device it will eliminate the need for the upper blowout preventer. It is small and compact and will therefore reduce the overall bending moments on the lubricator. This in turn makes it possible to reduce the strength and size of the tool housing and connectors.
The present invention utilises positively closing and opening rams to grip and hold the cable or wire. It also includes a shear/blind ram so that it will cut the wire or cable in a emergency. Because the unit is located in the pressure control head, e.g. above the tool housing, the internal size can be related to the wire diameter and not, as in the present, the tool diameter.
SUMMARY OF THE INVENTION
The invention thus provides a pressure containment device comprising a main housing, a first longitudinal through bore arranged to receive a wire or cable slidingly therethrough, at least two spaced apart transversal through bores intersecting the main bore, and a pair of opposing rams in each transversal bore.
The bore of the ram is preferably lined with a cylindrical sleeve, enabling several sizes of wire to be used by only changing the sleeves.
The invention will now be explained in connection with a preferred, non-limiting embodiment, with reference to the drawings.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is an illustration of a prior art lubricator.
FIG. 2 is an illustration of the lubricator of the present invention shown in a pressure control head assembly.
FIG. 3 is a partial cross sectional view of the pressure containment device of the invention.
FIG. 4 is an enlarged view of the pressure containment device of FIG. 3 .
DESCRIPTION OF THE PREFERRED EMBODIMENT
A prior art type subsea lubricator 1 is shown in FIG. 1 . This lubricator consists of a blowout preventer 2 , or Lower Intervention Package (LIP). Attached to the LIP is an Emergency Disconnect Package (EQDP) 3 . A lubricator tool housing 4 is connected to the EQDP. The tool housing is in the form of a pipe of a length that will contain a tool before lowering it into the well. A pressure control head 5 is connected to the tool housing. The pressure control head includes grease injectors 6 , a line wiper 7 , and a stuffing box (not shown). An upper blowout preventer 8 is located on top of the tool housing 4 .
When used on a surface well, the EQDP is omitted.
FIG. 2 shows the pressure control head assembly according to the invention. The pressure control head assembly comprises, from bottom to top, a connector 21 for coupling to the tool housing, a tool catcher unit 22 , a pressure containment device 30 (that will be described in more detail later), first 23 and second 24 grease inlets, a grease return 25 and a combined upper stuffing box and line wiper 26 . The numerals 27 - 29 depict grease tubes. The upper stuffing box and line wiper 26 can, as an example, be of the type shown in U.S. Pat. No. 5,863,022.
During intervention work, the pressure control head assembly acts as the primary seal barrier preventing hydrocarbons from escaping into the environment. Grease is injected under pressure through inlets 23 and 24 , travels up along grease tubes 27 - 29 , sealing and lubricating the wire, and is returned through grease outlet 25 . The stuffing box 26 is only used when there is a need to clamp and hold the wire securely, as can happen if hydrocarbons leak past the grease tubes 27 - 29 . The tool catcher unit 22 holds the tool as it is raised and lowered between the surface and the seabed.
The pressure containment device 30 according to the invention is shown to comprise a solid housing 31 , in the form of a rectangular solid metal block. The housing may have coupling parts such as flanges (not shown) at each end for connecting the housing with the rest of the pressure control head assembly. A main bore 32 extends through the length of the housing. When assembled into the pressure control head assembly, the main bore is aligned with the bore above and below to provide a fluid path through the lubricator.
Auxiliary bores 33 , 34 , 35 , 36 and 37 extend transversally through the housing 31 and intersect the main bore 32 . As shown, bores 33 - 37 may be located in the same vertical plane as the axis of main bore 32 . Grease supply bores 38 and 39 , which are also located in the same plane as the axis of the main bore 32 , extend from the side but end in ports (only port 40 is shown) in main bore 32 . As seen in FIG. 3 , bore 38 is located between bores 33 and 34 while bore 39 is located between bores 35 and 36 .
As an alternative, the bores 33 - 39 can be staggered around the sides of main housing 31 . For example, each bore can be located perpendicular to the next bore, or the bores can be distributed in a stepped fashion relative to each other.
In each bore 33 - 36 a pair of opposing rams 41 , 42 are arranged to move towards each other as is well known. As shown in FIG. 4 , ram consists of a main cylindrical part 43 that forms a sliding fit within its bore. A rod 44 is attached to cylindrical part 43 and is intended to be connected to an actuator (not shown) that can be bolted onto the housing. A cylindrical body 45 of an elastic material such as rubber is fixed to the front of main cylindrical part 43 . Rubber body 45 preferably has an outer diameter which is sized to enable it to seal against its bore. Rubber body 45 has a front surface 46 with a vertical slot 47 . When the two rams 41 , 42 are in their fully closed position, surfaces 46 will abut and seal against each other except for the slots 47 , which will define a circular opening for the passage of the wire or cable.
A conventional shear/blind ram for cutting wire or cable is located in bore 37 . Bores 38 , 39 are connected to a pump (not shown) for supplying grease under pressure to main bore.
Main bore 32 has an inner sleeve lining, which comprises. a number of smaller sleeves. Upper sleeve 51 extends from the top of housing 31 to first ram bore 33 . First intermediate sleeve 52 extends between first 33 and second 34 ram bores. As shown in FIG. 4 , sleeve 52 may be in two parts which are separated by a gap 54 located in the area of grease injection bore 38 , or alternatively may have a port oriented in line with grease injection bore 38 . Second intermediate sleeve 53 extends between second 34 and third 35 ram bores. A third intermediate sleeve (not shown) extends between ram bores 35 and 36 and is identical to sleeve 52 , while a fourth intermediate sleeve (not shown) extends between ram bores 36 and 37 and is identical to sleeve 53 . A lower sleeve (not shown) is identical to upper sleeve 51 .
Each sleeve forms a sliding fit within main bore 32 , that is, the sleeves are positioned in bore 32 with a very small clearance. When mounted, each sleeve is oriented in the correct angular position and fixed in place, for example, with screws or latches. Moreover, each sleeve has an inner diameter corresponding to the outer diameter of the wire or cable so that the wire or cable has a small clearance within the sleeves.
The sleeves have two functions. They are exchangeable and can therefore be sized to fit the size of the wire or cable in use to obtain the desired tight fit. Therefore, when using another size cable or wire, the sleeves can easily and quickly be exchanged with sleeves tailored to the wire or cable size. The sleeves will also prevent the rubber on the rams from extruding into main bore 32 when subjected to pressure as grease is pumped into main bore 32 .
The rams 33 - 35 , and the shear rams 36 and 37 , are actuated by means of controllable actuating means (not shown). The actuating means are preferably hydraulically or mechanically driven, and the force exerted by the controllable actuating means on the rams is controllable. Moreover, the force from the controllable actuating means can be controlled independently for each of the rams. A detecting device, such as a gas detector, television camera etc, is preferably used to detect the conditions in the well. The controllable actuating means can be controlled based on the detected condition.
In use, rams 33 - 35 will be actuated to close around the wire or cable to hold it securely. At the same time, grease is injected through grease injection ports 38 , 39 by means of grease injection means to seal between the wire and the sleeve. The grease injection means controls the pressure of the injected grease.
If necessary, shear ram 37 will be activated to shear off wire, allowing the main valve in the LIP and the Christmas tree master valve to be closed.
The use of rams allow for a precise control of the tightness around the wire. If so desired, the rams can be positioned with slightly reduced pressure to allow the wire to be drawn through the rams while maintaining control over grease pressure. This allows the tool to be moved to a safer location, for example into the tool housing while still maintaining control of the well. The continuous injection of grease under high pressure makes it possible to control and contain the well pressure.
In an emergency the shear ram will be activated to cut the wire or cable. This will cause the tool to fall into the well and allow the lubricator to be disconnected and removed. | The present invention concerns a pressure containment device for use in a lubricator. The device includes a housing having a first main bore extending throughout its length a number of transversal bores intersecting the main bore. Pairs of opposing rams are located in the transversal bores to grip and seal around a cable in the main bore. | 4 |
BACKGROUND
[0001] The design of graphical user interfaces (GUIs) that are to operate across a number of different platforms having different aspect ratios, sizes, and numbers of pixels poses significant challenges. Any given device may have two different aspect ratios that are operative in portrait or landscape mode. The particular mode is triggered by the device orientation during the running of the program, and hence, the program must provide at least two organizations for the GUI. Furthermore, the programmer is faced with the task of designing a GUI that must operate on a number of different devices having screen sizes that vary from a smart phone to a large fixed computer screen.
[0002] Many techniques exist for defining a GUI. The two most commonly used are those designed with “Code” where the programmer creates the layout for a specific application using a programmatic interface. Visual Basic or Visual C++ are examples of this type of layout. Another type is a declarative layout in a text form such as HTML or Microsoft XAML. These use the XML structure to map into a structure in the GUI representation.
[0003] These existing techniques require the user to define the GUI in terms of elements that have absolute size requirements in one form or another. Such GUIs do not respond well to orientation changes such as switching between portrait and landscape or when switching from a tablet to a phone to a wide screen monitor. One solution to the orientation problem requires that the designer create multiple “layouts” in which each layout is optimized for a different display.
SUMMARY
[0004] The present invention includes a method for operating a data processing system having a display screen on which a GUI is displayed. The GUI has a plurality of configurations having different aspect ratios or numbers of pixels. The method includes providing a layout description and a runtime system that generates the GUI in response to the layout description and the display configuration. The layout description defines a first container having a plurality of components to be shown in the GUI within a first container space. Each component has a component layout description within the first container. The runtime system automatically allocates the first container space depending on the display configuration, and automatically divides the first container space into a plurality of component spaces. Each component is shown in a corresponding one of the component spaces. The first container space and the component spaces automatically change when the display configuration changes.
[0005] In one aspect of the invention, the layout description defining the first container indicates a vertical or horizontal organization for the components, and the runtime system divides the first container space vertically or horizontally, respectively, assigning each component to a corresponding vertical, or horizontal, space. The relative space assigned to each component is specified by a layout weight parameter that can be altered from a default value by an entry in the layout description. Absent a change in the layout weights of the components, the vertical or horizontal spaces are divided equally.
[0006] In another aspect of the invention, a first one of the components includes text to be displayed in the GUI, and the runtime system automatically sets a text font for that component based on a first font group specification in the layout description for that component. If two components have the same font group specification, the runtime system automatically determines a font that ensures that both components have their text properly displayed, the font changing with the display configuration.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIGS. 1A and 1B illustrate a VGroup having three buttons in portrait and landscape mode, respectively.
[0008] FIG. 2 illustrates a three button VPanel in which the first button has twice the weight of the remaining two buttons.
[0009] FIG. 3 illustrates the HPanel equivalent of the VPanel shown in FIGS. 1A and 1B .
[0010] FIG. 4 illustrates the three-button panel with Button 1 allocated twice the space of the other buttons.
[0011] FIGS. 5A and 5B illustrate a nested display in portrait and landscape modes, respectively.
[0012] FIGS. 6A and 6B illustrate a nested display that includes a trace component that displays a graphic.
[0013] FIG. 7 illustrates a display in which the size of the Button 1 component has been explicitly set using layout code.
[0014] FIGS. 8A and 8B illustrate a GUI that is to run on a device such as a smart phone in either portrait or landscape orientation.
[0015] FIGS. 9A and 9B illustrate a display in which the individual components have their fonts adjusted based on the size of the component.
[0016] FIGS. 10A and 10B illustrate a display in which the same font size is used for a number of different components.
DETAILED DESCRIPTION
[0017] In general, a GUI according to the present invention is constructed from one or more “components”. Each component has a graphical representation and a code section that determines the behavior of the component and how the component is displayed. In general, each component has a default representation that automatically sizes the graphical representation for the amount of space assigned to that component on the current display. When the display changes orientation, the amount of space for the various components also changes, and the graphical representations are adjusted accordingly. A collection of components can be grouped together in a container. The space allocated for the container is divided among the components in the container. There is a default space allocation that is applied unless a different allocation is specified for the container. The entire display is the highest level of container.
[0018] The manner in which the present invention provides its advantages can be more easily understood in terms of two types of containers. In the first type of container, referred to as a VGroup in the following discussion, the default space allocation consists of dividing the vertical space in the container equally among the objects in the container. It should be noted that when the display screen changes from portrait mode to landscape mode, the available space in the container changes, the vertical space being reduced and the horizontal space being increased. Hence, each component in the container is assigned a new space when the change in orientation takes place and the components' representations are likewise resized.
[0019] The second type of container will be referred to as an HGroup. The default space allocation in an HGroup consists of dividing the horizontal space in the container equally among the objects in the container. Again, when the display screen changes from portrait mode to landscape mode, the available space in the container changes, the vertical space being reduced and the horizontal space being increased.
[0020] VPanels and HPanels are special types of VGroups and HGroups, respectively, in which the individual components and the panels are automatically provided with borders that delineate the elements in question. Refer now to FIGS. 1A and 1B , which illustrate displays on a data processing system which includes a VGroup having three buttons in portrait and landscape mode, respectively. When the orientation changes from portrait to landscape, the space available for each button changes such that the vertical height of each button is reduced and the width is increased. The fonts are changed accordingly to fit the available space.
[0021] In one aspect of the present invention, the user defines the layout of the display in a declarative language such as XML. Only those items that are not contained in the default specification of a component need be included in the file if the containers of the present invention are utilized. For example, the XML code for the three-button display shown in FIGS. 1A and 1B consists of
[0000]
<Vpanel>
<Button text=“Button1”/>
<Button text=“Button2”/>
<Button text=“Button3”/>
</Vpanel>
[0022] It should be noted that only the text needs to be specified, as the display space is automatically divided into three vertical sections which are allocated to the various buttons. The code associated with the buttons automatically takes care of sizing the text and buttons for the current display screen and orientation.
[0023] In the above-described example, the three buttons have the same size, which is the default allocation. However, the user may wish to provide more space for one of the buttons. In one aspect of the present invention, the user can specify the relative layout weights of the components within a container. The default weight is 1. To change the default layout weight, a corresponding entry is made in the layout file. For example, if the user wishes to assign more space to Button 1, the XML file would be
[0000]
<Vpanel>
<Button text=“Button1” layout_weight=“2”/>
<Button text=“Button2”/>
<Button text=“Button3”/>
</Vpanel>
[0024] Refer now to FIG. 2 , which illustrates a three button VPanel in which the first button has twice the weight of the remaining two buttons. In this case, Button 1 has a height that is twice that of the other two buttons. It should be noted that the width of the button remains the same as that of the other buttons. Since the width limits the font size used for the labels, Button 1 has the same font size in as the remaining buttons.
[0025] The present invention also implements a horizontal panel, HPanel, that provides an analogous function to the VPanel described above. In an HPanel, the horizontal space is divided equally. HPanel is the equivalent of the VPanel shown in FIGS. 1A and 1B . The layout file for the HPanel is as follows
[0000]
<Hpanel>
<Button text=“Button1” />
<Button text=“Button2”/>
<Button text=“Button3”/>
</Hpanel>
[0026] Refer now to FIG. 4 , which illustrates the three-button panel with Button 1 allocated twice the space of the other buttons. Again, if more space is to be allocated to one button, the layout weight parameter can again be used. However, since this is an HPanel, the increased layout weight increases the horizontal space allocated to Button 1 in the panel rather than the vertical space. The layout file for the HPanel with the increased weight is as follows:
[0000]
<Hpanel>
<Button text=“Button1” layout_weight=“2”/>
<Button text=“Button2”/>
<Button text=“Button3”/>
</Hpanel>
[0027] It should be noted that VPanels and HPanels, as well as the corresponding VGroup and HGroup, are themselves components that obey the same rules as other components. Hence, the various panels and groups can be nested within one another to provide more complex layouts without the need to specify the exact sizes of the components.
[0028] Refer now to FIGS. 5A and 5B , which illustrate a nested display in portrait and landscape modes, respectively. These displays include a number of nested panels. The layout description for the displays in question is as follows:
[0000]
<VPanel>
<HPanel layout_weight=“1.5”>
<HPanel>
<Button text=“Button1”/>
<Button text=“Button2”/>
<Button text=“Button3”/>
</HPanel>
<VPanel>
<Button text=“Button4” layout_weight=“2”/>
<Button text=“Button5”/>
<Button text=“Button6”/>
</VPanel>
</HPanel>
<HPanel>
<Button
text=“Button7”/>
<VPanel
layout_weight=“2”>
<Button text=“Button8”/>
<Button
text=“Button9”/>
</VPanel>
</HPanel>
</VPanel>
[0029] As noted above, a VPanel and an HPanel have a distinctive border around their child components. When nested HPanel and VPanel components are used for grouping the border shading which can sometimes lead to a cluttered display. The HGroup and VGroup components behave in the same manner as HPanel and VPanel but they do not have a border. In addition, in one aspect of the invention, HGroup and VGroup have a transparent background while HPanel and VPanel do not. This difference is illustrated in FIGS. 6A and 6B , which illustrate a nested display that includes a trace component 21 that displays a graphic. FIG. 6A shows the display when only VPanel and HPanel containers are used. The layout code for FIG. 6A is as follows:
[0000]
VPanel>
<Trace/>
<HPanel>
<Button text=“Button1”>
<VPanel layout_weight=“2”>
<Button text=“Button1”/>
<Button text=“Button2”/>
</VPanel>
</HPanel>
</VPanel>
[0030] The corresponding display when HGroups and VGroups are used is shown in FIG. 6B . The layout code for FIG. 6B is as follows:
[0000]
VPanel>
<Trace/>
<HGroup>
<Button text=“Button1”/>
<VGroup layout_weight=“2”>
<Button text=“Button1”/>
<Button text=“Button2”/>
</VGroup>
</HGroup>
</VPanel>
[0031] In the above described examples, the components have sizes that are automatically computed. However, there are situations in which a designer may prefer to assign specific sizes to one or more of the components. In one aspect of the present invention, components can also have explicit sizes assigned in a manner that is separate from the weight mechanism that assigns relative sizes. Components according to the present invention also have layout_width and layout_height attributes that can be assigned by the designer in the layout code.
[0032] Refer now to FIG. 7 , which illustrates a display in which the size of the Button 1 component has been explicitly set using the following layout code:
[0000]
<HPanel>
<Button text=“Button1”
layout_width=“60dp”
layout_height=“40dp”/>
<Button text=“Button2”/>
<Button text=“Button3”/>
</HPanel>
[0033] In this aspect of the invention, the layout width and height can be specified in display pixels, px, scale independent pixels, sp, or density independent pixels, dp. The sp unit selects a font size based on the display screen density as well as the user's font size preference. When this information is not available to an implementation, an sp value is interpreted as a dp value. In general, sp is used when a size is desired relative to user font selection preferences. The dp unit selects a font size based on a density independent pixel. These units are relative to a 160 dpi screen. A dp is one pixel on a 160 dpi screen but two pixels on a 320 dpi screen. For text, sp is preferred because it accommodates the users' font size preference. In general, the px unit should be avoided as it does not scale well between devices.
[0034] The introduction of a fixed size component can lead to extra space being available in a container. In one aspect of the present invention, the layout engine that is part of a runtime system library allocates space utilizing the layout description. The space in a container is divided according to the layout_weights of the components in that container. When a component uses less than that component's share of the space, the additional space is divided among the remaining components in proportion to their respective layout_weights. A component in which a fixed width and height have been defined can also have a non-zero layout_weight. In this case, the final space allocated to the component is the sum of the specified fixed width or height and its share of any remaining space. If the designer does not wish the fixed width or height component to be stretched in this manner, a layout_weight of zero can be assigned to that component, and hence, that component will not receive any additional space.
[0035] In one aspect of the present invention, components can be reduced in size beyond their intrinsic size that results from assigning fixed widths or heights. Such reductions take place if the available space is less than the sum of the intrinsic sizes of the objects specified through the layout_width and layout_height parameters. In this case, space is taken away from each component based on its layout_weight.
[0036] Automatically sizing components that include textual material poses additional challenges. Refer now to FIGS. 8A and 8B , which illustrate a GUI that is to run on a device such as a smart phone in either portrait or landscape orientation. In particular, the GUI includes a number of boxes that include text. The particular GUI in FIG. 8A is running with the device in landscape mode. When the device is rotated to portrait mode as shown in FIG. 8B , the sizes of the boxes are altered to make more efficient use of the display space.
[0037] Unfortunately, the text within the box cannot be re-sized with the same degree of flexibility without causing problems. The aspect ratio of the text for a given font is normally fixed. Consider a box that has text that just fits into the box when the screen is in the landscape mode. When the screen is rotated to portrait, the width of the box must be reduced. If the font size is not changed, as shown in FIG. 8B , the original text will no longer fit in the box. Hence, the text size is changed to accommodate the change in orientation. The amount by which the text font size must change to accommodate the change in orientation will be different for different objects in the GUI.
[0038] One method for changing the font size involves adjusting the font size to just fit in the object when the object size changes with a change in orientation. Unfortunately, this strategy can result in different components that started with the same text size having different text sizes in the new orientation as can be seen in FIGS. 9A and 9B , which illustrate a display in which the individual components have their fonts adjusted based on the size of the component. FIG. 9A shows the display with the device in landscape mode, and FIG. 9B shows the display with the device in portrait mode. As can be seen from these figures, this approach can lead to a display that lacks the aesthetic qualities of the original display.
[0039] In one aspect of the present invention, this problem is overcome by defining a group of elements that all need to share the same font size when the orientation or resolution changes to preserve the aesthetic quality of the display. A font group is defined for these elements, and this font is used rather than the font that would have been used by the layout engine in the absence of the font group. Refer now to FIGS. 10A and 10B , which illustrate a display in which the same font size is used for a number of different components even though one or more of the components could have used a different font size. For example, the objects shown at 71 in FIGS. 10A and 10B need to use the same font size in each orientation. The size of the objects changes when the orientation changes; however, the font size remains constant across the objects.
[0040] In this aspect of the present invention, a two step process is used for setting the font size for all components of a container that are part of the same group. In the first step, the font size that is required to fit the text into each component is determined. The font size is set such that no object has text that is cut-off in the new orientation. Different components may have different determined font sizes at this step.
[0041] In the second step, the minimum of the determined font sizes is then chosen for all of the components in the font group. This ensures that the components have a consistent appearance while ensuring that the text is not cut-off in any of the components. Once a font is determined for each object in a font group, the font is communicated to each object for use by that object.
[0042] The font group to which a component is to belong can be specified in the layout description for that component. In the case of the GUI shown in FIGS. 10A and 10B , the XML description could be as follows:
[0000]
<HPanel>
<VPanel>
<Button fontGroup=”Buttons” text=”Start”/>
<Button fontGroup=“Buttons” text=“Lap”/>
<Button fontGroup-“Buttons” text=“Reset/Stop”/>
</VPanel>
<HPanel>
<Text value=“00:00:00”/>
</HPanel>
</HPanel>
[0043] In some cases, it may be more efficient to define the font group for a “parent” component that includes a number of “children”. In this case, the font group assignment applies to all of the children of the parent, e.g.,
[0000]
<HPanel>
<VPanel fontGroup=“Buttons”>
<Button text=“Start”/>
<Button text=“Lap”/>
<Button text=“Reset/Stop”/>
</VPanel>
<HPanel>
<Text value-“00:00:00”/>
</HPanel>
</HPanel>
[0044] To simplify the layout code, an “implicit font group” is assigned to each container. The implicit font group only applies to the first level of children of the container. It ensures that the first level of children will all have the same font group. An explicit font group assignment is inherited by all of the children of the container. The implicit font group assignment can be avoided by providing a predetermined explicit font group assignment such as “none” or by assigning a property that is incompatible with an implicit font group such as a layout_weight=0.
[0045] In another aspect of the invention, Buttons, Text Boxes, and other primarily textual components have a number of additional properties that configure various aspects of the displayed text. The textSize property allows specification of a relative or absolute text size while maxChars specifies the maximum length of a text field.
[0046] The textSize property can specify text size in the same units as described for layout size specification. In addition, a % relative size is defined. For text, sp is preferred because it accommodates the user's font size preference. The % unit is a relative automatic font size. When textSize is not specified for a component the layout engine will choose a font size automatically. If the font size is specified with % units the resulting font size will be a percentage of the automatic font size. For example, setting textSize=50% will result in the font size being 50 percent of the automatic font size.
[0047] Text size and font group can both be used in the same container. This allows the same automatic font group to be used for all of the elements, except that some of the elements have a reduced font size.
[0048] In some cases, the contents of some of the text fields are not known at the time the layout is specified. For example, a text box may be populated by the output of a remote device and the size of the text string will not be known until the text string actually arrives. In one aspect of the present invention, a field property is provided that allows the designer to inform the layout engine of the maximum size of the expected input. This is referred to as the MaxChars property. When the MaxChars property is specified, the textual components choose a text size based on the specified length. The layout engine will then reserve space for that number of characters. If less than that number arrives, the font size is still defined as if the defined maximum number had arrived. This ensures that the appearance of the text does not change from input to input, since the text may change in length during the operation of the GUI.
[0049] In anther aspect of the invention, a width or height can be specified to match that of the parent container. A width or height specified as match_parent informs the layout engine that the component should be sized to match its parent container. That is, it will expand to fill available space. Children of HPanel, VPanel, HGroup, and VGroup default to match_parent if an explicit width or height is not specified.
[0050] In yet another aspect of the invention, a property that informs the layout engine to size the component just big enough to accommodate its contents is provided. A width or height can be specified as wrap content. This is typically used to wrap a set of fixed sized components. For example, a VPanel with the layout height=“wrap content” around a fixed size Text component would result in a panel just big enough to surround the text.
[0051] If the children in a container have either fixed or intrinsic sizes and the designer does not wish to calculate the minimum size container that will contain the children, the designer can use a special version of the VPanel and HPanel containers referred to as VWrap and HWrap, respectively. These containers automatically set the height or width of the container to a value that is just big enough to fit all of the children in the container.
[0052] The positioning of a component in a container can be explicitly controlled using two position specification parameters. A container can specify a layout for all of the children in the container by specifying a value for a parameter, “gravity”. For example, if gravity=“left”, all of the components in a container will be aligned on the left boundary of the container. In some cases, the designer may wish to explicitly specify the position of one of the components in a container without altering the positioning of the remaining contacts. The parameter, “layout_gravity” allows a component to define its position within the parent container. The values of gravity and layout_gravity do not affect the size of the components. For a vertical orientation container such as a VPanel, lay_out gravity can take on the values “left”, “center”, or “right”, which result in the object being aligned with the left boundary of the container, the center of the container, or the right boundary of the container, respectively. For a horizontal orientation container such as an HPanel, lay_out gravity can take on the values “top”, “center”, or “bottom”, which result in the object being aligned with the top boundary of the container, the center of the container, or the bottom boundary of the container, respectively. In addition, layout_gravity can have the values “center_vertical” and “center_horizontal that signal that the object is to be vertical center of its container or the horizontal center of its container, respectively.
[0053] The above-described embodiments utilize containers referred to as VGroup and HGroup. However, embodiments of the present invention that utilize different types of containers in which the component sizes are automatically set can be constructed. For example, a SwipePanel is defined in one embodiment of the present invention. The children of this panel are “pages” in a multi-page view in which the user moves between pages using a gesture such as a swipe gesture or “pushing” a button. A SwipePanel is equivalent to a display that is much larger than that provided on the device. The allocated space on the device is a “window” on the larger display. The positioning of the window is determined by the swipe gesture and the current position. In essence, the swipe moves the relative position of the window and the underlying display so that a different portion of the underlying display appears in the window after the gesture.
[0054] The children of the SwipePanel may be arranged in a manner that depends on the whether the device is in portrait or landscape mode. In one aspect of the invention, each child occupies a space on the display such that one child is visible at any time and fills the allocated space. The user changes children by performing the swipe gesture which replaces the currently visible child with one to the left or right of the current child, depending on the direction of the swipe.
[0055] The drawings in the present application show various display arrangement of components on a display of a data processing system or computer. The data processing system or computer is not explicitly shown as a separate “box”, since such components are well known in the art. However, it is to be understood that such displays also indicate the present of the underlying data processing system or computer and are a representation of the data processing system or computer as well as the display.
[0056] The above-described embodiments of the present invention have been provided to illustrate various aspects of the invention. However, it is to be understood that different aspects of the present invention that are shown in different specific embodiments can be combined to provide other embodiments of the present invention. In addition, various modifications to the present invention will become apparent from the foregoing description and accompanying drawings. Accordingly, the present invention is to be limited solely by the scope of the following claims. | A method for operating a data processing system having a display screen on which a GUI is displayed is disclosed. The GUI has a plurality of configurations having different aspect ratios or numbers of pixels. The method includes providing a layout description and a runtime system that generates the GUI in response to the layout description and the display configuration. The layout description defines a first container having a plurality of components to be shown in the GUI within a first container space. Each component has a component layout description within the first container. The runtime system automatically allocates the first container space depending on the display configuration, and automatically divides the first container space into plurality of component spaces. Each component is shown in a corresponding one of the component spaces. The first container space and the component spaces automatically change when the display configuration changes. | 6 |
TECHNICAL FIELD OF INVENTION
[0001] The present invention relates to inhibitors of p38, a mammalian protein kinase involved in cell proliferation, cell death and response to extracellular stimuli. The invention also relates to methods for producing these inhibitors. The invention also provides pharmaceutical compositions comprising the inhibitors of the invention and methods of utilizing those compositions in the treatment and prevention of various disorders.
BACKGROUND OF THE INVENTION
[0002] Protein kinases are involved in various cellular responses to extracellular signals. Recently, a family of mitogen-activated protein kinases (MAPK) has been discovered. Members of this family are Ser/Thr kinases that activate their substrates by phosphorylation [B. Stein et al., Ann. Rep. Med. Chem., 31, pp. 289-98 (1996)]. MAPKs are themselves activated by a variety of signals including growth factors, cytokines, UV radiation, and stress-inducing agents.
[0003] One particularly interesting MAPK is p38. p38, also known as cytokine suppressive anti-inflammatory drug binding protein (CSBP) and RK, was isolated from murine pre-B cells that were transfected with the lipopolysaccharide (LPS) receptor, CD14, and induced with LPS. p38 has since been isolated and sequenced, as has the cDNA encoding it in humans and mouse. Activation of p38 has been observed in cells stimulated by stress, such as treatment of lipopolysaccharides (LPS), UV, anisomycin, or osmotic shock, and by cytokines, such as IL-1 and TNF.
[0004] Inhibition of p38 kinase leads to a blockade on the production of both IL-1 and TNF. IL-1 and TNF stimulate the production of other proinflammatory cytokines such as IL-6 and IL-8 and have been implicated in acute and chronic inflammatory diseases and in post-menopausal osteoporosis [R. B. Kimble et al., Endocrinol., 136, pp. 3054-61 (1995)].
[0005] Based upon this finding, it is believed that p38, along with other MAPKs, have a role in mediating cellular response to inflammatory stimuli, such as leukocyte accumulation, macrophage/monocyte activation, tissue resorption, fever, acute phase responses and neutrophilia. In addition, MAPKs, such as p38, have been implicated in cancer, thrombin-induced platelet aggregation, immunodeficiency disorders, autoimmune diseases, cell death, allergies, osteoporosis and neurodegenerative disorders. Inhibitors of p38 have also been implicated in the area of pain management through inhibition of prostaglandin endoperoxide synthase-2 induction. Other diseases associated with 1′-1, IL-6, IL-8 or TNF overproduction are set forth in WO 96/21654.
[0006] Others have already begun trying to develop drugs that specifically inhibit MAPKs. For example, PCT publication WO 95/31451 describes pyrazole compounds that inhibit MAPKs, and, in particular, p38. However, the efficacy of these inhibitors in vivo is still being investigated.
[0007] Other p38 inhibitors have been produced, including those described in WO 98/27098, WO 99/00357, WO 99/10291, WO 99/58502, WO 99/64400, WO 00/17175 and WO 00/17204.
[0008] Accordingly, there is still a great need to develop other potent inhibitors of p38, including p38-specific inhibitors, that are useful in treating various conditions associated with p38 activation.
[0009] Another protein kinase that is involved in cellular responses to extracellular signals is ZAP70. When the T cell receptor (TCR) in T cells is triggered by binding an antigen, it in turn activates ZAP70. ZAP70 acts to couple the TCR to a number of essential signalling pathways that are required for T cell differentiation and proliferation.
[0010] Given ZAP70's role in T cell signalling, ZAP70 may have a role in T cell mediated diseases. Such diseases include, without limitation, transplantation, autoimune disease, e.g., RA, systemic lupus erythematosus (SLE), psoriasis, Sjogren's Syndrome, thyroiditis, pulmonary fibrosis, bronchiolitis obliterans, hemolytic anemia and Wegener's granulomatosis, cancer, including leukemia and lymphoma, multiple sclerosis, graft versus host disease, and Kawasaki syndrome.
[0011] Accordingly, there is a great need to develop inhibitors of ZAP70 that are useful in treating various conditions associated with ZAP70 activation.
SUMMARY OF THE INVENTION
[0012] The present invention addresses this problem by providing compounds that demonstrate inhibition of p38 and/or ZAP70.
[0013] These compounds have the general formula:
[0000]
[0000] wherein each of Q 1 and Q 2 are independently selected from a phenyl or 5-6 membered aromatic heterocyclic ring system, or a 8-10 membered bicyclic ring system comprising aromatic carbocyclic rings, aromatic heterocyclic rings or a combination of an aromatic carbocyclic ring and an aromatic heterocyclic ring.
[0014] A heterocyclic ring system or a heterocyclic ring contains 1 to 4 heteroatoms, which are independently selected from N, O, S, SO and SO 2 .
[0015] The rings that make up Q 1 are substituted with 1 to 4 substituents, each of which is independently selected from halo; C 1 -C 3 alkyl optionally substituted with NR′ 2 , OR′, CO 2 R′ or CONR′ 2 ; O—(C 1 -C 3 )-alkyl optionally substituted with NR′ 2 , OR′, CO 2 R′ or CONR′ 2 ; NR′ 2 ; OCF 3 ; CF 3 ; NO 2 ; CO 2 R′; CONR′; SR′; S(O 2 )N(R′) 2 ; SCF 3 ; CN; N(R′)C(O)R 4 ; N(R′)C(O)OR 4 ; N(R′)C(O)C(O)R 4 ; N(R′)S(O 2 )R 4 ; N(R′)R 4 ; N(R 4 ) 2 ; OR 4 ; OC(O)R 4 ; OP(O) 3 H 2 ; or N═C—N(R′) 2 .
[0016] The rings that make up Q 2 are optionally substituted with up to 4 substituents, each of which is independently selected from halogen; C 1 -C 3 straight or branched alkyl optionally substituted with R′, NR′ 2 , OR′, CO 2 R′, S(O 2 )N(R′) 2 , N═C—N(R′) 2 , R 3 , O—P(O 2 )H 2 , or CONR′ 2 ; O—(C 1 -C 3 )-alkyl; O—(C 1 -C 3 )-alkyl optionally substituted with NR′ 2 , OR′, CO 2 R′, S(O 2 )N(R′) 2 , N═CR′—N(R′) 2 , R 3 , OP(O 3 )H 2 , or CONR′ 2 ; NR′ 2 ; OCF 3 ; CF 3 ; NO 2 ; CO 2 R′; CONR′ 2 ; R 3 ; OR 3 ; NR 3 2 ; SR 3 ; C(O)R 3 ; C(O)N(R′)R 3 ; C(O)OR 3 ; SR′; S(O 2 )N(R′) 2 ; SCF 3 ; N═CR′—N(R′) 2 ; OR 4 ; O—CO 2 R 4 ; N(R′)C(O)R 4 ; N(R′)C(O)OR 4 ; N(R′)C(O)C(O)R 4 ; N(R′)S(O 2 )R 4 ; N(R′)R 4 ; N(R 4 ) 2 ; OR 4 ; OC(O)R 4 ; OP(O) 3 H 2 ; K; or CN.
[0017] Each R′ is independently selected from hydrogen; (C 1 -C 3 )-alkyl; (C 2 -C 3 )-alkenyl or alkynyl; phenyl or phenyl substituted with 1 to 3 substituents independently selected from halo, methoxy, cyano, nitro, amino, hydroxy, methyl or ethyl; or a 5-6 membered heterocyclic ring system optionally substituted with 1 to 3 substituents independently selected from halo, methoxy, cyano, nitro, amino, hydroxy, methyl or ethyl.
[0018] Each R is independently selected from hydrogen, —R 2 , —N(R 2 ) 2 , —OR 2 , SR 2 , —C(O)—N(R 2 ) 2 , —S(O 2 )—N(R 2 ) 2 , —C(O)—OR 2 or —C(O)R 2 wherein two adjacent R are optionally bound to one another and, together with each Y to which they are respectively bound, form a 4-8 membered carbocyclic or heterocyclic ring.
[0019] Each R 2 is independently selected from hydrogen; or (C 1 -C 3 )-alkyl or (C 1 -C 3 )-alkenyl, each optionally substituted with —N(R′) 2 , —OR′, SR′, —O—C(O)—N(R′) 2 , —C(O)—N(R′) 2 , —S(O 2 )—N(R′) 2 , —C(O)—OR′, —NSO 2 R 4 , —NSO 2 R 3 , —C(O)N(R′)(R 3 ), —NC(O)R 4 , —N(R′)(R 3 ), —N(R′)(R 4 )—C(O)R 3 , —C(O)N(R′)(R 4 ), —N(R 4 ) 2 , —C(O)N═C(NH) 2 or R 3 .
[0020] Each R 3 is independently selected from 5-8 membered aromatic or non-aromatic carbocyclic or heterocyclic ring systems each optionally substituted with R′, R 4 , —C(O)R′, —C(O)R 4 , —C(O)OR 4 or —K; or an 8-10 membered bicyclic ring system comprising aromatic carbocyclic rings, aromatic heterocyclic rings or a combination of an aromatic carbocyclic ring and an aromatic heterocyclic ring each optionally substituted with R′, R 4 , —C(O)R′, —C(O)R 4 , —C(O)OR 4 or —K.
[0021] Each R 4 is independently selected from R′; (C 1 -C 7 )-straight or branched alkyl optionally substituted with R′, N(R′) 2 , OR′, CO 2 R′, CON(R′) 2 , SO 2 N(R′) 2 or SO 2 N(R 5 ) 2 ; or a 5-6 membered carbocyclic or heterocyclic ring system optionally substituted with N(R′) 2 , OR′, CO 2 R′, CON(R′) 2 , SO 2 N(R′) 2 or SO 2 N(R 5 ) 2 .
[0022] Each R 5 is independently selected from hydrogen, (C 1 -C 3 )-alkyl, or (C 1 -C 3 )-alkenyl; each optionally substituted with —N(R′) 2 , —OR′, SR′, —C(O)—N(R′) 2 , —S(O 2 )—N(R′) 2 , —C(O)—OR′, —N—S(O 2 )(R′), —NSO 2 R 6 , —C(O)N(R′)(R 6 ), —NC(O)R′, —N(R′)(R 6 ), —C(O)R 6 , —C(O)N═C(NH) 2 or R 6 .
[0023] Each R 6 is independently selected from 5-8 membered aromatic or non-aromatic carbocyclic or heterocyclic ring systems each optionally substituted with R′, —C(O)R′ or —C(O)OR′; or an 8-10 membered bicyclic ring system comprising aromatic carbocyclic rings, aromatic heterocyclic rings or a combination of an aromatic carbocyclic ring and an aromatic heterocyclic ring each optionally substituted with R′, —C(O)R′ or C(O)OR′.
[0024] R 7 selected from H, halogen, or a (C 1 -C 3 ) straight chain or branched alkyl.
[0025] Each Y is independently selected from N or C. If either Y is N, then R or U attached to Y is a lone pair of electrons.
[0026] Z is CH, N, C(OCH 3 ), C(CH 3 ), C(NH 2 ), C(OH) or C(F).
[0027] Each U is independently selected from R or J.
[0028] Each J is independently selected from a (C 1 -C 4 ) straight chain or branched alkyl derivative substituted with T.
[0029] Each T is independently selected from either O(V) or N(H)(V).
[0030] Each V is independently selected from C(O)N═C(R)(N(R) 2 ), wherein the two geminal R on the nitrogen are optionally bound to one another to form a 4-8 membered carbocyclic or heterocyclic ring.
[0031] When the two R components form a ring, it will obvious to those skilled in the art that a terminal hydrogen from each unfused R component will be lost. For example, if a ring structure is formed by binding those two R components together, one being —CH 3 and the other being —CH 2 —CH 3 , one terminal hydrogen on each R component (indicated in bold) will be lost. Therefore, the resulting portion of the ring structure will have the formula —CH 2 —CH 2 —CH 2 —.
[0032] Each K is independently selected from a (C 1 -C 4 ) straight chain or branched alkyl derivative substituted with D, or —OP(O)(OH) 2 .
[0033] Each D is independently selected from either enantiomer of
[0000]
[0034] Each M is independently selected from either O or NH.
[0035] Each G is independently selected from NH 2 , OH, or H.
[0036] Each R 8 is independently selected from H, OH, C(O)OH, (C 1 -C 7 )-straight or branched alkyl optionally substituted with N(R′) 2 , OR′, CO 2 R′, CON(R′) 2 , or SO 2 N(R 5 ) 2 ; or a 5-6 membered carbocyclic, heterocyclic or heteroaryl ring system optionally substituted with N(R′) 2 , OR′, CO 2 R′, CON(R′) 2 , or SO 2 N(R 5 ) 2 . When G forms a ring with R 8 , it will be obvious to those skilled in the art that a terminal hydrogen from the unfused G and R 8 component will be lost. For example, if a ring structure is formed by binding the G and R 8 components together, one being —NH 2 and the other being —CH 2 —CH 2 —CH 2 —CH 3 , one terminal hydrogen on each R component (indicated in bold) will be lost. Therefore, the resulting portion of the ring structure will have the formula —NH—CH 2 —CH 2 —CH 2 —CH 2 —.
[0037] In another embodiment, the invention provides pharmaceutical compositions comprising the p38 and/or ZAP70 inhibitors of this invention. These compositions may be utilized in methods for treating or preventing a variety of p38-mediated disorders, such as cancer, inflammatory diseases, autoimmune diseases, destructive bone disorders, proliferative disorders, infectious diseases, viral diseases and neurodegenerative diseases or ZAP70-mediated disorders, including transplantation, autoimune disease, cancer, multiple sclerosis, graft versus host disease, and Kawasaki syndrome. These compositions are also useful in methods for preventing cell death and hyperplasia and therefore may be used to treat or prevent reperfusion/ischemia in stroke, heart attacks, and organ hypoxia. The compositions are also useful in methods for preventing thrombin-induced platelet aggregation. Each of these above-described methods is also part of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0038] These compounds have the general formula:
[0000]
[0000] wherein each of Q 1 and Q 2 are independently selected from a phenyl or 5-6 membered aromatic heterocyclic ring system, or a 8-10 membered bicyclic ring system comprising aromatic carbocyclic rings, aromatic heterocyclic rings or a combination of an aromatic carbocyclic ring and an aromatic heterocyclic ring.
[0039] The rings that make up Q 1 are substituted with 1 to 4 substituents, each of which is independently selected from halo; C 1 -C 3 alkyl optionally substituted with NR′ 2 , OR′, CO 2 R′ or CONR′ 2 ; O—(C 1 -C 3 )-alkyl optionally substituted with NR′ 2 , OR′, CO 2 R′ or CONR′ 2 ; NR′ 2 ; OCF 3 ; CF 3 ; NO 2 ; CO 2 R′; CONR′; SR′; S(O 2 )N(R′) 2 ; SCF 3 ; CN; N(R′)C(O)R 4 ; N(R′)C(O)OR 4 ; N(R′)C(O)C(O)R 4 ; N(R′)S(O 2 )R 4 ; N(R′)R 4 ; N(R 4 ) 2 ; OR 4 ; OC(O)R 4 ; OP(O) 3 H 2 ; or N═C—N(R′) 2 .
[0040] The rings that make up Q 2 are optionally substituted with up to 4 substituents, each of which is independently selected from halogen; C 1 -C 3 straight or branched alkyl optionally substituted with R′, NR′ 2 , OR′, CO 2 R′, S(O 2 )N(R′) 2 , N═C—N(R′) 2 , R 3 , O—P(O 3 )H 2 , or CONR′ 2 ; O—(C 1 -C 3 )-alkyl; O—(C 1 -C 3 )-alkyl optionally substituted with NR′ 2 , OR′, CO 2 R′, S(O 2 )N(R′) 2 , N═CR′—N(R′) 2 , R 3 , OP(O 3 )H 2 , or CONR′ 2 ; NR′ 2 ; OCF 3 ; CF 3 ; NO 2 ; CO 2 R′; CONR′ 2 ; R 3 ; OR 3 ; NR 3 2 ; SR 3 ; C(O)R 3 ; C(O)N(R′)R 3 ; C(O)OR 3 ; SR′; S(O 2 )N(R′) 2 ; SCF 3 ; N═CR′—N(R′) 2 ; OR 4 ; O—CO 2 R 4 ; N(R′)C(O)R 4 ; N(R′)C(O)OR 4 ; N(R′)C(O)C(O)R 4 ; N(R′)S(O 2 )R 4 ; N(R′)R 4 ; N(R 4 ) 2 ; OR 4 ; OC(O)R 4 ; OP(O) 3 H 2 ; K; or CN.
[0041] Each R′ is independently selected from hydrogen; (C 1 -C 3 )-alkyl; (C 2 -C 3 )-alkenyl or alkynyl; phenyl or phenyl substituted with 1 to 3 substituents independently selected from halo, methoxy, cyano, nitro, amino, hydroxy, methyl or ethyl; or a 5-6 membered heterocyclic ring system optionally substituted with 1 to 3 substituents independently selected from halo, methoxy, cyano, nitro, amino, hydroxy, methyl or ethyl.
[0042] Each R is independently selected from hydrogen, —R 2 , —N(R 2 ) 2 , —OR 2 , SR 2 , —C(O)—N(R 2 ) 2 , —S(O 2 )—N(R 2 ) 2 , —C(O)—OR 2 or —C(O)R 2 wherein two adjacent R are optionally bound to one another and, together with each Y to which they are respectively bound, form a 4-8 membered carbocyclic or heterocyclic ring.
[0043] Each R 2 is independently selected from hydrogen; or (C 1 -C 3 )-alkyl or (C 1 -C 3 )-alkenyl, each optionally substituted with —N(R′) 2 , —OR′, SR′, —O—C(O)—N(R′) 2 , —C(O)—N(R′) 2 , —S(O 2 )—N(R′) 2 , —C(O)—OR′, —NSO 2 R 4 , —NSO 2 R 3 , —C(O)N(R′)(R 3 ), —NC(O)R 4 , —N(R′)(R 3 ), —N(R′)(R 4 ), —C(O)R 3 , —C(O)N(R′)(R 4 ), —N(R 4 ) 2 , —C(O)N═C(NH) 2 or R 3 .
[0044] Each R 3 is independently selected from 5-8 membered aromatic or non-aromatic carbocyclic or heterocyclic ring systems each optionally substituted with R′, R 4 , —C(O)R′, —C(O)R 4 , —C(O)OR 4 or —K; or an 8-10 membered bicyclic ring system comprising aromatic carbocyclic rings, aromatic heterocyclic rings or a combination of an aromatic carbocyclic ring and an aromatic heterocyclic ring each optionally substituted with R′, R 4 , —C(O)R′, —C(O)R 4 , —C(O)OR 4 or —K.
[0045] Each R 4 is independently selected from R′; (C 1 -C 7 )-straight or branched alkyl optionally substituted with R′, N(R′) 2 , OR′, CO 2 R′, CON(R′) 2 , SO 2 N(R′) 2 or SO 2 N(R 5 ) 2 ; or a 5-6 membered carbocyclic or heterocyclic ring system optionally substituted with N(R′) 2 , OR′, CO 2 R′, CON(R′) 2 , SO 2 N(R′) 2 or SO 2 N(R 5 ) 2 .
[0046] Each R 5 is independently selected from hydrogen, (C 1 -C 3 )-alkyl, or (C 1 -C 3 )-alkenyl; each optionally substituted with —N(R′) 2 , —OR′, SR′, —C(O)—N(R′) 2 , —S(O 2 )—N(R′) 2 , —C(O)—OR′, —N—S(O 2 )(R′), —NSO 2 R 6 , —C(O)N(R′)(R 6 ), —NC(O)R′, —N(R′)(R 6 ), —C(O)R 6 , —C(O)N═C(NH) 2 or R 6 .
[0047] Each R 6 is independently selected from 5-8 membered aromatic or non-aromatic carbocyclic or heterocyclic ring systems each optionally substituted with R′, —C(O)R′ or —C(O)OR′; or an 8-10 membered bicyclic ring system comprising aromatic carbocyclic rings, aromatic heterocyclic rings or a combination of an aromatic carbocyclic ring and an aromatic heterocyclic ring each optionally substituted with R′, —C(O)R′ or C(O)OR′.
[0048] R 7 is selected from H, halogen, or a (C 1 -C 3 ) straight chain or branched alkyl.
[0049] Each Y is independently selected from N or C. If either Y is N, then R or U attached to Y is a lone pair of electrons.
[0050] Z is CH, N, C(OCH 3 ), C(CH 3 ), C(NH 2 ), C(OH) or C(F).
[0051] Each U is independently selected from R or J.
[0052] Each J is independently selected from a (C 1 -C 4 ) straight chain or branched alkyl derivative substituted with T.
[0053] Each T is independently selected from either O(V) or N(H)(V).
[0054] Each V is independently selected from C(O)N═C(R)(N(R) 2 ), wherein the two geminal R on the nitrogen are optionally bound to one another to form a 4-8 membered carbocyclic or heterocyclic ring.
[0055] When the two R components form a ring, it will obvious to those skilled in the art that a terminal hydrogen from each unfused R component will be lost. For example, if a ring structure is formed by binding those two R components together, one being —CH 3 and the other being —CH 2 —CH 3 , one terminal hydrogen on each R component (indicated in bold) will be lost. Therefore, the resulting portion of the ring structure will have the formula —CH 2 —CH 2 —CH 2 —.
[0056] Each K is independently selected from a (C 1 -C 4 ) straight chain or branched alkyl derivative substituted with D, or —OP(O)(OH) 2 .
[0057] Each D is independently selected from either enantiomer of
[0000]
[0058] Each M is independently selected from either O or NH.
[0059] Each G is independently selected from NH 2 , OH, or H.
[0060] Each R 8 is independently selected from H, OH, C(O)OH, (C 1 -C 7 )-straight or branched alkyl optionally substituted with N(R′) 2 , OR′, CO 2 R′, CON(R′) 2 , or SO 2 N(R 5 ) 2 ; or a 5-6 membered carbocyclic, heterocyclic or heteroaryl ring system optionally substituted with N(R′) 2 , OR′, CO 2 R′, CON(R′) 2 , or SO 2 N(R 5 ) 2 . When G forms a ring with R 8 , it will be obvious to those skilled in the art that a terminal hydrogen from the unfused G and R 8 component will be lost. For example, if a ring structure is formed by binding the G and R 8 components together, one being —NH 2 and the other being —CH 2 —CH 2 —CH 2 —CH 3 , one terminal hydrogen on each R component (indicated in bold) will be lost. Therefore, the resulting portion of the ring structure will have the formula —NH—CH 2 —CH 2 —CH 2 —CH 2 —.
[0061] A heterocyclic ring system or a heterocyclic ring contains 1 to 4 heteroatoms, which are independently selected from N, O, and S. A substitutable nitrogen on an aromatic or non-aromatic heterocyclic ring may be optionally substituted. N or S may also exist in oxidized form such as NO, SO and SO 2 .
[0062] One having ordinary skill in the art will recognize that the maximum number of heteroatoms in a stable, chemically feasible heterocyclic ring, whether it is aromatic or non-aromatic, is determined by the size of the ring, degree of unsaturation, and valence of the heteroatoms. In general, a heterocyclic ring may have one to four heteroatoms so long as the heterocyclic ring is chemically feasible and stable.
[0063] The term “chemically stable arrangement” or “chemically feasible and stable” as used herein, refers to a compound structure that renders the compound sufficiently stable to allow manufacture and administration to a mammal by methods known in the art. Typically, such compounds are stable at a temperature of 40° C. or less, in the absence of moisture or other chemically reactive conditions, for at least a week.
[0064] According to a preferred embodiment, Q 1 is selected from phenyl or pyridyl containing 1 to 3 substituents, wherein at least one of said substituents is in the ortho position and said substituents are independently selected from chloro, fluoro, bromo, —CH 3 , —OCH 3 , —OH, CF 3 , —OCF 3 , —O(CH 2 ) 2 CH 3 , —NH 2 , 3,4-methylenedioxy, —N(CH 3 ) 2 , —NH—S(O) 2 -phenyl, —NH—C(O)O—CH 2 -4-pyridine, —NH—C(O)CH 2 -morpholine, —NH—C(O)CH 2 —N(CH 3 ) 2 , —NH—C(O)CH 2 -piperazine, —NH—C(O)CH 2 -pyrrolidine, —NH—C(O)C(O)-morpholine, —NH—C(O)C(O)-piperazine, —NH—C(O)C(O)-pyrrolidine, —O—C(O)CH 2 —N(CH 3 ) 2 , or —O— (CH 2 ) 2 —N(CH 3 ) 2 .
[0065] Even more preferred are phenyl or pyridyl containing at least 2 of the above-indicated substituents both being in the ortho position.
[0066] Some specific examples of preferred Q 1 are:
[0000]
[0067] Most preferably, Q 1 is selected from 2-fluoro-6-trifluoromethylphenyl, 2,6-difluorophenyl, 2,6-dichlorophenyl, 2-chloro-4-hydroxyphenyl, 2-chloro-4-aminophenyl, 2,6-dichloro-4-aminophenyl, 2,6-dichloro-3-aminophenyl, 2,6-dimethyl-4-hydroxyphenyl, 2-methoxy-3,5-dichloro-4-pyridyl, 2-chloro-4,5 methylenedioxy phenyl, or 2-chloro-4-(N-2-morpholino-acetamido)phenyl.
[0068] According to a preferred embodiment, Q 2 is phenyl, pyridyl or naphthyl containing 0 to 3 substituents, wherein each substituent is independently selected from chloro, fluoro, bromo, methyl, ethyl, isopropyl, —OCH 3 , —OH, —NH 2 , —CF 3 , —OCF 3 , —SCH 3 , —OCH 3 , —C(O)OH, —C(O)OCH 3 , —CH 2 NH 2 , —N(CH 3 ) 2 , —CH 2 -pyrrolidine and —CH 2 OH.
[0000] Some specific examples of preferred Q 2 are:
[0000]
[0000] unsubstituted 2-pyridyl or unsubstituted phenyl.
[0069] Most preferred are compounds wherein Q 2 is selected from phenyl, 2-isopropylphenyl, 3,4-dimethylphenyl, 2-ethylphenyl, 3-fluorophenyl, 2-methylphenyl, 3-chloro-4-fluorophenyl, 3-chlorophenyl, 2-carbomethoxylphenyl, 2-carboxyphenyl, 2-methyl-4-chlorophenyl, 2-bromophenyl, 2-pyridyl, 2-methylenehydroxyphenyl, 4-fluorophenyl, 2-methyl-4-fluorophenyl, 2-chloro-4-fluorphenyl, 2,4-difluorophenyl, 2-hydroxy-4-fluorphenyl, 2-methylenehydroxy-4-fluorophenyl, 1-naphthyl, 3-chloro-2-methylenehydroxy, 3-chloro-2-methyl, or 4-fluoro-2-methyl.
[0070] According to another preferred embodiment, R 7 is a halogen. In a more preferred embodiment, R 7 is Cl.
[0071] According to another preferred embodiment, each Y is C.
[0072] According an even more preferred embodiment, each Y is C and the R and U attached to each Y component is hydrogen.
[0073] Some specific examples of preferred J are:
[0000]
[0074] According to another preferred embodiment, K is a 0-4 atom chain terminating in an ester.
[0075] According to another preferred embodiment, M is O.
[0076] Some specific examples of preferred K are:
[0000]
[0077] More preferably, K is selected from:
[0000]
[0078] Some preferred embodiments are provided in Tables 1 to 3 below:
[0000]
TABLE 1
Cmpd
Nmbr
Structure
101
102
103
104
105
106
107
108
109
110
[0000]
TABLE 2
Cmpd
Nmbr
Structure
111
112
113
114
115
116
117
[0000]
TABLE 3
Cmpd
Nmbr
Structure
118
119
120
121
122
123
124
125
[0079] Particularly preferred embodiments include:
[0000]
[0000] wherein Ar is
[0000]
[0000] and
[0000]
[0080] Particularly preferred embodiments also include:
[0000]
[0000] wherein Ar is
[0000]
[0081] Other particularly preferred embodiments include:
[0000]
[0000] wherein Ar is
[0000]
[0082] Other particularly preferred embodiments include:
[0000]
[0000] wherein
[0000]
[0083] Other particularly preferred embodiments include:
[0000]
[0000] wherein
[0000]
[0084] Other particularly preferred embodiments include:
[0000]
[0000] wherein X is N(CH 3 ) 2 ,
[0000]
[0085] Other particularly preferred embodiments include:
[0000]
[0000] wherein Y=Me or H; and X═(CH 2 ) 3 , CH 2 C(CH 3 ) 2 CH 2 , CH 2 N(Me)C(O)CH 2 .
[0086] Some most preferred embodiments include:
[0000]
[0087] According to another embodiment, the present invention provides methods of producing the above-identified compounds of the formulae (Ia), (Ib), (Ic) or (Id). Representative synthesis schemes are depicted below. In all schemes, the L1 and L2 groups on the initial materials are meant to represent leaving groups ortho to the nitrogen atom in a heterocyclic ring. For example, compound A may be 2,6-dichloro-3 nitro pyridine.
[0000]
[0088] One having skill in the art will recognize Scheme 1 may be used to synthesize compounds having the general formula of (Ia), (Ib), (Ic) and (Id).
[0089] According to another embodiment of the invention, the activity of the p38 inhibitors of this invention may be assayed in vitro, in vivo or in a cell line. In vitro assays include assays that determine inhibition of either the kinase activity or ATPase activity of activated p38. Alternate in vitro assays quantitate the ability of the inhibitor to bind to p38 and may be measured either by radiolabelling the inhibitor prior to binding, isolating the inhibitor/p38 complex and determining the amount of radiolabel bound, or by running a competition experiment where new inhibitors are incubated with p38 bound to known radioligands.
[0090] Cell culture assays of the inhibitory effect of the compounds of this invention may determine the amounts of TNF, IL-1, IL-6 or IL-8 produced in whole blood or cell fractions thereof in cells treated with inhibitor as compared to cells treated with negative controls. Level of these cytokines may be determined through the use of commercially available ELISAs.
[0091] An in vivo assay useful for determining the inhibitory activity of the p38 inhibitors of this invention are the suppression of hind paw edema in rats with Mycobacterium butyricum -induced adjuvant arthritis. This is described in J. C. Boehm et al., J. Med. Chem., 39, pp. 3929-37 (1996), the disclosure of which is herein incorporated by reference. The p38 inhibitors of this invention may also be assayed in animal models of arthritis, bone resorption, endotoxin shock and immune function, as described in A. M. Badger et al., J. Pharmacol. Experimental Therapeutics, 279, pp. 1453-61 (1996), the disclosure of which is herein incorporated by reference.
[0092] The p38 inhibitors or pharmaceutical salts thereof may be formulated into pharmaceutical compositions for administration to animals or humans. These pharmaceutical compositions, which comprise an amount of p38 inhibitor effective to treat or prevent a p38-mediated condition and a pharmaceutically acceptable carrier, are another embodiment of the present invention.
[0093] The term “p38-mediated condition”, as used herein means any disease or other deleterious condition in which p38 is known to play a role. This includes conditions known to be caused by IL-1, TNF, IL-6 or IL-8 overproduction. Such conditions include, without limitation, inflammatory diseases, autoimmune diseases, destructive bone disorders, proliferative disorders, infectious diseases, neurodegenerative diseases, allergies, reperfusion/ischemia in stroke, heart attacks, angiogenic disorders, organ hypoxia, vascular hyperplasia, cardiac hypertrophy, thrombin-induced platelet aggregation, and conditions associated with prostaglandin endoperoxidase synthase-2.
[0094] Inflammatory diseases which may be treated or prevented by the compounds of this invention include, but are not limited to, acute pancreatitis, chronic pancreatitis, asthma, allergies, and adult respiratory distress syndrome.
[0095] Autoimmune diseases which may be treated or prevented by the compounds of this invention include, but are not limited to, glomerulonephritis, rheumatoid arthritis, systemic lupus erythematosus, scleroderma, chronic thyroiditis, Graves' disease, autoimmune gastritis, diabetes, autoimmune hemolytic anemia, autoimmune neutropenia, thrombocytopenia, atopic dermatitis, chronic active hepatitis, myasthenia gravis, multiple sclerosis, inflammatory bowel disease, ulcerative colitis, Crohn's disease, psoriasis, or graft vs. host disease.
[0096] Destructive bone disorders which may be treated or prevented by the compounds of this invention include, but are not limited to, osteoporosis, osteoarthritis and multiple myeloma-related bone disorder.
[0097] Proliferative diseases which may be treated or prevented by the compounds of this invention include, but are not limited to, acute myelogenous leukemia, chronic myelogenous leukemia, metastatic melanoma, Kaposi's sarcoma, and multiple myeloma.
[0098] Angiogenic disorders which may be treated or prevented by the compounds of this invention include solid tumors, ocular neovasculization, infantile haemangiomas.
[0099] Infectious diseases which may be treated or prevented by the compounds of this invention include, but are not limited to, sepsis, septic shock, and Shigellosis.
[0100] Viral diseases which may be treated or prevented by the compounds of this invention include, but are not limited to, acute hepatitis infection (including hepatitis A, hepatitis B and hepatitis C), HIV infection and CMV retinitis.
[0101] Neurodegenerative diseases which may be treated or prevented by the compounds of this invention include, but are not limited to, Alzheimer's disease, Parkinson's disease, cerebral ischemias or neurodegenerative disease caused by traumatic injury.
[0102] “p38-mediated conditions” also include ischemia/reperfusion in stroke, heart attacks, myocardial ischemia, organ hypoxia, vascular hyperplasia, cardiac hypertrophy, and thrombin-induced platelet aggregation.
[0103] In addition, p38 inhibitors of the instant invention are also capable of inhibiting the expression of inducible pro-inflammatory proteins such as prostaglandin endoperoxide synthase-2 (PGHS-2), also referred to as cyclooxygenase-2 (COX-2). Therefore, other “p38-mediated conditions” which may be treated by the compounds of this invention include edema, analgesia, fever and pain, such as neuromuscular pain, headache, cancer pain, dental pain and arthritis pain.
[0104] The diseases that may be treated or prevented by the p38 inhibitors of this invention may also be conveniently grouped by the cytokine (IL-1, TNF, IL-6, IL-8) that is believed to be responsible for the disease.
[0105] Thus, an IL-1-mediated disease or condition includes rheumatoid arthritis, osteoarthritis, stroke, endotoxemia and/or toxic shock syndrome, inflammatory reaction induced by endotoxin, inflammatory bowel disease, tuberculosis, atherosclerosis, muscle degeneration, cachexia, psoriatic arthritis, Reiter's syndrome, gout, traumatic arthritis, rubella arthritis, acute synovitis, diabetes, pancreatic β-cell disease and Alzheimer's disease.
[0106] TNF-mediated disease or condition includes, rheumatoid arthritis, rheumatoid spondylitis, osteoarthritis, gouty arthritis and other arthritic conditions, sepsis, septic shock, endotoxic shock, gram negative sepsis, toxic shock syndrome, adult respiratory distress syndrome, cerebral malaria, chronic pulmonary inflammatory disease, silicosis, pulmonary sarcoidosis, bone resorption diseases, reperfusion injury, graft vs. host reaction, allograft rejections, fever and myalgias due to infection, cachexia secondary to infection, AIDS, ARC or malignancy, keloid formation, scar tissue formation, Crohn's disease, ulcerative colitis or pyresis. TNF-mediated diseases also include viral infections, such as HIV, CMV, influenza and herpes; and veterinary viral infections, such as lentivirus infections, including, but not limited to equine infectious anemia virus, caprine arthritis virus, visna virus or maedi virus; or retrovirus infections, including feline immunodeficiency virus, bovine immunodeficiency virus, or canine immunodeficiency virus.
[0107] IL-8 mediated disease or condition includes diseases characterized by massive neutrophil infiltration, such as psoriasis, inflammatory bowel disease, asthma, cardiac and renal reperfusion injury, adult respiratory distress syndrome, thrombosis and glomerulonephritis.
[0108] In addition, the compounds of this invention may be used topically to treat or prevent conditions caused or exacerbated by IL-1 or TNF. Such conditions include inflamed joints, eczema, psoriasis, inflammatory skin conditions such as sunburn, inflammatory eye conditions such as conjunctivitis, pyresis, pain and other conditions associated with inflammation.
[0109] According to another embodiment, the compounds of this invention may be used to treat ZAP70-mediated conditions including, without limitation, organ or tissue rejection associated with transplantation, autoimune disease, e.g., rheumatoid arthritis, systemic lupus erythematosus (SLE), psoriasis, Sjogren's Syndrome, thyroiditis, pulmonary fibrosis, bronchiolitis obliterans, hemolytic anemia and Wegener's granulomatosis, cancer, including leukemia and lymphoma, multiple sclerosis, graft versus host disease, and Kawasaki syndrome.
[0110] The ZAP70 inhibitors or pharmaceutical salts thereof may be formulated into pharmaceutical compositions for administration to animals or humans. These pharmaceutical compositions, which comprise an amount of ZAP70 inhibitor effective to treat or prevent a ZAP70-mediated condition and a pharmaceutically acceptable carrier, are another embodiment of the present invention.
[0111] In addition to the compounds of this invention, pharmaceutically acceptable salts of the compounds of this invention may also be employed in compositions to treat or prevent the above-identified disorders.
[0112] Pharmaceutically acceptable salts of the compounds of this invention include those derived from pharmaceutically acceptable inorganic and organic acids and bases. Examples of suitable acid salts include acetate, adipate, alginate, aspartate, benzoate, benzenesulfonate, bisulfate, butyrate, citrate, camphorate, camphorsulfonate, cyclopentanepropionate, digluconate, dodecylsulfate, ethanesulfonate, formate, fumarate, glucoheptanoate, glycerophosphate, glycolate, hemisulfate, heptanoate, hexanoate, hydrochloride, hydrobromide, hydroiodide, 2-hydroxyethanesulfonate, lactate, maleate, malonate, methanesulfonate, 2-naphthalenesulfonate, nicotinate, nitrate, oxalate, palmoate, pectinate, persulfate, 3-phenylpropionate, phosphate, picrate, pivalate, propionate, salicylate, succinate, sulfate, tartrate, thiocyanate, tosylate and undecanoate. Other acids, such as oxalic, while not in themselves pharmaceutically acceptable, may be employed in the preparation of salts useful as intermediates in obtaining the compounds of the invention and their pharmaceutically acceptable acid addition salts. Salts derived from appropriate bases include alkali metal (e.g., sodium and potassium), alkaline earth metal (e.g., magnesium), ammonium and N—(C1-4 alkyl)-4+ salts. This invention also envisions the quaternization of any basic nitrogen-containing groups of the compounds disclosed herein. Water or oil-soluble or dispersible products may be obtained by such quaternization.
[0113] Pharmaceutically acceptable carriers that may be used in these pharmaceutical compositions include, but are not limited to, ion exchangers, alumina, aluminum stearate, lecithin, serum proteins, such as human serum albumin, buffer substances such as phosphates, glycine, sorbic acid, potassium sorbate, partial glyceride mixtures of saturated vegetable fatty acids, water, salts or electrolytes, such as protamine sulfate, disodium hydrogen phosphate, potassium hydrogen phosphate, sodium chloride, zinc salts, colloidal silica, magnesium trisilicate, polyvinyl pyrrolidone, cellulose-based substances, polyethylene glycol, sodium carboxymethylcellulose, polyacrylates, waxes, polyethylene-polyoxypropylene-block polymers, polyethylene glycol and wool fat.
[0114] The compositions of the present invention may be administered orally, parenterally, by inhalation spray, topically, rectally, nasally, buccally, vaginally or via an implanted reservoir. The term “parenteral” as used herein includes subcutaneous, intravenous, intramuscular, intra-articular, intra-synovial, intrasternal, intrathecal, intrahepatic, intralesional and intracranial injection or infusion techniques. Preferably, the compositions are administered orally, intraperitoneally or intravenously.
[0115] Sterile injectable forms of the compositions of this invention may be aqueous or oleaginous suspension. These suspensions may be formulated according to techniques known in the art using suitable dispersing or wetting agents and suspending agents. The sterile injectable preparation may also be a sterile injectable solution or suspension in a non-toxic parenterally-acceptable diluent or solvent, for example as a solution in 1,3-butanediol. Among the acceptable vehicles and solvents that may be employed are water, Ringer's solution and isotonic sodium chloride solution. In addition, sterile, fixed oils are conventionally employed as a solvent or suspending medium. For this purpose, any bland fixed oil may be employed including synthetic mono- or di-glycerides. Fatty acids, such as oleic acid and its glyceride derivatives are useful in the preparation of injectables, as are natural pharmaceutically-acceptable oils, such as olive oil or castor oil, especially in their polyoxyethylated versions. These oil solutions or suspensions may also contain a long-chain alcohol diluent or dispersant, such as carboxymethyl cellulose or similar dispersing agents which are commonly used in the formulation of pharmaceutically acceptable dosage forms including emulsions and suspensions. Other commonly used surfactants, such as Tweens, Spans and other emulsifying agents or bioavailability enhancers which are commonly used in the manufacture of pharmaceutically acceptable solid, liquid, or other dosage forms may also be used for the purposes of formulation.
[0116] The pharmaceutical compositions of this invention may be orally administered in any orally acceptable dosage form including, but not limited to, capsules, tablets, aqueous suspensions or solutions. In the case of tablets for oral use, carriers commonly used include lactose and corn starch. Lubricating agents, such as magnesium stearate, are also typically added. For oral administration in a capsule form, useful diluents include lactose and dried cornstarch. When aqueous suspensions are required for oral use, the active ingredient is combined with emulsifying and suspending agents. If desired, certain sweetening, flavoring or coloring agents may also be added.
[0117] Alternatively, the pharmaceutical compositions of this invention may be administered in the form of suppositories for rectal administration. These can be prepared by mixing the agent with a suitable non-irritating excipient which is solid at room temperature but liquid at rectal temperature and therefore will melt in the rectum to release the drug. Such materials include cocoa butter, beeswax and polyethylene glycols.
[0118] The pharmaceutical compositions of this invention may also be administered topically, especially when the target of treatment includes areas or organs readily accessible by topical application, including diseases of the eye, the skin, or the lower intestinal tract. Suitable topical formulations are readily prepared for each of these areas or organs.
[0119] Topical application for the lower intestinal tract can be effected in a rectal suppository formulation (see above) or in a suitable enema formulation. Topically-transdermal patches may also be used.
[0120] For topical applications, the pharmaceutical compositions may be formulated in a suitable ointment containing the active component suspended or dissolved in one or more carriers. Carriers for topical administration of the compounds of this invention include, but are not limited to, mineral oil, liquid petrolatum, white petrolatum, propylene glycol, polyoxyethylene, polyoxypropylene compound, emulsifying wax and water. Alternatively, the pharmaceutical compositions can be formulated in a suitable lotion or cream containing the active components suspended or dissolved in one or more pharmaceutically acceptable carriers. Suitable carriers include, but are not limited to, mineral oil, sorbitan monostearate, polysorbate 60, cetyl esters wax, cetearyl alcohol, 2-octyldodecanol, benzyl alcohol and water.
[0121] For ophthalmic use, the pharmaceutical compositions may be formulated as micronized suspensions in isotonic, pH adjusted sterile saline, or, preferably, as solutions in isotonic, pH adjusted sterile saline, either with or without a preservative such as benzylalkonium chloride. Alternatively, for ophthalmic uses, the pharmaceutical compositions may be formulated in an ointment such as petrolatum.
[0122] The pharmaceutical compositions of this invention may also be administered by nasal aerosol or inhalation. Such compositions are prepared according to techniques well-known in the art of pharmaceutical formulation and may be prepared as solutions in saline, employing benzyl alcohol or other suitable preservatives, absorption promoters to enhance bioavailability, fluorocarbons, and/or other conventional solubilizing or dispersing agents.
[0123] The amount of p38 or ZAP70 inhibitor that may be combined with the carrier materials to produce a single dosage form will vary depending upon the host treated and the particular mode of administration. Preferably, the compositions should be formulated so that a dosage of between 0.01-100 mg/kg body weight/day of the inhibitor can be administered to a patient receiving these compositions.
[0124] It should also be understood that a specific dosage and treatment regimen for any particular patient will depend upon a variety of factors, including the activity of the specific compound employed, the age, body weight, general health, sex, diet, time of administration, rate of excretion, drug combination, and the judgment of the treating physician and the severity of the particular disease being treated. The amount of inhibitor will also depend upon the particular compound in the composition.
[0125] According to another embodiment, the invention provides methods for treating or preventing a p38-mediated condition comprising the step of administering to a patient one of the above-described pharmaceutical compositions. The term “patient”, as used herein, means an animal, preferably a human.
[0126] Preferably, that method is used to treat or prevent a condition selected from inflammatory diseases, autoimmune diseases, destructive bone disorders, proliferative disorders, infectious diseases, degenerative diseases, allergies, reperfusion/ischemia in stroke, heart attacks, angiogenic disorders, organ hypoxia, vascular hyperplasia, cardiac hypertrophy, and thrombin-induced platelet aggregation.
[0127] According to another embodiment, the inhibitors of this invention are used to treat or prevent an IL-1, IL-6, IL-8 or TNF-mediated disease or condition. Such conditions are described above.
[0128] Depending upon the particular p38-mediated condition to be treated or prevented, additional drugs, which are normally administered to treat or prevent that condition, may be administered together with the inhibitors of this invention. For example, chemotherapeutic agents or other anti-proliferative agents may be combined with the p38 inhibitors of this invention to treat proliferative diseases.
[0129] Those additional agents may be administered separately, as part of a multiple dosage regimen, from the p38 inhibitor-containing composition. Alternatively, those agents may be part of a single dosage form, mixed together with the p38 inhibitor in a single composition.
[0130] According to another embodiment, the invention provides methods for treating or preventing a ZAP70-mediated condition comprising the step of administering to a patient one of the above-described pharmaceutical compositions.
[0131] In order that the invention described herein may be more fully understood, the following examples are set forth. It should be understood that these examples are for illustrative purposes only and are not to be construed as limiting this invention in any manner.
Example 1
Synthesis of p38 Inhibitor Compound 7
[0132]
[0133] To a solution of LDA (60 mmol, 40 mLs) at −78° C., was added dropwise a solution of 2,6-dibromopyridine (40 mmol, 9.48 gms) in THF (30 mLs, dried). The mixture was stirred at −78° C. for 20 minutes. Ethyl formate (400 mmol, 32.3 mLs) was added and stirring was continued at −78° C. for 2 hours. Saturated ammonium chloride (200 mLs) was added and the mixture was warmed to room temperature. The reaction mixture was diluted with ethyl acetate and the organic layer was washed with aqueous acid and base. The organic layer was dried and evaporated in vacuo. The resulting material was purified by flash chromatography on silica gel followed by eluting with 10% ethyl acetate in n-hexane to afford 1 (32 mmol, 8.41 gms) as a white solid.
[0000]
[0134] A solution of 1 (776 mmol 205.6 gms) and triethyl orthoformate (200 mL) dissolved in ethanol (750 mL) was refluxed overnight. The reaction mixture was cooled, and evaporated in vacuo. The remaining red oil was dissolved in hexane and filtered over a plug of silica gel. The plug was eluted with 50% CH 2 Cl 2 /hexane. The filtrate was evaporated to afford 2 as an oil.
[0000]
[0135] To a suspension of 60% NaH (130 mmol, 5.20 g) and 2 (61.2 mmol, 20.76 g) in THF (100 mL) at reflux was added dropwise a solution of 2,6-difluoroaniline (61.3 mmol, 20 g) in THF (100 mL). After the aniline had been added, Pd(PPh 3 ) 4 (100 mg) was added. The mixture was refluxed for one hour and cooled. Hydrochloric acid (1N, 100 mL) was added and stirring was continued for one hour. The reaction mixture was extracted with CH 2 Cl 2 . The organic extract was dried and evaporated in vacuo. The resulting material was dissolved in a minimal amount of CH 2 Cl 2 and hexane was added. The solution was cooled precipitating 3 as a yellow solid.
[0000]
[0136] p-fluorophenylboronic acid (57.5 mmol, 8.05 g), and 3 (46.9 mmol, 14.70 g) were dissolved in a dimethoxyethane (300 mL). Cesium fluoride (68.6 mmol, 10.42 g) and tetrakis(triphenylphosphine)palladium (0) (100 mgs) were added to the solution and the suspension was allowed to reflux overnight. The reaction mixture was poured into water and extracted with CH 2 Cl 2 . The organic extract was washed with 1N NaOH, dried with MgSO o and filtered over a plug of silica gel. The plug was eluted with CH 2 Cl 2 and the filtrate was evaporated in vacuo. The resulting yellow solid was triturated with 50% CH 2 Cl 2 /hexane to afford 4 (9.50 g, 62%) as a yellow solid.
[0000]
[0137] A solution of 4 (70.1 mmol 23.01 g) in toluene (250 mL) was combined with a 20% solution of phosgene in toluene (151 mmol, 80 mL) and heated to reflux for two hours. The reaction was cooled and poured into ammonium hydroxide. The mixture was stirred for five minutes and extracted with methylene chloride. The organic extract was dried and filtered over a plug of silica gel. The plug was eluted with methylene chloride to remove residual starting material. It was then eluted with 50% ethyl acetate/methylene chloride to obtain 5. The filtrate was evaporated in vacuo to afford 5 (21.38 g, 86%) as a white solid.
[0000]
[0138] Sodium borohydride (36.5 mmol, 1.38 g) was added to a solution of 5 (60.0 mmol, 21.38 g) in THF (100 mL) and the solution was stirred for one hour at 0° C. and then two hours at room temperature. The reaction was poured into 1N HCl and extracted with methylene chloride. The organic extract was dried and filtered over a plug of silica gel. The plug was eluted with 5% ethyl acetate/methylene chloride to remove residual starting material. It was then eluted with ethyl acetate to obtain 6. The filtrate was evaporated to afford 6 as a white solid.
[0139] The spectral data for compound 6 was:
[0140] 1 H NMR (500 MHz, CDCl 3 ) δ7.90 (d, 1H), 7.60 (d, 2H), 7.5-7.3 (m, 5H), 6.30 (d, 2H), 4.5 (s, 2H), 2.3 (s, 2H).
[0000]
[0141] A solution of 6 (2.79 mmol, 1.00 g) and p-nitrophenyl chloroformate (5.56 mmol, 1.12 g) was cooled to 0° C. Triethylamine (14.3 mmol, 2.0 mL) was added and the solution was stirred for 15 minutes and poured into ammonium hydroxide. The solution mixture was poured into water and extracted with methylene chloride. The organic extract was washed with saturated aqueous sodium bicarbonate, dried, and evaporated in vacuo to afford 7 (730 mg, 65%) as a white solid.
Example 2
Synthesis of p38 Inhibitor Prodrugs 9 and 10
[0142]
[0143] A mixture of 8 (1.0 g, 2.30 mmol) and N,N-dimethylformamide dimethyl acetal (1.01 g, 6.91 mmol) in 10 mL of toluene was heated to 80° C. for 20 minutes. The resulting solution was cooled to room temperature. Normal workup followed by chromatography on silica gel (hexane/EtOAc:10/4) gave amidine 9 (compound 101 of Table 1) as a white solid. The spectral data for compound 9 was: 1 H NMR (500 MHz, CDCl 3 ) δ8.3 (s, 1H), 7.7 (d, 1H), 7.5-7.4 (m, 1H), 7.1-7.0 (m, 1H), 6.95-6.85 (t, 2H), 6.85-6.75 (m, 1H), 6.45-6.4 (d, 1H), 6.2 (s, 1H), 4.95 (s, 2H), 3.05 (s, 3H), 2.95 (s, 3H).
[0000]
[0144] A mixture of 8 (1.0 g, 2.30 mmol) and N,N-dimethylformamide dimethyl acetal (3.3 g, 22.4 mmol) in 10 mL of toluene was heated to 80° C. for 90 minutes. The resulting solution was cooled to room temperature. Normal workup followed by chromatography on silica gel (hexane/EtOAc:2/1) gave bis-amidine 10 (compound 107 of Table 1) as a white solid. The spectral data for compound 10 was: 1 H NMR (500 MHz, CDCl 3 ) δ8.4 (s, 1H), 8.3 (s, 1H), 8.05-7.95 (s, 1H), 7.15-7.05 (m, 2H), 6.85-6.75 (t, 2H), 6.75-6.65 (m, 4H), 4.95 (s, 2H), 3.0-2.95 (d, 9H), 2.65 (s, 3H).
Example 3
Synthesis of p38 Inhibitor Prodrug 13
[0145]
[0146] To a mixture of 6 (1.25 gm, 3.35 mmol) and 4-nitrophenyl chloroformate (0.81 gm, 4.02 mmol) in tetrahydrofuran (30 mL) was added triethylamine (1.16 mL, 8.38 mmol) dropwise at 0° C. The resulting slurry was allowed to stir at 0° C. for 30 minutes. Ethanolamine (0.6 mL, 10.0 mmol) was added and the solution was stirred at 0° C. for 30 minutes. Normal work-up followed by chromatography on silica (hexane/acetone:10/4) gave 11 (1.03 gm, 2.23 mmol) as a white solid. 1 H NMR (500 MHz, CDCl 3 ) 7.75 (d, 1H), 7.65-7.55 (m, 2H), 7.5-7.4 (m, 1H), 7.25-7.15 (t, 2H), 7.15-7.05 (t, 2H), 6.4 (d, 1H), 5.2-5.1 (bs, 1H), 5.15 (s, 2H), 3.75-3.65 (t, 2H), 3.4-3.3 (m, 2H).
[0000]
[0147] A mixture of 11 (1.03 gm, 2.23 mmol), (L)-BOC-Val-OH (0.97 gm, 4.46 mmol), and 1-(3-dimethylaminopropyl) 3-ethylcarbodiimide hydrochloride in methylene chloride (30 mL) was stirred at room temperature for 1.5 hours. Normal work-up followed by chromatography on silica (hexane/acetone:10/4) gave Val deriv. 12 (1.38 gms, 2.09 mmol) as a white solid. 1 H NMR (500 MHz, CDCl 3 ) 7.75 (d, 1H), 7.65-7.55 (m, 2H), 7.5-7.4 (m, 1H), 7.25-7.15 (t, 2H), 7.15-7.05 (t, 2H), 6.4 (d, 1H), 5.40-5.35 (bs, 1H), 5.05 (s, 2H), 5.00-4.95 (d, 1H), 4.4-4.3 (m, 1H), 4.25-4.15 (m, 1H), 4.15-4.05 (m, 1H), 3.55-3.45 (m, 2H), 2.15-2.05 (m, 1H), 1.45 (s, 9H), 1.0-0.85 (m, 6H).
[0000]
[0148] To a solution of 12 (1.38 gms, 2.09 mmol) in methylene chloride (20 mLs) was added trifluoroacetic acid (10 mLs). The solution was allowed to stir at room temperature for 1 hour. Normal work-up gave a white solid that was converted to its hydrochloride salt to give 13 (compound 111 of Table 2; 0.61 gms, 1.02 mmol) as a white solid. The spectral data for compound 13 was: 1 H NMR (500 MHz, CDCl 3 ) 7.65 (d, 1H), 7.55-7.45 (m, 2H), 7.4-7.3 (m, 1H), 7.15-7.05 (m, 2H), 7.05-6.95 (m, 2H), 6.35 (d, 1H), 5.05-5.00 (bs, 1H), 4.95 (s, 2H), 4.15-4.05 (m, 2H), 3.45-3.25 (m, 2H), 3.2 (s, 1H), 1.95-1.85 (m, 1H), 0.90-0.75 (m, 6H).
Example 4
Cloning of p38 Kinase in Insect Cells
[0149] Two splice variants of human p38 kinase, CSBP1 and CSBP2, have been identified. Specific oligonucleotide primers were used to amplify the coding region of CSBP2 cDNA using a HeLa cell library (Stratagene) as a template. The polymerase chain reaction product was cloned into the pET-15b vector (Novagen). The baculovirus transfer vector, pVL-(His)6-p38 was constructed by subcloning a XbaI-BamHI fragment of pET15b-(His)6-p38 into the complementary sites in plasmid pVL1392 (Pharmingen).
[0150] The plasmid pVL-(His)6-p38 directed the synthesis of a recombinant protein consisting of a 23-residue peptide (MGSSHHHHHHSSGLVPRGSHMLE, where LVPRGS represents a thrombin cleavage site) fused in frame to the N-terminus of p38, as confirmed by DNA sequencing and by N-terminal sequencing of the expressed protein. Monolayer culture of Spodoptera frugiperda (Sf9) insect cells (ATCC) was maintained in TNM-FH medium (Gibco BRL) supplemented with 10% fetal bovine serum in a T-flask at 27° C. Sf9 cells in log phase were co-transfected with linear viral DNA of Autographa califonica nuclear polyhedrosis virus (Pharmingen) and transfer vector pVL-(His)6-p38 using Lipofectin (Invitrogen). The individual recombinant baculovirus clones were purified by plaque assay using 1% low melting agarose.
Example 5
Expression and Purification of Recombinant p38 Kinase
[0151] Trichoplusia ni (Tn-368) High-Five™ cells (Invitrogen) were grown in suspension in Excel-405 protein free medium (JRH Bioscience) in a shaker flask at 27° C. Cells at a density of 1.5×10 6 cells/ml were infected with the recombinant baculovirus described above at a multiplicity of infection of 5. The expression level of recombinant p38 was monitored by immunoblotting using a rabbit anti-p38 antibody (Santa Cruz Biotechnology). The cell mass was harvested 72 hours after infection when the expression level of p38 reached its maximum.
[0152] Frozen cell paste from cells expressing the (His) 6 -tagged p38 was thawed in 5 volumes of Buffer A (50 mM NaH 2 PO 4 pH 8.0, 200 mM NaCl, 2 mM β-Mercaptoethanol, 10% Glycerol and 0.2 mM PMSF). After mechanical disruption of the cells in a microfluidizer, the lysate was centrifuged at 30,000×g for 30 minutes. The supernatant was incubated batchwise for 3-5 hours at 4° C. with Talon™ (Clontech) metal affinity resin at a ratio of 1 ml of resin per 2-4 mgs of expected p38. The resin was settled by centrifugation at 500×g for 5 minutes and gently washed batchwise with Buffer A. The resin was slurried and poured into a column (approx. 2.6×5.0 cm) and washed with Buffer A+5 mM imidazole.
[0153] The (His) 6 -p38 was eluted with Buffer A+100 mM imidazole and subsequently dialyzed overnight at 4° C. against 2 liters of Buffer B, (50 mM HEPES, pH 7.5, 25 mM 5-glycerophosphate, 5% glycerol, 2 mM DTT). The His 6 tag was removed by addition of at 1.5 units thrombin (Calbiochem) per mg of p38 and incubation at 20° C. for 2-3 hours. The thrombin was quenched by addition of 0.2 mM PMSF and then the entire sample was loaded onto a 2 ml benzamidine agarose (American International Chemical) column.
[0154] The flow through fraction was directly loaded onto a 2.6×5.0 cm Q-Sepharose (Pharmacia) column previously equilibrated in Buffer B+0.2 mM PMSF. The p38 was eluted with a 20 column volume linear gradient to 0.6M NaCl in Buffer B. The eluted protein peak was pooled and dialyzed overnight at 4° C. vs. Buffer C (50 mM HEPES pH 7.5, 5% glycerol, 50 mM NaCl, 2 mM DTT, 0.2 mM PMSF).
[0155] The dialyzed protein was concentrated in a Centriprep (Amicon) to 3-4 ml and applied to a 2.6×100 cm Sephacryl S-100HR (Pharmacia) column. The protein was eluted at a flow rate of 35 ml/hr. The main peak was pooled, adjusted to 20 mM DTT, concentrated to 10-80 mgs/ml and frozen in aliquots at −70° C. or used immediately.
Example 6
Activation of p38
[0156] p38 was activated by combining 0.5 mg/ml p38 with 0.005 mg/ml DD-double mutant MKK6 in Buffer B+10 mM MgCl 2 , 2 mM ATP, 0.2 mM Na 2 VO 4 for 30 minutes at 20° C. The activation mixture was then loaded onto a 1.0×10 cm MonoQ column (Pharmacia) and eluted with a linear 20 column volume gradient to 1.0 M NaCl in Buffer B. The activated p38 eluted after the ADP and ATP. The activated p38 peak was pooled and dialyzed against buffer B+0.2 mM Na 2 VO 4 to remove the NaCl. The dialyzed protein was adjusted to 1.1M potassium phosphate by addition of a 4.0M stock solution and loaded onto a 1.0×10 cm HIC (Rainin Hydropore) column previously equilibrated in Buffer D (10% glycerol, 20 mM 5-glycerophosphate, 2.0 mM DTT)+1.1MK 2 HPO 4 . The protein was eluted with a 20 column volume linear gradient to Buffer D+50 mM K 2 HPO 4 . The double phosphorylated p38 eluted as the main peak and was pooled for dialysis against Buffer B+0.2 mM Na 2 VO 4 . The activated p38 was stored at −70° C.
Example 7
p38 Inhibition Assays
A. Inhibition of Phosphorylation of EGF Receptor Peptide
[0157] This assay was carried out in the presence of 10 mM MgCl 2 , 25 mM 2-glycerophosphate, 10% glycerol and 100 mM HEPES buffer at pH 7.6. For a typical IC 50 determination, a stock solution was prepared containing all of the above components and activated p38 (5 nM). The stock solution was aliquotted into vials. A fixed volume of DMSO or inhibitor in DMSO (final concentration of DMSO in reaction was 5%) was introduced to each vial, mixed and incubated for 15 minutes at room temperature. EGF receptor peptide, KRELVEPLTPSGEAPNQALLR, a phosphoryl acceptor in p38-catalyzed kinase reaction (1), was added to each vial to a final concentration of 200 μM. The kinase reaction was initiated with ATP (100 μM) and the vials were incubated at 30° C. After 30 minutes, the reactions were quenched with equal volume of 10% trifluoroacetic acid (TFA).
[0158] The phosphorylated peptide was quantified by HPLC analysis. Separation of phosphorylated peptide from the unphosphorylated peptide was achieved on a reverse phase column (Deltapak, 5 μm, C18 100D, Part no. 011795) with a binary gradient of water and acteonitrile, each containing 0.1% TFA. IC 50 (concentration of inhibitor yielding 50% inhibition) was determined by plotting the percent (%) activity remaining against inhibitor concentration.
B. Inhibition of ATPase Activity
[0159] This assay is carried out in the presence of 10 mM MgCl 2 , 25 mM β-glycerophosphate, 10% glycerol and 100 mM HEPES buffer at pH 7.6. For a typical Ki determination, the Km for ATP in the ATPase activity of activated p38 reaction is determined in the absence of inhibitor and in the presence of two concentrations of inhibitor. A stock solution is prepared containing all of the above components and activated p38 (60 nM). The stock solution is aliquotted into vials. A fixed volume of DMSO or inhibitor in DMSO (final concentration of DMSO in reaction was 2.5%) is introduced to each vial, mixed and incubated for 15 minutes at room temperature. The reaction is initiated by adding various concentrations of ATP and then incubated at 30° C. After 30 minutes, the reactions are quenched with 50 μl of EDTA (0.1 M, final concentration), pH 8.0. The product of p38 ATPase activity, ADP, is quantified by HPLC analysis.
[0160] Separation of ADP from ATP is achieved on a reversed phase column (Supelcosil, LC-18, 3 μm, part no. 5-8985) using a binary solvent gradient of following composition: Solvent A—0.1 M phosphate buffer containing 8 mM tetrabutylammonium hydrogen sulfate (Sigma Chemical Co., catalogue no. T-7158), Solvent B—Solvent A with 30% methanol.
[0161] Ki is determined from the rate data as a function of inhibitor and ATP concentrations.
[0162] p38 inhibitors of this invention will inhibit the ATPase activity of p38.
C. Inhibition of IL-1, TNF, IL-6 and IL-8 Production in LPS-Stimulated PBMCs
[0163] Inhibitors were serially diluted in DMSO from a 20 mM stock. At least 6 serial dilutions were prepared. Then 4× inhibitor stocks were prepared by adding 4 μl of an inhibitor dilution to 1 ml of RPMI1640 medium/10% fetal bovine serum. The 4× inhibitor stocks contained inhibitor at concentrations of 80 μM, 32 μM, 12.8 μM, 5.12 μM, 2.048 μM, 0.819 μM, 0.328 μM, 0.131 μM, 0.052 μM, 0.021 μM etc. The 4× inhibitor stocks were pre-warmed at 37° C. until use.
[0164] Fresh human blood buffy cells were separated from other cells in a Vacutainer CPT from Becton & Dickinson (containing 4 ml blood and enough DPBS without Mg 2+ /Ca 2+ to fill the tube) by centrifugation at 1500×g for 15 min. Peripheral blood mononuclear cells (PBMCs), located on top of the gradient in the Vacutainer, were removed and washed twice with RPMI1640 medium/10% fetal bovine serum. PBMCs were collected by centrifugation at 500×g for 10 min. The total cell number was determined using a Neubauer Cell Chamber and the cells were adjusted to a concentration of 4.8×10 6 cells/ml in cell culture medium (RPMI1640 supplemented with 10% fetal bovine serum).
[0165] Alternatively, whole blood containing an anti-coagulant was used directly in the assay.
[0166] 100 μl of cell suspension or whole blood were placed in each well of a 96-well cell culture plate. Then 50 μl of the 4× inhibitor stock was added to the cells. Finally, 50 μl of a lipopolysaccharide (LPS) working stock solution (16 ng/ml in cell culture medium) was added to give a final concentration of 4 ng/ml LPS in the assay. The total assay volume of the vehicle control was also adjusted to 200 μl by adding 50 μl cell culture medium. The PBMC cells or whole blood were then incubated overnight (for 12-15 hours) at 37° C./5% CO 2 in a humidified atmosphere.
[0167] The next day the cells were mixed on a shaker for 3-5 minutes before centrifugation at 500×g for 5 minutes. Cell culture supernatants were harvested and analyzed by ELISA for levels of IL-1β (R & D Systems, Quantikine kits, #DBL50), TNF-α (BioSource, #KHC3012), IL-6 (Endogen, #EH2-IL6) and IL-8 (Endogen, #EH2-IL8) according to the instructions of the manufacturer. The ELISA data were used to generate dose-response curves from which IC50 values were derived.
[0168] Results for the kinase assay (“kinase”; subsection A, above), IL-1, and TNF in LPS-stimulated PBMC's (“cell”) and IL-1, TNF, and IL-6 in whole blood (“WB”) for various p38 inhibitors of this invention are shown in Table 7 below:
[0000]
TABLE 7
Kinase
Cell IL-1
Cell TNF
WB IL-1
WB TNF
WB IL-6
Compound
M.W.
IC50 (uM)
IC50 (uM)
IC50 (uM)
IC50 (uM)
IC50 (uM)
IC50 (uM)
13
559.55
0.031
0.012
0.022
0.140
0.055
0.083
9
489.43
1.0
0.05
0.05
12.2
20.0
11.0
10
544.51
5.0
2.2
4.3
0.8
[0169] Other p38 inhibitors of this invention will also inhibit phosphorylation of EGF receptor peptide, and will inhibit the production of IL-1, TNF and IL-6, as well as IL-8, in LPS-stimulated PBMCs or in whole blood.
D. Inhibition of IL-6 and IL-8 Production in IL-1-Stimulated PBMCs
[0170] This assay is carried out on PBMCs exactly the same as above except that 50 μl of an IL-1b working stock solution (2 ng/ml in cell culture medium) is added to the assay instead of the (LPS) working stock solution.
[0171] Cell culture supernatants are harvested as described above and analyzed by ELISA for levels of IL-6 (Endogen, #EH2-IL6) and IL-8 (Endogen, #EH2-IL8) according to the instructions of the manufacturer. The ELISA data are used to generate dose-response curves from which IC50 values were derived.
E. Inhibition of LPS-Induced Prostaglandin Endoperoxide Synthase-2 (PGHS-2, or COX-2) Induction in PBMCs
[0172] Human peripheral mononuclear cells (PBMCs) are isolated from fresh human blood buffy coats by centrifugation in a Vacutainer CPT (Becton & Dickinson). 15×10 6 cells are seeded in a 6-well tissue culture dish containing RPMI 1640 supplemented with 10% fetal bovine serum, 50 U/ml penicillin, 50 μg/ml streptomycin, and 2 mM L-glutamine. Compounds are added at 0.2, 2.0 and 20 μM final concentrations in DMSO. LPS is then added at a final concentration of 4 ng/ml to induce enzyme expression. The final culture volume is 10 ml/well.
[0173] After overnight incubation at 37° C., 5% CO 2 , the cells are harvested by scraping and subsequent centrifugation, the supernatant is removed, and the cells are washed twice in ice-cold DPBS (Dulbecco's phosphate buffered saline, BioWhittaker). The cells are lysed on ice for 10 min in 50 μl cold lysis buffer (20 mM Tris-HCl, pH 7.2, 150 mM NaCl, 1% Triton-X-100, 1% deoxycholic acid, 0.1% SDS, 1 mM EDTA, 2% aprotinin (Sigma), 10 μg/ml pepstatin, 10 μg/ml leupeptin, 2 mM PMSF, 1 mM benzamidine, 1 mM DTT) containing 1 μl Benzonase (DNAse from Merck). The protein concentration of each sample is determined using the BCA assay (Pierce) and bovine serum albumin as a standard. Then the protein concentration of each sample is adjusted to 1 mg/ml with cold lysis buffer. To 100 μl lysate an equal volume of 2×SDS PAGE loading buffer is added and the sample is boiled for 5 min. Proteins (30 μg/lane) are size-fractionated on 4-20% SDS PAGE gradient gels (Novex) and subsequently transferred onto nitrocellulose membrane by electrophoretic means for 2 hours at 100 mA in Towbin transfer buffer (25 mM Tris, 192 mM glycine) containing 20% methanol. After transfer, the membrane is pretreated for 1 hour at room temperature with blocking buffer (5% non-fat dry milk in DPBS supplemented with 0.1% Tween-20) and washed 3 times in DPBS/0.1% Tween-20. The membrane is incubated overnight at 4° C. with a 1:250 dilution of monoclonal anti-COX-2 antibody (Transduction Laboratories) in blocking buffer. After 3 washes in DPBS/0.1% Tween-20, the membrane is incubated with a 1:1000 dilution of horseradish peroxidase-conjugated sheep antiserum to mouse Ig (Amersham) in blocking buffer for 1 h at room temperature. Then the membrane is washed again 3 times in DPBS/0.1% Tween-20. An ECL detection system (SuperSignal™ CL-HRP Substrate System, Pierce) is used to determine the levels of expression of COX-2.
Example 8
ZAP70 Inhibition Assay
[0174] The activity of ZAP 70 is measured by determining the phosphorylation poly E4Y (Sigma Chemicals, St Louis Mo.) with γ- 33 P ATP (NEN, Boston, Mass.). Reactions are carried out at room temperature in a buffer containing 100 mM HEPES, pH 7.5, 10 mM MgCl 2 , 25 mM NaCl, 1 mM DTT and 0.01% BSA. Final concentrations of ZAP70 and poly E4Y are 20 nM and 5 μM respectively. Test compounds in DMSO (final concentration of compounds was 30 μM in 1.5% DMSO) are added to the reaction mixture containing the above-described components. The reaction is initiated by addition of γ- 33 P ATP (final concentration 20 μM, specific activity=0.018 Ci/mmol). The reaction is allowed to proceed for 12 minutes and then is quenched by the addition of 10% TCA containing 200 mM ATP. The quenched reaction is harvested onto GF/C glass fiber filter plates (Packard, Meriden, Conn.) using a Tomtec 9600 cell harvester (Tomtec, Hamden, Conn.). The plates are washed with 5% TCA containing 1 mM ATP and water. 50 μl of scintillation fluid is added to the plates, which are then counted using a Packard scintillation counter (Packard, Meriden, Conn.). 1050 values for inhibitory compounds were determined using the same assay at a series of compound concentrations.
[0175] While we have hereinbefore presented a number of embodiments of this invention, it is apparent that our basic construction can be altered to provide other embodiments which utilize the methods of this invention. | The present invention relates to inhibitors of p38, a mammalian protein kinase involved cell proliferation, cell death and response to extracellular stimuli. The invention also relates to inhibitors of ZAP70. The invention also relates to methods for producing these inhibitors. The invention also provides pharmaceutical compositions comprising the inhibitors of the invention and methods of utilizing those compositions in the treatment and prevention of various disorders. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Patent Application Ser. No. 61/292,466, filed Jan. 5, 2010, entitled “Crosstalk suppression in time sequential liquid crystal stereoscopic display systems,” the entirety of which is herein incorporated by reference.
TECHNICAL FIELD
[0002] This disclosure generally relates to direct view stereoscopic displays, and, more specifically, this disclosure relates to direct view 3D stereoscopic displays that provide alternately polarized left and right eye images encoded with a modulating liquid crystal (LC) panel and polarization control panel (PCP) on the front of the display.
BACKGROUND
[0003] Stereoscopic displays are seeing a revival following the success of 3D cinematic productions. Technology has played its part in making what used to be an uncomfortable experience into enjoyable and desirable entertainment.
[0004] Cinematic display technology is primarily polarization encoded projection of time-sequential left and right eye images. Alternate images are flashed onto a screen through a liquid crystal modulating element that imparts near orthogonal circularly polarized states onto the projected light. Reflection from a ‘silver’ screen preserves polarization so that viewers that don appropriate analyzing eyewear see only those images destined for correct eyes. The difference between left and right eye images produces stereoscopic disparity which is naturally interpreted by a user as depth.
[0005] An extension of this technology is to apply it to TVs in the home enabling 3D in the living room. Unfortunately, the response time used by time sequential 3D is at odds with the dominant display technology, particularly in liquid crystal display (LCD) based displays. Extending the cinema approach to high-quality stereoscopic TV is therefore difficult because it means being able to display alternate images at high frame rate without noticeable frame to frame mixing and motion blur.
SUMMARY
[0006] Methods for crosstalk suppression in a liquid crystal stereoscopic display system are provided. The methods include, after displaying a first eye image, stopping light to a viewer for a dark period. During the dark period, data is written sequentially on a liquid crystal (LC) panel and a reset pulse is applied to an electrode on the LC panel after the last line is written. The methods also include allowing light to the viewer after the reset pulse is applied for a viewing period.
[0007] According to an aspect, the dark period may include turning off a backlight, while the viewing period may include turning on the backlight.
[0008] According to another aspect, the dark period and viewing period may include synchronizing with shutter glasses blocking or allowing light to a viewer.
[0009] According to another aspect, the data may be written sequentially from top to bottom lines of the LC panel. Voltages may be applied to bottom electrodes corresponding to pixels of the LC panel and the reset pulse may be applied to a top electrode on the LC panel.
[0010] According to another aspect, during the dark period, substantially all pixels in the LC panel are globally reset to a common LC state. The common LC state may be a common dark state. A second eye image may be displayed.
[0011] According to another aspect, during the dark period, a polarization converting panel may be switched between a first-eye and a second-eye polarization mode.
[0012] These and other advantages of the present disclosure will become apparent to those skilled in the art from the following detailed description, the accompanying drawings, and the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 is a schematic diagram illustrating the operation of a continuously backlit LCD panel;
[0014] FIG. 2 is a schematic diagram illustrating the operation of a backlit LCD panel, employing a segmented polarization control element;
[0015] FIG. 3 is a schematic diagram illustrating the operation of a scrolling backlight LCD panel;
[0016] FIG. 4 is a schematic diagram illustrating the operation of a LCD panel system in which the back light unit is modulated globally to display images during periods where the line-by-line addressing is interrupted between complete frame addressed cycles;
[0017] FIG. 5 is a schematic diagram illustrating a cross section of a liquid crystal display during the transition time between alternate images;
[0018] FIG. 6 is a schematic diagram illustrating a cross section of a liquid crystal display during the transition time between alternate images, in accordance with the present disclosure;
[0019] FIG. 7 is a graph of pixel transmission of a twisted nematic (TN) LCD as a function of time, in accordance with the present disclosure;
[0020] FIG. 8A is a schematic diagram illustrating the operation of an LC display system;
[0021] FIG. 8B is a schematic diagram illustrating the operation of an embodiment of an LC display system using global reset of the LC panel, in accordance with the present disclosure;
[0022] FIG. 9 is a schematic diagram of a system in which an LC display is reset to a common state through scrolled addressing, in accordance with the present disclosure;
[0023] FIG. 10 is a flow diagram illustrating a process of crosstalk suppression in a time sequential LCD system, in accordance with the present disclosure; and
[0024] FIG. 11 is a schematic diagram illustrating a system for crosstalk suppression in a stereoscopic LCD system, in accordance with the present disclosure.
DETAILED DESCRIPTION
[0025] Generally, the disclosed approaches work by driving an LC quickly to a common state between frames, effectively erasing previous frame data and providing a common starting point for addressing next frame data. Appropriate common states may be those that are driven by high applied voltages. Common states may be reached in sub-milliseconds regardless of the LC's previous state. LC modes that drive to black (i.e., normally white) are particularly well-suited as they provide high-contrast, low-crosstalk stereoscopic images. For this reason, the embodiments discussed include, for example, normally white twisted nematic (TN) LC panels. Note, however, that the general concept may be applied according to the principles disclosed herein to other LC modes where the common driven state might be other than black.
[0026] The disclosed approaches assume conventional thin-film transistor (TFT) addressing of transmissive LCD panels, where images are updated through line-by-line deposition of charge onto local capacitors—one for each pixel. This charge imparts a voltage onto a transmitting indium tin oxide (ITO) electrode that acts to alter the LC state and its modulation properties. The time taken to deposit charge can be much faster than the response of the liquid crystal, which may result in incorrect specification of panel frame update rates. Currently-advertised 240 Hz LCD panels do not possess the capability yet of providing 240 viewable, independent frames per second. Furthermore, the effect of line-by-line addressing provides a scrolling update, where next frames appear to ‘grow’ from the top to the bottom of the display. Between the current and next frame is a moving region of intermediate display data whose size is dependent on both the address rate and the response of the LC. For fast TN LC panels addressed at 120 Hz, this intermediate region can be ˜25% of the display area. The display of intermediate information is cause for large crosstalk in time-sequenced stereoscopic LC displays, as witnessed by the recent Nvidia active eyewear shutter-glass solution (See http://www.nvidia.com/object/3D_Vision — Overview.html). Indeed, the Nvidia active eyewear shutter-glass solution has its drawbacks, including high cross-talk toward the bottom of the screen due to viewing the mixed data during the period toward the end of the addressing cycle.
[0027] There have been several approaches to overcoming the problems of scrolling mixed displayed data. Some approaches use segmented, scrolling polarization control panels (PCPs) and/or scrolling illumination, as discussed below.
[0028] This disclosure relates to avoiding viewing mixed data (i.e., crosstalk of left and right eye images) through a common reset of the LC state between viewable periods. This disclosure also relates to solving the problem of motion blur that typically occurs with LC panels by virtue of flashing the backlight at a low duty cycle.
[0029] At least two approaches are provided by this disclosure. One approach employs driving the common transparent ITO electrode deposited on the top substrate of the LC panel. This same substrate (or top-plate) contains the red, green, and blue color filter array (CFA) and the surrounding black matrix masking. Applying a voltage to this electrode drives the LC material to a common driven state independent of the addressed data value (i.e., charge on the local pixel capacitors). Some embodiments use this effect to accomplish the desired common reset. A second related approach drives the LC to a common state through modified TFT addressing exclusive of top-plate driving.
[0030] U.S. Pat. No. 4,281,341, (herein incorporated by reference) relates to the basic overall system concept of a display and liquid crystal modulator. It includes embodiments with scrolling polarization control panels. Commonly-owned U.S. Pat. No. 6,975,345 (herein incorporated by reference) relates to segmented pi-cells, includes methods to suppress boundary visibility, and is complementary to the systems disclosed herein. More recently, commonly-owned U.S. Patent Pub. No. 2008/0316303 includes teachings that encompass controlling the back light illuminator, while commonly-owned patent application Ser. No. 12/853,265 includes teachings that encompass altering the rate and/or intermittency of the line-by-line addressing scheme (both herein incorporated by reference).
[0031] The resurgent interest in 3D has also spurred some recent published material describing PCP LCD systems, for instance, as published in article LG Display Co., SID '09 DIGEST, pp. 348-351. A demonstration unit based on the LG-disclosed technology was also on show at the SID '09 conference.
[0032] General details concerning these teachings and how they relate to the present disclosure are discussed in the next section. One example of how the presently disclosed approach is distinct from the above teachings is that it involves driving the LC to a common state between displaying alternate left and right eye image data.
[0033] Some aspects of the present disclosure include top-plate voltage driving and double-line addressing. Unlike the approaches discussed in a series of U.S. patents, U.S. Pat. Nos. 5,920,298; 6,046,716; 6,078,303; 6,104,367; 6,144,353; 6,304,239; and 6,329,971 (hereinafter “'298 family”) (herein incorporated by reference), aspects of this disclosure relate to a top-plate drive approach for solving problems recognized herein relating to stereoscopic displays. More specifically, the present disclosure recognizes that existing TFT panels do not provide sufficient local pixel capacitance above and beyond that of the parallel electrode structure that sandwiches the LC material. As such, top-plate driving grossly affects the fidelity of conventional addressing because a top-plate voltage is applied during interrupted periods of addressing. In contrast, the teachings of the '298 family imply coincident address and hold with applied top plate voltage. Moreover, the present disclosure relates to top plate modulating schemes in which mixed data is displayed for a period prior to reset when a second displayed data is displayed solely and viewed. This is a consequence of adhering to conventional TFT panels and their line-by-line addressing which is not discussed in prior art approaches. In contrast, all patents in the '298 family claim a sequence of displayed data. According to the teachings of the '298 family, first an image is shown associated with one set of data. A resetting/holding voltage is then applied to the top-plate after which a new image associated with new data is displayed. In short, the '298 family describes top-plate driving in a general sense including sequential frame independence, but does not solve the problems recognized herein relating to stereoscopic displays nor discuss the above-mentioned approaches relating to addressing and mixed data display.
[0034] The presently-disclosed second approach relies on addressing lines to a common state (typically black) prior to being addressed with new data. Unlike the concepts disclosed in commonly-owned U.S. patent application Ser. No. 12/853,274, which relate to the concept of addressing alternate frames to black, the presently-disclosed prior black frame insertion approach uses a data period different from a frame period between driving a pixel to its correct value from when it is driven to black. In some embodiments, conventional panels can be addressed twice within a frame time, and having non-adjacent sequential row addressing, may use a modification to the row-enable driver circuitry.
[0035] FIG. 1 is a schematic diagram illustrating the operation of a conventional display 100 having a continuously backlit LCD panel. The conventional display 100 typically includes a continuously lit back light unit (BLU) 110 and a liquid crystal modulating panel 120 .
[0036] In FIG. 1 , two snapshots 130 , 140 are shown side by side, separated in time by a fraction of a frame update period. The first snapshot 130 shows operation at a time=t, and the second snapshot 140 shows operation at a time=t+Δt. In operation, update of an LCD is carried out line-by-line, shown by update line 150 . At any given time, a voltage is applied to a single row electrode, which enables pixel based thin-film transistor (TFT) elements along that row to direct current from data columns onto local storage capacitors. The desired data current is applied in parallel prior to disabling the row's TFTs through application of a second row voltage. The next row is then addressed in a similar fashion leaving behind the LC material to respond to the newly applied voltage. Gradually, as more and more lines are addressed, the LC material settles into a state determined by the deposited charge. This results in a scrolling update, where the line addressed at any given time leads a finite mixed imagery region 160 above it in its wake. This is shown schematically in FIG. 1 , illustrating the addressing of a LCD display.
[0037] A back light unit 110 continuously illuminates a modulating LCD panel 120 , whose display is updated using a line-by-line addressing scheme. The modest liquid crystal response time results in a gradual transition from one image to the next depicted here by a series of Rs and Ls for alternate right and left eye images respectively. FIG. 1 shows two time-delayed schematic snapshots 130 , 140 of a typical system where the scrolling update reveals the LC transition as a mixed region 160 above the address line 150 .
[0038] Optimally, the address time is maximized so current conventional 2D panels do not pause significantly between completing the addressing of a first frame and the beginning of the next. As a result, at no time is there a complete image corresponding to a single frame. Sequential stereoscopic viewing of independent left and right eye images is therefore not viable with conventional LCDs.
[0039] FIG. 2 is a schematic diagram 200 illustrating the operation of a known continuously backlit LCD panel 220 , employing a segmented polarization control panel 225 . Such approaches are described in commonly-owned U.S. patent application Ser. No. 12/853,265 and U.S. Pat. Pub. No. 2008/0316303 (both herein incorporated-by-reference) and overcome the problem outlined in the description of FIG. 1 to a considerable extent by using scrolling a segmented PCP 225 . Synchronizing the driving of each segment of the PCP 225 with the panel 220 addressing effectively splits the mixed imagery present on the display at any instant between the eyes. In this manner, right/left eye image admixture (crosstalk) of less than 2% is possible with commercially-available fast TN panels and with a fast pi-cell based PCP having at least 10 segments.
[0040] FIG. 3 is a schematic diagram 300 illustrating the operation of a known scrolling backlight LCD panel. Implementing a scrolling back light unit (BLU) 304 further reduces the crosstalk described above with reference to FIG. 2 , suppressing the visibility of undesired mixed imagery. A scrolling BLU 304 is becoming very feasible with the advent of local dimming LED illumination, as taught in commonly-owned U.S. Patent Pub. No. 2008/0316303.
[0041] FIG. 4 is a schematic diagram illustrating the operation of a known LCD panel system 400 in which the back light unit is modulated globally to display images only during periods 402 where the line-by-line addressing is interrupted between complete frame addressed cycle, as taught in commonly-owned U.S. patent application Ser. No. 12/853,274, herein incorporated by reference. The back light unit is turned off during periods 404 , 406 when the panel is addressed and the PCP is switched.
[0042] An alternative technique of reducing crosstalk without using a segmented PCP is similar to how shutter glass systems operate. Developed recently by Nvidia, this approach addresses each line faster than that required for continuous update (see http://www.nvidia.com/object/3D_Vision_Overview.html). This allows the addressing to cease for a period following update of a single frame. During this pause period, the transitioning LC has time to settle before further lines are addressed. If a sufficient pause period is introduced, the LC will have sufficient time to display a single image for viewing though active eyewear lenses. This same approach may be implemented in a panel-based LC PCP in conjunction with modulated illumination. Turning the BLU off is equivalent to making both lenses of an active eyewear unit opaque and hides the mixed imagery that exists during addressing. To view a settled (or, more realistically, a settling) LC image, the BLU is turned on with a correctly switched PCP.
[0043] Residual crosstalk at the bottom of the image may be traded against display brightness by adjusting the viewing period start time. In both the scrolling and globally-modulated prior art systems, not displaying mixed imagery substantially prevents crosstalk, which is one of the key features of the present disclosure.
[0044] A first aspect of the present disclosure is to avoid mixed imagery by applying a reset pulse to the top plate of an LCD in order to globally reset pixels to a common LC state between sequential images.
[0045] FIG. 5 and FIG. 6 show the displayed imagery of three adjacent row pixels as a function of time during addressing. The figures represent a horizontal cross section of a LCD panel at three different time periods.
[0046] FIG. 5 is a schematic diagram illustrating a cross section of a liquid crystal display 500 during the transition time between alternate images, for a conventional system. Here, in operation, switching the liquid crystal is accomplished as a result of the electric field imparted across the LC between plates 510 on the top and plates 512 , 514 , 516 on the bottom. This is adjusted from frame to frame by the application of a voltage (V) onto bottom transparent pixel electrodes 512 , 514 , 516 . The top electrode 510 common to all pixels remains at a constant voltage (Vt). For instance, in the Right (R) image state 530 , V=Vt is applied to a first bottom plate 512 , V=Vt-δV is applied to a second bottom plate 514 , and V=Vt-Δt is applied to a third bottom plate 516 . As shown in FIG. 5 , the finite response time of the LC results in mixed imagery (illustrated in the mixed image state 540 ) in the transition from the Right (R) image state 530 to the Left (L) image state 550 . To get to the Left (L) image state 550 , V=Vt-Δt is applied to the first bottom plate 512 , V=Vt is applied to the second bottom plate 514 , and V=Vt-δV is applied to the third bottom plate 516 . In this example, the intensity order (middle row 540 ) is neither that of the previous (top row 530 ) nor the addressed state (bottom row 550 ). Here, the LC responds to the applied voltage in a finite time, during which the pixels display incorrect relative intensities to that of the desired next image.
[0047] FIG. 6 is a schematic diagram illustrating a cross section of a liquid crystal display 600 during the transition time between alternate right and left images, in accordance with the present disclosure. FIG. 6 illustrates the introduction of a short reset voltage applied to the top electrode just following pixel addressing.
[0048] Here, in operation, switching the liquid crystal is accomplished as a result of the electric field imparted across the LC between plates 610 on the top and plates 612 , 614 , 616 on the bottom. This is adjusted from frame to frame by the application of a voltage (V) onto bottom transparent pixel electrodes 612 , 614 , 616 . The top electrode 610 , common to all pixels, remains at a constant voltage (Vt). For instance, in the Right (R) image state 630 , V=Vt is applied to a first bottom plate 612 , V=Vt-δV is applied to a second bottom plate 614 , and V=Vt-Δt is applied to a third bottom plate 616 .
[0049] Next, in a reset state 635 , the pixels are driven to a common state (assumed black here, although it could be any other common state in other embodiments), enabling them to globally relax into the desired state without mixing and suppressing any unwanted intensity reversal.
[0050] After the reset state 635 is applied, the Left (L) image state 650 may be achieved by applying, for instance, V=Vt-Δt to the first bottom plate 612 , V=Vt to the second bottom plate 614 , and V=Vt-δV to the third bottom plate 616 . After the reset state 635 , in the transition from the R image state 630 to the L image state 650 , a dim L image can be seen at 640 . Thus, in accordance with the present disclosure, applying a short reset voltage to the top electrode 610 after addressing resets the LC, allowing settling into the desired state with correct relative intensities. This means the overall intensity is slightly affected, but the desired image is nevertheless viewable with minimal stereoscopic crosstalk.
[0051] FIG. 7 is a graph 700 of pixel transmission of a TN LCD as a function of time. In accordance with the present disclosure, the two traces are from top 702 and bottom 704 line pixels. In this exemplary embodiment, alternate white and black frames are written to the display at 120 Hz with a single frame addressed in approximately 6 ms. The addressing is paused for the remaining approximately 2.5 ms. A Vsync pulse 720 is detected when the last line is addressed and precedes the viewing period where addressing is paused. The Vsync triggers a 15V, 0.1 ms pulse 720 which is applied to the panel's top plate to reset the LC to a near global dark state. This is shown by the almost equally low transmission of both top and bottom pixels at approximately 1 ms delay from the vsync. Viewing the display (e.g., BLU switched on) in the shaded window periods 710 provides image isolation and stereoscopic low crosstalk.
[0052] Graph 700 shows actual measured transmission from pixels in both the top and bottom rows of a TN panel during 120 Hz interrupted addressing of alternate full black and white images. At every Vsync instant, a 15V, 0.1 ms pulse 720 is driven to the panel's top plate which forces the normally white TN LC of all pixels into a near common low transmitting, substantially black state. Whatever charge was deposited at the pixels during addressing remains unchanged resulting in a relaxation to the desired addressed state near independent of when the pixel was addressed. The slight temporal offset of top and bottom lines due to the time difference between addressing is almost entirely negated by the similar offset used to achieve the next LC state. Graph 700 confirms the viability of a top plate reset scheme. The same experiment also showed that applying a top-plate drive voltage while addressing may result in insufficient local capacitance. Maintaining a high voltage during addressing resulted in unacceptable reverse contrast imagery. Although panels could be designed to avoid this, these findings illustrate that one implementation would be to drive the top plate following any addressing and to hide any mixed imagery through back light modulation. This time separation of addressing and top plate driving is an important distinction between this and prior art as discussed above.
[0053] A second aspect of this disclosure relates to driving pixels to a common state using the conventional line-by-line TFT drive techniques prior to correct addressing. In general, this approach results in a line being addressed twice during a frame update, which, in turn, uses two offset address lines to scroll down the panel. Conventional panel architecture does not allow this as it is deemed unnecessary. Fortunately, minor alteration to the row shift registers may be used to implement such a system.
[0054] The first aspect of the disclosure can be applied to systems employing both non-segmented and segmented PCPs whereas the second aspect uses a scrolling segmented approach, as described in the following section.
[0055] FIGS. 8A and 8B are schematic diagrams illustrating the operation of a conventional LC display system 800 against a disclosed embodiment of an LC display system 850 that uses global reset of the LCD panel. FIG. 8A illustrates a more conventional approach—void of top plate driving and without a reset. FIG. 8B illustrates a disclosed embodiment showing a reset 865 .
[0056] In FIG. 8A , the LC display system 800 includes a switchable BLU 801 , a uniform PCP 805 , and a normally white (drive to black) LCD panel 803 . While the LCD panel 803 is addressed from L to R image data (at 810 ), the BLU 801 is off, and any transitioning imagery, though displayed on the LCD panel 803 , is not viewable. Thus the viewer sees nothing in both the right and left eyes. Once the LCD panel 803 has substantially transitioned to R image data (at 820 ), the BLU 801 is turned on, and the R imagery displayed on the LCD panel 803 is viewable. The PCP 805 is also synced with the LC display system 800 , allowing for light to be viewed by a right eye of a user. As shown, the system 800 has mixed imagery (crosstalk) 822 corresponding to a settling region following the address line (see, e.g., FIG. 1 ). When the R imagery is substantially settled (at 830 ), the R image is displayed on the LC display system 800 .
[0057] In contrast, the disclosed embodiments (e.g., as shown in FIG. 8B ) avoid crosstalk and motion blur. In an embodiment, according to FIG. 8B , in operation, a global top plate driving scheme is applied in a system comprising a uniform, switchable BLU 851 , a uniform PCP 855 , and a normally white (drive to black) LCD panel 853 . In an embodiment, the panel 853 is addressed at 120 Hz using interrupted addressing methods.
[0058] As shown by the subdiagram at the top right 860 , the panel 853 is addressed line by line where the charge associated with a next image is deposited onto the local pixel capacitors. In an embodiment, the panel 853 is addressed line by line from top to bottom. In other embodiments, the panel 853 may be addressed in other ways including, but not limited to, bottom to top, middle to outer lines, etc. During the period 860 , the BLU 851 is off and any transitioning imagery, while displayed, is not viewable, thus the viewer sees nothing in both the right and left eyes.
[0059] As shown by the second subdiagram 865 , upon completing the frame update, addressing is paused and a high voltage pulse is applied for a short period of time to the top plate to drive the LC 853 globally to a substantially common dark state. In this stage 865 , the BLU 851 may be turned on. In an embodiment, the high voltage pulse is applied after a last line of a frame is written. In other embodiments, the high voltage pulse is applied substantially simultaneously with the last pixel of the last line of the frame being written.
[0060] As shown by the third and fourth subdiagrams 870 , 880 , when the top plate is returned to its common voltage level, the BLU 851 is turned on and the gradually settling image becomes viewable without any significant contamination from the display's prior state. In an embodiment, after 1/120 th second elapses from when the panel addressing began, the BLU 851 is turned off and addressing of the next frame commences (e.g., back to the subdiagram 860 , except this time, addressing of the left eye frame is performed on the LC instead of the right eye frame). The PCP 855 is switched during the period when the BLU 851 is off—effectively avoiding any crosstalk contribution from polarization mixing.
[0061] The application of top plate voltage would, ideally, be consistent with the DC balancing scheme. DC balancing may be used to avoid a net time average field to exist over the liquid crystal material which can cause ionic contaminants found within the LC material to migrate toward the substrate boundaries and can cause build up of a permanent cell voltage. Without DC balancing, it is very common to witness ‘image sticking’ where static images displayed for a long period of time remain visible regardless of later-displayed information. To prevent this phenomenon, the polarity of applied data voltages may be alternated between successive frames. Since this polarity is relative to the top plate voltage, a compatible top plate voltage reversal may be used to achieve equivalent DC balancing. This can be used for all disclosed embodiments.
[0062] In some embodiments, LCD addressing and illumination, as described above, is employed and used with active shutter glasses instead of employing a PCP and passive eyewear. The system is, effectively, viewable globally during the illumination period. This embodiment should yield improved crosstalk over incumbent LCD shutter glass systems, such as that taught by the above-referenced Nvidia shutter glass system.
[0063] In other embodiments, top plate electrode is segmented and scrolling methods are used. An LCD panel may be addressed as if comprised of separate display regions—each including a series of adjacent rows situated under a single horizontally striped top plate electrode. The display is effectively addressed with interrupted line-by-line addressing, where, at each interrupt, a voltage is applied to the top electrode above the previously addressed lines. Segments of a PCP may correspond to each of the display regions, being effectively aligned with the striped top plate electrodes (as would the elements of a segmented illuminator). Breaking the whole display into striped sections improves the duty cycle of the illumination and, hence, improves the overall brightness.
[0064] FIG. 9 is a schematic diagram of an embodiment in which the LC display 900 is reset to a common state through dual-line scrolled addressing. In operation, a panel 910 is addressed from top to bottom, line by line starting with the column data set to a common high voltage. In other embodiments, the panel 910 may be addressed from bottom to top. Either way, corresponding PCP 912 segments are synced with the panel 910 addressing.
[0065] A first row of pixels 904 is addressed with uniform high-data column voltages that cause the LC 910 to drive to a common state (black for normally white TN panels). A second row of pixels 902 , physically located above the first in the top to bottom embodiment, is then enabled allowing correct data voltages to charge pixel capacitors. This row 902 is separated from the first row 904 by a certain distance, which corresponds to a time offset between when it was driven to black. A third row 914 , one down from the first row 904 , would then be addressed black followed by a correctly addressed fourth row 912 located directly below the second row 902 , and so on.
[0066] This double scrolling of addressed lines allows an optimal period between the addressing of any one line within a frame update cycle while preserving adequate time for line addressing. This distinguishes it from black-frame insertion where alternate frames are driven to black with a conventional single scrolling line addressing scheme because the time between successive addressing is a frame period, which in general is non-optimal. In contrast, double line scrolled addressing may slightly alter the row shift register architecture allowing two passed ‘tokens’ to coexist and trigger alternately.
[0067] It is also possible to alter the panel electronics to further compliment dual line addressing. One option includes introducing split column electrodes where data can be applied simultaneously to the top and bottom half of the display. This doubles the addressing frame rate for any given line address time. It is particularly suitable when paired addressed lines are separated by at least half the display height. Another option reduces the line address time for driving to black by increasing the current drive capability of the column data lines. This can be achieved by reducing column electrode resistance and driver output impedance. Yet another approach could be to introduce an extra reset connection to all pixels for each row.
[0068] The scrolling nature of these embodiments may use a scrolling segmented PCP 920 . Furthermore, any residual crosstalk can be reduced using a scrolling back light 930 as introduced previously.
[0069] FIG. 10 is a flow diagram illustrating a process 1000 of crosstalk suppression in a time sequential LCD system. The process 1000 starts at action 1001 . Image data is displayed at action 1002 . For example, first eye image data may be displayed at action 1002 .
[0070] After image data is displayed at 1002 , light is stopped from reaching a viewer at action 1004 . In an embodiment, during action 1004 , a back-light is turned off to stop light from reaching a viewer. In another embodiment, during action 1004 , light is blocked by synchronizing with a viewer's shutter glasses.
[0071] Also during action 1004 , image data on the LC panel is updated at action 1006 . For example, second eye image data may be written to the LC panel at action 1006 . In an embodiment, data is written sequentially from a first line to a last line of an LC panel. For example, data may be written sequentially from a top line to a bottom line of an LC panel. In some embodiments, data is written by applying voltages to bottom electrodes corresponding to pixels associated with the lines of the LC panel.
[0072] Also during action 1004 , and substantially after action 1006 , a reset pulse is applied to an LC panel common electrode at action 1008 . In an embodiment, at action 1008 , the pixels of the LC are driven to a common state (e.g., a common black state), enabling them to globally relax into the desired written state without mixing imagery with the previously written image and while suppressing unwanted intensity reversal. In some embodiments, a reset pulse is applied to a top electrode on the LC panel.
[0073] Optionally during action 1004 , a polarization control panel (PCP) is switched or transitioned between polarization modes at action 1010 . For example, in an embodiment in which a PCP and passive analyzers are used, the PCP may be switched at some point during action 1004 .
[0074] Substantially after a reset pulse is applied at action 1008 , light is provided or allowed to a viewer of the LC display at action 1002 . The top electrode is returned to a common voltage level. The image data is displayed at action 1002 . In an embodiment, light is allowed by turning on a back light of the LC display. In another embodiment, light is allowed to the viewer by synchronizing shutter glasses of the viewer with the LC display at action 1002 , allowing a viewer to view the image data.
[0075] FIG. 11 is a schematic conceptual diagram illustrating an exemplary stereoscopic flat panel display system 1100 . The system 1100 may include a backlight 1102 , an LC modulation panel 1104 , and a polarization control panel 1106 . The system 1100 may also include a controller 1122 providing control interfaces for controlling the backlight 1102 , LC panel 1104 , and PCP 1106 .
[0076] For example, a backlight interface may provide a backlight control signal to a backlight 1102 , allowing for the backlight to be synchronized with the LC panel 1104 and with the PCP 1106 . An LC interface may provide an LC control signal to the LC panel 1104 , allowing for the LC panel to be synchronized with the backlight 1102 and with the PCP 1106 . A PCP interface may provide a PCP control signal to the PCP 1106 , allowing for the PCP to be synchronized with the backlight 1102 and with the PCP 1106 .
[0077] The controller 1122 may be in communication with a source 1120 . The source 1120 may include a DVD player, cable signal, internet signal, or any other signal capable of providing image data to the system 1100 .
[0078] The system 1100 , and other similar systems, may be used to employ the methods taught in the present disclosure. As discussed above, some embodiments may not include a PCP. Some embodiments may use an always-on backlight and synchronize with shutter glasses, resulting in light being stopped or allowed from reaching a viewer. Accordingly, all three components in FIG. 11 may not be used and/or synchronized in each embodiment of the disclosure. FIG. 11 is merely an exemplary system for certain disclosed embodiments and alternate arrangements and permutations to the system 1100 are understood.
[0079] While various embodiments in accordance with the disclosed principles have been described above, it should be understood that they have been presented by way of example only, and are not limiting. Thus, the breadth and scope of the invention(s) should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the claims and their equivalents issuing from this disclosure. Furthermore, the above advantages and features are provided in described embodiments, but shall not limit the application of such issued claims to processes and structures accomplishing any or all of the above advantages.
[0080] Additionally, the section headings herein are provided for consistency with the suggestions under 37 C.F.R. 1.77 or otherwise to provide organizational cues. These headings shall not limit or characterize the invention(s) set out in any claims that may issue from this disclosure. Specifically and by way of example, although the headings refer to a “Technical Field,” such claims should not be limited by the language chosen under this heading to describe the so-called technical field. Further, a description of a technology in the “Background” is not to be construed as an admission that technology is prior art to any invention(s) in this disclosure. Neither is the “Summary” to be considered as a characterization of the invention(s) set forth in issued claims. Furthermore, any reference in this disclosure to “invention” in the singular should not be used to argue that there is only a single point of novelty in this disclosure. Multiple inventions may be set forth according to the limitations of the multiple claims issuing from this disclosure, and such claims accordingly define the invention(s), and their equivalents, that are protected thereby. In all instances, the scope of such claims shall be considered on their own merits in light of this disclosure, but should not be constrained by the headings herein. | This disclosure primarily concerns 3D stereoscopic displays that provide alternately polarized left and right eye images encoded with a modulating LC polarization control panel (PCP) attached to the front of the display. Viewers then wear polarization analyzing eyewear to correctly see the different images. More specifically, the disclosure introduces global LC electrical reset during the addressing of liquid crystal time-sequential stereoscopic displays in order to reduce left/right eye contamination. LC materials in general do not respond fast enough with conventional addressing schemes to provide independent left and right eye images at the desired flicker-free, rate of sixty frames per second per eye. This disclosure and its embodiments may overcome this limitation, and also may address motion blur limitations, by driving pixels to a common LC state as part of the addressing cycle. | 7 |
This application is a continuation of U.S. patent application Ser. No. 10/154,594, entitled “Delivery of Compounds for the Treatment of Migraine Through an Inhalation Route,” filed May 23, 2002 now U.S. Pat. No. 6,740,309, Rabinowitz and Zaffaroni, which claims priority to U.S. provisional application, Ser. No. 60/294,203, entitled “Thermal Vapor Delivery of Drugs,” filed May 24, 2001, Rabinowitz and Zaffaroni and to U.S. provisional application Ser. No. 60/317,479, entitled “Aerosol Drug Delivery,” filed Sep. 5, 2001, Rabinowitz and Zaffaroni; the entire disclosures of which are hereby incorporated by reference.
FIELD OF THE INVENTION
The present invention relates to the delivery of migraine headache drugs through an inhalation route. Specifically, it relates to aerosols containing migraine headache drugs that are used in inhalation therapy.
BACKGROUND OF THE INVENTION
There are a number of compositions currently marketed for the treatment of migraine headaches. The compositions contain at least one active ingredient that provides for observed therapeutic effects. Among the active ingredients given in such anti-migraine compositions are lidocaine, verapamil, diltiazem, isometheptene, rizatriptan, zolmitriptan, sumitriptan, frovatriptan, naratriptan, and lisuride.
It is desirable to provide a new route of administration for migraine headache drugs that rapidly produces peak plasma concentrations of the compounds. The provision of such a route is an object of the present invention.
SUMMARY OF THE INVENTION
The present invention relates to the delivery of migraine headache drugs through an inhalation route. Specifically, it relates to aerosols containing migraine headache drugs that are used in inhalation therapy.
In a composition aspect of the present invention, the aerosol comprises particles comprising at least 5 percent by weight of a migraine headache drug. Preferably, the particles comprise at least 10 percent by weight of a migraine headache drug. More preferably, the particles comprise at least 20 percent, 30 percent, 40 percent, 50 percent, 60 percent, 70 percent, 80 percent, 90 percent, 95 percent, 97 percent, 99 percent, 99.5 percent or 99.97 percent by weight of a migraine headache drug.
Typically, the migraine headache drug is not ergotamine tartrate or an ergotamine derivative.
Typically, the aerosol has a mass of at least 10 μg. Preferably, the aerosol has a mass of at least 100 μg. More preferably, the aerosol has a mass of at least 200 μg.
Typically, the particles comprise less than 10 percent by weight of migraine headache drug degradation products. Preferably, the particles comprise less than 5 percent by weight of migraine headache drug degradation products. More preferably, the particles comprise less than 2.5, 1, 0.5, 0.1 or 0.03 percent by weight of migraine headache drug degradation products.
Typically, the particles comprise less than 90 percent by weight of water. Preferably, the particles comprise less than 80 percent by weight of water. More preferably, the particles comprise less than 70 percent, 60 percent, 50 percent, 40 percent, 30 percent, 20 percent, 10 percent, or 5 percent by weight of water.
Typically, at least 50 percent by weight of the aerosol is amorphous in form, wherein crystalline forms make up less than 50 percent by weight of the total aerosol weight, regardless of the nature of individual particles. Preferably, at least 75 percent by weight of the aerosol is amorphous in form. More preferably, at least 90 percent by weight of the aerosol is amorphous in form.
Typically, the aerosol has an inhalable aerosol particle density greater than 10 6 particles/mL. Preferably, the aerosol has an inhalable aerosol particle density greater than 10 7 particles/mL or 10 8 particles/mL.
Typically, the aerosol particles have a mass median aerodynamic diameter of less than 5 microns. Preferably, the particles have a mass median aerodynamic diameter of less than 3 microns. More preferably, the particles have a mass median aerodynamic diameter of less than 2 or 1 micron(s).
Typically, the geometric standard deviation around the mass median aerodynamic diameter of the aerosol particles is less than 3.0. Preferably, the geometric standard deviation is less than 2.5. More preferably, the geometric standard deviation is less than 2.2.
Typically, the aerosol is formed by heating a composition containing a migraine headache drug to form a vapor and subsequently allowing the vapor to condense into an aerosol.
In another composition aspect of the present invention, a dose form of a migraine headache drug is provided for the treatment of migraine, wherein the dose form comprises less than the typical oral dose of the drug. Preferably, the dose form comprises less than 80 percent by weight of the typical oral dose of the drug. More preferably, the dose form comprises less than 60 percent, 40 percent, or 20 percent by weight of the typical oral dose of the drug.
Typically, the dose form further comprises less than 90 percent by weight of water. Preferably, the dose form further comprises less than 80 percent by weight of water. More preferably, the dose form further comprises less than 70 percent, 60 percent, 50 percent, 40 percent, 30 percent, 20 percent, or 10 percent by weight of water.
Typically, the dose form further comprises less than 90 percent by weight of a pharmaceutically acceptable excipient. Preferably, the dose form further comprises less than 80 percent by weight of a pharmaceutically acceptable excipient. More preferably, the dose form comprises less than 70 percent, 60 percent, 50 percent, 40 percent, 30 percent, 20 percent, or 10 percent by weight of a pharmaceutically acceptable excipient.
In a method aspect of the present invention, a migraine headache drug is delivered to a mammal through an inhalation route. The method comprises: a) heating a composition, wherein the composition comprises at least 5 percent by weight of a migraine headache drug, to form a vapor; and, b) allowing the vapor to cool, thereby forming a condensation aerosol comprising particles, which is inhaled by the mammal. Preferably, the composition that is heated comprises at least 10 percent by weight of a migraine headache drug. More preferably, the composition comprises at least 20 percent, 30 percent, 40 percent, 50 percent, 60 percent, 70 percent, 80 percent, 90 percent, 95 percent, 97 percent, 99 percent, 99.5 percent, 99.9 percent or 99.97 percent by weight of a migraine headache drug.
Typically, the particles comprise at least 5 percent by weight of a migraine headache drug. Preferably, the particles comprise at least 10 percent by weight of a migraine headache drug. More preferably, the particles comprise at least 20 percent, 30 percent, 40 percent, 50 percent, 60 percent, 70 percent, 80 percent, 90 percent, 95 percent, 97 percent, 99 percent, 99.5 percent, 99.9 percent or 99.97 percent by weight of a migraine headache drug.
Typically, the condensation aerosol has a mass of at least 10 μg. Preferably, the aerosol has a mass of at least 100 μg. More preferably, the aerosol has a mass of at least 200 μg.
Typically, the particles comprise less than 10 percent by weight of migraine headache drug degradation products. Preferably, the particles comprise less than 5 percent by weight of migraine headache drug degradation products. More preferably, the particles comprise 2.5, 1, 0.5, 0.1 or 0.03 percent by weight of migraine headache drug degradation products.
Typically, the particles comprise less than 90 percent by weight of water. Preferably, the particles comprise less than 80 percent by weight of water. More preferably, the particles comprise less than 70 percent, 60 percent, 50 percent, 40 percent, 30 percent, 20 percent, 10 percent, or 5 percent by weight of water.
Typically, at least 50 percent by weight of the aerosol is amorphous in form, wherein crystalline forms make up less than 50 percent by weight of the total aerosol weight, regardless of the nature of individual particles. Preferably, at least 75 percent by weight of the aerosol is amorphous in form. More preferably, at least 90 percent by weight of the aerosol is amorphous in form.
Typically, the particles of the delivered condensation aerosol have a mass median aerodynamic diameter of less than 5 microns. Preferably, the particles have a mass median aerodynamic diameter of less than 3 microns. More preferably, the particles have a mass median aerodynamic diameter of less than 2 or 1 micron(s). In certain embodiments the particles have an MMAD of from about 0.2 to about 3 microns.
Typically, the geometric standard deviation around the mass median aerodynamic diameter of the aerosol particles is less than 3.0. Preferably, the geometric standard deviation is less than 2.5. More preferably, the geometric standard deviation is less than 2.2.
Typically, the delivered aerosol has an inhalable aerosol particle density greater than 10 6 particles/mL. Preferably, the aerosol has an inhalable aerosol particle density greater than 10 7 particles/mL or 10 8 particles/mL.
Typically, the rate of inhalable aerosol particle formation of the delivered condensation aerosol is greater than 10 8 particles per second. Preferably, the aerosol is formed at a rate greater than 10 9 inhalable particles per second. More preferably, the aerosol is formed at a rate greater than 10 10 inhalable particles per second.
Typically, the delivered condensation aerosol is formed at a rate greater than 0.5 mg/second. Preferably, the aerosol is formed at a rate greater than 0.75 mg/second. More preferably, the aerosol is formed at a rate greater than 1 mg/second, 1.5 mg/second or 2 mg/second.
Typically, the delivered condensation aerosol results in a peak plasma concentration of a migraine headache drug in the mammal in less than 1 h. Preferably, the peak plasma concentration is reached in less than 0.5 h. More preferably, the peak plasma concentration is reached in less than 0.2, 0.1, 0.05, 0.02, 0.01, or 0.005 h (arterial measurement).
Typically, less than 80 percent by weight of typical oral dose of a migraine headache drug is inhaled in any 2 hour period. Preferably, less than 60 percent by weight of a typical oral dose of a migraine headache drug is inhaled in any 2 hour period. More preferably, less than 40 percent or 20 percent of a typical oral dose of a migraine headache drug is inhaled in any 2 hour period.
In another method aspect of the present invention, a method of treating migraine is provided which comprises administering a dose of a migraine headache drug to a mammal that is less than the typical oral dose. Preferably, less than 80 percent by weight of the typical oral dose of a migraine drug is administered to the mammal in any 2 hour period. More preferably, less than 60 percent, 40 percent or 20 percent of the typical dose of a migraine drug is administered to the mammal in any 2 hour period.
In a kit aspect of the present invention, a kit for delivering a migraine headache drug through an inhalation route to a mammal is provided which comprises: a) a composition comprising at least 5 percent by weight of a migraine headache drug; and, b) a device that forms a migraine headache drug aerosol from the composition, for inhalation by the mammal. Preferably, the composition comprises at least 20 percent, 30 percent, 40 percent, 50 percent, 60 percent, 70 percent, 80 percent, 90 percent, 95 percent, 97 percent, 99 percent, 99.5 percent, 99.9 percent or 99.97 percent by weight of a migraine headache drug.
Typically, the device contained in the kit comprises: a) an element for heating the migraine headache drug composition to form a vapor; b) an element allowing the vapor to cool to form an aerosol; and, c) an element permitting the mammal to inhale the aerosol.
Typically, the kit comprises less than the typical oral dose of a migraine headache drug. Preferably, the kit comprises less than 80 percent by weight of the typical dose of a migraine headache drug. More preferably, the kit comprises less than 60 percent, 40 percent, or 20 percent by weight of a migraine headache drug.
BRIEF DESCRIPTION OF THE FIGURE
FIG. 1 shows a cross-sectional view of a device used to deliver migraine headache drug aerosols to a mammal through an inhalation route.
DETAILED DESCRIPTION OF THE INVENTION
Definitions
“Aerodynamic diameter” of a given particle refers to the diameter of a spherical droplet with a density of 1 g/mL (the density of water) that has the same settling velocity as the given particle.
“Aerosol” refers to a suspension of solid or liquid particles in a gas.
“Aerosol drug mass density” refers to the mass of migraine headache drug per unit volume of aerosol.
“Aerosol mass density” refers to the mass of particulate matter per unit volume of aerosol.
“Aerosol particle density” refers to the number of particles per unit volume of aerosol.
“Amorphous particle” refers to a particle that does not contain more than 50 percent by weight of a crystalline form. Preferably, the particle does not contain more than 25 percent by weight of a crystalline form. More preferably, the particle does not contain more than 10 percent by weight of a crystalline form.
“Condensation aerosol” refers to an aerosol formed by vaporization of a substance followed by condensation of the substance into an aerosol.
“Inhalable aerosol drug mass density” refers to the aerosol drug mass density produced by an inhalation device and delivered into a typical patient tidal volume.
“Inhalable aerosol mass density” refers to the aerosol mass density produced by an inhalation device and delivered into a typical patient tidal volume.
“Inhalable aerosol particle density” refers to the aerosol particle density of particles of size between 100 nm and 5 microns produced by an inhalation device and delivered into a typical patient tidal volume.
“Mass median aerodynamic diameter” or “MMAD” of an aerosol refers to the aerodynamic diameter for which half the particulate mass of the aerosol is contributed by particles with an aerodynamic diameter larger than the MMAD and half by particles with an aerodynamic diameter smaller than the MMAD.
“Migraine headache drug degradation product” refers to a compound resulting from a chemical modification of a migraine headache drug. The modification, for example, can be the result of a thermally or photochemically induced reaction. Such reactions include, without limitation, oxidation and hydrolysis.
“Rate of aerosol formation” refers to the mass of aerosolized particulate matter produced by an inhalation device per unit time.
“Rate of inhalable aerosol particle formation” refers to the number of particles of size between 100 nm and 5 microns produced by an inhalation device per unit time.
“Rate of drug aerosol formation” refers to the mass of aerosolized migraine headache drug produced by an inhalation device per unit time.
“Settling velocity” refers to the terminal velocity of an aerosol particle undergoing gravitational settling in air.
“Typical patient tidal volume” refers to 1 L for an adult patient and 15 mL/kg for a pediatric patient.
“Vapor” refers to a gas, and “vapor phase” refers to a gas phase. The term “thermal vapor” refers to a vapor phase, aerosol, or mixture of aerosol-vapor phases, formed preferably by heating.
Formation of Migraine Headache Drug Containing Aerosols
Any suitable method is used to form the aerosols of the present invention. A preferred method, however, involves heating a composition comprising a migraine headache drug to form a vapor, followed by cooling of the vapor such that it condenses to provide a migraine headache drug comprising aerosol (condensation aerosol). The composition is heated in one of four forms: as pure active compound (e.g., pure lidocaine, verapamil, diltiazem, isometheptene, or lisuride); as a mixture of active compound and a pharmaceutically acceptable excipient; as a salt form of the pure active compound; and, as a mixture of active compound salt form and a pharmaceutically acceptable excipient.
Salt forms of migraine headache drugs (e.g., lidocaine, verapamil, diltiazem, isometheptene, and lisuride) are either commercially available or are obtained from the corresponding free base using well known methods in the art. A variety of pharmaceutically acceptable salts are suitable for aerosolization. Such salts include, without limitation, the following: hydrochloric acid, hydrobromic acid, acetic acid, maleic acid, formic acid, and fumaric acid salts.
Pharmaceutically acceptable excipients may be volatile or nonvolatile. Volatile excipients, when heated, are concurrently volatilized, aerosolized and inhaled with the migraine headache drug. Classes of such excipients are known in the art and include, without limitation, gaseous, supercritical fluid, liquid and solid solvents. The following is a list of exemplary carriers within the classes: water; terpenes, such as menthol; alcohols, such as ethanol, propylene glycol, glycerol and other similar alcohols; dimethylformamide; dimethylacetamide; wax; supercritical carbon dioxide; dry ice; and mixtures thereof.
Solid supports on which the composition is heated are of a variety of shapes. Examples of such shapes include, without limitation, cylinders of less than 1.0 mm in diameter, boxes of less than 1.0 mm thickness and virtually any shape permeated by small (e.g., less than 1.0 mm-sized) pores. Preferably, solid supports provide a large surface to volume ratio (e.g., greater than 100 per meter) and a large surface to mass ratio (e.g., greater than 1 cm 2 per gram).
A solid support of one shape can also be transformed into another shape with different properties. For example, a flat sheet of 0.25 mm thickness has a surface to volume ratio of approximately 8,000 per meter. Rolling the sheet into a hollow cylinder of 1 cm diameter produces a support that retains the high surface to mass ratio of the original sheet but has a lower surface to volume ratio (about 400 per meter).
A number of different materials are used to construct the solid supports. Classes of such materials include, without limitation, metals, inorganic materials, carbonaceous materials and polymers. The following are examples of the material classes: aluminum, silver, gold, stainless steel, copper and tungsten; silica, glass, silicon and alumina; graphite, porous carbons, carbon yarns and carbon felts; polytetrafluoroethylene and polyethylene glycol. Combinations of materials and coated variants of materials are used as well.
Where aluminum is used as a solid support, aluminum foil is a suitable material. Examples of silica, alumina and silicon based materials include amphorous silica S-5631 (Sigma, St. Louis, Mo.), BCR171 (an alumina of defined surface area greater than 2 m 2 /g from Aldrich, St. Louis, Mo.) and a silicon wafer as used in the semiconductor industry. Carbon yarns and felts are available from American Kynol, Inc., New York, N.Y. Chromatography resins such as octadecycl silane chemically bonded to porous silica are exemplary coated variants of silica.
The heating of the migraine headache drug compositions is performed using any suitable method. Examples of methods by which heat can be generated include the following: passage of current through an electrical resistance element; absorption of electromagnetic radiation, such as microwave or laser light; and, exothermic chemical reactions, such as exothermic solvation, hydration of pyrophoric materials and oxidation of combustible materials.
Delivery of Migraine Headache Drug Containing Aerosols
Migraine headache drug containing aerosols of the present invention are delivered to a mammal using an inhalation device. Where the aerosol is a condensation aerosol, the device has at least three elements: an element for heating a migraine headache drug containing composition to form a vapor; an element allowing the vapor to cool, thereby providing a condensation aerosol; and, an element permitting the mammal to inhale the aerosol. Various suitable heating methods are described above. The element that allows cooling is, in it simplest form, an inert passageway linking the heating means to the inhalation means. The element permitting inhalation is an aerosol exit portal that forms a connection between the cooling element and the mammal's respiratory system.
One device used to deliver the migraine headache drug containing aerosol is described in reference to FIG. 1 . Delivery device 100 has a proximal end 102 and a distal end 104 , a heating module 106 , a power source 108 , and a mouthpiece 110 . A migraine headache drug composition is deposited on a surface 112 of heating module 106 . Upon activation of a user activated switch 114 , power source 108 initiates heating of heating module 106 (e.g, through ignition of combustible fuel or passage of current through a resistive heating element). The migraine headache drug composition volatilizes due to the heating of heating module 106 and condenses to form a condensation aerosol prior to reaching the mouthpiece 110 at the proximal end of the device 102 . Air flow traveling from the device distal end 104 to the mouthpiece 110 carries the condensation aerosol to the mouthpiece 110 , where it is inhaled by the mammal.
Devices, if desired, contain a variety of components to facilitate the delivery of migraine headache drug containing aerosols. For instance, the device may include any component known in the art to control the timing of drug aerosolization relative to inhalation (e.g., breath-actuation), to provide feedback to patients on the rate and/or volume of inhalation, to prevent excessive use (i.e., “lock-out” feature), to prevent use by unauthorized individuals, and/or to record dosing histories.
Dosage of Migraine Headache Drug Containing Aerosols
The dosage amount of a migraine headache drug in aerosol form is generally no greater than twice the standard dose of the drug given orally. A typical dosage of a migraine headache drug aerosol is either administered as a single inhalation or as a series of inhalations taken within an hour or less (dosage equals sum of inhaled amounts). Where the drug is administered as a series of inhalations, a different amount may be delivered in each inhalation.
One can determine the appropriate dose of a migraine headache drug containing aerosols to treat a particular condition using methods such as animal experiments and a dose-finding (Phase I/II) clinical trial. One animal experiment involves measuring plasma concentrations of drug in an animal after its exposure to the aerosol. Mammals such as dogs or primates are typically used in such studies, since their respiratory systems are similar to that of a human. Initial dose levels for testing in humans is generally less than or equal to the dose in the mammal model that resulted in plasma drug levels associated with a therapeutic effect in humans. Dose escalation in humans is then performed, until either an optimal therapeutic response is obtained or a dose-limiting toxicity is encountered.
Analysis of Migraine Headache Drug Containing Aerosols
Purity of a migraine headache drug containing aerosol is determined using a number of methods, examples of which are described in Sekine et al., Journal of Forensic Science 32:1271–1280 (1987) and Martin et al., Journal of Analytic Toxicology 13:158–162 (1989). One method involves forming the aerosol in a device through which a gas flow (e.g., air flow) is maintained, generally at a rate between 0.4 and 60 L/min. The gas flow carries the aerosol into one or more traps. After isolation from the trap, the aerosol is subjected to an analytical technique, such as gas or liquid chromatography, that permits a determination of composition purity.
A variety of different traps are used for aerosol collection. The following list contains examples of such traps: filters; glass wool; impingers; solvent traps, such as dry ice-cooled ethanol, methanol, acetone and dichloromethane traps at various pH values; syringes that sample the aerosol; empty, low-pressure (e.g., vacuum) containers into which the aerosol is drawn; and, empty containers that fully surround and enclose the aerosol generating device. Where a solid such as glass wool is used, it is typically extracted with a solvent such as ethanol. The solvent extract is subjected to analysis rather than the solid (i.e., glass wool) itself. Where a syringe or container is used, the container is similarly extracted with a solvent.
The gas or liquid chromatograph discussed above contains a detection system (i.e., detector). Such detection systems are well known in the art and include, for example, flame ionization, photon absorption and mass spectrometry detectors. An advantage of a mass spectrometry detector is that it can be used to determine the structure of migraine headache drug degradation products.
Particle size distribution of a migraine headache drug containing aerosol is determined using any suitable method in the art (e.g., cascade impaction). An Andersen Eight Stage Non-viable Cascade Impactor (Andersen Instruments, Smyrna, Ga.) linked to a furnace tube by a mock throat (USP throat, Andersen Instruments, Smyrna, Ga.) is one system used for cascade impaction studies.
Inhalable aerosol mass density is determined, for example, by delivering a drug-containing aerosol into a confined chamber via an inhalation device and measuring the mass collected in the chamber. Typically, the aerosol is drawn into the chamber by having a pressure gradient between the device and the chamber, wherein the chamber is at lower pressure than the device. The volume of the chamber should approximate the tidal volume of an inhaling patient.
Inhalable aerosol drug mass density is determined, for example, by delivering a drug-containing aerosol into a confined chamber via an inhalation device and measuring the amount of active drug compound collected in the chamber. Typically, the aerosol is drawn into the chamber by having a pressure gradient between the device and the chamber, wherein the chamber is at lower pressure than the device. The volume of the chamber should approximate the tidal volume of an inhaling patient. The amount of active drug compound collected in the chamber is determined by extracting the chamber, conducting chromatographic analysis of the extract and comparing the results of the chromatographic analysis to those of a standard containing known amounts of drug.
Inhalable aerosol particle density is determined, for example, by delivering aerosol phase drug into a confined chamber via an inhalation device and measuring the number of particles of given size collected in the chamber. The number of particles of a given size may be directly measured based on the light-scattering properties of the particles. Alternatively, the number of particles of a given size is determined by measuring the mass of particles within the given size range and calculating the number of particles based on the mass as follows: Total number of particles=Sum (from size range 1 to size range N) of number of particles in each size range. Number of particles in a given size range=Mass in the size range/Mass of a typical particle in the size range. Mass of a typical particle in a given size range=π*D 3 *φ/6, where D is a typical particle diameter in the size range (generally, the mean boundary MMADs defining the size range) in microns, φ is the particle density (in g/mL) and mass is given in units of picograms (g −12 ).
Rate of inhalable aerosol particle formation is determined, for example, by delivering aerosol phase drug into a confined chamber via an inhalation device. The delivery is for a set period of time (e.g., 3 s), and the number of particles of a given size collected in the chamber is determined as outlined above. The rate of particle formation is equal to the number of 100 nm to 5 micron particles collected divided by the duration of the collection time.
Rate of aerosol formation is determined, for example, by delivering aerosol phase drug into a confined chamber via an inhalation device. The delivery is for a set period of time (e.g., 3 s), and the mass of particulate matter collected is determined by weighing the confined chamber before and after the delivery of the particulate matter. The rate of aerosol formation is equal to the increase in mass in the chamber divided by the duration of the collection time. Alternatively, where a change in mass of the delivery device or component thereof can only occur through release of the aerosol phase particulate matter, the mass of particulate matter may be equated with the mass lost from the device or component during the delivery of the aerosol. In this case, the rate of aerosol formation is equal to the decrease in mass of the device or component during the delivery event divided by the duration of the delivery event.
Rate of drug aerosol formation is determined, for example, by delivering a migraine headache drug containing aerosol into a confined chamber via an inhalation device over a set period of time (e.g., 3 s). Where the aerosol is pure migraine headache drug, the amount of drug collected in the chamber is measured as described above. The rate of drug aerosol formation is equal to the amount of migraine headache drug collected in the chamber divided by the duration of the collection time. Where the migraine headache drug containing aerosol comprises a pharmaceutically acceptable excipient, multiplying the rate of aerosol formation by the percentage of migraine headache drug in the aerosol provides the rate of drug aerosol formation.
Utility of Migraine Headache Drug Containing Aerosols
The migraine headache drug containing aerosols of the present invention are typically used for the treatment of migraine headaches.
The following examples are meant to illustrate, rather than limit, the present invention.
Migraine headache drugs can either be purchased from a supplier (e.g., Sigma at www.sigma-aldrich.com), isolated from pharmaceutical preparations (e.g., tablets, caplets or vial solutions), or synthesized according to known methods in the art.
EXAMPLE 1
General Procedure for Obtaining Free Base of a Compound Salt
Approximately 1 g of salt (e.g., mono hydrochloride) is dissolved in deionized water (˜30 mL). Three equivalents of sodium hydroxide (1 N NaOH aq ) is added dropwise to the solution, and the pH is checked to ensure it is basic. The aqueous solution is extracted four times with dichloromethane (˜50 mL), and the extracts are combined, dried (Na 2 SO 4 ) and filtered. The filtered organic solution is concentrated using a rotary evaporator to provide the desired free base. If necessary, purification of the free base is performed using standard methods such as chromatography or recrystallization.
EXAMPLE 2
General Procedure for Volatilizing Compounds from Halogen Bulb
A solution of drug in approximately 120 μL dichloromethane is coated on a 3.5 cm×7.5 cm piece of aluminum foil (precleaned with acetone). The dichloromethane is allowed to evaporate. The coated foil is wrapped around a 300 watt halogen tube (Feit Electric Company, Pico Rivera, Calif.), which is inserted into a glass tube sealed at one end with a rubber stopper. Running 90 V of alternating current (driven by line power controlled by a variac) through the bulb for 5 s or 3.5 s affords thermal vapor (including aerosol), which is collected on the glass tube walls. Reverse-phase HPLC analysis with detection by absorption of 225 nm light is used to determine the purity of the aerosol. (When desired, the system is flushed through with argon prior to volatilization.) To obtain higher purity aerosols, one can coat a lesser amount of drug, yielding a thinner film to heat. A linear decrease in film thickness is associated with a linear decrease in impurities.
The following aerosols were obtained using this procedure: lidocaine aerosol (7.3 mg, 99.5% purity); verapamil aerosol (1.41 mg, 96.2% purity); diltiazem aerosol (1.91 mg, 97.1% purity); and, lisuride aerosol (0.2 mg, 100% purity).
EXAMPLE 3
Particle Size, Particle Density, and Rate of Inhalable Particle Formation of Lidocaine Aerosol
A solution of 12.2 mg lidocaine in 100 μL dichloromethane was spread out in a thin layer on the central portion of a 3.5 cm×7 cm sheet of aluminum foil. The dichloromethane was allowed to evaporate. Assuming a drug density of about 1 g/cc, the calculated thickness of the lidocaine thin layer on the 24.5 cm 2 aluminum solid support, after solvent evaporation, is about 5.0 microns. The aluminum foil was wrapped around a 300 watt halogen tube, which was inserted into a T-shaped glass tube. Both of the openings of the tube were sealed with parafilm, which was punctured with fifteen needles for air flow. The third opening was connected to a 1 liter, 3-neck glass flask. The glass flask was further connected to a large piston capable of drawing 1.1 liters of air through the flask. Alternating current was run through the halogen bulb by application of 90 V using a variac connected to 110 V line power. Within 1 s, an aerosol appeared and was drawn into the 1 L flask by use of the piston, with collection of the aerosol terminated after 6 s. The aerosol was analyzed by connecting the 1 L flask to an eight-stage Andersen non-viable cascade impactor. Results are shown in table 1. MMAD of the collected aerosol was 2.4 microns with a geometric standard deviation of 2.1. Also shown in table 1 is the number of particles collected on the various stages of the cascade impactor, given by the mass collected on the stage divided by the mass of a typical particle trapped on that stage. The mass of a single particle of diameter D is given by the volume of the particle, πD 3 /6, multiplied by the density of the drug (taken to be 1 g/cm 3 ). The inhalable aerosol particle density is the sum of the numbers of particles collected on impactor stages 3 to 8 divided by the collection volume of 1 L, giving an inhalable aerosol particle density of 4.2×10 6 particles/mL. The rate of inhalable aerosol particle formation is the sum of the numbers of particles collected on impactor stages 3 through 8 divided by the formation time of 6 s, giving a rate of inhalable aerosol particle formation of 7.0×10 8 particles/second.
TABLE 1
Determination of the characteristics of a lidocaine
condensation aerosol by cascade impaction using
an Andersen 8-stage non-viable cascade impactor
run at 1 cubic foot per minute air flow.
Mass
Particle size
Average particle
collected
Number of
Stage
range (microns)
size (microns)
(mg)
particles
0
9.0–10.0
9.5
0.1
2.2 × 10 5
1
5.8–9.0
7.4
0.3
1.4 × 10 6
2
4.7–5.8
5.25
0.1
1.3 × 10 6
3
3.3–4.7
4.0
0.7
2.1 × 10 7
4
2.1–3.3
2.7
0.9
8.7 × 10 7
5
1.1–2.1
1.6
1.0
4.7 × 10 8
6
0.7–1.1
0.9
0.5
1.3 × 10 9
7
0.4–0.7
0.55
0.2
2.3 × 10 9
8
0–0.4
0.2
0.0
0
EXAMPLE 4
Drug Mass Density and Rate of Drug Aerosol Formation of Lidocaine Aerosol
A solution of 10.4 mg lidocaine in 100 μL dichloromethane was spread out in a thin layer on the central portion of a 3.5 cm×7 cm sheet of aluminum foil. The dichloromethane was allowed to evaporate. Assuming a drug density of about 1 g/cc, the calculated thickness of the lidocaine thin layer on the 24.5 cm 2 aluminum solid support, after solvent evaporation, is about 4.2 microns. The aluminum foil was wrapped around a 300 watt halogen tube, which was inserted into a T-shaped glass tube. Both of the openings of the tube were sealed with parafilm, which was punctured with fifteen needles for air flow. The third opening was connected to a 1 liter, 3-neck glass flask. The glass flask was further connected to a large piston capable of drawing 1.1 liters of air through the flask. Alternating current was run through the halogen bulb by application of 90 V using a variac connected to 110 V line power. Within seconds, an aerosol appeared and was drawn into the 1 L flask by use of the piston, with formation of the aerosol terminated after 6 s. The aerosol was allowed to sediment onto the walls of the 1 L flask for approximately 30 minutes. The flask was then extracted with acetonitrile and the extract analyzed by HPLC with detection by light absorption at 225 nm. Comparison with standards containing known amounts of lidocaine revealed that 3.1 mg of >99% pure lidocaine had been collected in the flask, resulting in an aerosol drug mass density of 3.1 mg/L. The aluminum foil upon which the lidocaine had previously been coated was weighed following the experiment. Of the 10.4 mg originally coated on the aluminum, 10.2 mg of the material was found to have aerosolized in the 6 s time period, implying a rate of drug aerosol formation of 1.7 mg/s.
EXAMPLE 5
Volatilization of Rizatriptan
A solution of 10 mg rizatriptan in 1 mL diethyl ether was spread out in a thin layer on a 10 cm×15 cm sheet of aluminum foil. The diethyl ether was allowed to evaporate. Assuming a drug density of about 1 g/cc, the calculated thickness of the rizatriptan thin layer on the 150 cm 2 aluminum solid support, after solvent evaporation, is about 0.7 microns. The coated aluminum foil sheet was inserted into a glass tube in a furnace (tube furnace). A glass wool plug was placed in the tube adjacent to the foil sheet, and an air flow of 2 L/min was applied. The furnace was heated to 250° C. for 30 s to volatilize the coated rizatriptan and then was allowed to cool. The glass wool was extracted, and HPLC analysis of the collected material showed it to be at least 99% pure rizatriptan.
EXAMPLE 6
Particle Size, Particle Density, and Rate of Inhalable Particle Formation of Rizatriptan Aerosol
A solution of 11.3 mg rizatriptan in 200 μL dichloromethane was spread out in a thin layer on the central portion of a 4 cm×9 cm sheet of aluminum foil. The dichloromethane was allowed to evaporate. Assuming a drug density of about 1 g/cc, the calculated thickness of the rizatriptan thin layer on the 36 cm 2 aluminum solid support, after solvent evaporation, is about 3.1 microns. The aluminum foil was wrapped around a 300 watt halogen tube, which was inserted into a T-shaped glass tube. One of the openings of the tube was sealed with a rubber stopper, another was loosely covered with the end of the halogen tube, and the third was connected to a 1 liter, 3-neck glass flask. The glass flask was further connected to a large piston capable of drawing 1.1 liters of air through the flask. Alternating current was run through the halogen bulb by application of 90 V using a variac connected to 110 V line power. Within 1 s, an aerosol appeared and was drawn into the 1 L flask by use of the piston, with collection of the aerosol terminated after 7 s. The aerosol was analyzed by connecting the 1 L flask to an eight-stage Andersen non-viable cascade impactor. Results are shown in table 1. MMAD of the collected aerosol was 1.2 microns with a geometric standard deviation of 1.7. Also shown in table 1 is the number of particles collected on the various stages of the cascade impactor, given by the mass collected on the stage divided by the mass of a typical particle trapped on that stage. The mass of a single particle of diameter D is given by the volume of the particle, πD 3 /6, multiplied by the density of the drug (taken to be 1 g/cm 3 ). The inhalable aerosol particle density is the sum of the numbers of particles collected on impactor stages 3 to 8 divided by the collection volume of 1 L, giving an inhalable aerosol particle density of 3×10 7 particles/mL. The rate of inhalable aerosol particle formation is the sum of the numbers of particles collected on impactor stages 3 through 8 divided by the formation time of 7 s, giving a rate of inhalable aerosol particle formation of 5×10 9 particles/second.
TABLE 1
Determination of the characteristics of a rizatriptan
condensation aerosol by cascade impaction using
an Andersen 8-stage non-viable cascade impactor
run at 1 cubic foot per minute air flow.
Mass
Particle size
Average particle
collected
Number of
Stage
range (microns)
size (microns)
(mg)
particles
0
9.0–10.0
9.5
0.0
0
1
5.8–9.0
7.4
0.0
0
2
4.7–5.8
5.25
0.1
1.3 × 10 6
3
3.3–4.7
4.0
0.2
6.0 × 10 6
4
2.1–3.3
2.7
0.4
3.9 × 10 7
5
1.1–2.1
1.6
1.2
5.6 × 10 8
6
0.7–1.1
0.9
1.0
2.6 × 10 9
7
0.4–0.7
0.55
0.5
5.7 × 10 9
8
0–0.4
0.2
0.1
2.4 × 10 10
EXAMPLE 7
Drug Mass Density and Rate of Drug Aerosol Formation of Rizatriptan Aerosol
A solution of 11.6 mg rizatriptan in 200 μL dichloromethane was spread out in a thin layer on the central portion of a 4 cm×9 cm sheet of aluminum foil. The dichloromethane was allowed to evaporate. Assuming a drug density of about 1 g/cc, the calculated thickness of the rizatriptan thin layer on the 36 cm 2 aluminum solid support, after solvent evaporation, is about 3.2 microns. The aluminum foil was wrapped around a 300 watt halogen tube, which was inserted into a T-shaped glass tube. One of the openings of the tube was sealed with a rubber stopper, another was loosely covered with the end of the halogen tube, and the third was connected to a 1 liter, 3-neck glass flask. The glass flask was further connected to a large piston capable of drawing 1.1 liters of air through the flask. Alternating current was run through the halogen bulb by application of 90 V using a variac connected to 110 V line power. Within seconds, an aerosol appeared and was drawn into the 1 L flask by use of the piston, with formation of the aerosol terminated after 7 s. The aerosol was allowed to sediment onto the walls of the 1 L flask for approximately 30 minutes. The flask was then extracted with dichloromethane and the extract analyzed by HPLC with detection by light absorption at 225 nm. Comparison with standards containing known amounts of rizatriptan revealed that 3.2 mg of >99% pure rizatriptan had been collected in the flask, resulting in an aerosol drug mass density of 3.2 mg/L. The aluminum foil upon which the rizatriptan had previously been coated was weighed following the experiment. Of the 11.6 mg originally coated on the aluminum, all of the material was found to have aerosolized in the 7 s time period, implying a rate of drug aerosol formation of 1.7 mg/s.
EXAMPLE 8
Isolation of Zolmitriptan
To water was added 17 ZOMIG® Tablets, each containing 5 mg of zolmitriptan. The resulting milky solution was extracted three times with diethyl ether and three times with dichloromethane. The combined organic extracts were dried (MgSO 4 ), filtered and concentrated on a rotary evaporator to provide 100 mg (74% recovery) of zolmitriptan.
EXAMPLE 9
Vaporization of Zolmitriptan
A solution of 9.8 mg zolmitriptan in 300 μL dichloromethane was spread out in a thin layer on a 4 cm×9 cm sheet of aluminum foil. The dichloromethane was allowed to evaporate. Assuming a drug density of about 1 g/cc, the calculated thickness of the zolmitriptan thin layer on the 36 cm 2 aluminum solid support, after solvent evaporation, is about 2.7 microns. The aluminum foil was wrapped around a 300 watt halogen tube, which was inserted into a glass tube sealed at one end with a rubber stopper. Subjecting the bulb to one 15 s, 60 v (variac) treatment afforded volatilized zolmitriptan on the glass tube walls. HPLC analysis of the collected material showed it to be at least 98% pure zolmitriptan. To obtain higher purity aerosols, one can coat a lesser amount of drug, yielding a thinner film to heat. A linear decrease in film thickness is associated with a linear decrease in impurities.
EXAMPLE 10
Particle Size, Particle Density, and Rate of Inhalable Particle Formation of Zolmitriptan Aerosol
A solution of 3.2 mg zolmitriptan in 100 μL methanol was spread out in a thin layer on the central portion of a 3.5 cm×7 cm sheet of aluminum foil. The dichloromethane was allowed to evaporate. Assuming a drug density of about 1 g/cc, the calculated thickness of the zolmitriptan thin layer on the 24.5 cm 2 aluminum solid support, after solvent evaporation, is about 1.3 microns. The aluminum foil was wrapped around a 300 watt halogen tube, which was inserted into a T-shaped glass tube. Both of the openings of the tube were left open and the third opening was connected to a 1 liter, 3-neck glass flask. The glass flask was further connected to a large piston capable of drawing 1.1 liters of air through the flask. Alternating current was run through the halogen bulb by application of 90 V using a variac connected to 110 V line power. Within 1 s, an aerosol appeared and was drawn into the 1 L flask by use of the piston, with collection of the aerosol terminated after 6 s. The aerosol was analyzed by connecting the 1 L flask to an eight-stage Andersen non-viable cascade impactor. Results are shown in table 1. MMAD of the collected aerosol was 0.7 microns with a geometric standard deviation of 3.3. Also shown in table 1 is the number of particles collected on the various stages of the cascade impactor, given by the mass collected on the stage divided by the mass of a typical particle trapped on that stage. The mass of a single particle of diameter D is given by the volume of the particle, πD 3 /6, multiplied by the density of the drug (taken to be 1 g/cm 3 ). The inhalable aerosol particle density is the sum of the numbers of particles collected on impactor stages 3 to 8 divided by the collection volume of 1 L, giving an inhalable aerosol particle density of 4.9×10 7 particles/mL. The rate of inhalable aerosol particle formation is the sum of the numbers of particles collected on impactor stages 3 through 8 divided by the formation time of 6 s, giving a rate of inhalable aerosol particle formation of 8.1×10 9 particles/second.
TABLE 1
Determination of the characteristics of a zolmitriptan
condensation aerosol by cascade impaction using an
Andersen 8-stage non-viable cascade impactor run at
1 cubic foot per minute air flow.
Mass
Particle size
Average particle
collected
Number of
Stage
range (microns)
size (microns)
(mg)
particles
0
9.0–10.0
9.5
0.00
0
1
5.8–9.0
7.4
0.00
0
2
4.7–5.8
5.25
0.00
0
3
3.3–4.7
4.0
0.01
2.1 × 10 5
4
2.1–3.3
2.7
0.03
2.9 × 10 6
5
1.1–2.1
1.6
0.12
5.7 × 10 7
6
0.7–1.1
0.9
0.10
2.5 × 10 8
7
0.4–0.7
0.55
0.05
5.7 × 10 8
8
0–0.4
0.2
0.20
4.8 × 10 10
EXAMPLE 11
Drug Mass Density and Rate of Drug Aerosol Formation of Zolmitriptan Aerosol
A solution of 2.6 mg zolmitriptan in 100 μL methanol was spread out in a thin layer on the central portion of a 3.5 cm×7 cm sheet of aluminum foil. The dichloromethane was allowed to evaporate. Assuming a drug density of about 1 g/cc, the calculated thickness of the zolmitriptan thin layer on the 24.5 cm 2 aluminum solid support, after solvent evaporation, is about 1.1 microns. The aluminum foil was wrapped around a 300 watt halogen tube, which was inserted into a T-shaped glass tube. Both of the openings of the tube were left open and the third opening was connected to a 1 liter, 3-neck glass flask. The glass flask was further connected to a large piston capable of drawing 1.1 liters of air through the flask. Alternating current was run through the halogen bulb by application of 90 V using a variac connected to 110 V line power. Within seconds, an aerosol appeared and was drawn into the 1 L flask by use of the piston, with formation of the aerosol terminated after 6 s. The aerosol was allowed to sediment onto the walls of the 1 L flask for approximately 30 minutes. The flask was then extracted with acetonitrile and the extract analyzed by HPLC with detection by light absorption at 225 nm. Comparison with standards containing known amounts of zolmitriptan revealed that 0.4 mg of >96% pure zolmitriptan had been collected in the flask, resulting in an aerosol drug mass density of 0.4 mg/L. The aluminum foil upon which the zolmitriptan had previously been coated was weighed following the experiment. Of the 2.6 mg originally coated on the aluminum, 1.5 mg of the material was found to have aerosolized in the 6 s time period, implying a rate of drug aerosol formation of 0.3 mg/s.
EXAMPLE 12
Flash Device for Forming Aerosols
A high-power flashcube (GE or Sylvania), which can produce 300–400 J of energy, was inserted into an anodized aluminum tube. The flashcube/tube assembly was dipped into an organic solution containing a drug and quickly removed. Evaporation of residual solvent from the assembly was performed by placing it into a vacuum chamber for 30 min. This left a film of drug coated on the exterior surface of the aluminum tube. The flashbulb assembly was electrically connected to two 1.5 V batteries and a switch using copper wires and then enclosed in a sealed, glass vial. Ignition of the flashbulb was performed by momentarily turning on the switch between the flashbulb and batteries. After ignition, the vial was kept closed for 30 minutes such that particles of volatilized drug coagulated and condensed on the inside surface of the vial. Analysis of the aerosol involved rinsing the vial with 5 mL of acetonitrile and injecting a sample of the organic solution into an HPLC. Rizatriptan aerosol was obtained in 99.2% purity (1.65 mg) using this procedure. Zolmitriptan aerosol was obtained in 99.6% purity (0.31 mg) using this procedure.
EXAMPLE 13
Delivery of Rizatriptan to a Dog
Apnea was induced in a dog, which was subsequently exposed to a 15 SLPM flow of air containing 950 μg of rizatriptan (condensation aerosol formed by volatilizing triazolam off of a heated, metal substrate; MMAD ˜1.7) through an endotracheal tube. This corresponded to approximately a 625 cc volume of inhalation air delivered to the dog. Once the dog had received the rizatriptan aerosol, an air supply valve was shut off for 5 s, which simulated a 5 s breath hold. Following the hold, the dog was allowed to exhale through an exhalation filter. Arterial blood samples were taken at defined intervals. HPLC analysis of the blood samples indicated that the Tmax for rizatriptan was about 1 minutes, with a concentration of greater than 280 ng/mL reached.
EXAMPLE 14
Comparison of Inhaled, Subcutaneous and Oral Admistration of Rizatriptan in a Dog
The percent change in cerebral vascular resistance from a 30 minute baseline was compared after administration of 1 mg of rizatriptan to a dog using the following delivery routes: inhalation, subcutaneous, and oral. After inhalation administration, the resistance increased approximately 60 percent in approximately 1 minute. Subcutaneous administration produced about a 45 percent increase in resistance in about 20 minutes. Cerebral vascular resistance essentially did not change over an 80 minute period after oral administration of rizatriptan.
The same study was performed by administering either 3.5 mg or 3 mg of rizatriptan to a dog: inhalation (3.5 mg inhaled, ˜110% resistance increase in about one minute); subcutaneous (3 mg, ˜60% resistance increase over about 30 minutes); and, oral (3 mg, essentially no resistance increase over 80 min.).
EXAMPLE 15
General Procedure for Volatilizing Sumatriptan, Frovatriptan, and Naratriptan from Halogen Bulb
A solution of drug in approximately 120 μL dichloromethane is coated on a 3.5 cm×7.5 cm piece of aluminum foil (precleaned with acetone). The dichloromethane is allowed to evaporate. The coated foil is wrapped around a 300 watt halogen tube (Feit Electric Company, Pico Rivera, Calif.), which is inserted into a glass tube sealed at one end with a rubber stopper. Running 118 V of alternating current (driven by line power controlled by a variac) through the bulb for 2.2 s affords thermal vapor (including aerosol), which is collected on the glass tube walls. Reverse-phase HPLC analysis with detection by absorption of 225 nm light is used to determine the purity of the aerosol. (When desired, the system is flushed through with argon prior to volatilization.)
The following aerosols were obtained using this procedure: sumatriptan aerosol (˜0.56 mg, 97.2% purity); frovatriptan aerosol (0.39 mg, 94.8% purity); and, naratriptan aerosol (0.58 mg, 96.2% purity). To obtain higher purity aerosols, one can coat a lesser amount of drug, yielding a thinner film to heat. A linear decrease in film thickness is associated with a linear decrease in impurities.
EXAMPLE 16
Particle Size, Particle Density, and Rate of Inhalable Particle Formation of Frovatriptan Aerosol
A solution of 5.0 mg frovatriptan in 100 μL methanol was spread out in a thin layer on the central portion of a 3.5 cm×7 cm sheet of aluminum foil. The methanol was allowed to evaporate. Assuming a drug density of about 1 g/cc, the calculated thickness of the frovatriptan thin layer on the 24.5 cm 2 aluminum solid support, after solvent evaporation, is about 2.0 microns. The aluminum foil was wrapped around a 300 watt halogen tube, which was inserted into a T-shaped glass tube. Both of the openings of the tube were left open and the third opening was connected to a 1 liter, 3-neck glass flask. The glass flask was further connected to a large piston capable of drawing 1.1 liters of air through the flask. Alternating current was run through the halogen bulb by application of 90 V using a variac connected to 110 V line power. Within 1 s, an aerosol appeared and was drawn into the 1 L flask by use of the piston, with collection of the aerosol terminated after 6 s. The aerosol was analyzed by connecting the 1 L flask to an eight-stage Andersen non-viable cascade impactor. Results are shown in table 1. MMAD of the collected aerosol was 1.8 microns with a geometric standard deviation of 2.1. Also shown in table 1 is the number of particles collected on the various stages of the cascade impactor, given by the mass collected on the stage divided by the mass of a typical particle trapped on that stage. The mass of a single particle of diameter D is given by the volume of the particle, πD 3 /6, multiplied by the density of the drug (taken to be 1 g/cm 3 ). The inhalable aerosol particle density is the sum of the numbers of particles collected on impactor stages 3 to 8 divided by the collection volume of 1 L, giving an inhalable aerosol particle density of 7.3×10 5 particles/mL. The rate of inhalable aerosol particle formation is the sum of the numbers of particles collected on impactor stages 3 through 8 divided by the formation time of 6 s, giving a rate of inhalable aerosol particle formation of 1.2×10 8 particles/second.
TABLE 1
Determination of the characteristics of a
frovatriptan condensation aerosol by cascade
impaction using an Andersen 8-stage non-viable
cascade impactor run at 1 cubic foot per minute air flow.
Mass
Particle size
Average particle
collected
Number of
Stage
range (microns)
size (microns)
(mg)
particles
0
9.0–10.0
9.5
0.01
1.3 × 10 4
1
5.8–9.0
7.4
0.02
8.0 × 10 4
2
4.7–5.8
5.25
0.03
3.8 × 10 5
3
3.3–4.7
4.0
0.05
1.6 × 10 6
4
2.1–3.3
2.7
0.09
9.1 × 10 6
5
1.1–2.1
1.6
0.16
7.6 × 10 7
6
0.7–1.1
0.9
0.09
2.4 × 10 8
7
0.4–0.7
0.55
0.04
4.0 × 10 8
8
0–0.4
0.2
0.0
0
EXAMPLE 17
Drug Mass Density and Rate of Drug Aerosol Formation of Frovatriptan Aerosol
A solution of 5.0 mg frovatriptan in 100 μL methanol was spread out in a thin layer on the central portion of a 3.5 cm×7 cm sheet of aluminum foil. The methanol was allowed to evaporate. Assuming a drug density of about 1 g/cc, the calculated thickness of the frovatriptan thin layer on the 24.5 cm 2 aluminum solid support, after solvent evaporation, is about 2.0 microns. The aluminum foil was wrapped around a 300 watt halogen tube, which was inserted into a T-shaped glass tube. Both of the openings of the tube were left open and the third opening was connected to a 1 liter, 3-neck glass flask. The glass flask was further connected to a large piston capable of drawing 1.1 liters of air through the flask. Alternating current was run through the halogen bulb by application of 90 V using a variac connected to 110 V line power. Within seconds, an aerosol appeared and was drawn into the 1 L flask by use of the piston, with formation of the aerosol terminated after 6 s. The aerosol was allowed to sediment onto the walls of the 1 L flask for approximately 30 minutes. The flask was then extracted with acetonitrile and the extract analyzed by HPLC with detection by light absorption at 225 nm. Comparison with standards containing known amounts of frovatriptan revealed that 0.85 mg of >91% pure frovatriptan had been collected in the flask, resulting in an aerosol drug mass density of 0.85 mg/L. The aluminum foil upon which the frovatriptan had previously been coated was weighed following the experiment. Of the 5.0 mg originally coated on the aluminum, 2.8 mg of the material was found to have aerosolized in the 6 s time period, implying a rate of drug aerosol formation of 0.5 mg/s.
EXAMPLE 18
Flash Device for Forming Aerosols
A high-power flashcube (GE or Sylvania), which can produce 300–400 J of energy, was inserted into an anodized aluminum tube. The flashcube/tube assembly was dipped into an organic solution containing a drug and quickly removed. Evaporation of residual solvent from the assembly was performed by placing it into a vacuum chamber for 30 min. This left a film of drug coated on the exterior surface of the aluminum tube. The flashbulb assembly was electrically connected to two 1.5 V batteries and a switch using copper wires and then enclosed in a sealed, glass vial. Ignition of the flashbulb was performed by momentarily turning on the switch between the flashbulb and batteries. After ignition, the vial was kept closed for 30 minutes such that particles of volatilized drug coagulated and condensed on the inside surface of the vial. Analysis of the aerosol involved rinsing the vial with 5 mL of acetonitrile and injecting a sample of the organic solution into an HPLC. Frovatriptan (0.45 mg) aerosol was obtained in approximately 92% purity using this procedure. | The present invention relates to the delivery of a migraine headache drug through an inhalation route. Specifically, it relates to aerosols containing a migraine headache drug that are used in inhalation therapy. In a method aspect of the present invention, a migraine headache drug is administered to a patient through an inhalation route. The method comprises: a) heating a composition, wherein the composition a migraine headache drug, to form a vapor; and, b) allowing the vapor to cool, thereby forming a condensation aerosol comprising particles aerosol comprising particles with less than 5% drug degradation products. In a kit aspect of the present invention, a kit for delivering a migraine headache drug through an inhalation route is provided which comprises: a) a thin coating of an a migraine drug composition and b) a device for dispensing said thin coating as a condensation aerosol. | 0 |
This application is a continuation of application Ser. No. 11/333,919, filed Jan. 18, 2006, the disclosure of which is incorporated herein by reference.
BACKGROUND
The present invention relates to an intervertebral prosthetic device for stabilizing the human spine, and a method of implanting same.
Spinal discs that extend between adjacent vertebrae in vertebral columns of the human body provide critical support between the adjacent vertebrae while permitting multiple degrees of motion.
These discs can rupture, degenerate, and/or protrude by injury, degradation, disease, or the like to such a degree that the intervertebral space between adjacent vertebrae collapses as the disc loses at least a part of its support function, which can cause impingement of the nerve roots and severe pain.
In these cases, intervertebral prosthetic devices have been designed that can be implanted between the adjacent vertebrae, both anterior and posterior of the column and are supported by the respective spinous processes of the vertebrae to prevent the collapse of the intervertebral space between the adjacent vertebrae and provide motion stabilization of the spine. Many of these devices are supported between the spinous processes of the adjacent vertebrae.
In some situations it is often necessary to remove the laminae and the spinous process from at least one of the adjacent vertebrae to get proper decompression. In other situations, the defective disc is removed and two vertebral segments are fused together to stop any motion between the segments and thus relieve the pain. When two adjacent vertebrae are fused, the laminae and the spinous process of at least one vertebra are no longer needed and are therefore often removed.
However, in both of the above situations involving removal of a spinous process, it would be impossible to implant an intervertebral prosthetic device of the above type since the device requires support from both processes.
SUMMARY
According to an embodiment of the invention, an intervertebral prosthetic device is provided that is implantable between two adjacent vertebrae, at least one of which is void of a spinous process, to provide motion stabilization.
Various embodiments of the invention may possess one or more of the above features and advantages, or provide one or more solutions to the above problems existing in the prior art.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevational view of an adult human vertebral column.
FIG. 2 is a posterior elevational view of the column of FIG. 1 .
FIG. 3 is an enlarged, front elevational view of one of the vertebrae of the column of FIGS. 1 and 2 .
FIG. 4 is an enlarged, partial, isometric view of a portion of the column of FIGS. 1 and 2 , including the lower three vertebrae of the column, and depicting an intervertebral prosthetic device according to an embodiment of the invention implanted between two adjacent vertebrae.
FIG. 5 is an enlarged, isometric, exploded view of the prosthetic device of FIG. 4 .
FIG. 6 is a cross-sectional view of the implanted device of FIGS. 4 and 5 .
FIG. 7 is an enlarged, isometric, exploded view of an alternate embodiment of the prosthetic device of FIG. 5 .
DETAILED DESCRIPTION
With reference to FIGS. 1 and 2 , the reference numeral 10 refers, in general, to a human vertebral column 10 . The lower portion of the vertebral column 10 is shown and includes the lumbar region 12 , the sacrum 14 , and the coccyx 16 . The flexible, soft portion of the vertebral column 10 , which includes the thoracic region and the cervical region, is not shown.
The lumbar region 12 of the vertebral column 10 includes five vertebrae V 1 , V 2 , V 3 , V 4 and V 5 separated by intervertebral discs D 1 , D 2 , D 3 , and D 4 , with the disc D 1 extending between the vertebrae V 1 and V 2 , the disc D 2 extending between the vertebrae V 2 and V 3 , the disc D 3 extending between the vertebrae V 3 and V 4 , and the disc D 4 extending between the vertebrae V 4 and V 5 .
The sacrum 14 includes five fused vertebrae, one of which is a superior vertebrae V 6 separated from the vertebrae V 5 by a disc D 5 . The other four fused vertebrae of the sacrum 14 are referred to collectively as V 7 . A disc D 6 separates the vertebrae V 6 from the coccyx 16 which includes four fused vertebrae (not referenced).
With reference to FIG. 3 , the vertebra V 5 includes two laminae 20 a and 20 b extending to either side (as viewed in FIG. 2 ) of a spinous process 22 that projects posteriorly from the juncture of the two laminae. Two transverse processes 24 a and 24 b extend laterally from the laminae 20 a and 20 b , respectively, and two pedicles 26 a and 26 b extend inferiorly from the processes 24 a and 24 b to a vertebral body 28 . Since the other vertebrae V 1 -V 3 are similar to the vertebra V 5 they will not be described in detail. Also, V 4 is similar to V 5 with the exception that the spinous process 22 of V 4 has been removed for one or both of the reasons set forth below.
Referring to FIG. 4 , it will be assumed that, for one or more of the reasons set forth above, the vertebrae V 4 and V 5 are not being adequately supported by the disc D 4 and that it is therefore necessary to provide supplemental support and stabilization of these vertebrae. As stated above, it will also be assumed that the spinous process 22 of V 4 has been removed.
An intervertebral disc prosthetic device 40 according to an embodiment of the invention is provided which is adapted to be implanted between the spinous processes 22 of the vertebrae V 3 and V 5 . The prosthetic device 40 is shown in detail in FIGS. 5 and 6 and includes a spacer 42 which is substantially rectangular in shape with the exception that two curved notches 42 a and 42 b are formed in the respective end portions thereof. A laterally extending channel 42 c , having a substantially rectangular cross section, extends through the entire width of the spacer 42 approximately midway between the notches 42 a and 42 b.
An insert 44 is provided that is dimensioned so as to extend in the channel 42 c with minimum clearance. Tabs 46 a and 46 b extend out from the respective ends of the insert 44 and elongated openings 46 c and 46 d extend through the respective tabs. The length of the insert 44 substantially corresponds to the length of the channel 42 c so that when the insert is inserted in the channel, the tabs 46 a and 46 b project outwardly from the channel.
Two protrusions 48 a and 48 b extend from the sides of the tab 46 a and two protrusions 48 c and 48 d extend from the sides of the tab 46 b . The protrusions are for the purpose of receiving tethers, or the like, to tether the device 40 to the vertebrae V 4 and/or V 5 .
Since the spinous process of the vertebra V 4 has been removed, the device 40 is implanted between the spinous process 22 of the vertebra V 3 and the spinous process 22 of the vertebra V 5 . In the implanted position shown in FIGS. 4 and 6 , the spinous process 22 of the vertebra V 3 extends in the notch 42 a of the spacer 42 , and the spinous process 22 of the vertebra V 5 extends in the notch 42 b . The dimensions of the device 40 are such that, when it is implanted in this manner, the elongated openings 46 c and 46 d extend over the pedicles 26 a and 26 b ( FIG. 3 ) of the vertebra V 4 .
Then, two screws, one of which is referred to by the reference numeral 49 in FIGS. 4 and 6 , are inserted through the elongated openings 42 c and 42 d , respectively, of the spacer 42 . Torque is applied to the screws 49 so that they are driven into the pedicles 26 a and 26 b of the vertebra V 4 . The elongated openings 46 c and 46 d in the tabs 46 a and 46 b , respectively, enable the screws 49 to be adjusted laterally and to be angled towards the pedicles 26 a and 26 b as necessary so that they can be driven into the pedicles.
Although not shown in the drawing, tethers can be tied between the protrusions 48 a - 48 d and the vertebrae V 3 , V 4 , and/or V 5 to provide additional support and resistance.
As examples of the materials making up the spacer 42 and the insert 44 , the spacer can be of a relatively soft material, such as soft plastic, including silicone, while the insert can be of a relatively stiff material, such as hard plastic or rubber. In the latter context, the surgeon could be provided with several inserts 44 that vary in stiffness, and once the condition of the vertebrae V 4 and V 5 ( FIG. 4 ), and therefore the desired stiffness, is determined, the proper insert 44 can be selected.
When the device 40 is implanted in the manner discussed above, the relatively flexible, soft spacer 42 provides non-rigid connections to the vertebrae V 3 and V 5 that readily conforms to the spinous processes 22 of the vertebrae V 3 and V 5 and provides excellent shock absorption, while the insert 44 adds stiffness, compressive strength and durability, and the screws 49 provide a rigid connection to the vertebra V 4 .
A prosthetic device 50 according to another embodiment is shown in detail in FIG. 7 and includes a spacer 52 which is substantially rectangular in shape with the exception that a curved notch 52 a , is formed in one end portion. A tab 52 b projects from the other end of the spacer 52 for reasons to be described.
A spacer 54 is also provided which is substantially rectangular in shape with the exception that a curved notch 54 a is formed in one end portion and a tab 54 b projects from the other end of the spacer 54 .
A connector 56 is designed to fit over the tabs 52 b and 54 b of the spacers 52 and 54 , respectively, to connect them. To this end, the connector 56 has a through opening 56 a with a cross section slightly greater than the cross sections of the tabs 52 b and 54 b.
Two tabs 56 c and 56 b extend out from the respective ends of the connector 56 , and elongated openings 56 e and 56 d extend through the respective tabs for receiving screws, for reasons to be described.
Two protrusions 58 a and 58 b extend from the sides of the tab 56 b and two protrusions 58 c and 58 d extend from the sides of the tab 56 c . The protrusions are for the purpose of receiving tethers, or the like, to tether the device 50 to the vertebrae V 4 and/or V 5 .
To connect the spacers 52 and 54 , their respective tabs 52 b and 54 b are inserted into the opening 56 a of the connector 56 from opposite ends of the opening until the corresponding shoulders of the spacers 52 and 54 engage the corresponding ends of the connector 56 . The spacers 52 and 54 and the connector are sized so that the tabs 52 b and 54 b engage the inner wall of the connector 56 in a friction fit so as to retain the spacers 52 and 54 in the connector.
Since the spinous process of the vertebra V 4 has been removed, the device 50 is implanted between the spinous process 22 of the vertebra V 3 and the spinous process 22 of the vertebra V 5 . In the implanted position, the spinous process 22 of the vertebra V 3 extends in the notch 52 a of the spacer 42 , and the spinous process 22 of the vertebra V 5 extends in the notch 54 a . The dimensions of the device 50 are such that, when it is implanted in this manner, the elongated openings 56 d and 56 e extend over the pedicles 26 a and 26 b ( FIG. 3 ) of the vertebra V 4 .
Although not shown in the drawing, tethers can be tied between the protrusions 58 a - 58 d and the vertebrae V 3 , V 4 , and/or V 5 to provide additional support and resistance.
The spacers 52 and 54 could be fabricated from a relatively soft material, such as soft plastic, including silicone, while the connector 56 could be fabricated from a relatively stiff material, such as hard plastic or rubber. In the latter context, the surgeon could be provided with several connectors 56 that vary in stiffness. Thus, once the surgeon ascertains the condition of the vertebrae V 3 , V 4 , and V 5 ( FIG. 3 ) and determines the particular stiffness that is needed, the proper connector 56 can be selected.
Thus, when the device 50 is implanted between the spinous processes 22 of the vertebrae V 3 and V 5 in the manner discussed above, the relatively flexible, soft spacers 52 and 54 provide a non-rigid connection to the vertebrae V 3 and V 5 that readily conforms to the spinous processes 22 of the vertebrae V 3 and V 5 , and provides excellent shock absorption. Also, the connector 56 adds stiffness, compressive strength and durability, and the screws 49 provide a rigid connection to the vertebra V 4 .
It is understood that other variations may be made in the foregoing without departing from the invention and examples of some variations are as follows:
Any conventional substance that promotes bone growth, such as HA coating, BMP, or the like, can be incorporated in the prosthetic device of the above embodiments.
One or more of the components of the above devices may have through holes formed therein to improve integration of the bone growth.
The surfaces of the body member defining the notch can be treated, such as by providing teeth, ridges, knurling, etc., to better grip the spinous processes and the adapters.
The body member can be fabricated of a permanently deformable material thus providing a clamping action against the spinous process.
The spacers and associated components of one or more of the above embodiments may vary in shape, size, composition, and physical properties.
Through openings can be provided through one or more components of each of the above prosthetic devices to receive tethers for attaching the devices to a vertebra or to a spinous process.
The prosthetic device of each of the above embodiments can be placed between two vertebrae in the vertebral column 10 other than the ones described above.
The prosthetic device of each of the above embodiments can be fabricated from materials other than those described above.
The relative stiff components described above could be made of a resorbable material so that their stiffness would change over time.
The prosthesis of the above embodiments can be implanted between body portions other than vertebrae.
In the embodiment of FIG. 7 , the spacers 52 and 54 can be fabricated from a relatively stiff material and the connector 56 from a relatively soft, flexible material.
The prostheses of the above embodiments can be inserted between two vertebrae following a discectemy in which a disc between the adjacent vertebrae is removed, or a corpectomy in which at least one vertebra is removed.
The spatial references made above, such as “under”, “over”, “between”, “flexible, soft”, “lower”, “top”, “bottom”, etc. are for the purpose of illustration only and do not limit the specific orientation or location of the structure described above.
The preceding specific embodiments are illustrative of the practice of the invention. It is to be understood, therefore, that other expedients known to those skilled in the art or disclosed herein, may be employed without departing from the invention or the scope of the appended claims, as detailed above. In the claims, means-plus-function clauses are intended to cover the structures described herein as performing the recited function and not only structural equivalents but also equivalent structures. Thus, although a nail and a screw may not be structural equivalents in that a nail employs a cylindrical surface to secure wooden parts together, whereas a screw employs a helical surface, in the environment of fastening wooden parts a nail and a screw are equivalent structures. | A prosthetic device for insertion in a spinal column includes a first, second, and third members. The first member includes an inferiorly extending tab and is of a relatively flexible material. The second member includes a superiorly extending tab and is of a relatively flexible material. The third member defines a superior opening for receiving the inferiorly extending tab and an inferior opening for receiving the superiorly extending tab and is of a relatively stiff material. The device also includes a means for providing a rigid connection of the third member to a vertebra. | 0 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefits of U.S. 60/639,716 filed Dec. 28, 2004, which patent application is fully incorporated herein by reference.
FIELD OF THE INVENTION
The invention relates generally to a process for producing boron nitride using a borate mineral ore such as ulexite as a reactant material, and a boron nitride product thereof.
BACKGROUND OF THE INVENTION
Boron nitride (“BN”) is a thermally stable, highly refractory material of increasing commercial significance. Typically, boron nitride is produced by processes wherein boric acid is utilized as the boron source of reaction compositions. Suggested processes for producing boron nitride from boric acid are described in U.S. Pat. Nos. 2,922,699; 3,241,918; and 3,261,667 as well as in British Pat. Nos. 874,166; 874,165; and 1,241,206. U.S. Pat. No. 3,189,412 discloses a process to prepare boron nitride by passing nitrogen or ammonia or other nitrogen providing gas at 1200 to 1600° C. over a mixture comprising boric oxide, boric acid, or another boric oxide providing substance, carbon, and a catalyst, treating the reaction mixture with dilute mineral acid, and separating the boron nitride. JP Patent Publication No. 06-040713 discloses a process for producing boron nitride from colemanite, which is a hydrated calcium borate compound. It is thought that sodium compounds such as sodium borate can promote grain growth for BN particles in addition to the grain growth resulting from calcium borate compounds.
Applicants have discovered a process to use ulexite, a hydrated sodium calcium borate compound, in the direct manufacture of boron nitride instead of or in addition to boric acid as a reactant material. Using ulexite as a reactant in the boron nitride making process inherently enhances the grain growth of boron nitride, since ulexite contains sodium borate, providing an improved and economical process for making boron nitride of high purity and excellent yield.
SUMMARY OF THE INVENTION
The invention relates to a process for producing a polycrystalline hexagonal boron nitride compound by reacting ulexite with ammonia for at least one hour at a processing temperature of at least 1000° C.
DESCRIPTION OF THE INVENTION
As used herein, approximating language may be applied to modify any quantitative representation that may vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as “about” and “substantially,” may not to be limited to the precise value specified, in some cases.
The term “processing temperature” may be used interchangeable with the term “process temperature,” refers to the temperature in the equipment/step in the process for making hBN in the invention.
Generally in processes to produce boron nitride, a boron source and a nitrogen source are reacted to form a compound in which a boron atom and a nitrogen atom coexist. Instead of using boric acid as a boron source in the process of manufacturing boron nitride, applicants have discovered the use of ulexite as the boron source for excellent yields of high-purity, highly-crystalline hexagonal boron nitride.
Starting Raw Materials: In one embodiment of the invention, the starting boron material comprises of ulexite. Ulexite is a hydrated sodium calcium borate of the formula (Na 2 O) 0.2 (CaO) 0.5 (B 2 O 3 ) 0.16 H 2 O, and it also contains magnesium, silica, aluminum, and iron impurities. As opposed to boric acid, ulexite is not soluble in water. Ulexite, also called “TV rock,” has a unique optical property is that is transmits light along the long axis of the crystal by internal reflections, very much in the same way as in fiber optics.
In one embodiment, in addition to ulexite as the starting boron material, optionally up to 35 wt. % boric acid may be added as the boron source. In another embodiment, up to 50 wt. % boric acid may be added as the boron source. In yet another embodiment, alkaline earth metal salts of boric acid can be used instead of boric acid.
In one embodiment of the invention, the nitrogen-containing compound comprises organic primary, secondary, and tertiary amines such as diphenylamine, dicyandiamide, ethylene amine, hexamethylene amine, melamine, urea, and mixtures thereof. In one embodiment, melamine is used as the nitrogen-containing compound. In a second embodiment, dicyandiamide is used as a nitrogen containing promoter. In a third embodiment, the nitrogen-containing raw material is ammonia for the ulexite boron-containing material to be fired in an ammonia atmosphere.
In one embodiment of the invention, the nitrogen-containing compound in a powder form may be added to the ulexite-containing starting boron material in a ratio of about 30 to 55 wt. % of nitrogen-containing compound to starting boron material. In a second embodiment, the ratio of nitrogen-containing compound to starting boron material is about 40 to 50 wt. %. In a third embodiment, the ratio is about 30 to 55 wt. %.
Process Steps: The process for making hBN of the invention may be carried out as a batch process, or as a continuous process, including the following process steps.
Optional mixing/blending. In the initial step, the starting materials including the dopant are mixed or otherwise blended together in a dry state in suitable equipment such as a blender. The starting materials are used in powdery or compact form, whereby the grain size is not critical. If the starting materials comprise more than just ulexite (i.e., optional boric acid, optional nitrogen-containing promoters), the starting mixture is mixed in the dry state.
Optional pre-heating/drying step After the optional mixing/blending step, the starting material is dried at temperatures of about 100 to 400° C., and in one embodiment, from 150 to 250° C., to drive off any moisture in the reactants and create porosity between the raw materials, forming aggregates of materials in the form of nuggets, chunks, or pellets.
The drying operation can be carried out in air, or in a nitrogen or ammonia atmosphere. The drying time depends on the drying temperature and also whether the drying step is performed in a static atmosphere, or with circulating air or gas. In one embodiment, the drying time ranges from 4 hours at 200° C. to about 10 hours at 150° C. in a static environment. In a second embodiment, the drying time ranges from 1 to 15 hours.
Optional Crushing of the Precursors: After the drying step, the starting material is crushed or ground using conventional milling equipment such as roller mills, cross beater mills, rolling discs, and the like. In one embodiment, the crushed materials are broken into pieces weighing between 10 mg to 10 g each. In yet another embodiment, the materials are broken into pieces weighing about 0.2 g each.
Optionally in the next step, the crushed material is mixed with silica wherein the calcium in the ulexite reacts with the silica to give rise to calcium silicate to prevent the formation of 3CaO.B 2 O 3 which may otherwise be formed, thus giving a high yield of BN in the final reaction. In one embodiment, the total amount of silica to ulexite is maintained at a molar ratio of SiO 2 /CaO of less than 0.5. In a second embodiment, the molar ratio is maintained at a rate of less than 1.0.
Optional Combined Preheating and Densification (“Pilling”) Step: In one embodiment after the mixing/blending step, the mixed precursors are dried/crushed, and then densified using a process known in the art such as tableting, briquetting, extruding, pilling, and compacting, among others. In this step, the crushed mixture is densified into pellets weighing from 0.1 g to 200 g each. In one embodiment, the pellets have an average weight of ˜10 g. in a second embodiment, the crushed mixture is densified into pellets with an average weight of about 2 g.
In one embodiment, the densification/pelletizing steps are carried out in one extruding step, wherein the raw materials including ulexite and optional silica are fed in a twin screw extruder or similar equipment with a binder, such as polyvinyl alcohol; polyoxyethylene-based nonionic surfactants; polycarboxylic acid salts such as acrylic acid, methacrylic acid, itaconic acid, boletic acid, and maleic acid; polyoxazolines such as poly(2-ethyl-2-oxazoline); stearic acid; N,N′-ethylenebissteramide; sorbitan compounds such as sorbitan monostearate; and the like. The material is then subsequently dried and pelletized upon exit from the extruder.
The exit pellets can be fed in a continuous process directly into the reaction vessel for the next step, or in yet another embodiment, processed through a furnace of 200° C. for additional drying prior to being fed into the reaction vessel.
Calcinating Step: After drying and optional mixing with silica, the material is purged in a nitrogenous atmosphere such as ammonia at an elevated temperature of 700 to 1200° C. for an extended period of time of up to 18 hours to form an incompletely reacted boron nitride in the “turbostratic” form. In one embodiment, the material is maintained in ammonia while being fired at 1000 to 1200° C. for 1 to 24 hours. In a second embodiment, the material is fired at 1200° C. for about 4 hours.
Heat Treating/Sintering Step: After calcinations, the turbostratic boron nitride is sintered at a temperature of at least about 1500° C. for at least 10 minutes. In one embodiment, the sintering is for about 1 to about 4 hours. In one embodiment, the heat treatment/sintering is carried out from about 1800° C. to about 2300° C. for 2 to 3 hours. In another embodiment, from 2000° C. to 2300° C. In yet another embodiment, from 2000° C. to about 2100° C. in inert gas, nitrogen, or argon. In one embodiment, the sintering is carried out in a vacuum. In another embodiment, the sintering is carried out under conditions of at least 1 atmosphere of pressure.
Combined Single-step of Calcinating/Sintering: In yet another embodiment and instead of performing a two-step process of calcinations then heat-treating/sintering, the pellets are fired in a nitrogenous atmosphere in a reaction chamber, wherein the chamber is heated up from room temperature at a rate of 20 to 1200° C. per hour to at an elevated temperature of 1200 to 2300° C. The process temperature is then held for about 1 to 30 hours, wherein the nitrogen purge is maintained at a rate sufficient to sustain a non-oxidizing environment. In one embodiment of a single step process, the pellets containing the reactants including ulexite are fired in one single step at an elevated processing temperature forming BN crystals, for a high crystallinity boron nitride product.
In one embodiment, the pellets are maintained in ammonia while being fired to 1200 to 1600° C. for 2 to 12 hours. In a second embodiment, the pellets are fired at 1400° C. for about 4 hours. In a third embodiment, the pellets are fired from room temperature to a temperature of 1800° C. at a rate of 500° C. per hour. The temperature is then held at 1800° C. for 5 hours, wherein a nitrogen purge is maintained.
The single step reaction at high temperature is carried out using high temperature furnace equipment known in the art, for example, a plasma jet furnace. In one embodiment, the nitrogenous atmosphere is a mixture of ammonia and an inert gas.
The process of the invention can be carried out as a batch process or continuously, whereby the reaction mixture is introduced as a loose powder, or as a compacted mass into a reaction vessel, which in one embodiment is made of graphite.
Washing Step. After firing, the reaction product is cooled and the product is subject to a washing treatment. In one embodiment, the washing treatment is via leaching with an HCl solution of 26 vol. % to remove the impurities such as sodium borate and calcium borate, which come from ulexite. In a second embodiment, the leaching is via several cycles of HCl washing at an elevated temperature of at least 60° C., and then deionized water at room temperature.
Applications of the BN Powder Made from the Invention: The high purity boron nitride powder of the present invention can be used as a filler or additives for polymer compositions. In one embodiment, the BN powder is used in thermal management applications, such as in composites, polymers, greases, and fluids. The boron nitride powder can also be used in hot pressing applications, or as a precursor feed stock material in the conversion of hexagonal boron nitride to cubic boron nitride. In another embodiment, the material is used for making a hexagonal boron nitride paste. As used herein, paste is a semisolid preparation. This method involves providing a boron nitride slurry and treating the slurry under conditions effective to produce a boron nitride paste including from about 60 wt. % to about 80 wt. % solid hexagonal boron nitride.
EXAMPLES
The invention is further illustrated by the following non-limiting examples:
Example 1
200 grams of ulexite is placed in a crucible and dehydrated at 200° C. The material is then ground to granules of about 10 mm size. 150 grams of this material is then placed into a graphite tube, and ammonia gas is flowed through the tube. While ammonia gas is supplied at a rate of 0.5 litre/min. through the tube, it is heated to 1400° C. at the rate of 300° C. per minute. The temperature is maintained for 2 hours, and then the supply of ammonia is allowed to stop. The tube is allowed to cool naturally while argon gas is passed through. Powder x-ray diffraction analysis of the product confirms the presence of boron nitride.
The reaction product obtained is then finally ground in a mill, placed in 400 cc of 3N HCl, and the impurities are allowed to be thoroughly leached into the acid. It is then filtered and washed repeatedly with deionized water 6 times. After drying at 80° C. for 24 hours, a white powder is obtained. X-ray diffraction of the powder shows only the presence of BN. The white powder is then weighed, giving greater than 90% of theoretical yield. Content of impurities such as calcium, silicon, and magnesium is insignificant, indicating that the final product is high purity BN.
Example 2
The BN product of Example 1 is further heat-treated or sintered at 1700 to 2100° C. in a non-oxidizing gas atmosphere of nitrogen or argon. This treatment results in the progress of crystallization, yielding a BN product of improved crystallinity and purity.
This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to make and use the invention. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
All citations referred herein are expressly incorporated herein by reference. | A process for producing boron nitride using a boron containing ore as a starting material, by reacting naturally occurring ulexite with ammonia at high temperature, for a boron nitride with high impurity and at a high yield. | 2 |
BACKGROUND
Methods and apparatus for controlling downhole drilling and completion configurations are growing more complex and there is an ever increasing need for downhole control systems which include downhole computerized modules employing downhole computers for commanding downhole tools such as packers, sliding sleeves, valves, etc. based on input from downhole sensors. It will be appreciated that these control systems utilize downhole devices and circuits that require electrical power. Because of shortcomings associated with providing electricity via a wireline from the surface or via batteries housed in the downhole environment, downhole electric power generators have been suggested for use to provide power for downhole electronics. When turbines are employed as the downhole electric power generator, the turbine blades are provided within the flow path of the borehole, obstructing full bore access so that wireline or other operations cannot be performed, such as entry of completion equipment and other objects into the tubing, downhole of the level of the turbine. Other downhole electric power generators including turbines have been provided on a side of the bore so as not to significantly obstruct the main flow, but require a diversion of flow to move the blades. The diverted flow may not be as powerful as the flow through the main flow and the size of the electric power generator must be smaller to fit on the side of the tubing, both of which inevitably reduce the potential capacity for electric power generation.
BRIEF DESCRIPTION
A downhole electrical generating apparatus providing power to downhole electronics, the apparatus includes a tubular having a wall forming a tubular space which receives a flow in a flow direction; and, a retractable electrical generating apparatus positionable in a first condition facing the flow and in a second condition substantially opening the tubular space.
A method of providing power to downhole electronics, the method includes providing a retractable electrical generating apparatus within a flow passageway of a tubular, the retractable electrical generating apparatus positioned substantially perpendicular to a flow direction in a first condition and producing electricity using the retractable electrical generating apparatus in the first condition; and moving at least a portion of the retractable electrical generating apparatus to a position towards a wall of the tubular and providing a substantially clear borehole in the second condition.
BRIEF DESCRIPTION OF THE DRAWINGS
The following descriptions should not be considered limiting in any way. With reference to the accompanying drawings, like elements are numbered alike:
FIG. 1 is a cross-sectional view of an exemplary embodiment of a retractable power turbine apparatus;
FIG. 2 is a cross-sectional view of the exemplary retractable power turbine apparatus of FIG. 1 within a tubular;
FIG. 3 is a cross-sectional view of another exemplary embodiment of a retractable power turbine apparatus within a tubular;
FIG. 4 is a cross-sectional view taken along line I-I′ of FIG. 3 ;
FIG. 5 is a cross-sectional view of yet another exemplary embodiment of a retractable power turbine apparatus;
FIG. 6 is a cross-sectional view of the exemplary retractable power turbine apparatus of FIG. 5 within a tubular;
FIG. 7 is a cross-sectional view of still another exemplary embodiment of a retractable power turbine apparatus;
FIGS. 8A and 8B are partial cross-sectional views of an exemplary turbine blade of FIG. 7 in extended and retracted positions, respectively; and
FIG. 9 is a partial perspective view of the retractable turbine apparatus of FIG. 7 .
DETAILED DESCRIPTION
A detailed description of one or more embodiments of the disclosed apparatus and method are presented herein by way of exemplification and not limitation with reference to the Figures.
A downhole electrical generating apparatus 10 in accordance with exemplary embodiments is shown in FIGS. 1 and 2 for use in a borehole, such as a production well for producing oil, gas, or the like, for example. Such wells include a well casing, not shown, which may be positioned in the earth, and production tubing, not shown, connected to a tubular 12 of the downhole electrical generating apparatus 10 . An uphole section of production tubing is connectable to a first end 14 , such as one of an uphole or downhole end of the tubular 12 of the downhole electrical generating apparatus 10 , and a downhole section of production tubing is connectable to second end 16 , such as the other of an uphole or downhole end of the tubular 12 , of the downhole electrical generating apparatus 10 . The tubular 12 of the downhole electrical generating apparatus 10 includes a longitudinal axis 13 and a flow passageway that communicates with, and is generally in alignment with, uphole and downhole sections of production tubing. The tubular 12 includes a wall 18 providing a tubular space 20 for the flow passageway that has a first inner diameter 22 , substantially the same as a diameter of at least the connecting portions of the upper and lower sections of production tubing, for connecting therewith. The tubular space 20 also has a second inner diameter 24 , larger than the first inner diameter 22 , for providing a wall pocket 26 or side pocket that receives a retractable power turbine 30 of the downhole electrical generating apparatus 10 when a full bore is required in the production tubing and tubular 12 so that wireline or other operations can be performed downhole of the level of the retractable power turbine 30 . The longitudinal section of the tubular 12 that includes the wall pocket 26 may have different widths depending on the cross-section taken along the section.
With further reference to FIGS. 1 and 2 , the retractable power turbine 30 of the downhole electrical generating apparatus 10 includes turbine blades 32 , which are positioned, in a first condition, within the flow 34 of the flow passageway in the tubular space 20 . The turbine 30 may have a smaller diameter than the first diameter 22 of the tubular 12 . The turbine 30 may be less than half of the first diameter 22 , but may be larger, as long as it is sized to fit within the wall pocket 26 in the second condition of the turbine 30 . That is, the turbine 30 folds down into the wall pocket 26 in the side of the tubular 12 in the second condition and substantially out of the flow 34 . The wall pocket 26 forms an upset on the outside of the tubular 12 which provides the necessary wall thickness and second diameter 24 to substantially remove the turbine 30 from the flow 34 in the second condition. Thus, the turbine 30 is provided substantially perpendicular to the direction of flow 34 in the first condition, and substantially parallel to the direction of flow 34 in the second condition.
During a production operation, production fluid flowing upwardly through the production tubing and the tubular 12 (or during injection operation, fluid flowing downwardly through the tubing) will rotate the turbine blades 32 when the turbine 30 is positioned in the first condition within the flow 34 . The blades 32 are connected to a center bearing 36 , and the turbine blades 32 rotate around the center bearing 36 and around rotation axis 31 of the turbine 30 due to the force of fluid in the flow 34 pushing past the blades 32 . The center bearing 36 is supported by a support rod 38 connected to the tubular wall 18 by a pivot 40 . The support rod 38 folds with the turbine 30 into the wall pocket 26 . Surrounding the turbine blades 32 is a sealed unit 42 , which contains coils 41 for a generator. The blades 32 are provided with magnets 44 at ends thereof that interact with the coils 41 of the sealed unit 42 when the blades 32 are rotated. That is, the movement of the magnets 44 near the coils 41 creates a flow of electrons, which can be harnessed into electricity in a known manner. The turbine 30 , including the coils 41 within the sealed unit 42 , the turbine blades 32 having the magnets 44 , the bearing 36 , and the support rod 38 , all move together from the first condition within the flow 34 for electricity production to the second condition substantially out of the flow 34 for providing a clear borehole. The movement from the first condition to the second condition, and from the second condition to the first condition, may be performed by a pushing or pulling force from a downhole tool inserted through the tubular 12 and physically engaging the turbine 30 , or alternatively by remote actuation.
While a coil containing sealed unit 42 has been disclosed as surrounding the turbine blades 32 of the turbine 30 of the downhole electrical generating apparatus 10 , it would also be within the scope of these embodiments to utilize the central bearing 36 as a rotor by connecting the central bearing 36 to a generator positioned outside of the flow 34 , such as within the wall pocket 26 or a separate upset within the wall 18 . Rotation of the bearing 36 may provide the necessary rotation for the generation of electricity in a generator. In such an embodiment, the central bearing 36 may transmit rotational energy via the support rod 38 to the generator.
Also, in yet another exemplary embodiment, instead of providing the coil containing sealed unit 42 as part of the retractable portion that is folded into the wall pocket 26 , the coils may remain fixed around or inside a circumference of the wall 18 , similar to coil containing unit 126 as will be further described below with respect to FIG. 3 . In such an embodiment, the turbine blades 32 and the magnets 44 spin in the flow 34 in the first condition, and are retractable together into the wall pocket 26 in the second condition, but the coils remain fixed around the circumference of the wall 18 in both conditions. Also in such an embodiment, the support rod 38 may be positioned such that the turbine blades 32 are pulled into the wall pocket 26 , that is, the support rod 38 may be connected to an opposite side of the central bearing 36 , such as a downhole side of the central bearing 36 instead of an uphole side of the central bearing 36 , so that the support rod 38 does not interfere with the coils when the turbine is in the first condition.
Turning now to FIGS. 3 and 4 , in another exemplary embodiment, a downhole electrical generating apparatus 100 includes a turbine 102 that rotates on an annular bearing 104 with no support in the center 106 . In such an embodiment, the blades 108 of the turbine 102 are mounted on pivot or swivel attachment 110 along the annular bearing 104 and can rotate back to the wall 112 of a tubular 114 housing the turbine 102 to provide a clear path. The blades 108 include a first end 116 pivotally attached, such as by but not limited to a swivel attachment 110 , the annular bearing 104 and a second end 118 closer to a central area 106 of the tubular space 120 within the tubular 114 . In a first condition, the blades 108 are extended so as to be substantially perpendicular to the direction of the flow 122 , so that the force of the flow 122 rotates the blades 108 about the annular bearing 104 . In a second condition, to substantially remove the blades 108 from the flow passageway through the tubular space 120 , the blades 108 may be pivoted downwardly so as to lie substantially flush with the wall 112 of the tubular 114 and parallel with a direction of the flow 122 . For electricity production, the turbine 102 may be surrounded by a coil containing unit 126 , as in the first embodiment, where magnets may be provided in the annular bearing 104 and/or ends 116 of the turbine blades 108 . As in the first embodiment, actuation from the first condition to the second condition may occur using a downhole tool or via remote actuation. While the annular bearing 104 and sealed unit 126 are shown embedded within the wall 114 of the tubular 112 , it would also be within the scope of these embodiments to form upsets within the wall 114 or other supporting structures about the wall 114 to support the annular bearing 104 and/or the sealed unit 126 .
Turning now to FIGS. 5 and 6 , in yet another exemplary embodiment, a downhole electrical generating apparatus 200 includes a turbine 202 that rotates on an annular bearing 204 with no support in the center 206 , similar to the turbine 102 shown in FIGS. 3 and 4 . Unlike the turbine 102 shown in FIGS. 3 and 4 , the turbine 202 is pivotally connected to tubular 208 , as is the turbine 30 shown in FIGS. 1 and 2 . Thus, the downhole electrical generating apparatus 200 includes a combination of features shown in the previous embodiments, and additional details and alternatives of the downhole electrical generating apparatus 200 may be derived from a review of the detailed descriptions of those embodiments. With reference again to FIGS. 5 and 6 , the turbine 202 includes turbine blades 210 connected to the annular bearing 204 which may be rotatably supported within a sealed unit 212 for electricity production in a first condition when a flow 214 of fluid pushes past the turbine blades 210 causing rotation thereof. The turbine 202 is pivotally connected, such as by using a support rod 216 to the tubular 208 to fold the turbine 202 into wall pocket 218 in a second condition to provide a substantially clear borehole within the tubular 208 .
With reference to FIGS. 7 , 8 A- 8 B, and 9 , in still another exemplary embodiment, a downhole electrical generating apparatus 300 includes a turbine 302 that rotates on an annular bearing with no support in the center, similar to the previously described turbines 102 and 202 . Unlike the turbines 102 and 202 , however, the turbine blades 304 swivel sideways towards the wall of the tubular in the second condition instead of swiveling towards the wall in a downhole or uphole direction. The blades 304 are mounted on a rotor 306 on a swivel or pivot 308 . Magnets 310 are also positioned on the rotor 306 . When the flow through the tubular causes the blades 304 to spin, the rotor 306 spins relative to a coil-containing stator 312 containing coils 314 , where the stator 312 may be positioned in the tubular, as in the embodiment shown in FIG. 3 . FIG. 8A shows the turbine blade 304 extended in the first condition within the flow for rotating the rotor 306 relative to the stator 312 . FIG. 8B show the turbine blade 304 retracted in the second condition, substantially out of the flow, or at least substantially out of the central region of the tubular, to provide a substantially clear borehole in the second condition. As shown in FIG. 9 , the blade 304 is pivotally connected to an uphole end 316 and a downhole end 318 of the rotor 306 . In an exemplary embodiment, a magnet 310 is extended between the uphole end 316 and the downhole end 318 of the rotor 306 , and between each adjacent pair of blades 304 . Alternatively, each turbine blade 304 may include a magnet at each rotor side end thereof.
While the invention has been described with reference to an exemplary embodiment or embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material or blade shape to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the claims. Also, in the drawings and the description, there have been disclosed exemplary embodiments of the invention and, although specific terms may have been employed, they are unless otherwise stated used in a generic and descriptive sense only and not for purposes of limitation, the scope of the invention therefore not being so limited. Moreover, the use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another. Furthermore, the use of the terms a, an, etc. do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item. | A downhole electrical generating apparatus providing power to downhole electronics. The apparatus includes a tubular having a wall forming a tubular space which receives a flow in a flow direction. A retractable electrical generating apparatus positionable in a first condition facing the flow and in a second condition substantially opening the tubular space. Also included is a method of providing power to downhole electronics. | 5 |
FIELD OF THE APPLICATION
The present application relates to paving stones, and more particularly to a paving stone for use in an interlocking system of pre-cast paving stones.
BACKGROUND OF THE ART
Pre-cast paving stones of concrete are commonly used to lay out pavements, to define patios, driveways, walkways. When compared to natural stones, pre-cast paving stones are relatively inexpensive to make, and provide numerous advantages. The paving stones are for instance pre-cast with a flat surface, and generally uniform thickness. Accordingly, when they are laid out on compacted ground, an assembly of pre-cast paving stones forms a uniform flat surface. Moreover, the paving stones are usually sized for ergonomic handling.
The challenge in designing a pre-cast paving stone is to make it look like natural stones once laid out. Some paving stones generally have polygonal geometries, which geometry results in the paving stone lay out producing repetitive patterns. In instances, some paving stones have been designed to look like natural stones and consequently may have an irregular contour. However, such stones may be difficult to assemble, by a lack of distinguishable orientation due to their irregular contour. US Patent Application Publication no. 2007/0217865, by Castonguay et al. shows a flagstone having a generally hexagonal shape. Referring to FIG. 4 thereof, an arrangement of flagstone lay-out is illustrated. Due to the repetitive contour formations of the flagstone of Castonguay et al., the assembly of these stones may be difficult as some of the formations look alike. Moreover, the compact shape of these flagstones and relatively straight edges results in their lay-out being repetitive. It is therefore desirable to produce a pre-cast paving stone that can simulate natural flagstone and which is easy to install while having an irregular contour with non-repetitive projections and depressions.
Another disadvantage of the prior art stone is that its contour shape does not lend itself to forming paved areas with outer edges having generally well defined demarcations, such as when laying an assembly of such stones against a straight edge or when constructing pathways with well defined edges.
SUMMARY OF THE APPLICATION
It is therefore an aim of the present application to provide a novel paving stone, resembling a flagstone, and method for assembling same.
In accordance with a broad aspect of the present invention there is provided a concrete cast stone for use with other ones of the concrete cast stones for covering a surface. The concrete cast stone comprises an elongated shaped body having a longitudinal axis with the body tapering along the axis from opposed sides thereof to define a smaller tapering end resulting in a distinguishable orientation for the stone. The body has a peripheral contour of non-repetitive jagged shape for interlocking engagement of a plurality of the concrete cast stone. The peripheral contour has interlocking side sections and part-interlocking side sections such that the concrete cast stones placed side-by-side interlock by one or a combination of (1) matching the interlocking side sections in a linear arrangement of the concrete cast stones wherein the stones are aligned along their longitudinal axis, and (2) matching some of the concrete cast stones with their longitudinal axis transverse to the linear arrangement and partly interlocked with each other and the concrete cast stones of the linear arrangement to form a herringbone arrangement. The body has three pairs of side sections with (a) the side sections of different pairs being different from one another, (b) the side sections of a same pair generally being translated images of one another and being on opposite sides of the longitudinal axis of the body to define interlocking profiles, such that the concrete cast stones placed side-by-side interlock by matching equivalent pairs of side sections in the linear arrangement of the concrete cast stones, and (c) the adjacent side sections of a first pair and of a second pair of one of the concrete cast stone being an interlocking image of the adjacent combined side sections of the second pair and of a third pair of two of the stones, such that when a first row is defined by interlocking the concrete cast stones by the first pair, and a second row is defined by interlocking the concrete cast stones by the third pair, the first row and the second row are interlockable by the adjacent combined side sections of the first row interlocking with the adjacent side sections of the second row in the herringbone arrangement of the concrete cast stones.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a top plan view of a paving stone constructed in accordance with the present application and illustrating its distinctive irregular contour pattern;
FIG. 2 is a perspective view of a paving stone with the contour pattern of FIG. 1 , and wherein the top surface thereof is segmented into a variety of stone shapes;
FIG. 3 is a top plan view of an assembly of a plurality of the paving stones of FIG. 2 , as interlocked in a linear manner;
FIG. 4 is an exploded view illustrating the inter-relationship of the paving stones of FIG. 1 interlocked in the linear manner; and
FIG. 5 is an exploded view illustrating the inter-relationship of the paving stones of FIG. 1 interlocked in a herringbone manner.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to the drawings, and more particularly to FIG. 1 , there is illustrated the paving stone 10 of the present disclosure. Paving stones are fabricated so as to have a body 11 peripherally defining the pattern of the paving stone 10 . The periphery of the paving stone 10 of the present disclosure defines a jagged outline that is non-repetitive when contouring the paving stone 10 . The paving stone 10 has projections and depressions of different shapes and different sizes (i.e., receiving cavities). Moreover, the paving stone 10 has a generally elongated shape with one end along its longitudinal axis 12 being smaller than the opposite end, resulting in a distinguishable orientation. This elongated shape facilitates the positioning of the paving stones in an interlocked herringbone arrangement, as well as in an interlocked linear arrangement, or in a combination thereof, as described hereinafter.
Referring to FIG. 2 , there is illustrated a pre-cast paving stone 20 having a body 21 which is the same as the paving stone 10 of FIG. 1 , and with an exposed surface portion 22 projecting upwardly from the body 21 . The long face of the body 21 is the interface of the paving stone 20 with the ground, or other surface upon which the paving stones will be laid out (e.g., it is possible to lay out the paving stones on edges to form a stone face wall). In an embodiment, the exposed surface portion 22 is the visible portion of the paving stone 10 when laid out. The paving stone 20 is a pre-cast concrete stone, and may have the exposed surface portion 22 formed with a plurality of smaller distinct substones 23 spaced apart to form joints therebetween to simulate a flagstone assembly. The exposed face 23 ′ of the substones 23 may have a textured surface to simulate real stones. A shoulder 25 may be defined by the base 20 , at the outer periphery of the exposed surface portion 22 , to form joints with adjacent stones when the paving stones 10 are laid out. Alternatively, as is well known in the art, spacing formations can be cast at spaced intervals to form joints between adjacent stones when laid side-by-side. In the embodiment of the paving stone without the substones 23 and joints (e.g., FIG. 1 ), the shoulder 25 may be a slanted surface between the edge and the top surface of the paving stone 10 . Accordingly, when the paving stone 10 of FIG. 1 is assembled with others, a contour joint is defined by the side-by-side shoulders 25 .
In accordance with an embodiment, the paving stone 20 is pre-cast into a plurality of different models. Using the body 21 with the paving stone 10 , the different sub-stones have patterns to define a different exposed surface portion. One method considered to pre-cast a plurality of different models is to use a casting cavity with the paving stone 10 ( FIG. 1 ) to form the base of the paving stone 20 ( FIG. 2 ), and with inserts to simulate the exposed portion 22 ( FIG. 2 ). The inserts form the joints defining the substones 23 , and the surface texture of the substones 23 . Different pigments may be injected into the concrete mixture, to imitate discoloration and veins of real stones.
Referring to FIG. 3 , a plurality of the paving stones with the paving stone 10 ( FIG. 1 ) are illustrated as being assembled in a linear arrangement with their longitudinal axis 12 aligned. The paving stones are illustrated as 20 A to 20 E, with each of the paving stones 20 A- 20 E having its own exposed portion 22 . By the presence of different sets of sub-stones, for example six sets, the interlocking system of paving stones of FIG. 3 has a natural flagstone look, despite the fact that the system is made of pre-cast paving stones. The system may have more or less of the different sets of substones. However, in an embodiment, there are a sufficient amount of stones such that any paving stone 20 in a paving arrangement with multiple other paving stones 20 is preferably not interlocked with another paving stone 20 having the same set of substones.
Still referring to FIG. 3 , there is illustrated a set of half paving stones 20 F and 20 G. The half paving stones 20 F and 20 G are precise parts of any one of the paving stones 20 A- 20 E, but with a straight side 39 , for instance for installation against a wall or a linear abutment, or to form a paved surface having a substantially straight edge outline. Straight edge outlines are desirable when laying a walkway, for instance. The half paving stones 20 F- 20 G may be pre-cast by placing an insert in the casting cavity, thereby forming half of a paving stone. Alternatively, any of the paving stones 20 A- 20 E may be cut to form a half paving stone, or a paving stone portion. This cut could also be made by the installer if there is a need to do so during installation.
The paving stone 10 is defined to allow installation in both linear interlocking and herringbone interlocking. Referring to FIG. 4 , the paving stones 10 are shown in an exploded view to illustrate their inter-relationship when constructing a linear interlocking assembly, as all stones 10 are all oriented in the same direction with their longitudinal axis 12 aligned in each row and parallel with adjacent rows.
The paving stone 10 of FIG. 1 allows the linear interlocking of an assembly of stones by a sequence of three pairs of dissimilar side sections. Looking at the paving stone 10 of FIG. 1 , the paving stone 10 has a first pair of side sections 31 defined between the demarcation lines 13 and 13 ′, and 14 and 14 ′, a second pair of side sections 32 between demarcation lines 14 ′ and 15 , and 13 and 15 ′, and a third pair of side sections 33 between demarcation lines 25 and 13 ′, and 14 and 15 ′. The two side sections of a same pair are generally translated images of one another, and are on opposite sides of the paving stone 10 , thereby defining interlocking profiles.
Accordingly, when paving stones 20 are installed side by side, with equivalent pairs being adjacent, the side sections interlock. This is schematically illustrated in FIG. 4 , in a linear arrangement of the paving stones 20 of the present disclosure. For instance, paving stone 40 is placed side-by-side with paving stones 41 , whereby side sections 33 interlock. Similarly, the paving stone 40 interlocks with paving stones 42 , by interlocking of the side sections 32 . Finally, the paving stone 40 interlocks with paving stones 43 , by interlocking of side sections 31 . Therefore, by matching equivalent pairs of side sections, a linear arrangement of the paving stones 20 (i.e., 40 - 44 ) is obtained, in which the elongated shapes of the six paving stones surrounding any given paving stone are parallel to the elongated shape of that given paving stone.
It is pointed out that the side sections of different pairs (e.g., side section 31 and side section 32 ) are different from one another. Moreover, the side sections 31 and 33 have depressions and projections, facilitating the interlocking between paving stones 20 .
Referring to FIG. 5 , the paving stones 20 may also be interlocked in a herringbone arrangement. This is achievable by the paving stone 10 . More specifically, the pairs of side sections 31 , 32 and 33 are configured such that the adjacent side sections 31 A, 32 A of the first pair and of the second pair of the paving stone 10 (e.g., illustrated as stone 50 for clarity), are an interlocking image of the adjacent combined side sections 32 B, 33 B of the second pair and of the third pair of two of the patterns 10 (e.g., illustrated as stones 51 for clarity). Accordingly, when a first row B is defined by interlocking the paving stones 51 by the first pair of side sections 31 , and a second row A is defined by interlocking the paving stones 50 by the third pair of side sections 33 , the first row B and the second row A are interlockable by the adjacent combined side sections 32 B, 33 B of the first row B interlocking with the adjacent side sections 31 A, 32 A of the second row A. This defines a herringbone arrangement of the paving stones 20 , in which the elongated shapes of four paving stones surrounding any given paving stone are transverse to the elongated shape of the stone, whereas the elongated shapes of two paving stones surrounding that given paving stone are transverse to the elongated shape of that given paving stone.
Another row C is illustrated adjacent to the first row B, in view of being interlocked in the herringbone pattern. It is however pointed out that the paving stones 20 of row C may be oriented in a similar orientation as the paving stones of the first row B, for linear arrangement therebetween. In such a linear/herringbone arrangement, the elongated shapes of four paving stones surrounding any given paving stone are parallel to the elongated shape of that given paving stone, whereas the elongated shapes of two paving stones surrounding that given paving stone are parallel to the elongated shape of that given paving stone.
As all stones 20 have exposed surfaces 22 ( FIGS. 2 and 3 ), the linear arrangements and herringbone arrangements are not visible from a top plan view when the paving stones 20 are laid out (e.g., FIG. 3 ). Accordingly, any combination of the linear and herringbone arrangements may be used, to enhance the natural flagstone look of a pavement with the paving stones 20 .
In an embodiment, the side sections of any of the pairs 31 , 32 and 33 may not be exact translated images of one another. Accordingly, when the paving stones are laid out, the differences in shape of the side sections may result in joints of varying width between the substones 23 ( FIGS. 2 and 3 ), enhancing the natural look of the assembly of paving stones 20 . | A concrete cast stone resembling a flagstone for use with other ones of the concrete cast stones for covering a surface. The concrete cast stone comprising a body having a peripheral contour of non-repetitive jagged shape for interlocking engagement of a plurality of the concrete cast stone. The peripheral contour defining a distinguishable orientation with interlocking side sections and part-interlocking side sections such that said concrete cast stones placed side-by-side interlock by one or a combination of (1) matching the interlocking side sections in a linear arrangement of the concrete cast stones, and (2) matching the part-interlocking side sections in a herringbone arrangement. A method for assembling the concrete cast stone is also provided. | 4 |
FIELD OF THE INVENTION
This invention relates to telephone services and, in particular, to a system for allowing a subscriber to select features of the subscriber's telephone service.
BACKGROUND
People have used various means for limiting interruptions due to the telephone. In the past, people used switchboards and secretaries to screen incoming, or inbound, calls. Voice mail systems took over some of this role both in the home and in the central office. Today, there are web-based companies managing 3rd-party call control, via the toll-switch network, which allow users to enter call control information through a web portal. There are also edge devices in each of the public telephone company's central offices which provide local control, but offer an extremely limited number of features and do not provide true 3rd-party call control.
The web-based toll systems provide good user interaction but they are not economical and cannot take advantage of local number portability because they do not provide local control and connectivity.
The Public Switched Telephone Network (PSTN) consists of a plurality of edge switches connected to telephones on one side and to a network of tandem switches on the other. The tandem switch network allows connectivity between all of the edge switches, and a signalling system is used by the PSTN to allow calling and to transmit both calling and called party identity.
Until now, optional features were provided by the local service telephone company (telco) through the edge switch at the central office (CO). It was not possible to provide optional features through any other means. Control of these features was done through the first party (calling party) or the second party (called party), or worse yet, manually by calling the business office.
In the past, numerous devices have been built that allow the connection of two lines together at an edge switch. These devices can be used to add features to a telephone network by receiving a call on one line and then dialing out on another line. The problem with these devices is that, because they are connected through an edge switch, transmission losses and impairments occur, degrading the overall connection. In addition, signalling limitations prevent full control, by the subscriber or the system, over the call.
The invention described herein connects at the tandem, thereby eliminating these problems.
In the edge devices residing in the PSTN central offices, the 1st party (the calling party) has numerous features available (dialing options). The 2nd party (called party) also has options available such as call forwarding, but these features typically require access from the first or second party's device and are extremely awkward to program. The user interaction is not only awkward, it is limited and requires interaction with the telephone company to provision them. In other words, past systems for provisioning, meaning addition, modification, or control of telephone features, required a subscriber to make the feature selection through the telephone business office. Central office workers would then implement the provisioning under request of the business office.
Call Forwarding is one popular provision. There is significant transmission degradation for Call Forwarding to take place. The calling party pays for a call to the edge device, and the edge subscriber, the called party, pays for the call to the forwarding number. For enhanced inbound call control to occur, a direct 3-party call control means is needed.
A variety of services have arisen to address the problems mentioned above. Many of these systems allow the called party to make changes to his/her call forwarding attributes which do not allow direct 3rd-party call control. These services provide good user interaction, some via the internet, but they rely upon the toll network through the use of “800” numbers. This requires the subscriber to pay by the minute and does not allow the subscriber to take advantage of number portability in order to obtain 3rd-party call control. There are other toll network mechanisms for remote call forwarding. For example, MCI offers a service where the customer can remotely change the forwarding target number for “800” numbers. Contacting the ultimate end-user before terminating the first incoming call is similar to the manner in which “800” credit calls and collect calls are processed, but these are not done at the local subscriber level.
In addition to these toll services, there are edge devices that perform some of the same services. Edge devices such as phones and PBXs that include voice mail, inter-active voice response, call forwarding, speed calling, etc., have been used to provide additional call control. These devices allow the phone user direct control over incoming and outgoing calls. The disadvantage of edge devices is that they add cost, degrade voice and transmission quality, can be difficult to program, are not easily programmed remotely, can require the user to pay for two lines, provide lower quality of service, and cannot provide the same level of functionality as a system that controls the PSTN directly. There are Voice Over Internet Protocol (VoiP) products emerging that provide better user interfaces and control but they do not take advantage of the voice quality of the PSTN.
SUMMARY
The present invention adds direct control of third party call control features, but does not suffer from any of the disadvantages listed above, and allows the subscriber to manage his/her telephone system in a dynamic and exceptionally useful manner that is not currently available through the existing PSTN. The invention allows enhanced direct third-party call control features, such as selective call routing and remote dialing, to be added to the PSTN (Public Switched Telephone Network) using local call control and providing dynamic provisioning of the system by the subscriber. Direct 3rd-party control means that the ability to provision the 3rd-party features is directly available to a subscriber, eliminating the need to go through the telephone company (telco) business office.
In one embodiment, the system includes a processor (referred to herein as a tandem access controller) connected to the PSTN which would allow anyone to directly provision, that is to say set-up and make immediate changes to, the configuration of his or her phone line. In another embodiment, a tandem access controller (TAC) subsystem is connected internally to the PSTN in a local service area. The TAC provides features, selected by the subscriber, to all edge switches connected to the PSTN tandem switch. Connecting directly to the PSTN tandem switch (or embedding the system into the tandem switch) eliminates the signal degradation problems previously described.
In one embodiment, the system allows provisioning of features via the internet under direct control of the subscriber. Recently, several products have been introduced that provide a means of controlling features via the public internet. However, all these devices fall short in that they require the subscriber to obtain an “800” number or some other number that requires the subscriber to pay a toll charge each time a call is made. The present invention connects locally, so no toll charges are incurred.
The web-enhanced services in one embodiment of the invention coexist with and overlay the local phone service at the local level, thereby providing good economics and user interaction, single number access to multiple subscriber devices, connectivity without transmission impairments and true, direct 3rd-party call control.
The present invention relies upon use of local telephone facilities thereby eliminating all the extra charges associated with making toll calls. It also allows the user to take advantage of number portability and keep his/her existing public phone number.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates the tandem access controller (TAC) of the present invention connected to the existing PSTN tandem switch, the TAC providing features for the subscriber's telephone as requested by the subscriber via the web.
FIG. 2 illustrates a system similar to FIG. 1 but showing multiple tandem switches and TAC's and also showing how the subscriber may, in additional to using the standard telephone, make phone calls using Voice Over IP via a conventional digital telephone.
FIG. 3 is a flowchart of one method that a person may use to set up a subscriber account and to designate features the subscriber would like for his/her telephone.
FIG. 4 is a flowchart of a method that can be performed by the TAC in response to the subscriber (or other service) controlling the TAC, using the web (or other packet-based system), to change the subscriber's telephone provisioning or perform another function, such as make a VoIP call.
FIG. 5 is a flowchart of a method that can be performed by the TAC in response to an inbound call to the subscriber.
FIG. 6 is a flowchart of a method performed by the subscriber and the TAC when the subscriber desires to make an outbound call via the web or using a conventional telephone.
FIG. 7 illustrates a system, using the TAC, that allows wireless cell phones to obtain the same provisioning options as the conventional telephones.
FIG. 8 illustrates a system, using the TAC, that allows fax and modem calls to benefit from the provisioning offered by the TAC.
DETAILED DESCRIPTION OF THE EMBODIMENTS
FIG. 1 shows a tandem access controller (TAC) 10 that allows an authorized subscriber 12 to establish 3rd-party control criteria for calls to the subscriber's telephone 14 (having a “public” phone number that callers dial). In one embodiment, the TAC 10 is a programmed processor. The TAC 10 may use any combination of hardware, firmware, or software and, in one embodiment, is a conventional computer programmed to carry out the functions described herein.
The TAC 10 is connected to or inside the conventional PSTN tandem switch 16 such that calls may flow through the TAC 10 in the same manner as the existing PSTN tandem switch, except that additional 3rd-party features are applied to the call. As is well known, PSTN tandem switches are exchanges that direct telephone calls (or other traffic) to central offices 17 , 18 or to other tandem switches. Details of the operation of the existing phone network may be found in the publication entitled “New Net SS7 Tutorial,” by ADC Telecommunications, copyright 1999, incorporated herein by reference. Additional details may be found in the numerous books describing the PSTN.
The PSTN tandem switch 16 directs a first call (from the calling party 20 to the subscriber's phone 14 using the subscriber's public phone number) to the TAC 10 , which in turn places a second call, subject to 3rd-party control information, to the subscriber's “private” phone number without yet terminating the first call. When the subscriber 12 terminates (or answers) the second call, the TAC 10 terminates the first call and connects it to the second call, thereby connecting the calling party 20 to the subscriber 12 . Hence, the calling party essentially calls the TAC 10 , using the subscriber's public phone number, and the TAC 10 , after processing the call using the selected features, calls the subscriber, as appropriate, using the subscriber's private phone number and connects the two calls. The process is transparent to the parties.
The TAC 10 is connected inside the PSTN in the sense that it is not an edge device such as a PBX or central office (CO) switch because it does not connect directly to subscribers. Rather, it redirects calls to subscribers. The TAC 10 provides intelligent interconnection between a calling party and a subscriber.
The reader should keep in mind that although only one tandem switch 16 is shown in FIG. 1, the invention will apply equally well to a network of tandem switches, as shown in FIG. 2 . FIG. 2 also illustrates how the subscriber can make calls using voice over IP via a conventional digital telephone 21 .
FIG. 1 illustrates the preferred method for an authorized subscriber to modify the 3rd-party control criteria by means of the world wide web 22 (and web server 23 ) using an internet browser. By “authorized” we mean a subscriber who is registered and has “logged-in” with appropriate security and password controls. The subscriber 12 interacts with the web 22 via the Internet to quickly and easily specify the enhanced 3rd-party call control features. Web 22 then relays this information, in appropriate form, to the TAC 10 . Preferably, the link to the TAC 10 uses a secure protocol. Examples of features that can be selected by the subscriber include: conditional call blocking, call forwarding, call altering, time of day conditions, day of week conditions, follow-me, caller recognition/password, caller ID, call screening/retrieval from voice mail, speed dialing, interactive voice response, and speech recognition. Any other feature could be added. These features can be implemented in the TAC 10 using known software techniques since such features are known. Message outgoing call control includes: click-to-dial calling and group calling/messaging.
The invention may also include ivr/vm/voverip.
FIG. 1 uses a public internet portal connected via a data link to the TAC 10 or other interface system. As a registered subscriber, a user logs onto the portal (FIG. 3) and is granted access, allowing the user to make additions or changes to features such as speed calling, call forwarding, selection of such descriptors as time of day, busy status, callerID status, etc. A user-friendly web page leads the subscriber through the various procedures and available features. The selections made by the subscriber are translated into provisioning data and transmitted to the TAC 10 . The TAC 10 in turn keeps track of incoming and outgoing calls based on this information.
The subscriber can also program a set of the call control features via a telephone link in the event a data link connection is unavailable.
FIG. 4 is a flowchart of actions that may be taken by the TAC 10 in response to the subscriber (or other service) controlling the TAC, using the web or other packet-based system, to change the subscriber's telephone provisioning or perform another function, such as make a VoIP call.
FIG. 5 is a flowchart of actions taken by the TAC 10 in response to an inbound call (using the subscriber's public phone number) to the subscriber. Examples of some of the actions taken by the TAC 10 are:
Receives SS7 data indicating an incoming call
Stores phone numbers downloaded from provisioning system
Charts identity of calling party
Checks time of day
Stores lists of numbers in groups used for processing incoming calls
Places outgoing calls in response to incoming calls according to information downloaded on the data link.
Incoming call data is received by the TAC 10 from the tandem switch 16 . The TAC 10 processor checks calling and called numbers, class of service, time of day, number lists, etc. In some cases additional data is gathered from the calling party via a DSP (Digital Signal Processing) system and stored in the system memory. The DSP system is used to play call progress tones and voice announcements as required. Voice announcements can be played through the DSP system. In response to the call data, an outgoing call to the subscriber 12 may be placed back through the tandem switch 16 by TAC 10 . The TAC 10 links the two calls and monitors the connection.
Information about the call may be collected by the TAC 10 and sent to the subscriber or a 3rd party for display. Such information may be the length of the call or information used to bill the subscriber for the use of the system. The provisioning system can also collect control information from a 3rd party and relay it back to the TAC 10 , which will then affect the call accordingly.
FIG. 6 is a flowchart of actions taken by the subscriber 12 and the TAC 10 when the subscriber desires to make an outbound call via the web or using a conventional telephone. When using the web to place a call, the subscriber may simply click a name on the computer screen 26 using a mouse.
FIG. 7 illustrates a system, using the TAC 10 , that allows wireless cell phones 28 to obtain the same provisioning options as the conventional telephones 14 . A local cell 30 and a cell switch 32 are also shown in FIG. 7 .
FIG. 8 illustrates a system, using the TAC 10 , that allows fax and modem calls to benefit from the provisioning offered by the TAC 10 . The TAC 10 may interface the ISP 36 through the web 22 .
One embodiment of the invention allows a subscriber to view the current state of his/her telephone via the Internet. Internet is a term of art by which we mean an za z interconnection of packet switched networks. Prior to this invention there was no way for a user to examine the status of a telephone line. Recently, several products have been introduced that provide a means of examining the voice message boxes.
An internet portal is connected via a data link to the TAC 10 . When a user logs onto the internet portal and is granted access to an individual subscription, the user can examine the status of calls/features. This information is transmitted from the TAC 10 to the web portal and translated into user viewables. The TAC 10 keeps track of incoming and outgoing calls based on this information.
The TAC 10 may be implemented using conventional processor hardware. The connection to the tandem switch 16 may be as simple as a telephone circuit, since the TAC 10 receives an incoming call from a caller and processes the call. Devising the software/firmware use to control the TAC 10 is well within the capability of those skilled in the art since the various control features that can be made available are generally already known.
Certain advantages that can be obtained using the invention include the following:
Web-Based Telecom Navigator
Manage Incoming Call Control
Conditional Call Blocking/Forwarding/Alerting
Time-of-Day, Day-of-Week, Follow-Me, Caller Recognition/Password, Caller ID, etc.
Call Screening/Retrieval from Voice Mail
Interactive Voice Response and Speech Recognition
Manage Outgoing Call Control
Click-to-Dial Calling
Group Calling and Messaging
Web-Based Billing
Web-Driven Personal Communications Management
Cost-Effective Single Phone Number Access
On-Line “Personal Digital Assistant”
On-Line “Telcom Navigator”
Inspired User Interaction
Secure and Reliable Technology
Cost-Effective Single Phone Number Access
CLEC Status
Free Local Calls, Incoming Calls (not 800 Toll Service)
Retain Current Number (Local Number Portability)
Low-Cost Calling Throughout LATA
Flat-Rate Foreign Exchange
Single Installation Covers Entire LATA
VoIP Toll-Bypass
Compatible With Existing Devices, Standards
Standard DTMF and VoIP Phones
Wireless Phones
Standard Wired/Wireless and PIM Browsers
Web-Based Personal Digital Assistant
Centralized and Consistent Personal Data
Build Once, Use Anywhere
Private/Public Phone Directories and Calendars
“Post-It” Style Annotation of Numbers
Web Dialing
Click-to-Dial from Web Pages, Directories, Calendars
Multiple Phone List Management
Unified Messaging
Voice Mail Access, Prompts, Alert Via Web
User Interaction
Expected Behavior
Compatible with Familiar Products (e.g. Palm Pilot)
Commonality Between All Wired and Wireless
Mode-Based Definition and Selection
Vacation, Dinner Time, Go Away, Family Call Waiting
Templates
Learning Modes
Persona-Based User Interaction Design
Speech recognition
Windows drag and drop
Automatic Data Capture
Build Phone List Based on Collected Usage Information
Drag and Drop Into Lists
Secure and Reliable Technology
Separate Web-Site and Link Gateway
No Direct External Access to Gateway
Additional Security Layer
No Denial-of-Service to Voice Links
VoIP Link Degradation Detection
Automatic Cutover to PSTN
E-Commerce Security
Billing Encryption
While particular embodiments of the present invention have been shown and described, it will be obvious to those skilled in the art that changes and modifications may be made without departing from this invention in its broader aspects and, therefore, the appended claims are to encompass within the true spirit and spirit and scope of this invention. | In one embodiment, the system includes a processor (referred to herein as a tandem access controller) connected to the PSTN which would allow anyone to directly provision, that is to say set-up and make immediate changes to, the configuration of his or her phone line. In another embodiment, a tandem access controller (TAC) subsystem is connected internally to the PSTN in a local service area. The TAC provides features, selected by the subscriber, to all edge switches connected to the PSTN tandem switch. In one embodiment, the TAC is controlled by the subscriber using the web. | 7 |
This application claims priority of Provisional Application Ser. No. 60/853,070, filed Oct. 19, 2006, the entire disclosure of which is hereby incorporated herein by this reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to apparatus and methods using magnetoplastic and/or magnetoelastic materials for power generation. More specifically, the present invention relates to producing electrical current using magnetoelastic or magnetoplastic materials by “harvesting” or transducing energy from natural sources, especially from random, cyclic, and/or vibrational motion such as that produced by wind, waves, and human motion.
2. Related Art
Some magnetoplastic or magnetoelastic materials have been considered for use as actuators that convert electrical energy or changes in magnetic field to mechanical motion. Literature related to this topic is listed below:
Chernenko V A, Cesari E, Kokorin V V, Vitenko I N, Scripta Metal Mater 1995; 33:1239. Chernenko V A, L'vov V A, Cesari E, J Magn Magn Mater 1999; 196-197:859. Chernenko V A, L'vov V A, Pasquale M, Besseghini S, Sasso C, Polenur D A, Int J Appl Electromag Mech 2000; 12:3. Chernenko V A, Müllner P, Wollgarten M, Pons J, Kostorz G, J de Phys IV, 2003; 112:951. Ferreira P J, Vander Sande J B, Scripta Mater 1999; 41:117. Jääskeläinen A, Ullakko K, Lindroos V K, J de Phys IV, 2003; 112:1005. Murray S J, Marioni M, Allen S M, O'Handley R C, Lograsso T A, Appl Phys Lett 2000a; 77:886. Murray S J, Marioni M, Kukla A M, Robinson J, O'Handley R C, Allen S M, J Appl Phys 2000b; 87:5774. Müllner P, Int J Mater Res (Z f Metallk) 2006; 97:205. Müllner P, Chernenko V A, Wollgarten M, Kostorz G, J Appl Phys 2002; 92:6708. Müllner P, Chernenko V A, Kostorz G, J Magn Magn Mater 2003a; 267:325. Müllner P, Chernenko V A, Kostorz G, Scripta Mater 2003b; 49:129. Müllner P, Chernenko V A, Kostorz G, Mater Sci Eng A 2004; 387:965. Müllner P, Ullakko K, Phys Stat Sol (b) 1998; 208:R1. Pond R C, Celotto S, Intern Mater rev 2003; 48:225. Sozinov A, Likhachev A A, Lanska N, Ullakko K, Appl Phys Lett 2002; 80:1746. Straka L, Heczko O, Scripta Mater 2006; 54:1549. Soursa I, Pagounis E, Ullakko K, Appl. Phys. Lett. 2004a; 23:4658. Suorsa I, Tellinen J, Ullakko K, Pagounis E, J Appl Phys 2004b; 95:8054. Tickle R, James R D, J Magn Magn Mater 1999; 195:627. Ullakko K, J Mater Eng Perf, 1996; 5:405. Ullakko K, Huang J K, Kantner C, O'Handley R C, Kokorin V V, J Appl Phys 1996; 69:1966.
Magnetoplastic materials, including ferromagnetic shape-memory alloys with twinned martensite, tend to deform upon the application of a magnetic field (Ullakko 1996, Murray et al. 2000, Chernenko et al. 2000). The magnetic-field-induced deformation can be irreversible (magnetoplasticity, Mullner et al. 2002, Mullner et al. 2003a) or reversible (magnetoelasticity, Chernenko et al. 2000, Ullakko et al. 1996). The magnetoplastic effect is related to the magnetic-field-induced displacement of twin boundaries, in an irreversible process. The magnetoelastic effect is also related to the magnetic-field-induced displacement of twin boundaries, but in a process that is at least somewhat reversible. While a strict definition of “elastic” would imply that magnetoelastic materials return without hysteresis to their initial state after removal of the magnetic-field, the term “magnetoelastic,” as it is frequently used, may include materials that deform and return to their initial state upon removal of the magnetic field either without hysteresis or with some hysteresis.
While literature on the subject of magnetoplasticity and magnetoelasticity has indicated such materials to be relevant as actuators for converting electrical energy, or changes in magnetic field, to mechanical motion, the invention utilizes the reverse effect for power generation, that is, the effect of strain-induced change of magnetization due to twin deformation/rearrangement.
SUMMARY OF THE INVENTION
The invention comprises apparatus, and/or methods, that use motion, including random, cyclic, and/or vibrational motion, to produce electrical power, utilizing one or more materials that exhibit twin boundary deformation, also called “twin rearrangement,” upon application of a force to the material(s). The invention comprises using one or more of said materials as a magnetomechanical transducer from mechanical action to magnetic field production.
The invented apparatus and/or methods may utilize energy from passive motion such as walking, or naturally-occurring random, cyclic or vibrations motion such as that produced by wind or waves acting upon objects. Said motion may be transferred, through a mechanical connecting device, to linear motion. or motion with a linear vector, that deforms a magnetoplastic and/or magnetoelastic material. The magnetoplastic and/or magnetoelastic material, by means of the twin boundary deformation effect, transduces the linear motion/component into a change of magnetic field. This strain-induced change of magnetization due to twin boundary deformation may be considered the reverse effect of magnetoplasticity and/or magnetoelasticity that is discussed in the above Related Art Section.
In preferred embodiments, a bias magnetic field is provided in the vicinity of the magnetomechanical transducer to assure a net change of magnetization during said deformation and rearrangement. The bias magnetic field may be provided by an electromagnet or a permanent magnet system. The change of magnetization induces an electrical signal by a suitable second transducer, such as a coil or a Hall element, which transforms magnetization change into current or voltage.
Magnetoplastic/magnetoelastic materials are uniquely suitable as magnetomechanical transducers for power generation due to their large range of deformation, small threshold stress and significant change of magnetization. Furthermore, magnetization and deformation are linearly coupled, yielding the same efficiency over the full deformation range. Therefore, preferred embodiments of the invented system are superior to existing power generators due to a long stroke, low threshold stress, and large change of magnetization. These properties provide high efficiency and power output. Furthermore, in embodiments using a coil as second transducer, a low-impedance electric output is produced, which does not need to be further transformed. The system is further advantaged by a simple design, providing great potential for miniaturization, nanotechnology, and ease and economy of fabrication.
The magnetomechanical transducer, and the invented apparatus and methods using the transducer, may provide microgenerators for power production by capturing kinetic energy and converting it to electrical power. The microgenerators, or other systems utilizing the invented magnetomechanical transducers, may be connected in series or parallel, combined with solar cells or other power generation devices, and used to capture energy from motion such as walking, machine movement, movement of water or wind, and/or object movement caused by water or wind.
DESCRIPTION OF THE DRAWINGS
The drawings illustrate demonstrations, descriptions, and schematics relating to preferred embodiments of the invented apparatus and methods, but are not intended to illustrate all embodiments or to necessarily limit the invention to the particulars shown therein.
FIG. 1 shows the setup of the experiment with which deformation-induced change of magnetization was demonstrated.
FIG. 2 gives stress (squares) and magnetization (triangles) as a function of compressive deformation along <100>direction of a Ni.sub.51Mn.sub.28Ga.sub.21 single crystal measured at constant orthogonal magnetic field of 0.7 T along the x direction. Open and full symbols indicate values for increasing and decreasing deformation along the z direction.
FIG. 3 (comprising 3 a , 3 b , and 3 c ) is a schematic of the magnetization process through deformation in magnetoplastic martensitic materials.
FIG. 4 is a schematic of one embodiment of a power generator 10 according the invention, wherein the force transmitted to the transducer is a tensile force.
FIGS. 5 ( 5 A and 5 B) are schematics of one embodiment of a thin-film-based power generator 20 .
FIG. 6 is a table of magnetic and magneto-mechanical properties of some but not all (potentially) ferromagnetic materials. Values surrounded by a rectangle being least favorable, and values surrounded by a triangle being most favorable.
FIG. 7 lists and categorizes many, but not all, magnetoplastic and potentially magnetoplastic materials, as well as citations to scientific literature discussing these materials. For materials that are circled in FIG. 7 , magnetoplasticity has been demonstrated.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to the Figures, there are shown demonstrations, data, and schematics illustrating the preferred, but not the only, embodiments of the invention. The preferred embodiments make use of the deformation-induced-change of magnetization occurring in magnetoplastic and/or magnetoelastic materials, which magnetization change has been demonstrated by Müllner, et al. (Müllner P, Chernenko V A, Kostorz G, “Stress-induced twin rearrangement resulting in change of magnetization in a Ni—Mn—Ga ferromagnetic martensite,” Scripta Mater 2003b; 49:129, the entire disclosure of which is hereby incorporated by this reference). As noted above, the deformation-induced (strain-induced) change of magnetization due to twin rearrangement is the reverse effect to magnetoplasticity or magnetoelasticity.
Numerous publications deal with many aspects of the ferromagnetic martensites in Ni—Mn—Ga alloys such as martensitic transformations and martensite structure (e.g. Chernenko et al. 1995), magnetic-field-induced deformation (e.g. Murray et al 2000a, Sozinov et al 2002) and the associated magneto-stress (Chernenko et al. 2000, Mullner et al. 2002, Tickle and James 1999, Chernenko et al. 1999, Murray et al. 2000b). However, only few results concerning the reverse effect have so far been published (Mullner et al 2003b, Soursa et al 2004a, Soursa et al 2004b, Straka et Heczko 2006; see Related Art Section).
The magnetoplastic effect is related to the magnetic-field-induced displacement of twin boundaries, which is a thermodynamically irreversible process (Ullakko 1996, Mullner et al 2002). On the microscopic scale, a twin boundary moves by the motion of twinning disconnections (Pond and Celotto 2002), a process which can be triggered by a magnetic force on the dislocation (Mullner and Ullakko 1998, Ferreira and Vander Sande 1999, Mullner 2006). In Ni 2 MnGa, the cooperative motion of twinning dislocations finally leads to a strain of up to 10% (Müllner et al. 2004).
Uniaxial compression experiments under orthogonal magnetic field were done on a single crystal with composition Ni 51 Mn 28 Ga 21 (numbers indicate atomic percent). The sample was cut as a rectangular prism with {100} faces in all directions and measured 5.45(2) mm×3.26(2) mm×2.34(2) mm. In the ferromagnetic austenitic phase, i.e. above the reverse transformation temperature of 316 K, the sample was a single crystal with the ordered cubic L2 1 structure. At room temperature, the material is in the martensitic phase. The crystallographic directions a and c of all twin variants were parallel within 3° to the sample edges. The easy magnetization axis is parallel to the c direction.
The sample was deformed in uniaxial compression and unloaded at constant speed (2.times.10.sup.-6 M/s) in a mechanical testing machine equipped with a 500 N load cell and extensometers insensitive to magnetic fields. The magnetic field .mu.sub.0H=0.7 T was produced by a permanent magnet system. The sample was mounted in such a way that the longest edge was parallel to the compression axis (z direction). The x direction was defined parallel to the shortest edge of the sample, x-y-z constitute Cartesian coordinates. The magnetic field was applied in x direction. A Hall probe was positioned close to one of the sample surfaces which were parallel to the y-z plane. The set-up of the experiment is outlined in FIG. 1 , and may be described as follows. A magnetoplastic material in form of a parallelepiped ( 1 ) is fixed between two pressure pistons ( 2 ) that introduce the load. Two quartz glass push rods ( 3 ) transmit the displacement of the top and bottom surfaces of the sample/pistons to the extensometers (not shown on the figure). A Hallbach cylinder (cylindrical permanent magnet, 4 ) produces the magnetic field H.sub.x (large arrow). A Hall probe ( 5 ) measures the sum of H.sub.x and stray field H.sub.S (small arrows) on the side surface of the sample. The difference between measured field and H.sub.x is taken as a measure for the sample magnetization in the direction indicated by the mows.
FIG. 2 shows the results from the above experiment. Upon mechanical loading along the z direction at constant speed, the stress increases strongly at the beginning. The slope of the stress-strain curve decreases rapidly right after the onset of plastic deformation and is almost constant up to about 1.9% compressive strain and a corresponding stress of 6 MPa. At larger strain, the stress increases more rapidly. Over the whole deformation range, the relative magnetization in x direction M.sub.x/M.sub.x0=(H-H.sub.x)/(H.sub.0-H.sub.x) (H and M are the field detected with the Hall probe and the magnetization of the sample, H.sub.0 and M.sub.0 are the values in the undeformed state) decreases within experimental error linearly with increasing strain. Upon unloading, the stress decreases rapidly at the beginning and more slowly with decreasing strain until the full deformation is recovered. The relative magnetization increases again linearly until it reaches the initial value. The magnetization exhibits a negligible hysteresis. The slopes of the magnetization curves in both directions of deformation are constant and equal within experimental error over a wide range of strain whereas the stress curves have different shapes. More specifically, regarding FIG. 2 , squares portray stress and triangles portray magnetization as a function of compressive deformation along <100> direction of a Ni.sub.51Mn.sub.28Ga.sub.21 single crystal measured at constant orthogonal magnetic field of 0.7 T along the x direction. Open and full symbols indicate values for increasing and decreasing deformation along the z direction. Upon deformation, the stress increases quickly to about 1.5 MPa at 0.04% strain. Above 0.1% strain, stress increases slowly and almost linearly up to 1.9% strain. At larger strain, stress increases rapidly again. Upon unloading, the total strain is recovered, however at a lower stress level compared with loading. The magnetization along the x axis (divided by its value M.sub.0 in the undeformed state) decreases linearly with increasing deformation up to 1.9%. Upon unloading, the magnetization restores its initial value with a small hysteresis.
The twin rearrangement due to the action of a magnetic field and a mechanical force and the associated processes of deformation and magnetizing on the mesoscopic scale are shown schematically in FIGS. 3 ( 3 a , 3 b , and 3 c ). In the undeformed state and without magnetic field ( FIG. 3 a ), the twin structure contains self-accommodated elastic domains with the crystallographic c directions distributed irregularly. In the absence of 180.degree. magnetic domains (which is always true for magnetic fields of 0.1 T and larger and even, in some cases, without application of a magnetic field), there is a considerable stray-field H.sub.S caused by domains with the axis of easy magnetization (which is parallel to the c direction) perpendicular to the surface. More specifically, in FIG. 3 a , dark and bright gray indicate two twin variants. The local magnetization (arrows) aligns with the easy axis that is differently oriented for each twin variant. In FIG. 3 b , under an applied magnetic field H.sub.x, the twin boundaries move, causing growth of the twin variants with c parallel to the field. In the other twin variants, the magnetic moments rotate towards the direction of the magnetic field. In FIG. 3 c , under an applied load (F.sub.z), the twin boundaries move causing growth of one twin variant with c parallel to the load direction and shrinkage of the other. The specimen deforms since c<a. At the same time, the distribution of magnetic moments changes and alters the total magnetization.
In the schematic representation of FIGS. 3 ( 3 a , 3 b , and 3 c ), only one martensite domain with one set of twins is illustrated. Such a structure can be obtained after a suitable magnetic or mechanical treatment. In the present study, however, there are many martensite domains with differently oriented sets of twins.
When a magnetic field H x >>0.1 T is applied along the x direction, the twin boundaries move in such a way, that the twins with c parallel to the x direction grow on the expense to twins with c perpendicular to the x axis ( FIG. 3 b ). In regions, through which a twin boundary passes, the c direction switches from parallel to the z axis to parallel to the x axis. Since c/a<1, the sample shrinks along the x direction and expands along the z direction (magnetoplasticity). In addition to the motion of twin boundaries, the magnetic field H x causes the magnetic moments in the domains with c perpendicular to the x direction to rotate by an angle with sin =H x /H A (H A is the saturation field) towards the x direction ( FIG. 3 b ). In the present experiment, H x /H A ≅0.7 and ≅45°. Owing to the rotation of the magnetic moments, the stray-field increases. The Hall probe ( FIG. 1 ) detects the sum of the stray-field and the applied field.
When the sample is mechanically compressed along the z direction, the twin boundaries move in the opposite direction, i.e. the twins with c parallel to the z direction grow at the expense of twins with c perpendicular to the z axis ( FIG. 3 c ). In regions, through which a twin boundary has passed, the c direction switched from parallel to the x axis to parallel to the z axis. Thereby, the direction of the magnetic moments rotates from parallel to the x axis to about 45° inclined to the x axis. This causes a reduction of the stray field which is detected by the Hall probe. Very close to the sample surface, the magnetic induction originating from the stray field is a linear function of the fractions of each twin variant. Since the strain is a linear function of the twin variant fractions, too, the signal of the Hall probe decreases linearly with strain ( FIG. 2 ). Upon mechanical unloading, the reverse process occurs. The twin boundaries move again under the action of the magnetic field H x until the twin pattern and the shape of the unloaded state ( FIG. 3 b ) are reached. Because, in the present experiments, strain and magnetization are controlled by the fractions of twin variants, there is no significant hysteresis between loading and unloading curves ( FIG. 2 ).
The role of the magnetic bias field (H x in the above experiment) is twofold. First, the bias field removes all 180° domain boundaries and causes a net magnetization M x in x direction. This component of the magnetization induces voltage in the coil, for extraction of electrical power. Second, the magnetic bias field works against the applied force from the motion being “harvested” and restores the shape of the magnetoplastic and/or magnetoelastic material after removal of said force. The restoration of the shape implies a further change of magnetization generating electrical power, so that it is expected that some embodiments according the invention will generate electrical energy during the unloading and resetting step(s) of the process as well as the loading step. Below a bias field comparing (the same or generally the same) to the saturation field (about 1 T for Ni 2 MnGa), the recoverable strain decreases and vanishes below a threshold field (Müllner P, Chernenko V A, Wollgarten M, Kostorz G, J Appl Phys 2002; 92:6708, the entire disclosure is incorporated herein by this reference). Alternatively, or additionally, restoration of the initial state may also be achieved through the application of a bias stress, for example, by a lever system forcing the shape of the magnetoplastic and/or magnetoelastic material back to the same or generally the same shape as the initial state.
It may be noted that the initial-state-resetting bias magnetic field and/or the alternative stress bias are preferably supplied continuously, or substantially continuously, throughout the power generating process, but, alternatively, could also be supplied intermittently and/or variably, for example, in-between loading steps (in-between periods when force is supplied from the motion being “harvested”). An intermittent or variable resetting bias would tend to be more complex, however. Further, even with an intermittent or variable initial-state-resetting device, it is desired to provide a continuous or substantially continuous magnetic bias for the reasons stated in the preceding paragraph.
FIG. 4 is a schematic of one embodiment of a power generator 10 according the invention, wherein the force transmitted to the transducer is a tensile force. A force F from source S, which may be a random force from nature or a force from movement of a machine or human, for example, acts though the lever ( 11 ) on the magnetoplastic transducer ( 12 ), wherein the lever ( 11 ) and the transducer ( 12 ) are attached to the frame ( 13 ). Motion of the lever ( 11 ) deforms the transducer ( 12 ), which changes the magnetization and induces a time dependent voltage U(t) in the pick-up coil ( 14 ). The magnetic bias field produced by the magnet ( 15 ) restores the initial state. It is preferred that the magnetic bias field has a component parallel to the direction along which the magnetization change is used to generate an electrical signal. For instance, if a coil is used as second transducer ( FIG. 4 ), the bias field preferably has a component parallel to the coil axis. For magnetoplastic materials with c/a<1 and c being the easy axis of magnetization, the force F is preferably tensile if applied parallel to the bias field ( FIG. 4 ) and compressive if applied perpendicular to the bias field. If c/a>1, the sign of the force must be changed. Alternatively, the magnetic bias field may be perpendicular to the direction along which the magnetization change is used to generate an electrical signal. Alternatively, the magnetic bias field may be inclined at an arbitrary angle to the direction along which the magnetization change is used to generate an electrical signal.
The force in FIG. 4 may be transferred from an object or material that is undergoing rotational, cyclic, random or vibrational motion, for example, from a machine, human, or naturally-occurring fluid or solid. The transfer of force may be direct when the force from the motion source is linear or substantially linear, or may be indirect, via conventional mechanical structures, when the force from the motion source is non-linear or substantially non-linear. Examples of conventional mechanical structures that may transfer force from a source or motion may include connectors such as a rod, string, lever, or any other connector. While the magnetoplastic and/or magnetoelastic material is placed under tension by the applied force in FIG. 4 , alternative embodiments may be adapted to compress or bend the material, and/or otherwise move the material in any way that results in twin rearrangement. For example, preferred thin film transducer may be provided as a free-standing thin film or partially free-standing thin film that is flexed, bowed, or otherwise moved to produce said twin rearrangement. In the example of the thin film device of FIG. 5 , the applied force may bow an unsupported portion of a thin piece of material that is supported/fixed around its periphery.
The device may be produced in any size or shape. Thin film technology may be used for small scale applications. FIGS. 5 ( 5 A and 5 B) shows a schematic of another embodiment of the invention that is a thin film device. The magnetomechanical transducer according to this embodiment is a magnetoplastic and/or magnetoelastic thin film which forms a free standing membrane over a window in a supporting substrate. The one-turn pick-up coil is made by a conducting thin film. Alternatively, multiple-turn pick-up coils may be used. The magnetic bias field is provided by a permanent magnet located at the back side of the device. Thin film methods for producing embodiments of the invention will be apparent to those of skill in the art upon viewing this disclosure and the drawings. More specifically, in the thin-film-based power generator 20 of FIGS. 5A and B, a vibration (V) causes a portion 21 ′ of the magnetoplastic membrane 21 to bow and deform, wherein the portion 21 ′ is over a hole 24 in support 25 that is defined by hole edge 24 ′. The deformation causes a change of magnetization, which induces a time dependent voltage in the one-turn thin-film pick-up coil 22 . As shown in FIGS. 5A and B, coil 22 lies on the magnetoplastic membrane and has a coil opening 30 over said portion 21 ′. Coil opening 30 is defined by opening edge 30 ′, and opening 30 is coaxial with longitudinal axis A of the hole 24 and of the portion 21 ′. The magnet 23 produces a magnetic bias field that restores the initial state. FIG. 5A is a side cross-sectional view, and FIG. 5B is a top view, of the micro-generator 20 .
In many embodiments of the system, the motion to be transduced to electrical power is generated by wind, water, gas, particle flow, or vibration. For example, the system may be employed as part of a floatation device, wherein the motion of water is transduced to electrical power that may then be used to power a signaling or locator device. In other embodiments, a large number of small scale devices may be installed in a large area, such as an ocean beach or flowing waterway. In other embodiments, vibrational movement conducted through a solid medium is harvested and transduced to electrical power.
Other examples of motion that can be harvested and transduced by the system include human motion, which can be harvested to power personal electronic devices. For example the system can be employed by soldiers in the field to capture energy coincident with transportation of walking. One or more small devices may be attached to human clothing or footwear without being a heavy or cumbersome burden. Devices according to embodiments of the invention are expected to be efficient in transducing the movement to electrical energy. As calculated later in this document using the mass of the MSMA transducer, a micro-power-generator using a magnetic shape memory alloy (MSMA, which is one type of magnetoplastic and/or magnetoelastic material) as the magnetomechanical transducer, the power output due to the inverse magnetoplastic effect is estimated for an excitation frequency of 1 Hz to be 30 Ws/kg (equal to 30 mWs/g). If one assumes that the mass of a commercial device according to embodiments of the invention will be about 3-4 times the mass of the transducer (most of the additional mass being due to the permanent magnets and the copper coils), it is expected that a device with total mass 20 g (size about 1″×1″×¼″) operated at 3 Hz will produce a power output of about 300-600 mW. Such a power output may be sufficient for the power supply of a cell phone, which typically requires about 250-400 W.
Preferred Materials
The materials used for the magnetomechanical transducer are those which produce a strain-induced change in magnetization. Specifically, materials with mobile twin boundaries are shown to produce said change in magnetization, which is a reverse/inverse effect to magnetoplasticity or magnetoelasticity. Therefore, the materials used for the magnetomechanical transducer may be selected from the broad categories of magnetoplastic and magnetoelastic materials, including from the following subsets of magnetoplastic and/or magnetoelastic: magnetic shape memory alloys (MSMA, which are ferromagnetic or “magnetic”); materials resulting from martensitic transformation (typically called “martensite”); and other providers of twins. The terms “magnetoplastic” and “magnetoelastic,” as discussed above in the Related Art section, overlap to some extent, in that “magnetoelastic” is commonly used even for some materials that do exhibit hysteresis. Said magnetplasticity/magnetoelasticity (magnetoplastic/magnetoelastic materials) does not necessarily include all ferromagnetic materials, for example, preferably does not include “classical” magnetostriction (magnetostricitive materials). Whereas current magnetostrictive materials are limited to a maximum of about 0.2% strain (for Terfenol-D), the preferred magnetoplastic/magnetoelastic materials exhibit typically above 1% strain, and, in some embodiments, up to about 10% strain and possibly more. Further, the preferred magnetoplastic/magnetoelastic materials are not piezoelectric, and therefore the preferred magnetomechanical transducers are not piezoelectric, however, the inventors envision that there may be materials developed or discovered in the future that are both magnetoplastic/magnetoelastic and piezoelectric, and, hence, could be included in the preferred embodiments.
Requisite for magnetoplasticity is the magnetic-field-induced motion of twin boundaries. This requisite implies the following properties:
(i) The material must deform more easily by twinning than by dislocation motion. (ii) The twinning stress must be less than the magnetostress τ M , i.e. the stress which can be induced through a magnetic field.
Factors affecting (i) above include the crystal structure (trend: lower symmetry is better than higher symmetry), the lattice potential (trend: strong bonding is better than weak bonding), the size of the lattice parameter (trend: larger is better than smaller). Factors affecting (ii) include the magnetic anisotropy constant K (the higher the better) and the twinning shear (the smaller the better).
Regarding applications, a large strain might be desirable. This implies a large twinning shear, which is in conflict with (ii). Furthermore, it is desirable to obtain magnetoplasticity with a small magnetic field. This implies a large saturation magnetization M s . Thus, the desired materials properties are:
1. Large magnetic anisotropy K.
2. Large saturation magnetization M s .
3. For large stress output: small twinning shear.
4. For large strain output: large twinning shear.
FIG. 6 summarizes magnetic and magneto-mechanical properties of some (potentially) ferromagnetic materials. Materials in FIG. 6 for which magnetoplasticity has been reported in the literature are circled. Embodiments of the invention may include one or more of the materials in FIG. 6 , with values surrounded by a rectangle being least favorable, and values surrounded by a triangle being most favorable. The strain ε M,max is proportional to the twinning shear and marks the theoretical maximum of magnetic-field-induced strain. The saturation field μ 0 H a is the magnetic field at which the maximum magnetostress τ M,max is reached. Further increase of the magnetic field does not increase the magnetostress.
Current research in the field of magnetoplasticity focuses on ferromagnetic shape-memory alloys, because in these materials, the twinning stress is very low. Particular attention is being paid to Heusler alloys, particularly off-stoichiometric Ni 2 MnGa. Other ferromagnetic shape-memory alloys (i.e. non-Heusler alloys) which are under study include FePd, CoPt, FePt, and Fe 3 Pd. Recently, magnetoplasticity was reported for an antiferromagnetic (AFM) magnetic shape-memory alloy γ-Mn—Fe—Cu (J. H. Zhang, W. Y. Peng, S. Chen, T. Y. Hsu (X. Zaoyao), Appl. Phys. Lett. 86, 022506 (2005)). Non-shape-memory alloys which have been studied in context of magnetoplasticity include dysprosium and τ-MnAl—C.
FIG. 7 lists and categorizes many magnetoplastic and potentially magnetoplastic materials, as well as citations to scientific literature discussing these materials. Embodiments of the invention may include one or more of the listed materials and/or one or more materials selected from the broad categories of materials. For materials that are circled in FIG. 7 , magnetoplasticity has been demonstrated. The citations in FIG. 7 are:
[Cui 2004]
J. Cui, T. W. Shield, R. D. James, Acta mater. 52, 35
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A. Fujita, K. Fukamichi, F. Gejima, R. Kainuma, K.
Ishida, Appl. Phys. Lett. 77, 3054 (2000).
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R. D. James and M. Wuttig, Phil. Mag. A 77, 1273
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G. Kostorz and P. Müllner, Z. f. Metallk.
96, 703 (2005).
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H. H. Liebermann and C. D. Graham, Jr. Acta Met. 25,
715 (1976).
[Santa. 2006]
R. Santamarta, E. Cesari, J. Font, J. Muntasell, J.
Pons, J. Dutkiewicz, Scripta Mater. 54, 1985 (2006).
[Solo. 2004]
A. S. Sologubenko, P. Müllner, H. Heinrich,
K. Kostorz, Z. f. Metallk. 95, 486 (2004).
[Vlasova 2000]
N. I. Vlasova, G. S. Kandaurova, N. N. Shchegoleva, J.
Magn. Magn. Mater. 222, 138 (2000).
[Wada 2003]
T. Wada, T. Tagawa, M. Taya, Scripta Mater. 48, 207
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[Wuttig 2001]
M. Wuttig, J. Li, C. Craciunescu, Scripta Mater. 44,
2393 (2001).
[Zhang 2005]
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Zaoyao), Appl. Phys. Lett. 86, 022506 (2005).
Discussion of Features and Advantages of Preferred Embodiments
Current or “conventional” generators that harvest electrical energy from mechanical motion are based on piezoelectric transducers, magnetostrictive transducers, or induction due to the motion of a magnet. These conventional transducers and methods comprise at least one of the following disadvantages. (i) The strain which the conventional transducer can capture is small, typically much less than 1%. Since mechanical work density is proportional to strain (work is proportional to distance traveled), a small strain limits the power output (see, for example, the disclosures of U.S. Pat. No. 6,655,035 and U.S. Pat. No. 6,909,224). (ii) The threshold stress of conventional transducers is large. A large threshold stress leads to a severe hysteresis that causes loss by dissipation and reduces efficiency. (iii) Piezoelectric transducers produce a high-impedance charge signal which needs to be transformed to low-impedance voltage. (iv) A moving magnet, such as required for many conventional systems, causes only small relative changes of magnetic induction and permits only limited efficiency (see the disclosure of U.S. Pat. No. 5,568,005). Some of these devices have as their primary embodiments, acoustic or vibrational damping (see the disclosure of U.S. Pat. No. 6,995,496).
The preferred embodiments of the invention avoid all these issues. The advantages of the preferred embodiments include the following. (i) The strain that the preferred transducer can capture is large, typically more than 1%. Further, it may be noted that the current maximum strain covered by twin boundary motion in magnetic shape-memory alloys is 10%. Since mechanical work density is proportional to strain (work is proportional to distance traveled), a large strain permits large power output. (ii) The threshold stress for the preferred embodiments is low. A low threshold stress significantly reduces hysteresis and increases efficiency. (iii) The preferred magnetoplastic and/or magnetoelastic transducers produce a low-impedance voltage which does not need further transformation. (iv) The preferred magnetoplastic and/or magnetoelastic transducers produce a large change of magnetization (up to 30% or more depending on material), which causes a large change of magnetic induction leading to increased efficiency. (v) The design of the preferred system is very simple. The simplicity provides great potential for miniaturization, nanotechnology, and commercialization.
Thus, one advantage of the preferred embodiments is high efficiency and consequently high power density. Limits of these quantities can be estimated as follows. The maximum energy density E V which can be transformed by deformation of a magnetic shape-memory alloy, i.e. the output energy, equals the magnetic ansisotropy energy K. For obtaining the energy E m per kilogram, K needs to be divided by the density ρ (E m =E V /ρ). The maximum power output P o is obtained by multiplying with the frequency v.
P o = Kv ρ ( 1 )
Eq. 1 assumes that the full anisotropy is recoverable. Since a magnetic bias field is required for the operation, a factor f b <1 needs to be considered:
P o = f b Kv ρ ( 2 )
During a full straining cycle, the mechanical hysteresis energy E hme is dissipated. During a full cycle, twice the output energy is gathered. Thus, the total power P i to put into the system is
P i = E hme v + 2 f b Kv ρ ( 3 )
The ratio of hysteresis energy and output energy equals the ratio of the width Δσ h of the mechanical hysteresis loop and the magnetostress σ M :
E hme E m = Δ σ h σ M = P loss P o = g ( 4 )
where P loss is the power loss during one cycle. From (2-4) follows the efficiency η:
η = 2 P o P i = 2 2 + g ( 5 )
The width of the hysteresis loop is about twice the yield stress σ y and σ M =2K/s where s is the twinning shear. For current Ni—Mn—Ga magnetic shape-memory alloys, g≈1 and η≈67%. Thus, about 67% of the mechanical energy (motion) can be transformed into electrical energy. For Ni—Mn—Ga, K≈250 kJ/m 3 , ρ=8 g/cm 3 , f b ≈0.5. This gives for a frequency of 1 Hz a power output 2P o of about 30 W/kg, and for a 1 kHz vibration about 30 kW/kg (referring to the mass of the transducer). For high-frequency applications, losses due to induction should be considered.
Although this invention has been described above with reference to particular means, materials, and embodiments, it is to be understood that the invention is not limited to these disclosed particulars, but extends instead to all equivalents within the scope of the following claims. | A magnetoplastic and/or magnetoelastic material transduces linear motion, delivered to it by a mechanical connection, into a change of magnetic field, via twin boundary deformation. A bias magnetic field assures a net change of magnetization during the deformation, and a coil, coaxial with the magnetoplastic/elastic material, couples the magnetic field change to an electrical output. The bias magnetic field or a device that produces strain in a reverse direction resets the magnetomechanical transducer to its initial state. Microgenerators using the magnetoplastic/elastic material may be connected in series or parallel, combined with solar cells, and used to capture energy from passive motion such as random, cyclic or vibrational motion. | 7 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a Continuation of Application Ser. No. 09/377,094 of Gerald P. Price and Raymond R. Price filed Aug. 19, 1999 now U.S. Pat. No. 6,250,850 entitled Block With Multifaceted Bottom Surface.
BACKGROUND OF THE INVENTION
This invention relates generally to the construction of retaining walls used in landscaping applications. Such walls are used to provide lateral support between differing ground levels where the change in one elevation to the other occurs over a relatively short distance, thereby reducing the possibility of erosion and landslides. Retaining walls can be both functional and decorative and range from small gardening applications to large-scale construction. They are constructed of a variety of materials and shapes. Some have been constructed of wood timbers, others of rock in a natural form (such as limestone). Still others have been constructed of manufactured aggregate or concrete blocks. The present invention relates to a manufactured block.
Constructing a fit and true retaining wall can be an arduous endeavor. In addition to laying a level first course on ground which is usually located at the foot or in the side of a steep embankment, the builder must ensure that each subsequent course is level. An error made in a lower course usually gets exaggerated as higher courses are stacked above it. As a wall made of blocks necessarily develops somewhat of a grid-like appearance, interruptions or undulations in the lines of the wall become readily apparent to the human eye.
One particular problem the prior art has failed to overcome is developing a retaining wall block shaped to avoid these undulations and interruptions which are caused by blocks being stacked on dirt or debris found on the upper surface of the lower course of blocks. Dirt presents itself as a result of the fill material used to fill the gap between the rear of the wall and the earth it is being built to retain. This fill material usually consists of small, coarse rocks. They serve as a barrier between the earth and the wall and prevent wet earth from seeping through the bricks of the wall during inclement weather. Present wall building methods include laying a course of blocks, filling the space behind the course with fill material, packing the fill material, and carefully sweeping the dirt off of each completed course prior to the addition of the next course. This final, sweeping step is time consuming but necessary to ensure the next course of blocks lies flat on the lower course.
Some larger blocks incorporate continuous cavities that extend from their bottom surface to their top surfaces. These cavities are intended to reduce the amount of material required to form the block, thereby reducing its cost and weight, and also allow an area to be filled with fill material once a course is finished. At first blush it would appear that, because the presence of cavities reduces the surface area of the top and bottom of the block, they would also serve to decrease the area for interference by small stones and debris between courses. However, because the cavities are filled with fill material, the fill material spills over the upper surfaces and exacerbates, rather than alleviates, the problem. Furthermore, smaller blocks cannot incorporate cavity portions without jeopardizing their structural integrity.
The inability of smaller blocks to accommodate cavity portions creates further problems. Making a solid block out of concrete results in a dense rock which is heavy for its relatively small size. Working with these rocks can become cumbersome. The absence of cavities or interruption in the side walls makes these blocks difficult to lift. They have few areas which lend themselves to easy gripping and lifting. This becomes an important consideration in light of the number of blocks that must be lifted and set in place during the construction of even a relatively small retaining wall.
It would be desirable to develop a retaining wall block shaped to accept a certain amount of dirt and debris from course to course without adversely affecting the overall structure and aesthetics of the resulting wall. It would also be desirable to devise a small retaining wall block which is has a reduced unit weight due to the absence of block material in an area that will not adversely affect the strength of the block, nor its appearance. Finally, it would be desirable to provide a small retaining wall block which is relatively easy to grasp and pick up off of a stack of similar blocks.
SUMMARY OF THE INVENTION
The present invention advantageously provides a block for use in building a retaining wall that produces a level course of blocks, despite the presence of a small amount of debris on the lower course of blocks.
The present invention is also advantageous in that it provides a relatively small block with material removed from strategic locations to provide a block which is lighter than it would have been had it been solid, yet the removal of material has not adversely affected the strength of the block, nor the appearance of the resulting wall.
The present invention advantageously provides a block which has areas for a person building a retaining wall to grasp the block when lifting the block off of a stack of such blocks and placing the block on a lower course of blocks in the wall being constructed.
The instant invention relates to a retaining wall block so shaped that when placed on top of a lower course of similar blocks, it lies flat despite the inevitable presence of dirt, small stones, and other debris. This feature alleviates the time-consuming step of meticulously cleaning the top of each course of blocks before the next course may be laid on top of it.
The block generally comprises a continuous top surface, side surfaces extending from the top surface, front and back surfaces extending from the top surface and spanning laterally between the side surfaces and a bottom surface integral with the front, back and side surfaces.
In order to achieve the tolerance of small stones and debris between courses, a portion of the bottom face of the block of the present invention is non-planar, more specifically, concave. This concave surface significantly reduces the area for block to block contact between successive courses. Preferably, this non-planar portion covers more than one half of the area of the bottom surface of the block. It also functions to provide an area of clearance or a gap between the stones where debris can migrate without causing interference or instability between courses. The concave portion is preferably shaped to form a portion of a cylinder and extends from one side surface to the other. Alternatively, the concave portion could be shaped to form a portion of a sphere or any other shape.
In addition to the concave portion of the bottom surface, the present invention further comprises a plurality of grooves formed in the bottom surface and preferably extending transversely of the bottom surface between the front and back surfaces. The grooves preferably are angled inwardly to form an inverted “V” shape when the block is given its intended orientation. The grooves allow spaces of increased clearance for larger stones. The grooves preferably comprise two opposed surfaces of a predetermined width extending the length of the groove. The two surfaces are angled to form a “V” shape and meet to form an angle α. The angled walls of the grooves not only reduce the weight of the block, but also act to funnel larger stones into the grooves, thereby positioning them into an area of maximum clearance. Alternatively, the first and second surfaces may be joined by a third, curved or flat, surface juxtaposed between the first and second surfaces. Such a third surface would give the groove an inverted “U” shape. The grooves are cut into the block and have a set depth which follows the irregular contour of the non-planar bottom surface.
Preferably, the bottom surface further comprises one or more downward projections proximate the rear surface and having an abutting surface which contacts the rear surface of a lower course of blocks when the block is stacked thereon. It is envisioned that the abutting surface is either parallel to the rear surface of the block, or forms an angle β with the rear surface. These projections create an automatic and uniform setback among successive courses of blocks so that the resulting retaining wall is angled rearwardly. This adds resistive strength to the wall against the natural forces exerted on the wall by the earth the wall is retaining.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a block of the present invention, looking up at the bottom to reveal the details of the bottom surface;
FIG. 2 is a cross sectional view of the block of the present invention taken along lines 2 — 2 of FIG. 1;
FIG. 3 is a cross sectional view of the block of the present invention taken along lines 3 — 3 of FIG. 1 and shown with other blocks in phantom, stacked, as in a retaining wall;
FIG. 4 is a bottom plan view of the block of FIG. 1;
FIG. 5 is a perspective view of the block shown in FIG. 1 in a stacked relationship with other blocks, as in a wall, and showing debris resting on a lower course of blocks and accommodated for by the concave area of the bottom surface of the block of the present invention;
FIG. 6 is a perspective view of an alternative embodiment of the present invention, looking up at the bottom to show the detail of the bottom surface;
FIG. 7 is a sectional elevational view taken along lines 7 — 7 of FIG. 6;
FIG. 8 is an end elevational view of a block of the embodiment shown in FIG. 6, in stacked relation, as in a wall, with other blocks shown in phantom; and,
FIG. 9 is a bottom plan view of a block of the embodiment shown in FIG. 6 .
DETAILED DESCRIPTION
These and other objectives and advantages of the invention will appear more fully from the following description, made in conjunction with the accompanying drawings wherein like reference characters refer to the same or similar parts throughout the several views. And, although the disclosure hereof is detailed and exact to enable those skilled in the art to practice the invention, the physical embodiments herein disclosed merely exemplify the invention which may be embodied in other specific structures. While the preferred embodiment has been described, the details may be changed without departing from the invention, which is defined only by the claims.
Referring now to FIG. 1, there is shown a retaining wall block 10 having a front surface 12 , side surfaces 14 a and 14 b extending rearwardly from front surface 12 and integral with rear surface 16 . Top surface 18 is generally planar and continuous across its extents. Top surface 18 extends from side surface 14 a to side surface 14 b, and from front surface 12 to rear surface 16 . Preferably, top surface 18 is generally perpendicular to side surfaces 14 a and 14 b, and also to front surface 12 and rear surface 16 .
In the preferred embodiment shown in the Figures, front surface 12 comprises three parts, 12 a, 12 b, and 12 c. Part 12 c is generally parallel to rear surface 16 and lies between parts 12 a and 12 b. Parts 12 a and 12 b are angled such that the extend from part 12 c and diverge rearwardly to meet side surfaces 14 a and 14 b, respectively. Parts 12 a, 12 b, and 12 c are shown as split faces as opposed to formed faces. Creating a face with a rock splitter results in an irregular, more natural appearing surface. Also shown in the Figures is a rear surface 16 which has a smaller width than front surface 12 such that side surface 14 a and 14 b must converge rearwardly in order to be integral with rear surface 16 . This shape allows the construction of straight, concave, convex, or serpentine walls without interrupting the relatively uniform appearance created by the front surfaces 12 of a plurality of blocks 10 forming a wall.
Bottom surface 20 extends from front surface 12 to rear surface 16 and from side surface 14 a to side surface 14 b. Bottom surface 20 includes concave, or non-planar portion 22 . Concave portion 22 is depicted in FIGS. 1, 3 and 4 as a relatively cylindrical indentation in bottom surface 20 , extending from side surface 14 a to side surface 14 b. Preferably, portion 22 does not extend forward of where side surfaces 14 a and 14 b meet parts 12 a and 12 b of front surface 12 . This way concave portion 22 is not visible in a completed wall, regardless of whether the wall is straight, concave, convex, or serpentine.
Allowing concave portion 22 to extend from side surface 14 a to side surface 14 b creates a gap 24 between the bottom surface 20 and the upper surface of a lower course of blocks when block 10 is placed thereon. This gap 24 may be used for ease in picking the block up and setting the block down. Also, as shown in FIGS. 1, 3 and 4 , concave portion 22 extends rearwardly but ends forward of downward projection 34 , which is described in more detail below. Ending the concave or, non-planar portion 22 forward of downward projection 34 provides another flat surface for block to block contact to assist in the leveling and stabilization of block 10 on a lower course of blocks.
Alternatively, it is envisioned that concave portion 22 be an indentation of any shape, such as the generally spherical shape of the embodiment shown in FIGS. 6-9. Preferably, portion 22 is large enough to occupy at least 30 percent, more preferably on the order of 50 to 75 percent, of the surface area of bottom surface 20 .
In a preferred embodiment, bottom surface 20 also includes at least one, preferably a plurality of, grooves 28 . As shown in FIG. 2, grooves 28 are preferably “V”-shaped and extend from the bottom surface into the block toward top surface 18 . In the embodiment depicted in FIGS. 1 and 2, grooves 28 are spaced generally equidistant from each other and oriented such that they extend from front to back generally across the non-planar portion 22 . It is envisioned that grooves 28 could be located generally anywhere across bottom surface 20 . It is preferred, however, that grooves 28 do not intersect front surface 12 so that grooves 28 remain hidden from view when block 10 is part of a completed wall.
Grooves 28 having the preferred “V” shape generally comprise at least a first surface 30 and a second surface 32 . First surface 30 extends from bottom surface 20 and is integral with second surface 32 . Second surface 32 extends from first surface 30 to bottom surface 20 thereby forming an angle α between first surface 30 and second surface 32 as seen in FIGS. 2 and 7. Angle α is preferably less than 180 degrees. Alternatively, first surface 30 and second surface 32 could be joined by a third surface (not shown in the Figures) which extends along the length of the groove and is juxtapose between the first and second surfaces. This third surface could be curved, thereby forming a “U” shaped groove, or the third surface could be flat, thereby forming a rectangular groove. However, a “V” shaped groove generally eases manufacturing.
As shown in all Figures, bottom surface 20 also includes at least one downward projection 34 . Downward projection 34 may extend across bottom surface 20 , adjacent rear surface 16 as shown in FIGS. 1, 2 , and 4 . Alternatively, projection 34 may be broken into more than one projection 34 as shown in FIGS. 6, 7 and 9 . Projection 34 has an abutting surface 36 which is used to abut against the rear surface 16 of a lower course of blocks, thereby forming a setback between successive courses of blocks. This setback add strength and stability to the resulting wall.
Abutting surface 36 may be substantially parallel to rear surface 16 . Alternatively, for ease of manufacture, abutting surface 36 may angle rearwardly forming a relatively small angle β with rear surface 16 as shown in FIG. 3 . Angle β is preferably less than 45 degrees, more preferably less than 30 degrees. A smaller angle β provides more resistance to horizontal block slippage due to external forces against the back of the resulting wall.
The foregoing is considered as illustrative only of the principles of the invention. Furthermore, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation shown and described. While the preferred embodiment has been described, the details may be changed without departing from the invention, which is defined by the claims. | A block for use in constructing a retaining wall having a bottom with a non-planar portion which creates a gap between the bottom surface and the top surface of a lower course of similar blocks when the block is placed thereon. Preferably, the block's bottom surface further comprises a plurality of grooves. It is envisioned that these grooves be “V” shaped, thereby having angled walls which act to funnel the larger stones into an area of adequate clearance when the block is being placed on a lower course of similar blocks. | 4 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] Not applicable
REFERENCE TO A “MICROFICHE APPENDIX”
[0002] Not applicable
BACKGROUND OF THE INVENTION
[0003] 1. Field of the Invention
[0004] The present invention relates to nano-carbon synthesis. More particularly the present invention relates a process to reduce the pre-reduction step for catalysts for nano-carbon synthesis by approximately 90% of the conventional process time.
[0005] 2. General Background of the Invention
[0006] In synthesizing carbon nanofibers, in the conventional manner as taught by the prior art, there is a catalyst pre-reduction requirement involved followed by passivation, which provides a thin metal oxide cover over the metal core. This time consuming step usually takes more than 24 hours. In this conventional process, the first step is reduction of the metal oxide under 10-20% H 2 at 400-600° C. for 20 hours, followed by passivation at room temperature for another hour under 2% O 2 .
[0007] Reference is made first to a publication by R. T. Baker, et al., entitled “Growth of Graphite Nanofibers from the Iron-Copper Catalyzed Decomposition of CO/H 2 Mixtures,” where it is disclosed how catalysts for nano-carbon synthesis are conventionally prepared. The preparation as taught by the prior art entails reduction of metal oxide in 10% hydrogen for 20 hours at 400-600° C., preferably 450-550° C., followed by passivation in the presence of a small amount (e.g. 2%) of oxygen at room temperature, followed then by a shorter secondary reduction in 10% hydrogen at reaction temperature just prior to introduction of the carbonaceous feedstock to initiate the nano-carbon synthesis. This time frame is depicted in FIG. 1 , labeled as “Prior Art.” The aforementioned Baker publication, together with U.S. Pat. No. 6,159,538, which supports the Baker publication, are provided as part of the Information Disclosure Statement submitted herewith.
BRIEF SUMMARY OF THE INVENTION
[0008] The process of the present invention solves the problems confronted in the art in a straightforward manner. What is provided here, is a process to reduce the pre-reduction step for catalysts for nano-carbon synthesis by first, heating a metal oxide at 5° C./min to 350-500° C. over 70-90 minutes under 10-20% hydrogen to affect its reduction; optionally holding the temperature for 10 to 60 minutes; then initiating carbonaceous feedstock flow.
[0009] Accordingly, it is an object of the present invention to provide a method for reducing the pre-reduction step for catalysts for nano-carbon synthesis;
[0010] It is a further object of the present invention to provide a method to reduce the pre-reduction step for catalysts for nano-carbon synthesis from 20 hours in the conventional process down to one hour;
[0011] It is a further object of the present invention to provide a method to reduce the pre-reduction step for catalysts for nano-carbon synthesis by ≧90% of the time involved in the conventional method;
[0012] It is a further object of the present invention to reduce the pre-reduction step for catalysts for nano-carbon synthesis which provides the possibility of continuous catalyst preparation and nano-carbon synthesis;
[0013] It is a further object of the present invention to provide a method to the pre-reduction step for catalysts for nano-carbon synthesis which renders scale-up of nano-carbon synthesis easier.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] For a further understanding of the nature, objects, and advantages of the present invention, reference should be had to the following detailed description, read in conjunction with the following drawings, wherein like reference numerals denote like elements and wherein:
[0015] FIG. 1 illustrates a graph of the conventional prior art method of producing catalysts for nano-carbon synthesis;
[0016] FIG. 2 is a transmission electron micrograph of the morphology of the nano-carbon fibers produced in the conventional prior art method depicted in FIG. 1 ;
[0017] FIG. 3 illustrates a graph of the preferred embodiment of method of the present invention of producing catalysts for nano-carbon synthesis; and
[0018] FIG. 4 is a transmission electron micrograph of the morphology of the nano-carbon fibers produced in the preferred embodiment of the method of the present invention depicted in FIG. 3 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0019] Turning now to the Figures, FIG. 1 illustrates a graph of the conventional prior art method of producing catalyst for use in nano-carbon fiber production, while FIG. 2 is a transmission electron micrograph of the morphology of the nano-carbon fibers produced in the conventional prior art method depicted in FIG. 1 .
[0020] FIG. 3 illustrates the preferred method of the process to reduce the prereduction steps for catalysts in nano-carbon synthesis, while FIG. 4 is a transmission electron micrograph of the morphology of the nano-carbon fibers produced in the preferred embodiment of the method of the present invention depicted in FIG. 3 .
[0021] However, before a discussion of the method of the preferred embodiment of the present invention, reference is made to FIGS. 1 and 2 . In FIG. 1 , there is depicted a graph of the conventional metal oxide catalyst preparation plotting the Temperature vs. Time. As illustrated, the primary reduction of the catalyst is initiated at approximately 50° C. As seen in FIG. 1 , the temperature of the catalyst is raised to between 500-600° C., so that over a period of some twenty hours the reduction takes place at that constant temperature. At the end of the primary reduction phase, the passivation step is initiated where the catalyst is cooled to a temperature of around 50° C. or below, under a flow of 2% oxygen, for a period of approximately one hour. Finally, secondary reduction takes place, where the catalyst temperature is returned to between 500-600° C., under a flow of 10% hydrogen, at which point the carbon nano-fiber synthesis is initiated. As can be seen clearly from this graph the entire process of preparing the catalyst under the conventional manner takes over twenty some hours in order to complete.
[0022] FIG. 2 is a transmission electron micrograph of the morphology of the carbon nano-fibers produced from the conventional catalyst preparation as described in regard to FIG. 1 . The carbon production rate was approximately 2.40 g Carbon/g catalyst/hr.
[0023] Turning now to the method of the preferred embodiment of the present invention reference is first made to FIG. 3 , which illustrates the preferred method of the process to reduce the prereduction steps for catalysts in nano-carbon synthesis. As illustrated, the metal oxide catalyst is brought from a temperature of around 50° C. to a temperature of between 400-500° C. in approximately one hours time under 10-20% hydrogen. At this point there is a brief optional dwell time. The metal oxide catalyst temperature is increased from 400-500° C. to between 500-600° C. and a mixture of CO/H 2 in a ratio 1:4 to 4:1 by volume is then passed thereover to initiate the carbon nano-fiber synthesis. As seen in FIG. 3 , the entire catalyst preparation process takes place over a period of less than 2 hours. It is clear in comparing the present invention with the conventional catalyst preparation, that the time has been reduced from some twenty plus hours to a period of at least less than two hours.
[0024] FIG. 4 is a transmission electron micrograph of the morphology of the nano-carbon fibers produced in the preferred embodiment of the method of the present invention depicted in FIG. 3 . The carbon production rate was approximately 2.56 g Carbon/gcatalyst/hr.
[0025] The catalyst, which would consist of a metal oxide which would include, but not be limited to the oxides of iron, copper, nickle, molybdenum and combinations thereof, would be heated under 10-20% H 2 at a heating rate of 5°C. per minute to between 350-500° C. The heating of the metal oxide to this temperature would require somewhere in the neighborhood of 70-90 minutes. The system would then be ramped to the reaction temperature under nitrogen gas. There would be a change to reaction gas to commence carbon nano-fiber synthesis.
[0026] Example 1, discussed below, relates to the production of catalysts under the conventional prior art process. Example 2, also discussed below, relates to the process of the present invention. In both Examples 1 and 2 the production of carbon nano-fibers have approximately essentially equivalent production rates for the two catalysts. It is clear that if the catalyst preparation time is reduced as taught in the present invention, development of a process for the continuous production of carbon nano-fibers, will be facilitated.
EXAMPLE 1
[0027] Example 1 is the conventional prior art catalyst preparation, as shown in FIG. 1 . In this example, a mixture comprising of 0.1 grams of iron and copper oxides containing 98:2 weight ratio of Fe/Cu was placed in a tubular reactor and reduced at 600° C. for 20 hours and 10% hydrogen (balance nitrogen), cooled to room temperature, passivated for one hour utilizing 2% oxygen (balance nitrogen), then reheated to 600° C. under 10% hydrogen (balance nitrogen) for two hours. A mixture of CO/H 2 (1:4 by volume) was then passed thereover at a rate of 200 sccm to produce carbon nano-fibers as depicted in the transmission electron micrograph of FIG. 3 . Carbon production rate was 2.40 grams carbon/grams catalyst per hour.
[0028] The present invention will be illustrated in more detail with reference to the following Example 2, which should not be construed to be limiting in scope of the present invention.
EXAMPLE 2
[0029] Example 2 is the preferred embodiment of the process of the present invention, as shown in FIG. 2 . In this example, the catalyst preparation included a mixture comprising of 0.1 gram of iron and copper oxides containing 98:2 weight ratio of Fe/Cu was placed in a tubular reactor, heated at a rate of 5° C. per minute to 500° C. under 10% hydrogen (balance nitrogen) and held there for thirty minutes. The temperature was increased to 600° C. and a mixture of CO/H 2 (1:4 by volume) was then passed thereover at a rate of 200 sccm to produce carbon nano-fibers as depicted in the transmission electron micrograph of FIG. 4 . The entire catalyst preparation process takes less than two hours, and Carbon production rate was 2.56 grams of carbon per gram of catalyst per hour.
[0030] It should be noted that in both Examples 1 and 2, the carbon production rates are essentially equivalent for the two catalysts. Furthermore, the morphology of the carbons produced in Examples 1 and 2 are identical as shown in FIGS. 2 and 4 . The magnification of FIG. 4 is reduced only to show a larger field of product. The background “web” in the micrographs is the support grid. It should be noted that the inventive catalyst preparation taught herein is applicable to other catalysts used to produced nano-carbons of various morphology; and these may include, but are not limited to the oxides of iron, copper, nickel, molybdenum and combinations thereof.
[0031] The foregoing embodiments are presented by way of example only; the scope of the present invention is to be limited only by the following claims. | A process to eliminate or reduce the pre-reduction step for catalysts for nano-carbon synthesis by first, heating a metal oxide at 5° C./min to 350-500° C. for 70-90 minutes under 10-20% hydrogen; optionally holding the temperature for 10 to 60 minutes; then initiating carbonaceous feedstock flow. | 3 |
RELATED APPLICATIONS
The present application is a Continuation-in-Part of U.S. patent applicaiton Ser. No. 09/769,319, filed on Jan. 25, 2001, hereinafter abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to a table having separable components and, more particularly, to a system having separable, assembled components that form a table and benches.
2. Description of the Related Art
In the related art, picnic tables can be found in backyards, parks and campgrounds, and rest stops across the country. While most commonly used as an eating table, it is also pressed into service as a food preparation table, a work surface, a meeting table or the like. While the picnic table is certainly useful and versatile, it does suffer from the drawback that it is stored outside at all times, thus it is subjected to the sun's rays, rain, wind, and other inclement weather or harmful environmental conditions and/or elements. For those areas with a severe winter season, they are also subjected to snow and reduced temperatures. This extreme weather can induce damage and leads to increased repair costs or more frequent replacement costs. Those lucky enough to have a large garage or storage shed can store them inside during the off-season winter months thus extending its life. However, this takes a great deal of storage area due to the large footprint and volume occupied by an assembled picnic table.
A search of the prior art did not disclose any patents that read directly on the claims of the instant invention; however, the following references were considered related.
Of particular interest is U.S. Pat. No. 6,042,179, issued in the name of Wallace, III, which discloses a table and bench assembly moveable between a folded position and an unfolded position. Wallace, III discloses a table that is lockably secured and released via a ball-handle and a rod, allowing the device to foldably collapse into a single unit. However, Wallace, III suffers from several drawbacks, including the number of movable parts necessary to assemble and disassemble the apparatus. Furthermore, the collapse of the table into a single unit is not ideal for storage and or transportation, especially if storage space is limited.
Consequently, there is a need for a means by which the functionality of a picnic table can be provided in a small package for ease of assembly and disassembly, use and storage, thus addressing the shortcomings of conventional picnic tables as described above.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide an improved modular picnic table system.
It is a feature of the present invention to provide an improved modular picnic table system having separable, assembled components that form a table top, parallel benches and supportable pedestal base elements.
Briefly described according to one embodiment of the present invention, a picnic table system is provided that is modular in design for ease of storage out of inclement weather when not in use. The bench assembly sits atop two pedestal-type legs and the table top is supported by the upper portion of the pedestal legs. Both the table top and the benches are frictionally impinged to securely maintain the structural integrity of the assembled components. When the invention is to be moved, stored for the season, or otherwise not needed, the frictional impingement is removed and the resultant four pieces, namely the top, the bench assembly, and the two pedestal legs, may be stored in a manner conserving floor or storage space. The ability to store the invention inside during inclement weather or during off season allows for increased life of the invention, thus saving the user replacement or repair costs as well.
The use of a modular picnic table of the present design provides a firm, stable picnic table area that can be easily disassembled and assembled in a manner which is quick, easy and efficient.
Advantages of the collapsible design of the present invention, having separate individual pieces held together with pegs, allows for easily assembled and disassembled with no tools needed.
BRIEF DESCRIPTION OF THE DRAWINGS
The advantages and features of the present invention will become better understood with reference to the following more detailed description and claims taken in conjunction with the accompanying drawings, in which like elements are identified with like symbols, and in which:
FIG. 1 a is a perspective view of a modular picnic table according to the preferred embodiment of the present invention;
FIG. 1 b is an exploded perspective view thereof;
FIG. 2 is a top plan view of a dual cantilever bench element 30 for use with the modular picnic table;
FIG. 3 is a plan view of the underside of the table top 40 illustrating the stringer members 44 a and pedestal receiving slot 44 b, and the rib receiving orifices 46 therein;
FIG. 4 is an elevational view of a pedestal base element 50 comprising rounded (curvilinear) indentations 56 a for receiving rounded protuberances 36 a from the underside of the bench element 30 for frictional fit impingement thereon;
FIG. 5 a is a side view of the pedestal base element 50 illustrating the ribs 58 and the rounded indentation 56 a thereon;
FIG. 5 b is a side view of the pedestal base element 50 illustrating a pair of horizontal bench supporting elements 56 and a pair of horizontal stabilizing elements 54 , and a pair of rounded indentations 56 a thereon;
FIG. 6 is a perspective view of a modular picnic table according to the alternative embodiment of the present invention;
FIG. 7 is an exploded perspective view thereof;
FIG. 8 a is a top plan view of a dual cantilever bench element 30 for use with the modular picnic table of the present invention;
FIG. 8 b is a side elevational view of the dual cantilever bench element 30 of FIG. 8 a;
FIG. 9 a is a bottom plan view of a table top 40 for use with the modular picnic table of the present invention;
FIG. 9 b is a side elevational view of the table top 40 of FIG. 9 a;
FIG. 10 a is a side elevational view of a pedestal leg element 50 for use with the modular picnic table of the present invention;
FIG. 10 b is a side elevational view of the pedestal leg element 50 of FIG. 10 a;
FIG. 10 c is a side elevational view of the pedestal leg element 50 comprising a pair of horizontal bench supporting elements 56 and a pair of horizontal stabilizing elements 54 ; and
FIG. 10 d is a front view of an alternative embodiment of the pedestal leg element 50 , comprising a triangulated upper support column 52 , a wider supporting surface 53 , and optionally, a plurality of ribs 58 .
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The best mode for carrying out the invention is presented in terms of its preferred embodiment, herein depicted within the Figures.
1. Detailed Description of the Figures
Referring now to FIG. 1 a through FIG. 5 b, a modular picnic table 10 is shown, according to a preferred embodiment of the present invention, comprising a collapsible design of separate individual pieces held together through frictional fit impingement and/or by pin fasteners 20 , thereby allowing for easy assembly and disassembly without the need for specialized tools. A bench element 30 rests on and is supported by a pair of individually supported pedestal base elements 50 . A table top 40 rests atop the pair of pedestal base elements 50 as well. The four-unit components (bench, pair of base elements and table top, respectively) are held in place by the use of frictional fit impingement or pin fasteners.
FIG. 2 shows the bench element 30 in greater detail, herein envisioned as a unitary element and further described as a dual cantilevered bench element (a cantilevered element is balanced by counter-forces across a fulcrum, and because users may set on both bench slats 32 , there is counter-acting forces for both slats 32 , resulting in a dual cantilever action). As shown, a pair of lateral bench slats 32 are mounted parallel to each other and held together in a spaced-apart (offset) manner by a plurality of support stringer assemblies 34 (shown in FIG. 3 as a pair of support stringer assemblies). Each support stringer assembly 34 is formed of a pair of individual support stringer members 34 a separated by a pedestal receiving slot 34 b. At least one of each pair of individual support stringer members 34 a (e.g., one member 34 a on each end of the bench element 30 ) includes a contoured underside 36 that frictionally impinges with a correspondingly shaped pedestal base element 50 . It is envisioned that each individual support stringer member 34 a comprising the pair of members 34 may be provided with the contoured underside 36 to provide further structural stability to the modular picnic table 10 . The contoured underside 36 is envisioned as including a variety of combinations (including key-lock, jigsaw formations or otherwise frictionally interlocking combinations) with FIG. 4 serving as a representative model. As shown in FIG. 4 , the contoured underside includes a pair of curvilinear protuberances 36 a, formed along the support stringer assemblies 34 , corresponding to curvilinear indentations 56 a formed in the bench supporting element 56 (described below) in the pedestal base 50 . The protuberances 36 a frictionally and gravitationally impinge within the indentations 56 a, thereby providing structural support to the bench element 30 during use.
FIG. 3 show the table top 40 in greater detail. As shown, the table top 40 has a generally planar upper surface 42 . Attached to the lower surface of the table top 40 are a plurality of attachment stringer assemblies 44 . A pair of attachment stringer assemblies 44 are mounted parallel to, but on opposing ends, of each other. Each attachment stringer assembly 44 is formed of a pair of individual attachment stringer members 44 a forming a pedestal receiving slot 44 b therebetween. It is anticipated that the overall size and dimension and location of these support stringer members 44 a separated by a pedestal receiving slot 44 b would be comparable to the support stringer assemblies 34 of the bench element 30 , so as to substantially align the support stringer assemblies 34 and the attachment stringer assemblies 44 when the modular picnic table 10 is assembled. Between the individual attachment stringer members 44 a (corresponding to the pedestal receiving slot 44 b ), a plurality of rib receiving orifices 46 are provided for frictionally and gravitationally impinging a plurality of ribs 58 provided along the top supporting surface 53 of pedestal base element 50 .
FIG. 4 illustrate a single pedestal base element 50 . It is anticipated that two such pedestal base elements 50 will be necessary for use with the present modular picnic table 10 . Each pedestal base element 50 has a vertically elongated support column 52 with a top supporting surface 53 opposite a horizontal stabilizing element 54 . The horizontal stabilizing element 54 is perpendicularly affixed to the support column 52 , and is of sufficient lateral span to allow for sturdy support of the completed picnic table 10 . Additionally, a horizontally disposed bench supporting element 56 is affixed to the support column 52 to provide structural support for the bench element 30 . In another embodiment, it is envisioned that each pedestal base element 50 will include a pair of horizontal stabilizing elements 54 (first and second horizontal stabilizing elements 54 , respectively) and a pair of bench supporting elements 56 (as seen in FIG. 5 b, first and second bench supporting elements 56 respectively) so as to provide more surface area, and thus, greater structural support to the bench element 30 as it is affixed and is supported by the pedestal base elements 50 . In another embodiment, shown in FIG. 10 d, the top supporting surface 53 departs from the linear embodiment of FIG. 5 a and includes a substantially wider terminal end (depicted as substantially triangulated in shape). The substantially wider terminal end of the top supporting surface 53 provides greater surface area in contacting the lower surface (underside) of the table top and inserting into the pedestal receiving slot 44 b, thereby providing greater structural support to the table top 40 , but also preventing unnecessary tilting or movement of the table top 40 when items are placed thereon, or when seated users place elbows, arms or generally exert force on the margins of the table top 40 . A plurality of ribs 58 are provided to any and/or all of the embodiments of the pedestal base element 50 disclosed. The ribs 58 are vertically projected upward from the top supporting surface 53 and are inserted into corresponding rib orifices 46 formed in the lower surface (underside) of the table top 40 .
Referring now to an alternative embodiment of the present invention, FIG. 6 through FIG. 8 b shows the bench element 30 in greater detail. As shown, a pair of lateral bench slats 32 are mounted parallel to each other and held together in a spaced-apart (offset) manner by a plurality of support stringer assemblies 34 (shown in FIG. 3 a as a pair of support stringer assemblies). Each support stringer assembly 34 is formed of a pair of individual support stringer members 34 a separated by a pedestal receiving slot 34 b. Each bench slat 32 includes a plurality of pin fastener receiving orifices 22 , as shown, for accepting pin fasteners 20 . Further, a surface of each support stringer member 34 a includes a plurality of pin fastener receiving orifices 22 for receiving and frictionally impinging the pin fasteners 20 . In this manner, the lateral bench slats 32 can be fastened to the support stringer assemblies 34 in a quick and convenient manner, without the aid of additional hand tools (if necessary). Also, as shown in FIG. 3 b, at the center point of each individual support stringer members 34 a are additional pin fastener receiving orifices 22 formed for attachment to the pedestals 50 by pin fasteners 20 , as will be described in greater detail below.
FIG. 9 a and FIG. 9 b show the table top 40 in greater detail. As shown, the table top 40 has a generally planar upper surface 42 . Attached to the lower surface of the table top 40 are a plurality of attachment stringer assemblies 44 . A pair of attachment stringer assemblies 44 are mounted parallel to, but on opposing ends, of each other. Each attachment stringer assembly 44 is formed of a pair of individual attachment stringer members 44 a separated by a pedestal receiving slot 44 b. It is anticipated that the overall size and dimension and location of these support stringer members 44 a separated by a pedestal receiving slot 44 b would be comparable to the support stringer assemblies 34 of the bench element 30 , so as to substantially align the support stringer assemblies 34 and the attachment stringer assemblies 44 when the modular picnic table 10 is assembled. Also, and as shown in FIG. 4 b, at the center point of each individual attachment stringer members 44 a are a plurality of pin fastener receiving orifices 22 formed for attachment to the pedestals 50 by pin fasteners 20 , as will be described in greater detail below.
FIG. 10 a, FIG. 10 b, FIG. 10 c and FIG. 10 d illustrate a single pedestal base element 50 . It is anticipated that two such pedestal base elements 50 will be necessary for use with the present modular picnic table 10 . Each pedestal base element 50 has a vertically elongated support column 52 with a top supporting surface 53 opposite a horizontal stabilizing element 54 . The horizontal stabilizing element 54 is perpendicularly affixed to the support column 52 , abutting against the underside of the bench element 30 , and is of sufficient lateral span to allow for sturdy support of the completed picnic table 10 . Also, at both the top and near the center point of each individual support column 52 are a plurality of pin fastener receiving orifices 22 formed for attachment of both the table top 40 and bench element 30 , respectively, to the pedestal base elements 50 by pin fasteners 20 , as will be described in greater detail below. In another embodiment, it is envisioned that each pedestal base element 50 will include a pair of horizontal stabilizing elements 54 (first and second horizontal stabilizing elements 54 , respectively) and a pair of bench supporting elements 56 (as seen in FIG. 5 c, first and second bench supporting elements 56 , respectively) so as to provide more surface area, and thus, greater structural support to the bench element 30 as it is affixed and is supported by the pedestal base elements 50 . In another embodiment, shown in FIG. 10 d, the top supporting surface 53 departs from the linear embodiment of FIG. 10 a and includes a substantially wider terminal end (depicted as substantially triangulated in shape). The substantially wider terminal end of the top supporting surface 53 provides greater surface area in contacting the underside of the table top and inserting into the pedestal receiving slot 44 b, thereby providing greater structural support to the table top 40 , but also preventing unnecessary tilting or movement of the table top 40 when items are placed thereon, or when seated users place elbows, arms or generally exert force on the margins of the table top 40 .
2. Operation of the Preferred Embodiment
In accordance with a preferred embodiment of the present invention, as shown in FIG. 1 a through FIG. 5 b, the modular picnic table 10 is assembled by starting with the four-unit structure (bench element, pair of base pedestals and table top). The pair of base pedestals 50 are aligned about the bench element 30 . The support column 52 with ribs 58 is passed through the pedestal receiving slot 34 b. The protuberances 36 a are aligned with the indentations 56 a and frictionally and gravitationally impinged in a substantially interlocking manner. Thus, the pedestal base elements 50 are now freely standing and supporting the bench element 30 . Next, the table top 40 is aligned so that the rib receiving orifices 46 insertably receive the corresponding ribs 58 from the top supporting surface 53 . The ribs 58 frictionally and gravitationally impinge therein, thus the entire modular picnic table 10 is now assembled and ready for reliable use. To disassemble, simply reverse the assembly procedure.
The foregoing descriptions of specific embodiments of the present invention have been presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the invention to the precise forms disclosed, and obviously many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and its practical application, to thereby enable others skilled in the art to best utilize the invention and various embodiments with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims appended hereto and their equivalents. Therefore, the scope of the invention is to be limited only by the following claims. | A picnic table system is provided that is modular in design for ease of storage out of inclement weather when not in use. A bench assembly sits atop two pedestal-type legs and the table top and is supported by the upper portion of the pedestal legs. Both the top and the benches are secured by frictional impingement. When the structure is to be moved, the bench assembly, table top and the two pedestal legs are stored in a manner conserving floor or storage space. The ability to store the structure inside during inclement weather or during off season allows for increased life of the structure, thus saving the user replacement or repair costs as well. | 0 |
BACKGROUND
Automatic washers for cleaning the hands and arms of personnel such as doctors, nurses, and restaurant workers, have been developed. Such washers are known as lavage machines. These machines typically include an arrangement of nozzles, within a sealed cabinet for directing a pressurized mixture of water, cleaning solution and anti-microbial agent onto the arms and hands inserted into the machine. The particular cleaning solution which is used varies in accordance with the application, and such machines range from relatively simple devices to multiple cycle machines incorporating washing cycles, rinsing cycles and drying cycles.
One problem which exists with such machines is in the area of the entry holes or apertures through which the hands and arms of the user are inserted. Obviously, openings of sufficient size to permit the insertion of hands and arms are necessary in the front or top panel of such a machine. When the machine is operating, in either a washing or rinsing cycle, a substantial amount of liquid is splashed around within the machine. It is desirable to prevent this liquid from splashing out through the openings around the arms of the person using the machine. Since these machines also are used to produce a germ free or bacteria free cleansing of the hands and arms, the opening must be large enough; so that the clean and sterilized hands and arms can be withdrawn from the machine without touching the edge of the opening, which typically is not free of germs and bacteria.
A lavage machine which has been designed to prevent the cleaning solution and water within the machine from splashing out of the machine is disclosed in the patent to Vetter #4,688,585. This machine has two generally circular openings for insertion of the arms of the user into the machine. Each of these openings is surrounded with an elongated elastic sleeve attached around the opening and which extends into the machine. The sleeve presses against the arm of the person using the machine, and pressurized air is applied to the machine interior further to press the elastic material of the sleeve onto the arm. As a result, when the machine is operated to clean the hands of the person using it, an effective water tight seal is formed around the arms of the person to prevent water from splashing out through the openings. A difficulty arises in this machine, however, since upon withdrawal of the arms, the hands can come into contact with the sleeve (which presses against a portion of the arm not cleaned within the machine) and thus can become contaminated. As a result, the sleeve performs the function of preventing liquid from splashing out of the machine but also is capable of recontaminating the hands of the user immediately following cleansing and sterilization. This is a serious disadvantage of the device disclosed in this patent.
Another patent disclosing a lavage machine for hand and arm washing machine is the patent to Kopfer #3,918,987. In this patent, there is no seal whatsoever in the opening into which the arm is inserted, so that some fluid can splash out through the space between the arm and the edges of the opening during the operation of the machine.
A device for providing a pressure resisting seal for a variety of purposes, such as respirators, is disclosed in the Patent to Hopkins #3,450,450. The structure of this patent has a plurality of flexible closure members attached side-by-side around an aperture in the enclosure to press against an object inserted through the closure members. Essentially they extend to fill the space in the aperture completely and are displaced when an object such an arm, torso or the like is inserted through them. Pressurized air within the enclosure then presses the members against an object inserted through the aperture to prevent the pressurized air within the device from passing outwardly. It is readily apparent, however, from an examination of the various structures disclosed in this patent, that upon removal of the object from the device, contact is made with the closure members. Thus, these structures are not suitable for use in a lavage machine where the cleansed and sterilized arm and hand must be withdrawn without coming into contact with any contaminated surface.
Four patents which disclose flexible, inflatable seals for sealing doors or lids against a frame or a container, are the patents to Reeves #2,785,824; Clark #3,178,779; Stachiw #3,266,657 and Hunt #4,106,661. In all of these patents, an inflatable seal surrounds the opening between a door or lid and a frame or container. When the door or lid is closed, the seal is inflated to expand into the space between the door or lid and the container or frame with which it is used, thereby tightly sealing the opening. The distance that the inflatable seal moves is relatively small in all of the devices disclosed in these patents, since the covers or doors close the openings within relatively close tolerances. Consequently, only a slight movement of the seal or a slight expansion of it is sufficient to securely close the opening and seal it off. None of the devices of these patents are lavage machines or hand washing machines.
It is desirable to provide a closure for the hand and arm entry openings in a lavage machine which effectively prevents liquid from splashing out of the machine during the washing operation and which also is withdrawn or pulled away from the opening a sufficient amount to permit withdrawal of the clean arms and hands from the machine without touching the closure or the opening following the washing cycle. It further is desirable to provide such a device which is capable of quickly and effectively accomplishing this purpose with persons having differing physical measurements.
SUMMARY OF THE INVENTION
Accordingly, it is an object of this invention to provide an improved closure for sealing an opening in a cabinet against an object inserted through the opening.
It is an additional object of this invention to provide an improved seal for the opening in a lavage machine.
It is another object of this invention to provide an improved expandable cuff assembly for the opening in a lavage machine.
It is a further object of this invention to provide a self-draining cuff assembly for the opening in a lavage machine.
It is yet another object of this invention to provide an expandable cuff assembly for the opening in a lavage machine for sealing the opening against the arm of a user during the washing cycle of the machine and further for permitting unobstructed removal of the arm and hand of the user of the machine following the washing cycle.
In accordance with a preferred embodiment of this invention, an expandable cuff assembly for closing an opening in a panel against an object includes an expandable cuff member formed at least in part of resilient material for mounting about the periphery of the opening through the panel. In a first state, the cuff member provides an enlarged opening through the panel for ready insertion of an object through the opening. In a second state, the cuff member expands to substantially restrict the opening and to conform against the object inserted through the opening to provide an effective seal of the opening against objects of varying sizes inserted through it. A control is provided to selectively cause the cuff member to attain the first and second states.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A is a sectionalized, perspective view of a preferred embodiment of the invention, illustrating a control system in a first operating condition;
FIG. 1B illustrates a portion of the control system of the embodiment of FIG. 1A in a second condition of operation;
FIG. 2 is a cross-sectional view of the embodiment of FIG. 1A illustrating first and second states of operation;
FIG. 3 is an alternative structure of a portion of the embodiment shown in FIGS. 1A and 2;
FIGS. 4A through 4E illustrate the manner of construction of a portion of the embodiment shown in FIGS. 1A and 2;
FIG. 5 illustrates a cross-sectional view of a portion of an alternative embodiment of the invention;
FIG. 6 is an exploded perspective view of another preferred embodiment of the invention;
FIG. 7 is a cross-sectional view of the embodiment of FIG. 6; and
FIG. 8 is an enlarged detail of a portion of FIG. 7.
DETAILED DESCRIPTION
Reference now should be made to the drawings in which the same reference numbers are used throughout the difference figures to designate the same components. The embodiments of the invention which are disclosed are for use in the arm insertion openings of a hand washing machine or lavage machine of the type shown, for example, in the Patent to Vetter, discussed above.
The invention as shown in the embodiment of FIGS. 1 through 4 is an inflatable cuff for sealing the arm openings in the front of a lavage machine against the arms of the user when the machine is operated to clean the hands and/or forearms of a person. Following the cleaning operation, the cuff assembly operates to enlarge the opening to permit free removal of the hands and arms of the user from the machine without touching the cuff or opening in the machine.
The structure of the cuff member itself is illustrated in FIGS. 4A through 4E, and reference first should be made to those figures. The cuff member may be made from an elongated neoprene extrusion or elastomeric material having a relatively thin central portion 21 with a downwardly turned thickened rib 23 at one end (the left-hand end shown in FIG. 4A) and a thickened portion 24 at the right-hand end, with an upward extension 26 to form a shoulder 27 between the extension 26 and the thickened portion 24. Since this extrusion has a uniform cross-section throughout its length, the cuff 20 simply is formed from a section of a continuous extrusion. The length of the section depends upon the final diameter of the opening in which the cuff member is to be placed.
After a fixed length of the extrusion shown in FIG. 4A is cut, the material is folded back on itself by pulling the edge 23 underneath the edge 24, as illustrated in FIG. 4B, to abut the shoulder 27. A continuous bead of glue 28 may be placed along these abutting edges to form an airtight seal between them. Alternatively, thermal bonding may be employed, if desired. The result is an elongated open ended, folder over section as illustrated in FIGS. 4B and 4C. It should be noted that the relatively thin portion 21 extends from side-to-side across the bottom of this subassembly and substantially half of the length on the upper side, extending to the left of the thickened section 24, as illustrated in FIGS. 4A and 4B.
A hole 30 then is formed through the thickened portion 24, and an air hose stem 29 is inserted into the hole 30 and is glued to or otherwise bonded to the portion 24 to form an airtight seal. The lower end of the stem 29 extends into the interior of the envelope formed by the folded-over portion 21, as illustrated most clearly in FIGS. 1A and 2.
After the device has been assembled in its flat form shown in FIGS. 4A and 4B, it is rolled up as illustrated in FIG. 4D; and the opposite edges are bonded together along the bond line 31 to form an airtight envelope within the interior of the folded over portion 21. This is illustrated in FIG. 4E. The assembly of FIG. 4E then comprises a hollow cuff member which is secured into an opening 11 of the front panel 10 of a lavage machine.
When the cuff member is configured as illustrated in FIGS. 4A through 4E, the relatively rigid thickened extension 26 snap fits into a channel 14 formed behind the opening 11 in the front face of the panel 10, as illustrated most clearly in FIGS. 1A and 2. This causes the edge 23 to extend upwardly behind the lower edge of the panel 10 at the opening 11. The dimensions of the channel 14 are made to cause this to be a relatively tight fit. Because of the nature of the extrusion, the rolled cuff member of FIG. 4E tends to press outwardly into the channel 14, so that it is held securely in place behind the front panel 10 once it has been snapped into the channel 14. There is sufficient resiliency in the stiffened portions 24, 26 and 23 to permit installation of the assembly in the channel 14 simply by "popping" it into place, as illustrated in FIGS. 1A and 2.
After the cuff member 20 has been inserted into the channel 14, an air pipe 32 for one opening 11 or 33 for the other opening (not shown) in the panel 10 of the lavage machine is connected to the stem 29. This permits the supply of air into and the removal of air from the enclosed cavity formed within the cuff member 20 between the folded over portions 21, forming the outer and inner sides of the elongated annular sleeve of the cuff assembly.
Typical dimensions for the cuff assembly and the lavage machine opening are for the opening 11 to be approximately five (5) inches in diameter for wrist sealing and six (6) inches for arm sealing. This permits ready passage of the hand and forearm of a user of the machine through the opening with adequate clearance. The depth of the member 20 from right to left, as viewed in FIGS. 1A and 2, is approximately four (4) inches. The relaxed thickness of the member 20 (when air pressure has been removed from it), as illustrated in FIGS. 1A and 2 in solid lines, is approximately one-half inch from the outer surface to the inner surface. The channel 14 is approximately one-half inch wide; and the depth of the channel 14 from the portion which touches the upper surface of the extension 26 to the edge of the opening 11 is approximately one inch. Also, as illustrated most clearly in FIG. 2, the relatively rigid thickened portion 24 extends approximately one-half of the front to back distance of the cuff member 20.
When the device is in its relaxed state, as illustrated in FIGS. 1A and 2, the rigidity of the portion 24 causes it to assume the configuration shown in solid lines in FIG. 2. This provides easy access for insertion of the forearm 60 of a person using the device through the opening 11 in the front panel 10. A system is provided for pumping air under pressure into the envelope within the walls 21 to expand the flexible walls 21 on the inside of the device from the solid line position to the dotted line position shown in FIG. 2. To accomplish this, a motor 35 is used to drive a pump 36 to supply air through a valve 38 (in the position shown in FIG. 1A) through a pressure limit switch 39 into the supply pipe 32 (and 33). The pipe 32 then supplies air through the stem 29 to increase the pressure within the envelope 21 of the cuff member 20. The wall portion 21 is relatively thin; and since the inner surface is made entirely of this thin wall section, the portion 21 resiliently stretches downwardly to the dotted line configuration of FIG. 2. This forms an annular air-filled ring, the inside surface of which expands to substantially restrict the size of the opening.
When the inner surface 21 of the cuff member engages the forearm of a person using the machine it firmly and gently presses against the forearm 60 on all sides to securely seal the opening against the arm. As illustrated in FIG. 2, the resiliency of the portion 21 causes the cuff member to conform to the shape of the arm 60 and the angle at which it is inserted into the machine; so that arms of different sizes, and entering the opening 11 at different angles, all are accomodated with a secure seal. It has been found that an air pressure of approximately one to five pounds per square inch is sufficient when the wall thickness 21 of the sleeve is approximately 0.025 to 0.040 inches thick.
The time at which the motor 35 is turned on is determined by operation of a switch 42 in conjunction with the operating cycle of the lavage machine. This can be affected automatically or manually to supply power from a suitable power source 41 to operate the motor 35 and to control the limit switch 39. A control device 40, also part of the lavage machine, is used to operate the valve 38 to the position shown in FIG. 1A when air is to be supplied through the stem 29 into the interior of the cuff to expand it, as shown in dotted lines in FIG. 2.
Upon completion of a washing cycle, the switch 42 is opened, and the control device 40 rotates the valve 38 to the position shown in FIG. 1B. This permits the natural resiliency of the cuff member 20 to expel air through the valve 38 into the surrounding room as the cuff member resumes its original shape, as shown in solid lines in FIGS. 1A and 2. If desired, the motor 35 and pump 36 can be operated to evacuate air through the valve 38 by interconnecting these elements through suitable conduits and additional valves. It has been found, however, that the cuff, having the characteristics and dimensions described above, has sufficient "memory" to quickly and effectively expel the air when the valve 38 is opened, as shown in FIG. 1B. Thus, evacuation of the air by means of a pump usually is not necessary.
FIG. 1A also illustrates an optional second switch 44 for operating the motor 35, since a variety of control sequences may be used in various lavage machines for causing the operation to take place. Once the internal surface 21 of the cuff member engages the arm of a user, pressure builds up relatively rapidly within the cuff member; and a pressure limiting switch 39 may be employed to prevent excess pressure from occurring. The switch 39 is set to operate when a desired maximum pressure is reached. Upon occurance of this pressure, the switch 39 functions to open the circuit to the motor 35 to turn off the pump 36. This provides an accurate control point for determining that the cuff member 20 has, in fact, closed the opening around the arm 60 of the user, since the amount of air delivered into the cuff member 20 varies, depending upon the size of the arm 60 of the person using the machine.
FIG. 3 illustrates an alternative construction for the cuff member and the channel 14 which may be used in place of the one shown in FIGS. 1A and 2, if desired. In the device shown in FIG. 3 a channel 14' is formed as an extension of the panel 12 inwardly from the edge of the opening 11. The cuff assembly is formed in the same manner described in conjunction with FIGS. 4A through 4E, except that the shoulder 27 may be eliminated and the edge 23 is extended parallel to the upper edge of the extension 26. An annular ring 40 then is secured by means of a series of screws or other fasteners 41 around the edge of the opening to firmly clamp the edge 23 and the portion 26 together against the left hand edge of the channel 14', as illustrated in FIG. 3. In all other respects, the construction of the device made in this manner is the same as the embodiment described above in conjunction with FIGS. 1A, 2 and 4.
FIG. 5 shows another variation of the invention which may be employed, if desired. In the embodiment of FIG. 5, the expandable or inflatable cuff member simply is in the form of a flat sheet 51 of neoprene. This sheet is rolled and joined at its edges to form an elongated cylindrical sleeve. The material 51 is of uniform thickness throughout its length or may include thickened edges similar to the edge 23, if desired. It should be noted, however, that in the embodiment of FIG. 5 the sleeve is not an enclosed balloon or tube-like member, but simply is a cylindrical member with upturned or outwardly turned edges. The channel 14 then is replaced with an elongated U-shaped channel 54, extending from the inside of the panel 10 to the interior of the lavage machine the full depth of the member 51. Thus, the channel 54 is approximately five (5) inches or six (6) inches wide in contrast to the approximately one inch width of the channel 14 of the embodiment of FIGS. 1A and 2. The stem 29 is inserted through the channel 54, as illustrated in FIG. 5.
The assembly of FIG. 5 is completed by means of threaded fasteners 56 placed about the periphery of the opening 11 in the panel 10 and extending through the upwardly turned edge of the sleeve 51 into the downwardly turned right-hand flange on the channel 59. An annular ring 50 (similar to the ring 40 of FIG. 3) is provided on the inside of the assembly and is secured to the other flange of the channel 54 by means of threaded fasteners 57 about the periphery. When the fasteners 56 and 57 are secured around the annular openings formed at each end of the channel 54, an air tight seal is formed between the channel 54 and the member 51. The member 51 may be inflated and deflated in the same manner described above in conjunction with the operation of the system of FIGS. 1A and 2. It should be noted, however, that because the member 51 is securely held at both ends, the central portion expands inwardly to the greatest amount, so that the contact with the arm of a user inserted through the opening 11 is a narrower region of contact than it is with the device of FIGS. 1A and 2. In all other respects, however, the cuff member of FIG. 5 operates in a manner similar to the cuff member of the embodiment of FIGS. 1A and 2.
Reference now should be made to FIGS. 6, 7 and 8 which illustrate another preferred embodiment of the invention directed to a cuff member which is made of a molded elastomer, such as rubber, instead of the extrusion construction which is shown in the embodiments of FIGS. 1 through 5. In the embodiment shown in FIGS. 6 through 8, a cuff 60 is made as a unitary molded element by dipping a preformed mold (not shown) into a liquid elastomer, such as rubber latex or the like, one or more times to obtain the desired wall thickness for the cuff. The overall shape of the cuff is established by the shape of the mold to produce an outwardly flaring frusto-conical shape to the finished product. The mold is completely immersed to form a hollow, completely enclosed structure. To remove the finished cuff 60 from the mold, a circular cut 70 is made around the periphery of an outwardly extending flange, shown most clearly in FIG. 6. Once this cut has been made all of the way around the mold, the molded cuff member 60 may be stripped from the mold and then returned to its original shape as illustrated in FIG. 6.
A second part of the cuff assembly of the embodiment of FIGS. 6 through 8 is in the form of a relatively thick molded elastomer ring 66 having a inwardly extending flange 64 on it. This ring 66 is comparable to the thickened portion or upward extension 26 of the embodiment shown in FIGS. 1 through 5.
To assemble the embodiment of FIG. 2, a suitable adhesive is placed on the outer surface of the flange 64 on the ring 66 to secure the inner edge of the conical sleeve 61 of the cuff 60 to the flange 64 in an airtight and watertight relationship. Similarly the inner surfaces of the cuff 60 along the cut 70 and extending around the flange 64 are also secured together with a suitable adhesive to form an airtight seal.
When the device is thus assembled, it then snap fits into the channel 14 formed behind the opening 11 in the front face of the panel 10 of the lavage machine. This is shown most clearly in FIGS. 7 and 8. It should be noted that the inner downwardly turned flange of the channel 14 extends between the upward edges of the outwardly turned portion of the cuff 60 adjacent the cut line 70.
It also is possible, however, to configure the channel 14 in a way to cause the inner flange to overlie the opposite side of the outwardly turned portion of the sleeve member 60, so that the cut line 70 and the adjacent portions of the adhesively secured together flange member, all are located within the channel 14. In either event, the operation of the cuff 60 is the same; and it should be noted that the assembly is held securely in place behind the front panel 10 of the lavage machine once it is snapped into place. This permits easy replacement of the cuff 60 in the event it should become damaged or worn out. The existing worn cuff 60 and its assembled ring 66 is simply pulled out of the channel 14 and a new one is pressed into place.
The air hose nipple 69 of the embodiment shown in FIGS. 6 through 8 also is molded into the assembly as a part of the original mold. The closed end then is cut off and a rigid connector (not shown) for attachment to the supply pipe 32 or 33 is inserted.
In operation, the embodiment of FIGS. 6 through 8 functions much in the same manner as the embodiments of FIGS. 1 through 5. When the machine is to be used, air is introduced into the hollow interior of the cuff 60 through the air hose nipple 69. This air is supplied at a pressure of approximately one to five pounds per square inch and inflats the region between the inner and outer surfaces 61 to expand this region much in the order of an expanding balloon. To focus the expansion on the inside surface, which causes the cuff to engage the arm or wrist of the user, a non-expandable ring 80 is placed over the cuff portion 60, with the air hose nipple 69 extending through a hole 81 in the ring 80. The ring 80 may be made of any suitable plastic material in the form of a solid ring or a mesh-like structure. It must exhibit the characteristics of resisting expansion in the radial direction. The ring 80 may be bonded to the outer surface of the sleeve 61, if desired.
As is shown most clearly in FIG. 7, when the ring 80 is in place, the expansion of the material of the conical sleeve 61 of the cuff 60 in the outer direction is significantly inhibited by the ring 80, while the inner expansion toward the axis of the opening through the ring 66 is unrestricted. This is illustrated by the dotted lines in FIG. 7 which illustrate the expanded position of the inner and outer portions of the conical sleeve 61 of the cuff member 60. When the device is expanded to the dotted line configuration the arm or wrist of the user is engaged by the cuff to prevent cleaning solution from splashing out of the lavage machine.
Upon completion of the washing cycle, the air pressure through the nipple 69, is removed and the cuff member either is subjected to a vacuum or reverse air flow through the nipple 69 or simply is permitted to collapse to its "memory" state, which is shown in solid lines in FIG. 7. The arm and hand of the user then easily may be withdrawn through the opening in the ring 66 in the manner described previously.
The conical shape gives a type of hoop memory to the device and provides a smooth water free-surface when the cuff 60 attains its uninflated or retracted condition of operation as, shown in solid lines in FIG. 7. It can be seen that any liquid which may be present on the inside portion of the cuff will drain downwardly and outwardly to the bottom edge, where it is returned to the interior of the lavage machine. This self-draining feature is important for minimizing contamination.
It should be noted that with all of the embodiments disclosed, a substantial expansion of the cuff member from its relaxed state to its expanded state occurs. That is, the cuff member portion 21 or 51 has sufficient resiliency in the range of pressures used within the system to cause it to close the opening through the cuff member from approximately five or six inches (when the cuff member is in its relaxed state) down to approximately one inch diameter. Thus, arms of persons having considerable different physical characteristics may be accomodated within the machine.
The foregoing embodiments of the invention which have been described and which are illustrated in the drawings are to be considered illustrative of the invention and not as limiting. Various changes and modifications will occur to those skilled in the art. For example the dimensions which have been given are typical of an actual embodiment of the invention, but may be varied in accordance with different physical requirements of different lavage machine installations. Although the structure for the expandable and inflatable cuff member has been described as latex or neoprene, other rubber-like materials may be used, if desired. In addition, different configurations of the inflatable cuff also will occur to those skilled in the art without departing from the true scope of the invention. | An expandable cuff assembly encloses a circular opening in the front panel of a lavage machine. The opening is made large enought to permit arms of a user to be inserted freely through the opening. After this is done, the expandable cuff member is filled with air to cause it to expands from a first state, having an enlarged opening through it, to a second state where it resiliently closes against the arm of the user to prevent liquid from splashing out of the lavage machine during use. After the operation of the machine is completed, the expandable cuff member returns to its first state, with a large opening therethrough to permit withdrawal of the arms of the user freely through the enlarged opening. | 5 |
BACKGROUND OF THE INVENTION
This invention relates generally to vehicle brakes, and particularly to an improved automatic brake shoe clearance adjusting device for shoe drum type brakes.
One of the conventional automatic brake shoe clearance adjusting devices comprises a first strut member with a fork-shaped portion on one end and threaded stem portion on the other end, a second strut member having a hollow end portion for loosely receiving the threaded stem portion of the first strut member, and an adjusting nut screw-threadingly engaging with the threaded stem and abutting with the open end of the hollow end portion of the second strut member and having ratchet teeth on the outer circumference. An adjusting lever having a pawl portion cooperating with the ratchet teeth is pivotally mounted on a hand brake lever, and a bent portion of the adjusting lever is normally biassed against a shoulder of the hand brake lever acting as a stop by means of a spring extending between the hand brake lever and the adjusting lever. The adjusting lever is mounted on a pin secured to the hand brake lever with some amount of play or degree of freedom of movement in the direction of the thickness of the hand brake lever or the direction of the axis of the pin so that the pawl portion of the adjusting lever can move towards or away from the ratchet teeth of the adjusting nut. However, the bent portion of the adjusting lever can also move in the direction of the thickness of the hand brake lever due to the play aforementioned, and thus there is a tendency for the adjusting lever to disengage from the stop of the hand brake lever due to vibrations of the vehicle in usage or due to mishandling of a tool in assembling the brake. It is possible to overcome such drawbacks by reducing the amount of play, but the movement of the adjusting lever in passing over the ratchet teeth will accordingly be restricted, and the adjusting nut may be rotated in the reverse direction upon releasing the hand brake lever.
SUMMARY OF THE INVENTION
An object of the present invention is to overcome drawbacks aforementioned by providing, at least on a line passing the center of the pin pivotally mounting the adjusting lever on the hand brake lever and the stop formed on the hand brake lever, means for restricting rocking movement of the adjusting lever relative to the hand brake lever in the direction of the thickness of the hand brake lever (or of the axis of the pin), thereby preventing disengagement of the adjusting lever from the stop in the direction of the thickness of the hand brake lever.
BRIEF DESCRIPTION OF THE DRAWINGS
Some embodiments of the present invention will, by way of example, be described with reference to the accompanying drawings, in which;
FIG. 1 is a front view of a disc brake according to the present invention;
FIG. 2 is a cross-sectional view taken along line II--II in FIG. 1;
FIG. 3 is a cross-sectional view taken along line III--III in FIG. 1;
FIG. 4 is a perspective view of an assembly of the hand brake lever and adjusting lever of FIG. 1;
FIG. 5a is a plan view showing a portion of the assembly of FIG. 4;
FIG. 5b is a cross-sectional view showing a projection formed on the adjusting lever of FIGS. 4 and 5a;
FIGS. 6 and 7 are enlarged partial views showing the assembling process of the assembly of FIG. 4;
FIG. 8 is a view similar to FIG. 4, but showing a second embodiment wherein the projection is formed on a head portion of the pin;
FIG. 9a is an enlarged side view of the pin of the second embodiment;
FIG. 9b is a plan view of FIG. 9a;
FIGS. 9c and 9d are views showing forming process of a projection of a modified form;
FIG. 10a is a plan view showing a portion of hand brake lever having thereon the projection according to the invention;
FIG. 10b is a cross-sectional view taken along line X--X in FIG. 10a;
FIG. 11 is a view similar to FIG. 4 but showing another embodiment of the invention;
FIG. 12a is a view showing the essential portion of FIG. 11 as viewed from the upper side thereof;
FIG. 12 b is a right side view of FIG. 12a;
FIG. 13 is a slightly enlarged perspective view similar to FIG. 11 but showing a modified form; and
FIG. 14 is a perspective view of the washer illustrated in FIG. 13.
DETAILED DESCRIPTION OF THE INVENTION
The shoe drum brake shown in FIGS. 1,2 and 3 comprises a stationary backing plate 1 mounted to a non-rotatable part (not shown) of a vehicle, and having a wheel cylinder 2 and an anchor 3 secured thereon at diametrically opposed positions. Two pistons 4 and 4' are fitted in the wheel cylinder 2 and are slidable in opposite directions therein. First ends of webs 5a and 6a of arcuate brake shoes 5 and 6 engage respectively with the pistons 4 and 4', and the other ends of webs 5a and 6a abut the anchor 3. The brake shoes 5 and 6 are urged in directions away from a brake drum (not shown) by return springs 7 and 8 extending between the brake shoes 5 and 6. Brake linings 9 and 10 are mounted on brake shoes 5 and 6, respectively, on the sides thereof adjacent to the brake drum.
A fork-shaped end of a first strut member 11 engages with a recess formed in the web 5a of the brake shoe 5 at a position adjacent to the wheel cylinder 2, and a fork-shaped end of a second strut member engages with the web 6a of the brake shoe 6. A threaded stem portion or another end portion 11a of the first strut member 11 slidably extends into a hollow end portion of the second strut member 12. The threaded stem portion 11a of the first strut member 11 screw-threadingly engages with an adjusting nut 13 having ratchet teeth on the outer periphery thereof, and one side surface 13a of the nut 13 abuts with the open end of the second strut member 12. A hand brake lever 14 is pivotally mounted on the brake shoe 6 by a pin 15, and the pin 15 also acts to pivotally mount on the hand brake lever 14 an adjusting lever 16 having a pawl portion for engaging with the ratchet teeth of the adjusting nut 13. A shoulder portion 14a acting as a stop is formed on the hand brake lever 14, as shown in FIGS. 1 and 4, and a projection or bent portion 16a formed on one end (remote from the pawl portion) of the adjusting lever 16 normally engages with the stop 14a by means of a spring 17 extending between the hand brake lever 14 and the adjusting lever 16. The adjusting lever 16 can rotate in the counterclockwise direction in FIG. 1 with respect to hand brake lever 14 around the pin 15, and also can move around and along the pin 15 relative to the plane of FIG. 1 by some amount so that the pawl portion of the adjusting lever 16 can move towards and away from the ratchet teeth of the adjusting nut 13. Namely, the adjusting lever 16 is mounted on a stem portion of the pin 15 with some amount of play or degree of freedom of movement in the direction of the thickness of the hand brake lever 14.
A projection 19 acting as means for restricting movement of the adjusting lever according to the present invention is formed on the adjusting lever 16, as shown in FIGS. 5a and 5 b, and projects generally on a line 18 passing through the stop 14a of the hand brake lever 14 and the center of the pin 15 and abuts with a flange or a head portion 15a of the pin 15. Thus, the projection 19 effectively restricts movement of the adjusting lever 16 with respect to the side surface of the hand brake lever 14 such that the adjusting lever 16 rotates around the line 18. Therefore, the pawl portion of the lever 16 can sufficiently move towards and away from the ratchet teeth of the adjusting nut 13 while the bent portion 16a of the lever 16 reliably engages with the stop 14a. Incidentally, the fork-shaped end of the second strut member 12 also engages with the hand brake lever 14 so that the brake shoes 5 and 6 can expand against the force of return springs 7 and 8 by operating the hand brake lever 14.
In assembling the adjusting lever 16 on the hand brake lever 14, the pin 15 is firstly inserted through an opening 16b of the adjusting lever 16 and is located to align with an opening 14b of the hand brake lever 14, and is forcibly but partially inserted into the opening 14b, as shown in FIG. 6. The clearance or play of the adjusting lever 16 in the direction of the thickness of the hand brake lever or the clearance δ' defined between the head portion 15a of the pin 15 and the hand brake lever 14 is larger than the normal clearance δ (as shown in FIG. 7), thus, it is possible to rotate the adjusting lever 16 with respect to the hand brake lever 14. The spring 17 can easily be mounted between the hand brake lever 14 and the adjusting lever 16 and, then, the adjusting lever 16 is rotated around the pin 15 against the force of the spring 17 so that the bent portion 16a of the adjusting lever 16 aligns with the stop 14a of the hand brake lever 14. By rockingly move the adjusting lever 16, the bent portion 16a can engage with the stop 14a.
Thereafter, the pin 15 is tightly inserted into the hand brake lever 14 as shown in FIG. 7 so that the normal clearance δ is left between the head portion 15a of the pin 15 and the hand brake lever 14. The projection 19 formed on the adjusting lever 16 abuts with the head portion 15a of the pin 15 so as to allow rocking movement of the adjusting lever 16 in the direction of the thickness of the hand brake lever 14 only around the line 18, thus, engagement between the bent portion 16a of the lever 14 and the stop 14a will not be accidentally released.
FIGS. 8, 9a and 9b show a modified form wherein projection 19 is formed on the pin 15. The projection 19 is located on a line connecting the center of the pin 15 with the stop 14a of the hand brake lever 14. FIGS. 9c and 9d show the process for forming the projection 19 on the pin 15. In FIG. 9c a pin 19' has been partially inserted into an opening 15a' formed in the head portion 15a of the pin 15. When the adjusting lever 16 and the spring 17 are assembled with the hand brake lever 14, the pin 19' is further pressed into the opening 15a' as shown in FIG. 9d to form a downwardly extending projection 19.
FIGS. 10a and 10b show another embodiment of the present invention wherein the projection 14c is formed on the hand brake lever 14 such that the projection 19 projects toward the adjusting lever 16 at a location generally on an extension of a line connecting the stop 14a and the center of the pin fitting within opening 14b of the hand brake lever 14.
FIGS. 11, 12a and 12b show a further modified form of the present invention, in which, a spacer having the form of conventional C-shaped clip formed of a sheet-like material or a rod-shaped member is interposed between the head portion 15a of the pin and the adjusting lever 16 so as to restrict movement of the adjusting lever in the direction of the thickness of the hand brake lever to a very small range such that the bent portion 16a of the adjusting lever 16 will not disengage from the stop 14a on the hand brake lever while the pawl portion (the lower end as viewed in FIG. 11) of the adjusting lever can move towards or away from the ratchet teeth of adjusting nut 13. In assembling the adjusting lever 16 with the hand brake lever 14 as illustrated in FIG. 11, firstly, the lever 16 is mounted on the lever 14 by means of the pin 15. At that time, there is sufficient clearance between the head portion 15a of the pin 15 and the lever 14 such that the lever 16 can freely rotate around the pin 15. Nextly, the spring 17 is mounted between levers 14 and 16 and the bent portion 16a of the lever 16 is located to engage with the stop 14a of the lever 14. Thereafter, the spacer 20 is inserted between the head portion 15a and the adjusting lever 16. The thickness of the spacer 20 is so determined that the adjusting lever can rockingly move in the direction of the thickness of the hand brake lever 14 by a small range so as to prevent accidental disengagement of the bent portion 16a from the stop 14a and to allow the pawl portion of the lever 16 to ride over the teeth of the adjusting nut 13 as desired, and so that when the spacer 20 is not mounted on the pin 15 the spring 17 can easily be assembled on levers 14 and 16.
FIGS. 13 and 14 show a modified form of the spacer 20. As shown in FIG. 14, a projection 19 is formed on the spacer 20, and the spacer 20 is mounted on the pin 15 and between the head portion 15a of the pin 15 and the adjusting lever 16, with the projection 19 being located generally along line 18 which extends between the center of the pin 15 and the stop 14a of the hand brake lever 14, similar to the embodiments of FIG. 4 to FIG. 9d inclusive. The projection 19 of the spacer 20 effectively restricts rocking movement of the adjusting lever 14 in a plane defined by the line 18 and the axis of the pin 15 to a small range while allowing rocking movement of the lever 14 around the line 18 by a relatively large range. Therefore, it is possible to afford a relatively large dimensional tolerance as compared with the embodiment of FIG. 11, thus reducing machining or assembling costs.
As described heretofore in detail, the shoe drum brake according to the present invention comprises an adjusting lever pivotally mounted on a hand brake lever for rotating an adjusting nut, and means for restricting rocking movement of the adjusting lever with respect to the hand brake lever in the direction of the thickness of the hand brake lever. Thus, one end portion of the adjusting lever which normally engages with a stop formed on the hand brake lever will not accidentally disengage from the stop, thereby reliably assuring the brake shoe clearance adjusting function. | An automatic brake shoe clearance adjusting device includes a first strut member having a threaded stem screw-threadingly engaging with an adjusting nut, a second strut member having a hollow portion for receiving the threaded stem and abutting with the adjusting nut, an adjusting lever mounted on a hand brake lever by a pin and cooperating with the adjusting nut, and a spring acting between the hand brake lever and the adjusting lever for urging the adjusting lever against a stop formed on the hand brake lever. There is provided, at least on a line passing through the center of the pin and the stop, an element for restricting movement of the adjusting lever in the direction of the axis of the pin. | 5 |
BACKGROUND OF THE INVENTION
This invention relates to polyoxazolidone polymers and a process for preparing same. More particularly, this invention relates to polyoxazolidone polymers containing relatively small proportions of trimerized polyisocyanates.
It is well known to react an epoxide with an isocyanate to form an oxazolidone. Such reactions are generally carried out in the presence of a catalyst. Typical catalysts for this reaction include lithium bromide, quaternary ammonium salts, tertiary amines, Lewis acids, such as aluminum chloride, complexes of these Lewis acids with a Lewis base, and similar materials.
In similar manner, polyoxazolidone polymers can be prepared by reacting a diepoxide (i.e. a compound having at least two oxirane groups) with a polyisocyanate (i.e. a compound having at least two isocyanate groups). However, whereas the reaction of a monoepoxide and a monoisocyanate to form an oxazolidone proceeds relatively cleanly and in good yield, the corresponding reaction between higher functionality epoxides and isocyanates results in the formation of substantial quantities of undesirable byproducts. The major by-products are polyethers prepared by the homopolymerization of the polyepoxide and isocyanurates formed by the trimerization of the polyisocyanate. Of these, the trimerization reaction is particularly disadvantageous since the trimerization leads to the formation of very high functionality materials which give rise to very highly crosslinked, brittle polymers. Unfortunately, the catalysts conventionally used in preparing polyoxazolidones do not selectively catalyze the oxazolidone reaction, and substantial quantities of isocyanurates are formed. Generally, the polyoxazolidone contains about 20 to 40 mole percent or more of isocyanurates.
For this reason, it would be desirable to provide a process whereby a polyepoxide and polyisocyanate are reacted to form a polyoxazolidone polymer containing relatively small quantities of trimerized isocyanates.
SUMMARY OF THE INVENTION
This invention is such an improved process for preparing polyoxazolidones.
In one aspect, this invention comprises an oxazolidone-containing polymer or polymer precursor which is a reaction product of a polyepoxide and a polyisocyanate, characterized in that said polymer or polymer precursor contains less than about 15 mole percent of isocyanurate groups. Such polymer, or a polymer derived from such precursor, exhibits improved thermal and mechanical properties compared to similar polymers containing a higher proportion of isocyanurate groups.
In another aspect, this invention is an improvement in a process by which a polyepoxide and a polyisocyanate are reacted to form an oxazolidone containing polymer or polymer precursor. This improvement comprises conducting said reaction in the presence of a catalytic amount of an organoantimony iodide catalyst. In such improved process, the oxazolidone forming reaction proceeds much more rapidly than the trimerization reaction of the polyisocyanate or the homopolymerization of the polyepoxide. As a result, the product polymer or polymer precursor contains a surprisingly small proportion of isocyanurates. In addition, the overall rate of reaction is substantially increased as compared to that achieved with conventional catalysts, thereby reducing the time and stringency of conditions required to form the desired product.
DETAILED DESCRIPTION OF THE INVENTION
In this invention a polyepoxide is reacted with a polyisocyanate in the presence of certain antimony catalysts to prepare a polyoxazolidone polymer or polymer precursor containing a low proportion of isocyanurate groups. This reaction is conducted in the presence of an organoantimony iodide catalyst. Suitable catalysts are as represented by the structure
R.sub.x SbI.sub.y
wherein R is as defined hereinafter, and x and y are each numbers from about 1 to 4, provided that x+y≦7. Preferably, the antimony is pentavalent, i.e. the oxidation state of the antimony atom is +5.
The antimony catalysts most preferred herein are are triorganoantimony di- or tetraiodides corresponding to the structure
R.sub.3 Sb(V)I.sub.n
wherein n is 2 or 4. Each of the groups R is independently aliphatic, cycloaliphatic, aromatic, alkyl or similar organic group which may contain hetero atoms or other substituent groups which are inert to the reaction of the polyepoxide and the polyisocyanate to form a polyoxazolidone polymer or polymer precursor. In the case of a polymer precursor, the substituent group is also advantageously inert to the reaction thereof to form a polymer. Suitable substituent groups include aryl-bonded halogen, alkoxy and the like.
Preferred as the R groups are aromatic groups having 12 or fewer carbon atoms such as phenyl, tolyl, naphthyl, o-, m- or p-halo-benzyl and the like; alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl and other alkyl groups having from about 4 to 12 carbon atoms as well as alkoxylated or halogenated derivatives thereof; benzyl and inertly substituted benzyl groups; and the like.
The preferred di- and tetraiodide catalysts are substantially equivalent in their activity and selectivity in the oxazolidone forming reaction. However, the tetraiodide is more preferred in making isocyanate-terminated polyoxazolidone polymer precursors because the products of the diiodide-catalyzed reaction tend to form small quantities of isocyanurates upon standing. The tetraiodide-catalyzed isocyanate terminated reaction products are significantly more stable.
Exemplary antimony catalysts useful herein include trimethylantimony diiodide, trimethylantimony tetraiodide, triethylantimony diiodide, triethylantimony tetraiiodide, triisopropylantimony diiodide, triisopropylantimony tetraiiodide, methyldiethylantimony diiodide methyldiethylantimony tetraiodide, tri-n-butylantimony diiodide, tri-n-butylantimony tetradiiodide, triphenylantimony diiodide, triphenylantimony tetradiiodide, tribenzylantimony diiodide, tribenzylantimony tetraiiodide, tri-n-hexylantimony di- or tetraiiodide and the like.
The preferred antimony catalyst is advantageously employed in relatively small amounts in the reaction. Typically from about 0.5 to about 20, preferably about 1 to about 5, and more preferably about 2 to about 3 moles of the antimony catalyst are employed in the reaction per 100 mole of the polyepoxide. Use of the catalyst in the preferred and more preferred ranges provides for minimal isocyanurate formation without using unnecessary amounts of catalyst.
The antimony catalyst is readily prepared by reacting the corresponding organoantimony compound (R x Sb) with iodine (I 2 ). When equimolar quantities thereof are employed, the diiodide is formed. Addition of a second mole of iodine forms the tetraiodide. Generally, the reaction of the iodide and the organoantimony compound is conducted in a solvent. Polyepoxides and polyisocyanates are suitable such solvents. The reaction of the organoantimony compound with iodine proceeds readily at ambient or elevated temperature. This reaction proceeds particularly well at the conditions of the polymerization of the polyepoxide and the polyisocyanate. Accordingly, it is possible, and generally preferable, to prepare the antimony catalyst in situ by charging the organoantimony compound and iodine to the polymerization vessel and carrying out the polymerization reaction and the catalyst-forming reaction simultaneously. The organoantimony compound used as a starting material is readily formed in the reaction of the corresponding organomagnesium halide and antimony trichloride or tribromide.
The polyepoxide used in this invention contains a plurality of epoxy, i.e. α,β-oxirane groups. Although said polyepoxide can have as many as 100 or more epoxy groups, it is highly preferred that the functionality of the polyepoxide be relatively low, i.e. from about 2 to about 10, more preferably about 2 to about 4, and most preferably about 2 to 3. Lower functionalities are preferred because they give rise to less highly crosslinked polymers, which tend to have better physical and thermal properties as well as being more easily processed. Diepoxides give rise to linear, thermoplastic polymers when reacted with a diisocyanate.
Among the polyepoxides usefully employed herein are those represented by the general structure ##STR1## wherein X is the residue of an active hydrogen-containing moiety after removal of said active hydrogen, R' is an organic polyradical and n is at least 2. n is preferably from about 2 to 4 more preferably about 2 to 3. Such polyepoxides are advantageously prepared by reacting a compound having a plurality of groups containing active hydrogen atoms with a halogen-containing oxirane such as epichlorohydrin or epibromohydrin.
In structure I, the group X is advantageously --O--, --NH--, ##STR2## or a similar group, wherein R 2 is inertly substituted lower alkyl or phenyl. Preferably, the group X is --O-- and the polyepoxide is one prepared in the reaction of a polyhydroxyl containing compound with a halogenated oxirane as discussed hereinbefore.
Exemplary polyepoxides include epoxy-terminated derivatives of bisphenols, such as are represented by the structure ##STR3## wherein each A is independently a lower alkylene group such as methylene, ethylene, isopropylidine and the like, --O--, --S--, ##STR4## and the like, each B is as defined by A, and/or --OCH 2 CHOHCH 2 O--, each R 5 is independently hydrogen, halogen or lower alkyl, and m is a number from about 0 to about 30, preferably 0 to about 10 and more preferably about 0.1 to about 3. In addition, derivatives of the materials represented by structure II in which one or more of the positions on the group A is substituted with an inert substituent such as halogen, aryl, alkyl and the like are also useful herein. Suitable such epoxides include the commercially available resinous reaction products of an epihalohydrin with the diverse bisphenols and halogenated bisphenols, particularly the reaction products of an epihalohydrin with bisphenol A or bisphenol F or halogenated derivatives thereof. These resins preferably have an average equivalent weight from about 155 to about 2000. Suitable such epoxy resins include those sold commercially as DER* 317, DER 330, DER 331, DER 332, DER 333, DER 337, DER 642U, DER 661, DER 662, DER 663U, DER 664, DER 664U, DER 667, DER 673MF, DER 542, DER 511-A80, DER 521-A75, and DER 599 epoxy resins, all available from The Dow Chemical Company. Also suitable are the corresponding aromatic glycidyl amine resins wherein the various ether linkages are replaced by --NH-- groups.
Also useful herein are the so called polynuclear phenol glycidyl ether derived resins.
Also suitable are the so-called epoxy phenol novolac resins and epoxy cresol novolac resins which can be represented by the structure ##STR5## wherein n is a number from about 0-20 and each R 3 is independently hydrogen, halogen, lower alkyl, aryl or aralkyl. Halogenated derivatives of such resins are also useful herein.
In addition, epoxy resins prepared by reacting an organic diene with an aromatic hydroxyl-containing compound and subsequently reacting the resulting product with an epihalohydrin, as are described in U.S. Pat. No. 4,390,680 to Nelson, are useful herein.
Suitable aliphatic epoxy resins include the hydrogenated derivatives of the foregoing aromatic epoxy resins, as well as those in which the group R' of Structure I is lower alkylene, especially ethylene and isopropylene, a dialkylene ether or a polyoxyalkylene group. Such resins are advantageously prepared by reacting an alkylene glycol or polyether polyol with an epihalohydrin. Examples of such resins include DER 732 and DER 736, both of which are available from The Dow Chemical Company.
Also useful are aliphatic epoxy resins prepared in reaction of cycloolefins with peracetic acid, as well as diglycidyl ethers of cyclic dicarboxylic acids.
The foregoing polyepoxide is reacted with a polyisocyanate in the presence of the aforedescribed antimony catalyst to form a polyoxazolidone. The polyisocyanate may be highly functional but preferably has the functionality of less than about 10, preferably about 2 to 4, and more preferably about 2 to 3.
Organic polyisocyanates which may be employed include aromatic, aliphatic and cycloaliphatic polyisocyanates and combinations thereof. Representative of these types are diisocyanates such as m-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, xylenediisocyanate, tetramethylxylene diisocyanate, isophorone diisocyanate, hydrogenated diphenyl methane diisocyanate, hydrogenated xylene diisocyanate, hexamethylene-1,6-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotolylene diisocyanate (and isomers), naphthalene-1,5-diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, diphenylmethane-4,4'-diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, and 3,3'-dimethyl-4,4'-diphenyl diisocyanate, the triisocyanates such as trifunctional polymethylene polyphenylisocyanates and tolylene-2,4,6-triisocyanate; and tetraisocyanates such as 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate and the like.
A crude polyisocyanate may also be used in the practice of the present invention, such as the crude toluene diisocyanate obtained by the phosgenation of a mixture of toluene diamines or the crude diphenylmethylene diisocyanate obtained by the phosgenation of crude diphenylmethylenediamine. The preferred undistilled or crude isocyanates are disclosed in U.S. Pat. No. 3,215,652.
Alternatively, an isocyanate-terminated prepolymer or quasi-prepolymer prepared by reacting an excess of a polyisocyanate with a polyol of low or high equivalent weight may be employed as the polyisocyanate herein.
The relative proportions of the polyepoxide and polyisocyanate employed control to a large extent the characteristics of the product polyoxazolidone. By using a stoichiometric excess of the polyisocyanate, an isocyanate-terminated polyoxazolidone polymer is prepared. Similarly, the use of an excess of the polyepoxide leads to the formation of epoxide terminated polymers. The use of excess amounts of the polyepoxide or polyisocyanate can also be used to control the molecular weight of the polymer, since larger excesses of either component tend to produce lower molecular weight polymers. Using substantially equivalent amounts of the polyepoxide and polyisocyanate provides a process where higher molecular weight polyoxazolidones can be formed. Thus, the relative amounts of polyepoxide and polyisocyanate employed may vary over a relatively wide range, such as for example 10:1 to 1:10, on a molar basis.
The oxazolidone-forming reaction is advantageously carried out by heating together the polyisocyanate and polyepoxide in the presence of the antimony catalyst described herein. In general, a reaction temperature from about 80° to about 180° C. is suitable. The optimum reaction temperature depends somewhat on the particular polyisocyanate employed. Aromatic polyisocyanates which trimerize relatively slowly, such as diiphenylmethane diisocyanate are preferably reacted at a temperature from about 80° to 120° C. Those such as toluenediisocyanate which more rapidly trimerize are preferably reacted at a temperature from about 120° to 175° C. Aliphatic polyisocyanates are also preferably reacted at about 120°-175° C. It has been found that the use of significantly higher or significantly lower temperatures than described in this paragraph tends to promote the formation of higher amounts of isocyanurate groups. It will also be apparent that changes in temperature and amount of catalyst will affect the rates of the reaction. Under the conditions of temperature and amount of catalyst described herein, the reaction is typically completed in from about 5 minutes to 8 hours, and more typically from about 5 minutes to 4 hours.
The oxazolidone forming reaction is generally carried out neat, but may if desired be carried out in the presence of a suitable diluent or solvent for the reactants. Ketones, aromatic hydrocarbons or other solvents which are inert to the polymerization reaction are suitable. Solvents which only weakly or negligibly coordinate with the catalyst are preferred since they tend to inhibit the oxazolidone forming reaction. The reaction can be run batch-wise or continuously, as in a coil reactor.
Isocyanate-terminated oxazolidone polymer precursors prepared according to this invention can be reacted with a polyol, polyamine or other material containing a plurality of active hydogen atoms to form a polyurethane or polyurea. Generally speaking, the isocyanate-terminated oxazolidone polymer precursor is used in the same manner as conventional polyisocyanates to prepare a polyurethane. The use of the oxazolidone polymer or precursor does not generally require any special processing conditions, and any of the conventional techniques for preparing polyurethanes are suitably used. In particular, polyurethane films, elastomers, structural foams, rigid foams, flexible foams and the like all can be prepared with the oxazolidone polymer or precursor of this invention. Techniques for preparing polyurethane polymers which may be employed in conjunction with the isocyanate-terminated oxazolidone polymer precursor include, for example, those described in U.S. Pat. Nos. 3,821,130, 3,888,803, 4,280,007, 4,294,934 and 4,374,210.
Similarly, the epoxy terminated oxazolidone polymer precursor can be reacted in conventional manner with epoxy curing agents to form epoxy coatings, resins, adhesives and the like. Epoxy curing agents include diamines and other compounds containing two or more groups which react with epoxy groups to form a bond thereto. Exemplary epoxy curing agents and methods for preparing cured epoxy resins are described, for example, in Lee and Neville, Handbook of Epoxy Resins, McGraw-Hill Book Co., New York (1967).
Those polyurethane polymers and cured epoxy resins prepared using the oxazolidone polymer or precursor in this invention exhibit excellent thermal properties. In addition, such polymers exhibit good chemical and solvent stability. Further, these polymers have generally good impact properties as compared to conventional oxazolidones polymers.
In preparing polyurethanes or cured epoxy resins according to this invention additives such as fillers, fibers, antioxidants, internal mold release agents, pigments, surfactants, catalysts, blowing agents and the like can all be employed in conventional manner.
The following examples are provided to illustrate the invention but not to limit the scope thereof. All parts and percentages are by weight unless otherwise indicated.
EXAMPLES 1 AND 2
In a suitable flask are charged 6.6 grams of a 174 equivalent weight bisphenol A/epichlorhydrin epoxy resin, 15.4 grams of toluenediisocyanate, 0.2 grams triphenyl antimony and 0.39 grams of iodine. With stirring, the mixture is heated to 150° C. and held at this temperature for 10 minutes. The reaction mixture is then cooled and analyzed by infrared spectroscopy and gel permeation chromatography. These tests indicate the formation of oxazolidone rings, the complete disappearance of the epoxide groups and the substantial absence of isocyanurate groups. Nuclear magnetic resonance spectroscopy verifies the existence of only very small quantities of isocyanurate groups.
This experiment is repeated, this time employing 1.0 gram of the epoxy resin, 9.0 grams of toluene diisocyanate and as the catalyst 0.3 milliliters of tri-n-butylantimony and 0.3 g iodine. The reaction is conducted for 8 min. at 150° C. The analysis of this product again shows the formation of essentially no trimerized isocyanurates.
EXAMPLES 3 TO 7
Isocyanate terminated oxazolidone precursors are prepared from a brominated bisphenol A/epichlorohydrin epoxy resin having an equivalent weight of about 325, toluene diisocyanate (TDI) or diphenylmethane diisocyanate (MDI) and an triorganoantimony di- or tetraiodide catalyst as indicated in the following table. The reaction conditions are also specified in the following table. All of these reactions produce isocyanate terminated oxazolidone polymer precursors containing insignificant quantities of trimerized isocyanates.
TABLE I__________________________________________________________________________Example Catalyst ReactionNo. Starting Material Volume (ml) Type Amount Temp (°C.) Time (min)__________________________________________________________________________3 30 wt % epoxy resin in TDI 25 ml Ph.sub.3 SbI.sub.4 0.34 g .sup. 150-175° 104 30 wt % epoxy resin in MDI 50 ml Ph.sub.3 SbI.sub.4 0.80 g 95 305 21 wt % epoxy resin in MDI 25 ml Ph.sub.3 SbI.sub.2 0.19 g 85-115 206 20 wt % epoxy resin in MDI 25 ml Ph.sub.3 SbI.sub.4 0.27 g 95 207 40 wt % epoxy resin in MDI 50 ml Ph.sub.3 SbI.sub.4 1.08 g 95-135 10__________________________________________________________________________
EXAMPLE 8
In a test tube are placed 1 gram of a 3.5 functional epoxy phenol novolac resin, 9 grams toluene diisocyanate, 0.02 gram triphenyl antimony and 0.03 gram iodine. The test tube and its contents are heated to 150° C. for 20 minutes. Infrared analysis of the resulting isocyanate-terminated polymer precursor verifies the formation of oxazolidone groups, but does not reveal any detectable isocyanurate.
EXAMPLE 9
In a test tube are reacted at 150° C. for 20 minutes, 1 gram of a 320 equivalent weight epoxy-terminated poly(propylene oxide), 9 gram toluene diisocyanate 0.02 gram triphenyl antimony and 0.03 gram iodine. Infrared analysis verifies the existence of oxazolidone groups in the product, but no isocyanurates are detected. The resulting isocyanate-terminated polymer precursor has an average molecular weight of about 1000.
EXAMPLE 10
To one equivalent (163.3 g) of a triglycidyl ether of 4,4',4"-trihydroxy triphenyl methane are added, at 95° C., 0.44 g triphenylantimony and 0.64 g iodine. Isophorone diisocyanate, 11.1 g (0.1 equivalent) is then added and the mixture heated to 150° C. After reacting for six hours at 150° C., the product epoxy-terminated polymer precursor contains 88 mole percent oxazolidone and 12 mole percent residual carbamate groups, with essentially no trimer. The equivalent weight of the product is about 206.
To 80 g of the polymer precursor is added 19.2 g methylene dianiline to form a cured epoxy resin. A film cast from the curing resin exhibits excellent thermal stability.
EXAMPLE 11
To one equivalent (163.3 g) of a triglycidyl ether of 4,4',4"-trihydroxy triphenyl methane are added, at 110° C., 0.44 g of triphenylantimony and 0.64 g iodine. Toluene diisocyanate (2.68 g, 0.031 eq) is added and the reaction mixture is heated at 105° C. for 20 minutes. Hexamethylene diisocyanate (HMDI) (3 ml, ˜0.035 eq) is then added and allowed to react for ten minutes, at which time an additional 0.11 eq of HMDI are added. The mixture is then permitted to react an additional 6 hours at 110° C. The product epoxy-terminated polymer precursor contains 3 mole percent isocyanurate groups. | This invention is an improvement in a process by which a polyepoxide and a polyisocyanate are reacted to form an oxazolidone containing polymer or polymer precursor. This improvement comprises conducting said reaction in the presence of a catalytic amount of an organoantimony iodide catalyst. In such improved process, the oxazolidone forming reaction proceeds much more rapidly than the trimerization reaction of the polyisocyanate or the homopolymerization of the polyepoxide. As a result, the product polymer or polymer precursor contains a surprisingly small proportion of isocyanurates. In addition, the overall rate of reaction is substantially increased as compared to that achieved with conventional catalysts, thereby reducing the time and stringency of conditions required to form the desired product. | 2 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This is a continuation-in-part of International Application PCT/FR2006/000360, filed Feb. 16, 2006, the disclosure of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to the field of articles intended for the preparation and the cooking of food and more particularly the cooking surface of these articles in contact with food to be treated.
[0003] For many years, great efforts have been developed in order to facilitate the daily preparation of meals. Among the notable progress, coatings containing fluorocarbonated polymers as a non-stick coating in kitchen utensils quickly developed since the end of 1950. Such coatings are universally known since the process presented in the patent FR 1120749 allowed a sure fixing of such coatings on various metals, such as aluminum.
[0004] However, such coatings remain fragile and resist scratching poorly. Thus, clever ways were developed in order to mechanically reinforce the layer on its support. Numerous improvement patents describe methods and means making it possible to increase the scratch resistance of such coatings, by acting on the coating and/or the substrate. Despite everything, such coatings remain sensitive to the repeated use of sharpened or pointed metallic materials, such as knives or forks.
[0005] In parallel, developments were carried out on mechanically resistant surfaces on which attempts were made to improve the ease of cleaning. Deposits of metal, such as chrome plating on stainless steel, quasi-crystals, or nonmetals (silicates, . . . ) thus appeared. The results remain however disappointing, in particular in comparison with coatings of the PTFE type.
[0006] There is also known, from the document FR 2 848 797, a cooking surface composed in major part of metallic zirconium, surface which has a very good hardness, since the layer is nitrided or carburized, presenting satisfactory ease of cleaning but without attaining the ease of cleaning of layers of the PTFE type.
BRIEF SUMMARY OF THE INVENTION
[0007] The present invention aims at remedying the above mentioned disadvantages of the prior art, by proposing a cooking surface with improved ease of cleaning characteristics, durably presenting a reduction of the adherence of food during cooking, corrosion resistance, while having a good mechanical resistance, and in particular a high hardness.
[0008] The present invention is achieved by a food cooking surface for a kitchen utensil or cooking appliance, characterized in that this cooking surface is a compound developed starting from an alloy whose two principal components are zirconium and cobalt.
DETAILED DESCRIPTION OF INVENTION
[0009] Metal alloys containing cobalt are known for their good wear resistance.
[0010] Surprisingly, it has been noted, during tests, that alloys, based on cobalt and zirconium, also presented properties of ease of cleaning when such surfaces were used as a cooking surface and when foodstuffs remained attached to the surface, for example after a calcination of the cooked products. This ease of cleaning can be expressed by the possibility of easily removing elements carbonized on the cooking surface.
[0011] This ease of cleaning is completed, at the time of production of the compound, by an increase in hardness of said compound.
[0012] Moreover, the use of zirconium makes it possible to obtain very varied colors of the coating, which it is not possible to obtain only with cobalt. It is then possible to define a coating color making it possible to identify clearly, for the user, that the coating used is specific and corresponds to an “easy to clean” coating. One can even envision connecting the various colors to the results of the tests of ease of cleaning of cooking surfaces according to the food, so that this color code makes it possible for users to easily identify the good cooking surface for cooking a given type of food (eggs, fish, meat, . . . ).
[0013] Advantageously, the alloy essentially contains zirconium, cobalt and chromium. Chromium and cobalt alloys, such Alacrite®, are generally known for their exceptional resistance to corrosion (primarily by chromium), and their good wear resistance (primarily by cobalt). They are primarily used, in mechanics, for interior lining of piston bearings. Certain slight differences are used in the medical field for the fabrication of implants and prostheses.
[0014] The presence of chromium thus makes it possible to reinforce the resistance of the cooking surface to chemical agents and corrosion.
[0015] The development of the cooking surface has a step of deposition of the components, in an appropriate thickness, on a substrate, followed by a nitriding of the components. Such a nitriding, primarily of the zirconium, makes it possible to increase considerably the hardness of the cooking surface, while bringing diversity to the colors obtained, primarily by exploiting the stoichiometry of zirconium nitride.
[0016] Advantageously, the development of said surface has a step of carburization or carbonitriding of the surface after the stage of nitriding, making it possible to further increase the surface hardness of the layer, to make it almost insensitive to scratching, without altering its ease of cleaning properties. In addition, the nitriding step allows a good adherence of the carbide or carbonitride layer of Co/Cr/Zr. It is indeed known in addition, that it is very difficult to cause a layer of carbide or carbonitride to adhere to a substrate of the aluminum or stainless steel type without an intermediate layer. In addition, the deposition rate of a layer of carbide is definitely higher than the deposition rate of a layer of nitride.
[0017] The gradient of the composition thus obtained combines the properties of ease of cleaning of Co/Cr alloy surfaces with the high potential of hardening, of coloring and of corrosion resistance of the layers of nitride, carbide and carbonitride of zirconium. The hardnesses obtained can go up to 2500 Vickers for a zirconium carbide.
[0018] According to a preferred mode of preparation, the deposition of the components on a substrate will be a physical deposition in vapor phase from one or several massive targets. In this latter case the target can be obtained by assembly on a copper substrate of one or more sheets or plates of material having the desired composition, said sheets or plates being obtained either by powder sintering or thermal projection of powder, or resulting from casting. These targets thus constitute the source of the materials that will be deposited on the cooking surface. Generally, all the techniques of physical deposition in vapor phase can be used.
[0019] This implementation has the advantage of using little material and of being able to adjust a small thickness of material on the substrate in order to produce the cooking surface. This deposition technique makes it possible, in addition, to obtain deposits in strong cohesion with the substrate on which they are deposited. The risks of separation of the deposit during use are thus minimized.
[0020] The substrate can be composed of one or more metal sheets of following materials: aluminum, stainless steel, cast iron, steel, copper.
[0021] Other advantages resulting from tests will appear from a reading of the description that will follow, relating to an illustrative example of the present invention given as a nonlimiting example.
[0022] The various examples of realization of the invention relate to a deposition, on a stainless steel substrate, by PVD, of a Co/Zr alloy by using the four eutectic points of the binary diagram of Co/Zr. The percentage, in weight, of zirconium, for these four eutectics, is thus 14%, 57.5%, 74% and 85%. One face of this deposit has undergone a mechanical surface treatment, before the performance of tests, in order to make it similar to other cooking surfaces so that the tests of evaluation of the ease of cleaning such a surface, in a domestic cooking use, can be compared. The deposited thickness is of the order of several microns, e.g. 3-4 microns.
[0023] After deposition of the components, the layer underwent a nitriding, then a carbonitriding. The longer the phase of carbonitriding, the more the surface will be hard.
[0024] The system for evaluation of the ease of cleaning makes it possible to quantify the capacities of a cooking surface to return its original appearance after use. This system of evaluation comprises the following steps:
the surface is locally covered with a food mixture of known composition, this mixture is carbonized in a furnace under defined conditions, for example 210° C. during 20 minutes, after cooling, the surface is put to soak for a controlled time in a mixture of water and detergent, an abrasive pad is then applied under a defined constraint using an apparatus to abrade (plynometer) the soiled surface in a back and forth movement during a given number of cycles, the percentage of the correctly cleaned surface is noted and characterizes the ease of cleaning of the cooking surface.
[0030] The tests carried out on various types of surface thus make it possible to comparatively evaluate the quality of the surfaces as regards their ease of cleaning. Of course, the tests are carried out by respecting the same parameters for each step of the system of evaluation: the same food mixture, the same surface of application of the food mixture, the same temperature of carbonization, . . . .
[0031] The following comparative table shows the results obtained on three different cooking surfaces, namely polished stainless steel, quasi-crystals, and the cobalt/zirconium alloy according to one of eutectics cited, deposited on stainless steel, nitrided then carbonitrided, as previously described, after polishing, in a severe test with a food composition containing milk and rice considered to be difficult to clean once carbonized. Such a test thus makes it possible to highlight well the differences between quality of cleaning of the surfaces.
Polished Co/Zr alloy stainless Quasi- nitrided/carbonitrided steel crystals on stainless steel Quantity of carbonized 50% 60% 90% residue removed
[0032] The table shows without ambiguity the very favorable results obtained with the Co/Zr alloy deposited on stainless steel, and in particular the results compared with other cooking surfaces. Other tests carried out on an aluminum base show similar results. The ease of cleaning for an alloy according to the invention, as set forth in the table above, is substantially the same for any of the eutectic composition percentages cited earlier herein.
[0033] It should be noted that the number of cycles of abrasion on the plynometer was fixed at 18. This reduced number of cycles highlights well the quality of ease of cleaning of the surface according to the invention since there remains not more than 10% of the surface soiled after 18 back and forth passes of the abrasive pad.
[0034] Repetitive tests after complete cleaning of the surface show that the ease of cleaning of the alloy presented is not altered.
[0035] When the implementation of the invention implies the use of a substrate, this latter is then composed of one or more metal sheets of the following materials: aluminum, stainless steel, cast iron, steel, copper.
[0036] According to certain preferred embodiments, the compound, or ally, according to the invention could be composed of 50% to 90% Zr, with the balance being Co or Co and Cr. Nitriding can be performed with N 2 as the reactant and carbonitriding can be performed with N 2 +CH 4 or C 2 H 2 gas as the reactant, the reactant preferably being in a stoichiometric quantity.
[0037] Typically, the PVD process is carried out at low pressure, equal to or less than 1 Pa, and at a temperature in the range of 100° C. to 300° C. Higher temperatures may be employed, for example to modify the microstructure of the layer forming the cooking surface, for example to reduce porosity.
[0038] Layers providing cooking surfaces according to embodiments of the invention may include nitrides or carbonitrides of Zr, Co, Cr in the form of a binary or ternary alloy.
[0039] The conditions for fabricating a coating according to the present invention depend on the characteristics of the deposition apparatus employed and, for a given apparatus and given coating composition, can be readily determined by those skilled in the art. | Food cooking surface for a kitchen utensil or cooking appliance, constituted by the surface of a compound fabricated starting from an alloy whose two principal components are zirconium and cobalt. | 2 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a § 371 application of PCT/US92/04973, filed Jun. 19, 1992, which claims priority of U.S. patent application 07/731,577, filed Jul. 17, 1991, now abandoned.
BACKGROUND OF THE INVENTION
The present invention is directed to neuroprotective (antiischemic excitatory amino acid receptor blocking) 2-(4-hydroxypiperidino)-1-alkanol derivatives defined by formula (I) below; pharmaceutically acceptable salts thereof; a method of using these compounds in the treatment of stroke, traumatic injury to the brain and spinal cord, and neuronal degenerative diseases including (but not limited to) senile dementias such as Alzheimer's disease, Huntington's disease and Parkinson's disease in mammals, especially humans; and to certain intermediates therefor.
Ifenprodil (A) is a racemic, so-called dl-erythro compound having the relative stereochemical formula
which is marketed as a hypotensive agent, a utility shared by a number of close analogs. Carron et al., U.S. Pat. No. 3,509,164; Carron et al., Drug Res., v. 21, pp. 1992-1999 (1971). More recently, ifenprodil has been shown to possess antiischemic and excitatory amino acid receptor blocking activity. Gotti et al., J. Pharm. Exp. Therap., v. 247, pp. 1211-21 (1988); Carter et al., loc. cit., pp. 1222-32 (1988).
See also French Patent 2546166 and EPO publication EP-A1-351282, published Jan. 17, 1990. A goal, substantially met by the present invention, has been to find compounds possessing neuroprotective activity in good measure, while at the same time having lowered or no significant hypotensive effect.
Certain 1-phenyl-3-(4-aryl-4-acyloxy-piperidino)-1-propanols have also been reported to be useful as analgesics, U.S. Pat. No. 3,294,804; 1-[4-(amino- and hydroxy-alkyl)phenyl]-2-(4-hydroxy-4-tolylpiperazino)-1-alkanols and alkanones have been reported to possess analgesic, antihypertensive, psycho-tropic or antiinflamatory activity, Japanese Kokai 53-02,474 (CA 89:43498y; Derwent Abs. 14858A) and 53-59,675 (CA 89:146938w; Derwent Abs. 48671A); and 2-piperidino-1-alkanol derivatives have been reported to be active as antiischemics, EP 398,578-A and Der 90-350,327/47.
SUMMARY OF THE INVENTION
The present invention is directed to compounds of the formula
wherein R 1 , R 2 and R 3 are each selected from the group consisting of hydrogen, alkyl having 1 to 6 carbons,
phenyl and substituted phenyl, wherein the substituent on said substituted phenyl is selected from the group consisting of hydroxy, alkyl having 1 to 4 carbons, chloro, bromo, fluoro, trifluoromethyl, amino, nitro and alkoxy having 1 to 4 carbons;
or R 1 and R 2 when taken together form a methylene, ethylene, propylene or butylene group;
m is 0 to 2;
n is 1 or 2;
X and Y are each selected from the group consisting of hydrogen, chloro, bromo, fluoro, trifluoromethyl, alkoxy having 1 to 4 carbons, alkyl having 1 to 4 carbons, hydroxy, amino, nitro and substituted phenoxy, wherein the substituent on said substituted phenoxy is selected from the group consisting of hydrogen, hydroxy, alkyl having 1 to 4 carbons, chloro, bromo, fluoro, trifluoromethyl, nitro, amino and alkoxy having 1 to 4 carbons;
M and Q are each selected from the group consisting of hydrogen, hydroxy, amino, chloro, bromo, fluoro, trifluoromethyl, nitro, alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons, N,N-dialkylamino having 1 to 4 carbons in each of said alkyls, N-alkylamino having 1 to 4 carbons, NHCOR 4 , NHCOOR 5 and NHSO 2 R 6 ;
wherein R 4 is selected from the group consisting of hydrogen, alkyl having 1 to 6 carbons, phenyl and substituted phenyl, wherein the substituent on said substituted phenyl is selected from the group consisting of hydroxy, chloro, bromo, fluoro, trifluoromethyl, amino, nitro, alkyl having 1 to 4 carbons and alkoxy having 1 to 4 carbons;
and wherein R 5 and R 6 are each selected from the group consisting of alkyl having 1 to 6 carbons, phenyl and substituted phenyl, wherein the substituent on said substituted phenyl is selected from the group consisting of hydroxy, chloro, bromo, fluoro, trifluoromethyl, amino, nitro, alkyl having 1 to 4 carbons and alkoxy having 1 to 4 carbons;
or M and Q when taken together form a divalent radical Z, wherein Z is selected from the group consisting of
wherein R 7 and R 8 are each selected from the group consisting of hydrogen and methyl;
and the pharmaceutically acceptable acid addition salts of these compounds.
The expression “pharmaceutically acceptable acid addition salts” is intended to include but is not limited to such salts as the hydrochloride, hydrobromide, hydroiodide, nitrate, hydrogen sulfate, dihydrogen phosphate, mesylate, maleate, and succinate. Such salts are conventionally prepared by reacting the free base form of the compound (I) with an appropriate acid, usually one molar equivalent, and in a solvent. Those salts which do not precipitate directly are generally isolated by evaporation of the solvent and/or addition of a non-solvent followed by filtration.
A preferred group of compounds of the present invention are those in which N and Q form a radical Z, wherein Z is
R 1 and R 2 are hydrogen and R 3 is methyl and the compounds possess 1 r* , 2 s* or erythro relative stereochemistry at the 1- and 2-positions of the propanol chain, i.e.,
A second preferred group of compounds of this invention are those in which N and Q form a radical Z, wherein Z is
R 1 and R 2 are hydrogen and R 3 is methyl and the compounds possess 1 s* , 2 s* or threo relative stereochemistry at the 1- and 2- positions of the propanol chain, i.e.,
The present invention is also directed to pharmaceutical compositions containing a compound of the invention of formula I, and to methods of treating a mammal, particularly human subject, suffering from a central nervous disorder, which comprises administering to said mammal a neuroprotective effective amount of a compound of the formula (I). Said compositions and methods are particularly valuable in the treatment of traumatic injury to the brain and spinal cord, stroke, Alzheimer's disease, Parkinson's disease, Huntington's disease and related disorders of the central nervous system.
The present invention is further directed to intermediate compounds of the formula
wherein
R 2 and R 3 are each selected from the group consisting of hydrogen, alkyl having 1 to 6 carbons, phenyl and substituted phenyl, wherein the substituent on said substituted phenyl is selected from the group consisting of hydroxy, alkyl having 1 to 4 carbons, chloro, bromo, fluoro, trifluoromethyl, amino, nitro and alkoxy having 1 to 4 carbons;
m is 0 to 2;
n is 1 or 2;
X and Y are each selected from the group consisting of hydrogen, chloro, bromo, fluoro, trifluoromethyl, alkoxy having 1 to 4 carbons, alkyl having 1 to 4 carbons, hydroxy, amino, nitro and substituted phenoxy, wherein the substituent on said substituted phenoxy is selected from the group consisting of hydrogen, hydroxy, alkyl having 1 to 4 carbons, chloro, bromo, fluoro, trifluoromethyl, nitro, amino and alkoxy having 1 to 4 carbons;
M and Q are each selected from the group consisting of hydrogen, hydroxy, amino, chloro, bromo, fluoro, trifluoromethyl, nitro, alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons, N,N-dialkylamino having 1 to 4 carbons in each of said alkyls, N-alkylamino having 1 to 4 carbons, NHCOR 4 , NHCOOR 5 and NHSO 2 R 6 ;
wherein R 4 is each selected from the group consisting of hydrogen, alkyl having 1 to 6 carbons, phenyl and substituted phenyl, wherein the substituent on said substituted phenyl is selected from the group consisting of hydroxy, chloro, brono, fluoro, trifluoromethyl, amino, nitro, alkyl having 1 to 4 carbons and alkoxy having 1 to 4 carbons;
and wherein R 5 and R 6 are each selected from the group consisting of alkyl having 1 to 6 carbons, phenyl and substituted phenyl, wherein the substituent on said substituted phenyl is selected from the group consisting of hydroxy, chloro, bromo, fluoro, trifluoromethyl, amino, nitro, alkyl having 1 to 4 carbons and alkoxy having 1 to 4 carbons;
or N and Q when taken together form a divalent radical Z, wherein Z is selected from the group consisting of
and wherein R 7 and R 8 are each selected from the group consisting of hydrogen and methyl.
Depending on the precise values of R 1 , R 2 and R 3 , the compounds of formula (I) can have one or two asymmetric centers, and can therefore exist in various isomeric forms. All such isomers are within the scope of this invention. The individual isomers can be separated by classical methods well-known to those skilled in the art.
DETAILED DESCRIPTION OF THE INVENTION
The compounds of the present invention, having the formula (I) defined above, are readily and generally prepared by reaction of chloro compound (II) with piperidine (III), followed by reduction of the resulting ketone (IV) to an alcohol as detailed below.
The precursor ketones are generally initially prepared with —OH and —NH 2 substituent groups in protected form, i.e., as —OA 1 , or —NHA 2 groups in the compounds of formula (IV). A 1 and A 2 are defined below. Such protected ketones are generally formed by reacting an appropriately substituted 2-halo-1-alkanone (II) with an appropriately substituted piperidino derivative (III), e.g.,
Reaction of compound (II) with compound (III) is carried out under conditions typical of nucleophilic displacements in general. Where the two reactants are about equivalent in availability, close to substantially molar equivalents may be used; although when one is more readily available, it is usually preferred to use that one in excess, in order to force this bimolecular reaction to completion in a shorter period of time. The reaction is generally carried out in the presence of at least 1 molar equivalent of a base, the piperidine derivative itself, if it is readily available, but more usually a tertiary amine which is at least comparable in base strength to the nucleophilic piperidine; and in a reaction inert solvent such as ethanol. If desired, the reaction is catalyzed by the addition of up to one molar equivalent or more of an iodide salt (e.g., NaI, KI). Temperature is not critical, but will generally be somewhat elevated in order to force the reaction to completion within a shorter time period, but not so high as to lead to undue decomposition. A temperature in the range of 50-120° C. is generally satisfactory. Conveniently, the temperature is the reflux temperature of the reaction mixture.
As used in the preceding paragraph, and elsewhere herein, the expression “reaction inert solvent” refers to any solvent which does not interact with starting materials, reagents, intermediates or products in a manner which adversely affects the yield of the desired product.
If desired, those ketone intermediates (IV) having OH or NH 2 groups in protected form (OA 1 or NHA 2 ), can be deprotected at this stage by conventional methods.
For example when A 1 is triisopropylsilyl or tertbutyldimethylsilyl, the protecting group is conveniently removed by reaction with tetrabutylammonium fluoride (generally, substantially 2 molar equivalents) in a reaction inert solvent such as tetrahydrofuran. When A 1 is benzyl or A 2 is benzyloxycarbonyl, the protecting group will generally be removed by conventional hydrogenolysis over a noble metal catalyst in a reaction inert solvent, e.g., using 10% Pd/C as catalyst, preferable at low pressures (e.g., 1-10 atmospheres) and temperatures (e.g., 20-750° C.) and generally in a reaction inert solvent such as methanol.
Generally, the ketone intermediates (IV) are conveniently converted to corresponding alcohols by one of two conventional reduction methods, to selectively produce either the threo compounds or the erythro compounds of formula (I).
As used in the preceding paragraph, and elsewhere herein, the term “threo” or 1 r* , 2 s* refers to the relative stereochemistry at the 1- and 2- positions of the propanol chain, i.e.,
and the term “erythro” or 1 r* , 2 s* refers to the relative stereochemistry at the 1- and 2-positions of the propanol chain, i.e.,
To obtain the desired erythro compounds of formula (I) the corresponding ketone intermediates (IV) are conveniently reduced with potassium borohydride, usually in excess (e.g. greater than 5 mole equivalents), in the presence of glacial acetic acid in a protic solvent such as ethanol, generally at a temperature range of 15-250° C.
To obtain the desired threo compounds of formula (I) the corresponding ketone intermediates (IV) are conveniently reduced with sodium borohydride, usually in excess (e.g. greater than 5 mole equivalents), in a protic solvent such as ethanol, generally at a temperature range of 15-25° C. The resulting reaction mixture is chromatographed on a silica gel column to obtain the said threo compounds of formula (I).
Any protecting groups which are still in place after ketone reduction are then removed according to standard methods described above.
The starting materials and reagents required for the synthesis of the compounds of the present invention are readily available, either commercially, according to literature methods, or by methods exemplified in Preparations below.
The present compounds of the formula (I) possess selective neuroprotective activity, based upon their antiischemic activity and ability to block excitatory amino acid receptors, while at the same time having lowered or no significant hypotensive activity. The antiischemic activity of the present compounds is determined according to one or more of the methods which have been detailed previously by Gotti et al. and Carter et al. cited above, or by similar methods.
The ability of the compounds of the present invention to block excitatory amino acid receptors is demonstrated by the drugs ability to rescue fetal rat neurons in culture which have been exposed to the excitotoxic amino acid glutamate. The following is a typical procedure.
Part I: Cell Isolation:
Embryos at 17 days gestation are removed from rats and placed into Tyrode's solution. The brainsiare then removed and placed into fresh Tyrode's solution. Using fine iris knives, the hindbrain and thalamus are removed. The forebrain is then separated into two hemispheres. Next, the meninges are removed gently. The hippocampus appears as a darkened folded area on the inner side of the cortex edge. The hippocampus is carefully cut away from the rest of the tissue and placed in a separate corner of the dish. When all of the dissection is completed, the hippocampal tissue reserved in the corner is minced into 1 mm pieces. These pieces are removed, using a Pasteur pipette and placed into a sterile tube. The Tyrode's solution is aspirated off gently and Calcium-Magnesium Free Tyrode's solution is added. The tissue is washed 3 times with Calcium-Magnesium Free Tyrode's solution. This final wash is incubated 15 minutes at 37 degrees Centigrade. The buffer is again removed and replaced with 1 ml fresh Calcium-Magnesium Free Tyrode's solution. Trypsin is now added at 0.1% (100 μl of a 10 mg/ml stock sterile solution). The tube is incubated for 1 hour at 37 degrees Centigrade. After trypsin incubation the tissue is washed with serum containing medium in order to stop the action of the trypsin. The tissue is resuspended in 1 ml of fresh medium and triturated with a fine bore Pasteur pipette.
Cells are then counted using a hemocytometer. Cells are then seeded onto a 96-well Falcon Primeria tissue culture plates at 75000 cells per well in complete medium. Complete medium is composed of Minimal Essential Medium (MEN) with Earle's salts, 10% Fetal Calf Serum (Hyclone), 10% Equine Serum, L-glutamine (2 mM), Penicillin-Streptomycin (100 U per ml) and Glucose (to make the final concentration 21 mM a 100× stock containing 27.8 g per 100 ml is prepared). The plates are fed on day 3 with fresh medium. Then on day 6 cytosine arabinoside at 10 μm is added to the cultures with fresh medium. Then two days later the cytosine arabinoside is removed and replaced with Maintenance medium, which is complete medium minus the Fetal Calf Serum. The plates are then fed twice a week. Three weeks from the time of dissection the plates are used in the glutamate toxicity experiments, in order to insure proper development of the neurons in culture.
Part 2: Glutamate Treatment and Post-Glutamate Drug Addition:
After three weeks in culture, the medium is removed from the cells and the cells are washed three times in chloride free controlled salt solution (CSS-Cl). CSS-Cl contains 69 mM Na 2 SO 4 , 2.67 mM K 2 SO 4 , 0.33 mM NaHPO 4 , 0.44 mM KH 2 PO 4 , 1 mM NaHCO 3 , 1 mM MgSO 4 , 10 mM HEPES (N-2-hydroxyethylpiperazine-N 1 -2-ethanesulfonic acid), 22.2 mM glucose, and 71 ml sucrose at pH 7.4. After washing, glutamate is added at 1 to 3 mM in CSS-Cl buffer with appropriate control wells containing buffer without glutamate. The plates are incubated at 37 degrees celsius for 15 to 20 minutes. Following glutamate incubation, the plates are washed with serum free medium twice. The test drugs are prepared at the appropriate concentrations in serum free medium and added to the corresponding wells of the microtiter plate (100 μl per well). Negative control wells receive serum free medium with no drug. Several glutamate treated wells are also given serum free medium with no drug to serve as positive controls. The plate is incubated overnight at 37 degrees celsius and the following day viability is assessed using the LDH (lactate dehydrogenase) and MTT (methyl thiotetrazolinium) assays.
Part 3: Assessment of Cell Viability:
The 100 μl of medium from each plate is removed and transferred to a clean plate to be assayed for the amount of LDH released. Then 100 μl per well of MTT solution is added. This MTT solution is prepared by adding 10 μl of MTT stock (5 mg/ml in PBS, phosphate buffered saline) for every 100 μl serum free medium. Plates are incubated at 37 degrees for 4 to 6 hours. Then 100 μl of acid-alcohol solution (0.08 N HCl in isopropanol) is added to each well and the wells were mixed vigorously in order to dissolve the purple crystals. Control wells should contain medium with MTT and acid-alcohol, but no cells. The plates are then read on a microplate reader, using a dual wavelength setting test filter at 570 nm and reference filter at 630 nm. The plates must be read within 1 hour.
The medium which is removed is then assayed for LDH. Equal volumes of the samples removed are added to LDH reaction mixture. In this case appropriate wells are pooled to make 500 μl samples. For each sample, reaction mixture is prepared by mixing 480 μl of 0.1 M sodium phosphate buffer, pH 7.5, 10 μl of sodium pyruvate (66 mN) and 10 μl NADH reduced (each vial of NADH containing 5 mg is reconstituted in 440 μl 0.1 N NaOH and 10 μl of this is used per sample). The sample is quickly added to the reaction mixture in cuvettes and the disappearance of absorbance at 340 nm is measured on a Beckman DU-8 spectrophotometer.
Undesired hypotensive activity is also determined by known methods, for example, according to the methods of Carron et al, also cited above.
Such selective neuroprotective antiischemic and excitatory amino acid blocking activities make the compounds of the present invention useful in the treatment of traumatic injury to the brain and spinal cord, degenerative CNS (central nervous system) disorders such as stroke, Alzheimer's disease, Parkinson's disease and Huntington's disease, without significant potential for concurrent undue drop in blood pressure. In the systemic treatment of such diseases in a human subject with a neuroprotective amount of compounds of the formula (I), the dosage is typically from about 0.02 to 10 mg/kg/day (1-500 mg/day in a typical human weighing 50 kg) in single or divided doses, regardless of the route of administration. Of course, depending upon the exact compound and the exact nature of the individual illness, doses outside this range may be prescribed by the attending physician. The oral route of administration is generally preferred. However, if the patient is unable to swallow, or oral absorption is otherwise impaired, the preferred route of administration will be parenteral (i.m., i.v.) or topical.
The compounds of the present invention are generally administered in the form of pharmaceutical compositions comprising at least one of the compounds of the formula (I), together with a pharmaceutically acceptable vehicle or diluent in a ratio of 1:20 to 20:1 respectively. Such compositions are generally formulated in a conventional manner utilizing solid or liquid vehicles or diluents as appropriate to the mode of desired administration: for oral administration, in the form of tablets, hard or soft gelatin capsules, suspensions, granules, powders and the like; for parenteral administration, in the form of injectable solutions or suspensions, and the like, and for topical administration, in the form of solutions, lotions. ointments, salves and the like.
The present invention is illustrated by the following examples, but is not limited to the details thereof.
All non-aqueous reactions were run under dry, oxygen free nitrogen for convenience and generally to maximize yields. All solvents/diluents were dried according to standard published procedures or purchased in a predried form. All reactions were stirred either magnetically or mechanically. NMR spectra are recorded at 300 MHz and are reported in ppm downfield from trimethylsilane. The NMR solvent was CDCl 3 unless otherwise specified. IR spectra are reported in micrometers, generally specifying only strong signals.
EXAMPLE 1
(±)-3,4-Dihydro-6-(1-hydroxy-2-(1-(4-hydroxy-4-phenoxy-methyl)piperidinyl)ethyl)quinoline-2-(1H)-one
A mixture of 300 mg (1.23 mol) of 4-hydroxy-4-(phenoxy-methyl)piperidine hydrochloride, 409 mg (1.84 mmol) of 6-(2-chloroacetyl)-3,4-dihydroquinolin-2-(1H)-one and 0.514 mL (0.373 g, 3.7 mmol) of triethylamine in 25 mL of acetonitrile was heated at 60° C. overnight. The solvent was then removed in vacuo and the residues partitioned between water and ethyl acetate and the organic layer was washed again with water and with brine. The ethyl acetate layer was dried with brine and magnesium sulfate and the solvent was evaporated to give 3,4-dihydro-6-(1-oxo-2-(1-(4-hydroxy-4-phenoxymethyl)piperidinyl)ethyl) quinoline-2-(1H)-one as a brown solid which was used in the subsequent reduction step without further purification.
The above ketone was dissolved in 25 mL of absolute ethanol and 500 mg (13.1 mmol) of NaBH 4 was added portionwise over 20 min. The reaction mixture was stirred at room temperature for 4 hrs. and then the solvent was removed and the residues were partitioned between water and ethyl acetate. After drying, the ethyl acetate was removed in vacuo and the residue was chromatographed on silica gel to give the product, 73 mg (15%), m.p. 186-188° C. NMR (CD 3 OD) δ 1.70-2.10 (4H, m), 2.52-3.07 (10H, m), 3.33 (2H, s), 3.83 (2H, s), 6.82-7.38 (8H, m).
EXAMPLE 2
(±)-5-(1-Hydroxy-2-(1-(4-hydroxy-4-phenoxymethyl)-piperidinyl)ethyl)benzimidazolin-2-one
Following the procedure of Example 1, the present title compound was obtained from 4-hydroxy-4-(phenoxymethyl)piperidine hydrochloride (1.23 mmol), 5-(2-chloroacetyl)-2-hydroxybenzimidazole (1.84 mmol) and triethylamine (3.7 mmol) in 25 ml of acetonitrile. The resulting ketone was stirred with sodium borohydride (13.1 mmol) in absolute ethanol to yield the desired compound after chromatography on silica gel. Yield 35%, m.p. 232-235° C.
Anal. Calcd. for C 21 H 25 N 3 O 4 .H 2 O: C, 62.81; H, 6.77; N. 10.46. Found: C, 62.98; H, 6.54; N, 10.32.
EXAMPLE 3
(±)-5-(1-Hydroxy-2-(1-(4-hydroxy-4-phenoxymethyl)-piperidinyl)ethyl-2-oxindole
Following the procedure of Example 1, the present title 10 compound was obtained from 4-hydroxy-4-(phenoxymethyl)piperidine hydrochloride (1.23 mmol), 5-(2-chloroacetyl)oxindole (1.84 mmol) and triethylamine (3.7 mmol) in 25 ml of acetonitrile. The resulting ketone was stirred with sodium borohydride (13.1 mmol) in absolute ethanol to yield the desired compound after chromatography on silica gel. Yield 40%, m.p. 171-174° C.
EXAMPLE 4
(±)-Erythro-5-(1-hydroxy-2-(1-(4-hydroxy-4-phenoxymethyl)piperidinyl)propyl)benzimidazolin-2-one
A solution of 933 mg (2.36 mol) of (±)-1-(5-(2-hydroxybenzimidazolyl))-2-(1-(4-hydroxy-4-phenoxymethyl) piperidinyl)propan-1-one in 10 mL of glacial acetic acid and 50 mL of absolute ethanol was treated portionwise with 944 mg (17.48 mol) of potassium borohydride between 15-20° C. and the resulting solution was stirred overnight at room temperature. The reaction mixture was then evaporated to dryness and the residues taken up in minimal water. The pH of this solution was adjusted to 7-8 with solid NaHCO 3 . precipitating a solid. This material was insoluble in chloroform and relatively insoluble in ethyl acetate. The whole was again evaporated to dryness and the residues, which had crystallized, were taken up in ethanol and filtered to remove salts. The ethanol was evaporated and the residue taken up in isopropanol and treated with HCl gas in ether to precipitate a non-crystalline salt which was separated by filtration and dried in a stream of dry nitrogen. This material was dissolved in hot ethyl acetate with methanol and clarified with decolorizing charcoal and then the methanol was boiled off. Cooling gave a colorless crystalline product, 410 mg (40%), m.p. 254-255° C. IR (KBr) 5.90 μm; NMR (CD 3 OD) δ 1.22 (3H, d, J=7), 1.95-2.09 (2H, m), 2.15-2.30 (2H, m), 3.42-3.76 (4H, m), 3.91 (2H, s), 5.47 (1H, s), 6.92-7.35 (8H, m).
EXAMPLE 5
(±)-Threo-5-(1-hydroxy-2-(1-(4-hydroxy-4-phenoxymethyl)-piperidinyl)propyl)benzimidazolin-2-one
A total of 700 mg (18.4 mol) of sodium borohydride was added portionwise to a suspension of 325 mg (0.82 mmol) of (±)-1-(5-(2-hydroxybenzimidazolyl)-2-(1-(4-hydroxy-4-phenoxymethyl)piperidinyl)propan-1-one in 20 mL of absolute ethanol and the reaction mixture was stirred overnight at room temp. The solvent was then evaporated and the residual foam was taken up between ethyl acetate and water and the aqueous layer was extracted with ethyl acetate. The combined ethyl acetate extracts were dried and evaporated and the residual foam was chromatographed on silica gel using 1:1 ethanol/ethyl acetate to give the product as a white solid, m.p.>250° C. NMR (Acetone-d 6 ) δ 0.79 (3H, d, J=7), 1.71-1.88 (2H, m), 11.90-2.08 (2H, m), 2.48-2.88 (4H, m), 3.01 (1H, t, J=7), 3.88 (2H, s), 4.26 (1H, d, J=7), 6.86-7.32 (8H, m);
Anal. Calcd for C 22 H 27 N 3 O 4 .1.5 H 2 O:C, 62.24; H, 7.12; N, 9.89. Found: C, 61.72; H, 6.73; N, 9.03.
EXAMPLE 6
(±)-Erythro-3,4-dihydro-6-(1-hydroxy-2-(1-(4-hydroxy-4-phenoxymethyl)piperidinyl)propyl)quinolin-2 (1H)one
A solution of 7.13 g (17.5 mmol) of (±)-1-(6-(1,2,3,4-etrahydro-2-oxoquinolinyl))-2-(1-(4-hydroxy-4-phenoxymethyl)piperidinyl)propan-1-one in 135 mL of absolute ethanol and 70 mL of glacial acetic acid was treated portionwise with 6.22 g (115 mmol) of KBH 4 at 15-20° C. and was then allowed to warm to room temperature for 30 min. The reaction mixture was evaporated to dryness and the residue was taken up in ice and cold water and this was basified with solid NaHCO 3 . The solid which precipitated was separated by filtration, washed with water and air dried to give 3.66 g of crystalline free base, m.p. 192-196° C. The filtrate was extracted with ethyl acetate and the combined extracts were dried with brine and with MgSO 4 and evaporated to give an additional 786 mg of product (total yield 62%). A 510 mg sample of this material was dissolved in ethyl acetate and treated with a solution of HCl gas in ether to give 475 mg of the crystalline hydrochloride salt, m.p. 214-216° C. (dec). IR (KBr) μm; NMR (CD 3 OD) δ 1.15 (3H, d, J=7), 1.86-2.04 (2H, m), 3.52-3.66 (2H, m), 3.69-3.80 (1H, m), 3.86 (2H, s), 5.34 (1H, s), 6.81-6.96 (4H, m), 7.17-7.28 (4H, m).
EXAMPLE 7
(±)-Threo-3,4-dihydro-6-(1-hydroxy-2-(1-(4-hydroxy-4-phenoxymethyl)piperidinyl)propyl)quinolin-2(1H)one
A total of 1.50 g (39.5 umol) of NaBH 4 was added portionwise to a suspension of 700 mg (1.71 mmol) of (±)-1-(5-(2-hydroxybenzimidazolyl))-2-(1-(4-hydroxy-4-phenoxymethyl)piperidinyl)propan-1-one in 20 mL of absolute ethanol and the reaction mixture was stirred overnight at room temperature. The solvent was then evaporated and the residual foam was taken up between ethyl acetate and water and the aqueous layer was extracted with ethyl acetate. The combined extracts were dried and evaporated and the residual foam was chromatographed on silica gel using 1:1 ethanol/ethyl acetate to give the product as a white solid, m.p. 192-196° C. A small amount of the erythro compound was formed in this reduction and could be separated from the column. NMR (CD 3 OD) δ 0.82 (3H, d, J=7), 1.72-2.06 (4H, m), 2.50-2.82 (6H, m), 2.88-3.02 (2H, t, J=7), 3.02 (1H, t, J=7), 3.84 (2H, s), 4.28 (1H, d, J=7), 6.80-7.34 (8H, m);
Anal. Calcd for C 22 H 27 N 3 O 4 .1.5 H 2 O:C, 65.88; H, 7.60; N, 6.40. Found: C, 65.74; H, 7.09; N, 6.31.
EXAMPLE 8
(±)-Erythro-5-(1-hydroxy-2-(1-(4-hydroxy-4-phenoxymethyl) piperidinyl)propyl)oxindole
A mixture of 0.5 g (2.05 mmol) of 4-hydroxy-4-phenoxymethyl)piperidine hydrochloride, 0.5 g (2.25 mmol) of 5-(2-chloropropionyl)oxindole and 1 ml (0.725 g, 7.18 mmol) triethylamine in 20 mL of acetonitrile was refluxed for 24 h. The solvent was then removed in vacuo and the residues were partitioned between ethyl acetate and water. The ethyl acetate layer was washed with water and brine and was dried over MgSO 4 and concentrated to yield the ketone as a tan foam which was used for the following reaction without further purification, 537 mg (66%).
A solution of 500 mg (1.26 mmol) of the ketone in 20 mL of ethanol was treated portionwise with 1.0 g (26.3 mmol) of NaBH 4 and the resulting mixture was stirred at room temperature for 24 h. The solvent was removed in vacuo and the residues were partitioned between ethyl acetate and water. The ethyl acetate layer was washed and dried with brine and MgSO 4 and then evaporated to dryness. The residues were chromatographed on silica gel using ethyl acetate and gradually increasing concentrations of ethanol to give the threo product in pure fractions, 121 mg (24%), m.p. 204-207° C. NMR (DMSO-d 6 ) δ 0.70 (3H, d, J=7), 1.58-1.92 (4H, m), 2.40-2.65 (4H, m), 2.86 (1H, m), 3.32-3.40 (2H, m), 3.79 (2H, s), 4.20 (1H, d, J=7), 6.70-7.35 (8H, m), 10.34 (1H, s).
EXAMPLE 9
(±)-1-(6-(1,2,3,4-Tetrahydro-2-oxoquinolinyl))-2-(1-(4-hydroxy-4-phenoxymethyl)piperidinyl)propan-1-one
A suspension of 8.30 g (34.06 mmol) of 4-hydroxy-4-phenoxymethylpiperidine hydrochloride and 8.09 g (34.06 mmol) of 6-(2-chloro-1-propionyl)-1,2,3,4-tetrahydroquin-olin-2(1H)-one in 100 mL of acetonitrile was treated with 16.61 mL (12.04 g, 0.12 mol) of triethylamine and the mixture was heated at reflux for 3 h and then stirred overnight at room temperature.
The reaction mixture was poured into water and extracted 3 times with ethyl acetate and the combined extracts were dried with brine solution and magnesium sulfate and evaporated to give a foam. This foam was dissolved in hot methanol and ethyl acetate and cooled to give a tan solid which was found to be starting chloroketone and discarded. The filtrates were evaporated and dissolved in ethyl acetate and ether was added to facilitate crystallization. The product was filtered and washed with ether to give 8.84 g (63.6.%) of the product as a cream-colored solid, m.p. 137-139° C. The analytical sample was crystallized from hot ethyl acetate. NMR (CD 3 OD) δ 1.28 (3H, d, J=7), 1.60-1.92 (4H, m), 2.52-2.84 (6H, m), 3.00 (2H, t, J=7), 3.75 (2H, s), 4.22 (1H, q, J=7), 6.82-7.00 (4H, m), 7.16 (2H, m), 7.82-7.98 (2H, m);
Anal. Calcd for C 24 H 28 N 2 O 4 :C, 70.56; H, 6.91; N, 6.86. Found: C, 70.16; H, 6.78; N, 6.76.
EXAMPLE 10
(±)-1-(5-(2-Hydroxybenzimidazolyl))-2-(1-(4-hydroxy-4-phenoxymethyl)piperidinyl)propan-1-one
A suspension of 2.43 g (10.0 mol of 4-hydroxy-4-phenoxymethylpiperidine hydrochloride and 2.25 g (10.0 mmol) of 5-(2-chloro-1-propionyl)-2-hydroxybenzimidazole in 40 mL of acetonitrile was treated with 4.88 mL (3.53 g, 35.0 mmol) of triethylamine and the reaction mixture was heated at reflux for 90 min and then let sit over a weekend at room temperature.
The reaction mixture was then poured into a mixture of water and ethyl acetate and the resulting suspended solid was separated by filtration and found to be pure product, 1.15 g after drying. The filtrate was adjusted to pH=7.0 and extracted with ethyl acetate several times to give, after drying with brine solution and MgSO 4 , a colorless solid which was recrystallized from hot ethyl acetate/methanol to give an additional 560 mg of product (total yield, 43%), m.p. 230-235° C. (dec.). NMR (CD 3 OD/DMSO-d 6 ) δ 1.29 (2H, d, J=7), 1.60-1.92 (4H, m), 2.54-2.84 (4H, m), 3.77 (2H, s), 4.26 (1H, q, J=7), 6.86-7.10 (6H, m), 7.75-7.92 (2H, m).
EXAMPLE 11
(±)-1-(5-(Oxindolyl))-2-(1-(4-hydroxy-4-phenoxymethyl) piperidinyl)propan-1-one
Following the procedure of preparation 10, the present title compound was obtained from 4-hydroxy-4-phenoxymethylpiperidine hydrochloride (10.0 mmol), 5-(2-chloropropionyl)oxindole (10 mmol) and triethylamine (35 mmol) in 50 ml of acetonitrile. The title compound was isolated by crystallization from hot ethyl acetate/methanol to give an amorphous foam. Yield 66.4%. NMR (CDCl 3 ) δ 1.28 (3H, d, J=7), 1.58-1.78 (4H, m), 2.40-2.84 (4H, m), 3.54 (2H, s), 3.76 (2H, s), 4.09 (1H, q, J=7), 6.78-6.96 (3H, m), 7.14-7.26 (2H, m), 7.84-8.05 (3H, m), 9.52 (1H, broad s), 9.64 (1H, broad s).
Preparation 1
3,4 Dihydroquinolin-2-(1H)-one
A slurry of 50.0 g (0.259 mol) of o-nitrocinnamic acid in 500 mL of ethanol was treated with 5 teaspoons of Raney Ni and hydrogenated on a Parr shaker overnight at an initial pressure of 50 psi. In the morning, the pressure was increased again to 50 psi and the reaction was continued for an additional 5 h. The reaction mixture was filtered to remove the catalyst and then washed through a bed of silica gel with a mixture of ethyl acetate and ethanol to remove traces of nickel salts. Evaporation of the filtrate gave the desired product in 57% yield. NMR (DMSO-d 6 ) δ 2.45 (2H, t, J=7), 2.87 (2H, t, J=7), 6.87 (2H, d of d, J=7, 7), 7.12 (2H, d of d, J=7, 10), 10.08 (1H, s). m.p. 165-166° C.
Preparation 2
6-(2-Chloropropionyl)-3,4-dihydroquinolin-2-(1H) -one
A suspension of 72.5 g (0.544 mol) of AlCl 3 in 800 mL of CS 2 was stirred under dry N 2 while 14.1 mL (20.0 g, 0.177 mol) of 2-chloropropionyl chloride was added followed by 20.0 g (0.136 mol) of 3,4-dihydroquinolin-2(1H)-one. The reaction mixture was refluxed for 4 h at which time a separation of phases was noted. The reaction was quenched by pouring onto ice with vigorous stirring. The pale yellow precipitate which formed was separated by filtration, washed with water and dried overnight over P 2 O 5 to give 27.7 g (91%) of the desired product, m.p. 236.5-238° C.
Preparation 3
5-(2-Chloropropionyl)-2-hydroxybenzimidazole
Following the procedure of Preparation 2, the present title compound was obtained from 2-hydroxybenzimidazole (0.136 mol), aluminum chloride (0.544 mol) and 2-chloropropionyl chloride (0.177 mol) in 800 ml CS 2 . The title compound was isolated by filtration. Yield 92%, m.p. 245° dec.
Anal. Calcd for C 10 H 9 ClN 2 O 2 : C, 53.47; H, 4.04; N, 12.47. Found C, 54.41; H, 4.07; N, 13.25.
Preparation 4
5-(2-Chloropropionyl)oxindole
Following the procedure of Preparation 2, the present title compound was obtained from oxindole (0.136 mol), aluminum chloride (0.544 mol) and 2-chloropropionyl chloride (0.177 mol) in 800 ml CS 2 . The title compound was isolated by filtration. Yield 91%, m.p. 157-158° C.
Preparation 5
6-(2-Chloroacetyl)-3,4-dihydroquinolin-2(1H)-one
Following the procedure of Preparation 2, the present title compound was obtained from 3,4-dihydroquinolin-2-(1H)-one (0.136 mol), aluminum chloride (0.544 mol) and 2-chloroacetyl chloride (0.177 mol) in 800 ml CS 2 . The title compound was isolated by filtration. Yield 50%, m.p. 215-216° C.
Preparation 6
5-(2-Chloroacetyl)-2-hydroxybenzimidazole
Following the procedure of Preparation 2, the present title compound was obtained from 2-hydroxybenzimidazole (0.13.6 ol), aluminum chloride (0.544 ol) and 2-chloroacetyl chloride (0.177 mol) in 800 ml CS 2 . The title compound was isolated by filtration. Quantitative yield, m.p. 273-275° C. (dec).
Preparation 7
5-(2-Chloroacetyl)-oxindole
Following the procedure of Preparation 2, the present title compound was obtained from oxindole (0.136 mol), aluminum chloride (0.544 mol) and 2-chloroacetyl chloride (0.177 mol) in 800 ml CS 2 . The title compound was isolated by filtration. Yield 90%, m.p. 236.5-239° C.
Preparation 8
4 -fydroxy-4-2henoxymethylpiperidine hydrochloride
Oil free sodium hydride (2.16 g, 0.09 M) was added to dry dimethyl sulfoxide (250 mL) under nitrogen gas and the mixture was heated to 60-65° C. until a uniform black solution was formed, about 1 h. Then 19.83 g (0.09 M) of trimethylsulfoxonium iodide was added (slight exotherm) and the mixture was stirred until a brown solution occurred, about 30 min. Then a solution of 13.40 g (67.3 mM) of N-t-butyloxycarbonyl-4-piperidone in 50 mL of dimethyl sulfoxide was stirred at room temperature for 1 h. The reaction mixture was then poured into 1 L of cold water and the whole was extracted 4× with 100 mL portions of hexane. The combined hexane extracts was back-washed with 50 mL of water and with brine solution and was dried with magnesium sulfate, filtered and evaporated to give 11.75 g of white crystalline product, 6-t-butyloxycarbonyl-1-oxa-6-azaspiro[2.5]octane, (78% yield).
Further extraction of the aqueous layers with 3×50 mL of hexane gave a further 650 mg of product for a total yield of 82.5%.
m.p. 57.5-59.5° C.; IR(KBr) 5.90 μm; NMR δ 1.32-1.48 (2H, m), 1.42 (9H, s), 1.74-1.80 (2H, m), 2.65 (2H, s), 3.31-3.43 (2H, m), 3.61-3.72 (2H, m);
Anal. Calcd for C 11 H 19 NO 3 : C, 61.94; H, 8.98; N, 6.57. Found: C, 62.05; H, 9.09; N, 6.58.
A solution of 10.37 g (0.11 M) of phenol in 100 mL of dry dimethyl sulfoxide treated portionwise with 1.99 g (82.8 mmol) of oil-free sodium hydride keeping the temperature between 20-25° C. with a cold water bath. The reaction mixture was then stirred at room temperature for 45 min to give a grey suspension. The 11.75 g (55.2 mmol) of 6-t-butyloxycarbonyl-1-oxa-6-azaspiro[2.5]octane dissolved in 65 mL of dimethyl sulfoxide was added dropwise after which the reaction mixture was heated to 55-60° C. for 7 h and was then stirred at room temperature overnight.
The reaction mixture was then poured into 1 L of cold water and extracted 4× with ether. The combined ether extracts was backwashed with 10% NaOH and with brine and was dried with magnesium sulfate evaporated to give the desired product, N-t-butyloxycarbonyl-4-hydroxy-4-phenoxymethylpiperidine, as an oil weighing 17.01 g (100%).
IR (Film) 5.91, 2.95 μM; NMR (CDCl 3 ) δ 1.46 (9H, s); 1.53-1.80 (4H, m), 3.13-3.30 (2H, m), 3.80 (2H, s), 3.80-3.98 (2H, m), 6.84-6.99 (2H, m), 7.22-7.44 (3H, m);
Anal. Calcd for C 17 H 25 NO 4 : C, 66.42; H, 8.20; N, 4.56. Found: C, 65.72; H, 8.21; N, 4.77.
A solution of 17.0 g (0.055 M) of N-t-Butyloxycarbonyl-4-hydroxy-4-phenoxymethylpiperidine in 150 mL of methanol was saturated with HCl gas. After the mixture had cooled, it was again treated with HCl gas and this procedure was again repeated. After crystals had formed, the reaction mixture was treated with 500 mL of anhydrous ether and let stir at room temperature overnight.
The product was filtered and washed with dry ether and dried under a stream of dry N 2 to give 10.85 g (80.6%) of crystalline material, m.p. 202-204° C. IR (KBr) 3.06, 3.14, 3.44, 3.57, 3.56, 6.33, 8.06 μm; NMR (D 2 O) δ 2.00 (4 H, broad s), 3.34 (4H, broad s), 4.00 (2H, s), 6.98-7.09 (3H, m), 7.30-7.43 (2H, m).
Anal. Calcd for C 12 H 17 NO 2 .HCl: C, 59.13; H, 7.44; N, 5.75. Found: C, 58.98; H, 7.11; N, 5.65. | A series of 2-(4-hydroxypiperidino)-1-alkanol derivatives are useful as medicaments for the treatment of traumatic injuries to the brain and spinal cord and neuronal degenerative diseases including senile dementias, in mammals, especially humans. | 2 |
RELATED APPLICATIONS
This application is a continuation of and claims the benefit of priority from application Ser. No. 10/045,231, filed Nov. 9, 2001 now U.S. Pat. No. 6,749,317, entitled “Miniature LED Flashlight,” which is a continuation-in-part of application Ser. No. 09/851,685, filed May 8, 2001, having the same title, now U.S. Pat. No. 6,511,214, issued Jan. 28, 2003, which is a continuation-in-part of application Ser. No. 09/653,646, filed Sep. 1,2000, having the same title, now U.S. Pat. No. 6,357,890, issued Mar. 19, 2002, which is a continuation of application Ser. No. 09/226,322, filed Jan. 6, 1999, having the same title, now U.S. Pat. No. 6,190,018, issued Feb. 20, 2001.
BACKGROUND OF INVENTION
1. Field of Invention
This invention is directed generally to flashlights, and more particularly to a miniature flashlight using a light emitting diode (“LED”) as a light source that is useful for law enforcement personnel and civilians alike.
2. Background of the Invention
Conventional general purpose flashlights are well known in the prior art and have often been used by law enforcement personnel in the execution of their duties and by them and civilians in emergency situations. Flashlights are used for a wide variety of purposes. For example, they are often used during traffic stops to illuminate the interior of a stopped vehicle or to complete a police report in the dark. They are also used to facilitate searches of poorly lit areas and may be used to illuminate dark alleys or stairwells. Also, they are used to check or adjust equipment when positioned in a darkened area or at night time, and can be used to send coded signals to one another. Generally, small incandescent lightbulbs and LED flashlights were not dependable when needed.
However, the size and weight of conventional flashlights add to the inconvenience and reduce the mobility of law enforcement personnel required to carry such flashlights along with the other law enforcement equipment. Sometimes the flashlight is purposefully or inadvertently left behind. This presents a problem when the need for a flashlight arises and the flashlight is not located on the person, or otherwise readily available In addition to the use of flashlights by law enforcement personnel, civilians also use flashlights for a number of different reasons. Besides the traditional, home uses of flashlights, smaller flashlights are used in today's society for various security purposes. For example, when going to one's car late in the evening, it is not uncommon for an individual, especially a female, to carry a small flashlight with her. She can use the flashlight to assist in getting the key in the keyhole in the dark. Additionally, she can use the flashlight to check whether someone is hiding in the back seat before getting into the car. Even small conventional flashlights, however, are generally cumbersome and inconvenient to carry for this purpose.
Thus, there is a need for a compact, lightweight flashlight that may easily be carried on the person of a law enforcement officer or civilian and conveniently attached to one's keychain or carried on one's clothing to help insure that the flashlight remains in possession of the user and can be quickly and easily retrieved and removed when needed.
3. Description of the Prior Art
Although not having been proven useful to law enforcement personnel, there exists in the prior art a small flashlight known as the Photon Micro Light. The Micro Light consists of two flat, circular 3 volt batteries, a light emitting diode (“LED”) and an outer shell that encloses the batteries and leads of the LED. The Micro Light uses a slide switch or pressure switch that activates the light by moving the leads of the LED into direct engagement with the batteries. The outer shell consists of two hard plastic parts opposite either side of the batteries and may be held together with four threaded screws.
The Micro Light, however, has a number of disadvantages. The Micro Light lacks the durability required for a miniature flashlight. It lacks an internal structure for protecting and securing the batteries and LED. Only the hard plastic outer shell protects the internal components of the flashlight. Thus, little protection is provided for the internal components of the flashlight and the Micro Light may be adversely affected when subjected to shock.
The Micro Light operates by using either a slide switch or pressure switch which upon activation brings both the leads of the LED into direct engagement with the batteries. This results in increased fatigue on the leads of the flashlight and undesirable wear that affects the reliability of the switch. Moreover, because of its external shape and hard plastic outer shell construction, the Micro Light is not suitable for receiving markings or engravings on the outside surfaces thereof, cannot have a medallion installed thereon, have a die struck panel, or disclose using a translucent housing. In many instances it is desirable to color code the exterior of the flashlight, or to provide medallions, die struck panels, engravings, markings, or other indicia on the exterior surface. However, the construction of the Micro Light is not well suited or adapted to allow for any such color coding or desired markings or engravings.
4. Summary of the Invention
The subject invention is specifically directed to a small, compact LED flashlight useful to both law enforcement personnel and civilians. One embodiment of the invention may include an LED flashlight wherein the LED has first and second leads extending therefrom; a power source; a power source frame enclosing at least a portion of the power source; a power source frame housing containing the power source frame, light source and power source; a switch located adjacent the power source and operable to close a circuit including the light source and the power source; a keyring extension extending from the power source frame, said keyring extension having an opening whereby an article can be attached to the keyring extension, and the keyring extension further includes a keyring lock connected to the power source frame or power source frame housing wherein upon exerting a force against the keyring lock, the keyring lock is opened to permit the article to be attached to the keyring extension.
The power source frame is non-conductive and has a cavity adapted to house the power source. The power source frame may also have a receptacle for receiving and housing a connector end of the light source. The power source frame therefore serves as a fitted compartment for holding in place and protecting the various internal components of the flashlight. The power source frame provides significant protection to the power source and the light source and serves to cushion these elements from the adverse affects of any shock the flashlight might receive. The power source frame housing encases the power source frame, and provides further protection to the internal components of the flashlight, in addition to that provided by the power source frame. The power source frame housing thus serves to provide an additional level of protection to the light source and the power source and enhances the durability of the flashlight.
Another embodiment of the invention may include an LED flashlight wherein the LED has first and second leads extending therefrom; a power source having a first side and a second side, the second side being opposite the first side; a housing enclosing the leads of the LED and the power source, wherein the housing is comprised of translucent material; and a switch operable to close a circuit including the LED and the power source.
Still a further embodiment of the invention may include an LED flashlight wherein the LED has first and second leads extending therefrom; a power source; a housing containing the LED and the power source; the housing includes at least one side cover which is not integral with the housing; the at least one side cover being selected from anodized metal, anodized metal which includes indicia, die struck metal, laser engraved metal, and a side cover having a separate medallion attached thereto; and a switch located adjacent the power source and operable to close a circuit including the light source and the power source.
The LED is preferably an LED that has a high luminous intensity. Manufacturers of LEDs grade the LED according to its quality. The highest quality LEDs are given an “E” grade. The next highest quality is a “D” grade. LEDs with a “D” grade can be equipped with a lens to approximate the quality of an “E” grade LED. LEDs of this quality were initially used in medical applications and are sometimes referred to as having medical grade application. Although the flashlight of the present invention can be used with any conventional LED, in a preferred embodiment, the light source is an “E” grade LED or lensed “D” grade LED. Such a high intensity LED may be obtained from Hiyoshi Electric, Co., Ltd. located in Tokyo, Japan, having Part No. E1L533BL. The high intensity LED herein described has from three to five times the luminous intensity of a conventional LED. The LED preferably emits blue light, although the present invention may be used with any color LED. Blue light helps to preserve a user's night vision compared with conventional flashlights emitting white light. For other applications bluegreen LEDs can be used, for example, in situations where compatibility with night vision equipment is desired. Other colored LEDs can also be used. Red LEDs can be used in applications where the preservation of night vision is desired or for use with pilots and photographers, and even infrared LEDs can be used where certain signalling capabilities are required or for use with equipment that senses infrared light. The LED includes first and second leads extending from a connector end of the LED. The LED leads may be provided with extensions that can be soldered onto the leads of the LED.
The power source may be any battery having sufficient power to energize an LED. The power source is preferably round and has oppositely disposed generally flat sides, sometimes referred to as coin cells. A pair of stacked 3 volt batteries of this type may be used as the power source. Three-volt lithium batteries are preferably used to provide for longer life, and greater shelf life.
The power source frame may be made of nonconductive plastic and preferably has generally flat oppositely disposed first and second sides. The power source frame may be adapted to receive and house a power source, and includes a power source cavity for this purpose. The power source frame also includes a receptacle at a front end to receive and house a connector end of an LED. The leads of the LED are preferably positioned so that one lead extends over the first side of the power source and another lead extends over the second side of the power source. The power source frame protects and secures the internal components of the flashlight. The power source frame also provides resistance to shock and safeguards the light source and power, source within its frame. The power source frame may include a power source cavity cover that serves to further enclose the power source, and may include a bottom support beneath the cavity for further supporting the power source.
A switch element is preferably located on the side opposite of the power source cavity. The side of the power frame opposite the side having the power source cavity may include a counterbore having a terminus in the power source frame that houses a switch element. The counterbore may be included in the power source cavity cover as well. The switch element is preferably a dome plate that is located between one of the leads of the LED and the power source, but out of contact with the power source. The dome plate is sometimes referred to as a tactile dome plate or a snap dome plate. The switch is activated by applying pressure to the dome plate, thereby completing a circuit that includes the leads of the LED and the power source. With this switch arrangement, a switch button is depressed forcing one lead of the LED into contact with the dome plate which in turn contacts the power source. Thus, in this embodiment, one lead of the LED never comes into direct contact with the power source. Once pressure is removed from the button, the contact between the dome plate and power source is broken and the flashlight returns to its normal “off” position. Thus, the switching arrangement reduces the wear on the leads of the LED and increases the overall reliability.
The power source frame may be adapted to receive a weight, which is preferably round and has opposite ends coplanar with the opposite sides of the power source frame. The weight may be press fit into a cavity or tapered hole in the power source frame specifically adapted to receive the weight. The weight provides for a heavier flashlight and improved balance. In addition, the weight provides the flashlight with greater substance and as a result a higher perceived value in the hands of the user. With the additional weight added to the flashlight, the flashlight appears more substantial and of a higher quality than a lighter weight flashlight.
The power source frame housing is preferably of a two piece construction, with each piece disposed on either side of the power source frame. The power source frame housing includes a first housing side disposed about the first side of the power source frame and a second housing side disposed about the second side of the power source frame, the two sides conforming to the periphery of the power source frame. The housing is preferably constructed of plastic. In one embodiment, the housing may be translucent. In this manner, the light from the LED may be dispersed throughout the housing to effectively illuminate the light. In one embodiment, the entire housing may be translucent. It may also be colored to match the color of the LED. For example, a red translucent housing may be used with a red LED, a blue translucent housing may be used with a blue LED, etc.
The power source frame may have a plurality of pegholes located about the periphery of either side thereof. In addition, the first and second housing sides of the power source frame housing may be provided with a plurality of pegs extending from an inner periphery thereof. The pegs are positioned to engage in a mating relationship with the plurality of pegholes located about the periphery of the sides of the power source frame such that the housing sides can be engaged with the power source frame. The mating of the pegs and the pegholes facilitates assembly of the flashlight by allowing the parts to be precisely aligned during their assembly. It has been found that gluing the power source frame housing to the power source frame provides for a suitable adhesion of the parts. Alternately, ultrasonic welding can be used to attach the parts. Unlike the prior art, separate screws are not needed to attach the parts of the flashlight together and thus assembly is facilitated. In this manner, the housing sides may include notches that mate with corresponding notch receptacles on the power source frame. The housing sides may thus be advantageously ultrasonically welded to the power source frame.
The flashlight housing may be provided with at least one separate side cover and preferably be provided with first and second side covers that are positioned between the first and second housing sides of the power source frame housing and with the housing sides sandwiches the power source frame. The side covers preferably lie in parallel planes and may have flat outer surfaces that are capable of receiving engravings or markings. It is often desirable to engrave or imprint the side covers with surface indicia. For example, a company logo or name of a product could be located on either of the side covers. The use of engraving or printing on the side covers can be used for promotional or advertising purposes. In addition, a flashlight bearing certain markings on the side covers could serve as a prize or be used to commemorate an important event. In one embodiment, a die struck medallion could be inset in the side cover.
The side covers can be made of a variety of materials, such as metal, plastic, or other protective materials. The side covers are preferably made of anodized aluminum. Aluminum provides the desired strength to the side covers and is easily anodized aluminum engraved or imprinted. Indicia may be laser engraved, silk screened, inked, pad printed, or marked in any known manner. In the embodiment where the housing is translucent, the side covers may also be made of a translucent plastic material, or they may be made of non-translucent plastic or metal. Thus, a flashlight may be provided with a translucent housing, and translucent side covers, or a translucent housing and opaque side covers. Where both the housing and side covers are translucent, they may of different colors, to present a two, or even three, tone flashlight. Further, the flashlight may include a translucent power source frame as well. Where translucent side covers are used, indicia may be engraved or printed on the inside surface of the side cover. Thus, the side cover protects the indicia from being marred by normal wear and tear, and also by virtue of being translucent, may provide an attractive gloss finish highlighting the indicia.
In another embodiment, the side covers are a die struck, or coined metal, preferably brass, in which physical indicia may be formed in the metal side cover. Most preferably, both sides of a side cover are struck to provide finer detail in the physical indicia, which may include a company logo, name, or other suitable information.
In another embodiment, a side cover can have a medallion therein. One way of doing this is to cut a hole the size of the medallion in the side cover. An appropriate support and single faced adhesive is attached to the inside of the side cover so that the adhesive can be used to attach the medallion too the side cover.
The side covers provide additional protection to the internal components of the flashlight. The sturdy aluminum construction serves to guard the light source and power source from external forces. Moreover, there is an insulated pocket located between the power source frame and the side covers that provides an air cushion that serves to further protect the light source and power source within the power source frame housing. The side covers may be manufactured as separate components of the flashlight from the power source frame housing. Thus, side covers of varying colors may used to assemble flashlights of varying and contrasting colors. For example, flashlights having side covers bearing corporate colors can be easily assembled. Similarly, flashlights having side covers bearing the colors of a favorite team can be provided. For example, a flashlight having a green side cover on one side and a yellow side cover on the other side could be used to represent the colors of the Green Bay Packers. In addition, a Green Bay Packers logo could be included on one or both side covers of the flashlight.
One of the side covers is adapted to receive a switch button that is secured to the side cover. The button may be made of rubber, and is preferably made of Kraton, the trade name of a thermoplastic rubber made by the Shell Oil Company, and located adjacent the power source. When the button is pushed, a circuit including the leads of the LED and the power source is completed.
The power source frame or power source frame housing may be provided with a keyring extension. The keyring extension may directly extend from the housing or power source frame. The keyring extension includes a keyring lock that opens and closes the keyring extension when a force is exerted against the keyring lock. The keyring extension is opened to permit an item such as a keyring to be attached to the keyring extension. The keyring lock is preferably springbiased and may be attached to the power source frame. The keyring lock may pivot about a circular post positioned on the power source frame. Alternatively, the keyring lock may extend from the interior of the housing, or if a power source frame is used, extend from the power source frame. The keyring extension may be easily attached and detached from any number of items, such as the zipper of a coat or backpack, the handle of a purse or briefcase, a beltloop, or any other handle or case.
The flashlight of the present invention is small, compact and easy to operate. The flashlight may easily be carried in the pocket, on the clothing, or on the keychain of law enforcement personnel or civilians. The flashlight may also be quickly and easily retrieved and operated.
In another embodiment of the invention, a magnet may be provided on the flashlight. It may be internal, external, or coextensive with the housing sides or side covers. Preferably, the magnet is internally positioned within the flashlight. It may be positioned within the interior of the housing, or if a power source frame is used may be positioned on the power source frame or within a cavity on the power source frame. An internal magnet allows for indicia to be marked, printed, or engraved on the housing or side covers of the flashlight. When internally positioned, the magnet is protected from chipping or scratching that could occur if the magnet were externally mounted to the flashlight. Moreover, the magnet itself does not scratch the surface to which it may be mounted as the magnet is protected by the housing or side covers. The magnet may be of sufficient strength to allow the flashlight to be mounted to metal objects. In a preferred embodiment using a magnet, the magnet is of sufficient strength to allow the magnet to attach to metal objects even when using side covers that are made of aluminum or other metals.
It will be understood by those of skill in the art that the various aspects of the disclosed embodiments may be used alone or in connection with the other aspects of the disclosed embodiments. For example, the various disclosed keyring extensions may be used with a housing, with a power source frame and power source frame housing together, with or without side covers, with a translucent housing, with a magnet, etc.
BRIEF DESCRIPTION OF THE DRAWINGS
Further advantages of the present invention will become apparent to those skilled in the art with the benefit of the following detailed description of the preferred embodiments and upon reference to the accompanying drawings in which:
FIG. 1 is a perspective view of an embodiment of the flashlight of the present invention.
FIG. 2 is a side view of the flashlight depicted in FIG. 1 .
FIG. 3 is a side view of a first side of the power source frame.
FIG. 4 is a side view of a second side of the power source frame opposite the first side.
FIG. 5 is a side view of a power source consisting of two circular batteries having generally flat sides.
FIG. 6 is a side view of a light emitting diode (LED).
FIG. 7 is a perspective view of a weight.
FIG. 8 is a side view of a first side of the power source frame including a power source, an LED, a keyring lock, and a spring.
FIG. 9 is a side view of a second side of the power source frame including an LED, a weight, a keyring lock, a spring, and a switch element.
FIG. 10 is a cross-sectional view of the power source frame of FIG. 4 taken along plane 11 .
FIG. 11 is a side view of the exterior of a first side of the power source frame housing.
FIG. 12 is a side view of the interior of a first side of the power source frame housing.
FIG. 13 is a side view of the exterior of a second side of the power source frame housing.
FIG. 14 is a side view of the interior of a second side of the power source frame housing.
FIG. 15 is a side view of a first side cover.
FIG. 16 is a side view of a second side cover.
FIG. 17 is a cross-sectional view of a switch button.
FIG. 18 is a partial cross-sectional view of the flashlight of FIG. 2 taken along the plane 22 .
FIG. 19 is a side view of an alternate embodiment of the power source frame.
FIG. 20 is the opposite side view of the power source frame shown in FIG. 19 .
FIG. 21 is a side view of a power source cavity cover.
FIG. 22 is an opposite side view of the power source cavity cover shown in FIG. 21 .
FIG. 23 is a perspective view showing the power source cavity cover of FIGS. 21 and 22 used in connection with the power source frame of FIGS. 19 and 20 .
FIG. 24 is atop view of an alternate embodiment of a keyring extension and keyring lock in a connecting relationship.
FIG. 25 is a top view of the keyring lock of FIG. 24 .
FIG. 26 a is a top view of another alternate embodiment of a keyring lock showing a latch receptacle in dotted lines.
FIG. 26 b is a bottom view of the keyring lock of FIG. 26 a.
FIG. 27 is a side view of an alternate embodiment of a power source frame having a cavity for a magnet.
FIG. 28 is an opposite view of the power source frame of FIG. 27 .
FIG. 29 is a view of the power source frame of FIG. 28 along line 29 — 29 showing a magnet and magnet cavity in dotted lines.
FIG. 30 is side view of an alternate embodiment of the present invention showing a flashlight with a translucent housing.
FIG. 31 is an opposite side view of the flashlight of FIG. 30 .
FIG. 32 is a side view of a flashlight having an alternate embodiment of a keyring lock.
FIG. 33 is a side view of the inside of a die struck cover according to the present invention.
FIG. 34 is a side view of the outside of the die struck panel of FIG. 33 .
FIG. 35 is a front side view of a cover having a medallion pocket.
FIG. 36 is FIG. 35 with the medallion in the pocket.
While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the drawings and detailed description thereof are not intended to limit the invention to the particular form disclosed, but on the contrary, the invention is to cover all modifications, equivalents and alternatives falling within the spirit and scope of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
A handheld flashlight 10 made in accordance with the principles of the subject invention is depicted in FIG. 118 . As shown in FIG. 2 , flashlight 10 preferably includes a side cover 12 , a power source frame housing 14 , a keyring extension 16 , a keyring lock 80 , a switch button 18 , and a light source 20 , extending from a front end of the flashlight.
As depicted in FIGS. 3 and 4 , the flashlight of the subject invention further includes a power source frame 22 . The power source frame 22 has oppositely disposed first and second sides 26 , 33 that are generally flat and lie in parallel planes. The power source frame 22 further includes a cavity 24 located on the first side 26 of the power source frame adapted to receive a power source, such as that depicted in FIG. 5 . The frame 22 also is provided with a receptacle 28 at a front end 30 thereof, adapted to receive a light source, such as that depicted in FIG. 6 . The first side 26 further includes a light source lead channel 29 extending from receptacle 28 to cavity 24 to allow a lead from the light source 20 to extend over cavity 24 .
As depicted in FIG. 3 , the power source frame 22 may also include an area 32 adapted to receive a weight. In the embodiment shown in the figures, although not required, the area 32 is a throughhole extending from the first side 22 of the frame to the second side 33 of the frame. Area 32 is tapered at a slight angle to allow the weight to be friction fit within area 32 . The power source frame 22 is further provided with a plurality of pegholes 100 positioned about an outer periphery of the first side 26 of the power source frame. The pegholes 100 are adapted to receive a corresponding set of pegs located on the power source frame housing 14 . The mating of the pegs with the pegholes positions the power source frame housing 14 in proper alignment with the power source frame 22 . The power source frame housing may be ultrasonically welded to the power source frame and/or glued thereto. Thus, there is no need to use threaded screws or other fastening means to hold the frame and the housing together. As a result, the flashlight of the invention is assembled without difficulty.
The power source frame 22 is preferably made of a nonconductive material. Preferably, the power source frame 22 is comprised of Acrylonitrile Butadiene Styrene “ABS” which provides for exceptional durability and toughness. However, any nonconductive material may be employed to construct the frame 22 . Polycarbonate is preferred where the power source frame is translucent.
FIG. 4 depicts a side view of the second side 33 of power source frame 22 . The second side 33 is provided with a counterbore 34 having a terminus 36 within the power source frame 22 . As shown in FIG. 4 , the counterbore 34 is adapted to receive a switch element. The counterbore 34 is preferably located opposite the power source cavity 24 and includes a throughhole 38 extending into cavity 24 that is located on the first side 26 of the power source frame 22 .
As with the first side 26 , the second side 33 preferably includes a light source lead channel 39 extending from receptacle 28 to counterbore 34 to allow a lead from the light source 20 to extend over counterbore 34 . The second side 33 of power source frame 22 may preferably further include a post 40 about which an element of the keyring lock 80 may pivot. Power source frame 22 is also provided with a hub 42 located on a rear side 44 of the frame 20 that is adapted to secure one end of a spring element associated with the keyring lock 80 . As with the first side, the second side 33 of the power source frame may be provided with a plurality of pegholes 110 positioned about its outer periphery to mate with a corresponding set of pegs located on the power source frame housing 14 .
The power source may be any type of battery with sufficient power to energize the light source. As shown in FIG. 5 , the power source is preferably one or more circular batteries 50 having generally flat oppositely disposed first and second sides 52 and 54 . In a preferred embodiment, the power source consists of two 3 volt lithium coin cell batteries available from Panasonic bearing the CR2016 marking. These lithium batteries provide for exceptionally long life and durability. In addition, they operate at a low temperature, are leakproof, and vibration resistant.
The light emitting diode light source may be of any type suitable for flashlight use. As shown in FIG. 6 , the light emitting diode (“LED”) 60 has first and second leads 62 and 64 extending therefrom. An LED provides great advantages over conventional neon or incandescent light sources, since it requires much less energy, is smaller in size, and more resistant to shock than conventional light sources. It also generates less heat and is more durable than a conventional light source. LEDs are widely available, inexpensive, and can be replaced easily and quickly. In a preferred embodiment, the light source is a high intensity LED having a high luminous intensity emitting blue light. The LED may be a “E” grade LED or a lensed “D” grade LED.
The flashlight may include a weight 70 positioned in area 32 on the power frame housing 14 . The weight provides for a heavier flashlight and for improved balance. It also provides a more substantial feel to the flashlight resulting in a higher perceived value. In a preferred embodiment shown in FIG. 7 , the weight 70 has a cylindrical shape and has oppositely disposed first and second faces that are generally flat and lie in parallel planes. The weight 70 preferably has a thickness equal to the thickness of the power source frame 14 . It is preferably made of a dense metal material, preferably stainless steel, and preferably weighs approximately eleven grams. The weight is friction fit or press fit into the corresponding portion of the power source frame housing.
FIG. 8 is a side view of the first side 26 of the power source frame 22 and depicts power source 50 , LED 60 , keyring lock 80 , and spring 82 . The power source frame 22 preferably has a thickness in the range of approximately 0.15 and 0.25 inch, and preferably 018 inches, which is approximately equal to the diameter of LED 60 . As shown in FIG. 8 , the LED 60 is positioned in receptacle 28 of the power source frame 22 , and the power source SO is positioned in the cavity 24 of the power source frame 22 .
A first lead 62 of the LED 60 preferably extends over the first side 52 of the power source 50 , which is preferably coplanar with the first side 26 of the power source frame 22 . A lead extension 75 may be attached to the first lead 62 of the LED to extend the length of the lead. The lead extension 75 may be soldered to the first lead 62 . The weight 70 may be positioned within the power source frame 22 , and preferably has a first side 72 that is coplanar with the first side 26 of the power source frame. The weight 70 is preferably press fit or friction fit within the power source frame 22 .
FIG. 9 is a side view of the second side 33 of the power source frame 22 and depicts LED 60 , weight 70 , keyring lock 80 , spring 82 and switch element 90 . As shown in FIG. 9 , the switch element 90 is positioned in the counterbore 34 . The switch element 90 has an outer periphery that contacts the terminus 36 of the counterbore 34 , but is out of contact with the power source 50 . The second lead 64 of LED 60 preferably extends over the switch element 90 . A lead extension may be attached to the second lead 64 , as required.
The switch element 90 is preferably a dome plate 92 or a convex conductor that is positioned in the counterbore 34 , but out of contact with the power source 50 . The dome plate is preferably made of a thin, flexible conductive metal stamping. The lead 64 of the LED contacts the dome plate. To ensure contact, the lead may be taped to the dome plate using, for example, 1.5 millimeter thick tape manufactured by 3M. The dome plate preferably has an engaging element 91 located at the center of its inner surface.
When pressure is applied to the dome plate, the dome plate flexes from a convex to a concave configuration, thereby completing the circuit through the first and second leads of the LED, the engaging element of the dome plate, and the power source. When the pressure is removed, the dome plate returns to its convex position breaking contact with the power source and returning the flashlight to its normal “off” position. In this manner, the lead does not come into direct contact with the power source. It should be noted that a number of alternative push button switch arrangements could be used. For example, the power source frame could include a flexible tongue adjacent to the power source. A lead of the LED could be wrapped around the tongue such that depression of the tongue would bring the lead of the LED into contact with another switch element or into direct contact with the power source to complete the circuit. Alternatively, the lead of the LED could be connected to a flexible tongue having a split metal eyelet adjacent the power source, such that depression of the tongue would complete the circuit. In addition, a number of other mechanical or electrical switches could be utilized, such as slide switches and pressure switches.
As shown in FIG. 9 , the keyring lock 80 includes hub 84 operatively connected to a coil spring 82 which is in turn operatively connected to hub 42 of power source frame 22 . It should be understood that many types of springs can be used to bias the keyring lock including coil springs, leaf springs, and U-shaped or plastic springs to name a few. The coil spring may be a separate component, or may be made integral with the power source frame. Spring 82 exerts a force to bias keyring lock 80 to pivot outwardly and about post 40 . The keyring lock 80 is preferably adapted to pivot about post 40 for only a limited distance. Keyring lock 80 further includes a stop 86 that abuts the power source frame 22 to limit the travel of the keyring lock 80 . Preferably, the stop 86 prevents an outer edge 88 of the keyring lock to travel beyond the position where the edge 88 is parallel to an edge 89 of the power source frame. Other keyring locking mechanisms could be used having other forms of springs or resistance to bias the keyring lock. Alternately, the keyring lock could be externally or internally hinged.
The keyring extension 16 and keyring lock 80 of the present invention provide a user with significant versatility in attaching the flashlight to the user's person. For example, the keyring lock 80 may be moved to its open position to allow the flashlight to be easily attached to the zipper of a coat or backpack, the handle of a purse or briefcase, a beltloop, or any other handle or case. In addition, because the keyring lock 80 is normally biased into its closed position, the keyring extension and keyring lock 80 can serve as a clip to easily fasten the flashlight to a shirt pocket or directly to one's clothing. In this manner the shirt pocket or portion of clothing is pinched between an outer end 134 of keyring lock 80 and an outer end 132 of keyring extension 16 . (See FIG. 2 ). The ability to easily clip the flashlight to one's clothing provides the user with great flexibility in carrying the flashlight on one's person.
FIG. 10 is a cross-sectional view of the power source frame 22 of FIG. 4 taken along line 11 . Cavity 24 on side 26 preferably has a depth equal to the thickness of the power source 50 and encloses all but an outer surface of the power source. Counterbore 34 on side 33 is located opposite the cavity 24 and has a terminus 36 in the power source frame and throughhole 38 extending therethrough into cavity 24 . The diameter of the counterbore 34 is preferably slightly larger than throughhole 38 .
FIGS. 3–10 depict the inner workings of an embodiment of the present invention. However, the invention is not intended to be limited by the particular geometry, locations, and components depicted herein, which are illustrative.
FIG. 11 is a side view of the exterior of a first housing side 150 of the power source frame housing 14 depicted in FIG. 1 . First housing side 150 is adapted to fit over and enclose the first side 26 of the power source frame 22 .
FIG. 12 is a side view of the interior 156 of first housing side 150 . A plurality of pegs 158 are preferably positioned about an inner periphery of the first housing side 150 . As mentioned above, the pegs 158 are adapted to engage in a mating relationship a corresponding plurality of pegholes 100 located on an outer periphery of the first side 26 of the power source frame 22 .
FIG. 13 is a side view of an exterior 142 of a second housing side 140 of power source frame housing 14 depicted in FIG. 2 . The second housing side 140 is adapted to fit over and enclose the second side 33 of the power source frame 22 . With reference to FIGS. 2 and 13 , the exterior 142 includes a keyring extension 16 extending from a rear side 144 thereof. An outer end 132 of keyring extension 16 engages an outer end 134 of keyring lock 80 (as shown in FIG. 2 ). Alternatively, the keyring extension could be attached to, or integral with, the power source frame, such that the power source frame housing could fit over and enclose the power source frame, except for the keyring extension. In such an alternate embodiment, the second housing side 140 will be identical to the first housing side 150 , shown in FIG. 12 .
FIG. 14 is a side view of an interior 146 of second housing side 140 . A plurality of pegs 148 are preferably positioned about an inner periphery of second housing side 140 . The pegs 148 are adapted to engage in a mating relationship a corresponding plurality of pegholes 110 located on an outer periphery of the second side 33 of the power source frame 22 .
FIGS. 11–14 show first and second power source frame housing sides having an opening therein to accommodate the side covers shown in FIGS. 15 and 16 . It should be understood, however, that the power source frame housing sides are not limited to accommodating the particular side covers shown in FIGS. 15 and 16 . They could be modified to be used with side covers of any geometry. In addition, the housing sides could be made without any openings and used without side covers, such that the power source frame housing sides would completely enclose the power source frame housing. Also, the power source frame housing can be made from any suitable material, and is preferably strong and durable. In a preferred embodiment, the power source frame housing is made of ABS.
FIGS. 15 and 16 are side views of first and second side covers 160 and 170 . The first and second side covers are preferably positioned between the power source frame 22 and the power source frame housing 14 . First and second side covers 160 and 170 are generally flat and adapted to conform to the outer surfaces of the power source frame 22 such that the side covers preferably lie in parallel planes when positioned between the power source frame 22 and the power source frame housing 14 . The power source frame housing 14 conceals the edges of the side covers when they are positioned between the power source frame 22 and the power source frame housing 14 . The side covers may be of any suitable material including metals, rubbers, and plastics. Preferably the side covers are made of stamped aluminum, preferably anodized 6061 aluminum, and have surfaces suitable for marking or engraving. As noted above, it is often desirable to engrave or imprint the side covers with surface indicia. For example, a company logo or name of a product could be located on either of the side covers. The use of engraving or printing on the side covers can be used for promotional or advertising purposes. In addition, a flashlight bearing certain markings on the side covers could serve as a prize or be used to commemorate an important event.
FIGS. 35 and 36 illustrate a die struck medallion 161 inset in one of the side covers 162 . A hole 163 is cut in the side cover 162 the size of the medallion 161 . The medallion is shown as cylindrical, but could be any shape, i.e., box, oval, etc. A piece of adhesive 164 is placed inside of the cover so that an adhesive portion 165 faces the outside of the side cover and forms a medallion pocket that permits the medallion to be attached to the side cover. Other mechanisms can be used to attach the medallion to the side cover such as adhering a support piece within the side cover to form the base of the medallion pocket and using an appropriate adhesive to attach the medallion to the side cover. Also, although the medallion is generally metal, it can be any suitable material, i.e., plastic.
A further embodiment is shown in FIGS. 33 and 34 wherein the side cover 166 is die struck metal, i.e., brass, aluminum, wherein the entire side cover 166 is die struck metal, i.e., brass, aluminum having the desired depiction 167 (positive), 167 a (negative) die struck on both sides 168 and 169 for greater detail. This provides a special flashlight for a designated group of people.
The side covers can be made of a variety of materials, such as metal, plastic, or other protective materials. Generally, the side covers are preferably made of anodized aluminum. Aluminum provides the desired strength to the side covers and is easily engraved or imprinted. Indicia may be laser engraved, silk screened, inked, pad printed, or marked in any known manner.
The side covers are on both sides of the power source frame and are held by the power source frame housing. The side covers provide additional protection to the internal components of the flashlight. The sturdy aluminum construction serves to guard the light source and power source from external forces. Moreover, there is an insulated pocket located between the power source frame and the side covers that provides an air cushion that serves to further protect the light source and power source within the power source frame housing. As noted above, in applications where no side covers are used, it is desirable to similarly provide a spaced pocket of air between the power source and the power source frame housing sides to further protect the light source and power source.
As shown in FIG. 15 , the second side cover 170 has a hole 172 therethrough adapted to receive a switch button 18 (shown in FIG. 17 ). When the side cover 170 is positioned between the power source frame 22 and the power source frame housing 14 , hole 172 is located adjacent the switch element 90 . In a preferred embodiment, a thin piece of foam (not shown) is attached to the inner surface of the first side cover 160 . When the flashlight is assembled, the piece of foam serves to compress the first lead 62 of the light source 20 into engagement with power source 50 . The piece of foam also serves to keep the elements of the power source frame 22 tightly enclosed therein, and prevents the internal components from rattling or making noise when in use.
FIG. 17 is a side view of switch button 18 . Switch button 18 is preferably circular with a circular recess 182 about its periphery. The recess 182 is adapted to secure the switch button 18 to the second side cover 170 . Switch button 18 is preferably made of a resilient material, such as rubber, to allow the button to deform when a force is exerted thereon. In a preferred embodiment, the switch button 18 is made of Kraton, the trade name of a thermoplastic rubber made by the Shell Oil Company.
The switch button 18 further includes an engaging element 184 on an interior surface thereof. When a force is exerted on the button, the engaging element 184 contacts the switch element 90 located in the power source frame 22 . When not engaged, the engaging element 184 is preferably out of contact with the switch element 90 .
FIG. 18 is a partial cross-sectional view of the flashlight 10 taken along the line 22 of FIG. 2 . As shown in FIG. 18 , switch button 18 is secured to second side cover 170 , which is positioned between the second housing side 140 of power source frame housing 14 and the power source frame 22 . The engaging element 184 of switch button 18 is preferably positioned adjacent to, but out of contact with, dome plate 92 . An outer periphery 186 of the interior surface of switch button 18 engages an outer periphery of dome plate 92 . As a force is exerted on switch button 18 , the engaging element 184 contacts dome plate 92 . The dome plate 92 then moves in a direction towards the power source 50 until it comes in contact with power source 50 . Once contact is made, a circuit including the leads of the light source 60 , the dome plate 92 , and the power source 50 is completed.
Typically, a flashlight pressure switch makes noise upon its engagement. With the switch button configuration shown herein, the noise created by the dome plate 92 coming in contact with the power source 50 is muffled because the switch button 18 completely encloses the dome plate 92 in the power source frame. Moreover, a raised annular portion 190 of the power source frame partially encloses the outer diameter of the switch button to further enclose the switch button and muffle any sound from the operation of the dome plate. In addition, 1.5 millimeter thick 3M tape may be placed over the lead and dome plate to further muffle the sound of the switch operation. In addition, a small notch is placed in the outer periphery 186 of the interior surface of switch button to allow air to escape through the notch when the button is depressed.
Thus, any noise created is muffled within the switch button 18 . In addition, with the disclosed switch button configuration, when a force is exerted on the dome plate 92 , the user is able to feel the flexure of the dome plate as it moves into contact with the power source 50 . Thus, the switch button configuration provides tactile feedback to the user so that the user is able to feel when the dome plate has come into contact with the power source, and when it is released. This tactile feedback is particularly useful where the flashlight is being operated out of the direct sight of the user, and it is not possible to tell by sight whether the flashlight is on or off.
FIGS. 19–23 depict an alternate embodiment of a miniature LED flashlight. As shown in FIGS. 19 and 20 , power source frame 222 has oppositely disposed first and second sides 226 , 233 that are generally flat and lie in parallel planes. The power source frame 222 further includes a cavity 224 located on the second side 233 of the power source frame adapted to receive a power source, such as that depicted in FIG. 5 . The frame 222 also is provided with a receptacle 228 at a front end 230 thereof, adapted to receive a light source, such as that depicted in FIG. 6 . The first side 226 further includes a light source lead channel 229 extending to cavity 224 from receptacle 228 to allow a lead from the light source 220 to extend into cavity 224 .
As depicted in FIG. 20 , the power source frame 222 may also include a cavity 232 adapted to receive a weight. In the embodiment shown in the FIGS. 19 and 20 , although not required, the power source cavity 224 and the weight cavity 232 have a bottom support 235 positioned on side 226 of the power source frame 222 . The bottom support 235 may be separate from, but is preferably molded integrally with, the power source frame 222 . In addition, the bottom support 235 is shown supporting both the power source cavity 224 and the weight cavity 232 , but also could be limited to support only one or the other.
As shown in FIGS. 21 and 22 , a power source cavity cover 240 may be used in connection with the power source frame 222 shown in FIGS. 19 and 20 . Power source cavity cover 240 may include pegs 242 that mate in pegholes 244 located on side 233 of power source frame 222 . While such pegs are preferred for proper alignment of the power source cavity cover, any number of known conventions, such as notches, tabs, etc. could be used to properly position and secure the power source cavity cover to the power source frame. The power source cavity cover may be provided with a counterbore 250 having a terminus 252 within the power source cavity cover 240 . As shown in FIGS. 21 and 22 , the counterbore 250 is adapted to receive a switch element. Preferably, the switch element is a dome plate, such as that shown as element 92 in. FIG. 18 . Of course, other types of flexible switch plates can be suitably used. As shown in FIG. 23 , when the power source cavity cover 240 is positioned on the power source frame 222 , the counterbore 250 is preferably located opposite the power source cavity 224 and includes a throughhole 254 extending into cavity 224 that is located on the side 233 of the power source frame 222 .
Referring back to FIGS. 19 and 20 , keyring extension 260 extends from power source frame 222 . Keyring extension 260 includes an outer end 262 adapted to engage and connect to an outer end of a keyring lock of the type shown in FIG. 2 . In an embodiment shown in FIGS. 24 and 25 , the outer end 262 includes a latch 264 that connects to a latch receptacle 266 of the keyring lock 268 . This configuration provides for a positive lock between the outer end 262 of the keyring extension 260 and the keyring lock 268 . The keyring lock may be attached to the interior of the housing, or to the power source frame, using any suitable means of attachment. Preferably, the keyring lock is springbiased and may pivot about a circular post 270 (shown in FIG. 20 ) in the same manner as shown in FIG. 9 . Alternatively, as shown in FIGS. 26 a and 26 b , the keyring lock may include a receptacle hood 270 that extends over the receptacle 272 , such that the receptacle hood 270 abuts the keyring extension latch 264 , thus preventing an over-extension of the keyring lock 268 . Preferably, the keyring extension is made of ABS, Acrylonitrile Butadiene Styrene, along with the power source frame, although any suitable nonconductive material may be used. The keyring lock is preferably made of a different material, such as nylon, so that it does not become welded to the keyring extension during ultrasonic welding of the power source frame housing sides.
In yet an additional embodiment, shown in FIGS. 27 through 29 , a power source frame 322 may include a magnet cavity 370 positioned in bottom support 335 that is adapted to receive a magnet 372 . The magnet attracts both the power source and the weight, if used, to further maintain the placement of the internal components. In the absence of a power source frame, the magnet is preferably positioned within the housing. In a preferred embodiment, the internal magnet 372 is approximately 0.060 inches thick and a half inch in diameter. The magnet is advantageously made of Neodymium alloyed with iron and boron. Most preferably it is a NEP3042NP Neodymium 30 magnet having a Rockwell C scale hardness of 55 available from Bunting Magnets. It is also preferably nickel plated to protect against corrosion. The magnet weighs only 0.003 pounds and has a holding force of three pounds. The use of an internal magnet allows the outer surfaces of the light to maintain their distinctive smooth lines and allows for engravings or other indicia to be placed on the outer surfaces of the light. With this magnet, the light can be attached to refrigerators, toolboxes, or any metal surface. An adhesive steel disc may be provided that may be mounted on any surface in any location to provide a place to attach the light. For example, the steel disc can be mounted to the interior dashboard of a car to provide a resting place for the light and allow for quick retrieval when needed.
A further alternative embodiment is shown in FIGS. 30 and 31 . This embodiment includes a translucent housing 400 . The translucent housing may be made of polycarbonate. The flashlight may be constructed using any of the various embodiments disclosed herein. Preferably it includes a power source frame 410 that may also be made of translucent material. In a preferred embodiment, the flashlight includes a translucent power source frame housing 420 having integral side covers that together completely enclose the power source frame. The housing is preferably made of a colored translucent material that may include a matching colored LED 430 . For example, a flashlight having a red colored translucent housing may be used with a red LED. With the translucent housing, the light emitted from the LED is dispersed throughout the housing to provide an illuminated housing. Alternatively, the housing may be provided with separate side covers that are either translucent or opaque. Different colored LEDs may be used with a different colored housing, as well as different colored side covers to provide a rainbow, or kaleidoscope of colors. Or, if the side covers are opaque, the light is only dispersed throughout the translucent portion of the housing.
In an further alternative embodiment, shown in FIG. 32 , flashlight 500 may include a keyring extension 510 extending from the housing, or power source frame if used, and may further include a keyring lock 520 extending from the interior of the housing, or the power source frame if used. The keyring lock 520 is preferably springbiased, or most preferably internally hinged, as shown in FIG. 32 . The keyring lock 520 includes an outer end 530 that is biased towards and abuts an outer end 540 of keyring extension 510 . The keyring lock operates to allow a keyring to be slipped between the outer end 530 of the keyring lock and the outer end 540 of the keyring extension 510 . This embodiment also may include side covers 550 that are made of santoprene.
While certain features and embodiments of the invention have been described herein, it will be readily understood that the invention encompasses all modifications and enhancements within the scope and spirit of the present invention. | A flashlight having a light-emitting diode light source with first and second leads extending therefrom, a power source, a power source frame enclosing at least a portion of the power source; a housing containing the light source and power source, a switch located adjacent the power source and operable to close a circuit including the light source and the power source, and wherein one or all of the following may be included 1) a keyring extension extending from a power source frame or the housing with the keyring extension having an opening whereby an article can be attached to the keyring extension and includes a keyring lock wherein upon exerting a force against the keyring lock, the keyring lock is opened to permit the article to be attached to the keyring extension; 2) the housing is comprised of translucent material; and 3) the housing includes at least one side cover which is not integral with the housing and the at least one side cover being selected from anodized aluminum, anodized metal, anodized metal which includes indicia, die struck metal, laser engraved metal, and a side cover having a separate medallion attached thereto. | 5 |
BACKGROUND OF THE INVENTION
I. Field of the Invention
The present invention is related generally to transdermal delivery of therapeutic agents by the use of an applied electro motive force (emf), commonly known as iontophoresis. More specifically, this invention relates to the transdermal delivery of agents such as the anti-emesis agent granisetron.
II. Related Art
The process of iontophoresis was described by LeDuc in 1908 and has since found commercial use in the delivery of ionically charged therapeutic agent molecules such as pilocarpine, lidocaine and dexamethasone. In this delivery method, ions bearing a positive charge are driven across the skin at the site of an electrolytic electrical system anode while ions bearing a negative charge are driven across the skin at the site of an electrolytic system cathode.
Earlier, and some present, iontophoretic devices have been typically constructed of two electrodes attached by adhesive materials to a patient, each connected by a wire to a remote power supply, generally a microprocessor-controlled electrical instrument. More recently, self-contained wearable iontophoretic systems have been developed. These systems are advantageous in that they do not have external wires and are much smaller in size. Examples of such systems can be found in a variety of U.S. patents, examples of which include U.S. Pat. Nos. 4,927,408; 5,358,483; 5,458,569; 5,466,217; 5,533,971; 5,605,536; 5,651,768; 5,685,837; 6,421,561; WO 00/12172; U.S. Pat. No. 6,653,014. These systems also include two electrodes fixed to the skin of patients by means of adhesive materials.
Unlike passive delivery patches, iontophoretic devices can incorporate an ability to modify delivery rates with simple adjustments to the magnitude of current flow. This ability can be used to create a wearable system, wherein patients can self-adjust medication delivery in accordance to individual needs. U.S. Pat. Nos. 6,171,294; 6,216,033; 6,425,892; and 6,745,071 describe iontophoretic devices where patients can self-adjust pain management dosing of fentanyl or sufentanyl using either on-demand bolus dosing or changes in continuous delivery rate.
Two-stage iontophoretic devices have also been described, where an initially high level of current can be used to induce a rapid onset of action, followed by a automated decrease in current to a lower continuous level in order to provide a “maintenance” dosage over an extended time-period. U.S. Pat. Nos. 5,207,752 and 6,421,561 are examples that serve to describe devices having such staged delivery profiles.
The present invention relates to an improved application of iontophoresis useful for the treatment of emesis. Emesis, in the form of nausea and vomiting, commonly occurs following chemotherapy, post-operatively following treatment with anesthetic agents, or after exposure to biologic agents and/or radiation, possibly in a military setting. It will be appreciated that oral dosage forms are convenient, but are unreliable because in the case of emesis, patients may be unable to keep the medication ingested.
Granisetron is a selective antagonist of 5-hydroxytryptamine (5-HT3) receptors, and commercially available in oral or injectable dosage forms. It is known to be an effective agent for the management of emesis, as both a primary dose and as a “rescue dose” medication. The term “rescue dose” is defined as an additional dose necessary to treat breakthrough or recurring symptoms. For additional information see, for example, “Dose finding study of granisetron in patients receiving high-dose cisplatin chemotherapy”, by A. Riviere in Br. J. Cancer, 69, 967-971 (1994), which provides an informative summary of clinical effectiveness of granisetron administered both as primary and rescue dosing medication.
As to the mode of administration, the disadvantage of oral administration is evident as noted above. A disadvantage of injectable administration forms lies in the invasive nature of injections, which can be painful, require clinical skill, can lead to infection, and are therefore are not suitable to self administration in a field or home setting.
Recognizing the shortcomings of oral and injectable dosage forms for granisetron, several companies have described methodologies for a transdermal administration process. Included are delivery systems for transdermal administration by: passive patches, heated passive patches, passive patches applied onto RF treated skin, and spray-on-skin systems where the total amount applied is fixed and delivery is improved by co-formulated permeation enhancers.
One advantage of transdermal systems is an ability to provide a sustained release of medication over time, which may serve to provide a longer duration of action. However, a significant limitation and disadvantage of passive transdermal administration is a slow onset of sufficient action to provide relief. It is not uncommon for a passive transdermal patch to take several hours (3 or more) before a therapeutic dosage is achieved. With passive transdermal delivery, the skin can act as a depot, and release to the bloodstream will not occur until that skin depot area is saturated. This slow onset of action acts as a clinical limitation in two respects: 1) it cannot replace an existing oral or injectable form because it is a necessity to apply a patch several hours prior to a chemotherapy or operative procedure, and 2) a slow acting transdermal patch cannot reasonably serve as a rescue medication form, where a patient will prefer, for obvious reasons, a faster acting treatment. This second limitation is significant, in that it has been shown that, in many cases of highly emetogenic therapies, such as high dose chemotherapy, a significant percentage of patients will not be adequately served by a first, primary dosage form alone.
A more rapid onset of action can be achieved transdermally by using a system that includes iontophoresis. Granisetron in its hydrochloride salt form, is positively charged and can be delivered rapidly from a positively charged anode pad. Recent reports, for example, Scientific Abstract 1: Evaluation of iontophoretic permeation kinetics of granisetron through skin by subcutaneous microdialysis, presented at the 2003 AAPS meeting October, 2003; Scientific Abstract 2: IVIVC of Iontophoretic Delivery of granisetron by subcutaneous microdialysis, presented at the 2004 AAPS meeting October, 2004, have demonstrated that with iontophoresis, a therapeutic dosage can be achieved (in a hairless rat animal model) within approximately two-hours.
The two-hour system described in the reports, however, is not likely to provide additional benefit for emesis which may occur for up to several days after an exposure to an emetogenic procedure. Additionally, even the two-hour timeframe for achievement of a therapeutic dosage level is also an unacceptably long period of time necessary for clinician and patient to be waiting prior to an emetogenic treatment such as chemotherapy. Finally, the known iontophoresis patches do not provide a means to administer a second or rescue dosage for emesis management in the event the primary dosing from the patch is inadequate.
Therefore, a need exists for a simple-to-operate, inexpensive transdermal dosage form which can not only provide benefit afforded by a transdermal release of agents such as granisetron, but can also provide an initial or primary dose and one or more follow-on self-administered rescue doses treatment very rapidly.
SUMMARY OF THE INVENTION
The present invention provides a transdermal iontophoresis device and method that has the ability to administer a bolus dosage of a therapeutic agent, particularly a therapeutic granisetron bolus dosage rapidly using a single-use, disposable transdermal patch. In the case of granisetron, the patch of the invention provides an onset of a therapeutic level of action in generally less than one hour. Additionally, at least one embodiment of the patch device enables a patient to rapidly self-administer at least a second or rescue dose after the initial primary dose.
In one embodiment illustrating the invention, there is provided a disposable skin-worn patch device for the transdermal delivery of a plurality of doses of a charged therapeutic substance such as granisetron by iontophoresis. The device includes a reservoir from which the therapeutic agent is delivered into the body (donor reservoir) containing an amount of the substance to be delivered transdermally by iontophoresis and one or more donor electrodes, a counter reservoir containing a counter electrode which serves to complete the electrical circuit through the body, a source of electric power connected in a circuit between the donor reservoir and the counter reservoir and a user-operable control system for controlling current flow in the circuit to enable a plurality of successive doses of therapeutic substance to be administered from the donor reservoir. The multiple doses may be controlled by switching and selectively connecting each one of a plurality of donor electrodes designed to be oxidized or reduced in the iontophoresis circuit operation.
Those skilled in the art will recognize that microprocessor or other electronic or electrical control circuits can be used to regulate the rate of current flow, and therefore the rate of medication delivery. In an alternative embodiment, such a control circuit is implemented to create a device which can provide bolus and/or alternative waveform dosing from a single donor electrode configuration.
A first dose may be provided automatically by the application of the patch to the skin of a patient by a pre-determined switching device in the circuit. Optionally, the patch also can be employed to supply a sustained, lower-level delivery rate of granisetron following an initial bolus dose. Such as system is illustrated and described, for example, in U.S. Pat. No. 6,421,051 assigned to the same assignee as the present application and which is deemed incorporated herein by reference for any purpose.
In another detailed embodiment, a disposable skin-worn patch is provided that incorporates an activation system to automatically administer granisetron after a sensor triggers the system based on an alarm signal. That control system is designed to respond to an externally generated signal, such as a radio frequency signal which may be given to a plurality of such devices as might be worn by soldiers in a military setting. A switch device may be provided in the circuit to prevent accidental activation from occurring in stored patches.
Whereas other substances may be delivered from either an anode or a cathode chamber, using the iontophoresis device of the invention, as indicated above, one preferred therapeutic substance to be delivered is granisetron. The granisetron may preferably be contained in a hydrogel formulation and preferably as a charged species which can only successfully be delivered in a therapeutic dose utilizing an active iontophoresis technique. Generally, granisetron and other therapeutically active species contained in an ionic or charged form, for iontophoresis deliveries migrate transdermally only slightly using passive application systems. Such an approach would not deliver a therapeutically effective level of material. Hydrogels based on polyvinylalcohol, hydroxypropylmethylcellulose (HPMC), and polyethylene oxide are examples of hydrogels that can co-formulated with the granisetron.
A therapeutic dose of granisetron is generally accepted to be between about 300 μg and 1000 μg. Patches in accordance with the present invention have the capacity to administer or deliver a bolus dosage between about 300 μg and 1000 μg, in less than about 1 hour. In this regard, it has been determined that an iontophoretic charge dosage between 20 and 60 mAmin can be used to successfully deliver this amount, so that current in the range of 0.3 and 1.0 mA would be required for a one-hour delivery period. Further, it has been learned that an optimal range of current density falls between 50 μA and 250 μA per square centimeter. Therefore, the delivery pad contact area needs to be sized with consideration given to this as a desired current density range.
With respect to the successful and rapid administration of granisetron by iontophoresis, it has also been determined that the total granisetron content supplied in the donor reservoir or pad should exceed the desired total quantity to be delivered by a significant amount. Generally, this has been found to be a factor of two or even more. Thus, if the desired total dosage to be delivered, for example, is 2 milligrams (2 mg), it has been found that at least 4 mg should be provided in the donor reservoir or pad. Generally, significant loss of delivery efficiency is seen in a second or rescue dose if the total content of granisetron in the patch is less than twice the total amount of granisetron desired to be delivered.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings where like reference characters depict like parts:
FIG. 1 is a schematic representation of an embodiment of a transdermal patch in accordance with the invention capable of delivering a plurality of doses of a therapeutic agent;
FIG. 2 is a schematic representation of an alternate embodiment of a transdermal patch in accordance with the invention selectively designed to be activated by an external signal;
FIG. 3 is a schematic representation of another embodiment of the invention capable of delivering a plurality of doses of a therapeutic agent utilizing a single donor electrode; and
FIG. 4 is a schematic representation of an embodiment similar to that in FIG. 2 including an element to preclude untimely activation.
DETAILED DESCRIPTION
The detailed description contained in this specification is intended to illustrate the principles of the invention and not to limit them. A limited number of illustrative embodiments are presented as examples and, it is anticipated, that others would occur to those skilled in the art which would be within the scope of the inventive concept.
FIG. 1 represents an iontophoretic patch device that automatically releases a dosage of granisetron or other therapeutic agent upon application of the device to the skin. That device is additionally capable of releasing a second dosage after a patient activates a switching device.
The embodiment of FIG. 1 illustrates an iontophoretic self-powered skin-applied adhesive patch device generally at 10 . The patch includes a cathode chamber or counter reservoir 12 containing a cathode or counter electrode 14 and an anode chamber or donor reservoir 16 containing a pair of anodes 18 and 20 spaced and electrically isolated from each other, but electrically connected to respective conductors 22 and 24 and to the material in the reservoir 16 . A two-position switch element is shown at 26 and a pair of power sources, which may be conventional button-type batteries are shown connected in series at 28 and 30 . Additional interconnecting conductor elements are shown at 32 , 34 and 36 . Thus, using the switch 26 , either anode 18 or 20 can be selectively connected or patched into a circuit which is completed by the application of the patch 10 to the skin of a patient, as is well known.
The charge capacity and so the dosage associated with either anode 18 or 20 can further be adjusted to any desired amount as by adjusting the content of oxidizable species at each anode such that depletion of the oxidizable species or isolation of the connection will produce an open circuit condition with that anode connected. Techniques for this are illustrated and described in U.S. Pat. No. 6,653,014 assigned to the same assignee as the present application and which is hereby incorporated by reference herein for any purpose.
Although one and two-anode devices are shown in the figures, it will be appreciated that, optionally, additional anodes, conductors and switch positions could readily be added, if desired. The circuit, optionally, can include elements to limit or control current flow in a known manner to produce a longer-lasting lower dosage at any switch position. For example, it may be desired to administer a low steady dose of granisetron of perhaps about 40 μg/hr over a long period of time after an initial bolus or first primary dose has been administered. Also, additional or other types of DC power sources and controls including programmed controls optionally such as shown in FIG. 3 , for example, can be used.
In operation, when the iontophoresis patch device of FIG. 1 is adhesively applied to the skin of a patient, this will complete a first circuit including a selectively included anode 18 , 20 and the patch will immediately activate and begin to deliver a dosage of granisetron or other therapeutic agent contained in the anode or donor reservoir commensurate with the amount of oxidizable species available to the circuit at the then connected anode. This will preferably be preset by the position of the switch 26 set at the point of manufacture so that a known initial bolus of the granisetron as an initial therapeutic dosage can be delivered rapidly as soon as the device is applied to the skin of a user. Thereafter, if a second or so-called “rescue” dose is required, it can be triggered when the user operates the switch 26 to the alternate position to connect a second or alternate anode 18 , 20 in the circuit to self-administer an additional dose of granisetron.
The alternate embodiment of FIG. 2 includes a similar skin-applied, self-powered adhesive patch 40 which includes a cathode chamber or counter reservoir 42 with cathode or counter electrode 44 , an anode chamber or donor reservoir 46 provided with a single anode or donor electrode 48 . A normally open switch or other activation element or device 50 , connected with an associated sensor 52 for receiving external activation signals, is provided in the circuit between anode 48 and a pair of series-connected power sources 54 and 56 . Connecting conductive elements are shown at 58 , 60 , 62 and 64 .
This embodiment is designed to be worn by one potentially in need of receiving a dose of the therapeutic material of the patch. Activation of the patch and delivery of the medication, however, is controlled by an externally generated signal being received by sensor 52 which, in turn, triggers the element 50 to close a switch or otherwise function to complete the circuit. The embodiment 40 is shown with a single anode and so is designed to deliver a single dose to the wearer.
It will be appreciated that the sensing device 52 may be designed to receive any of many types of signals including radio frequency, audio, infrared, etc., and a single signal may activate the patches of many wearers as might occur among troops commonly engaged in a military setting. This embodiment provides a means for automated iontophoretic transdermal granisetron administration in a military field setting, as may be required for example, with an unexpected exposure of soldiers to radiation and/or chemical and biological agents.
FIG. 4 depicts a sensor-activated embodiment 40 a , similar to that shown in FIG. 2 that is provided with a user activated element to provide protection against unwanted activation of the patch (such as in storage). Thus, the embodiment of FIG. 4 is provided with a manually-operated switch as at 70 which is designed to be closed by the user prior to sensor-controlled activation. In an open position, switch 70 interrupts the power on conductor 60 thereby disconnecting the power source 56 . The closing of the switch 70 also actives the sensor 52 which is otherwise in an off mode. This embodiment is shown with a single power source 56 but as was the case in the embodiment of FIG. 2 , additional power sources, or other controls as in FIG. 3 , of course, may be used. Once the switch 70 is adjusted to the closed position by the user, the system is enabled for automated sensor-controlled activation.
A further embodiment 10 a is shown in FIG. 3 in which an electronic control circuit or element 37 is connected by a conductor 38 to switch 26 and by a conductor 39 to power source 28 . The electronic control circuit element 37 may include a microprocessor or a microprocessor-operated control which may be a timing controller such as are well known and which may operate in conjunction with a single donor electrode 20 a to deliver a plurality of doses from the patch as controlled by the element 37 and switch 26 . This is an alternative operating scheme to that of sequential electrode depletion shown in FIG. 1 . The control system may be used to provide a sustained or steady low-level delivery of therapeutic agent. In the case of granisetron, this may be about 30-50 μg/hr and preferably about 40 μg/hr, for example.
The examples of the detailed description show the administration of a therapeutic agent in which the donor reservoir is the anode chamber. Of course, as previously indicated, for example, it will be recognized by those skilled in the art that an oppositely charged material might be administered using the cathode chamber as the donor reservoir and the anode chamber as the counter reservoir. Other variations in configuration and control are also contemplated. These may include circuit components to control delivery power over time or the like.
This 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 and operating procedures, as well as materials, can be accomplished without departing from the scope of the invention itself. | A disposable skin-worn device for the transdermal delivery at least one dose of charged therapeutic substances, including granisetron, by iontophoresis, the device comprising a donor reservoir containing an amount of a therapeutic substance to be delivered transdermally by iontophoresis, a counter reservoir, a source of electric power connected in a circuit between the donor reservoir and the counter reservoir and a control system for controlling current flow in the circuit to enable at least one dose of the therapeutic substance to be delivered transdermally by iontophoresis and wherein the control system includes a control element selected from the group consisting of a sensor activated by an external signal and a switch. | 0 |
BACKGROUND OF THE INVENTION
The present invention relates to the use of certain substituted spiro pyridine derivatives in suppressing the immune response.
The preparation of a spiro[cyclopentane]-quinolinedione is described in Chem. Pharm. Bull., 17, 1290 (1969). Several additional spiroquinoline diones are disclosed in Bull. Soc. Chim. Fr., 364 (1968). The references do not describe pharmaceutical uses for these compounds.
SUMMARY OF THE INVENTION
The present invention is drawn to a method for suppressing the immune response in a mammal which comprises administering to a mammal in need of such treatment an immunosuppressing effective amount of a compound having the structural formula I: ##STR1## or solvate thereof, wherein:
two of the ring groups a,b,c and d may be CH or N and the remaining two groups represent CH;
Y and Z independently represent O or S;
V represents O, S(O) n , ##STR2##
each R independently represents hydrogen, C 1 to C 6 alkyl, CH 2 OH, COR 7 (wherein R 7 represents hydrogen or C 1 to C 6 alkyl) or hydroxy, with the proviso that only one hydroxy group can be attached to one carbon atom;
each R' independently is as defined for R above, except that when V represents O, S(O) n or N-R 8 , R' may not be hydroxy;
R 8 is hydrogen, alkyl having from 1 to 6 carbon atoms, carboxylic acyl having from 2 to 7 carbon atoms, alkylsulfonyl having from 1 to 6 carbon atoms, carboalkoxy having from 2 to 7 carbon atoms, CONH 2 , phenyl or pyridyl of which the last two may be substituted with up to three substituents, Q, whereby each Q independently is hydroxy, alkyl having from 1 to 6 carbon atoms, halogen, nitro, alkoxy having from 1 to 6 carbon atoms, trifluoromethyl, cyano, cycloalkyl having from 3 to 7 carbon atoms, alkenyloxy having from 3 to 6 carbon atoms, alkynyloxy having from 3 to 6 carbon atoms, S(O) n -R a {wherein n is defined herein and R a is alkyl having from 1 to 6 carbon atoms}, NHSO 2 R a {wherein R a is defined herein}, NHSO 2 CF 3 , SO 2 NH 2 , COR b {wherein R b is OH, NH 2 or OR a (wherein R a is defined herein)}, O-B-COR b {wherein B is alkylene having from 1 to 4 carbon atoms and R b is defined herein}, or NHCOR c {wherein R c is hydrogen, alkyl having from 1 to 6 carbon atoms, alkoxy having from 1 to 6 carbon atoms, COR d (wherein R d is hydroxy or alkoxy having from 1 to 6 carbon atoms) or NHR e (wherein R e is hydrogen or alkyl having 1 to 6 carbon atoms)};
R 5 and R 6 may be the same or different and are hydrogen, alkyl having from 1 to 6 carbon atoms, halogen, nitro, alkoxy having from 1 to 6 carbon atoms, trifluoromethyl, alkylthio having 1 to 6 carbon atoms or cyano;
n is 0, 1 or 2;
r is 0, 1 or 2;
q is an integer of from 1 to 5; and
A is phenyl, naphthyl, indenyl, indanyl, 2-, 3- or 4-pyridyl, 2-, 4-, 5- or 6-pyrimidyl, 2- or 3-pyrazinyl, 2- or 3-furyl, 2- or 3-thienyl, 2-, 4- or 5-imidazolyl, 2-, 4- or 5-thiazolyl or 2-, 4- or 5-oxazolyl, any of which may be substituted with up to three substituents Q as defined herein above.
A preferred subgenus of compounds is that wherein Y and Z are both oxygen.
Preferably, a, b and c represent CH and d is either CH or N. A further preferred feature is that r is zero, i.e. the group A is directly attached to the ring-nitrogen atom. q is preferably 2, 3 or 4, V most preferably is CH 2 or O and R 5 and R 6 are both hydrogen.
Particularly preferred are compounds of the structural formula II ##STR3## wherein d is CH or N, q is 2, 3 or 4 and A, V, R and R' are as defined above.
As disclosed in European published application No. 84114974.3 (European patent publication No. 0 144 966 A2), these compounds possess anti-allergy and anti-inflammatory activities. It has now unexpectedly been found that these compounds possess immunosuppressive activity.
DESCRIPTION OF THE INVENTION
When utilized herein and in the appended claims the below listed terms, unless specified otherwise, are defined as follows:
halogen - comprises fluorine, chlorine, bromine and iodine;
alkyl and alkoxy - comprises straight and branched carbon chains containing from 1 to 6 carbon atoms;
alkenyloxy - comprises straight and branched carbon chains containing from 3 to 6 carbon atoms and comprising a carbon to carbon double bond; and
alkynyloxy - comprises straight and branched carbon chains containing from 3 to 6 carbon atoms and comprising a carbon to carbon triple bond.
The compounds of the invention include a ##STR4## substituent wherein the R groups may vary independently. Thus, for example, when r or q equals 2 the following patterns of substitution (wherein hydrogen and CH 3 are used to represent any substituents R) are contemplated: --C(CH 3 ) 2 CH 2 --, --CH 2 C(CH 3 ) 2 --, --CH 2 CH(CH 3 )--, --CH(CH 3 )CH 2 --, --(C(CH 3 )H) 2 -- and the like. In addition when r or q equals 2, substituents such as --C(CH 3 ) 2 CH(C 2 H 5 )--, --CH(CH 3 )CH(C 2 H 5 ) are also contempleted.
It would be obvious to one of ordinary skill in the art that due to problems of stability there are limitations involving the R and R' groups. One limitation is that neither R can be a hydroxy group attached to the carbon alpha to the ring nitrogen atom. Another limitation is that the R and R' groups cannot both be hydroxy groups attached to the same carbon atoms.
Certain compounds of the invention may exist in isomeric forms. The invention contemplates all such isomers both in pure form and in admixture, including racemic mixtures. In the structural formulas I and II herein, when V represents a hetero atom in the spiro ring, V is attached directly to the spiro carbon atom, i.e., the carbon atom identified as number 3 in structural formula I.
The compounds of formula I can exist in unsolvated as well as solvated forms, including hydrated forms. In general, the solvated forms, with pharmaceutically acceptable solvents such as water, ethanol and the like are equivalent to the unsolvated forms for purposes of the invention.
Representative compounds of formula I are exemplified below in Table I:
TABLE I__________________________________________________________________________ ##STR5##Compound No. d a A Y Z V CR'R'(CRR).sub.q m.p. (°C.)__________________________________________________________________________1 N CH phenyl O O CH.sub.2 trimethylene 174-1782 N CH 3-hydroxyphenyl O O CH.sub.2 trimethylene 218-2203 N CH 3-methoxyphenyl O O CH.sub.2 trimethylene 159-160.54 CH CH phenyl O O CH.sub.2 trimethylene 168-1685 N CH 3,4-chlorophenyl O O CH.sub.2 trimethylene 143-145.56 N CH 4-chlorophenyl O O CH.sub.2 trimethylene 168.5-1727 N CH 4-methylphenyl O O CH.sub.2 trimethylene 177-178.58 N CH 3-chlorophenyl O O CH.sub.2 trimethylene 165-1679 N CH 3-chlorophenyl S O CH.sub.2 trimethylene 168-17010 N CH phenyl S O CH.sub.2 trimethylene 188-189.511 N CH 3-ethyloxalylamino phenyl O O CH.sub.2 trimethylene 158-16012 N CH 3-fomylaminophenyl O O CH.sub.2 trimethylene 222-22413 N CH 3-aminophenyl O O CH.sub.2 trimethylene 200-20214 N CH 3-(ethyloxycarbonylmethoxy)phenyl O O CH.sub.2 trimethylene 103-10515 N CH phenyl O O O trimethylene 241.5-243 (1/3 hydrate)16 N CH phenyl O O O ethylene 233-235.518 N CH phenyl O O S trimethylene19 N CH 3,4-dichlorophenyl O O O tetramethylene20 N CH 3-chlorophenyl O O O tetramethylene 158.5-16021 N CH 4-chlorophenyl O O O tetramethylene 229-231.5 (hemihydrate)22 N CH 3-methoxyphenyl O O O tetramethylene 181-18323 N CH 4-methoxyphenyl O O O tetramethylene__________________________________________________________________________
The compounds which are utilized in the method of this invention are among those disclosed in U.S. application Ser. No. 561,416 filed Dec. 14, 1983, in U.S. application Ser. No. 641,076, filed Aug. 15, 1984, and in European Published Patent Application No. 841149743 (publication number: 0 144 966 A2). These compounds may be prepared by methods described in those U.S. applications and European published application, the disclosures of which are incorporated herein by reference for that purpose.
The compounds are useful in the treatment of autoimmune and other immunological diseases including graft rejection in which T cell proliferation is a contributing factor to the pathogenesis of disease. The effectiveness of these compounds as immunosuppressing agents may be demonstrated by the following tests which involve the inhibition of T cell functions using these compounds.
GRAFT VS. HOST REACTION (GVHR)
To induce a GVHR, C57 B1/6XA/J(B6AF1) male mice were injected intravenously with parental (C57B1/6J) spleen and lymph node cells. The compound 1-phenyl-3',4',5',6'-tetrahydro-spiro-[1,8]-naphthyridine-3,2'[2H]pyran]-2,4-dione 1/4 hydrate (Compound A) was then administered orally for 10 days beginning on the day prior to the cell transfer. On the day following the last treatment, the animals were sacrificed, and their spleens were excised and weighed. The enlargement of the spleen of the host is a result of a GVHR. To some extent it is the host's own cells which infiltrate and enlarge the spleen although they do this because of the presence of graft cells reacting against the host. The amount of spleen enlargement, splenomegaly, is taken as a measure of the severity of the GVHR.
In carrying out the GVHR the animal in the experimental group is injected with parental cells, cells of the same species but of different genotype, which cause a weight increase of the spleen. The animal in the control group is injected with syngeneic cells, genetically identical cells which do not cause a weight increase of the spleen. The effectiveness of Compound A administered to the mice in the experimental group is measured by comparing the spleen weight of the untreated and treated GVH animal with that of the syngeneic control. Compound A reduced spleen weight by 30% as compared to the untreated animals at a dose of 100 mg/kg, i.e., ED 30 =100 mg/kg.
SPLENIC ATROPHY
The immunosuppressive activity of the compounds may also be shown by a decrease in spleen weight after dosing BDF 1 mice orally with the drug for seven (7) consecutive days. The mice are sacrificed on the eighth day. The percent decrease in spleen weight is measured for each dosage level. In this procedure 1'-(3-chlorophenyl)-spiro-[cyclopentane-1,3'-[1,8 ]-naphthyridine]-2'-4'-(1'H)-dione (Compound B) provided a 30% spleen weight decrease at a dosage level of 100 mg/kg.
As noted, European patent publication No. 0 144 966 A2 discloses that the subject compounds possess anti-allergy and anti-inflammatory activities. For example, Compound A has an ED 50 value of about 2 mg/kg p.o. in tests measuring the inhibition of anaphylactic bronchospasm in sensitized guinea pigs having antigen-induced bronchoconstriction and an ED 50 value of about 19 mg/kg p.o. in tests measuring the reverse passive Arthus reaction in the pleural cavity of rats (as described by Myers et al., Inflammation, Vol. 9 , No. 1 , 1985, pp. 91- 98). Compound A has an ED 30 value of about 100 mg/kg in the GVHR test as described above. These results for Compound A and similar results obtained for other compounds of formula I tested to date indicate that an immunosuppressive effective dose (ED 30 ) for such compounds is about 5 times or more their anti-inflammatory and anti-allergy effective doses (ED 50 s).
The usual dosage range for the compounds of formula I in a 70 kg mammal is an oral dose of about 0.1 to 250 mg/kg, preferably 0.1 to 150 mg/kg, in 3 or 4 divided doses per day. Of course, the dose will be regulated according to the potency of compound employed, the immunological disease being treated, and the judgment of the attending clinician depending on factors such as the degree and the severity of the disease state and age and general condition of the patient being treated.
To treat immunological diseases, the active compounds of formula I can be administered in unit dosage forms such as tablets, capsules, pills, powders, granules, sterile parenteral solutions or suspensions, suppositories, transdermal compositions and the like. Such dosage forms are prepared according to standard techniques well known in the art.
For preparing pharmaceutical compositions from the compounds described by this invention, inert, pharmaceutically acceptable carriers can be either solid or liquid. Solid form preparations include powders, tablets, dispersible granules, capsules, cachets and suppositories. A solid carrier can be one or more substances which may also act as diluents, flavoring agents, solubilizers, lubricants, suspending agents, binders or tablet disintegrating agents; it can also be an encapsulating material. In powders, the carrier is a finely divided solid which is in admixture with the finely divided active compound. In the tablet the active compound is mixed with carrier having the necessary binding properties in suitable proportions and compacted in the shape and size desired. The powders and tablets preferably contain from 5 to about 70 percent of the active ingredient. Suitable solid carriers are magnesium carbonate, magnesium strearate, talc, sugar, lactose, pectin, dextrin, starch, gelatin, tragacanth, methylcellulose, sodium carboxymethylcellulose, a low melting wax, cocoa butter and the like. The term "preparation" is intended to include the formulation of the active compound with encapsulating material as carrier providing a capsule in which the active component (with or without other carriers) is surrounded by carrier, which is thus in association with it. Similarly, cachets are included. Tablets, powders, cachets and capsules can be used as solid dosage forms suitable for oral administration.
For preparing suppositories, a low melting wax such as a mixture of fatty acid glycerides or cocoa butter is first melted, and the active ingredient is dispersed homogeneously therein as by stirring. The molten homogeneous mixture is then poured into convenient sized molds, allowed to cool and thereby solidify.
Liquid form preparations include solutions, suspensions and emulsions. As an example may be mentioned water or water-propylene glycol solutions for parenteral injection. Liquid preparations can also be formulated in solution or suspension in aqueous polyethylene glycol solution. Aqueous solutions suitable for oral use can be prepared by adding the active component in water and adding suitable colorants, flavors, stabilizing, sweetening, solubilizing and thickening agents as desired. Aqueous suspensions suitable for oral use can be made by dispersing the finely divided active component in water with viscous material, i.e., natural or synthetic gums, resins, methylcellulose, sodium carboxymethylcellulose and other well-known suspending agents.
Also included are solid form preparations which are intended to be converted, shortly before use, to liquid form preparations for either oral or parenteral administration. Such liquid forms include solutions, suspensions and emulsions. These particular solid form preparations are most conveniently provided in unit dose form and as such are used to provide a single liquid dosage unit. Alternately, sufficient solid may be provided so that after conversion to liquid form, multiple individual liquid doses may be obtained by measuring predetermined volumes of the liquid form preparation as with a syringe, teaspoon or other volumetric container. When multiple liquid doses are so prepared, it is preferred to maintain the unused portion of said liquid doses at low temperature (i.e., under refrigeration) in order to retard possible decomposition. The solid form preparations intended to be converted to liquid form may contain, in additions to the active material, flavorants, colorants, stabilizers, buffers, artificial and natural sweeteners, dispersants, thickeners, solubilizing agents and the like. The solvent utilized for preparing the liquid form preparation may be water, isotonic water, ethanol, glycerine, propylene glycol and the like as well as mixtures thereof. Naturally, the solvent utilized will be chosen with regard to the route of administration, for example, liquid preparations containing large amounts of ethanol are not suitable for parenteral use.
The composition of the invention may also be deliverable transdermally. The transdermal compositions can take the form of creams, lotions and/or emulsions and can be included in a transdermal patch of the matrix or reservoir type as are conventional in the art for this purpose.
Preferably, the pharmaceutical preparation is in unit dosage form. In such form, the preparation is subdivided into unit doses containing appropriate quantities of the active component. The unit dosage form can be a packaged preparation, the package containing discrete quantities of preparation, for example, packeted tablets, capsules and powders in vials or ampoules. The unit dosage form can also be appropriate number of any of these in packaged form. The compositions can, if desired, also contain other therapeutic agents.
The dosages may be varied depending upon the requirements of the patient, the severity of the condition being treated and the particular compound being employed. Determination of the proper dosage for a particular situation is within the skill of the art. Generally, treatment is initiated with smaller dosages which are less than the optimum dose of the compound. Thereafter, the dosage is increased by small increments until the optimum effect under the circumstances is reached. For convenience, the total daily dosage may be divided and administered in portions during the day if desired.
The following examples are intended to illustrate, but not to limit, the present invention. The term "Compound A" refers to 1'-phenyl-3',4',5',6'-tetrahydro-spiro-[1,8]naphthyridine -3',2'-[2H]-pyran]-2,4-dione 1/4 hydrate. It is contemplated, however, that this compound may be replaced by equally effective quantities of other compounds of formula I as defined above.
EXAMPLE 1
______________________________________TabletsNo. Ingredient m/tablet mg/tablet______________________________________l Compound A 100 5002 Lactose USP 122 1133 Corn Starch, Food Grade, 30 40as a l0% paste inPurified Water4 Corn Starch, Food Grade 45 405 Magnesium Strearate 3 7Total 300 700______________________________________
Method of Manufacture
Mix Item Nos. 1 and 2 in a suitable mixture for 10-15 minutes. Granulate the mixture with Item No. 3. Mill the damp granules through a coarse screen (e.g., 1/4") if needed. Dry the damp granules. Screen the dried granules if needed and mix with the Items No. 4 and mix for 10-15 minutes. Add Item No. 5 and mix for 1-3 minutes. Compress the mixture to appropriate the size and weight on a suitable tablet machine.
EXAMPLE 2
______________________________________CapsulesNo. Ingredient mg/capsule mg/capsule______________________________________1. Compound A 100 5002. Lactose USP 106 1233. Corn Starch, Food Grade 40 704. Magnesium Strearate NF 4 7Total 250 700______________________________________
Method of Manufacture
Mix Item Nos. 1,2 and 3 in a suitable blender for 10-15 minutes. Add Item No. 4 and mix for 1-3 minutes. Fill the mixture into suitable two-piece hard gelatin capsules on a suitable encapsulating machine.
EXAMPLE 3
______________________________________ParenteralIngredient mg/vial m/vial______________________________________Compound A Sterile Powder 100 500______________________________________
Add sterile water for injection or bacteriostatic water for injection for reconstruction.
EXAMPLE 4
______________________________________InjectableNo. Ingredient mg/vial mg/vial______________________________________1. Compound A 100 5002. Methylparaben 1.8 1.83. Propylparaben 0.2 0.24. Sodium Bisulfite 3.2 3.25. Disodium Edetate 0.1 0.16. Sodium Sulfate 2.6 2.67. Water for Injection q.s. ad 1.0 ml 1.0 ml______________________________________
Method for Manufacture
1. Dissolve parabens in a portion (85% of the final volume) of the water for injection at 65°-70° C.
2. Cool to 25°-35° C. Charge and dissolve the sodium bisulfite, disodium edetate and sodium sulfate.
3. Charge and dissolve drug.
4. Bring the solution to final volume by added water for injection.
5. Filter the solution through 0.22 membrane and fill into appropriate containers.
6. Terminally sterilize the units by autoclaving.
While the present invention has been described in conjunction with the specific embodiments set forth above, many alternatives, modifications and variations thereof will be apparent to those of ordinary skill in the art. All such alternatives, modifications and variations are intended to fall within the spirit and scope of the present invention. | A method and composition for suppressing the immune response are disclosed which employ an immunosuppressing effective amount of certain substituted spiro pyridine derivatives. | 8 |
BACKGROUND OF THE INVENTION
1. Field of the invention.
This invention relates to a ceramic welding process in which a mixture of refractory and fuel particles is projected from an outlet at an end of a lance in a gas stream against a target surface where the fuel particles combust in a reaction zone to produce heat to soften or melt the projected refractory particles and thereby form a coherent refractory weld mass. The invention extends to ceramic welding apparatus for projecting a mixture of refractory and fuel particles from an outlet at an end of a lance in a gas stream against a target surface where the fuel particles combust in a reaction zone to produce heat to soften or melt the projected refractory particles and thereby form a coherent refractory weld mass, and in particular to ceramic welding apparatus comprising a lance having an outlet for the discharge of a ceramic welding powder mixture.
Ceramic welding processes are principally used for the repair of worn or damaged refractory linings of furnaces of various types.
2. Description of the Related Art
In the ceramic welding process as commercially practised, a ceramic welding powder mixture which comprises grains of refractory material and fuel particles is projected against a refractory surface to be repaired in a carder gas stream which wholly or mainly consists of oxygen. The refractory surface is best repaired while it is substantially at its operating temperature, which may be in the range of 800° to 1300° C. or even higher. This has advantages in avoiding any need to wait for the refractory under repair to be cooled or reheated, so minimising furnace down-time, in avoiding many problems due to thermal stress in the refractory material due to such cooling and reheating, and also in promoting the efficiency of the ceramic welding reactions whereby the fuel particles bum in a reaction zone against the target surface and there form one or more refractory oxides while releasing sufficient heat to melt or soften at least the surfaces of the projected refractory grains so that a high quality weld repair mass may be built up at the repair site as the lance is played across it. Descriptions of ceramic welding processes can be found in British patent specifications GB 1330894 and GB 2110200-A.
It has been found that the working distance, that is the distance between the reaction zone at the target surface and the outlet of the lance from which the ceramic welding powder is projected, is of importance for various reasons. If that working distance is too small, there is a risk that the lance tip may enter the reaction zone so that refractory material is deposited on the end of the lance possibly blocking its outlet. There may even be a risk that the reaction could propagate back into the lance, though this possibility may be largely avoided by ensuring that the velocity of the carrier gas stream exiting the lance is higher than the speed of propagation of the reaction. There are also the possibilities that the lance may become overheated due to its close proximity to the reaction zone, and that it may contact the target surface again leading to possible blockage of its outlet. If, on the other hand, the working distance is too great, the ceramic welding powder stream will have an opportunity to spread out so that the reaction will not be so concentrated leading to a loss in efficiency, increased rebound of material from the target surface, a weld of less high quality, and even a risk that the reaction will fail.
The optimum distance between the lance outlet and the target surface will depend on various factors. For example, in a welding operation in which ceramic welding powder is discharged at a rate of between 60 and 120 kg/hr from a lance outlet having a bore diameter of 12 to 13 ram, such optimum distance is found to be between 5 and 10 cm. That optimum distance is rarely greater than 15 cm.
Because of the high temperatures typically encountered at a repair site, the target surface and other parts of the furnace lining tend to radiate strongly in the visible spectrum, and the reaction zone is itself highly incandescent. This renders direct observation of the lance outlet difficult, and this difficulty is increased as the length of the lance increases. Indeed lances with a length of 10 meters are not unknown, and nor is it unknown to perform a welding operation at a site which is out of direct view of the welding operator.
SUMMARY OF THE INVENTION
It is an object of this invention to provide a method and apparatus whereby a welding operator may more easily control the distance between the outlet of a ceramic welding lance and a repair site.
According to this invention, there is provided, in a ceramic welding process in which a mixture of refractory and fuel particles is projected from an outlet at an end of a lance in a gas stream against a target surface where the fuel particles combust in a reaction zone to produce heat to soften or melt the projected refractory particles and thereby form a coherent refractory weld mass, a method of monitoring the distance between the lance outlet and the reaction zone, characterized in that the reaction zone and at least part of the gap between that reaction zone and the lance outlet is monitored by a camera and an electronic signal is produced indicative of the distance ("the working distance") between the lance outlet and the reaction zone.
The present invention also includes ceramic welding apparatus for projecting a mixture of refractory and fuel particles from an outlet at an end of a lance in a gas stream against a target surface where the fuel particles combust in a reaction zone to produce heat to soften or melt the projected refractory particles and thereby form a coherent refractory weld mass, characterized in that such apparatus further comprises means for monitoring the distance between the lance outlet and the reaction zone ("the working distance") which comprises a camera for monitoring the reaction zone and at least part of the gap between that reaction zone and the lance outlet and means for producing an electronic signal indicative of the working distance.
It will be apparent that by virtue of a method and apparatus according to this invention, a welding operator may make use of the electronic signal produced so that he can more easily control the distance between the outlet of a ceramic welding lance and the reaction zone at a repair site and so that he is better able to ensure the continuing achievement of optimum welding conditions. It is surprising that it is possible to obtain a control signal indicative of the working distance by using a camera in the very hot and bright environment of a furnace at its operating temperature.
In preferred embodiments of the invention, the reaction zone and at least part of the gap between that reaction zone and the lance outlet is monitored using a charge-coupled device ("CCD") camera. Such a camera may be made quite small so that it is convenient to manipulate, and its operation is convenient for the simple production of a said electronic signal indicative of the working distance. Many CCD cameras currently available have the additional advantage of being particularly sensitive to wavelengths of light which are emitted from a ceramic welding reaction zone.
The control signal may be used directly for the automatic maintenance of a correct working distance. For example a lance may be mounted on a carriage so that it is movable with respect to three perpendicular axes by three motors under the control of a computer which is fed with that signal.
Alternatively, or in addition, and as preferred, an audible and/or visual signal is generated to distinguish between operating conditions in which (a) the actual working distance falls within a tolerance range of a predetermined working distance and (b) the actual working distance falls outside such a tolerance range. The welding operator may thereby more easily control the position of the lance outlet in relation to the work when this is under manual control, or he may more easily be able to monitor an automatic welding operation.
In some embodiments of the invention, said camera is independently movable with respect to said lance and is used simultaneously to monitor the positions of said lance outlet and said reaction zone. Such embodiments of the invention can be put into practice using ceramic welding lances of known type. Appropriate positioning of the camera will enable monitoring of the working distance between the outlet end of the lance and the reaction zone. Since the lance outlet is also monitored, the size of the image of the outlet end of the lance in the focal plane of the camera may be used to give an indication of the distance between the camera and the end of the lance, and this enables the distance between the end of the lance and the reaction zone to be calculated. It is preferred that such calculation be performed automatically, and it is therefore preferred that a signal is generated proportional to the size of the image of the outlet end of the lance as monitored by said camera and that that signal is used as a scaling factor for an image of the working gap between the reaction zone and the lance outlet.
Calibration of the apparatus is much simplified when said camera is mounted in a fixed position and orientation on said lance, and the adoption of this feature is preferred.
Indeed, the invention extends to ceramic welding apparatus comprising a lance having an outlet at an end thereof for the discharge of a ceramic welding powder mixture, characterised in that such lance incorporates a fixed electronic camera directed towards a path along which such powder mixture may be discharged.
Such a lance does not need to be of particularly complicated construction and the performance of the method of the invention is also simplified since it is assured that the camera will always be pointing in the correct direction. The field of view of the camera in such embodiments may, but need not, include the outlet end of the lance, since the position of that outlet end in relation to that field of view will be known. Calibration is also greatly simplified, and can easily be performed under ambient conditions external of any furnace by laying up a graduated scale to the outlet end of the lance in alignment with the discharge path for the powder mixture and viewing that scale through the camera. Such a graduated scale may suitably take the form of a strip light which is surrounded by a mask which is perforated at intervals along its length, for example at 1 cm intervals, so that the camera can record spaced illuminated patches.
In order to protect the camera against overheating when in use, it is preferred that said camera is held within a jacket arranged and adapted for the circulation of coolant. Many embodiments of commercially used ceramic welding lances already incorporate a water jacket whose principal purpose is to prevent overheating of the lance, especially towards its outlet end, and such a water-jacket may readily be modified in order to accommodate a said camera.
Advantageously, a filter is provided for screening said camera from infra-red radiation. Cameras presently commercially available are most often not designed for converting infra-red radiation to electrical signals, so the provision of such a filter will act further to protect the camera against overheating without detracting in any way from the operation of the camera. Such a filter may for example be constituted by a thin gold film which is at least partially transparent to visible radiation but reflects a very high proportion of radiation in the infra-red spectrum.
Many such cameras are indeed blind to radiation having wavelengths greater than 900 nm, and it is found that the spectral emissivity of a typical ceramic welding reaction zone has its maximum at a wavelength below 850 nm. Thus in order to provide the maximum protection against infra-red radiation to the camera with minimum effect on its response, it is preferred that a said filter is arranged and adapted to screen said camera from radiation having wavelengths greater than 900 nm.
A further filter is preferably provided for screening said camera from radiation having wavelengths shorter than 600 nm. Such shorter wavelength radiation may be screened by means of a red filter, and this has the advantage of greatly reducing the registration by the camera of light which does not emanate from the reaction zone as such. It also reduces glare which enables the reaction zone to be more accurately monitored. In a specific practical embodiment adopting both these preferred optional features, the camera is provided with filters which substantially screen off radiation having wavelengths less than 630 or 650 nm and wavelengths greater than 850 nm so that most of the radiant energy incident on the camera has a wavelength falling within that band.
In some preferred embodiments of the invention, a filter is provided for screening said camera from radiation having wavelengths shorter than 670 nm. As the lance is played across the surface of the area under repair, there will obviously be an increment of that area which the reaction zone has just moved away from. Because of the intense heat at the reaction zone, that surface increment will have been heated strongly and it may well continue to glow brightly after the reaction zone has passed to a neighbouring part of the repair area. That residual glow may be reduced or even eliminated by the use of a sub-670 nm filter so reducing or avoiding any apparent distortion of the reaction zone as registered by the camera.
Advantageously, means is provided for supplying a current of gas to sweep across said camera. It will be appreciated that the atmosphere in the interior of a furnace which is undergoing repair is likely to be heavily laden with dust and fumes, including dust and fumes produced by the ceramic welding process itself, and the adoption of this preferred feature helps to keep the camera clear of dust and fume condensates which might otherwise blind it. The temperature of such gas is preferably such that it also has a cooling effect on the camera.
The location of such a camera on a said lance is not critical, provided that the field of view of the camera encompasses the required length of the powder discharge path. Said camera is preferably mounted on said lance at a distance between 30 and 100 cm from the lance outlet. In association with a charge-coupled device of half inch (12.7 mm) size, a 15 mm objective lens gives a field of view of 24°. If such is located 70 cm from the end of the lance, a powder discharge path length of 30 cm may be viewed.
In order to generate the signal indicative of the actual working distance at any given moment, signals corresponding to the image recorded by the camera may be passed to an analyser to determine the position of the reaction zone. This position is recognised as being that zone of the camera screen where the luminous intensity exceeds a predetermined threshold value. Following a previous calibration by which the actual spacing of two points is correlated with the spacing of the images of those points, and the position of the end of the lance with respect to the image, it is a simple matter to derive a signal which is indicative of the working distance.
Signals generated by the camera in use may be stored as an electronic image and used in various ways. That image does not in fact need to be displayed. It may for example be used for the control of a welding robot. Alternatively, or in addition, the signal indicative of the actual working distance may readily be compared electronically, after suitable calibration, with a signal corresponding to a notional optimum working distance, and any difference can be used to generate an audible signal. For example the arrangement might be such that when the lance outlet approaches the work too closely, a high pitched signal of increasing intensity is generated, while as separation between the lance outlet and the work increases a low-pitched signal of increasing intensity is generated. The aim of the welding operator would then be to keep the audible signals generated at as low a volume as possible.
It is preferred, however, that signals produced by said camera are used to generate an image on a video monitor screen. Providing a video monitor screen for displaying an image of the scene viewed by said camera enables the welding operator to gain the information he requires more easily. It is not necessary that this image should be a full two-dimensional image of the working scene. Since all the operator requires to know is the way in which a linear measurement is changing, a linear CCD camera may be mounted on the lance with consequent cost savings. Such a linear camera may also be used for generating an audible signal as aforesaid.
But it is preferred that such a camera be able to provide a full two-dimensional image. If displayed, this gives a more natural view to the welding operator, and it may also allow greater accuracy in monitoring the distance between the work and the lance outlet as will be adverted to later in this specification.
Advantageously, said video monitor screen is used to display an image of the reaction zone superimposed on a calibration scale. The provision of means for storing a calibration scale and displaying an image of that scale on said screen greatly facilitates the task of the welding operator since he can at once see how far the lance outlet is from the work and then take any corrective measures necessary.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will now be further described by way of example only with reference to the accompanying diagrammatic drawings in which:
FIG. 1 is a general view of an embodiment of ceramic welding lance according to the invention whose outlet end is directed towards a wall to be repaired, with the extremity of the lance being shown in cross-section for added clarity;
FIG. 2 is a cross-sectional view of the stem of the lance taken on the line A-B in FIG. 1,
FIG. 3 illustrates a stage in the calibration of monitoring equipment associated with the lance of FIG. 1, and
FIG. 4 shows a video monitor screen as it might appear during the performance of a ceramic welding process performed in accordance with this invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In the drawings, a lance 10 has a working end 11 provided with an outlet 12 for the projection of a stream of oxygen rich carrier gas which transports a ceramic welding powder mixture.
The composition of the projected stream may depend on the nature of the surface to be repaired. For example, for repairing a silica refractory, the carrier gas may consist of commercial grade dry oxygen, and the ceramic welding powder may consist of 87% by weight silica particles having sizes of about 100 μm to 2 mm as refractory component, and 12% silicon and 1% aluminium particles both with a nominal maximum size of about 50 μm as fuel components.
Ceramic welding powder is supplied to the lance outlet 12 by a lance tube 13 which is surrounded by median and outer lance tubes 14 and 15 respectively which are in communication at the outlet end 11 of the lance. Median lance tube 14 is provided with an inlet 16a for the supply of coolant such as water, and outer lance tube 15 has an outlet 16b for that coolant. Thus the lance is provided with a water jacket to avoid overheating.
A CCD camera 17 is located a few tens of centimeters, for example 30 to 100 cm, from the lance outlet, where it is surrounded by a short extension 18 of the water jacket. As illustrated, the field of view 19 of the camera 17 encompasses the outlet end 11 of the lance 10 and also a damaged area 20 of a refractory wall 21 which is to be repaired. A reaction zone 22 may be established against the repair site 21 as indicated. Signals from the camera 17 are passed along a cable 23 located within a pipe, having an air supply line 24, itself located within the median lance tube 14 of the water jacket. Note that the reference 24 is used for the air supply line in FIG. 1, and for the pipe itself in FIG. 2. The pipe 24 enters the water jacket extension 18 and its end is disposed so that a continuous draft of cool air is blown across the camera to keep it free from dust and fume condensates to preserve image quality, and to help cool the camera. The camera is provided with a strong red filter and a reflective filter, for example of gold, for screening off infra-red radiation so that radiation outside the wavelength band 630 (or 650) to 850 nm, preferably outside the wavelength band 670 to 850 nm, is impeded from reaching the camera.
A suitable CCD camera is that commercially available under the Trade Name ELMO Color Camera System 1/2" CCD image sensor, effective pixels: 579 (H)×583 (V): image sensing area: 6.5×4.85 mm: external diameter 17.5 mm by about 5 cm long. As an alternative, a colour CCD camera may be used, such as "WV-CDIE" from Panasonic or "IK-M36PK" from Toshiba.
Such an apparatus may be calibrated very easily as illustrated in FIG. 3. A graduated scale 25 is laid up and clamped to the outlet end of the lance and is recorded by the camera 17. This may be done at the operator's convenience outside any furnace under ambient workshop conditions. Because of the rather heavy filtering with which the camera is preferably provided it is convenient to form the scale 25 as a mask for a strip light which mask is formed with regularly spaced holes such as the holes 1 to 7 which may for example be one centimeter apart. The camera will then record a line of light spots which may be displayed on a video monitor screen during performance of a ceramic welding repair. This establishes a line of datum points on the charge-coupled device of the camera which correspond with known actual distances from the outlet of the lance, and this enables a correlation to be established between each pixel of the camera image and an actual distance from the lance outlet.
Such a video monitor screen is shown at 26 in FIG. 4. On that screen, the outlet end 11 of the lance will register as a dark silhouette, and the ceramic welding reaction zone 22 which is spaced from that outlet end by a given working distance will show as an bright, incandescent area. The calibration spots indicated at 0 to 8 may be presented either as white or as black on the screen. The remainder of the screen area will be an intermediate shade of grey assuming that a monochrome monitor is used.
It will be seen that the reaction zone 22 is represented as a circular area with a lobe projecting from one side. Because of the intense heat evolved during the ceramic welding operation, the wall area being repaired is also heated, and as the lance is played across the repair site, an increment of its area which has been subjected to the direct effects of the reaction zone may continue to glow so that it radiates sufficient energy to register on the monitoring equipment. The appearance of such a lobe may be and preferably is attenuated by using a filter which screens off radiation having wavelengths shorter than 670 nm.
Various degrees of sophistication are possible in monitoring the distance between the reaction zone 22 at the working area and the outlet end 11 of the lance, depending on the degree of accuracy required.
For example, considering FIG. 4, a brightness threshold could readily be established to give an indication of the start of the reaction zone, on the right-hand side of that zone as shown in that Figure. Looking at FIG. 4, this would give an indication that the working distance was 7 units. But it may be that the reaction zone will fluctuate in size from time to time depending on operating conditions and that what is required is the distance from the center of the reaction zone. This may be approximated by also taking a brightness threshold applicable to the end of the reaction zone at the left hand side of FIG. 4 to give an average result: such working distance would be about 81/2 units. Either of these methods may also be used when the CCD camera used is a linear camera rather than a camera giving a full two-dimensional representation of the work as shown on the video monitor screen illustrated by FIG. 4.
On a more sophisticated level, the signals from the CCD camera may be monitored to give an indication of the location where the image of the reaction zone of FIG. 4 has its greatest height. This will give a more accurate indication of the center of the reaction zone which is at a working distance of 8 units in FIG. 4. This degree of sophistication requires the use of a full two-dimensional camera.
It is not of any great significance that different numerical results are given for what is in fact the same working gap by these different methods. Assuming that the reaction zone depicted in FIG. 4 is at the optimum working distance from the outlet end of the lance, one would simply call that optimum distance 7, 81/2 or 8 distance units as the case might be, and working tolerances would be based on the appropriate optimum value for the working distance.
Whether working with a linear or a two-dimensional camera, it is not necessary to display a visible image, though doing so is very much preferred. Those same signals that would be used to control the video screen could be passed to a processor to give an indication of the distance between the reaction zone and the lance outlet end. The processor output could be used to control a digital or analogue display giving an indication of the working distance at any given time. Alternatively, or in addition, such a processor could be used to control an audible signal generator. The arrangement could for example be such that when the working distance was within a small tolerance of the optimum working distance (whatever the latter was set at) no audible signal was given. The signal generator might be set to give an audible signal of increasing pitch and volume as the working distance decreased below the tolerance range, and a lower pitch signal of increasing volume as the working distance increased beyond the tolerance range. Another option is for the camera signals to be passed to a computer arranged to control a welding robot.
It will be appreciated that any of the arrangements described in the immediately preceding paragraph could also be used in conjunction with a video display as described with reference to FIG. 4, and in particular that a digital indication of the working distance at any given time could be displayed on such a video screen.
Also with reference to FIG. 4, it will be appreciated that it is not essential to display, or indeed to monitor, the full extent of the working gap and the outlet end of the lance used. When the camera 17 is mounted in a fixed location and with a fixed orientation with respect to the lance outlet, then the notional position of that outlet is known whether it is displayed or not. If it is known that the correct working distance will never be less than, for example. 2 units, then there is no need to display the lance end or those two units of the working distance. It will be appreciated, however, that useful information about conditions in the immediate vicinity of the lance outlet may be derived if the full extent of the working distance and that outlet are monitored.
It will also be appreciated that it is not essential for the performance of at least the method of the invention that the CCD camera should be fixed to the lance. It might be a quite separate piece of equipment, and still give useful results. This can be done in the following way. The CCD camera is manipulated so that it views the working distance including the outlet end of the lance and the reaction zone much as illustrated in FIG. 4. As before, the CCD camera will view the end of the lance as a dark silhouette and the reaction zone as a bright area. The apparent separation of the reaction zone and the outlet end of the lance as recorded in the focal plane of the camera can readily be derived in a processor fed with signals from the camera. Also, the apparent size of the outlet end of the lance can be derived. Since the outlet end of the lance is of known diameter, it is not difficult to arrange for the processor to convert the apparent separation of the reaction zone and the outlet end of the lance into an approximate linear measurement of the working distance. A continuous re-assessment of the working distance would take place during the welding operation in order to take account of changes in the relative positions of the welding lance and the camera. As before, a synthesised scale and/or a digital indication of the working distance may be fed to a video monitor screen along with the image viewed by the camera, and/or other visible or audible signals may be generated to give an indication of the actual working distance as compared with the optimum working distance. | The invention concerns a ceramic welding process in which a mixture of refractory and fuel particles is projected from an outlet at an end of a lance in a gas stream against a target surface where the fuel particles combust in a reaction zone to produce heat to soften or melt the projected refractory particles and thereby form a coherent refractory weld mass. A method of monitoring the distance between the lance outlet and the reaction zone is disclosed in which the reaction zone and at least part of the gap between that reaction zone and the lance outlet is monitored by a camera and an electronic signal is produced indicative of the distance ("the working distance") between the lance outlet and the reaction zone. | 5 |
TECHNICAL FIELD
[0001] This disclosure relates generally to systems for cleaning surfaces in printers, and more particularly, to systems for cleaning surfaces in printers with a wiper blade.
BACKGROUND
[0002] In general, inkjet printing machines or printers include a device that removes materials from an image forming surface. In previously known aqueous printers, the cleaning device includes a foam roller followed by a separate squeegee blade to remove ink from a thin skin layer on the surface. However, a portion of the water accumulates in front of these cleaning devices when the squeegee blade is retracted. The accumulated water remains on the image forming surface after the squeegee blade is retracted.
[0003] Some previously known printers employ techniques, such as changing the angle of the squeegee blade, to reduce the amount of water remaining on the surface. However, because the skin on the surface of certain aqueous printers contains a surfactant, the water accumulating in front of the squeegee blade can become contaminated and its wetting properties can change. This contamination can reduce the effectiveness of changing the angle of the blade. Other previously known printers implement techniques, such as increasing the amount of time between retraction of the foam roller and the retraction of the squeegee blade, to allow for more time for the water bead in front of the squeegee blade to drain down the squeegee blade after input of water from the foam roller has stopped. However, water still remains on the surface after the squeegee blade is retracted. Furthermore, changes in the cleaning device orientation relative to gravity have similar effects on the accumulations of water in front of the squeegee blade.
[0004] In other previously known printers, the cleaning device includes a foam roller to apply oil to a surface and a wiper blade to meter the oil to a desired thickness. The wiper blade accumulates a bead of oil in front of the blade. When the blade is retracted, the oil bead remains and produces a band or bar on prints. Previously known printers are unable to eliminate the released oil bead. As such, some previously known printers employ techniques to minimize the amount of oil released and constrain the process by retracting the blade at a position that enables the oil bar to be positioned in a non-imaging area for minimum print quality degradation. However, this constraint in the process has an impact on productivity, especially with changes in media size. As such, improvements in inkjet printers that enable cleaning of the imaging surface are desirable.
SUMMARY
[0005] A printer cleaning device has been configured to enable the removal of material from a cleaning surface of a printer. The printer cleaning device includes a blade having a body that terminates into an edge, an actuator operatively connected to the blade to move the blade into and out of engagement with a surface to remove selectively a material from the surface, an absorbent pad attached to the body of the blade and disposed across a predetermined length of the cleaning blade, the absorbent pad being positioned at a predetermined distance from the edge of the blade, and a controller operatively connected to the actuator, the controller being configured to operate the actuator to move the blade into and out of engagement with the surface to remove material from the surface selectively.
[0006] A new method of printer cleaning operation that enables removal of material from a cleaning surface of a printer. The method includes operating a blade using a controller to position the blade to contact an edge of the blade with a surface of the printer, the blade having a body portion to which a pad is attached and disposed across a predetermined length of the blade to enable a first corner of the pad to be located at a first end of the body portion at a predetermined distance from the edge of the blade, the operating of the blade includes compressing the pad on the surface to release a cleaning fluid against the first corner of the pad and the surface.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] The foregoing aspects and other features of a printer cleaning device that removes a material are explained in the following description, taken in connection with the accompanying drawings.
[0008] FIG. 1 is an exemplary printer cleaning device.
[0009] FIG. 2 is an exemplary process of cleaning a cleaning surface of a printer using the printer cleaning device.
[0010] FIG. 3A is an exemplary device engaging with the cleaning surface of the printer during the process illustrated in FIG. 2 .
[0011] FIG. 3B depicts an exemplary blade partially retracted from contact with the cleaning surface during the process illustrated in FIG. 2 .
[0012] FIG. 3C depicts an exemplary blade completely retracted from contact with the cleaning surface during the process illustrated in FIG. 2 .
DETAILED DESCRIPTION
[0013] For a general understanding of the present embodiments, reference is made to the drawings. In the drawings, like reference numerals have been used throughout to designate like elements.
[0014] FIG. 1 illustrates an exemplary printer cleaning device 100 . The printer cleaning device 100 includes a blade 104 . The blade 104 comprises a body with a cleaning edge 128 . A pad 112 is attached to the blade 104 across a predetermined length 124 of the body of the blade 104 . The pad 112 can be attached to the blade 104 using a material, examples of which include, but are not limited to, a double-back adhesive tape, appropriate glue, spray adhesive, or the like. The pad 112 consists of an applicator edge 132 that engages with the cleaning surface of the printer during the cleaning process. The applicator edge 132 of the pad 112 is offset at a predetermined distance 116 from the cleaning edge 128 of the blade 104 . The offset 116 enables the blade 104 to engage with the cleaning surface of the printer during the cleaning process without interference from the pad 112 .
[0015] In one example, an applicator positioned downstream from the cleaning device 100 deposits cleaning fluid onto the surface and most of the cleaning fluid is removed from the surface by blade 104 and directed to, for example, a waste collector. A portion of the cleaning fluid remaining on the cleaned surface saturates the pad 112 as the cleaning device 100 remains engaged with the cleaned surface. The downstream applicator stops depositing cleaning fluid onto the surface prior to the retraction of the blade 104 . When the blade 104 retracts from contact with the cleaning surface, the compressed pad 112 expands. The volume of the expanded pad 112 enables the pad 112 to absorb a portion of the cleaning fluid remaining on the surface along with any other material freed from the surface by the blade 104 . When the blade 104 reengages with the surface of the printer, the pad 112 compresses and expels a portion of the absorbed cleaning fluid from the pad onto the surface being cleaned. The expelled cleaning fluid does not significantly contribute to the amount of the cleaning fluid used to clean the surface. The expelled portion of cleaning fluid replenishes the capacity of the pad 112 to absorb a bead of cleaning fluid in front of the blade 104 when the blade 104 is again retracted from the cleaning surface and the pad expands. Absorbing a portion of the accumulated cleaning fluid enables the pad 112 to dry the surface being cleaned to some degree. To further dry the cleaning surface, additional equipment such as an air knife, a blade, a combination of both, or the like can be used. The cleaning fluid can be any known solvent for removing a material or a combination of materials such as inks, skin layers, release agents, or the like. Examples of the cleaning fluid include, but are not limited to, water, water with surfactants, oil, hydrocarbon solvents, or the like.
[0016] The blade 104 has a predetermined thickness or height 108 and the pad 112 has a predetermined thickness or height 120 useful for cleaning a surface in the printer. The blade 104 engages with the surface at a predetermined angle. In one example, the predetermined angle and the predetermined height 120 are determined by setting the volume of the pad 112 compression to at least equal to the volume of a portion of the cleaning fluid, material, or a combination of both the fluid and material that accumulates in front of the blade 104 . In one example, the thickness 120 of the pad 112 is about 2 to 3 mm, preferably about 3 mm. The offset 116 is about 0.5 mm, the thickness 108 of the blade 104 is about 2 mm, and the pad 112 is attached to the blade 104 across a length 124 of about 5 to 10 mm. The reader should understand that while specific ranges are described herein, any other suitable ranges and values can be used for the design of the blade 104 and the pad 112 .
[0017] The pad 112 is made up of a material such as a foam strip material. In one example, the foam strip material can be relatively thin and swell only a little when the cleaning fluid is absorbed. Examples of a foam strip material that swells an appropriate amount include, but are not limited to, polyurethane foams, polymer foams, or the like. The foam strip material can be fabricated from open cell material having a relatively high pore density. The foam strip material of the pad 112 can be either hydrophilic or hydrophobic depending on the nature of material that needs to be cleaned from the surface in the printer. For example, using a hydrophilic foam pad 112 to clean aqueous ink from a surface results in an accumulation of ink in the pad 112 because aqueous ink is not easily rinsed out of a hydrophilic pad 112 .
[0018] Additionally or alternatively, the pad 112 has compression stiffness or compression strength to enable the pad 112 to be compressed against the surface being cleaned. The pad 112 can have a relatively low compression stiffness to enable the pad 112 to be compressed against the cleaning surface with a little additional force applied to the end of the blade 104 . Additionally, the pad 112 can have a relatively high rebound to enable the pad 112 to expand quickly and return to its original shape when the blade 104 is retracted. The reader should understand that high rebound can also be known as low hysteresis loss during compression cycles.
[0019] Additionally or alternatively, the pad 112 is chemically resistant to materials to be removed from a surface by the pad 112 . Examples of materials to be removed include, but are not limited to, ink, dust, debris, chemicals, cleaning fluid, or the like. Additionally, the pad 112 has relatively high water absorption to enable the pad 112 to absorb a higher capacity of the cleaning fluid or other materials from the cleaning surface of the printer.
[0020] FIG. 2 illustrates an exemplary process of cleaning a surface in a printer using the printer cleaning device 100 . In the exemplary process, an actuator positions the cleaning device 100 to engage the surface to be cleaned with the blade 104 (block 204 ). The actuator is connected to the blade 104 and a controller to enable the controller to operate the actuator and move the blade 104 into and out of engagement with the surface. FIG. 3A , FIG. 3B , and FIG. 3C depict an exemplary device 100 engaging with the surface 304 of the printer during the process illustrated in FIG. 2 . As illustrated in FIG. 3A , the actuator can position the device 100 to contact the surface 304 at a predetermined angle. The cleaning surface 304 moves in a direction opposite to the motion of the blade 104 coming into engagement with the surface.
[0021] When the edge 128 of the blade 104 engages the surface 304 , a portion of the pad 112 compresses against the surface 304 . A portion of the pad 112 , for example, the applicator edge of the pad 112 , can be saturated with cleaning fluid prior to the engagement of the blade 104 with the surface 304 . FIG. 3A further illustrates the compressed pad 112 expelling a portion of the cleaning fluid 308 onto the surface 304 (block 208 ). The expelled cleaning fluid 308 can accumulate in front of the blade 104 and the pad 112 . Additionally, the blade 104 continues to remain in a state of contact with the cleaning surface 304 for a predetermined amount of time to enable the expelled cleaning fluid 308 to travel from the applicator edge of the pad 112 to the contact edge of the blade 104 . During this predetermined amount of time, the amount of cleaning fluid 308 accumulated in front of the blade 104 and the pad 112 may decrease in volume.
[0022] The actuator retracts the blade 104 from contact with the surface 304 (block 212 ). As the blade 104 retracts from contact, the pad 112 expands as the compression against the surface 304 decreases. The expansion of the pad 112 allows a portion of the accumulated cleaning fluid 308 to be drawn into the pad 112 due to expanding voids in the pad 112 (block 216 ). As such, by absorbing the accumulated cleaning fluid 308 as the blade 104 retracts, the pad 112 prevents the accumulated cleaning fluid 308 from remaining on the surface 304 after the blade 104 is retracted. FIG. 3B depicts the blade 104 partially retracted from contact with the surface 304 and a portion of the accumulated fluid 308 is absorbed into the pad 112 . In one example, if the pad 112 has sufficient capacity, then it can absorb most of the expelled cleaning fluid 308 from the surface 304 and the surface 304 is left relatively dry. FIG. 3C depicts the blade 104 completely retracted from contact with the surface 304 and most of the accumulated fluid 308 has been absorbed into the pad 112 . To absorb most of the expelled cleaning fluid 308 , the volume of fluid that can be absorbed by the pad 112 when the pad 112 is retracted must be at least as much as the volume of expelled cleaning fluid 308 . This volume can be a function of the water absorption property and the compression volume property of the pad 112 . The compression volume of the pad 112 can be determined by the thickness 120 of the pad 112 , the offset 116 of the pad 112 from the blade 103 , and the angle of contact of the blade 104 with the surface 304 . The reader should understand that the volume can be a function of other properties of the pad 112 or the device 100 as well. Additionally, an air knife 312 can be used to direct air flow 316 towards the surface 304 and further dry the surface 304 .
EXAMPLES
[0023] The following example of the printer cleaning device 100 is to be considered illustrative in nature, and is not limiting in any way.
Example 1
[0024] In this example, a small bench fixture is used to clean a surface. The fixture comprises a glass tube that is about 4 inches long and about 1.5 inches in diameter. The glass tube is connected, through a coupling, to a motor to enable the glass tube to rotate. A pivoting blade holder is connected to the fixture so the blade swings into contact with the rotating glass tube. The blade is a Synztec 238707 blade, which is a urethane cleaning blade and is about an inch long. The blade 104 is oriented in a wiper mode and angled in order to wipe and clean materials from the surface of the rotating glass tube. In Trial 1 and Trial 2, no pad 112 is attached to the blade 104 and a water bottle is used to squirt water onto the surface of the rotating glass tube. Without an attached pad 112 , the blade is used as a squeegee to clean the surface of the glass tube. In Trial 3, a pad 112 is attached to the blade 104 . The following trials are conducted on this structure:
Trial 1
[0025] This trial illustrates the functioning of the blade, such as blade 104 described above, without an attached pad, such as pad 112 discussed above. In this trial, after the water is squirted on the rotating glass tube, the pivoting blade holder swings the blade into engagement with the glass tube. When the blade engages with the surface of the glass tube, the squirted water is wiped from the surface of the glass tube and accumulates in front of the blade as a bead of water. A small slip of paper is held in contact with the surface of the glass tube to detect moisture on the surface of the glass tube. Paper is used because it is absorbent and allows for a visual inspection of whether the glass tube is dry. In this trial, when the load of the blade was sufficiently high, water was not detected on the surface of the glass tube since the paper did not become wet. As a result, when the load of the blade was sufficiently high, the surface of the glass surface was dry. However, when the load of the blade was relatively low, water was detected on the glass tube and the paper absorbed a very thin film of water escaping under the blade. The paper turned dark as a result of absorbing the thin film of water from the surface of the glass tube.
Trial 2
[0026] This trial illustrates the release of the water when the blade is retracted from contact with the surface of the glass tube when a pad is not attached to the blade. In this trial, water is reapplied to the surface of the glass tube. The pivoting blade holder swings the blade into engagement with the glass tube with sufficient pressure to dry the glass tube. A slip of paper is then held against the surface of the glass tube after the blade retracts from contact. The paper is used to verify that the surface of the glass surface is dried by the blade. In this trial, when the blade was retracted from contract with the surface of the glass tube, the paper turned dark, which indicates a release of the bead of water from the blade.
Trial 3
[0027] This trial illustrates the functioning of blade, such as blade 104 described above, when a pad, such as pad 112 , is attached to the blade. The pad is a 3 mm thick foam strip and is cut using a scalpel blade. The pad is attached with double back tape to the blade and mounted as close to the edge of the blade as possible without interfering with the edge of the blade. In this trial, water is applied to the surface of the glass tube. The pivoting blade holder swings the blade into engagement with the glass tube with sufficient pressure to dry the glass tube. The paper slip is used to detect moisture on the surface of the glass tube after the blade retracts from the surface of the glass tube. The paper indicated that the surface of the glass tube was dry. This trial illustrates that the pad absorbed a portion of the cleaning fluid as the blade retracted from contact with the cleaning surface. This trial was performed a number of times using TMP CapuCell, hydrophilic, Ultra-Fine, and hydrophobic foam materials and positive results were observed after the blade 104 retracted from contact with the cleaning surface.
[0028] The reader should understand that the cleaning device 100 having a blade 104 and an absorbent pad 112 can be used in other systems as well. Examples of such system include, but are not limited to, solid inkjet (SIJ) printers, indirect inkjet printing, such as Landa Nanography, non-printing systems, and the like. The cleaning device 100 can be used to clean imaging surfaces as well as other types of surfaces to which ink and other printing materials may attach.
[0029] It will be appreciated that variations of the above-disclosed apparatus and other features, and functions, or alternatives thereof, may be desirably combined into many other different systems or applications. Various presently unforeseen or unanticipated alternatives, modifications, variations, or improvements therein may be subsequently made by those skilled in the art, which are also intended to be encompassed by the following claims. | A printer cleaning device includes a cleaning blade that is operatively disposed on a cleaning surface to contact and remove a material from the cleaning surface. The cleaning blade has a body portion and a cleaning edge adjoining the body portion adapted to contact the cleaning surface. The printer cleaning device further includes a pad that is attached to the body portion of the cleaning blade and is disposed across a predetermined length of the cleaning blade. The pad has a first corner that is located at a first end of the body portion wherein the first end is at a predetermined distance from the cleaning edge. The printer cleaning device further includes a controller configured to control the cleaning blade to contact and wipe the cleaning surface. | 1 |
FILING DATA
[0001] This application is associated with and claims priority from Australian Provisional Patent Application No. 2007906558, filed on 30 Nov. 2007, the entire contents of which, are incorporated herein by reference.
FIELD
[0002] The present invention relates generally to the field of cell biology and in particular the cellular processes surrounding inflammation. Even more particularly, the present invention provides targets for medicaments useful in reducing levels of an extracellular pro-inflammatory mediator. The medicaments are therefore useful in ameliorating the effects on an inflammatory response. Model inflammatory disease systems also form part of the present invention.
BACKGROUND
[0003] Bibliographic details of the publications referred to by the author in this specification are collected at the end of the description.
[0004] Reference to any prior art in this specification is not, and should not be taken as, an acknowledgment or any form of suggestion that this prior art forms part of the common general knowledge in any country.
[0005] Tumor Necrosis Factor alpha (TNFα) is the main pro-inflammatory cytokine made and secreted by inflammatory macrophages. Early release of TNFα in response to lipopolysaccharide (LPS) or other inflammatory signals works to activate and recruit T cells and ensures robust innate and acquired immune responses. The excessive secretion of TNFα is also a prevalent and clinically significant problem in acute inflammation and in chronic inflammatory disease. Anti-TNFα treatments have shown success in the treatment of rheumatoid arthritis, inflammatory bowel disease and other conditions. Now improved anti-TNFα strategies that can offer more constrained or cell type specific control of TNFα secretion are being sought. This requires identification of molecular mediators of TNFα secretion, particularly those that can be targeted to block TNFα release.
[0006] The export of TNFα requires a secretory pathway whereby the transmembrane precursor of TNFα is transported from the trans-Golgi network (TGN) in tubular carriers that fuse with the recycling endosome (RE) as an intermediate compartment. The RE contributes membrane for the formation of phagocytic cups during ingestion of microbes or particles in these phagocytic cells. TNFα, but not other cytokines, is delivered to the phagocytic cup along with the RE as a means of surface delivery for TACE-mediated cleavage and release. While the latter stages of TNFα secretion via this pathway are beginning to come to light, an earlier but critical phase of TNFα transport out of the TGN is not yet understood.
[0007] One class of components which regulates membrane transport from the TGN is the golgins; long coiled coil proteins which are specifically recruited to the subdomains and tubules which emerge from the TGN. There are four human TGN golgins, namely p230/golgin-245, golgin-97, GCC185 and GCC88. These golgins are peripheral membrane proteins that have a TGN targeting sequence located at the C-terminus, called the GRIP domain. Recruitment of p230/golgin-245 and golgin-97 to the TGN is mediated through an interaction with the small G protein, Arl1.
[0008] Although both p230 and golgin-97 are effectors of Arl1, the two golgins are localized to distinct membrane domains of the TGN. Distinct spatial segregation of p230 and golgin-97 is also reflected in their function. Golgin-97, but not p230, is associated with distinct membrane extensions of the TGN loaded with E-cadherin from the Golgi and knock-down of golgin97 selectively blocked exit of E-cadherin cargo from the TGN.
[0009] There is a need to investigate golgin proteins as possible targets to modulate protein export and trafficking out of and within a cell.
SUMMARY
[0010] Throughout this specification, unless the context requires otherwise, the word “comprise”, or variations such as “comprises” or “comprising”, will be understood to imply the inclusion of a stated element or integer or group of elements or integers but not the exclusion of any other element or integer or group of elements or integers.
[0011] Nucleotide and amino acid sequences are referred to by a sequence identifier number (SEQ ID NO). The SEQ ID NOs correspond numerically to the sequence identifiers <400>1 (SEQ ID NO:1), <400>2 (SEQ ID NO:2), etc. A summary of the sequence identifiers is provided in Table 1. A sequence listing is provided after the claims.
[0012] A list of Abbreviations is provided in Table 2.
[0013] The present invention identifies p230/golgin-245 (also referred to “p230”, “p230/golgin”, “golgin-245”) as an essential component in post-Golgi trafficking and exocytosis of TNFα from eukaryotic cells. Inhibition of TNFα trafficking reduces levels of precursor membrane bound TNFα and hence exogenous TNFα. Medicaments which target p230 or a molecule associated therewith are therefore useful in the treatment and prophylaxis of inflammatory diseases conditions in a subject.
[0014] Accordingly, one aspect of the present invention is a method for controling post-Golgi exocytosis of TNFα, the method comprising introducing to a cell an amount of an agent which modulates the function, activity, level or operability of p230/golgin-245 or a molecule associated therewith, the amount effective to inhibit or promote the ability of p230/golgin-245 to facilitate exocytosis of TNFα.
[0015] Whilst inhibition of TNFα exocytosis is desired for therapeutic purposes to reduce an inflammatory response, promotion of TNFα exocytosis is contemplated in animal disease model systems. Such systems are useful inter alia for screening potential anti-inflammatory drugs.
[0016] In a particular embodiment, the agent is an antagonist of p230/golgin-245. Hence, a method is provided for reducing post-Golgi exocytosis of TNFα from a cell, the method comprising contacting the cell with an antagonist of p230/golgin-245 in an amount effective to reduce p230/golgin-245-mediated IFNα exocytosis.
[0017] An “antagonist of p230/golgin-245” includes an antagonist of p230/golgin-245 function, level and/or activity and/or of a component associated therewith.
[0018] In another embodiment, a method is provided for enhancing post-Golgi exocytosis of TNFα from a cell, the method comprises contacting the cell with an agonist of p230/golgin-245 in an amount effective to enhance p230/golgin-245-mediated IFNα exocytosis. Such a method is useful in animal model systems to screen for anti-inflammatory drugs or to study the inflammatory response. An “agonist of p230/golgin-245” includes an agonist of p230/golgin-245 function, level and/or activity and/or of a component associated therewith.
[0019] Hence, the antagonists and agonists of the present invention may target p230 directly, expression of a gene encoding p230, multimer formulation and/or a molecule associated with p230 such as a G protein required for binding of p230 to a tubule. The antagonist (or agonist) may be administered to the cell or produced in the cell such as via a viral vector or via stem cells. The antagonists and agonists encompass small molecules, proteins and peptides and nucleic acid molecules.
[0020] The present invention is particularly directed to a method for the treatment or prophylaxis of inflammation in a subject, the method comprising administering to the subject an effective amount of an antagonist of p230/golgin-245-mediated TNFα exocytosis from cells of the subject.
[0021] A further aspect provides for the use of an antagonist of p230/golgin-245 in the manufacture of a medicament in the treatment of an inflammatory condition in a subject. In addition, the present invention contemplates the use of p230/golgin-245 in the manufacture of a medicament in the treatment of an inflammatory condition in a subject.
[0022] Particular subjects are primates such as humans.
[0023] Disease animal model systems are contemplated herein for testing of potential anti-inflammatory medicaments. Such systems may have reduced levels of p230 or p230 function or may over express p230. For example, the present invention provides an animal model comprising an elevated level of p230/golgin-245 and which is prone to inflammatory conditions. In one embodiment, the animal model is in the form of a retrogenic murine animal (e.g. mouse or rat) which expresses miRNA to silence the p230 gene. For example, stem cells may be genetically modified to express miRNA directed to the p230 gene and used to generate retrogenic animals.
[0000]
TABLE 1
Sequence Identifiers
Sequence Identifier
Sequence
1
Primer miRmp230a for RNAi designer
2
Primer miRmp230b for RNAi designer
3
Primer miRmGCC185 for RNAi designer
[0000]
TABLE 2
Abbreviations
Abbreviation
Definition
Arl1
G protein which recruits p230/golgin-245 and
golgin-97 to TGN
GCC185
Human TGN golgin
GCC88
Human TGN golgin
Golgin
Long coiled protein from TGN
golgin-97
Human TGN golgin
golgin-245
p230/golgin-245
LPS
Lipopolysaccharide
p230/golgin-245
Human TGN golgin
p230
p230/golgin-245
RE
Recycling endosome
TGN
Trans-Golgi network
TNFα
Tumor Necrosis Factor Alpha
245
p230/golgin-245
BRIEF DESCRIPTION OF THE FIGURES
[0024] Some figures contain color representations or entities. Color photographs are available from the Patentee upon request or from an appropriate Patent Office. A fee may be imposed if obtained from a Patent Office.
[0025] FIGS. 1 a through d are photographic representations showing the TNFα trafficking is inhibited by silencing p230/golgin-245 in HeLa cells (a-c) HeLa cells transfected with control siRNA or p230 siRNA for 48 hrs and then transfected a second time with (a, b) YFP-TNFa and (c) GFP-Ecad for a further 24 h. In (b) myc-p230 was co-transfected with siRNA. Monolayers were then incubated with TACE inhibitor for 2 h, fixed in paraformaldehyde and cell surface TNFα stained with rabbit anti-TNFα antibodies followed by Alexa647-conjugated anti-rabbit IgG. Monlayers were then permeabilized and stained with (a, c) human anti-p230 antibodies followed by goat anti-human IgG or (b) monoclonal anti-myc antibodies followed by Alexa568-conjugated anti-mouse IgG. (d) HeLa were transfected with control siRNA or p230 siRNA for 48 hrs and lysed in SDS-PAGE reducing buffer and extracts subjected to SDS-PAGE on a 7.5% (w/v) polyacrylamide gel. Proteins were transfer to a PVDF membrane and probed with affinity purified rabbit anti-p230 antibodies using a chemiluminescence detection system. The membrane were then stripped and reprobed with anti-α-tubulin, followed by anti-golgin-97 antibodies. Bar represents 10 μm
[0026] FIGS. 2 a and b are photographic and graphical representations showing TNFα in p230 labeled tubules leaving the TGN in live macrophages.
[0027] FIGS. 3 a through c are photographic and graphic representations showing the Post-Golgi TNFa trafficking is inhibited by silencing p230 in stimulated RAW macrophages. RAW macrophages were transfected with control miRNA or p230 miRNA-1, as indicated, for 48 hrs and treated with 100 ng/ml of LPS in serum free RPMI at 37° C. for 2 hrs in the presence of presence of 10 μM of TAPI-1. Stimulated macrophages were then fixed in 4% (v/v) paraformaldehyde. (a) Fixed macrophages were permeabilized and stained with human anti-p230 antibodies followed by goat anti-human IgG and with rabbit anti-TNFa antibodies followed by Alexa647-conjugated anti-rabbit IgG. (b, c) Fixed macrophages were analyzed for cell surface TNFa by staining with rabbit anti-TNFα antibodies followed by Alexa647-conjugated anti-rabbit IgG. Representative flow cytometry plots of GFP+ cells shown in c. Bar represents 10 μm.
[0028] FIGS. 4 a through d are photographic representations showing that Peritoneal macrophages from transgenic mice expressing p230 miRNA are depleted in p230 and impaired in TNFα secretion. Peritoneal macrophages obtained from either empty miRNA vector (control) or p230 miRNA retrogenic mice were fixed in 4% (v/v) paraformaldehyde and stained with (a) antihuman p230 antibodies followed by goat Alexa 594 conjugated anti-human IgG or (b) rabbit anti-human GCC88 antibodies or rabbit anti-human GCC185 antibodies, followed by goat Alexa 568 conjugated anti-rabbit IgG. (c,d) Peritoneal macrophages obtained from control and p230 miRNA transgenic mice were activated with 100 ng/ml of LPS in the presence of 50 nM of TAPI-1 for 2 hrs prior to fixation. Macrophage were fixed in 4% (v/v) paraformaldehyde and cell surface TNFα was detected using a rabbit anti-mouse TNFα antibodies, followed by goat Alexa 568 conjugated anti-rabbit IgG in non-permeabilized cells. (d) For internal TNFα detection, peritoneal macrophages were activated in 100 ng/ml of LPS for 2 hrs, fixed in 4% (v/v) paraformaldehyde and permeabilized, and stained with rabbit anti mouse TNFα antibodies, followed by goat anti rabbit Alexa 568 conjugated antibodies. p230/golgin-245 molecules were stained with affinity purified anti-human p230/golgin-245 antibodies, followed by goat anti-human Alexa 647 conjugated antibodies. Bar=10 μm.
DETAILED DESCRIPTION
[0029] The present invention is predicated in part on the identification of a carrier of post-Golgi trafficking and exocytosis of IFNα. In particular, TGN golgin, p230/golgin-245, is required for transport of the membrane precursor of TNFα. The p230/golgin-245 carrier may also be referred to herein as “p230”, “245”, “golgin-245” or “p230/golgin”. Reference to this TGN golgin includes any and all of its homologs, orthologs, polymorphic variants, splice variants and natural and artificially induced derivatives. It also includes multimeric foul's such as homo- and hetero-dimers comprising a p230 monomer.
[0030] p230/golgin-245 and co-factors or associated molecules all form targets to inhibit p230-mediated post-Golgi TNFα exocytosis. The ability to control TNFα secretion by selective silencing of trafficking machinery has a range of applications including controling inflammatory processes.
[0031] Hence, one aspect of the present invention contemplates a method for controling post-Golgi exocytosis of TNFα, the method comprising introducing to a cell an amount of an agent which modulates the function, activity, level or operability of p230/golgin-245 or a molecule associated therewith the amount effective to inhibit or promote the ability of p230/golgin-245 to facilitate exocytosis of TNFα.
[0032] Reference to “TNFα” includes its homologs, orthologs, polymorphic variants and derivatives.
[0033] The “cell” is generally a eukaryotic cell and in particular a mammalian cell such as but not limited to a macrophage, monocytes, dendritic cell, lymphocyte or other cells of the immune system or their precursors. Generally, the mammal is a human or other primate. However, the present invention extends to veterinary and animal husbandry applications and hence the mammal may also be a livestock animal, companion animal or captive wild animal.
[0034] Examples of molecules associated with p230 include those molecules which are required for binding of the p230 to the tubule of the TGN. One example of a molecule is the G protein, Arl1. Hence, the agent may target inter alia p230, Arl1, p230 interaction with Arl1 and p230/Arl interaction with the membrane of the tubule or may target a gene encoding any of those components.
[0035] As indicated above, the ability to control p230 function enables inflammatory processes to be modulated and in a particular embodiment, inhibited.
[0036] Accordingly, another aspect provides a method for reducing post-Golgi exocytosis of TNFα from a cell, the method comprising contacting the cell with an antagonist of p230/golgin-245 in an amount effective to reduce p230/golgin-245-mediated IFNα exocytosis.
[0037] Reference to an “antagonist of p230/golgin-245” includes an antagonist of p230/golgin-245 function or level or activity. Inhibiting p230/golgin-245 function may also include inhibiting a component which associates with p230. An “agonist of p230/golgin-245” includes an agonist of p230/golgin-245 function or level or activity or of a component associated therewith.
[0038] Another aspect contemplates a method for ameliorating the effects of an inflammatory disease or condition in a subject, the method comprising administering to the subject an effective amount of an agent which reduces the function or level of p230/golgin-245 or a molecule associated therewith the administration being for a time and under conditions sufficient to reduce TNFα-mediated inflammatory processes.
[0039] Examples of inflammatory disease conditions contemplated by the present invention include but are not limited to those diseases and disorders which result in a response of redness, swelling, pain, and a feeling of heat in certain areas that is meant to protect tissues affected by injury or disease. Inflammatory diseases which can be treated using the methods of the present invention, include, without being limited to, acne, angina, arthritis, asthma, aspiration pneumonia disease, chronic obstructive pulmonary disease (COPD), colitis, empyema, gastroenteritis, intestinal flu, necrotizing enterocolitis, pelvic inflammatory disease, pharyngitis, pleurisy, raw throat, rubor, sore throat, urinary tract infections, chronic inflammatory demyelinating polyneuropathy, chronic inflammatory demyelinating polyradiculoneuropathy. Pathogenic infection such as by Leischmonia may also be treated. COPD, asthma and colitis are particularly useful targets for the medicaments contemplated herein.
[0040] The terms “inflammation”, “inflammatory response”, inflammatory condition” and “inflammatory disease” are used interchangeably throughout this specification. Generally, the inflammatory response is regarded as being caused by, associated with or exacerbated by, TNFα.
[0041] The present invention provides, therefore, agents which modulate either the level of p230 gene or the activity of a gene encoding p230 or the activity or level of a molecule associated with p230 (such as a G protein required for coupling of p230 to a tubule membrane) for use in the treatment and prophylaxis of inflammation or inflammatory conditions such as asthma, COPD or colitis. The agents are conveniently in a composition comprising the agent and one or more pharmaceutically acceptable carriers, diluents and/or excipients. Two or more agents may be co-administered in the same composition or in separate compositions.
[0042] Notwithstanding, agents which are agonists of p230 functions are also contemplated to assist in animal disease model systems.
[0043] The agents include antagonists and agonists and may be administered to the cell or produced in the cell via for example, viral vectors. Examples of antagonists include intracellular antibodies, RNA species (e.g. miRNA siRNA, dsRNA, ssRNA) and small molecules which cross cellular membranes.
[0044] A method is provided for enhancing post-Golgi exocytosis of TNFα from a cell, the method comprises contacting the cell with an agonist of p230/golgin-245 in an amount effective to enhance p230/golgin-245-mediated IFNα exocytosis. In addition, the present invention provides an animal model comprising an elevated level of p230/golgin-245 and which is prone to inflammatory conditions.
[0045] Unless otherwise indicated, the subject invention is not limited to specific formulations of components, manufacturing methods, dosage regimens, or the like, as such may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.
[0046] As used in the subject specification, the singular forms “a”, “an” and “the” include plural aspects unless the context clearly dictates otherwise. Thus, for example, reference to “a cell” includes reference to a single cell or more than one cell; reference to “an active agent” includes a single active agent, as well as two or more active agents; reference to “the invention” includes reference to single or multiple aspects of an invention; and so forth.
[0047] The terms “compound”, “active agent”, “pharmacologically active agent”, “medicament”, “active” and “drug” are used interchangeably herein to refer to a chemical compound that induces a desired biological effect. This biological effect includes modulating the level or activity or function of p230/golgin-245 or any molecule associated therewith such as a G-protein (e.g. Arl1) or co-factor or a monomer involved in a multimeric (e.g. dimer) complex comprising p230. Although generally the dimmers or other multimers are generally homo-multimers, hetero-multimers are also contemplated herein. The biological effect may also be a reduced level of exogenous TNFα or membrane-associated precursor TNFα. The effect may also be an amelioration of symptoms of inflammation. The terms also encompass pharmaceutically acceptable and pharmacologically active ingredients of those active agents specifically mentioned herein including but not limited to salts, esters, amides, prodrugs, active metabolites, analogs and the like. When the terms “compound”, “active agent”, “pharmacologically active agent”, “medicament”, “active” and “drug” are used, then it is to be understood that this includes the active agent per se as well as pharmaceutically acceptable, pharmacologically active salts, esters, amides, prodrugs, metabolites, analogs, etc.
[0048] The term “compound” is not to be construed as a chemical compound only but extends to peptides, polypeptides and proteins as well as genetic molecules such as RNA, DNA and chemical analogs thereof. An RNA species, for example, includes miRNA, SiRNA, dsRNA and ssRNA. The term “modulator” is an example of a compound, active agent, pharmacologically active agent, medicament, active and drug which up-regulates or down-regulated either the level of expression of the p230 gene or the activity of p230 (or a molecule associated therewith). The term “down-regulates” encompasses the inhibition, reduction or prevention of expression of the p230 gene or of the activity of p230, so as to correspondingly reduce an inflammatory response or the risk of an inflammatory response being elicited. Such a modulator may be referred to herein as an “inhibitor” or antagonist. Similarly, the term “up-regulates” encompasses the induction, increase or potentiation of expression of p230 gene or of the activity of p230, so as to correspondingly enhance an inflammatory response or the risk of an inflammatory response being elicited. Such a modulator may, therefore, be referred to herein as a “potentiator” or agonist. The latter class of agents are likely to be useful in model disease systems to test for anti-inflammatory agents.
[0049] The present invention contemplates, therefore, compounds useful in modulating either the level of expression of a p230 gene or the activity of the p230 or of a molecule associated therewith. The compounds, when antagonists, have an effect on reducing or preventing or treating inflammatory conditions. Reference to a “compound”, “active agent”, “pharmacologically active agent”, “medicament”, “active” and “drug” includes combinations of two or more actives such as one or more inhibitors and/or potentiators. A “combination” also includes a two-part or more such as a multi-part pharmaceutical composition where the agents are provided separately and given or dispensed separately or admixed together prior to dispensation.
[0050] The terms “effective amount” and “therapeutically effective amount” of an agent as used herein mean a sufficient amount of the agent to provide the desired therapeutic or physiological effect. Ultimately, as far as an inhibitor/antagonist is concerned, the desired physiological effect is a reduction in TFNα-mediated inflammation. The agent may induce or prevent the expression of a p230 gene; act as an antagonist of p230; act as an antagonist of a co-factor of p230 or a molecule required by p230 to bind to a tubule, inter alia. Undesirable effects, e.g. side effects, are sometimes manifested along with the desired therapeutic effect; hence, a practitioner balances the potential benefits against the potential risks in determining what is an appropriate “effective amount”. The exact amount required will vary from subject to subject, depending on the species, age and general condition of the subject, mode of administration and the like. Thus, it may not be possible to specify an exact “effective amount”. However, an appropriate “effective, amount” in any individual case may be determined by one of ordinary skill in the art using only routine experimentation.
[0051] By “pharmaceutically acceptable” carrier, excipient or diluent is meant a pharmaceutical vehicle comprised of a material that is not biologically or otherwise undesirable, i.e. the material may be administered to a subject along with the selected active agent without causing any or a substantial adverse reaction. Carriers may include excipients and other additives such as diluents, detergents, coloring agents, wetting or emulsifying agents, pH buffering agents, preservatives, and the like.
[0052] Similarly, a “pharmacologically acceptable” salt, ester, emide, prodrug or derivative of a compound as provided herein is a salt, ester, amide, prodrug or derivative that this not biologically or otherwise undesirable.
[0053] The terms “treating” and “treatment” as used herein refer to reduction in severity and/or frequency of symptoms, elimination of symptoms and/or underlying cause, prevention of the occurrence of symptoms and/or their underlying cause, and improvement or remediation of damage. Thus, for example, “treating” a patient involves prevention of an inflammatory disease or condition in a subject as well as treatment of a clinically symptomatic subject by inhibiting or causing regression of an inflammatory condition or disorder. Generally, such a condition or disorder is an inflammatory response or mediates or facilitates an inflammatory response or is a downstream product of an inflammatory response. Thus, for example, the present method of “treating” a patient with an inflammatory condition or with a propensity for one to develop encompasses both prevention of the condition, disease or disorder as well as treating the condition, disease or disorder. In any event, the present invention contemplates the treatment or prophylaxis of any inflammatory-type condition and, in particular, an inflammatory condition exacerbated by TNFα.
[0054] “Patient” or “subject” as used herein refers to an animal, particularly a mammal and more particularly human who can benefit from the pharmaceutical formulations and methods of the present invention. There is no limitation on the type of animal that could benefit from the presently described pharmaceutical formulations and methods. A patient regardless of whether a human or non-human animal may be referred to as an individual, subject, patient, animal, host or recipient. As indicated above, the compounds and methods of the present invention have applications in human medicine, veterinary medicine as well as in general, domestic or wild animal husbandry.
[0055] The compounds of the present invention may be large or small molecules, nucleic acid molecules (including antisense or sense molecules and microRNAs), peptides, polypeptides or proteins or hybrid molecules such as RNAi- or siRNA-complexes, ribozymes or DNAzymes. The compounds may need to be modified so as to facilitate entry into a cell.
[0056] The present invention provides, therefore, medicaments which modulate either the level of p230 gene expression or the activity of p230 or a molecule associated therewith which modulate levels or activities of inhibitors or potentiators of p230. Furthermore, the present invention contemplates the use of p230/golgin-245 in the manufacture of a medicament for the treatment of an inflammatory condition in a subject.
[0057] The present invention contemplates, therefore, methods of screening for medicaments comprising, for example, contacting a candidate drug with p230 or a gene encoding same. For convenience, the term “target” is used to collectively describe p230, its gene or a molecule (or gene) associated with p230 such as Arl1. The screening procedure includes assaying (i) for the presence of a complex between the drug and target, or (ii) for an alteration in the expression levels of a target gene.
[0058] One form of assay involves competitive binding assays. In such competitive binding assays, the target is typically labeled. Free target is separated from any putative complex and the amount of free (i.e. uncomplexed) label is a measure of the binding of the agent being tested to target molecule. One may also measure the amount of bound, rather than free, target. It is also possible to label the agent rather than the target and to measure the amount of agent binding the target in the presence and in the absence of the drug being tested. Such compounds may inhibit the target which is useful, for example, in finding inhibitors of p230.
[0059] Another technique for drug screening provides high throughput screening for compounds having suitable binding affinity to a target and is described in detail in Geysen (International Patent Publication No. WO 84/03564). Briefly stated, large numbers of different small peptide test compounds are synthesized on a solid substrate, such as plastic pins or some other surface. The peptide test compounds are reacted with a target and washed. Bound target molecule is then detected by methods well known in the art. This method may be adapted for screening for non-peptide, chemical entities. This aspect, therefore, extends to combinatorial approaches to screening for target antagonists or agonists.
[0060] Purified target can be coated directly onto plates for use in the aforementioned drug screening techniques. However, non-neutralizing antibodies to the target may also be used to immobilize the target on the solid phase.
[0061] The present invention also contemplates the use of competitive drug screening assays in which neutralizing antibodies capable of specifically binding the target compete with a test compound for binding to the target or fragments thereof. In this manner, the antibodies can be used to detect the presence of any peptide which shares one or more antigenic determinants of the target.
[0062] Analogs of p230 may also be useful as antagonists. These analogs may compete for G-proteins required for binding to the tubule membrane.
[0063] Analogs contemplated herein include but are not limited to modification to side chains, incorporating of unnatural amino acids and/or their derivatives during peptide, polypeptide or protein synthesis and the use of crosslinkers and other methods which impose conformational constraints on the proteinaceous molecule or their analogs.
[0064] Another useful group of compounds is a mimetic. The terms “peptide mimetic”, “target mimetic” or “mimetic” are intended to refer to a substance which has some chemical similarity to p230 but which antagonises or agonises or mimics p230. A peptide mimetic may be a peptide-containing molecule that mimics elements of protein secondary structure (Johnson et al, “Peptide Turn Mimetics” in Biotechnology and Pharmacy , Pezzuto et al, Eds., Chapman and Hall, New York, 1993). The underlying rationale behind the use of peptide mimetics is that the peptide backbone of proteins exists chiefly to orient amino acid side chains in such a way as to facilitate molecular interactions such as those of antibody and antigen, enzyme and substrate or scaffolding proteins. A peptide mimetic is designed to permit molecular interactions similar to p230. Peptide or non-peptide mimetics may be useful, for example, to inhibit p230 activity or to compete with any molecules associated therewith.
[0065] A substance identified as a modulator of p230 expression or p230 activity or function may be a peptide or non-peptide. Non-peptide “small molecules” are often preferred for many in vivo pharmaceutical uses. Accordingly, a mimetic or mimic of the peptide may be designed for pharmaceutical use.
[0066] The designing of mimetics of p230 to a pharmaceutically active compound is a known approach to the development of pharmaceuticals based on a “lead” compound. Mimetic design, synthesis and testing are generally used to avoid randomly screening large numbers of molecules for a desired property.
[0067] There are several steps commonly taken in the design of a mimetic of p230. First, the particular parts of p230 that are critical and/or important in conferring function are determined. This can be done by systematically varying the amino acid residues in the protein, e.g. by substituting each residue in turn. Alanine scans of polypeptide are commonly used to refine such motifs. These parts or residues constituting the active region of p230 are known as its “pharmacophore”.
[0068] Once the pharmacophore has been found, its structure is modeled according to its physical properties, e.g. stereochemistry, bonding, size and/or charge, using data from a range of sources, e.g. spectroscopic techniques, x-ray diffraction data and NMR. Computational analysis, similarity mapping (which models the charge and/or volume of a pharmacophore, rather than the bonding between atoms) and other techniques can be used in this modeling process.
[0069] In a variant of this approach, the three-dimensional structure of the pharmacophore and/or its binding partner are modeled. Modeling can be used to generate inhibitors which interact with the linear sequence or a three-dimensional configuration.
[0070] A template molecule is then selected onto which chemical groups which mimic the pharmacophore can be grafted. The template molecule and the chemical groups grafted onto it can conveniently be selected so that the mimetic is easy to synthesize, is likely to be pharmacologically acceptable, and does not degrade in vivo, while retaining the biological activity of the lead compound. In addition, further stability can be achieved by cyclizing the peptide, increasing its rigidity. The mimetic or mimetics found by this approach can then be screened to see whether they have the target property, or to what extent they exhibit it. Further optimization or modification can then be carried out to arrive at one or more final mimetics for in vivo or clinical testing.
[0071] The goal of rational drug design is to produce structural analogs of p230 or of small molecules with which they interact (e.g. agonists, antagonists, inhibitors or enhancers) in order to fashion drugs which are, for example, more active or stable forms of the polypeptide, or which, e.g. enhance or interfere with the function of p230 in vivo. See, e.g. Hodgson ( Bio/Technology 9:19-21, 1991).
[0072] It is also possible to use a p230-specific antibody, and then to generate an anti-idiotypic antibody (anti-ids) As a mirror image of the p230 binding site of the first mentioned antibody, the binding site of the anti-ids would be expected to be an analog of the binding site. The anti-id could then be used to identify and isolate peptides from banks of chemically or biologically produced banks of peptides. Selected peptides would then act as the pharmacore.
[0073] Two-hybrid screening is also useful in identifying co-factors of p230. Two-hybrid screening conveniently uses, for example, Saccharomyces cerevisiae and Saccharomyces pombe . This approach screens for ligands of p230 and takes advantage of transcriptional factors that are composed of two physically separable, functional domains. The most commonly used is the yeast GAL4 transcriptional activator consisting of a DNA binding domain and a transcriptional activation domain. Two different cloning vectors are used to generate separate fusions of the GAL4 domains to genes encoding potential binding proteins. The fusion proteins are co-expressed, targeted to the nucleus and if interactions occur, activation of a reporter gene (e.g. lacZ) produces a detectable phenotype. In the present case, for example, S. cerevisiae is co-transformed with a library or vector expressing a cDNA GAL4 activation domain fusion, and a vector expressing the p230 gene fused to GAL4. If lacZ is used as the reporter gene, co-expression of the fusion proteins will produce a blue color. Small molecules or other candidate compounds which interact with p230 will result in loss of color of the cells. Reference may be made to the yeast two-hybrid systems as disclosed by Munder et al, ( Appl. Microbiol. Biotechnol. 52(3):311-320, 1999) and Young et al, Nat. Biotechnol. 16(10):946-950, 1998).
[0074] Another useful potential inhibitor of p230 is a cartilaginous fish-derived immunoglobulin-like molecule which binds to p230 or a co-factor thereof. More particularly, the immunoglobulin-like molecule comprises the variable domain of an IgNAR (Immunoglobulin new antigen receptor), referred to as “V NAR ”. The immunoglobulin-like molecules of the present invention enable the selective targeting of p230 and its precursor or processed forms which include monomeric or multimeric forms thereof or of molecules associated therewith.
[0075] Accordingly, the present invention provides an isolated, cartilaginous fish-derived immunoglobulin-like molecule which binds to p230/golgin-245.
[0076] In a particular embodiment, the immunoglobulin-like molecule comprises a variable domain of an IgNAR, referred to herein as V NAR . IgNARs are described in International Patent Application No. WO 2005/118629.
[0077] IgNARs are classified in relation to their time of appearance during fish development and disulfide bonding patterns within variable domains. The categories are Type I V NAR , Type 2 V NAR and Type 3 V NAR (Nuttal et al, Mol. Iminunol. 38:313-316, 2001; Nuttal et al, Eur j Biochem 270:3543-3554, 2003). Hence, the present invention encompasses an isolated Type 1 or 2 or 3 V NAR from an IgNAR which binds to HBeAg and/or HBcAg or a precursor or processed form thereof.
[0078] Reference to a “cartilaginous fish” includes a member of the families of shark and ray. Reference to a “shark” includes a member of order Squatiniformes, Pristiophoriformes, Squaliformes, Carcharinformes, Laminiformes, Orectolobiformes, Heterodontiformes and Hexanchieformes. Whilst not intending to limit the shark to any one genus, immunoglobulins from genus Orectolobus are particularly useful and include the bamboo shark, zebra shark, blind shark, whale shark, nurse shark and Wobbegong. Immunoglobulins from Orectolobus maculates (Wobbegong) are exemplified herein.
[0079] The “immunoglobulins” from cartilaginous fish may be referred to herein as “immunoglobulin-like” to emphasize that the cartilaginous fish-derived molecules are structurally different to mammalian or avian-derived immunoglobulins. See Nuttal et al, 2003 supra. For brevity, all cartilaginous fish-derived immunoglobulin-like molecules are referred to herein as “IgNARs”. The variable domain from an IgNAR is referred to as a V NAR .
[0080] Reference to “derived” includes vaccination of a fish and collection of blood or immune sera or other body fluid as well as the generation of molecules via recombinant means. By “recombinant means” includes generation of cartilaginous fish-derived nucleic acid libraries and biopanning expression libraries (such as phagemid libraries) for IgNAR proteins which interact with p230.
[0081] The present invention extends to a genetic approach to down-regulating expression of the p230 gene. In one example, nucleic acid molecules that induce temporary or permanent silencing of the p230 gene may be used to reduce levels of p230.
[0082] The terms “nucleic acids”, “nucleotide” and “polynucleotide” include RNA, cDNA, genomic DNA, synthetic forms and mixed polymers, both sense and antisense strands, and may be chemically or biochemically modified or may contain non-natural or derivatized nucleotide bases, as will be readily appreciated by those skilled in the art. Such modifications include, for example, labels, methylation, substitution of one or more of the naturally occurring nucleotides with an analog (such as the morpholine ring), internucleotide modifications such as uncharged linkages (e.g. methyl phosphonates, phosphotriesters, phosphoamidates, carbamates, etc.), charged linkages (e.g. phosphorothioates, phosphorodithioates, etc.), pendent moieties (e.g. polypeptides), intercalators (e.g. acridine, psoralen, etc.), chelators, alkylators and modified linkages (e.g. α-anomeric nucleic acids, etc.). Also included are synthetic molecules that mimic polynucleotides in their ability to bind to a designated sequence via hydrogen binding and other chemical interactions. Such molecules are known in the art and include, for example, those in which peptide linkages substitute for phosphate linkages in the backbone of the molecule.
[0083] Antisense polynucleotide sequences, for example, are useful in silencing transcripts of the p230 gene. Furthermore, polynucleotide vectors containing all or a portion the p230 gene may be placed under the control of a promoter in an antisense orientation and introduced into a cell. Expression of such an antisense construct within a cell will interfere with target transcription and/or translation. Furthermore, co-suppression and mechanisms to induce RNAi or siRNA or microRNA may also be employed. Alternatively, antisense or sense molecules may be directly administered. In this latter embodiment, the antisense or sense molecules may be formulated in a composition and then administered by any number of means to target cells.
[0084] A variation on antisense and sense molecules involves the use of morpholinos, which are oligonucleotides composed of morpholine nucleotide derivatives and phosphorodiamidate linkages (for example, Summerton and Weller, Antisense and Nucleic Acid Drug Development 7:187-195, 1997). Such compounds can also be injected into embryos and the effect of interference with mRNA observed.
[0085] In one embodiment, the present invention employs compounds such as oligonucleotides and similar species for use in modulating the function or effect of the p230 gene, i.e. the oligonucleotides induce pre-transcriptional or post-transcriptional gene silencing. This is accomplished by providing oligonucleotides which specifically hybridize with a p230 gene transcript. The oligonucleotides may be provided directly to a cell or generated within the cell. As used herein, the term “target nucleic acid” is used for convenience to encompass DNA encoding the p230 transcript (including pre-mRNA and mRNA or portions thereof).
[0086] In an alternative embodiment, genetic constructs including DNA vaccines are used to generate sense or antisense molecules in vivo.
[0087] Following identification of an agent which modulates the level of expression of the p230 gene or p230, it may be manufactured and/or used in a preparation, i.e. in the manufacture or formulation or a composition such as a medicament, pharmaceutical composition or drug. These may be administered to individuals in a method of treatment or prophylaxis. Alternatively, they may be incorporated into a patch or slow release capsule or implant or incorporated into a microparticle, inhalant spray or otherwise suitable medium.
[0088] Thus, the present invention extends, therefore, to a pharmaceutical composition, medicament, drug or other composition including a patch or slow release formulation or inhalant formulation comprising an agonist or antagonist of p230 gene or p230. Another aspect of the present invention contemplates a method comprising administration of such a composition to a patient such as for treatment or prophylaxis of an inflammatory condition. Furthermore, the present invention contemplates a method of making a pharmaceutical composition comprising admixing a compound of the instant invention with a pharmaceutically acceptable excipient, vehicle or carrier, and optionally other ingredients. Where multiple compositions are provided, then such compositions may be given simultaneously or sequentially. Sequential administration includes administration within nanoseconds, seconds, minutes, hours or days. Preferably, within seconds or minutes.
[0089] Two- or multi-part pharmaceutical compositions or packs are also contemplated with multiple components, such as comprising those which down-regulate or up-regulate the level of expression of the p230 gene or the activity of p230.
[0090] Accordingly, another aspect of the present invention contemplates a method for the treatment or prophylaxis of an inflammatory condition in an animal, the method comprising administering to the animal an effective amount of a compound as described herein or a composition comprising same.
[0091] The term “administering to” includes the inhalant or nasal application of a composition.
[0092] This method also includes providing a wild-type or mutant target gene function to a cell. This is particularly useful when generating an animal model. Alternatively, it may be part of a gene therapy approach. This may be particularly useful when an infant or fetus comes from one or more parents which are likely to pass on the genetic predisposition of, for example, asthma. A target gene or a part of the gene may be introduced into the cell in a vector such that the gene remains extrachromosomal. In such a situation, the gene will be expressed by the cell from the extrachromosomal location. If a gene portion is introduced and expressed in a cell carrying a mutant target allele, the gene portion should encode a part of the target protein. Vectors for introduction of genes both for recombination and for extrachromosomal maintenance are known in the art and any suitable vector may be used. Methods for introducing DNA into cells such as electroporation calcium phosphate co-precipitation and viral transduction are known in the art.
[0093] Gene transfer systems known in the art may be useful in the practice of genetic manipulation. These include viral and non-viral transfer methods. A number of viruses have been used as gene transfer vectors or as the basis for preparing gene transfer vectors, including papovaviruses (e.g. SV40, Madzak et al, J. Gen. Virol. 73:1533-1536, 1992), adenovirus (Berkner, Curr. Top. Microbiol. Immunol. 158:39-66, 1992; Berkner et al, BioTechniques 6:616-629, 1988; Gorziglia and Kapikian, J. Virol. 66:4407-4412, 1992; Quantin et al, Proc. Natl. Acad. Sci. USA 89:2581-2584, 1992; Rosenfeld et al, Cell 68:143-155, 1992; Wilkinson et al, Nucleic Acids Res. 20:2233-2239, 1992; Stratford-Perricaudet et al, Hum. Gene Ther. 1:241-256, 1990; Schneider et al, Nature Genetics 18:180-183, 1998), vaccinia virus (Moss, Curr. Top. Microbiol. Immunol. 158:25-38, 1992; Moss, Proc. Natl. Acad. Sci. USA 93:11341-11348, 1996), adeno-associated virus (Muzyczka, Curr. Top. Microbiol. Immunol. 158:97-129, 1992; Ohi et al, Gene 89:279-282, 1990; Russell and Hirata, Nature Genetics 18:323-328, 1998), herpesviruses including HSV and EBV (Margolskee, Curr. Top., Microbiol. Immunol. 158:67-95, 1992; Johnson et al, J. Virol. 66:2952-2965, 1992; Fink et al, Hum. Gene Ther. 3:11-19, 1992; Breakefield and Geller, Mol. Neurobiol. 1:339-371, 1987; Freese et al, Biochem. Pharmacol. 40:2189-2199, 1990; Fink et al, Ann. Rev. Neurosci. 19:265-287, 1996), lentiviruses (Naldini et al, Science 272:263-267, 1996), Sindbis and Semliki Forest virus (Berglund et al, Biotechnology 11:916-920, 1993) and retroviruses of avian (Bandyopadhyay and Temin, Mol. Cell. Biol. 4:749-754, 1984; Petropoulos et al, J. Viol. 66:3391-3397, 1992], murine [Miller, Curr. Top. Microbiol. Immunol. 158:1-24, 1992; Miller et al, Mol. Cell. Biol. 5:431-437, 1985; Sorge et al, Mol. Cell. Biol. 4:1730-1737, 1984; and Baltimore, J. Virol. 54:401-407, 1985; Miller et al, J. Virol. 62:4337-4345, 1988] and human [Shimada et al, J. Clin. Invest. 88:1043-1047, 1991; Helseth et al, J. Virol. 64:2416-2420, 1990; Page et al, J. Virol. 64:5270-5276, 1990; Buchschacher and Panganiban, J. Virol. 66:2731-2739, 1982] origin.
[0094] Non-viral gene transfer methods are known in the art such as chemical techniques including calcium phosphate co-precipitation, mechanical techniques, for example, microinjection, membrane fusion-mediated transfer via liposomes and direct DNA uptake and receptor-mediated DNA transfer. Viral-mediated gene transfer can be combined with direct in vivo gene transfer using liposome delivery, allowing one to direct the viralvectors to particular cells. Alternatively, the retroviral vector producer cell line can be injected into particular tissue. Injection of producer cells would then provide a continuous source of vector particles.
[0095] In an approach which combines biological and physical gene transfer methods, plasmid DNA of any size is combined with a polylysine-conjugated antibody specific to the adenovirus hexon protein and the resulting complex is bound to an adenovirus vector. The trimolecular complex is then used to infect cells. The adenovirus vector permits efficient binding, internalization and degradation of the endosome before the coupled DNA is damaged. For other techniques for the delivery of adenovirus based vectors, see U.S. Pat. No. 5,691,198.
[0096] Liposome/DNA complexes have been shown to be capable of mediating direct in vivo gene transfer. While in standard liposome preparations the gene transfer process is non-specific, localized in vivo uptake and expression have been reported in tumor deposits, for example, following direct in situ administration.
[0097] Cells and animals which carry mutant p230 alleles or where one or both alleles are deleted can be used as model systems to study the effects of modulating the expression of the p230 gene, and/or the activity of p230, on inflammation. Mice, rats, rabbits, guinea pigs, hamsters, zebrafish and amphibians are particularly useful as model systems. A particularly useful insertion is a loxP sequence flanking a target gene which can be excised by cre. Alternatively, the model system may be a tissue culture system. An “animal model” may, therefore, be tissues from an animal.
[0098] The present invention provides, therefore, a mutation in or flanking a genetic locus encoding p230. The mutation may be an insertion, deletion, substitution or addition to the p230-coding sequence or its 5′ or 3′ untranslated region.
[0099] The animal model of the present invention is useful for screening for agents capable of ameliorating or mimicking the effects of p230. In one embodiment, the animal model produces low amounts of a p230. In another animal model, excess p230 is produced.
[0100] The compounds, agents, medicaments, nucleic acid molecules and other target antagonists or agonists of the present invention can be formulated in pharmaceutical compositions which are prepared according to conventional pharmaceutical compounding techniques. See, for example, Remington's Pharmaceutical Sciences, 18 th Ed. (1990, Mack Publishing, Company, Easton, Pa., U.S.A.). The composition may contain the active agent or pharmaceutically acceptable salts of the active agent. These compositions may comprise, in addition to one of the active substances, a pharmaceutically acceptable excipient, carrier, buffer, stabilizer or other materials well known in the art. Such materials should be non-toxic and should not interfere with the efficacy of the active ingredient. The carrier may take a wide variety of forms depending on the form of preparation desired for administration, e.g. topical, intravenous, oral, intrathecal, epineural or parenteral.
[0101] For oral administration, the compounds can be formulated into solid or liquid preparations such as capsules, pills, tablets, lozenges, powders, suspensions or emulsions. In preparing the compositions in oral dosage form, any of the usual pharmaceutical media may be employed, such as, for example, water, glycols, oils, alcohols, flavoring agents, preservatives, coloring agents, suspending agents, and the like in the case of oral liquid preparations (such as, for example, suspensions, elixirs and solutions); or carriers such as starches, sugars, diluents, granulating agents, lubricants, binders, disintegrating agents and the like in the case of oral solid preparations (such as, for example, powders, capsules and tablets). Because of their ease in administration, tablets and capsules represent the most advantageous oral dosage unit form, in which case solid pharmaceutical carriers are obviously employed. If desired, tablets may be sugar-coated or enteric-coated by standard techniques. The active agent can be encapsulated to make it stable to passage through the gastrointestinal tract while at the same time allowing for passage across the blood brain barrier. See for example, International Patent Publication No. WO 96/11698. Microparticle sprays, inhalants and fumes are particularly useful compositions.
[0102] For parenteral administration, the compound may dissolved in a pharmaceutical carrier and administered as either a solution of a suspension. Illustrative of suitable carriers are water, saline, dextrose solutions, fructose solutions, ethanol, or oils of animal, vegetative or synthetic origin. The carrier may also contain other ingredients, for example, preservatives, suspending agents, solubilizing agents, buffers and the like. When the compounds are being administered intrathecally, they may also be dissolved in cerebrospinal fluid.
[0103] The active agent is preferably administered in a therapeutically effective amount. The actual amount administered and the rate and time-course of administration will depend on the nature and severity of the condition being treated. Prescription of treatment, e.g. decisions on dosage, timing, etc. is within the responsibility of general practitioners or specialists and typically takes account of the disorder to be treated, the condition of the individual patient, the site of delivery, the method of administration and other factors known to practitioners. Examples of techniques and protocols can be found in Remington's Pharmaceutical Sciences, supra.
[0104] Alternatively, targeting therapies may be used to deliver the active agent more specifically to certain types of cell, by the use of targeting systems such as antibodies or cell specific ligands or specific nucleic acid molecules. Targeting may be desirable for a variety of reasons, e.g. if the agent is unacceptably toxic or if it would otherwise require too high a dosage or if it would not otherwise be able to enter the target cells.
[0105] Instead of administering these agents directly, they could be produced in the target cell, e.g. in a viral vector such as described above or in a cell based delivery system such as described in U.S. Pat. No. 5,550,050 and International Patent Publication Nos. WO 92/19195, WO 94/25503, WO 95/01203, WO 95/05452, WO 96/02286, WO 96/02646, WO 96/40871, WO 96/40959 and WO 97/12635. The vector could be targeted to the target cells. The cell based delivery system is designed to be implanted in a patient's body at the desired target site and contains a coding sequence for the target agent. Alternatively, the agent could be administered in a precursor form for conversion to the active form by an activating agent produced in, or targeted to, the cells to be treated. See, for example, European Patent Application No. 0 425 731A and International Patent Publication No. WO 90/07936.
[0106] The present invention is further described by the following non-limiting Examples. Materials and Methods used in these Examples are provided below.
Antibodies, Plasmids and Reagents
[0107] Plasmids construct containing YFP-TNFα and GFP-Ecadherin were previously described (Lock et al, Traffic 6(12):1142-1156, 2005). Myc tagged full length p230 have been previously described (Erlich et al, J Biol Chem 271 (14):8328-8337, 1996). To generate retroviral DNA constructs expressing microRNA, PCR amplification was used to amplify the microRNA insert from pcDNATM 6.2 GW/EmGFP expression vector and then subcloned into pMIG-MSCV vector to produce pMIG-MSCV mp 230a or mp 230b constructs.
[0108] The following primary antibodies were used:Human autoantibodies to p230 and affinity purified rabbit polyclonal antibodies to p230/golgin245 have been previously described. Rabbit polyclonal antibodies to human GCC88 and GCC185 were prepared by standard procedures. Mouse monoclonal antibody to GM130 and golgin-97 were purchased from BD Biosciences (NSW, Australia). Mouse monoclonal anti α-tubulin was obtained from Amersham, UK. A rabbit polyclonal antibody to mouse TNFα was purchased from Chemicon (Millipore, NSW, Australia). The 9E10 mouse monoclonal antibody specific for the myc epitope has been described. HECD1 a mouse monoclonal antibody was used to detect human E cadherin. Murine MHC class II were detected using anti-I-E antibodies (clone 14-4-4S) from Escherichia coli 011:B4 was purchased from Sigma Adrich (NSW, Australia). TACE inhibitor TAPI-1 was purchased from Calbiochem (Merck, Victoria, Australia). Secondary antibodies used for immunofluorescence were goat anti-rabbit IgG-Alexa Fluor (Trade Mark) 568, goat anti-rabbit IgG-Alexa Fluor (Trade Mark) 488, Goat anti-human Alexa Fluoro (Trade Mark) 647 nm and goat anti-human Alexa Fluor (Trade Mark) 594 nm were from Molecular Probes (Invitrogen, Carlsbad, Calif., USA). Horse-radish peroxidase-conjugated sheep anti-rabbit Ig and anti-mouse Ig were from DAKO Corporation (Carpinteria, Calif., USA)
Cell Culture and Transfection
[0109] HeLa cells and 3T3 mouse fibroblasts were maintained as semi-confluent monolayer in Dulbecco's Modified Eagle's media (DMEM) supplemented with 10% (v/v) fetal calf serum (FCS), 2 mM L-glutamine, 100 units/μl. RAW264.7 murine macrophages were cultured in RPMI 1640 medium (Invitrogen, Carlsbad, Calif., USA) containing 10% (v/v) heat inactivated serum supreme (BioWhittaker, Australia) and 1% (w/v) Lglutamine. For transfections, HeLa cells and 3T3 mouse fibroblast were seeded as monolayers and transfected using Fugene 6 (Roche Diagnostic, Basel, Switzerland) according to manufacturer's instructions. Transfections were carried out in C-DMEM at 37° C., 10% (v/v) CO 2 for 24-96 hrs. Transient transfection of siRNA was performed using Oligofectamine (Invitrogen, Carlsbad, Calif., USA) according to manufacturer's instruction for 72 hrs at 37° C. prior to analysis. RAW 264.7 murine macrophages were transfected with miRNA constructs either by electroporation or using Lipofactamine 2000 (Invitrogen). For electroporation, 2.5×10 7 cells were mixed with 20 μg of DNA with a high capacitance setting (240V and 950 μF on exponential decay setting) using an electroporation system (Gene Pulser II; BioRad Laboratories). Cells were then washed in cold SF RPMI, plated out on non-coated 10 cm plates in warmed C—RPMI with 10% (v/v) serum supreme and incubated at 37° C. for 96 hrs. For Lipofectmine 2000 transfection, 2 μg of DNA was mixed with 10 μl of Lipofectamine 2000 and then added to 2.5×10 7 cells in the presence of Optimum (Invitrogen, Carlsbad, Calif., USA) at 37° C. overnight. Optimun medium in transfected macrophages were replace with C—RPMI the next day and incubate at 37° C. for another 72 hrs.
[0000] siRNA and miRNA
[0110] Mouse and human p230/golgin245 and human GCC88 was targeted with siRNA duplex.
[0111] For knockdown of mouse p230/golgin245 using a miRNA system (Invitrogen) the following primer sets were designed using Invitrogen BLOCK-iT (Trade Mark) RNAi designer, annealed and cloned into pcDNA (Trade Mark) 6.2 GW/EmGFP miR expression vector containing a GFP expression cassette according to manufacturer's instructions.
[0000]
miRmp230a
(SEQ ID NO: 1)
5′TGCTGAATAGCGTCGGCTTTGTCACGGTTTTGGCCACTGACTGAC
CGTGACAACCGACGCTATT-3′
miR mp230b
(SEQ ID NO: 2)
5′TGCTGAATTGTTACACTGTCCTTGGTGTTTTGGCCACTGACTGAC
ACCAAGGAGTGTAACAATT-3′
miR mGCC185
5′TGCTGTAAGATGGCCGTTTCTTTGCTGTTTTGGCCACTGACTGAC
AGCAAAGACGGCCATCTTA-3′
Assay for TNFα Secretion by Activated Macrophage
[0112] The trafficking of TNFα from the Golgi to the cell surface was measured. Briefly, macrophages were activated with 100 ng/ml of LPS in serum free RPMI at 37° C. for 2-4 hrs and fixed in 4% (v/v) PFA to stop activation. For internal staining of TNFα, macrophages were fixed in 4% (v/v) PFA, permeabilized in 0.1% (v/v) triton x-100 and then stained for mouse TNFα. To detect for cell surface TNFα, activated macrophages were stimulated as described above in the presence of 10 μM of TAPI-1, fixed in 4% (v/v) PFA, stained with rabbit polyclonal antibodies to mouse TNFα in non-permeabilized cells. For FACS quantification of cell surface TNFα, macrophages were activated in the presence of 10 μM of TAPI-1 as described above, stained with rabbit polyclonal antibody to mouse TNFα and then FACS analyzed by gating on GFP+ cells.
Generation of Retroviral Producer Cells and Stable Transduction of 3T3
[0113] 293T cells were transiently cotransfected with the murine stem cell vector containing microRNA and its packaging plasmids. Retroviral producer cell lines were then generated by repeatedly transducing GP+E86 cells (6-8 times) with viral supernatant harvested from 293T transfection. To test viral titre of retroviral producer lines, 3T3 fibroblast were transduced with supernatant harvested from producer cells in the presence of polybrene (hexadimethrine bromide; 6 μg/ml) for 72 hrs. Transduced cells were analyzed for GFP expression by FASC analysis.
[0000] Generation of p230 Depleted Retrogenic Mice
[0114] Bone marrow was harvested from 6-8 weeks old donor mice, 48 hrs after treatment with 150 mg/kg of 5-fluoruracil (Sigma). Bone marrow cells were cultured in C-DMEM with 20% (v/v) FCS and the stem cells induced to proliferate with 20 ng/ml murine interleukin-3 (mIL-3), 50 ng/ml of human interleukin-6 (hIL-6) and 50 ng/ml of murine stem cell factor (mSCF) (Invitrogen, Biosource international). Bone marrow cells were co-culture for 48 hrs with the retroviral produced lines described above. The nonadherent, transduced bone marrow cells were collected and washed. Sub lethally irradiated (600rad-750rad) recipient mice were injected via the tail vein with 4×106 bone marrow cells with 2% (v/v) FCS and 20 u/ml of heparin (Sigma). Mice were analyzed 8-10 week post transplant.
Isolation of Peritoneal Macrophage
[0115] 8 to 10 weeks old reconstituted retrogenic mice or wild type Balb/C mice were injected with 8 ml of prewarmed C—RPMI into their peritoneal cavity. Macrophages were liberated by massage and the medium recollected back into the syringe. Peritoneal macrophages were washed once in warm C—RPMI, plated on coverslips and incubate overnight at 37° C. After incubation, non-adherent cells were then washed off with CRPMI.
Indirect Immunofluorescence
[0116] Cells were fixed in 4% (v/v) paraformaldehyde for 15 min, followed by quenching in 50 mM NH4Cl/PBS for 10 min. Cells were either permeabilized by 0.1% (v/v) Triton X-100/PBS or 0.1% (v/v) saponin/PBS for 4 mins. Cell monolayer were blocked in PBS containing 5% (v/v) fetal calf serum for 20 mins to reduce non-specific binding. Monolayers were incubated in primary antibodies, diluted in 5% FCS/PBS for 1 h at room temperature. Cells were hen washed 6 times in PBS over 30 mins, before fluorochrome conjugate, antibodies were added and incubated for 30 mins at room temperature. Washes were carried out as above. Monolayers were then rinsed with milliQ water before mounting in Mowiol. Confocal microscopy was performed using a Leica TCS SP@ imaging system. For multi-color labeling, images were collected separately. To quantitate cell surface TNFα in activated peritoneal macrophages, images were collected on the same confocal settings for both control (empty) vector (n=46) and p230 miRNA macrophages (n=46) at each timepoint after LPS stimulation. Total fluorescence intensity for GFP and TNFα were determined by Leica confocal software (version beta 2000). GFP-intensity values were used to categorize macrophages into weak GFP positive cells, medium GFP positive cells and bright GFP positive cells before analysis of TNFα fluorescence intensity. Results were expressed as means and p-value were determined by student t-test.
Immunoblot
[0117] Cell extracts were obtained by resuspending cell pellet in 4× reducing sample buffer. Protein samples were resolved on a 4-12% (w/v) NuPAGE gradient gel (Invitrogen) according to manufacturer's instructions and transferred overnight onto a polyvinylidene fluoride membrane (Millipore, NSW Australia). The membrane was blocked by drying at room temperature. The blocked membrane was incubated with primary antibodies, diluted in 1% (w/v) Blotto (1% (w/v) Skim milk powder in PBS) for 1 h with rocking before the addition of HRP-conjugated secondary antibodies for 30 min. The membrane was then rinsed with 0.05% (w/v) Tween-20/PBS before and after incubation with primary and secondary antibodies. Bound antibodies were detected by chemiluminescence (NEN, Boston, USA) and captured using the Gel Pro analyzer program (MediaCybernetics, Bethesda, Md. USA). Densitometry of the protein bands were measured using the Gel Pro analyzer program (MediaCybernetics, Bethesda, Md.).
Example 1
TGN Golgin, p230 is Required for TNFα Secretion in HeLa Cells
[0118] Golgins mark different subdomains of the TGN and tubules arising from these subdomains have different golgins associated with them. To determine if p230 was required for post-Golgi export of TNFα, HeLa cells were depleted of p230 using siRNA and then transfected with TGN38-YFP. p230 was depleted to >75% in siRNA transfected cells, whereas the related TGN golgin, golgin-97, was unaffected ( FIG. 1 d ). In both control and p230-depleted cells, YFP-TNFα showed intracellular perinuclear Golgi-like staining ( FIG. 3 ). To allow detection of TFNα at the cell surface, a TNFα converting enzyme (TACE) inhibitor was included to block proteolytic release of surface TNFα. Cell surface TNFa was readily detected on non-permeabilized control cells ( FIG. 1 ), however, there was very little surface TNFα detected on p230 siRNA transfected cells. In contrast, and as expected from our previous findings, the membrane cargo E-cadherin was efficiently transport to the plasma membrane of p230-depleted cells ( FIG. 1 c ). Depletion of another TGN golgin, GCC88, has no affect on cell surface transport of TNFα, demonstrating that the block in TNFα export was p230 specific.
[0119] To rule out the possibility of off-target affects by the siRNA, p230-depleted HeLa were transfected with a myc-tagged full-length p230 construct (myc-p230) to determine if overproduction of wild-type p230 would rescue the observed block in TNFa transport. In p230 depleted HeLa expressing myc-p230FL, cell surface TNFα was readily detected in all cells examined (>20 cells analyzed) ( FIG. 1 b ), indicating that full length exogenous p230 protein rescued the block in TNFα export from the Golgi.
Example 2
Characterization of TNFα in p230 Tubules Leaving the TGN in Live Macrophages
[0120] Newly-synthesized cytokines, including the transmembrane precursor of TNFα, initially accumulate in the Golgi complex and are then loaded into carriers which bud off the TGN for post-Golgi transport and secretion. Having established a role for p230 in the post-Golgi export in HeLa cells, the relevance of these findings in macrophages was examined. LPS-stimulated RAW264.7 macrophages cells were examined for the relationship between p230 and TFNα at the TGN. Macrophages were transiently transfected with GFP-TNFα and/or with YFP-labeled GRIP domains of p230 or golgin97 TGN-derived tubules and budding carriers were viewed in live macrophages and also analyzed by immunolabeling in a series of fixed cells. Typically, endogenous TNFα or GFP-TNFα was seen emerging from the TGN as a bolus in tubules labeled with the YFP-p230GRIP ( FIG. 2 a ). The transport of TNFα from the TGN to the recycling endosome involves the SNARE complex of syntaxin6/syntaxin7/Vtilb and accordingly p230 tubules can be seen colabeled with syntaxin6. Neither endogenous TNFα nor GFP-TNFα in macrophages was seen associated with golgin-97 labeled tubules, thus TNFα transport is selectively accomplished by p230-labeled tubules and carriers. This selectivity emulates the same combinations of cargo and golgins on tubules recorded in transfected HeLa cells where TNFα was also seen exclusively in p230 labeled tubules. Thus, TNFα trafficking and secretion in activated macrophages relies preferentially on p230-labeled tubules.
Example 3
p230 Tubule Formation is LPS Regulated
[0121] Upon activation with LPS, macrophages undergo a dramatic increase in exocytic trafficking activity and, to accomplish that, upregulate the expression of key components of their trafficking machinery. There is a significant increase in the number of GFP-TNFα labeled tubules and carriers emerging from the TGN in LPS activated cells, reflecting the heightened secretory capacity of these cells. The activities of p230GRIP- and golgin-97GRIP-labeled membranes on the TGN were monitored in live cells before and after treatment with LPS. The relative frequency of p230 or golgin97-labeled tubules emerging from the TGN was counted in live activated or resting macrophages. In the absence of LPS, the TGN gives rise to approximately equal numbers of p230 or golgin-97 labeled tubules and carriers ( FIG. 2 b ). However, after LPS activation, the number of golgin-97 tubules/carriers did not change but there was a marked (three fold) increase in the number of p230 tubules emerging from the TGN and an equivalent increase in p230 labeled budding events ( FIG. 2 b ). Thus, there is a selective increase in p230 tubules and carriers accompanying the need to secrete TNF.
[0122] To test whether p230 has a functional role in TNFα secretion in macrophages, a vector-based micro RNA (miRNA) system was used to deplete intracellular p230. RAW cells were transfected with the BLOCK-iT (Trade Mark) Pol II miR RNAi Expression Vectors, which contain a GFP reporter gene, and the extent of p230 depletion was determined 48 or 96 hrs after transfection by immunofluorescence. Very little p230 was detected in GFP+ macrophages transfected with miRNA target sequence one (miRNA-1) ( FIG. 3 a ) or two (miRNA-2) whereas control miRNA had no apparent affect on endogenous p230 levels ( FIG. 3 a ). On LPS activation, both control and p230-depleted macrophages showed strong perinuclear staining for TFNα 0 ( FIG. 3 a ), demonstrating the production of precursor TNFα in LPS-stimulated macrophages. However, whereas control miRNA macrophages showed high levels of surface TNFα by immunofluorscence and flow cytometry, p230 miRNA transfected macrophages showed very little surface TNFα staining ( FIGS. 3 b, c ). The level of surface TNFα on p230-depleted macrophages was <10% of control macrophages ( FIG. 3 c ). A dramatic reduction of surface TFNα was also observed with a second independent miRNA p230 target as well as an siRNA p230 target thereby ruling out off-target affects of the p230 RNAi. To determine whether all cell surface components were affected by p230 depletion in RAW cells, the surface MHC class II expression was analyzed, which increases following LPS stimulation of macrophages. Surface MHC class II expression was elevated to similar levels in both control and p230-depleted LPS-stimulated macrophages following LPS treatment. Therefore, as for HeLa cells, p230 depletion results in a block of specific cargo from the Golgi apparatus of macrophages. Collectively, these findings demonstrate that p230 is an essential component of the tubules at the TGN required for post-Golgi transport of TNFα.
Example 4
Peritoneal Macrophages from Transgenic Mice Expressing p230 miRNA are Blocked in TNFa Secretion
[0123] To determine if depletion of p230/golgin-245 could block TNFα secretion in vivo, w transgenic mice were generated expressing RNAi. p230/golgin-245 was silenced in mice by retroviral transduction and bone marrow transplantation. p230 and control miRNA constructs were cloned into a MSCV-based retroviral vector, retrovirus produced and bone marrow cells transduced with the recombinant retrovirus in the presence of IL3, IL6 and SCF. Two days after infection with retrovirus, transduced stem cells were injected into sublethally irradiated recipient mice and peritoneal macrophages were analyzed 8-10 weeks after the transplant. GFP+ macrophages from control and p230 miRNA expressing mice showed the characteristics of wildtype macrophages including extensive membrane ruffling after LPS stimulation. p230miRNA resulted in depletion of p230/golgin-245 in peritoneal macrophages of transgenic mice ( FIG. 4 a ), whereas strong p230 staining was present in control miRNA peritoneal macrophages ( FIG. 4 a ). The staining patterns of other TGN golgins, namely GCC88 and GCC185, were unaffected by the depletion of p230 ( FIG. 4 b ). Following LPS stimulation in the presence of TACE inhibitor, intracellular TNFα was readily detected in both control and p230miRNA macrophages, whereas there was a marked difference in the level of surface TNFα ( FIGS. 4 c, d ). Control miRNA GFP+ macrophages had high levels of surface TNFα whereas there was a considerably lower level of surface TFNα in the miRNA p230 macrophages. Surface TNFα was quantified by confocal microscopy, as described in methods, and GFPbright p230 miRNA macrophages showed no increase in surface fluorescence after LPS treatment compared with resting macrophages, whereas GFPdull macrophages showed an increase in surface fluorescence to ˜25% the level measured in control miRNA macrophages. These findings indicate that the level of expression of the miRNA construct is sufficient to inhibit p230 in vivo, and moreover p230 depletion results in block in post-Golgi transport of TFNα. Furthermore, these analyses demonstrate the applicability of miRNAs to deplete cellular components and disrupt membrane trafficking pathways in vivo.
Example 5
Use of miRNA Antagonists
[0124] Constructs encoding miRNA directed to the p230/golgin-245 gene are generated and include the receptor GFP as a marker. These are then used to genetically modify stem cells. Enrichment of GFP + stem cells prior to transplantation results in highly efficient reconstitution with ˜80% of thymocytes in transplanted mice GFP + . Experiments indicate that p230 miRNA retrogenic mice are resistant to cytokine shock following challenge with LPS, compared with wild-type mice. Groups of two wild-type and p230 miRNA retrogenic mice are administered with 100 mg of LPS intraperitoneally and mice are monitored. Within two hours after treatment, both wild-type mice develop signs of cytokine shock as expected, and showed evidence of distress as assessed by loss of mobility, hunched appearance, and huddling in the corner of the cage. On the other, and the two LPS-treated p230 retrogenic mice, remained healthy and showed no signs of distress two hours after treatment or up to 10 days following LPS treatment. These results show that the silencing of p230 resulted in a physiological reduction in total TNF secretion in the mice. Overall, the studies demonstrate an approach to control cytokine secretion by the specific silencing of p230-mediated trafficking machinery.
[0125] Those skilled in the art will appreciate that the invention described herein is susceptible to variations and modifications other than those specifically described. It is to be understood that the invention includes all such variations and modifications. The invention also includes all of the steps, features, compositions and compounds referred to or indicated in this specification, individually or collectively, and any and all combinations of any two or more of said steps or features.
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Wilkinson et al, Nucleic Acids Res. 20:2233-2239, 1992 | The present invention relates generally to the field of cell biology and in particular the cellular processes surrounding inflammation. Even more particularly, the present invention provides targets for medicaments useful in reducing levels of TNF-alpha, an extracellular pro-inflammatory mediator. The medicaments are therefore useful in modulating inflammatory responses. Model inflammatory disease systems also form part of the present invention. | 2 |
FIELD OF THE INVENTION
The present invention generally relates to blends of produce, grown in any method ranging from vertical, greenhouse, and hydroponic to aeroponic, and whether the produce is started from seeds, sprouts, or at staggered durations of prior growth such that each of the individual produce types reach their peak nutrient density concurrently for ease of harvesting, menu preparation, and ultimately dietary consumption of optimized nutrient rich foods.
BACKGROUND OF THE INVENTION
This invention addresses when the most beneficial time to harvest produce is based on nutrient optimization. Historically, growers were paid a certain price by weight whether per bushel or per pound. Therefore, measures of success were determined by how many bushels or pounds could be produced. This traditional metric was solely price-driven. In the past, the level of nutrients in the harvested produce was not taken into consideration.
Others have evaluated and made dietary recommendations on the consumption of nutrient dense fruits and vegetables based on the levels of micronutrients where the density is purely correlated with the fewest calories (e.g., Joel Fuhrman, M.D.). Today, with food being grown and shipped from far away and/or being harvested early and artificially ripened with chemicals the amount of nutrients consumers are actually receiving has been adversely impacted. Harvard Medical School's Center for Health and the Global Environment has shown that foods grown far away that spend significant time on the road have more time to lose nutrients before reaching the marketplace. In other words, consuming fruits and vegetables, all things equal, that are more devoid of nutrients defeats the purpose of consuming such fruits and vegetables in the first place.
Plants make a variety of compounds, many of which act as antioxidants when consumed. In reality, it is understood that plants in their natural form are superior to pure and highly processed antioxidants as compared to the full range of micronutrients present in live plants. Plants produce a unique pattern of reaching their maximum nutrient compound capacity, which is often concurrent with maximum flavor compound capacity. A landmark study by Donald Davis and his team of researchers from the University of Texas (UT) at Austin's Department of Chemistry and Biochemistry was published in December 2004 in the Journal of the American College of Nutrition . They studied U.S. Department of Agriculture nutritional data from both 1950 and 1999 for 43 different vegetables and fruits, finding “reliable declines” in the amount of protein, calcium, phosphorus, iron, riboflavin (vitamin B2) and vitamin C over the past half century. Davis and his colleagues chalk up this declining nutritional content to the preponderance of agricultural practices designed to improve traits (size, growth rate, pest resistance) other than nutrition. “Efforts to breed new varieties of crops that provide greater yield, pest resistance and climate adaptability have allowed crops to grow bigger and more rapidly,” reported Davis, “but their ability to manufacture or uptake nutrients has not kept pace with their rapid growth.” There have likely been declines in other nutrients, too, he said, such as magnesium, zinc and vitamins B-6 and E, but they were not studied in 1950 and more research is needed to find out how much less we are getting of these key vitamins and minerals. This further validates the requirement for the disclosed invention, a system to maximize nutrient and flavor and NOT to maximize revenue as traditionally directly correlated with weight of fruits and vegetables.
It is understood in the background that a wide range of sensors, ranging from spectrum analyzers (i.e., optical, and generally real-time and non-destructive) to chemical analyzers (i.e., GC mass spec, generally not real-time and destructive testing), exists in the art.
Furthermore, it is understood that plants grow (in nature as provided by the sun) the full light spectrum. Testing, originally attributed to space exploration, has lead to a more detailed understanding that red and blue are the two primary colors necessary to complete photosynthesis—the energy conversion where the plant transforms light into food and oxygen. The amount of red and blue light within a light source will affect plant growth in different ways. Blue light regulates the rate of a plants growth and is especially helpful in plants with lots of vegetation and few to no flowers. Blue light regulates many plant responses including stomata opening and phototropism. Stomata are openings on or beneath the surface of the leaves. A plant's moisture loss is primarily due to the stomata and blue light controls the degree of stomata opening, therefore blue light regulates the amount of water a plant retains or expels. Phototropism is the definition of a plant's response to light; the stems grow up toward the light and the roots grow down, away from the light. Metal halide grow lights emit more light in the blue spectrum and are the best source of indoor lighting to use for plant growth if there is no sunlight available. Red and orange light triggers hormones in plants that increase flowering and budding, but plants cannot grow with red light alone. They also need blue light to help regulate other types of responses. Red light stimulates flowering and foliage growth, but too much red light will cause a plant to become spindly. HPS (high-pressure sodium) grow lights emit a red orange glow and are excellent companion lights for growing conditions that include some natural sunlight or other light sources with high levels of blue light. Red light induces germination and blue light promotes seed growth, but far-red light inhibits germination.
Furthermore, it is understood that several phases of plant growth and resultant nutrient capacity are measured. Phase I is the early/immature stage of plant growth. During Phase I the plant has not reached the maximum peak potential of growth or nutrient optimization. Phase II is the mature stage of plant growth. During Phase II the plant has reached peak growth as well as peak nutrient optimization. Phase III is the post-mature stage of plant growth. During Phase III the plant is typically past the stage of optimal nutrient levels.
SUMMARY OF THE INVENTION
The present invention preferred embodiment relates to the creation of vegetable produce blends so that individual nutrient delivery is maximized for each vegetable produce and that the blend is created so that the peak of each vegetable produce nutrient delivery occurs at concurrent times for ease of preparation through consumption.
Another embodiment of the invention is the selective modification of the vegetable seeds through the use of seed coatings as known in the art to impact germination timing.
Yet another embodiment of the invention is the selective modification of the growing conditions including lighting intensity, lighting spectrum, pH, temperature such that each of the individual vegetable produce variety responds differently so as to relatively shift growth and ultimately harvest time with peak nutrient delivery.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagram depicting the difference between a coated and un-coated (i.e., standard) seed.
FIG. 2 is a diagram depicting a first seed growing under a first group of grow parameters, that differs from a second seed growing under a second group of grow parameters.
FIG. 3 is a diagram depicting a first seed growing under a first group of grow lighting conditions, that differs from a second seed growing under a second group of grow lighting conditions.
FIG. 4 is a peak nutrient curve for each of first seed and second seed, in which the natural state of growth takes place for each seed.
FIG. 5 is a peak nutrient curve for each of first seed and second seed, in which the natural state of growth is altered for the first seed to reduce the time difference of reaching peak nutrient relative to the second seed.
FIG. 6 is a peak nutrient curve for each of first seed and second seed, in which the natural state of growth is altered for the second seed to accelerate reaching peak nutrient content relative to its natural state of growth.
FIG. 7 is a peak nutrient curve for each of first seed and second seed, in which the natural state of growth is altered for the first seed to decelerate reaching peak nutrient content relative to its natural state of growth.
FIG. 8 is a nutrient blend control/management system depicting the architecture of the hardware/software system.
DETAILED DESCRIPTION OF THE INVENTION
The term “controlled farm”, as used herein, includes any type of indoor farming such as a greenhouse, hoop house, vertical farm, aeroponic, hydroponic or aquaponic farm. These various types of indoor farms control the environment to varying degrees including lighting, temperature and irrigation.
The term “uncontrolled farm”, as used herein, includes any type of outdoor farming. These types of farms do no control for environmental factors such as lighting, temperature and irrigation and are subject to natural variations in sunlight, temperature and rainfall.
The term “nutrient optimization”, as used herein, includes methodologies to determine the more precise point in the growth of a plant such that the peak amounts of nutrients are delivered at the time of consumption. When the precise knowledge of consumption is not known, the peak amounts of nutrients are determined for harvest and/or packaging time. Nutrient optimization also refers to that precise point when the plant has reached the inflection point of nutrient normalized over the fully time amortized cost basis. It is understood that nutrients and flavors are used interchangeably in this invention, as nutrient and flavor compounds are closely linked at worst and at best are one of the same. Any use of nutrient optimization can be substituted for flavor optimization.
The term “sensors”, as used herein, includes devices to measure important growing parameters for growing plants. These growing parameters include light level, temperature, carbon dioxide levels, oxygen levels, water levels, plant intake nutrients, and plant produced nutrients.
The term “O2:CO2”, as used herein, is the ratio of oxygen to carbon dioxide present in the environmental air present. Air exchange in the context of consumer located spaces is currently based entirely on carbon dioxide ppm (parts per million), as absent of a co-located farm it is impractical to raise the amount of oxygen on a ppm basis without a complete fresh air exchange. Furthermore, it is equally impractical to raise the amount of oxygen for many combustion processes unless specific radiant qualities are desired due to the cost of oxygen generating equipment. However, a co-located oxygen-generating source enables superior cost effective recovery of waste heat from a co-located combustion process.
Here, as well as elsewhere in the specification and claims, individual numerical values and/or individual range limits can be combined to form non-disclosed ranges.
Exemplary embodiments of the present invention will now be discussed with reference to the attached Figures. Such embodiments are merely exemplary in nature. With regard to FIGS. 1 through 3 , like reference numerals refer to like parts.
Turning to FIG. 1 , FIG. 1 is a diagramming in which the first seed 50 . 1 has a coating 20 and the second seed 50 . 2 is void of a coating. The coating, as known in the art, decelerates the growth of the seed into a germinated seedling by reducing the water transmission (i.e., reducing moisture migration) into the seed. It is anticipated that other coatings, also as known in the art, can accelerate the growth of the seed into a germinated seedling by increasing the water transmission into the seed (i.e., high water retaining gels), or by having very localized fertilizer (or other active ingredients) to accelerate the growth. Though not typically used, localized presence of negative “actives” can slow down the growth into a seedling by other coatings. The creation of a blend of seeds of different species and/or varieties will typically have different harvest times. Thus FIG. 1 depicts on such method of delaying the harvest time relative to the second seed. This invention desires to maximize nutrient delivery, as opposed to maximum weight, in which each seed ideally reaches its peak nutrient content concurrently. At the very least, it is desired that the cumulative nutrient content of the aggregate summation of the seed blend is maximized. It is understood that a blend of seeds is selected to treat the same disease state, though where a first seed provides one active nutrient (e.g., lutein) for the same disease state (e.g., eye health) and the second seed provides another nutrient (e.g., beta-carotein) for that same disease state. It is further understood that the blend can consist of additional seeds with either similar active nutrients or ideally additional active nutrients in order to maximize health benefits. The seed coating both delays the sprouting (it is understood that germination and sprouting are used interchangeably, fundamentally referring to the state in which a dormant seed becomes an active/growing seedling) of the first seed relative to the second seed.
Turning to FIG. 2 , FIG. 2 is a diagramming in which the first seed 50 . 1 has a first grouping of grow parameters 30 . 1 and the second seed 50 . 2 has a second grouping of grow parameters 30 . 2 . It is known in the art that a range of grow parameters impact the rate of growth of the seed into a seedling and then finally into the harvestable state at which time the seed has transformed itself into a nutrient rich vegetable. These grow parameters include temperature, pH, nutrients in the soil, water, or growing media. It is further understood that each species and variety of seeds responds differently to these grow parameters thus providing the opportunity to practice the invention thus shifting the timing of reaching “maturity” with peak nutrient content. Additional grow parameters in which seed species and varieties have different sensitivity is the inclusion of actives selected from the group including a fertilizer selection process, a mineral selection process, a pesticide selection process, or a herbicide selection process.
Turning to FIG. 3 , FIG. 3 is a diagramming in which the first seed 50 . 1 has a first grouping of lighting spectrum parameters Light 1 Red 45 . 1 and Light 1 Blue 40 . 1 and the second seed 50 . 2 has a second grouping of lighting spectrum parameters Light 2 Red 45 . 2 and Light 2 Blue 40 . 2 . It is known in the art that blue and red spectrum of lighting, which can be precisely regulated by the utilization of LEDS, are best controlled independently as the spectrum desired and the relative intensities between the blue and red spectrum varies as a function of time beginning from seed planting through seed/plant harvesting. A range of lighting spectrum impacts the rate of growth of the seed into a seedling and then finally into the harvestable state at which time the seed has transformed itself into a nutrient rich vegetable. These lighting spectrum parameters impact both the rate of nutrient accumulation and nutrient intensity. It is further understood that each species and variety of seeds responds differently to these lighting spectrum parameters thus providing the opportunity to practice the invention thus shifting the timing of reaching “maturity” with peak nutrient content. A light regulator, preferably precisely controlled by a nutrient blend management system, varies the lighting spectrum output and more preferably has the ability to vary relative intensities of the blue and red portion of the visible spectrum individually and independently of each other. Another portion of the spectrum in which independent control is desired and critical to nutrient density and accumulation is within the ultraviolet “UV” portion of the lighting spectrum. The increased seed sensitivity to the blue spectrum or red spectrum, of one first seed over a second seed has the ability to accelerate the harvest time relatively between the first seed and the second seed by a minimum of 30 minutes. It is understood that it is desirable to have both the first seed and the second seed reach peak nutrient content concurrently, and the fastest/most impactful method to shift peak nutrient content is through regulating blue and red spectrum, and most importantly taking advantage of the different responses of each first seed relative to each second seed to force this shift in timing. The ability to shift harvest time, through broad spectrums of lighting, and/or grow parameters is less responsive but nevertheless important with the shift being on the order of hours. The preferable performance is less than 24 hours, the more preferable performance is less than 6 hours, and the particularly preferable performance shift is less than 30 minutes. Lighting regulator, in terms of spectrum, intensity, and timing is best achieved in a vertical farm. Less control is achieved in terms of lighting, but ample control of grow parameters are also achieved in a greenhouse (which in the broadest definition is the inclusion of any physical structure to modify the environment, such as lighting spectrum or humidity levels, in which the seeds are grown).
The inventive process includes the specific selection of species and varieties such that each seed reaches peak nutrient content (or at least density) within the same time schedule. The more preferred selection of species and varieties have sufficiently different responses to lighting spectrum and/or grow parameters so that the inventive nutrient optimization system has the ability to utilize real-time monitoring throughout the growth stage to alter and correct for differences from scheduled nutrient levels as a function of time versus the historic/prior experience for each seed and or blend of seeds.
Turning to FIG. 4 , FIG. 4 is a time domain 2-axis chart that depicts seed nutrient density levels. The Y-axis is a normalized level for each individual seed and/or aggregate of an individual nutrient within the seed blend. The X-axis is time, where the origin of X-axis is time (zero) where the seed blend is planted. The first seed 10 . 1 nutrient density curve is depicted by the dashed curve and the second seed 10 . 2 nutrient density curve is depicted by the solid curve. P 1 depicts the lower of the peak nutrient densities between the first seed and the second seed, with P 2 depicting the higher of the peak nutrient densities. FIG. 4 is the natural, non-modified rate of growth for each seed type within the blend. As depicted a delta-T “dT” (where T is time) occurs between the two separate peaks as indicated between T 3 and T 4 .
Turning to FIG. 5 , FIG. 5 is also a time domain 2-axis chart that depicts seed nutrient density levels. The Y-axis is a normalized level for each individual seed and/or aggregate of an individual nutrient within the seed blend. The X-axis is time, where the origin of X-axis is time (zero) where the seed blend is planted. The first seed 10 . 1 nutrient density curve is depicted by the dashed curve and the second seed 10 . 2 nutrient density curve is depicted by the solid curve. P 1 depicts the lower of the peak nutrient densities between the first seed and the second seed, with P 2 depicting the higher of the peak nutrient densities. FIG. 5 is representative of results that are obtained when the first seed ( 10 . 1 nutrient density curve) is coated to deter moisture migration such that the otherwise natural dT between the seeds is reduced relative to second seed ( 10 . 2 nutrient density curve). The optimal reduction is such that T 3 and T 4 closely approximate each other. The preferable reduction for dT is less than 24 hours, the more preferable reduction is less than 6 hours, and the particularly preferred reduction is less than 30 minutes.
Turning to FIG. 6 , FIG. 6 is also a time domain 2-axis chart that depicts seed nutrient density levels. The Y-axis is a normalized level for each individual seed and/or aggregate of an individual nutrient within the seed blend. The X-axis is time, where the origin of X-axis is time (zero) where the seed blend is planted. The first seed 10 . 1 nutrient density is depicted by the dashed curve with shorter dashes and the second seed 10 . 2 is depicted by the solid curve. The new addition of the dashed curve (with longer dashes), as indicated by seed 10 . 3 , is relative to the natural non-modified growth cycle of second seed 10 . 2 . P 1 depicts the lower of the peak nutrient densities between the first seed and the second seed, with P 2 depicting the higher of the peak nutrient densities. FIG. 6 is representative of results such that at time T 2 (instead of T 3 ) a grow parameter or lighting spectrum is regulated to accelerate the relative growth rate of second seed to shift from seed nutrient curve 10 . 2 to seed nutrient curve 10 . 3 . The optimal reduction is such that T 3 and T 4 closely approximate each other. The preferable reduction for dT is less than 24 hours, the more preferable reduction is less than 6 hours, and the particularly preferred reduction is less than 30 minutes.
Turning to FIG. 7 , FIG. 7 is also a time domain 2-axis chart that depicts seed nutrient density levels. The Y-axis is a normalized level for each individual seed and/or aggregate of an individual nutrient within the seed blend. The X-axis is time, where the origin of X-axis is time (zero) where the seed blend is planted. The first seed 10 . 1 nutrient density is depicted by the dashed curve with shorter dashes and the second seed 10 . 2 is depicted by the solid curve. The new addition of the dashed curve (with longer dashes), as indicated by seed 10 . 4 , is relative to the natural non-modified growth cycle of first seed 10 . 1 . P 1 depicts the lower of the peak nutrient densities between the first seed and the second seed, with P 2 depicting the higher of the peak nutrient densities. FIG. 7 is representative of results such that at time T 2 (instead of T 3 ) a grow parameter or lighting spectrum is regulated to decelerate (i.e., reduce) the relative growth rate of first seed to shift from seed nutrient curve 10 . 1 to seed nutrient curve 10 . 4 . The optimal reduction is such that T 3 and T 4 closely approximate each other. The preferable reduction for dT is less than 24 hours, the more preferable reduction is less than 6 hours, and the particularly preferred reduction is less than 30 minutes.
Turning to FIG. 8 , FIG. 8 is a figure depicting the major components of the nutrient blend optimization control/management system The control system 100 has at least one database 110 , which has at least one record 120 for each seed variety with individual parametric matrix including impact of lighting spectrum (e.g., blue and red intensity) and each of the aforementioned grow parameters. The record 120 contains a time domain analysis of nutrient density, which further includes optimal time of harvest for every parametric matrix. The time domain is preferably having a nutrient density level for each 30 minutes (or at least a multi-variate parameter representation centered around a scheduled harvest time/date relative to seed planting). The control system 100 utilizes the database and its full set of records to regulate (i.e., regulator 130 ) of the range of grow parameters (which includes lighting spectrum of blue/red intensities, though not shown). It is understood that a second set of records may be necessary for each grow media 140 in which the individual seeds of the blend are grown concurrently (such as first seed 50 . 1 , and second seed 50 . 2 ) as indicated.
The plants grown in the invented nutrient blend optimization system is best utilized within a food formulation system to meet personalized recipes that modulate the ingredients used within the recipe in accordance to at least nutrient content and flavor content. It is understood that optimizing for concurrent nutrient peaks can be substituted for concurrent flavor peaks. The use of certain nutrient rich plants have significant flavor impact, in which case both nutrient and flavor normalization are appropriate in order to make/create great tasting food.
Although the invention has been described in detail with particular reference to certain embodiments detailed herein, other embodiments can achieve the same results. Variations and modifications of the present invention will be obvious to those skilled in the art and the present invention is intended to cover in the appended claims all such modifications and equivalents. | The growing management system optimizes peak aggregate nutrients for individual edible plants including vegetables, and herbs such that the individual edible plants are organized into a blend such that the aggregate of the individual edible plants are grown in a blend and that growing parameters including the use of seed coatings shift the occurrence of each of the individual edible plants peak nutrients to occur concurrently to maximize overall nutrient delivery. It is understood that nutrient and flavor peaks can be used interchangeably. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a transmission system comprising a transmitter having, signal combining means for combining a first and a second signal forming a combined signal and having transmission means for transmitting the combined signal. Such a transmission system can be a broadcasting system for broadcasting stereo signals to receivers, or a system for recording and reproducing stereophonic signals, or any other system for combined signals.
The present invention further relates to a transmitter for use in such a system.
The present invention further relates to a receiver for use in such a system.
2. Description of the Related Art
A transmission system of this kind is known from "Electronics Engineer's Reference Book", L. W. Turner, London, Newnes-Butterworths, 1976, pp. 15-56 to 59, and pp. 15-166 to 170. In this handbook, a well-known stereophonic system is described, in which first and second stereophonic audio signals, the so-called left and right stereo channels, are combined forming a stereophonic transmission signal for broadcasting to receivers. First, a summing signal is formed from the first and the second signal, and further, with the help of a balanced modulator and a sub-carrier at a double frequency of a so-called pilot tone, a difference signal is built. Then, a combined signal, formed from the summing signal, the difference signal, and the pilot tone, is modulated onto a carrier and is transmitted to the receivers. In the receivers, after demodulation, the summing and the difference signals are separated from the pilot tone, and the first and second signals are extracted from the summing and difference signals by respective summing and subtraction of the same by means of a stereo decoder. Such a stereo transmission system is complicated as regards coding and decoding of the left and right stereo signals. Besides, the phase relationship between the pilot tone frequency and the sub-carrier is very critical. Also, such a system requires relatively complicated and time consuming adjustment procedures.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a simple, non-critical and easily adjustable transmission system of the above kind.
To this end a transmission system according to the present invention is characterized in that the signal combining means comprises a signal generating means providing a signal as the combined signal of which successive periods are alternately modulated by samples of the first and the second signals, respectively. Because information about the first and second signals is comprised in separate parts of a single signals, e.g. a block signals, the first and second signals can be easily retrieved in a receiver. Such a receiver can also be implemented easily.
In an embodiment of a transmission system according to the present invention, the system further comprises a transmission channel and a receiver for receiving the transmitted combined signal through the transmission channel, the receiver having signals separation means for alternately separating the first and the second signal from the received combined signal, the receiver comprising first and second pulse integration means for respective integration of pulses corresponding to the first and second signals, an output of the second integration means being reset when the pulses of the first signal are detected, and vice versa. In this way, pulsed integrator outputs are obtained, peak values of which corresponding to transmitted samples of the first and second signals. The analog first and second signals can be obtained from the peak values by means of simple peak detection means.
In further embodiments of a transmission system according to the present invention, the first and the second signals are stereophonic audio signals, and the combined signal comprises stereo encoded information about the first and the second signals. The system can be used advantageously for wireless transmission of stereo signals, e.g. to a stereo headphone comprising a receiver as according to the present invention. Such a wireless transmission can be carried out by means of an infra-red signal, or by means of a radio signal. In the latter case, the system further comprises an FM (Frequency Modulation) modulator at transmitter side, and an FM alemodulator at receiver side.
In another embodiment of a transmission system according to the present invention, the first and the second signals are measurement signals. The system can thus also be used advantageously for efficient transmission of measurement signals, such as blood pressure signals or the like. In a measurement environment, the encoded signals can be conveyed from a measurement site to a central site by means of glass fiber transmission means.
The present invention will now be described, by way of example, with reference to the accompanying drawings, wherein
FIG. 1 shows a transmission system according to the present invention, comprising a transmitter, a receiver, and an infra-red transmission channel,
FIG. 2a-2g show timing diagrams for illustrating the operation of a transmitter according to the present invention and
FIGS. 3a-3d show timing diagrams for illustrating the operation of a receiver according to the present invention.
Throughout the figures the same reference numerals are used for the same features.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 shows a transmission system 1 according to the present invention, comprising a transmitter 2, a receiver 3, and an infra-red transmission channel 4. The transmission channel 4 may also be a radio channel, or a glass fiber channel, or the like. In case of a radio channel, the transmitter 2 and the receiver 3 additionally comprise an FM-modulator (not shown) and an FM-demodulator (not shown), respectively, both well-known in the art. The transmitter 2 comprises a first transmission branch 5 to which a left-hand channel stereo signal L in as a first signal is fed, and a second transmission branch 6 to which a right-hand channel stereo signal R in is fed. The first transmission branch 5 comprises a preamplifier with pre-emphasis consisting of a amplifier 7 of which resistors 8, 9, and 10, and a capacitor 11 determine its frequency response. Pre-emphasis is applied for improving the signal-to-noise ratio of the system 1. For achieving a linear overall system response, the receiver 3 comprises corresponding de-emphasis means. A capacitor 12, bridging the amplifier 7, is applied for cutting off signals above the audio frequency band to be transmitted. Correspondingly, the second transmission branch 6 comprises an amplifier 13, resistors 14, 15, and 16, and capacitors 17 and 18. Outputs of the amplifiers are DC-biased to halve the supply voltage of the transmitter 2. The transmitter 2 further comprises controllable block signal generating means 19 comprising an integrator stage with an amplifier 20 and a capacitor 21, and a Schmitt-trigger with amplifiers 22 and 23, and resistors 24 and 25, and further a resistor 26 and a diode 27 for the first transmission branch 5, and a resistor 28 and a diode 29. The resistor 26 and the diode 27 determine the positive block signal period, and the resistor 28 and the diode 29 determine the negative block signal period. A DC-superimposed left-hand channel stereo signal at an output of the amplifier 7 is injected in the junction point formed by the resistor 26 and the diode 27, through a resistor 30, and a DC-superimposed right-hand channel stereo signal at an output of the amplifier 13 is injected in the junction point formed by the resistor 28 and the diode 29. These injected signals modify the integration time of the integrator stage 20, 21 according to momentary values of the supplied audio signals L in and R in . In an embodiment, the polarity of the signal P in is inverted by means of an inverting stage comprising an amplifier 32, and resistors 33 and 34. The inverter 32 compensates for the pulse direction caused by the diode 29. For a positive value of the block signal generated by the means 19, the transmission branch 5 is inoperative because the diode 27 is blocking then, while for a negative value of the block signal, the transmission branch 6 is inoperative because the diode 29 is blocking. It is thus achieved that the block signal is alternately modulated by samples of the first and the second signals L in and R in . The thus encoded stereo signal is fed to the receiver 3. In the embodiment given, the infra-red transmission channel 4 comprises infra-red transmission means 40 at the transmitter side, and infra-red reception means 41 at the receiver side. Such infra-red transmission means 40 and 41 are well-known in the art. The receiver 3 comprises a first reception branch 50 and a second reception branch 51 for separating the first and the second transmitted stereo signal from the received combined signal. The first reception branch 50, to which the received combined signal is fed, comprises a first part of a alemultiplex switch comprising a parallel arrangement of oppositely arranged diodes 52 and 53, in which a resistor is series connected with the diode 52. From the direction of the transmission channel, the diode 52 is reverse biased. The second reception branch 51, to which the received combined signal is also fed, comprises a corresponding second part of the alemultiplex switch comprising a parallel-series arrangement of a diode 54, a diode 55, and a resistor 56. In the second reception branch 51 an inverter 57 is switched before the second part of the demultiplexer for shifting the phase of the received signal by 180°. The reception branch 50 further comprises a series arrangement of an integrator with an amplifier and a capacitor 59, a peak detector 60 with a diode 61, a resistor 62, and a capacitor 63, and de-emphasis amplifier 64 with an amplifier 65, a resistor 66, a resistor 67, a capacitor 69. At an output of the amplifier 65, a detected left-hand stereo signal L out is available. The second reception branch 51 comprises correspondingly an amplifier 70, a capacitor 71, a diode 72, a resistor 73, a capacitor 74, a capacitor 75, a resistor 76, an amplifier 77, a resistor 78, and a capacitor 79 in series with a resistor 79A. The amplifier 77 is followed by an inverting amplifier 80 with resistors 81 and 82, or not. In case the encoder in the transmitter 2 comprises the inverting amplifier 32, the inverting amplifier 57 in the receiver compensates for its phase shift. In case the transmitter 2 does not comprise the inverting amplifier 32, the inverting amplifier 80 has to be present in order to obtain a phase correct right-to-left signal. For mono operation, the stereo output signals signals can simply be fed to a resistor each (not shown). At a junction of these resistors, a mono signal is then available. For mono operation, the combination of having the inverter 32 in the transmitter 2 and no inverter in the receiver 3, is advantageous as to compensation for pulse phase jitter introduced into the transmission path when the transmitted signals are weak. Due to the inverse mode addition, then occurring, noise contributions to the signals are strongly reduced. Although, advantageously, the same type of peak detectors are used for the left and right channel, because then all signals are with respect to ground, alternatively, complementary peak detectors can be used. In the latter case, the inverter 57 is not present. Such a complementary peak detector can be obtained by reversing the diode 72 and by connecting the resistor 73 and the capacitor 74 to the positive rail (not shown in detail, here). The stereo decode operation in the receiver 3 is as follows. The received combined signal is polarity splitted. The respective left and right channel pulses are convened into respective voltage amplitude signals in the respective integrators 58, 59 and 70, 71. During transmission of a left channel pulse, an output of the fight channel integrator is reset to the negative supply voltage, and vice versa. At the integrator outputs, peak values occur which correspond to samples of the transmitted first and second signals. The peak detector 60 with the successive integrator 64 achieves that sampling frequency is further suppressed. The integration time is chosen such that the transmitter pre-emphasis is compensated for. As to the integration stage 58, 59, the positive integration time is determined by the internal resistance paths of the demultiplexer and by the forward resistance of the diode 53. This resistance is so small that the integration stage 58, 59 reacts very fast. With positive input signals, the capacitor 59 is quickly charged, so that the output of the integration stage 58, 59 is pulled to the negative supply voltage. As a result of this, the peak detector 60 will not rectify any signal. In the reception branch 50, negative received combined signals are coupled to the integration stage 58, 59 via the series arrangement of the resistor 54 and the diode 52. Herewith, the negative integration time essentially is determined by the resistor 54. Thus, with each received pulse, an end value of the integration stage output corresponds to the pulse width of the received pulse, and each negative pulse is converted to a corresponding analog peak voltage. Correspondingly, in the reception branch 51, positive pulses are converted to analog peak voltages. Both in the transmitter 2 and in the receiver 3, for cost reduction purposes, ahex amplifier IC, type PC 74 HCU, can advantageously be applied.
FIGS. 2a-2g show timing diagrams for illustrating the operation of the transmitter 2 according to the present invention. Shown are time diagrams as a function of time t, in which FIG. 2a shows the left-hand stereo signal L in the transmitter branch 5. FIG. 2b shows the right-hand stereo signal R in the transmitter branch 6, where R=L. In this case, alternate samples of the left-hand stereo signal (in FIG. 2a) and the right-hand stereo signal (in FIG. 2b) are converted into a frequency modulated block pulse signal with a constant pulse width duty cycle (FIG. 2e). FIG. 2c shows the right-hand stereo signal in the transmitter branch 6, where -R=L. In this case, alternate samples of the left-hand stereo signal (in FIG. 2a) and right-hand stereo signal (in FIG. 2c) are converted into a pulse width modulated signal with constant frequency (FIG. 2f). The diagrams for R=L and -R=L represent an extreme mono signal and an extreme stereo signal as the input signals L in and R in , respectively, and are shown for illustrating how the input information is encoded into a signal to be transmitted. Thus, in practical situations, the transmitted signal is a combined frequency and pulse width modulated signal, and no summing signals or difference signals, such as in conventional stereo systems, are formed. FIG. 2d shows the situation where there is no right-hand stereo signal, and FIG. 2g shows the modulated block pulse signals when, as such, only the left-hand stereo signal (in FIG. 2a) is available. the block pulse period is indicated with T, e.g., corresponding to a frequency of 38 kHz. With infra-red transmission this intermediate frequency may be between 60 and 80 kHz.
FIGS. 3a-3d show timing diagrams for illustrating the operation of the receiver 3 according to the present invention. Only the fight-hand channel is shown. Shown are received pulses RP (FIG. 3b), inverse received pulses IRP (FIG. 3c) an output signal LI (FIG. 3a), of the left-hand channel integrator 58, 59, and an output signal RI (FIG. 3d) of the right-hand channel integrator 70, 71. As shown in FIG. 3d with a dashed line dl, a reconstructed right-channel stereo signal is indicated. | A simple and effective stereophonic transmission system (1) wherein the transmitter (2) alternatively encodes successive block periods of a block signal with samples of the left-hand channel signal (L in ) and the right-hand channel signal (R in ). At receiver side, the left-hand and right-hand stereo signals are decoded from the encoded block signal by alternate integration and peak detection of positive and negative received pulses, the pulse widths of the received pulses corresponding to amplitudes of the transmitted samples. When detecting the pulses for one stereophonic channel, the corresponding other stereophonic channel is blocked. | 7 |
TECHNICAL FIELD
This invention pertains to integrated circuitry and to methods of forming integrated circuitry. The invention is thought to have particular significance in application to methods of forming dynamic random access memory (DRAM) cell structures, to DRAM cell structures.
BACKGROUND OF THE INVENTION
A commonly used semiconductor memory device is a DRAM cell. A DRAM cell generally consists of a capacitor coupled through a transistor to a bitline. A continuous challenge in the semiconductor industry is to increase DRAM circuit density. Accordingly, there is a continuous effort to decrease the size of memory cell components.
Another continuous trend in the semiconductor industry is to minimize processing steps. Accordingly, it is desirable to utilize common steps for the formation of separate DRAM components. For instance, it is desirable to utilize common steps for the formation of the DRAM capacitor structures and the DRAM bitline contacts.
A semiconductor wafer fragment 10 is illustrated in FIG. 1 showing a prior art DRAM array 83. Wafer fragment 10 comprises a semiconductive material 12, field oxide regions 14, and wordlines 24 and 26. Wordlines 24 and 26 comprise a gate oxide layer 16, a polysilicon layer 18, a silicide layer 20 and a silicon oxide layer 22. Silicide layer 20 comprises a refractory metal silicide, such as tungsten silicide, and polysilicon layer 18 typically comprises polysilicon doped with a conductivity enhancing dopant. Nitride spacers 30 are laterally adjacent wordlines 24 and 26.
Electrical node locations 25, 27 and 29 are between wordlines 24 and 26 and are electrically connected by transistor gates comprised by wordlines 24 and 26. Node locations 25, 27 and 29 are diffusion regions formed within semiconductive material 12.
A borophosphosilicate glass (BPSG) layer 34 is over semiconductive material 12 and wordlines 24 and 26. An oxide layer 32 is provided between BPSG layer 34 and material 12. Oxide layer 32 inhibits diffusion of phosphorus from BPSG layer 34 into underlying materials.
Conductive pedestals 54, 55 and 56 extend through BPSG layer 34 to node locations 25, 27 and 29, respectively. Capacitor constructions 62 and 64 contact upper surfaces of pedestals 54 and 56, respectively. Capacitor constructions 62 and 64 comprise a storage node layer 66, a dielectric layer 68, and a cell plate layer 70. Dielectric layer 68 comprises an electrically insulative layer, such as silicon nitride. Cell plate layer 70 comprises conductively doped polysilicon, and may alternatively be referred to as a cell layer 70. Storage node layer 66 comprises conductively doped hemispherical grain polysilicon.
A conductive bitline plug 75 contacts an upper surface of pedestal 55. Bitline plug 75 may comprise, for example, tungsten. Together, bitline plug 75 and pedestal 55 comprise a bitline contact 77.
A bitline 76 extends over capacitors 62 and 64 and in electrical connection with bitline contact 77. Bitline 76 may comprise, for example, aluminum.
The capacitors 62 and 64 are electrically connected to bitline contact 77 through transistor gates comprised by wordlines 26. A first DRAM cell 79 comprises capacitor 62 electrically connected to bitline 76 through a wordline 26 and bitline contact 77. A second DRAM cell 81 comprises capacitor 64 electrically connected to bitline 76 through wordline a 26 and bitline contact 77. DRAM array 83 comprises first and second DRAM cells 79 and 81.
SUMMARY OF THE INVENTION
The invention includes a number of methods and structures pertaining to integrated circuit technology, including: methods of forming DRAM memory cell constructions; methods of forming capacitor constructions; methods of forming capacitor and bitline constructions; DRAM memory cell constructions; and capacitor constructions.
The invention encompasses a method of forming an integrated circuit wherein an insulative material layer having an uppermost surface is formed over a first node location and a second node location, and wherein first and second conductive pedestals are formed extending through the insulative material layer and in electrical connection with the first and second node locations, respectively. The conductive pedestals has exposed uppermost surfaces above the uppermost surface of the insulative material layer.
The invention also encompasses an integrated circuit which includes a first node location and a second node location within a semiconductor substrate, the first and second node locations being connectable through a transistor gate and being under an insulative material which has an uppermost surface. The integrated circuit further includes a first conductive pedestal extending through the insulative material layer and in electrical connection with the first node location and a second conductive pedestal extending through the insulative material layer and in electrical connection with the second node location, the conductive pedestals having uppermost surfaces which are substantially at a common elevational height relative to one another and which are above the uppermost surface of the insulative material layer.
BRIEF DESCRIPTION OF THE DRAWINGS
Preferred embodiments of the invention are described below with reference to the following accompanying drawings.
FIG. 1 is a schematic cross-sectional view of a semiconductor wafer fragment comprising a prior art DRAM cell.
FIG. 2 is a schematic cross-sectional process view of a semiconductor wafer fragment at preliminary processing step of a processing method of the present invention.
FIG. 3 is a view of the FIG. 2 wafer fragment at a processing step subsequent to that of FIG. 2.
FIG. 4 is a view of the FIG. 2 wafer fragment at a processing step subsequent to that of FIG. 3.
FIG. 5. is a view of the FIG. 2 wafer fragment at a processing step subsequent to that of FIG. 4.
FIG. 6 is a view of the FIG. 2 wafer fragment at a processing step subsequent to that of FIG. 5.
FIG. 7 is a view of the FIG. 2 wafer fragment at a processing step subsequent to that of FIG. 6.
FIG. 8 is a view of the FIG. 2 wafer fragment at a processing step subsequent to that of FIG. 7.
FIG. 9 is a view of the FIG. 2 wafer fragment at a processing step subsequent to that of FIG. 8.
FIG. 10 is a view of the FIG. 2 wafer fragment at a processing step subsequent to that of FIG. 9.
FIG. 11 is a view of the FIG. 2 wafer fragment at a processing step subsequent to that of FIG. 10.
FIG. 12 is a view of the FIG. 2 wafer fragment at a processing step subsequent to that of FIG. 11.
FIG. 13 is a view of the FIG. 2 wafer fragment at a processing step subsequent to that of FIG. 12.
FIG. 14 is a view of the FIG. 2 wafer fragment at a processing step subsequent to that of FIG. 13.
FIG. 15 is a view of the FIG. 2 wafer fragment at a processing step subsequent to that of FIG. 14.
FIG. 16 is a view of the FIG. 2 wafer fragment at a processing step subsequent to that of FIG. 15.
FIG. 17 is a view of the FIG. 2 wafer fragment at a processing step subsequent to that of FIG. 16.
FIG. 18 is a view of the FIG. 2 wafer fragment at a processing step subsequent to that of FIG. 17.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
This disclosure of the invention is submitted in furtherance of the constitutional purposes of the U.S. Patent Laws "to promote the progress of science and useful arts" (Article 1, Section 8).
A method of forming a DRAM cell of the present invention is described with reference to FIGS. 2-18. In describing the method, like numerals from the preceding discussion of the prior art are utilized where appropriate, with differences being indicated by the suffix "a" or with different numerals.
Referring to FIG. 2, a semiconductor wafer fragment 10a is illustrated at a preliminary step of the present invention. Wafer fragment 10a comprises a semiconductive material 12a, field oxide regions 14a, and a thin gate oxide layer 16a. Over gate oxide layer 16a is formed polysilicon layer 18a, silicide layer 20a and silicon oxide layer 22a. Silicide layer 20a comprises a refractory metal silicide, such as tungsten silicide, and polysilicon layer 18a typically comprises polysilicon doped with a conductivity enhancing dopant. Layers 16a, 18a, 20a and 22a can be formed by conventional methods.
Referring next to FIG. 3, polysilicon layer 18a, silicide layer 20a and silicon oxide layer 22a are etched to form wordlines 24a and 26a. Such etching can be accomplished by conventional methods. Between wordlines 24a and 26a are defined electrical node locations 25a, 27a and 29a, with wordlines 26a comprising transistor gates which electrically connect node locations 25a, 27a, and 29a. Node locations 25a, 27a and 29a are typically diffusion regions formed within semiconductive material 12a by ion implanting conductivity enhancing dopant into the material 12a. Such ion implanting may occur after patterning wordlines 24a and 26a, utilizing wordlines 24a and 26a as masks. Alternatively, the diffusion regions may be formed prior to deposition of one or more of layers 18a, 20a and 22a (shown in FIG. 2). In yet other alternative methods, the diffusion regions may be formed after formation of doped polysilicon pedestals (such as the pedestals 136, 138 and 140 shown in FIG. 12, and to be described subsequently) by out-diffusion of conductivity enhancing dopant from the pedestals.
For the above-discussed reasons, defined electrical node locations 25a, 27a, and 29a need not be electrically conductive at the preliminary step of FIG. 3. Node locations 25a, 27a and 29a could be conductive at the step of FIG. 3 if formed by ion implanting of dopant into semiconductive material 12a. On the other hand, node locations 25a, 27a and 29a may be substantially non-conductive at the preliminary step of FIG. 3 in, for example, embodiments in which node locations 25a, 27a and 29a are ultimately doped by out-diffusion of dopant from a conductively doped pedestal, such as the pedestals of FIG. 12.
Referring to FIGS. 4 and 5, a nitride layer 28a is provided over wordlines 24a and 26a, and subsequently etched to form nitride spacers 30a laterally adjacent wordlines 24a and 26a.
Referring to FIG. 6, an overlying oxide layer 32a is provided over wordlines 24a and 26a, and a BPSG layer 34a is provided over oxide layer 32a. Overlying oxide layer 32a is typically about 500 Angstroms thick, and BPSG layer 34a is typically about 14,000 Angstroms thick.
BPSG layer 34a is planarized, for example, by chemical-mechanical polishing to form a planar upper surface 35a. After the planarization, insulative layer 34a comprises a thickness "P" over the node locations which is preferably about 15,000 Angstroms. A patterned masking layer 100, preferably comprising photoresist, is formed over upper surface 35a.
Referring to FIG. 7, an anisotropic oxide etch is conducted to form openings 102, 104 and 106 extending into insulative layer 34. Openings 102, 104 and 106 may be referred to as first, second and third openings, respectively. Openings 102, 104 and 106 are over node locations 25a, 27a and 29a, respectively, but do not extend entirely to node locations 25a, 27a and 29a. Instead, openings 102, 104 and 106 comprise bases 108, 110 and 112, respectively, which are above node locations 25a, 27a and 29a by a distance "Y". Preferably, depth "X" is greater than thickness "Y". Accordingly, depth "X" is preferably greater than one-half of the original thickness "P" (shown in FIG. 6) of insulative layer 34. As discussed below with reference to FIG. 10, such preferred relative depths of "X" and "Y" permit a blanket etch to extend openings 102, 104 and 106 to node locations 25a, 27a and 29a without removing layer 34a from over wordlines 24a or 26a. A preferred depth "X" is from about 7500 Angstroms to about 10,000 Angstroms, and a preferred distance "Y" is from about 5000 Angstroms to about 7500 Angstroms.
Referring to FIG. 8, photoresist layer 100 (shown in FIG. 7) is removed. Subsequently, a spacer material layer 114 is provided over upper surface 35a of insulative material 34a and within openings 102, 104 and 106. Layer 114 is provided to a thickness which conformably deposits a layer in openings 102, 104 and 106 and thereby narrows openings 102, 104 and 106.
Layer 114 preferably comprises an insulative material, and may comprise, for example, silicon dioxide or silicon nitride. Layer 114 is preferably formed to a thickness which will narrow a cross-sectional dimension of openings 102, 104 and 106 by about a factor of three. For instance, if openings 102, 104 and 106 comprise a circular shape along a horizontal cross-section, layer 114 will preferably narrow a diameter of the circular shape by about a factor of three. Methods for depositing layer 114 are known to persons of skill in the art, and may comprise, for example, chemical vapor deposition utilizing tetraethylorthosilicate (TEOS).
Referring to FIG. 9, spacer material 114 (shown in FIG. 8) is anisotropically etched to form spacers 116, 118 and 120 within openings 102, 104 and 106, respectively. Spacers 116, 118 and 120 rest upon bases 108, 110 and 112 of openings 102, 104 and 106, respectively, and comprise bottom surfaces 122, 124 and 126, which are above node locations 25a, 27a, and 29a.
Spacers 116, 118 and 120 appear discontinuous in the shown cross-sectional view of FIG. 9. However, the spacers are preferably not discontinuous. Instead, spacers 116, 118 and 120 preferably extend entirely around inner peripheries of openings 102, 104 and 106 respectively.
Referring to FIG. 10, a blanket oxide etch is conducted to extend narrowed openings 102, 104 and 106 to node locations 25a, 27a and 29a respectively. The blanket oxide etch also removes insulative layer 34a adjacent openings 102, 104 and 106, and thus forms a new upper surface 128 of layer 34a. Upper surface 128 is below an elevational height of previous upper surface 35a (shown in FIG. 9) of insulative material 34a. The blanket oxide etch will preferably comprise an anisotropic oxide etch. Methods for conducting such anisotropic oxide etch are known to persons of ordinary skill in the art. The preferred relative distances of "X" (shown in FIG. 7) and "Y" (shown in FIG. 7), discussed above with reference to FIG. 7, enable the blanket etch to extend openings 102, 104 and 106 to node locations 25a, 27a and 29a before layer 34a is etched from over wordlines 24a or 26a.
Referring to FIG. 11, a conductive material layer 129 is provided over insulative material 34a and within openings 102, 104, and 106. Conductive material layer 129 is preferably provided to a thickness of about 12,000 Angstroms, which fills openings 102, 104 and 106. Conductive layer 129 can be formed, for example, by depositing conductively doped polysilicon. An alternative example method of forming conductive layer 129 comprises alternating doped and substantially undoped layers of polysilicon and subsequently distributing dopant throughout the alternating polysilicon layers with a thermal treatment step. To aid in interpretation of this specification and the claims that follow, a doped polysilicon layer is defined as a polysilicon layer comprising greater than about 1×10 19 atoms/cm 3 of dopant and a substantially undoped polysilicon layer is defined as a polysilicon layer comprising less than about 1×10 19 atoms/cm 3 of dopant. Preferably, a substantially undoped polysilicon layer will have about 0 atoms/cm 3 of dopant.
An example method for forming and thermally treating alternating doped and substantially undoped polysilicon layers is as follows. First, a lower conductively doped polysilicon layer is formed to a thickness of about 2,000 Angstroms. Second, a substantially undoped polysilicon layer is formed to a thickness of about 9,000 Angstroms over the lower doped polysilicon layer. Third, an upper doped polysilicon layer is formed to a thickness of about 1,000 Angstroms over the substantially undoped polysilicon layer. Fourth, the alternating doped and undoped polysilicon layers are heated to a temperature of about 1000° C. for a time of greater than about 20 seconds to distribute the conductivity enhancing dopant throughout the alternating polysilicon layers. Preferably, such heating involves a rapid thermal process (RTP) wherein the temperature of the polysilicon layers is ramped to 1000° C. at a rate of greater than 25° C./second.
After formation of conductive layer 129, a patterned masking layer 130, preferably comprising photoresist, is provided to form exposed portions 132 and masked portions 134 of material 129.
Referring to FIG. 12, exposed portions 132 of material 129 (shown in FIG. 11) are removed to form isolated conductive pedestals 136, 138 and 140. Pedestals 136, 138 and 140 comprise uppermost surfaces 142, 144 and 146, respectively, and comprise exposed lateral surfaces 148, 150 and 152, respectively. Uppermost surfaces 142, 144 and 146 are all above upper surface 128 of insulative material 34a in the illustrated region about conductive pedestals 136, 138 and 140. Also, as the exposed uppermost surfaces 142, 144 and 146 were formed from a common conductive layer 128 (shown in FIG. 11), uppermost surfaces 142, 144 and 146 are at a substantially common elevational height relative to one another.
The etch to form isolated conductive pedestals 136, 138 and 140 preferably comprises an etch selective to the material of layer 129 (shown in FIG. 11) relative to the material of insulative layer 34a and relative to the material of spacers 116, 118 and 120. An example etch for the preferred condition in which conductive material 129 comprises conductively doped polysilicon, insulative material 34a comprises BPSG, and spacers 116, 118 and 120 comprise silicon dioxide, comprises an anisotropic dry polysilicon etch utilizing Cl 2 , or Cl 2 /N 2 .
As discussed previously, conductive layer 129 (shown in FIG. 11) may comprise alternating layers of doped and undoped polysilicon, and the dopant can be distributed throughout the layers with a subsequent thermal treatment step. Such thermal treatment step can occur either before or after the formation and isolation of pedestals 136, 138 and 140.
Referring to FIG. 13, a storage node layer 154 is formed over insulative layer 34a, over exposed lateral surfaces 148, 150 and 152, and over uppermost surfaces 142, 144 and 146 of conductive pedestals 136, 138 and 140. Storage node layer 154 preferably comprises a rugged polysilicon layer, and most preferably comprises at least one material selected from the group consisting of cylindrical grain polysilicon and hemispherical grain polysilicon. The cylindrical grain polysilicon and/or hemispherical grain polysilicon create a surface roughness of storage node layer 154. Storage node layer 154 may be formed by conventional methods.
Referring to FIG. 14, storage node layer 154 (shown in FIG. 13) is subjected to an isotropic polysilicon etch. Such isotropic polysilicon etch transfers surface roughness from storage node layer 154 to lateral surfaces 148, 150 and 152, and uppermost surfaces 142, 144 and 146 of conductive pedestals 136, 138 and 140. The isotropic etch also isolates pedestals 136, 138 and 140 by removing storage node layer 154 from between pedestals 136, 138 and 140. The isotropic etch may, in embodiments which are not shown, transfer surface roughness from storage node layer 154 to upper surface 128 of insulative layer 34a.
Referring to FIG. 15, a dielectric layer 156 and a cell plate layer 158 are formed over and between conductive pedestals 136, 138 and 140. Specifically, dielectric layer 156 and cell plate layer 158 extend over lateral surfaces 148, 150 and 152, and over uppermost surfaces 142, 144 and 146 of pedestals 136, 138 and 140.
Dielectric layer 156 typically comprises an electrically insulative layer, such as silicon nitride or a composite of silicon nitride and silicon oxide. Cell plate layer 158 typically comprises an electrically conductive layer, such as conductively doped polysilicon. Dielectric layer 156 and cell plate layer 158 may be formed by conventional methods.
Pedestal 136, together with dielectric layer 156 and capacitor 158 comprises a first capacitor construction 160. Pedestal 140, together with dielectric layer 156 and cell plate layer 158 comprises a second capacitor construction 162. A patterned masking layer 164, preferably comprising photoresist, is formed over first and second capacitor construction 160 and 162. Patterned masking layer 164 masks first and second capacitor constructions 160 and 162 while leaving portions of cell plate layer 158 and dielectric layer 156 exposed between capacitor constructions 160 and 162.
Referring to FIG. 16, an isotropic etch is conducted to remove the exposed portions of cell plate layer 158 and dielectric layer 156. Removal of cell plate layer 158 electrically isolates pedestal 138 from capacitor constructions 160 and 162.
After such electrical isolation of pedestal 138, an insulative layer 166 is formed over capacitors 160 and 162, and over pedestal 138. Insulative layer 166 may comprise, for example, BPSG. A patterned masking layer 168, preferably comprising photoresist, is formed over insulative layer 166 to mask portions of insulator 166 over capacitor constructions 160 and 162, and to leave a portion of insulative layer 166 exposed over pedestal 138.
Referring to FIG. 17, the exposed portion of insulative layer 166 over pedestal 138 is removed to form a bitline plug opening 170 extending through insulative layer 166 to pedestal 138. Bitline plug opening 170 exposes uppermost surface 144 of pedestal 138.
A bitline plug layer 172 is provided over insulative material 166 and within bitline plug opening 170 to electrically contact the exposed uppermost surface 144 of pedestal 138. A portion of bitline plug layer 172 within opening 170 forms a bitline plug 174. Bitline plug layer 172 may comprise a number of materials known to persons of ordinary skill in the art, including, for example, tungsten.
Referring to FIG. 18, bitline plug layer 172 is removed from over insulative layer 166. Methods for removing bitline plug layer 172 from over layer 166 may include, for example, chemical mechanical planarization (CMP).
After removal of bitline plug layer 172 from over insulative layer 166, a bitline 176 is formed in electrical connection with bitline plug 174. Bitline 176 may comprise a number of materials known to persons of ordinary skill in the art, including, for example, aluminum ii or titanium.
The final construction of FIG. 18 is a DRAM array comprising a first node location 25a, a second node location 27a, and a third node location 29a. Node locations 25a, 27a and 29a are diffusion regions within a substrate 12a. Node locations 25a and 27a are electrically coupled through a transistor gate of a wordline 26a. Similarly, node locations 27a and 29a are electrically coupled through a transistor gate of a wordline 26a. An insulative layer 34a is over substrate 12a and comprises an uppermost surface 128. First, second and third conductive pedestals 136, 138 and 140, respectively, extend through insulative material 34a and in electrical connection with first, second and third node locations 25a, 27a and 29a, respectively.
Conductive pedestals 136, 138 and 140 comprise uppermost surfaces 142, 144 and 146, respectively, and comprise lateral surfaces 148, 150 and 152, respectively. Uppermost surfaces 142, 144 and 146 are at a substantially common elevational height relative to one another, and are above uppermost surface 128 of insulative material layer 34a.
A dielectric layer 156 and a cell plate layer 158 are adjacent uppermost surfaces 142 and 146 of pedestals 136 and 140. Dielectric layer 156 and cell plate layer 158 are also adjacent lateral surfaces 148 and 152 of pedestals 136 and 140. Together, pedestal 136, dielectric layer 156 and cell plate layer 158 comprise a first capacitor construction 160. Similarly, third pedestal 140, together with dielectric layer 156 and cell plate layer 158 comprises a second capacitor construction 162. First capacitor construction 160 and second capacitor construction 162 are connected to pedestal 138 through wordlines 26a. Pedestal 138 is connected to a bitline 176 through a bitline plug 174. Accordingly, pedestal 138 and bitline plug 174 together comprise a bitline contact 180. The DRAM array of FIG. 18 may be incorporated into monolithic integrated circuitry, such as microprocessor circuitry.
To aid in interpretation of the claims that follow, the term "semiconductive substrate" is defined to mean any construction comprising semiconductive material, including, but not limited to, bulk semiconductive materials such as a semiconductive wafer (either alone or in assemblies comprising other material they are on), and semiconductive material layers (either alone or in assemblies comprising other materials. The term "substrate" refers to any supporting structure, including, but not limited to, the semiconductive substrates described above.
In compliance with the statute, the invention has been described in language more or less specific as to structural and methodical features. It is to be understood, however, that the invention is not limited to the specific features shown and described, since the means herein disclosed comprise preferred forms of putting the invention into effect. The invention is, therefore, claimed in any of its forms or modifications within the proper scope of the appended claims appropriately interpreted and in accordance with the doctrine of equivalents. | The invention includes a number of methods and structures pertaining to integrated circuitry. The invention encompasses a method of forming an integrated circuit comprising: a) forming an insulative material layer over a first node location and a second node location, the insulative material layer having an uppermost surface; and b) forming first and second conductive pedestals extending through the insulative material layer and in electrical connection with the first and second node locations, the conductive pedestals comprising exposed uppermost surfaces which are above the uppermost surface of the insulative material layer. The invention also encompasses an integrated circuit comprising: a) a first node location and a second node location within a semiconductor substrate; b) a transistor gate electrically connecting the first and second node locations; c) an insulative material layer over the semiconductor substrate, the insulative material layer comprising an uppermost surface; d) a first conductive pedestal extending through the insulative material layer and in electrical connection with the first node location; e) a second conductive pedestal extending through the insulative material layer and in electrical connection with the second node location; f) the conductive pedestals comprising uppermost surfaces which are at a common elevational height relative to one another and are above the uppermost surface of the insulative material layer in a region proximate the pedestals. | 7 |
BACKGROUND OF THE INVENTION
The present invention relates to compositions for use in the washing of fabrics in washing machines. More particularly, the invention is directed to a composite, unitary packet including, as distinct components, a detergent or washing composition and a fabric treating composition, and in which the several different components are released in a predetermined, controlled sequence.
Many different types of fabric washing preparations have been developed for use in rotary and agitator-type washing machine. The commercial embodiments of these washing compositions have taken various physical forms. The products currently being marketed include many and varied functional chemical ingredients for both general an specialized applications.
Special products, each intended to perform a principal limited function such as fabric cleaning, bleaching, fabric "softening" and freeing fabric of static electrical charges have been offered to the consumer. In addition, multi-purpose compositions which include two or more different functional components, intermixed or combined physically have also been widely promoted.
The addition, all at the same time, of separate compositions such as detergents, fabric softeners, and anti-static agents into the tub of a washing machine has proven unsatisfactory in that interference and interaction between the various chemical ingredients occurs with the result that there is product deactivation and failure. As a result, the full intended function or role of at least one of the "special" agents added is not realized. In some instances a given functional utility is lost entirely.
The alternative procedure of adding each specialized product separately but in turn, at sequential time-spaced increments of the washing operation, is exceedingly inconvenient in that it is necessary that one be present during and to follow the time-controlled stages of the washing cycle.
The problems described above have been recognized; various approaches have been explored to provide solutions. Products have been devised which contain multi-functional compositions, but which, upon introduction into a washing machine, act to release the different functional ingredients in a particular sequence, for example, the bleach being released only after the washing cycle has been in progress for some period of time.
The general method for achieving such delayed or sequential addition or incorporation of ingredients into a fabric washing system is to use specially controlled, multi-compartment pouches, bags, envelopes or sachets, including such structures having walls of varying water permeability. In other such pouches, the walls themselves are impermeable to water, but are water-disintegratable. Water disintegrateable seals have been used to control or delay the release of a particular packaged ingredient. In still other arrangements a combination of water impermeable and water permeable walls and/or seals has been employed. The structural composition of the pouch walls themselves includes plastics, woven and non-woven fabrics, and porous walls of plastic or fabric, but coated with a permanent water sealant film or with a film which dissolves in water at a rate dependent upon the coating composition and the thickness.
In still other arrangements the release of a particular ingredient from a given compartment of a composite package has been rendered temperature-dependent so that above a critical temperature the confining wall disintegrates or becomes permeable to the encapsulated, or confined ingredient. Another method to achieve a time-spaced, sequential release of two component compositions has been totally to encapsulate or to encase one component physically within the other. In still another type of arrangement coatings the solubility of which depends upon the pH of the ambient aqueous system are used to control the release of a confined composition.
In some of the packages of the type referred to, the precise properties, including the critical solubilities of the structural walls of the pouches used, have been difficult to control. Requisite reliability and consistency of operation have not been realized. Others of the packages have lacked the physical strength and have fractured or otherwise failed during shipment and handling. In still others fusion seals or adhesive seals have opened prematurely or have failed to open as intended, or have otherwise proved unreliable and inoperative. Products of the encasement or encapsulation type and without protective mechanical enclosures have fractured prematurely resulting in simultaneous dissolution, thus obviating the intended utility.
It is, therefore, a principal aim of the present invention to provide a multi-functional fabric washing and treating product in which separate components are released into the washing system sequentially, at time-spaced intervals, in a controlled manner, and in which shortcomings and deficiencies of prior art preparations have been overcome.
SUMMARY OF THE INVENTION
In accordance with the present invention there is provided a unitary, composite jacket including a fabric washing composition and a fabric treating agent contained in an open-top receptacle. The article of the invention makes it possible to add all desired washing mateials into a washer simultaneously in a laundering operation while also ensuring that the different components are automatically released in a predetermined time-spaced, controlled sequence.
In a preferred embodiment of the invention the packet consists of a plug-like, multi-layer laminate bonded to or otherwise sealed contiguously against the base and to a circumscribing bounding wall of a plastic, cup-like receptacle. In the physical arrangement described, initial access of washing solution to the laminate is limited to an exposed top surface only of an uppermost layer of the laminate.
It is an important feature of the packet of the invention that the layers of the materials in the laminate are arranged to define an order, from top to bottom, correlated with a particular dissolution sequence desired.
In a preferred embodiment of the invention a top, exposed layer of the laminate, and the first to be dissolved in the wash water, is a detergent composition, and the layer therebeneath, the next to be dissolved, is a fabric softener and anti-stat.
A related functional feature of the invention is that dissolution of the various definitive layers in the laminate occurs in a free-programmed, predetermined sequence, with the outermost layer being essentially completely dissolved and functioning in the washing solution before the next layer is brought into solution.
An important feature of the invention is that packaging films or fabrics which are difficult to control as to their water permeability are avoided.
A related feature of the invention is its simplicity, the need for barriers of controlled permeability and the need for plastic-to-plastic seals being eliminated.
A practical advantage of the packet of the invention is that it is rapidly and effectively assembled without resort to special techniques such as heat sealing, fusion, and without the use of special machines or devices.
It is a feature of the invention that dissolving delay and sequence control are achieved through an essentially water-tight seal established between the lateral wall of the layered laminate and the contiguous bounding wall surface of the circumscribing receptacle, thus ensuring that the dissolution rate of the top, exposed disc or wafer mateial of the laminate constitutes that parameter which determines the time delay before entry of the next, lower layer into the washing solution.
A utilitarian feature of the composite assembly of the invention is that the introduction of the fabric treating component is effectively delay until essentially all of the detergent fraction has dissolved in the wash water.
A related feature of the packet of the invention is that the delay between dissolution of the detergent composition and dissolution of the fabric conditioner is conveniently adjustable, in the range of from about 2 to about 6 minutes.
A related feature of the invention is that sequential addition of the several different components of the packet is achieved without interrupting the washing cycle and without any demand on the time or attention of the user.
The packet of the invention facilitates the simultaneous presentation to the washing system of two or more separate and distinct laundry ingredients while providing that the dissolution of each occurs at predetermined, controlled, time-spaced intervals in a selected sequence.
Yet another feature of the invention is that the packet contains a premeasured aliquot of each of various functional agents obviating the need to measure out or to mete out the several individual ingredients used in the fabric washing operation.
The present invention is further characterized in that the carrier or receptacle in which the several distinct components of the chemical laminate are contained may be fabricated of any of a diverse group of inert, water-insoluble materials such as molded or formed plastic.
An advantageous marketing feature of the packets of the invention is that they may be conveniently packed or displayed as an internesting lineal array in an attractive tubular package, with attendant economic employment of space.
In a preferred embodiment of the present invention, the second (lower) layer, for example fabric softener, in the receptacle does not dissolve and will not deposit on the fabric until the rinse cycles have been reached and a major degree of cleaning has been completed. The softener, therefore, does not interfere with the cleaning process.
Other and further objects, features and advantages of the invention will become evident from a reading of the following detailed description considered in conjunction with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the packet of the invention showing the container with its encased laminate; and
FIG. 2 is a schematic, cross-sectional view representation of a packet according to the invention, incorporating the features thereof, and showing a plastic receptacle containing a multi-layered plug-like laminate contiguously bonded to the floor and to the bounding wall of the container.
DESCRIPTION OF PREFERRED EMBODIMENTS
The aims and objects of the invention are realized by providing, in an article for use in a washing machine, a unitary packet including an open-top, dish-like receptacle which serves as a housing for a multi-layer, plug-like laminate.
In a preferred embodiment of the invention the laminate is formed of a lower, disc-like layer of a fabric conditioner bonded to the floor and to the circumscribing sidewall of the receptacle in contiguous, fluid-tight abutment. Superimposed on the lower layer, and bonded thereto and to the confining receptacle wall, is a second layer which constitutes a washing agent.
When the article is introduced into the washing water, the exposed washing agent layer dissolves and is dispersed to effectuate its intended cleaing role. Only after a finite delay period, correlated with the time required for the top layer of the laminate to dissolve (about 2 to about 6 minutes depending on the particular formulation and upon the wash water temperature, etc.) will the fabric conditioner enter the washing solution. Thus, a simple yet most effective procedure has been provided for releasing two functionally different laundering compositions into a fabric washing system in an optimum, predetermined, time-spaced sequence. It will be appreciated that the rate of solution of each layer of the composite laminate can be adjusted, controlled and varied, as desired, by altering the specific composition utilized.
In the specific embodiment of the invention described above, the addition and the functional availability of fabric conditioner, for example, is deferred until the washing agent or cleansing composition has had sufficient time to act effectively on the fabrics in the wash machine. The two distinct and different functions occur, optionally, in a predetermined time delay sequence, even though both compositions are introduced into the wash system simultaneously.
Optionally, other functional compositions, delineated by additional distinct "layers" may be used for special applications and generally to enhance the washing operation.
Referring now to the drawing, there is shown, for purposes of illustrating disclosure, and not in any limiting sense, a packet 10 embodying the features of the present invention. The packet 10 is in the form of an open-top, dish-like or cup-like receptacle or container 14 of a generally cylindrical or tubular configuration and having a flat base or floor 16 with an integrally formed, circumscribing, upwardly-extending wall 20. In the specific example depicted, the receptacle is of a water-impermeable and water-insoluble, light-weight foamed plastic (for example, closed cell molded polystyrene) such as used commercially in throw-away drinking cups.
As indicated schematically, the receptacle 14 contains a laminate 24 consisting of two contiguous layers 28 and 30 in superimposed relationship. Each layer constitutes a distinct physical composition; each performs a different, important function in a fabric washing system. In the example shown, the lower layer 28 is a fabric conditioning, for example, a fabric softener and anti-static agent. The upper layer 30 is a washing agent.
The term "washing agent" as used herein is intended to include one or more of soaps, synthetic organic detergents, water conditioners, binders, builders, sequestrants and anti-soil and redeposition additives.
The term "fabric conditioner" may include such ingredients as softeners, anti-static agents, brighteners, dispersing agents, and binders.
Neither the dimensions of the cup 14 or the cup configuration are critical. A cup about 2 inches in average diameter and having a height of about 11/2 inches and a wall thickness in the range of about 1/16 inch has been found to be quite suitable as a container in which the height of each of the two housed layers is about 9/16 inch. As indicated schematically, this arrangement will provide a slight head space of about 1/4 to about 1/2 inch. In the specific embodiment shown, the cup has a slight upward and outward flair.
It is important, however, that each of the contained layers, especially the top layer 30 of the laminate 24 be firmly and contiguously bonded in fluid-tight adhesion to the bounding, circumscribing wall 20 of the receptacle 14. Such fluid-impervious bonding ensures that the lower, fabric conditioning layer 28, does not go into the washing system until the upper, washing agent layer 30 has dissolved and dispersed in the wash system.
With the physical arrangement as described, the fabric treating composition 29 will not enter into the washing solution to act upon the fabrics until the washing agent (the upper layer 30) has been at its work for about 2 to about 6 minutes. Preferably, the fabric conditioner 28 will first come into contact with the fabrics during a rinse cycle, after the wash machine has cycled through a major fraction of the washing period.
In the specific embodiment of the invention illustrated, the cup 14 contains about 15.5 grams of fabric conditioner (a "softener" blend) as the lower laye 28 and about 33 grams of a washing agent (detergent blend) as the upper layer 30. Generally, the amount of fabric conditioner may lie in the range of from about 7 to about 30 grams, and the amount of washing agent in the range of from about 15 to about 50 grams.
The product of the invention is conveniently assembled by first heating the fabric conditioner composition to form a fluid slurry. The slurry is poured, while hot, into the cup 14 where, upon cooling, it forms a solid waxy wafer 28 or layer. The washing agent composition, mixed and heated to form a fluidized mass, is then poured into the cup 14 on top of the lower layer and, upon cooling, bonds thereto and to the sidewall 20 of the cup 14. A unitary, composite container and bonded plug-like laminate results--ready for use.
In a somewhat modified procedure, a small quantity of a powdered potassium carbonate, a polyelectrolyte or equivalent chemical agent may be sprinkled on the surface of the fabric conditioner layer 28 as an interface medium 34 before pouring the washing agent into the assembly. This refinement establishes a definitive demarcation and serves to enhance separation of the two principal components of the laminate during the dissolution process.
DETAILED EXAMPLES OF PREFERRED ENFORMULATIONS
It will be appreciated that, within the teachings and intended use of the present invention, many varied, different formulations of both the "washing agent" and the "fabric conditioners" may be utilized. In the following sections of the specifications typical examples of suitable blends are described. The principal functional roles of each component ingredient are identified, and preferred concentration ranges are given. (Tables I and II).
TABLE I__________________________________________________________________________Fabric Softener Composition FormulationIngredient Compound and Conc.No. (% by Wt.) Concentrational Range Function__________________________________________________________________________1. 28.0% Ditallow- 10.0 to 40.0% Primary fabric Alkyl Dimethyl softener and Ammonium Chloride antistat agent2. 18.6% Dioleyl 5.0 to 30.0% Secondary fabric Alkyl Imidazolinium Softener and Methyl Sulfate antistat, rewet additive, co- solublizer3. 15.5% Isopropyl 3.5 to 18.0% Solvent for alcohol cationic fabric softeners4. 12.4% Trisodium 2.5 to 25.0% Aid in dis- salt of nitrilo- persing softener triacetic acid blend. Also a water softener5. 6.2% Nonyl- 2.0 to 14.0% Surfactant phenol-10 mole disperser for ethoxylate cationics6. 12.3% Polyoxy- 4.0 to 25.0% Binder and propylene (POP) surfactant polyoxyethylene disperser for (POE) block copolymer cationics.7. 6.2% Propylene 0.0 to 15.0% Cosolvent glycol8. 0.7% Optical 0.1 to 1.5% Fabric optical brightener brightener (cationic-compatible)9. 0.1% Dye or 0.01 to 0.2% Colorant for colorant softener layer10. q.s. perfume, 0 to 3% water__________________________________________________________________________
TABLE II______________________________________Washing Agent FormulationsIngre-dient Compound and Conc. ConcentrationalNo. (% by Wt.) Range Function______________________________________1. 19.0% POP/POE 8.0 to 30.0% Binder and block copolymer surfactant2. 44.6% Nonylphenol 20.0 to 55.0% Basic non- -10 mole ethoxylate ionic detergent ingredient3. 21.1% Trisodium 4.0 to 30.0% Water softener, salt of nitrilo- calcium/ triacetic acid magnesium sequestrant, detergent builder4. 5.8% Potassium 1.0 to 12.0% Detergent carbonate builder, alkalinity agent5. 3.2% polyvinyl- 1.5 to 4.5% Cationic- pyrrolidone (PVP) compatible, anti-soil redeposition additive6. 4.2% Propylene 0.0 to 6.0% Cosolvent, glycol Solublizer7. q.s. colorant, 0.0 to 3.0% perfume, water______________________________________
Alternative compounds may be substituted for the primary and secondary softeners and the other functional ingredients of the softener formulation. Possible alternative components are listed below, keyed with reference to the numbered categories identified above as "Ingredient No.".
Ingredient No. Key (1)
C-12, C-14, C-16, C-20, C-22, di-alkyl dimethyl ammonium chlorides, bromides, methyl sulfates and blends thereof, including deriving alkyl groups from coconut oil, palm oil, soya and oleyl fatty acids. Mono-alkyl trimethylammonium salts of the above and including mono-tallow alkyl constituents.
Ingredient No. Key (2)
C-12, C-14, C-16, C-18 (tallow alkyl), C-20, C-22 di-alkyl dimethyl imidazolinium methyl sulfates and blends thereof, including alkyl groups derived from coconut, palm oil, soya, and oleic fatty acids. Also ethoxylated quaternaries.
Ingredient No. Key (1)-(2)
Other cationic candidates may be selected from the generic types of: (a) cylical alkylammonium compounds, including as examples: pyridinium, quinolinium, isoquinolinium, phthalzinium, benzimidazolinium, benzothiazolium, benzotriazolium, pyrrolidinium, and various imidazolinium derivatives (unsaturated heterocyclic compounds); or may possess saturated ring structures, such as: piperidinium, morpholinium, thiamorpholinium, piperazinium, 1,3-benzoxizinium; 1,3,5-trialkylexahydro-1,3,5-triazinium derivatives, or N-hexahydroazeinium derivatives. They may be derived from petroleum, or may be polymeric, or may be non-nitrogen-containing cationics such as: sulfoxonium and sulfonium compounds, phosphonium compounds, or iodonium compounds to mention some examples. (See reference 3). Bisquaternaries are also included as candidate cationic surfactants.
Ingredient No. Key (3)
Propylene glycol, low molecular weight polyoxyethylene glycols, nonionic surfactants (e.g. nonylphenol-10 mole ethoxylate), alkyl monoethyl ethers (e.g. butyl cellosolves, etc.
Ingredient No. Key (4)
Potassium salts of nitrilotriacetic acid. Sodium and potassium salts of ethylene-diaminetetraacetic acid; pyro-tripoly-hexameta-phosphates; glassy phosphates. Potassium and sodium carbonates; low molecular weight polyelectrolytes such as ethylene-maleic anhydride copolymers or polyacrylates. Potassium and sodium salts of citric and gluconic acids.
Ammonium and moni-, di, and tri-ethanolammonium salts of the above.
Ingredient No. Key (5)
Hexyl-, heptyl, octyl-, and nonyl- decyl-, and undecyl-, dodecyl-, tetra-decyl phenol 5-20 mole ethoxylates. Secondary and primary alcohol (C-10 to C-22)--5 to 30 mole ethoxylates.
Polyolefin-derived (C 8 to C 20 alcohol--5 to 30 mole ethoxylates. C 10 -C 22 fatty acid 5 to 30 mole ethoxylates including abietyl acid derivatives. Epichlorohydrin and other intermediary bridged nonionics. Polyoxethylene/polyoxypropylene block copolymers of ethylene glycol (Pluronics), products of BASF Wyandotte Corporation, polyoxyethylene/polyoxypropylene block copolymers of ethylene diamine. (Tetronics), product of BASF Wyandotte Corporation. Sucrose esters, polyoxyethylene sorbitol esters, amine oxides e.g. alkyl dimethyl amine oxides.
Ingredient No Key (6)
Same as above, but with EO (ethylene oxide) or PO (propylene oxide) ranges high enough to produce solid surfactants at room temperature. For example with ethoxylates, the EO mole ratios for solids would be appropriately 20-40.
Ingredient No. Key (7)
Isopropyl alcohol, ethanol, nonionic surfactants, low molecular weight polyoxyethylene glycols.
Ingredient No. Key (8)
Cationic-compatible fabric brighteners such as Tinopal LPW or Tinopal UNPA free acid, based on diaminostilbene disulfonic acids/cyanuric chloride. (Products of Ciba-Geigy).
Ingredient No. Key (9)-(10)
Dyes and perfumes may be selected from numerous candidates which are cationic-compatible.
Alternative ingredients as specially identified above with respect to cationic blend components but omitting cationics may be used. Additionally, with respect to ingredient (5) polyvinylalcohol (PVA) and PVA/PVP blends may be used (Table II).
The cup or receptacle 14 of the packet 10 in which the fabric cleaning and conditioning compositions are contained may be any of preferred-insoluble and water-impermeable plastics. In addition to polystyrene, containers fabricated of cellulose acetate, polyolefins, polycarbonates, and polyvinylchloride are suitable. Butadiene, isoprene and vinylidene halide polymers as well as halo alkane polymers and acrylates may be used.
While the invention has been described with reference to specific preferred embodiments, such examples are not to be construed as a basis for limiting the scope of the invention itself. That is, although the chemical components in the exemplary forms of the invention are identified as a "washing agent" and a "fabric conditioner", other functional compositions such as a bleaching preparation or enzyme mixture may be used, either instead of or in addition to the washing agent and the fabric conditioner. Suitable "solid" bleaches are well known in the art.
Clearly, the invention is not to be viewed as limited to a two-layer laminate. Three or more layered products, each layer performing its own unique functional role, and in a predetermined time-spaced sequence, are within the inventive concept of the present invention. | A unitary package for use in the washing and in the conditioning treatment of fabrics in a laundering operation. There is provided a packet in which a multi-layer plug-like laminate is contained in and is bonded within a cup-like water-insoluble and water-impermeable receptacle having an open top. The laminate presents an exposed upper surface to the wash water in the tub of a washing machine. Only after the materials (for example, detergents) in the top layer of the laminate have dissolved and dispersed does the washing water reach to solubilize the second layer containing the fabric conditioner (for example, a fabric softener). Thus, the article of the invention ensures the simple and highly reliable manner time-spaced sequential incorporation of two different functional agents into a fabric washing system, even though the agents are added simultaneously. | 3 |
CROSS-REFERENCE TO RELATED APPLICATION
This is a continuation, under 35 U.S.C. §120, of copending International Application No. PCT/EP2012/066365, filed Aug. 22, 2012, which designated the United States; this application also claims the priority, under 35 U.S.C. §119, of German Patent Application DE 10 2011 112 326.5, filed Sep. 2, 2011; the prior applications are herewith incorporated by reference in their entirety.
BACKGROUND OF THE INVENTION
Field of the Invention
The invention relates to a device for providing liquid reducing agent, including a tank for the liquid reducing agent and a delivery unit associated with the tank for delivering the liquid reducing agent from the tank to an injector for supplying the reducing agent into an exhaust-gas treatment device.
Recently, exhaust-gas treatment devices have been increasingly used for the purification of exhaust gases of (mobile) internal combustion engines. The exhaust-gas treatment devices purify the exhaust gas of the internal combustion engine with the aid of a reducing agent supplied to the exhaust gas. Mobile internal combustion engines are used, for example, for driving motor vehicles.
For example, the method of selective catalytic reduction (SCR) is known, in which the exhaust gases of an internal combustion engine are purified of nitrogen oxide compounds, by supplying a medium which reduces the nitrogen oxide compounds to the exhaust gas. Such a medium is, for example, ammonia. Ammonia is normally not stored in motor vehicles directly but rather in the form of a precursor medium, which is also referred to as reducing agent precursor. The reducing agent precursor is subsequently converted, in a reactor provided specifically for that purpose or in an exhaust-gas treatment device, to form ammonia, the actual reducing agent.
Such a reducing agent precursor is, for example, a 32.5% urea-water solution which is available under the trademark AdBlue®. Such a reducing agent precursor solution does not pose a health hazard and can therefore be stored without problems.
The reducing agent precursor or the reducing agent may contain various impurities. On one hand, those impurities should not be supplied to the exhaust gas of the internal combustion engine, because they can lead to residues in the exhaust system. On the other hand, such impurities also should not pass into a device for delivering the reducing agent, because the impurities could lead to blockages of ducts and/or valves in the device.
One important demand on devices for providing reducing agent is also the fact that such devices should be as inexpensive as possible. The purification of exhaust gases by using a supplied reducing agent constitutes a considerable additional cost factor in the production and the operation of a motor vehicle.
It is already known for the reducing agent to be filtered. Such filters are however often very expensive and/or can be used (in a space-saving manner) only to a limited extent. Furthermore, there is the risk of such filters becoming blocked during ongoing operation, because the particles become stuck in the pore system and can no longer be removed. That makes it necessary for such filter systems to be exchanged at periodical intervals in order to ensure fault-free operation. That is associated with considerable costs because the filters are often difficult to access, and/or the tank must be emptied for that purpose.
SUMMARY OF THE INVENTION
It is accordingly an object of the invention to provide a device with a particle screen for providing liquid reducing agent, which overcomes the hereinafore-mentioned disadvantages and at least partially solves the highlighted technical problems of the heretofore-known devices of this general type. It is sought, in particular, to propose a particularly inexpensive, technically simple, space-saving and/or effective device for providing liquid reducing agent.
With the foregoing and other objects in view there is provided, in accordance with the invention, a device for providing liquid reducing agent, comprising a tank with an interior space and a vessel disposed at least partially in the interior space of the tank. The vessel is surrounded on the outside at least partially by a particle screen through which a flow can pass. A delivery unit which is disposed in the vessel is set up or configured to deliver reducing agent from the tank, through the particle screen through which the reducing agent can flow, and out to a take-off or delivery point for reducing agent.
In particular, a circumferential surface of the vessel is surrounded over a predominant part, or even (substantially) entirely, by the particle screen.
In this case, a liquid reducing agent is to be understood, in particular, to mean a liquid reducing agent precursor, such as for example a 32.5% urea-water solution, which can be converted into a reducing agent.
In particular, the tank for the reducing agent is produced from plastic or metal. Corresponding materials may also be used for the vessel. The vessel may be connected detachably or cohesively to the tank. The vessel is preferably disposed in the base region of the tank, in particular at the lowest point of the tank if such a point exists.
The delivery unit includes at least one of the following components: a pump, a pressure/temperature/conductivity sensor or the like, a delivery line, a heater, and an expansion element (against ice pressure). The delivery unit is positioned within the vessel. The vessel is constructed so as to be liquid-tight with respect to the tank, in such a way that the delivery unit itself is disposed not in the reducing agent bath but rather in a cavity of the vessel. The vessel has a leadthrough through which the interior space of the tank is connected through the particle screen, and through an intermediate space between the particle screen and the vessel, to the delivery unit within the vessel. Reducing agent is transferred from the tank into the delivery unit through the leadthrough, with the reducing agent being conducted from there to an injector, for example, which transfers the reducing agent into an exhaust line.
The vessel is preferably inserted into the tank wall in such a way that the vessel closes off an opening in the tank wall and the vessel extends into the interior space of the tank.
The particle screen which at least partially surrounds the vessel preferably encompasses the circumferential surface of the vessel, and if appropriate also the top side of the vessel, preferably completely. The particle screen is, in particular, disposed only between the tank wall and the vessel, in such a way that the vessel and the particle screen together can be disposed in a space-saving manner in the tank. This means, in particular, that no further component is disposed between the tank wall and the particle screen and/or between the particle screen and the vessel.
In particular, the particle screen is disposed so as to be at least partially spaced apart from the vessel, in such a way that an intermediate space is formed between the particle screen and the vessel, and purified reducing agent collects in the intermediate space. The purified reducing agent is extracted from the intermediate space by the delivery unit.
The particle screen has an outer screen surface and an inner screen surface. In this case, the outer screen surface means that side of the particle screen which faces away from the vessel and faces toward the interior space of the tank. The particle screen has an inner screen surface facing toward the vessel. The outer screen surface and the inner screen surface are spaced apart from one another by a depth. A particle screen differs from a—in particular porous—filter (for example a foam) in that the separation efficiency can be described by a step function.
Thus, in contrast to (depth) filters, the screen filters approximately 100% of particles ranging from particles of infinitely large diameter to particles with an, in this case, defined largest diameter (the largest diameter being precisely defined by the openings), so that particles with a smaller diameter than the largest diameter defined in this case can pass practically unhindered through the screen. In particular, the screen acts (merely) as a blockade, and/or itself has (practically) no capability for absorbing particles (for example pores). In this case, the advantages of a screen are firstly the simple construction and the high inherent rigidity, so that no further supporting structures are required. Secondly, a screen has a lower tendency to become blocked than filters, because no particles can collect in the interior of the screen. In this way, it is possible for an inexpensive and permanently ready-to-operate device to be provided which, by using the delivery unit and further components required for the provision of the reducing agent, provides adequately purified reducing agent for the exhaust system.
In particular, the particle screen used in this case is the only device provided, during operation, between the tank and the exhaust line for the removal of particles from the reducing agent. In this case it should be noted that, if appropriate, (only) a so-called assembly filter may also be provided which prevents (very large) chips or other parts formed during the assembly of the individual components from penetrating into the delivery unit and into the other required components. The assembly filters generally have a largest diameter at least 50% larger than the particle screen provided in this case. The assembly filter thus performs no appreciable function during normal operation, instead performing its function only once at the start of operation.
In accordance with another advantageous feature of the invention, the particle screen has predominantly equally dimensioned openings for the throughflow of reducing agent. In particular, the openings on the outer screen surface are connected to the oppositely disposed, in particular equally dimensioned, openings on the inner screen surface by a duct that is apart from that of closed form. There are thus no pores or other branches in the particle screen between the outer screen surface and the inner screen surface. The duct run preferably (substantially) rectilinearly. In particular, the openings are in each case congruent, that is to say correspond to one another in terms of shape, size and position/orientation. It is also preferable for all of the openings of the particle screen to have equally dimensioned openings for the through flow of reducing agent.
In accordance with a further feature of the invention, the openings each have a largest diameter of at most 50 μm, in particular of at most 30 μm.
In accordance with an added preferred feature of the invention, the particle screen includes at least one wire mesh and/or a foil. It is preferable in this case for the (metallic) foil to be formed with etched and/or punched openings. A refinement is preferable in this case in which the particle screen is formed at least partially or entirely by a (metallic) foil. The refinement of the particle screen as a foil is particularly advantageous because, in this way, it is possible for highly uniform openings to be provided, and the foil has adequate inherent rigidity in such a way that, in particular, no supporting structures are required. A wire mesh is distinguished in that the openings in the particle screen are formed by wires interwoven with one another. In this case, in the depth direction, the openings are formed in each case only by one layer of the wire mesh.
The screen may have a multi-layer form. In this context, it is particularly advantageous for a first layer of the screen to be a screen layer with a screen function. The screen layer has the openings required for the screen function (with a diameter of at most 50 μm, preferably at most 30 μm). A second layer is then preferably a support structure which has a support function. The support structure preferably has considerably larger openings than the screen layer, for example openings with a diameter of at least 10 mm. For this purpose, the support structure has considerably increased mechanical stability in relation to the screen layer, wherein the increased mechanical stability may, for example, be realized by using a large depth (material thickness) of the support structure in relation to the screen layer.
In accordance with an additional preferable feature of the invention, the openings become smaller proceeding from the outer screen surface toward the inner screen surface. This characteristic of the openings should be observed in particular during the production of the particle screen. Specifically in the case of etching or also in the case of punching, it is often the case that openings are produced which are not completely cylindrical, with a slight conicity instead being generated. In this context, however, that conicity is desirable because, through the use thereof, the reducing agent can be prevented from flowing through the particle screen back into the interior space of the tank. Through the use of the particle screen and the openings thus configured, a retention element is thus provided in such a way that an adequate fill level continues to be ensured in the vessel and/or in the intermediate space for example during cornering, under other acceleration or when the tank is inclined.
In accordance with yet another preferable feature of the invention, the particle screen has a depth between the outer screen surface and the inner screen surface of at most 0.5 mm. The particle screen is, in particular, at least partially constructed from metal or from plastic. The particle screen is preferably manufactured from a metallic material, because metallic materials exhibit particularly good heat conduction. Furthermore, a particle screen composed of metal is mechanically highly stable at all temperatures that arise during operation, and in particular, the screen action thereof (that is to say, in particular, the size of the openings that are definitive of the screen action) thus does not change, or changes only very little, with changes in temperature.
In accordance with yet a further advantageous feature of the invention, the particle screen exhibits a self-cleaning action during operation. For this purpose, it is for example expedient for the particle screen to be positioned in such a way that it can be intensively flushed with reducing agent during operation. This is, in particular, also achieved in that the outer screen surface is constructed to be as smooth as possible, that is to say it has as low a roughness as possible with an average roughness Ra of at most 0.5 μm. Through the use of a particle screen surface configured in this way, it is possible for any adherent particles to be detached again due to the flow of reducing agent passing over it. The same applies correspondingly to the refinement of the particle screen as a wire mesh. A flow passes over the particle screen during operation, for example due to sloshing movements in the tank. A particle screen is distinguished from a depth filter by the fact that particles are detached from a particle screen again by a flow passing over it. In the case of a particle screen, particles are deposited (at the outside) on a surface and can be detached again by reducing agent flowing over that surface. By contrast, in the case of a depth filter, particles are deposited primarily within the depth filter (in pores). The particles thus in fact cannot be detached purely by a flow passing over the depth filter.
In accordance with yet an added preferable feature of the invention, at least the outer screen surface (if appropriate also the inner screen surface) at least partially has hydrophobic or hydrophilic properties; if appropriate, both properties may be provided jointly. In particular, a corresponding coating is provided. A hydrophobic embodiment has the effect that an adhesion of reducing agent is prevented and reducing agent correspondingly rolls off the surface. A hydrophilic embodiment may, however, likewise also be particularly advantageous, in such a way that a liquid film is formed on the outer screen surface and any adherent particles are correspondingly flushed away even in the case of low liquid flow rates. In this connection, contact angles between the liquid, in this case reducing agent, and solid material, in this case material of the particle screen, are preferably between zero and 20° (hydrophilic), or greater than 90°, in particular greater than 120° (hydrophobic). A contact angle refers to the angle that a liquid droplet on the surface of a solid material forms relative to that surface. In the case of small contact angles (approximately 0°), the surface is referred to as hydrophilic. In the case of angles of around 90°, the surface is hydrophobic, or in the case of even greater angles, the surface is superhydrophobic.
In accordance with yet an additional advantageous feature of the invention, the particle screen has a corrugation. The corrugation serves, in particular, to enlarge the available outer screen surface and inner screen surface, in such a way that even in the case of a small largest diameter of the openings, there is an adequate passage of reducing agent into the vessel.
The particle screen may (alternatively or additionally) have a profiling and/or structuring. A profiling describes for example pattern-like surface elevations and surface depressions, wherein these preferably interact with one another and/or adjoin one another and/or are superposed on one another. In this case, the shape (as viewed in cross section) in particular deviates from a corrugated shape, and may for example include steps, teeth and the like. A structuring may include structures which are spaced apart from one another and which, in particular, do not (directly) adjoin one another, such as for example indentations, furrows and the like.
In accordance with a concomitant advantageous feature of the invention, the particle screen is connected at least to the vessel or to the tank by at least one of the following fastening types:
a) connection by at least one of the methods of clamping, pressing and bracing;
b) cohesive connection, in particular by way of adhesive bonding, brazing and/or welding;
c) at least partially encased, in particular by the vessel;
d) connection by a screw thread.
A connection by clamping, pressing and/or bracing may be realized, for example, by virtue of the particle screen having an elastic form and correspondingly having, for example, a smaller diameter than the vessel. In this case, the particle screen must be expanded in order to be mounted on the vessel, and clamping is correspondingly realized on the basis of elasticity of the particle screen. It is also possible for an elastic insert to be provided between the vessel and the particle screen, which insert is compressed between the vessel and the particle screen and thus braces the particle screen against the vessel. The particle screen may be formed in the manner of a closable bracket that can be placed around the vessel. The particle screen may have a clip element by which the bracket can be closed, placed under stress and braced circumferentially against the vessel. It is also possible for the particle screen to be braced against the vessel by way of at least one rubber band. Furthermore, detent elements may be provided which are elastically deformable and onto which the particle screen is mounted for configuration on the vessel. Furthermore, clip elements may be provided which fix the particle screen to the vessel. The particle screen is preferably fastened to the vessel by screws and/or rivets. In particular, the particle screen has, in sections, a thread in such a way that a connection between the particle screen and vessel or between the particle screen and tank base can be realized by using a screwing motion of the particle screen itself.
In particular, the particle screen is embedded into the vessel or into the vessel material. In this case, the particle screen is at least partially encased by the vessel and/or a vessel material. This may be realized by casting or deformation.
In a further advantageous embodiment, the particle screen has a heater. In particular, the particle screen is itself in the form of a heater. This may be realized by virtue of the particle screen being (at least partially) formed from a correspondingly electrically conductive material which is utilized as a resistance heater. It is preferable for corresponding heating structures to be provided on and/or in the particle screen, in such a way that frozen reducing agent can be thawed in a targeted manner at predetermined locations.
The invention may also be configured in the manner of a module for providing and delivering a reducing agent, which module has a device according to the invention and has an injector which can be disposed in/on an exhaust system. The reducing agent is thus delivered from the tank into the exhaust system through the device and the injector, wherein the particle screen is the only particle separation device between the tank and the exhaust system. The statements made above regarding the so-called assembly filters apply correspondingly in this case.
Furthermore, the invention is also directed to a motor vehicle, at least having an internal combustion engine and an exhaust system for purification of the exhaust gases of the internal combustion engine, wherein the exhaust system has an injector for supplying a reducing agent into the exhaust system, and the injector is connected to a device according to the invention for providing liquid reducing agent.
In a further advantageous embodiment, the particle screen has sufficient thermal conductivity to introduce the heat from a heater disposed in the vessel into the reducing agent in the tank. Such sufficient thermal conductivity may be realized, for example, by using a metallic particle screen and/or by using (metallic) heat-conducting bridges which extend through the particle screen from the vessel.
Provision may also be made for at least one fill level sensor to be disposed and/or integrated in and/or on the particle screen. The fill level of the reducing agent in the tank can be monitored by using a fill level sensor. The fill level sensor may be a continuous fill level sensor which permits continuous, permanent monitoring of the fill level in a (predefined) range between a minimum measurable fill level and a maximum measurable fill level. A continuous fill level sensor of that type is, for example, an ultrasound sensor.
The fill level sensor may also exhibit discrete characteristics. A discrete fill level sensor can detect only whether reducing agent is present at a certain level in the tank, and the actual fill level in the tank is thus above or below the level monitored by the fill level sensor. In particular, in the case of discrete fill level sensors, it is expedient for multiple fill level sensors to be disposed in and/or on the particle screen. It is thus possible to obtain more precise information regarding the fill level in the tank. A discrete fill level sensor of that type may be in the form of a float.
The at least one fill level sensor may, for example, be realized in the form of an electrical conductor and/or in the form of an electrical contact. The measurement of the fill level may preferably be performed by using an electrical resistance and/or electrical capacitance. The electrical resistance and/or electrical capacitance between two electrical contacts and/or two electrical conductors changes as a function of whether or not reducing agent is present at/between the contacts or at/between the conductors. This can be utilized for the determination of the fill level. The electrical contacts and/or the electrical conductors may, for example, be adhesively bonded, welded and/or brazed to the particle screen. The particle screen may also be realized in the form of a fabric or mesh. The electrical contacts and/or electrical conductors may then also be woven into the particle screen.
Other features which are considered as characteristic for the invention are set forth in the appended claims, noting that the features specified individually in the claims may be combined with one another in any desired technologically meaningful way and may be supplemented by explanatory facts from the description, with further embodiments of the invention being highlighted.
Although the invention is illustrated and described herein as embodied in a device with a particle screen for providing liquid reducing agent, it is nevertheless not intended to be limited to the details shown, since various modifications and structural changes may be made therein without departing from the spirit of the invention and within the scope and range of equivalents of the claims.
The construction and method of operation of the invention, however, together with additional objects and advantages thereof will be best understood from the following description of specific embodiments when read in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
FIG. 1 is a diagrammatic, vertical-sectional view of an exemplary embodiment of a device according to the invention;
FIG. 2 is a plan view of a further exemplary embodiment of a device according to the invention;
FIG. 3 is a block diagram of a motor vehicle having a module and a device according to the invention;
FIG. 4 is a fragmentary, perspective view of a particle screen;
FIG. 5 is a plan view showing a fastening of the particle screen to the vessel by a clamping connection;
FIG. 6 is an enlarged, sectional view showing a fastening of the particle screen to the vessel by a detent element;
FIG. 7 is a fragmentary, elevational view showing a fastening of the particle screen by a clip element;
FIG. 8 is a partly sectional view showing a fastening of the particle screen to the vessel by a cohesive connection;
FIG. 9 is a fragmentary, elevational view showing a connection of a particle screen and a vessel by further cohesive connections;
FIG. 10 is an elevational view showing a connection of a particle screen and a vessel by screw and rivet connections;
FIG. 11 is an elevational view showing a connection of a particle screen and a vessel by a thread;
FIG. 12 is a plan view showing a fastening of the particle screen to a cutout of the vessel by a clamping connection; and
FIG. 13 is an elevational view showing the clamping connection of FIG. 12 .
DETAILED DESCRIPTION OF THE INVENTION
Referring now in detail to the diagrammatic figures of the drawing, in which the same reference numerals are used for identical objects for explaining the invention and the technical field in more detail by showing particularly preferred structural variants to which the invention is not restricted, and first, particularly, to FIG. 1 thereof, there is seen an exemplary embodiment of a device 1 from the side. The device includes a tank 2 with an interior space 3 in which a vessel 4 is disposed. A delivery unit 8 is disposed in the vessel 4 for delivering reducing agent 15 from the tank 2 to a non-illustrated injector. The vessel 4 is surrounded, at its circumferential surface 26 , by a particle screen 5 .
The particle screen 5 also extends over a top side 31 of the vessel 4 . The particle screen 5 has an outer screen surface 6 and an inner screen surface 12 . The outer screen surface 6 and the inner screen surface 12 are spaced apart from one another by a depth 7 . The particle screen 5 has openings 13 through which the reducing agent 15 passes from the interior space 3 of the tank 2 , through an intermediate space 18 illustrated therein and an extraction opening or a leadthrough 19 , to the delivery unit 8 within the vessel 4 . The particle screen 5 also has a coating 14 which has hydrophilic and/or hydrophobic properties, so that particles that adhere to the outer screen surface 6 are flushed away by the reducing agent 15 . It is thus possible to realize a self-cleaning effect of the particle screen 5 , in such a way that the particle screen 5 is permanently operable.
The tank 2 has a tank wall 29 and a sump 28 in the region of a tank base 33 . The vessel 4 is fastened to the tank base 33 in the region of the sump 28 . In the exemplary embodiment shown herein, the tank base 33 has a tank opening 30 in the region of the sump 28 . In this case, the vessel 4 extends through the tank opening 30 into the tank 2 . The vessel has a vessel base 32 . In this case, the delivery unit 8 has a pump 24 , a pressure sensor 25 and a take-off or removal point 9 through which the reducing agent 15 is delivered into a non-illustrated reducing agent delivery line and then to a non-illustrated injector.
FIG. 2 shows a further exemplary embodiment of a device 1 in a plan view. The reducing agent 15 is delivered from the interior space 3 of the tank 2 through the particle screen 5 into the intermediate space 18 , and from there through the extraction opening or leadthrough 19 to the delivery unit 8 . In this case, the reducing agent 15 is transported from the intermediate space 18 into the delivery unit 8 by the pump 24 . The reducing agent 15 passes from the pump 24 through the pressure sensor 25 to the take-off point 9 . The reducing agent 15 passes through the openings 13 into a duct 43 of the particle screen 5 , and flows out of the particle screen 5 at the inner screen surface 12 . The particle screen 5 has a corrugation 17 . Furthermore, a heater 27 is disposed on the particle screen 5 , so that the particle screen 5 can be correspondingly heated in order to liquefy frozen reducing agent 15 . In this case elements 34 , which are disposed on the particle screen 5 itself, extend from the outer screen surface into the interior space 3 and permit thawing of frozen reducing agent 15 in the tank interior space 3 . For this purpose, the elements 34 may likewise have a heater 27 , or are in heat-conducting connection with the heater 27 of the particle screen 5 . Furthermore, the elements 34 serve for the calming and retention of reducing agent 15 . In this way, in the event of accelerations of the tank 2 (for example as a result of accelerations of a motor vehicle), sloshing of the reducing agent 15 can be prevented, and furthermore, a minimum amount of reducing agent 15 is retained in the region of the particle screen 5 , so that the openings 13 of the particle screen 5 continue to be charged with reducing agent 15 .
FIG. 3 shows a motor vehicle 20 having an internal combustion engine 21 and having an exhaust system 22 . An injector 23 is disposed in or on the exhaust system 22 . The injector 23 is supplied with reducing agent 15 by a device 1 , in such a way that the reducing agent 15 can be transferred through the injector 23 into the exhaust system 22 for exhaust-gas treatment purposes. In this case, the device 1 and injector 23 form a module 11 .
FIG. 4 shows a portion of a particle screen 5 with an outer screen surface 6 and with openings 13 through which the reducing agent 15 enters the intermediate space 18 from the interior 3 of the tank 2 . The openings 13 have a largest diameter 10 . Due to the construction as a particle screen, particles with a diameter larger than the largest diameter 10 are prevented from passing through the opening 13 , whereas particles with a diameter smaller than the largest diameter 10 pass substantially unhindered through the opening 13 . Thus, in contrast to filters (pore filter, nonwoven, fabric, knit, foam or the like), a clear-cut separation efficiency is realized. A continuous clogging of the particle screen 5 with particles of different sizes, and thus progressive blockage, are thus prevented in an effective manner. In this case, a heater 27 is disposed on the outer screen surface 6 . The heater may also be disposed on the inner screen surface 12 or in the particle screen 5 . In the case of a metallic construction of the particle screen 5 , it is also possible for the entire particle screen 5 to be utilized as a heater 27 .
FIGS. 5 to 12 show different fastening types for the fastening of the particle screen 5 to the vessel 4 and/or to the tank 2 . The connection types shown in the figures represent merely particularly advantageous exemplary embodiments, although a person skilled in the art may derive from these further connection types which are likewise encompassed by the present invention. The invention is thus expressly not restricted to the exemplary embodiments illustrated in the following figures.
FIG. 5 shows, in a plan view, the vessel 4 onto which a small particle screen 5 , illustrated by dashed lines, is to be mounted. The particle screen 5 has a smaller diameter or a form of smaller dimensions, so that it must be expanded in order to be mounted on the vessel 4 . After the particle screen 5 (outer, solid line) has been mounted on the vessel 4 , the particle screen has been elastically deformed and correspondingly enlarged in such a way that a connection 16 is produced between the vessel 4 and particle screen 5 by clamping.
FIG. 6 shows the fastening of the particle screen 5 to the vessel 4 by using a detent element 36 . The particle screen 5 is mounted, by way of a recess 42 provided for that purpose, onto the detent element 36 . The detent element 36 has a flexibly deformable upper part which is compressed by the relatively small recess 42 during the mounting process and which springs back into the original form after the mounting process. A connection 16 is thus produced between the components by using a detent action.
FIG. 7 shows the fastening of the particle screen 5 to the vessel 4 by using a clip element 37 , which in this case extends over the top side 31 of the vessel. The clip element 37 encompasses the particle screen 5 at its outer screen surface 6 , and thus generates a connection 16 by clamping. In this case, a seal 41 is also illustrated between the particle screen 5 and the vessel base 32 . The seal 41 prevents non-purified reducing agent 15 from penetrating into the intermediate space 18 . The seal 41 may be used correspondingly in the further exemplary embodiments illustrated herein.
FIG. 8 shows the fastening of the particle screen 5 to the vessel 4 by using a cohesive connection 16 . In this case, the particle screen 5 is fastened by way of an intermediate piece 35 and a cohesive connection 16 , for example by welding, brazing or adhesive bonding, to the vessel 4 , in this case to the top side 31 of the vessel. The particle screen 5 is partially embedded in, or encased by, the material of the intermediate piece 35 . For this purpose, the intermediate piece 35 may be produced together with the particle screen 5 by casting. The intermediate piece 35 may also be correspondingly deformed after the configuration of the particle screen 5 . The statements made regarding the intermediate piece 35 apply correspondingly to the vessel 4 , that is to say the vessel 4 may also be correspondingly directly connected to the particle screen 5 .
FIG. 9 shows the connection 16 between the particle screen 5 and the vessel 4 by using a roll seam weld.
FIG. 10 shows the connection 16 between the particle screen 5 and the vessel 4 by using a screw 38 or a rivet 39 , which in this case is disposed on the top side 31 of the vessel.
FIG. 11 shows the connection 16 of the particle screen 5 and the vessel 4 by using screw threads 40 , which in this case are disposed in the region of the vessel base 32 . The particle screen 5 and the vessel 4 or a part of the vessel base 32 each have a screw thread 40 , in such a way that the particle screen 5 can be screwed into the screw thread 40 disposed on the vessel 4 , or as illustrated herein on the vessel base 32 , by rotation of the particle screen 5 itself.
FIG. 12 shows the vessel 4 in a plan view. A connection 16 of the particle screen 5 to the vessel 4 is generated by clamping, as in the structural variant according to FIG. 5 . The particle screen 5 is braced with respect to the vessel, in particular clamped to a cutout 44 of the vessel 4 .
An ultrasound sensor 45 disposed in the cutout 44 can be used to monitor a fill level in a reducing agent tank. The ultrasound sensor 45 is not covered by the vessel 4 from above.
The vessel 4 illustrated in FIG. 12 is illustrated in yet a further view in FIG. 13 . In this case, it is possible to see the cutout 44 to which the particle screen 5 is clamped.
The ultrasound sensor 45 is situated in the cutout 44 . The dotted lines illustrate the ultrasound beams, running upward from the ultrasound sensor 45 , for the purpose of monitoring the fill level. The ultrasound sensor 45 is disposed in the cutout 44 so as to be free in the upward direction and not covered by regions of the vessel 4 .
The present invention proposes a construction of a particle screen which is as simple and inexpensive as possible. Blockage of the particle screen can be prevented over a relatively long period of time. Furthermore, a self-cleaning effect of the particle screen can be utilized in such a way that all components for the retention of particles from the reducing agent up to the pump and/or dosing unit are practically maintenance-free. Due to the metallic construction, the particle screen itself can also be utilized as a heater. The reducing agent is correspondingly successively thawed out proceeding from the particle screen. | A device for providing a liquid reducing agent includes a tank having an interior space, a vessel at least partly disposed in the inner space of the tank, the vessel being at least partly surrounded by a particle screen through which a liquid can flow, and a delivery unit located in the vessel and configured for delivering reducing agent from the tank, through the particle screen and then out to a take-off or delivery point for reducing agent. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for deasphalting an asphalt-containing mineral oil. More specifically, the process relates to the preparation of lubricating oils having a low asphalt content. Still more specifically, the process comprises contacting an asphalt-containing hydrocarbon feedstock with a deasphalting solvent.
2. Description of the Prior Art
Propane has been used extensively in deasphalting asphalt-containing hydrocarbon feedstocks, especially in the preparation of high quality lubricating oils. The use of propane has necessitated elaborate solvent cooling systems utilizing cold water, which is a relatively expensive cooling agent. While it is desirable to use alternative cooling equipment such as air fin coolers, this has not always been possible in the case of propane deasphalting in locations where ambient air temperature reaches about 100°F. This is due to the fact that relatively low extraction tower temperatures are required (e.g. 110°F. extraction tower bottoms temperature with an Aramco vacuum residuum) to achieve satisfactory yield and quality of deasphalted oil, thereby resulting in poor heat exchange.
Thus, attempts have been made in the past to develop a solvent system useful in deasphalting processes, which would allow operation at elevated temperatures relative to conventional propane deasphalting temperatures, thereby permitting easy heat exchange in those instances where the utilization of air-fin cooling techniques are preferred. In addition, it would be desirable to integrate dewaxing operations with deasphalting operations by having a common solvent recovery system.
Typical of prior art deasphalting processes is the process described in U.S. Pat. No. 2,337,448 in which a heavy residuum is deasphalted by contacting it at elevated temperature with a deasphalting solvent such as ethane, ethylene, propane, propylene, butane, butylene, isobutane, and mixtures thereof. In the process of this patent may be utilized such other solvents as pentane, gasoline, mixtures of alcohol and ether, acetone and other solvents capable of dissolving the oil and resins but not the asphaltenes.
SUMMARY OF THE INVENTION
In accordance with the invention, there is provided a process for deasphalting an asphalt-containing mineral oil, which comprises: contacting said mineral oil at elevated temperature and elevated pressure with a deasphalting three carbon atom-containing hydrocarbon selected from the group consisting of propylene, propane and mixtures thereof, in combination with acetone in an amount ranging from about 2 to about 25 liquid volume percent (based on the total solvent).
The process is particularly useful in deasphalting residual petroleum oil fractions for the production of high viscosity lubricating oils generally referred to as "bright stock".
The deasphalting solvent of the present invention preferably comprises propylene in combination with acetone. It is to be understood that besides said three carbon containing hydrocarbons, minor amounts of other hydrocarbons may be present in the solvent without substantially affecting the overall efficiency of the process. Preferably, the C 3 hydrocarbon component will be present in an amount of at least 95 liquid volume percent (LV%) of the total hydrocarbons or 95 LV% of the 98 to 75 LV% remaining balance of the total deasphalting solvent. The amount of deasphalting solvent employed and the operating temperatures and pressures utilized must be controlled to suit the particular solvent composition and the oil feedstock being treated to obtain a deasphalted oil of the desired viscosity and Conradson carbon residue content. In general, from about 4 to about 10 volumes of deasphalting solvent are mixed with the oil, preferably from about 6 about 8 volumes of solvent.
The contacting step takes place at a temperature ranging from about 110° to about 200°F., preferably from about 135° to about 190°F. and at a pressure ranging from about 450 to about 650 pounds per square inch gauge (psig), preferably from about 550 to about 600 psig. The overall contacting operation results in the formation of two layers, an upper layer of viscous oil dissolved in the solvent and a lower layer of asphaltenes containing some oil and solvent. The upper layer is withdrawn from the asphaltene layer and then each layer is subjected to flash vaporization and stripping to remove the solvent from the deasphalted oil and asphalt byproducts.
The process of the invention is suitable for removing asphalt from any mineral oil feedstock containing asphaltenes. Suitable mineral oil feedstocks include residual petroleum oil fractions having initial boiling points (at atmospheric pressure) ranging from about 650° to about 1,100°F. It is particularly suited for treating atmospheric residua and vacuum residua. Preferably the oil feedstock treated is a petroleum vacuum residuum having an initial atmospheric boiling point ranging from about 950° to about 1,050°F., a gravity of about 5° to 15° API and a viscosity ranging from about 500 to about 30,000 SSU/210°F. The contacting of the mineral oil feed with the deasphalting solvent may be carried out in one or more mixer-settler units or in a countercurrent liquid-liquid contacting tower. In the latter case, the mineral oil feed enters the top of the tower and the deasphalting solvent enters near the bottom. The tower is provided with internals such as packing, staggered rows of angle irons or liquid-liquid contacting trays to provide efficient contacting of the two liquid phases. The asphalt phase passes through the tower, countercurrently to the bulk of the rising solvent stream and leaves the bottom of the tower. The solvent stream containing the dissolved deasphalted oil, passes by the feed stage and then usually through a zone provided with heating coil to reject some of the heavier components in the oil and to promote reflux. It should be noted that with the deasphalting solvent of the present invention, as is typical with most deasphalting solvents, the solubility of the dissolved deasphalted oil is reduced as the temperature increases. This is contrary to the nature of most other types of solvent extraction processes wherein the solubility of the extract in the solvent increases with increasing temperature.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic flow plan of an embodiment of the invention.
FIG. 2 is a graph showing yield-gravity relationships for various deasphalted feedstocks.
FIG. 3 relates the effect of extraction temperature to overall deasphalted oil yield.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The preferred embodiments will be described with reference to the figures.
Referring to FIG. 1, a vacuum residuum feed of 4.9° API gravity at a typical temperature of 200° to 250°F. enters via line 1 into a countercurrent deasphalting tower 2 near the top and flows down over contacting means such as staggered rows of angle irons 35, while being contacted with propylene-acetone deasphalting solvent entering the tower near the bottom via line 3. The propylene-acetone solvent comprises 96 LV% propylene and 4 LV% acetone, and the treat rate is 800 LV% on feed. The tower bottom temperature is 170°F. and the tower top temperature is 190°F. because of the hotter feedstock entering near the top and because of additional heat input above the feed point introduced by steam heating coil 34. The deasphalted oil phase 4 leaving the top of the tower is heated by heating means 5 to a temperature of about 300°-350°F. at a pressure of about 350 to about 500 psig whereupon most of the solvent is flashed off in high pressure flash tower 6. Bottoms from the tower, containing small amounts of propylene and acetone, pass through line 7 to low pressure flash tower 8 where most of the remaining solvent flashes off. The bottoms from the tower pass through line 9 to stripper 10 where the bottoms are stripped with steam entering through line 11 to correct the explosivity by removing all traces of solvent. The final stripped deasphalted oil product goes out to storage via line 12.
The asphalt phase leaves the bottom of the deasphalting tower 2 via line 14 to heater 36 where it is heated to about 550° to 600°F. at a pressure of 530 to 500 psig, and the bulk of the solvent is flashed off in high pressure flash tower 15. Bottoms from this tower are passed via line 16 to low pressure flash tower 17 where most of the remaining solvent is flashed off at near atmospheric pressure. The bottoms from the low pressure flash, containing only traces of solvent, proceed via line 18 to stripper 19 where they are stripped with steam entering via line 20. The stripped asphalt by-product leaves the unit via line 21.
Overhead solvent vapor from high pressure flash tower 6 leaves via line 23 and is combined with a vapor from high pressure flash tower 15 via line 24 and proceeds to air fin condenser 25 where it is condensed. Liquid solvent flows via line 26 into solvent surge drum 27 from which it is recycled via line 3 to the deasphalting tower.
Overhead solvent vapor from low pressure deasphalted oil flash tower 8 leaves via line 28 and a portion thereof is combined with vapor from low pressure asphalt flash tower 17 leaving via line 29 and proceeds to compressor 31 via line 30. The compressor discharge is combined with the overhead from high pressure flash towers 6 and 15 and proceeds via air fin condenser 25 to the solvent surge drum 27. If desired, the solvent vapor from the low pressure flash towers 8 and 17 may be sent to a compressor of a dewaxing plant (not shown) using also propylene-acetone solvent as dewaxing solvent, and the condensed liquid solvent make up returned from the dewaxing plant to the deasphalting solvent surge drum 27 via line 33. Incremental capacity in the dewaxing compressor is less costly than providing a separate compressor 31 in the deasphalter.
Overhead vapors from the deasphalted oil stripper 10 and asphalt stripper 19 are mixtures of stripper steam and traces of propylene and acetone. They leave, respectively, via lines 13 and 22 and may be disposed by burning in a process furnace of flare or the steam condensed and the trace amounts of propylene and acetone recovered in the facilities normally provided in a propylene-acetone dewaxing plant (comprising a decanting drum and a deketonizing tower).
For the above-described specific embodiment, it is estimated that a deasphalted oil of lubricating oil quality having a gravity of 19.9° API is obtainable in amounts of about 23 LV% of the residuum feed.
The following example is presented to further illustrate the invention.
EXAMPLE
Several experiments were conducted to determine the quality and yield of deasphalted oil obtained in propylene-acetone deasphalting relative to propane deasphalting of an Aramco vacuum residuum of 1.02 specific gravity. In the course of these experiments, a single stage batch bomb comprising 70 cubic centimeter volume was utilized. A propylene-acetone solvent/oil ratio of 8:1 (by volume) was utilized. The solvents comprised from 4 to 10 LV% acetone dissolved in the propylene. Comparative runs were made on the same Aramco vacuum residuum with propane solvent. Because of the small samples of deasphalted oil obtained in these experiments, the main criterion of product quality was the specific gravity of the deasphalted oil. The data are plotted in FIG. 2. Although the data are somewhat scattered, the results show that the propylene-acetone solvent gives a deasphalted oil yield at least equal to that of propane at a given quality, and possibly slightly higher. Another more qualitative test made was the asphaltene spot test, which is carried out by allowing a drop of hot deasphalted oil to flow onto a piece of filter paper. Asphaltenes present in the oil remain as a black spot at the point where the oil flows onto the paper, while the oil diffuses out through the paper. The size of the black spot is a qualitative measure of the asphaltene content of the oil. In these tests, deasphalted oil (DAO) samples from propylene-acetone deasphalting showed a lower asphaltene content than those from propane at a given yield. These data indicate that propylene-acetone not only allows more convenient operting conditions but also gives equal or better selectivity than the conventional propane deasphalting solvent.
In FIG. 3, the yields of deasphalted oil are plotted versus operating temperatures in the bomb for propylene containing, respectively, 4 LV% and 10 LV% acetone, as well as for propane alone and propylene alone. It may be seen that for this particular residuum feed, propylene containing only 4 LV% acetone gave the same deasphalted oil yield as propane at about 35°F. higher operating temperature. Propylene with 10 LV% acetone could give the same yield at about 100°F. higher operating temperature than propane. Thus, by controlling the acetone content of the solvent over a narrow range, a desired range of operating temperatures in the deasphalting tower can be achieved to accommodate minimum cost equipment in the plant. | An asphalt-containing mineral oil is deasphalted by contacting the oil at elevated temperature and elevated pressure with a deasphalting solvent comprising acetone and a three carbon atom containing-hydrocarbon, such as propylene, for a time sufficient to remove a substantial portion of the asphaltenes from the oil. Utilization of propylene-acetone as the deasphalting solvent permits utilization of higher treating tower temperatures, which may be desirable in those instances where air cooling of the solvent is provided. This process is particularly suited for the preparation of lubricating oils of low asphalt content. | 2 |
TECHNICAL FIELD
[0001] The present invention relates to a continuous digester system.
BACKGROUND AND SUMMARY OF THE INVENTION
[0002] In the pulping of comminuted cellulosic fibrous material, preferably but not excluded to wood chips, in a continuous digester the material is first treated to remove air bound in the cellulosic fibrous material. Typically, the cellulosic fibrous material is steamed to remove the material of air while simultaneously increasing the temperature to about 80-100° C. The steaming process will normally release the natural acidity of the wood material and the pH value in any drained steam condensate could easily reach 4-5. The steamed cellulosic fibrous material is thereafter slurried or impregnated in an impregnation or slurrying liquid with sufficient amount of chemicals, i.e. alkali and sulfidity in case of a kraft process.
[0003] The slurried cellulosic fibrous material is transported as slurry to the pressurized digester or impregnation vessel using high pressure pumps or a high pressure sluice feeder, and with a top separator arranged in the top of the pressurized impregnation vessel or in the top of the digester. The typical digester pressure is more than 5 bar (>0.5 MPa).
[0004] In conventional systems these steaming and slurrying systems have been installed as a system preceding the pressurized impregnation vessel or the pressurized digester vessel. The systems preceding the pressurized vessel have included expensive and energy consuming machines.
[0005] For a typical digester system, following systems and machines have been used;
Chip bins, Steaming vessels Slurrying chutes High pressure sluice feeder and/or high pressure pumps Impregnation vessels
[0011] Only to transport the slurried chips to the pressurized impregnation or digester vessel requires some 400 kW per ADT pulp produced. In a digester with a capacity of some 5000 ADT per day is thus required and a pumping system with an installed power available in the order of some 2 MW.
[0012] These systems and associated equipment and building structure are a large part of the total investment costs of a continuous digester system. Also, the operating costs of these systems and machines take a large part of the production costs for the pulp produced.
[0013] U.S. Pat. No. 3,303,088 disclosed already in mid 1960-ties a process using a single hydraulic digester, but with separate chip bin, steaming vessel, slurring tank and high pressure pumps ahead of the single hydraulic digester.
[0014] U.S. Pat. No. 5,635,025 disclosed an effort to patent the concept of a single vessel for the entire pre-treatment of chips, including the functions of a chip bin, a steaming vessel and the chip chute. This single pre-treatment vessel was located ahead of the transfer system including the high pressure sluice feeder. The corresponding Swedish application was abandoned as the concept with a common chip bin, steaming vessel and chip chute was anticipated by U.S. Pat. No. 3,532,594 from the mid 1960-ties.
[0015] A further improvement of the pre-treatment systems in a single impregnation vessel is disclosed in U.S. Pat. No. 7,381,302, where the impregnation vessel is held substantially at atmospheric pressure, and impregnation liquids at successively higher temperatures where added at successively increasing depth in the liquid volume established in the impregnation vessel. Still, the conventional high pressure sluice feeder was located after this impregnation vessel for feeding the impregnated chips to the pressurized digester. This type of atmospheric impregnation vessel, called the IMPBIN™ system guarantees that the chips are both steamed and impregnated at low temperature, resulting in easy cooking at low reject volumes and high pulp quality. The IMPBIN concept has been installed in a number of new digester systems throughout the world, in mills having capacities in the order of 3000-6000 ADT per day and has proven to be a success. One further advantage with the IMPBIN™ system is that this could be operated with “cold top” control, i.e. avoiding blow trough of steam, which reduce energy losses in gas handling systems needed as the amount of hot gases driven off from the chips and needing condensation is dramatically reduced.
[0016] The fait of the IMPBIN™ system has been challenged as the conventional approach has been using excessive steaming systems in chip bins and steaming vessels, and this excessive steaming has been perceived as a necessity in order to purge all air from chips and be able to establish a correct column movement of the chips in the digester. However, excessive steaming in pre-treatment establish a high chip temperature and in subsequent impregnation stages is the cooking chemicals consumed as they penetrate the chips, preventing cooking chemicals from penetrating into the core of the chips and as a consequence causing high reject volumes.
[0017] The IMPBIN™ system has in spite of this proven to be fully sufficient in establishing the necessary impregnation of the chips and a smooth column movement inside the digester.
[0018] The present invention is related to a further improvement and simplification of the digester system, where both the installation costs, i.e. investment costs, and operating costs are dramatically reduced.
[0019] In view of the success of the IMPBIN™ system, this general impregnation concept could be integrated with the actual digester, and a true “single vessel” digester system would be obtained. By this integration are several major advantages obtained, such as;
No need to classify the digester vessel as a pressure vessel; and Guaranteed low temperature impregnation, and No power losses in chip transfer to a pressurized digester; and No high pressure transfer systems, and No expensive top separator mounted at the top of the digester; and No need for chip bins, steaming vessels, and chip chutes etc.
[0026] In following parts are an atmospheric vessel referred to, and this implies a vessel not qualified as a pressure vessel and associated required testing and certification for a pressure vessel. According to European legislation a vessel must be classified as a pressure vessel if the pressure applied in the vessel is exceeding 0.5 bar. Thus, the atmospheric vessel could thus have a pressure established in the top substantially at atmospheric pressure, i.e. 0 bar (g), or a slight positive pressure of up to 0.5 bar(g) or slight negative pressure of down to −0.5 bar (g). The small deviation from a perfect atmospheric pressure is most often wanted for a controlled venting of the atmospheric phase in the top of the vessel as air may enter into the vessel with the raw material, i.e. chips, and a small leakage flow of malodorous gases could escape from the underlying chip volume. Preferably only an incremental positive pressure or negative pressure in the order of 0.1-0.2 bar is implemented, but still qualifying the vessel as an atmospheric vessel. The actual pressure established is controlled by the venting system, and parallel safety valves in form of reliable water-locks.
[0027] The establishment of a single vertically oriented atmospheric vessel enables a successive implementation of hotter treatment zones throughout the digester, and no need for a pressurized digester vessel is at hand, nor any separate pre-treatment systems, nor any high pressure transfer devices. The principle applied is similar to that one shown for the impregnation vessel IMPBIN™ as shown in U.S. Pat. No. 7,381,302, but now applied to the entire cooking process. The possible temperature profiling throughout the vessel is given by following table;
[0000]
T LIQ
(° C.)
Sat. P (kPa)
ΔH atm (meter)
ΔH +0.5 (meter)
ΔH −0.5 (meter)
105
120.8
>2
—
>7
110
143.3
>4.3
—
>9.3
115
169.1
>6.9
>1.9
>11.9
120
198.5
>9.8
>4.8
>14.8
125
232.1
>13.2
>8.2
>18.2
130
270.1
>17.0
>12
>23
135
313.0
>23.3
>18.3
>28.3
140
361.3
>26.1
>21.1
>31.1
145
415.4
>31.5
>26.5
Where;
T LIQ is the possible temperature of the liquid in vessel
Sat. P is the saturation pressure at the actual temperature
ΔH atm /ΔH +0.5 /ΔH −0.5 are minimum depths under liquid level at atmospheric/+0.5 bar/−0.5 bar pressures in vessel top.
[0028] According to the present invention a continuous digester system is used that has only a single generally vertically oriented atmospheric vessel having a top and a bottom for receiving comminuted cellulose fibrous raw material and within the vessel steaming, slurrying, impregnating and digesting the fibrous material before feeding out digested fibrous material from the bottom of the vessel.
[0029] In the inlet of the vessel is any suitable metering means installed for continuously feeding the fibrous raw material into the vessel from the top thereof. The metering means could be a conventional chip meter having a rotor with pockets of a predefined volume.
[0030] The vessel also has means for establishing a first level of fibrous raw material in the vessel. This level could be monitored by any suitable conventional chip level meter available in the field.
[0031] In order to control the atmospheric pressure in the top of the vessel also the vessel has means for establishing a pressure in the top of the vessel at substantially atmospheric pressure in the range of +0.5 to −0.5 bar(g). The vessel also has means for establishing a second level of liquid in the vessel. The second level is below the first level thus creating a fibrous raw material volume in a pile above a total liquid volume in the vessel.
[0032] This pile of raw material volume provides a triple function, as
condensation surfaces for any steam penetrating upwards, and a location for steaming action from underlying hotter liquids, purging air from chips, and a thrust force for the chips downward into the liquid volume.
[0036] The vessel also includes means for supplying impregnation liquids to a first end of a first upper volume of liquid in the total liquid volume held by the vessel, and also means for supplying cooking liquids to a first end of a second lower volume of liquid in the total liquid volume held by the vessel.
[0037] For heating to cooking temperature the vessel also has means for heating at least the cooking liquids in the second lower volume of liquid in the total liquid volume held by the vessel.
[0038] The first upper volume of liquid containing the impregnation zone has preferably a height of at least 17 meters, and preferably in the range of 17-40 meters, and more preferably in the range of 20-30 meters, which will enable typical cooking temperatures in the subsequent second lower volume of liquid containing the cooking zone.
[0039] The second lower volume of liquid containing the cooking zone has preferably a height of at least 30 meters, and more preferably at least 40-50 meters, which will enable sufficient retention time in the cooking zone at normal cooking temperatures, resulting in the required H-factor for successful delignification process.
[0040] The total height of the vessel, containing the impregnation and cooking zones is thus preferably at least 70 meters high, and preferably in the range of 75-90 meters, but should not result in a total height of liquid in the vessel exceeding 100 meters or a height of comminuted cellulose fibrous raw material exceeding 120 meters, as to high chip column may impede operation of the digester circulations due to compacting effects in the bottom of the digester. The total height should more preferably be 75-90 meters, but should not result in a total height of liquid in the vessel exceeding 100 meters or a height of comminuted cellulose fibrous raw material exceeding 120 meters. The required heights of liquids are controlled by controlling the net liquid flows entering and leaving the vessel in a conventional manner.
[0041] The vessel also has means for withdrawing spent cooking liquid from the end of the second lower volume of liquid. The vessel preferably also includes a final zone for cooling and washing the processed material. Finally, the vessel has means for continuously withdrawing slurry of digested fibrous raw material from adjacent the bottom of the vessel and feeding the slurry to subsequent post cooking systems.
[0042] Typically the digested fibrous raw material is sent to post cooking systems such as brown washing, screening, mechanical refining or any chemical pre-bleaching stages such as oxygen delignification, ozone bleaching or similar first pre-bleaching stages, all depending on the subsequent use of the digested pulp.
[0043] According to the present invention now described will the atmospheric vessel be the only handling vessel where the fibrous raw material is purged from air, impregnated and digested to an extent that the digested fibrous raw material is delignified and reaching a kappa number below 120.
[0044] High yield pulp typically used for liner is digested to a kappa number in the order of 60-90, but other pulps used for bleached grades of paper are typically digested to a kappa number in the order of 15-30.
[0045] In a preferred embodiment, the present invention has the means for heating the cooking liquids comprising a first liquid circulation conduit having a screen in the wall of the vessel in first end of the circulation conduit and an outlet pipe in the centre of the vessel at the second end of the circulation conduit, and a pump in the circulation conduit, wherein the liquid in the circulation conduit is passing a heater for heating the liquid circulated in the circulation conduit and wherein the first and second end of the first circulation conduit is located in the second lower volume of liquid.
[0046] In the most simplified form of the present invention all or the overwhelming part of the heating could be made to the cooking stage, and preceding stages could be heated by sending hot liquids from cooking stage in counter current flow upwards in the vessel. Either in a displacement function, where the hotter liquid is displacing the colder liquid, or using the heat in the liquids in heat exchangers.
[0047] In a further preferred embodiment of the present invention the means for supplying cooking liquids, preferably in form of white liquor, has a second liquid circulation conduit having a screen in the wall of the vessel in first end of the circulation conduit and an outlet pipe in the center of the vessel at the second end of the circulation conduit, and a pump in the circulation conduit, wherein the liquid in the circulation conduit receives fresh cooking chemicals to the liquid circulated in the circulation conduit and wherein the first and second end of the second circulation conduit are located in the second lower volume of liquid. Alternatively cooking liquids could be used such as white liquor, kraft black liquor, green liquor, or sulfite cooking liquor.
[0048] In the simplest embodiment of the present invention the first and second liquid circulation conduits used for heating and supplying cooking chemicals, could be one and the same liquid circulation conduit.
[0049] The means for heating the cooking liquids includes preferably a heater in the form of an indirect heat exchanger, where the heating medium used is steam. Indirect heating is preferred as the clean condensate obtained from any such indirect heaters could be used again in the clean steam production systems, and further dilution of cooking liquors with water is avoided.
[0050] In a yet a further preferred embodiment, the present invention has means for supplying impregnation liquids using as a liquid source at least partly a liquid withdrawn from the cooking zone in the second lower volume of liquid. Preferably a semi-spent cooking liquor is used, which still has a relatively high residual alkali content, well over 6 g/l and typically in the range of 6-12 g/l. Such semi-spent cooking liquor is also typically having a high sulfidity level which is advantageous for the impregnation process. The means for supplying impregnation liquids could also use as liquid source at least partly fresh cooking chemicals, preferably white liquor. This additional charge of fresh cooking liquors could be made to establish a sufficient neutralization of the wood acidity released from the original raw material, and establishment of sufficient level of alkali throughout the impregnation process, avoiding precipitation of lignin on the raw material if spent or semi-spent cooking liquor, i.e. black liquor, is used in impregnation.
[0051] In some vessels, depending on type of raw material and cooking process, it could also be preferable that the vessel has means for withdrawing spent impregnation liquids from the other end of the first upper volume of liquid. This reduces the level of dissolved lignin in the subsequent cooking stage, thus promoting further dissolution of lignin in the raw material.
[0052] An early withdrawal of impregnation liquid and condensate could also preferably be made at a position in the vessel close to the liquid surface and hence could a large part of the acidic condensate released from the steamed chips be withdrawn, reducing need for charging alkali for neutralization purposes. Such early withdrawal will also reduce harmful content of calcium, which metal is dissolved in acidic conditions and may cause scaling problems in the digester.
[0053] An early withdrawal of impregnation liquid at lower temperature also improves the overall heat economy as less mass volumes needs heating in subsequent stages.
[0054] One of the primary objects of the present invention is to provide for a simplified continuous digester, with a true single vessel system, having less investment costs as well as less operating costs, but still capable of producing pulp at commercial grades.
BRIEF DESCRIPTION OF THE DRAWINGS
[0055] FIG. 1 , shows a first embodiment of the single vessel digester system of the present invention;
[0056] FIG. 2 , shows a second embodiment of the single vessel digester system of the present invention;
[0057] FIG. 3 shows a third embodiment of the single vessel digester system of the present invention;
[0058] FIG. 4 shows a prior art digester system with an IMPBIN™ ahead of the digester, used for comparison; and
[0059] FIG. 5 shows an embodiment of the present invention replacing the system shown in FIG. 4 .
DETAILED DESCRIPTION
[0060] Instead of the conventional pre-treatment systems such as chip bins, steaming vessels, chip chutes, and high pressure transfer device as well as preceding impregnation vessel, a single atmospheric vessel 30 is provided according to the present invention.
[0061] The vessel, as shown in FIG. 1 , is a single generally vertically oriented atmospheric vessel having a top and a bottom for receiving comminuted cellulose fibrous raw material CH. Within the vessel 30 are all the stages in digestion of the raw material performed, such as steaming, slurrying, impregnating and digesting the fibrous material before feeding out digested fibrous material from the bottom 10 of the vessel 30 .
[0062] The raw material CH, preferably in the form of chips, is fed to the top of the vessel by any conventional conveyer belt system, and enters an inlet chute 1 having a conventional chip metering rotor 2 for continuously feeding the fibrous raw material into the vessel from the top thereof.
[0063] The chips that are fed into the vessel 30 are thus preferably unheated and untreated chips that normally have the same temperature as the ambient temperature.± 0 . 5 ° C.
[0064] The vessel includes conventional control for establishing a first level (CH LEV) of fibrous raw material in the vessel. This control could use a chip level meter and the in-feed of chips is controlled in order to maintain a predetermined minimum chip level (CH LEV). An alternative chip level control could use conventional gamma or radar radiation systems. In a simple control mode the speed of any conveyer belt system and the chip metering rotor 2 are increased if the chip level detected is decreasing below any set-point.
[0065] The pressure in the vessel can be adjusted as necessary through a control valve 13 arranged in a valve line 4 at the top of the vessel, possibly also in combination with control of the steam ST via input lines 5 . When atmospheric pressure is to be established, this valve line can open out directly to the atmosphere. It is preferable that a pressure is established at the level of atmospheric pressure, or a slight negative pressure by the outlet 4 of magnitude −0.5 bar (−50 kPa), or a slight positive pressure of magnitude up to 0.5 bar (50 kPa). A parallel safety valve (not shown) could also preferably be implemented, such as a water seal with a 1-3 dm height of water, to ensure the establishment of the intended atmospheric pressure.
[0066] Input of a ventilating flow, SW_AIR (sweep air), can be applied at the top as necessary, which ensures the removal of any excess air or gases present. When impregnation primarily easily cooked types of wood, such as eucalyptus and other annual plants, additional steaming can be essentially avoided. The steam that penetrates the chip pile from the underlying liquid volume is in many cases fully sufficient for effective steaming. Fresh steam is thus not added to the chip pile above the fluid level established in the vessel during normal steady-sate operation. The present invention can also be applied even if coniferous and deciduous wood (softwood and hardwood) are used as raw material, giving a markedly reduced need for using fresh steam ST.
[0067] When treating primarily wood raw material that is difficult to cook, coniferous and deciduous wood, and in operational cases with extremely low temperature of the chips, (in cold seasons), the chips that lie above the fluid level established by the impregnation fluid can be heated by the addition to the impregnation vessel of external steam such that a temperature of the chips of at least 20 degrees C. and up to 80 degrees C. at the most is obtained on the chips before the chips reach the fluid level that has been established by the impregnation fluid.
[0068] A maximum liquid level LIQ_LEV is established in the vessel under the chip level CH_LEV in the vessel. Control of the level occurs by adjusting the balance between the addition of liquids to the vessel and withdrawal of liquids from the vessel by any appropriate control system. The liquid level must thus be established such that it lies under the chip level CH_LEV in the vessel. The second level of liquid (LIQ LEV) in the vessel establish a total liquid volume (Z 1 & Z 2 ) in the vessel.
[0069] The level CH_LEV of the chips above the level LIQ_LEV of the liquid, i.e, the distance marked H 0 in figure, is preferably at least 2 meters and more preferably at least 5 meters when impregnating eucalyptus. In the case of wood raw material of lower density, for example, softwood, which has a density that is up to 30% lower, a corresponding increase in the height of the pile of chips over the surface of the fluid is established. This height is important in order to provide an optimal chip column movement in the vessel.
[0070] In order to establish appropriate conditions for the first impregnation stage impregnation liquids are supplied by a central pipe CP 1 to a first end, in FIG. 1 the upper end, of a first upper volume of liquid Z 1 in the total liquid volume at a position preferably slightly below the liquid level, i.e. the distance marked H 1 in figure. Here is the impregnation liquids supplied via pump P 3 and central pipe CP 1 as a mixture of semi spent cooking liquor withdrawn from screen S 3 in the cooking zone, and preferably with addition liquids in form of fresh cooking chemicals WL S and possible dilution liquid LIQ 1 , the latter preferably alkaline filtrates from subsequent washing or bleaching stages. The supply of impregnation liquids thus uses as a liquid source at least partly a liquid withdrawn from the cooking zone in the second lower volume of liquid. The supply of impregnation liquids preferably also uses as liquid source at least partly fresh cooking chemicals, preferably white liquor. The impregnation stage is thus established in a concurrent impregnation stage in the upper liquid volume Z 1 down to the screens S 2 .
[0071] As the hot semi-spent cooking liquor is added to the chips ascending down from the pile, a mixed temperature is obtained lying between that of the chips and that of the semi-spent cooking liquor. The temperature established in the liquid surface is preferably close to or slightly above 100° C., such that this liquid may provide a small release of steam upwards into the ascending chip pile, where it condenses. In an alternative embodiment the central pipe CP 1 could end slightly above the liquid surface, such that the impregnation liquid will flash off steam at the very release into chip pile in the vessel.
[0072] The atmospheric conditions in the top of the vessel will guarantee that no excessive temperature is established in this first upper part of the impregnation zone Z 1 , as steam would flash upwards against the descending chip pile.
[0073] In order to establish appropriate chemical conditions for the subsequent cooking stage cooking liquids are supplied to a first end, in FIG. 1 the upper end, of a second lower volume of liquid Z 2 in the total liquid volume. Here is the liquid a mixture of fresh cooking chemicals WL M , added to a circulation with screen S 2 , pump P 2 and a central pipe CP 2 ending above screen S 2 .
[0074] In order to establish appropriate temperature conditions for the subsequent cooking stage in the second lower volume Z 2 of liquid in the total liquid volume heating is performed by heater HE in the same first liquid circulation, having a screen S 2 in the wall of the vessel in first end of the first circulation conduit and an outlet pipe CP 2 in the center of the vessel at the second end of the circulation conduit, and a pump P 2 in the circulation conduit, wherein the liquid in the circulation conduit is passing the heater HE for heating the liquid circulated in the circulation conduit.
[0075] As shown in the table in preceding part of the description a cooking temperature of 140° C. could easily be implemented if this circulation, i.e. the outlet of central pipe CP 2 , ends up more than 26 meters below the second liquid level if pressure in vessel top is held at 0 bar (g), i.e. at the total distance H 1 +H 2 in the figure.
[0076] The means for heating the cooking liquids includes preferably a heater in form of an indirect heat exchanger, where the heating medium used is steam. This indirect heater is also suitable for cooling purposes in case of unplanned stops in the operations, as the indirect heater instead could use cold water instead of steam. By this forced cooling could heat merger upwards trough the chip column be prevented.
[0077] The first and second end, i.e. screen S 2 and central pipe CP 2 respectively, of the first circulation conduit is located in the second lower volume of liquid Z 2 , and in FIG. 2 at the very start of this lower liquid volume Z 2 . The cooking stage is thus established as a concurrent cooking stage in the lower liquid volume Z 2 down to the screens S 3 and S 4 .
[0078] When the cooking stage is ended at screens S 4 spent cooking liquor, i.e. black liquor, is withdrawn from the other end, in FIG. 1 the lower end, of the second lower volume Z 2 via screens S 4 . The withdrawn spent cooking liquor could be sent directly or indirectly to recovery REC, preferably via recovery of the heat energy in the liquors by heat exchange against other liquids or flashing off steam in a flash tank and using the flashed steam in heat exchangers or chip steaming ST.
[0079] In FIG. 1 some wash or displacement liquid LIQ 2 is also added via a central pipe CP 3 in order to improve displacement and withdrawal of the spent cooking liquor. This kind of wash or displacement liquid LIQ 2 could also be added via conventional vertical and/or horizontal supply nozzles (not shown) located in the lower cupped gable of the vessel below the screens S 4 .
[0080] Finally, in the bottom of the vessel are installed means for continuously withdrawing slurry of digested fibrous raw material from adjacent the bottom of the vessel and feeding the slurry to a subsequent post cooking systems BW via line 11 . The withdrawal and feeding means is typically of a conventional outlet design, with an outlet bucket 10 and associated bottom scraper (the latter not shown) and where dilution liquid LIQ 3 is added to the outlet bucket in order to facilitate feed out of the digested raw material. Dilution liquid LIQ 3 could also in part be liquid supplied via conventional vertical and/or horizontal supply nozzles (not shown) located in the lower cupped gable of the vessel, or integrated with the bottom scraper.
[0081] By the embodiment shown in FIG. 1 the atmospheric vessel 30 is the only handling vessel where the fibrous raw material is impregnated and digested to an extent that the digested fibrous raw material is reaching a kappa number below 120.
[0082] In FIG. 2 is an alternative embodiment of the invention shown having the same features as shown in FIG. 1 , but for an additional withdrawal screen S 1 in the lower part of the impregnation zone Z 1 . Here the vessel has means for withdrawing spent impregnation liquids from the other end of the first upper volume of liquid, which in FIG. 2 is the lower end of the first upper volume. This withdrawal screen is preferably located at a position in the vessel that lies above the position for addition of cooking liquid via central pipe CP 2 , and a displacement flow of the spent impregnation liquid towards screen S 1 is established, in the lower part of the fluid-filled zone Z 1 in the vessel 30 .
[0083] In FIG. 3 yet another alternative embodiment of the present invention is shown that have the same features as shown in FIG. 1 , but for;
separate liquid circulations for adding cooking chemicals, i.e. S 2 ′—P 2 ′—CP 2 ′; separate liquid circulations for heating, i.e. S 2 ″—P 2 ″—HE—CP 2 ″; and early withdrawal of impregnation liquid and condensate via screen S 5 and pump P 5 .
[0087] In FIG. 3 the means for supplying cooking liquids, preferably in form of white liquor, has a second liquid circulation conduit having a screen S 2 ′ in the wall of the vessel in first end of the circulation conduit and an outlet pipe CP 2 ′ in the center of the vessel at the second end of the circulation conduit, and a pump P 2 ′ in the circulation conduit. The liquid in the circulation conduit is passing a mixer for adding fresh cooking chemicals WL M to the liquid circulated in the circulation conduit and wherein the first and second end of the second circulation conduit is located in the second lower volume of liquid Z 2 , which in FIG. 3 is the upper end of the lower volume of liquid.
[0088] The early withdrawal of impregnation liquid and condensate is made via screen S 5 located close to the liquid surface and pump P 5 . By this location of the screen S 5 could a large part of the acidic condensate released from the steamed chips be withdrawn, reducing need for charging alkali only for neutralization purposes.
COMPARATIVE EXAMPLES
[0089] In FIG. 4 a state of the art digester system is shown with an IMPBIN™ located ahead of the digester. In FIG. 5 a comparative example of the present invention is shown applied for the same process. In both examples shown in FIG. 4 and 5 the screens with similar functions are given similar reference numbers, such as S 5 for the early withdrawal screen close to the liquid surface, S 3 for the withdrawal of semi-spent cooking liquor, and S 4 for the final spent cooking liquor drawn from the digester and subsequently sent to recovery, together with liquor from the early withdrawal from S 5 . The figures also show a fiber filter FF in the stream of spent liquors, which sifts out fiber residues in the liquor streams and circulates these fiber residues back to appropriate positions in the digester system. In FIG. 4 is the conventional high-pressure sluice feeder 41 is also in the transfer system from the low pressure part, i.e. the IMPBIN 20, and the digester.
[0090] The system shown in FIG. 4 is a typical implementation of the Compact Cooking™ G2 Process for cooking Eucalyptus (Hardwood) pulp, having a production capacity of 1500 ADMT/day.
[0091] The IMPBIN™ 20 has a diameter of 5.2 meters and a height of 40.5 meters, reaching a total volume of 550 m 3 . The digester 40 has a diameter of 7.4 meters and a height of 49 meters, reaching a total volume of 1950 m 3 . The total volume in the system thus, i.e. IMPBIN™ 20 plus digester 40 , amounts to 2500 m 3 .
[0092] The total installed available power amounts to 1950 kW, and the power consumption per ton of pulp amounts to 21.8 kW/ADT. This system needs a total heat exchanger area of 600 m 2 and the MP (Medium Pressure) steam consumption amounts to 400 kg/ADT. The process needs a total alkali charge of 18% EA.
[0093] The system shown in FIG. 5 is an implementation of the present invention using the principles of the Compact Cooking™ G2 Process for cooking Eucalyptus (Hardwood) pulp and has the same production capacity of 1500 ADMT/day at a total alkali charge of 18% EA. The single vessel system according to the present invention has a digester having a diameter of 7.4 meters and a height of 82 meters, reaching a total volume of 2700 m 3 .
[0094] However, the total installed available power amounts to only 1400 kW, and the power consumption per ton of pulp amounts to only 15.7 kW/ADT, which corresponds to savings in the order of 28%. The large part of the savings is obtained from lack of pumps for pressurizing and feeding the impregnated slurry to the digester top (i.e. sluice feeder and/or pumps), lack of any top separator and lack of any bottom scraper in IMPBIN. The only increase in power consumption is the extended height of operation of the existing chip conveyer, which additional power requirement, is negligible in comparison to the power consumption of deleted machines. This system needs a total heat exchanger area of 650 m 2 and the MP (Medium Pressure) steam consumption amounts to the same order of 400 kg/ADT.
[0095] The difference in heating in the systems shown is that the cooking temperature in the system shown in FIG. 4 is established largely in part by direct steam heating in digester top, resulting in that clean steam condensate is diluting the cooking chemicals and putting extra capacity requirement in the evaporation process. In the system shown in FIG. 5 cooking temperature is reached only by using liquor circulations and indirect steam heating, which enables a recovery of the clean steam condensate, thus decreasing net thermal energy usage. In both systems it is possible to mix different liquors, i.e. total liquor flows or parts thereof, to reach any desired temperature profiling and heat economy.
[0096] It will thus be seen that according to the present invention a simplified digester system is provided which would require far less investment costs and lower operation costs. The operating costs are of ever increasing interest in order to save energy and obtain an environmental friendly system.
[0097] The embodiments shown are principle designs utilizing the inventive concept of the present invention, and it will be apparent to those skilled in digester operations that many modifications can be made within the scope of the present invention.
[0098] As examples of modifications are changes of the impregnation or digester zones or both to counter current operation, in parts or the entire zone. More circulations could also be implemented in order to modify the concentration of cooking chemicals or amount of dissolved lignin or total dissolved organic material or dissolved amount of metals such as calcium, which need for additional circulations is depending upon the type of cellulose fibrous raw material fed to the vessel.
[0099] While the present invention has been described in accordance with preferred compositions and embodiments, it is to be understood that certain substitutions and alterations may be made thereto without departing from the spirit and scope of the following claims. | In a continuous digester system the digester system is greatly simplified by using a single vertical atmospheric vessel, replacing the conventional chip bin, steaming vessel, chip chute, high pressure pumping or sluice feeders, impregnation vessels and top separator. Chips are simply fed to the top of the atmospheric vessel, and a chip level is established in the vessel. Treatment liquids are added to the vessel such that a total liquid volume (Z 1 +Z 2 ) with a liquid level (LIQ LEV) is established under the chip level (CH LEV). Impregnation stage and subsequent cooking stages are implemented in the atmospheric vessel at successively increasing temperature and depths into the total liquid volume, thus preventing boiling in the stages and preferably reducing steam blow trough of the chip surface in the top of the vessel. | 3 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of Korean Patent Application No. 10-2006-0065596, filed on Jul. 12, 2006 in the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a dish washing machine. More particularly, to a dish washing machine capable of improving spatial utilization of a washing tub through the enlargement of the washing tub.
[0004] 2. Description of the Related Art
[0005] A conventional dish washing machine is a machine that automatically washes dishes using cold water or hot water. A conventional dish washing machine includes a machine body, a washing tub formed in the machine body, baskets mounted in the washing tub, and main and sub nozzles mounted at the upper part, the middle part, and the lower part of the washing tub to inject wash water, which is disclosed in Korean Unexamined Patent Publication No. 2005-54700.
[0006] A sump is mounted at the bottom of the washing tub to receive wash water and pump the wash water to the respective nozzles. The sump includes a sump housing forming the external appearance of the sump, a heater mounted in the sump housing, a washing impeller disposed in the sump housing to pump wash water, a channel to guide the wash water pumped from the washing impeller to the respective nozzles, a channel control valve mounted in the channel to control the flow of wash water, and a pump motor mounted at the outside of the sump housing to drive the washing impeller.
[0007] In the conventional dish washing machine, however, the heater is mounted in the sump housing such that the height of the sump housing is increased. Furthermore, the pump motor is mounted at the bottom of the sump housing such that the height of an assembly of the sump and the pump motor is increased.
[0008] Consequently, a ratio of the height of the sump and pump motor assembly to the height of the machine body of the dish washing machine is increased, and therefore, the space of the washing tub is relatively reduced.
SUMMARY OF THE INVENTION
[0009] Accordingly, it is an aspect of the present invention to provide a dish washing machine capable of reducing the height of a sump and pump motor assembly and, at the same time, enlarging the space of a washing tub, thereby improving spatial utilization of the washing tub.
[0010] Additional aspects and/or advantages of the invention will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the invention.
[0011] The foregoing and/or other aspects of the present invention are achieved by providing a dish washing machine including a washing tub, a sump mounted in the washing tub to receive and pump wash water, a sump housing forming an external appearance of the sump, a washing impeller to pump wash water from the sump housing, a drainage channel disposed at an inner edge of the sump housing, a pump motor surrounded by the drainage pump to drive the washing impeller, and a pump motor receiving part to receive the pump motor, the pump motor receiving part protruding above the drainage channel.
[0012] According to an aspect of the present invention, the pump motor receiving part is formed at a bottom of the sump housing, and the pump motor receiving part includes an open lower part, through which the pump motor is inserted into and mounted to the pump motor receiving part.
[0013] The pump motor includes screw insertion holes formed in an edge thereof such that screws are inserted through the screw insertion holes, and the pump motor receiving part includes screw coupling protrusions protruding therefrom such that the screws inserted through the screw insertion holes are coupled to the screw coupling protrusions.
[0014] The dish washing machine further includes a heater disposed in a shape surrounding the sump.
[0015] The dish washing machine further includes a heater receiving groove formed at the bottom of the washing tub in a shape surrounding the sump such that the heater is received in the heater receiving groove, and a heater cover disposed at the heater receiving groove to cover the heater, the heater cover having a plurality of through-holes, through which wash water contacts the heater.
[0016] The dish washing machine further includes main nozzles disposed in the washing tub to constantly inject wash water at the time of washing dishes, a sub nozzle disposed in the washing tub to selectively inject wash water at the time of washing dishes, a main channel disposed in the sump, the main channel communicating with the main nozzles, a sub channel disposed in the sump while being separated from the main channel, the sub channel communicating with the sub nozzle, and a channel control valve disposed in the sub channel to selectively intermit the flow of wash water flowing to the sub nozzle.
[0017] The dish washing machine further includes an impeller casing to receive the washing impeller, and an impeller casing cover disposed on the impeller casing to cover the impeller casing, the impeller casing cover having a guide channel communicating with the sub channel to guide the wash water to the sub nozzle.
[0018] The impeller casing includes a filth chamber communicating with the main channel to collect dirt contained in wash water.
[0019] The filth chamber includes an open upper part, and the dish washing machine further includes a mesh filter disposed at the open upper part of the filth chamber to separate dirt from wash water such that only the wash water overflows from the filth chamber.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] These and/or other aspects and advantages of the invention will become apparent and more readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
[0021] FIG. 1 is a side sectional view of a dish washing machine according to an embodiment of the present invention;
[0022] FIG. 2 is a perspective view illustrating an interior of a machine body of the dish washing machine according to an embodiment of the present invention;
[0023] FIG. 3 is an exploded perspective view of a sump according to an embodiment of the present invention;
[0024] FIG. 4 is an exploded perspective view of a sump housing and a pump motor according to an embodiment of the present invention;
[0025] FIGS. 5 and 9 are assembled views of the sump housing and the pump motor according to an embodiment of the present invention;
[0026] FIG. 6 is a perspective view illustrating the upper part of the sump according to an embodiment of the present invention;
[0027] FIG. 7 is a perspective view illustrating the upper part of the sump housing according to an embodiment of the present invention; and
[0028] FIG. 8 is an assembled perspective view of the sump housing and an impeller casing according to an embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0029] Reference will now be made in detail to the embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout. The embodiments are described below to explain the present invention by referring to the figures.
[0030] As shown in FIG. 1 , the dish washing machine comprises a machine body 1 forming an external appearance of the dish washing machine, a washing tub 2 disposed in the machine body 1 , and a rack 5 fixed to a sidewall of the washing tub 2 . The rack 5 comprises an upper rack 5 a and a lower rack 5 b , by which an upper basket 7 a and a lower basket 7 b are supported, respectively. Dishes are placed in the upper basket 7 a and the lower basket 7 b.
[0031] At the upper part, the middle part, and the lower part of the washing tub 2 are mounted main nozzles 10 a and 10 b and a sub nozzle 10 c , respectively, to inject wash water. The wash water injected through the nozzles 10 a , 10 b and 10 c is directed toward the baskets 7 a and 7 b . The nozzles 10 a , 10 b and 10 c are rotated by the injection pressure of the wash water injected through the nozzles 10 a , 10 b and 10 c . The wash water injected through the nozzles 10 a , 10 b , and 10 c collides with the dishes in the baskets 7 a and 7 b to strongly wash the dishes.
[0032] A sump 13 is mounted at the bottom of the washing tub 2 to receive, pump, and supply wash water to the respective nozzles.
[0033] A feeding pipe 11 is disposed at a rear of the washing tub 2 to supply wash water to the main nozzles 10 a and 10 b . The lower end of the feeding pipe 11 is connected to the sump 13 . Consequently, the wash water flows to the main nozzles 10 a and 10 b through the feeding pipe 11 due to strong pumping pressure of the sump 13 .
[0034] The sub nozzle 10 c is directly connected with an upper center part of the sump 13 . Consequently, some of the wash water is injected through the sub nozzle 10 c to wash dishes placed in the lower basket 7 b adjacent to the sub nozzle 10 c.
[0035] When the quantity of dishes is relatively small, the dishes may be placed only in the upper basket 7 a , and wash water be injected only through the main nozzles 10 a and 10 b while the wash water is not injected through the sub nozzle 10 c , and vice versa.
[0036] The sump 13 comprises a sump housing 16 forming the external appearance of the sump, a sump cover 19 to cover the sump housing 16 , a washing impeller 21 disposed in the sump housing 16 , an impeller casing 24 to which the washing impeller 21 is mounted, and an impeller casing cover 27 disposed on the impeller casing 24 .
[0037] A pump motor 30 is mounted at the bottom of the sump housing 16 to drive the washing impeller 21 . Specifically, a pump motor receiving part 300 is disposed at the bottom of the sump housing 16 such that the pump motor 30 is received in the pump motor receiving part 300 .
[0038] The pump motor 30 is securely coupled with the sump housing 16 by means of screws. However, the present invention is not limited hereto and other coupling members may used to accomplish the coupling between the pump motor 30 and the sump housing 16 .
[0039] As shown in the drawings, the lower part of the sump 13 overlaps with the upper part of the pump motor 30 by a predetermined height.
[0040] Thus, a height of an assembly of the sump 13 and the pump motor 30 is reduced by the overlap. The decrease of the height of the sump and pump motor assembly leads to the relative increase of the vertical height of the washing tub 2 .
[0041] A drainage pump 33 is mounted at the side of the sump housing 16 ito discharge wash water and dirt in the sump 13 out of the dish washing machine.
[0042] A heater 36 is mounted at an edge of the sump 13 to heat wash water. At the bottom of the washing tub 2 is formed a heater receiving groove 39 , which extends along the edge of the sump 13 . The heater 36 is received in the heater receiving groove 39 .
[0043] After the heater 36 is received in the heater receiving groove 39 , the heater 36 is covered by a heater cover 42 to prevent the heater 36 from being exposed to the outside.
[0044] In FIG. 2 , an inlet port 3 is formed through one side of the washing tub 2 such that wash water can be introduced into the washing tub 2 through the inlet port 3 . Wash water introduced through the inlet port 3 falls to the bottom of the washing tub 2 and is introduced into the sump 13 .
[0045] The sub nozzle 10 c is rotatably coupled to a center of the sump 13 . The feeding pipe 11 is connected with a rear end of the sump 13 such that wash water is guided to the main nozzles 10 a and 10 b through the feeding pipe 11 .
[0046] The sump cover 19 is mounted on the sump 13 . Inlet holes 19 a are formed along an edge of the sump cover 19 and are arranged in regular intervals. Consequently, wash water is introduced into the sump 13 through the inlet holes 19 a.
[0047] On the sump cover 19 is mounted a filter cover 20 . A mesh filter 20 a is mounted to the filter cover 20 to prevent dirt collected in a filth chamber (to be described later), from overflowing from the filth chamber and to allow only wash water to flow out of the filth chamber.
[0048] The heater 36 is mounted at an edge of the sump 13 in the shape of a ring. The heater cover 42 is mounted on the heater 13 . In the heater cover 42 comprises a plurality of through-holes 42 a , through which wash water flows to the heater 36 . The wash water is heated by the heater 36 , and is then introduced into the sump 13 .
[0049] FIG. 3 illustrates the structure of the sump 13 , according to an embodiment of the present invention. At one side of the sump housing 16 is disposed a pump fixing part 50 , to which the drainage pump 33 is fixed. To one side of the pump fixing part 50 is connected a drainage pipe 51 , through which wash water and filth are discharged.
[0050] The pump motor 30 is mounted at the bottom of the sump housing 16 , specifically, to the pump motor receiving part 300 . Around the pump motor receiving part 300 is disposed a drainage channel 160 , which surrounds the pump motor receiving part 300 . The drainage channel 160 comprise first, second, and third drainage channels 161 , 162 , and 163 surrounding the pump motor receiving part 300 . The first and second drainage channels 161 and 162 communicate with each other through the third drainage channel 163 , which serves to guide wash water and filth to the drainage pump 33 .
[0051] The top surface of the pump motor receiving part 300 is located above the bottom surface of the drainage channel 160 .
[0052] Consequently, the pump motor 30 is received in the pump motor receiving part 300 without reduction of the wash water and filth discharge operation through the drainage channel 160 , and therefore, the height of the sump and pump motor assembly is considerably reduced.
[0053] A rotary shaft 30 a of the pump motor 30 extends through the pump motor receiving part 300 . At the pump motor receiving part 300 is disposed a sealing member 53 , which surrounds the rotary shaft 30 a to prevent wash water from leaking to the pump motor 30 .
[0054] The impeller casing 24 is disposed on the sump housing 16 . A communication hole 24 a is formed in a center of the impeller casing 24 and communicates with the sump housing 16 . Around the communication hole 24 a is disposed an impeller receiving part 24 b , in which the washing impeller 21 is received.
[0055] The washing impeller 21 is coupled with the rotary shaft 30 a of the pump motor 30 such that the washing impeller 21 is rotated to pump wash water introduced into the sump housing 16 upward.
[0056] The impeller casing 24 comprises a main channel 24 c and a sub channel 24 d , which diverge from the impeller receiving part 24 b . The main channel 24 c guides wash water to the main nozzles 10 a and 10 b (see FIG. 1 ). The sub channel 24 d guides wash water to the sub nozzle 10 c (see FIG. 1 ).
[0057] The main channel 24 c serves as a primary channel to guide the flow of wash water in the sump 13 . Consequently, wash water constantly passes along the main channel 24 c during a washing operation of the dish washing machine.
[0058] The main channel 24 c extends from the impeller receiving part 24 a in a shape of a curve, to prevent drop of the injection pressure of wash water flowing along the main channel 24 c.
[0059] When the main channel 24 c is sharply bent, wash water collides with the sharply bent part of the main channel 24 c with the result that kinetic energy of the wash water is lost. Consequently, the main channel 24 c is formed in the shape of a curve to minimize the loss of kinetic energy.
[0060] A channel control valve 25 is rotatably mounted in the sub channel 24 d to intermit the flow of wash water to the sub channel 24 d . When the quantity of dishes to be washed is small, the sub channel 24 d is closed by the channel control valve 25 such that wash water can flow only to the main channel 24 c.
[0061] Wash water flowing along the main channel 24 c is injected through the main nozzles 10 a and 10 b (see FIG. 1 ) to wash dishes. Consequently, the amount of wash water used is reduced when the quantity of dishes to be washed is small.
[0062] A filth chamber 24 e is formed beside the main channel 24 c to collect dirt introduced into the main channel 24 c together with wash water. A drainage connection pipe 26 is mounted adjacent to the inlet of the filth chamber 24 e , which is connected to the drainage pump 33 . When the drainage pump 33 is operated, dirt collected in the filth chamber 24 e is discharged to the drainage pipe 51 through the drainage connection pipe 26 .
[0063] According to an embodiment of the present invention, the main channel 24 c , the sub channel 24 d , and the filth chamber 24 e are formed at the impeller casing 24 .
[0064] The impeller casing cover 27 is disposed on the impeller casing 24 . The impeller casing cover 27 comprises a guide channel 27 a , which communicates with the sub channel 24 d . The guide channel 27 a extends from an edge of the impeller casing cover 27 to the center of the impeller casing cover 27 in a shape of a curve.
[0065] Consequently, when the sub channel 24 d is opened by the channel control valve 25 , wash water pumped by the washing impeller 21 passes through the channel control valve 25 , and flows along the sub channel 24 d . At this time, the wash water is guided to the sub nozzle 10 c (see FIG. 1 ) along the guide channel 27 a , which communicates with the sub channel 24 d , and is then injected through the sub nozzle 10 c.
[0066] The sump cover 19 is disposed on the impeller casing cover 27 . In the center of the sump cover 19 is formed an engaging hole 19 c , in which the lower end of the sub nozzle 10 c (see FIG. 1 ) is engaged. The inlet holes 19 a , through which wash water is introduced, are formed along the edge of the sump cover 19 such that the inlet holes 19 a are arranged in regular intervals.
[0067] In the sump cover 19 is formed a connection hole 19 b , through which the feeding pipe 11 (see FIG. 2 ) extends to the main channel 24 c.
[0068] The filter cover 20 is disposed on the sump cover 19 . The mesh filter 20 a is mounted to the filter cover 20 . The mesh filter 20 a covers an upper surface of the filth chamber 24 e to prevent dirt collected in the filth chamber 24 e from passing through the mesh filter 20 a together with wash water.
[0069] Specifically, when dirt and wash water are introduced into the filth chamber 24 e , the wash water passes through the mesh filter 20 a . However, the dirt is filtered by the mesh filter 20 a and is left in the filth chamber 24 e.
[0070] The wash water separated from the dirt is introduced into the sump 13 through the inlet holes 19 a , and is then continuously circulated through the above-described course.
[0071] The heater 36 (see FIG. 2 ) and the heater cover 42 are disposed at the edge of the sump 13 such that the heater 36 and the heater cover 42 surround the edge of the sump 13 .
[0072] As shown in FIG. 4 , the pump motor receiving part 300 is disposed in the center of the sump housing 16 . Screw coupling protrusions 16 a are formed at the pump motor receiving part 300 and protrude downward from the pump motor receiving part 300 .
[0073] The first, second, and third drainage channels 161 , 162 , and 163 are formed around the pump motor receiving part 300 . The drainage channel 160 is disposed below the pump motor receiving part 300 .
[0074] Screw insertions holes 30 a are formed in an edge of the pump motor 30 corresponding to the screw coupling protrusions 16 a.
[0075] When screws 31 are inserted through the screw insertion holes 30 a and coupled with the screw coupling protrusions 16 a , as shown in FIG. 5 , the pump motor 30 is surrounded by the drainage channels 161 , 162 , and 163 while the pump motor 30 is received in the pump motor receiving part 300 .
[0076] The pump fixing part 50 is disposed at one side of the sump housing 16 . The drainage pump 33 is fixed to the pump fixing part 50 . At the sump housing 16 is mounted a sensor 170 to detect the turbidity and the water level of wash water received in the sump housing 16 . The drainage pump 33 discharges wash water and dirt out of the sump housing 16 based on information detected by the sensor 60 .
[0077] At the bottom of the sump housing 16 is mounted a valve driving motor 62 to drive the channel control valve (not shown) such that the sub channel (not shown) can be opened or closed by the channel control valve.
[0078] As shown in FIG. 6 , wash water is heated by the heater 36 , and is then introduced into the sump 13 . As shown in FIG. 7 , the wash water received in the sump housing 16 is pumped upward to the impeller casing 24 as the washing impeller 21 mounted to the rotary shaft is rotated.
[0079] The pumped wash water is moved from the impeller receiving part 24 b to the main channel 24 c (in the direction indicated by arrow ‘A’) and the sub channel 24 d (in the direction indicated by arrow ‘B’) due to the rotating force of the washing impeller. When the sub channel 24 d is closed by the channel control valve 25 , the wash water is moved only to the main channel 24 c.
[0080] The wash water flowing along the main channel 24 c in the direction indicated by arrow ‘A’ is raised through the feeding pipe 11 (see FIG. 2 ), due to the strong pressure of the washing impeller 21 , and then reaches the main nozzles 10 a and 10 b (see FIG. 1 ).
[0081] When the quantity of dishes to be washed is small, and therefore, it is necessary to operate only the main nozzles 10 a and 10 b (see FIG. 1 ), the sub channel 24 d is closed by the channel control valve 25 . As a result, wash water flows along only the main channel 24 c . The wash water flowing along the main channel 24 c reaches the main nozzles 10 a and 10 b through the feeding pipe 11 , and is then injected through the main nozzles 10 a and 10 b.
[0082] When the quantity of dishes to be washed is large, and therefore, it is necessary to operate the sub nozzle 10 c (see FIG. 1 ) as well as the main nozzles 10 a and 10 b , the sub channel 24 d is opened by the channel control valve 25 . As a result, wash water flows in the direction indicated by arrow B. Subsequently, the wash water reaches the sub nozzle 10 c , and is then injected through the sub nozzle 10 c.
[0083] The filth chamber 24 e is connected to the main channel 24 c . Consequently, dirt mixed with some wash water is moved (in the direction indicated by arrow ‘C’), and is then collected in the filth chamber 24 e.
[0084] The drainage connection pipe 26 connected to the drainage pump 33 is adjacent to the inlet of the filth chamber 24 e . Consequently, the dirt collected in the filth chamber 24 e is discharged to the outside (in the direction indicated by arrow ‘D’) during an operation of the drainage pump 33 .
[0085] As shown in FIG. 8 , the guide channel 27 a is formed at the impeller casing cover 27 disposed on the impeller casing 24 such that the guide channel 27 a communicates with the sub channel 24 d (see FIG. 7 )
[0086] When the washing impeller 21 (see FIG. 7 ) is operated in the state that the sub channel 24 d is opened by the channel control valve 25 (see FIG. 7 ), wash water also flows along the sub channel 24 d . The wash water flowing along the sub channel 24 d is guided to the center of the impeller casing cover 27 along the guide channel 27 a , is moved to the sub nozzle 10 c (see FIG. 1 ) in the direction indicated by arrow ‘A’, and is injected through the sub nozzle 10 c.
[0087] Arrow ‘B’ indicates the flow direction of the wash water flowing to the main nozzles 10 a and 10 b (see FIG. 1 ).
[0088] As shown in FIG. 9 , wash water and dirt introduced into the filth chamber 24 e (see FIG. 7 ) along the main channel 24 c (see FIG. 7 ) are pushed toward the mesh filter 20 a due to the pressure of subsequent wash water. However, the dirt does not pass through the mesh filter 20 a . Consequently, the dirt is left in the filth chamber 24 e (see FIG. 7 ). Only the wash water passes through the mesh filter 20 a in the direction indicated by arrow ‘E’, and is then discharged out of the sump 13 .
[0089] The discharged wash water is reintroduced into the sump 13 , and flows inside the sump 13 to perform the washing operation as previously described.
[0090] As apparent from the above description, according to an embodiment of the present invention, the pump motor is mounted to the sump housing while the pump motor is received in the sump housing. Consequently, a height of the sump and pump motor assembly is reduced by the height of the pump motor received in the sump housing, and therefore, a ratio of the volume of the washing tub to the volume of the machine body is increased.
[0091] Although a few embodiments of the present invention have been shown and described, it would be appreciated by those skilled in the art that changes may be made in this embodiment without departing from the principles and spirit of the invention, the scope of which is defined in the claims and their equivalents. | A dish washing machine capable of improving spatial utilization of a washing tub through the enlargement of the washing tub. The dish washing machine includes a washing tub, a sump mounted in the washing tub to receive and pump wash water, a sump housing forming an external appearance of the sump, a washing impeller to pump wash water from the sump housing, a drainage channel disposed at an inner edge of the sump housing, a pump motor surrounded by the drainage pump to drive the washing impeller, and a pump motor receiving part to receive the pump motor. The pump motor receiving part protrudes above the drainage channel. | 0 |
BACKGROUND OF THE INVENTION
Telephone operating companies ("telcos") provide telephonic communications to subscribers of their services by utilizing telephone network systems which are comprised of telephone lines (and airwave communications), switching equipment, terminal equipment (including telephones and computer terminals), and other equipment. The telcos offer such services in accordance with tariffs approved by governmental regulatory agencies. Customers are allowed to use existing systems and services as they have evolved within the telcos and their parent companies and the research and manufacturing subsidiaries of the parent companies. The two largest American telco holding companies and their research and manufacturing subsidiaries, and their telcos, have never conceived of or allowed the internal use of their systems, equipment, services and procedures to supplement the programs and/or services offered by subscribers to other subscribers.
SUMMARY OF THE INVENTION
The method provides for the transmission of data from a data supplier to a data user utilizing the internal systems, equipment, services and procedures of a telco to supplement the service center equipment to the data supplier and the access terminal equipment of the data user. It includes the use the automatic number identification equipment ("ANI") of the telco to identify the data user, the counting and timing equipment of the telco to count and time access calls by the data user, the counting and timing equipment of the telco to count and time calls to the service numbers of the data supplier's service center, the automatic billing by the telco of both the telco charges and the data supplier's charges to the data user, and financial settlements between the telco and the data supplier.
Alternative 1 is one embodiment of the invention. Alternative 2 is a second embodiment of the invention.
Alternative 1, depicted in FIG. 1, would be used when the total of the telco charges and the data supplier's charges are within the standard message unit charges of the telco. The telco (or the data supplier) would merely count and time the calls to the service center numbers, and the telco would pay the data supplier for its portion of the standard message unit charges.
Alternative 2, depicted in FIG. 2, would be used when the total of the telco charges and the data supplier's charges exceed the standard message unit charges of the telco. The telco would use its ANI equipment to identify the data user, the telco would count and time the incoming calls from each data user, the telco would bill and collect from the data user at special rates agreed upon between the telco and the data supplier (the total of the telco charges and the data supplier's charges) using its standard equipment and procedures for counting, timing and billing, and the telco would pay the data supplier for its charges.
The data supplier could use any method of storing and retrieving data including, but not limited to, holographic systems, magnetic tapes, discs and cards, and solid state, or paralled combinations of these devices.
The service center or data bank could be located either within the premises of the telco, or elsewhere.
Access to the data by the data user would usually be through Touch-Tone pads or rotary dials on telephones, or through terminal equipment such as Transaction Phones.
The basic advantages of the method is that data can be supplied to data users in a more efficient and economical manner than can be done through the use of any existing systems and methods. The data supplier need only announce the availability of the data and the telephone service numbers of the service center. This can be done in part by announcements distributed with the regular telco billings to its commercial users. There is no need for the data supplier to contract with individual data users. There is no need for the data user to identify itself either by voice or number when it accesses the data bank at the service center. There is no need for any voice contact, although voice contact may be used in some applications. There is no need for the telco to transmit any information or data to the data supplier except for summary information relative to the total number and total time of calls to each data bank service number. Duplicate billing (by the telco and the data supplier) is eliminated. There is no need for the data supplier to require a minimum monthly payment from the data user. The equipment and lines of the telco are used for much shorter periods of time than they are used through the use of any existing systems and methods. The method is particularly desirable to the telcos when the response time of the data bank is very short, such as a simple approval or disapproval signal in a credit card or bank account verification system.
The data bank can include a paralleling of memory systems. This leads to the advantage, for example, of paralleling a holographic memory, which is dense and fast but which may not be current, with a magnetic memory, which is slower but easier to keep current.
Both the Data Supplier and the Data User are subscribers of the telcos. The Data Supplier would pay at negotiated rates for all services provided by the telco including the regular use of its equipment and lines, and for special services such as billing, advertising, and perhaps operational functions (i.e., isertion of updated information), and the use of space on the telco premises. The Data User, under Alternative 1, would pay the standard message unit rate for calls to the Data Bank and, under Alternative 2, would pay a special surcharge rate for calls to the Data Bank service numbers.
DETAILED DESCRIPTION OF INVENTION
Refernce is made to FIG. 1 (Flow Chart Alternative 1) and
FIG. 2 (Flow Chart Alternative 2), included herewith.
Following are descriptions of the lettered network blocks:
A--the Data Supplier is any party which has data to provide on either a profit or a non-profit basis to any party who would want to call the service number of the Data Supplier.
B--the Data Bank is the physical location of the information provided by the Data Supplier. The memory could be in any form including, but not limited to, holographic film, magnetic tape or disc, solid state, or paralleled combinations of these devices, or human access to computerized or printed data. It could be located on the premises of either the telco or the Data Supplier.
C--data User is any party which may desire to access the Data Bank.
D--telco Switching is any type of switching equipment or manual switching used by the telco.
E--call Counter (To Data Bank) is call counting and timing equipment used to count and time calls to the service number of the Data Bank. It could be located on telco premises and operated by telco personnel, or it could be located on the premises and operated by the Data Supplier.
F--the ANI Equipment is the automatic number identification equipment of the telco used to identify the Data User calling the Data Bank.
G--call Counter (From Data User) is telco call counting and timing equipment used to count and time calls from the Data User.
H--telco Billing Computer is the equipment used by the telco to automatically bill the Data User. It could be electronic, electro-mechanical, mechanical, or human.
I--telco Accounting is the telco accounting office which receives information from the Call Counter (To Data Bank) in Alternative 1 and from the Telco Billing Computer in Alternative 2, receives payments from the Data User, and transmits payments to the Data Supplier.
Following are descriptions of the steps in the method of Alternative 1, depicted in FIG. 1, and indicated by the numbered interconnecting lines:
Data Supplier A, via line 1, sets up Data Bank B and provides updated information as required.
Data User C, via line 2, accesses Data Bank B through Telco Switching D and Call Counter (To Data Bank) E.
Data Bank B, via line 4, transmits data to Data User C through Telco Switching D.
Information is provided via line 5 by Telco Switching D and Call Counter (from Data User) G to Telco Billing Computer H regarding number and timing of calls from Data User C. p1 Data User C via line 7 is billed by Telco Billing Computer H at standard message unit rate.
Data User C, via line 9, makes payment to Telco Accounting I.
Call Counter (To Data Bank) E, via line 10, provides information to Telco Accounting I, relative to the number and total time of calls to Data Bank B.
Telco Accounting I, via line 12, makes payment to Data Supplier A at negotiated rate based on the number and timing of calls to Data Bank B.
Following are descriptions of the steps in the process of Alternative 2, depicted in FIG. 2, and indicated by the numbered interconnecting lines;
Data Supplier A, via line 1, sets up Data Bank B and provides updated information as required.
Data User C, via line 3, accesses Data Bank B through Telco Switching D.
Data Bank B, via line 4, transmits data to Data User C through Telco Switching D.
Information is provided, via line 6, by ANI equipment F and Call Counter (From Data User) G to Telco Billing Computer H regarding number and timing of calls from Data User C.
Data User C, via line 7, is billed by Telco Billing Computer H at special surcharge rate.
Data User C, via line 8, makes payment to Telco Accounting I.
Telco Billing Computer H, via line 11, provides information to Telco Accounting I relative to the number and total time of calls to the Data Bank B.
Telco Accounting I, via line 12, makes payment to Data Supplier A at negotiated rate based on the number and timing of calls to the Data Bank B. | A method whereby data is transmitted from a data supplier's data bank to a data user upon request, using the data supplier's system and internal systems, equipment, services and procedures of telephone companies, including automatic number identification equipment, counters and timers, and billing procedures. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an improved high voltage device, and more particularly, relates to the construction of a high burst strength one piece enclosure for a high-voltage device. The enclosure is formed from a flexible material reinforced with glass fiber, so that when the device operates, high pressure generated by the device causes the flexible material to give, thereby loading the glass fiber in tension.
2. Description of the Prior Art
The construction of high-voltage devices, such as fuses and fault limiters, including current-limiting fuses, is difficult and often expensive because internal forces which are generated during operation of the devices require a sturdy, well-constructed fault limiter enclosure. Furthermore, such devices are often mounted outdoors, where they are subjected to rough handling, the elements, and other adverse conditions such as pollution. Therefore, special care must be taken to ensure that the enclosures of such fault limiters are rugged and resistant to surface leakage currents.
The prior art discloses the use of rigid, multiple piece, resin enclosures for current limiting fuses wherein the space between a fusible element and the rigid enclosure is filled with a particulate arc-quenching medium. For example, such enclosures are shown in U.S. Pat. No. 4,035,753--Reeder, and pending U.S. patent application Ser. No. 817,985--Biller, filed July 22, 1977 as a continuation of Ser. No. 708,146, filed July 23, 1976 and now abandoned, both assigned to the same assignee as the present invention. The prior art also discloses the use of multiple-piece rigid glass-reinforced resin enclosures as shown in U.S. Pat. Nos. 3,983,525--Healey; 3,986,157--Salzer; and 3,986,158--Salzer. These prior art devices do not utilize one-piece enclosures, and therefore their structural integrity may be compromised, since separate end caps must usually be attached to the enclosure after it is filled with the arc-quenching material. A one-piece housing can be achieved utilizing the invention described in copending application Ser. No. 8,424 filed Feb. 1, 1979 in the name of Guleserian, and assigned to the same assignee as the present invention; however, the Guleserian device is not glass reinforced, and therefore is not as strong as the present invention.
When the present invention is used with a current-limiting fuse, the foregoing disadvantages are overcome because the arc-quenching material may be positioned around the fusible element within a subassembly prior to molding a one-piece glass-reinforced flexible enclosure around the subassembly. Accordingly, the present invention provides a desirable advance in the art by providing a highvoltage current-limiting fuse construction which permits relatively simple, inexpensive manufacturing techniques, while preserving the requisite strength and leakproof characteristics necessary for proper operation.
SUMMARY OF THE INVENTION
An improved enclosure for a high-voltage device in accordance with the present invention comprises a strong, durable, and inexpensive one-piece, glass-reinforced flexible enclosure. The enclosure is formed around a subassembly which can incorporate any of a variety of high-voltage devices which are suited to use in conjunction with an enclosure of the type disclosed. The enclosure is formed by applying glass fiber or glass cloth reinforcing material around the subassembly in any one of several suitable techniques. A flexible one-piece enclosure is then molded around the glass enclosed subassembly in a manner which permits the housing material to fill the interstices of the glass reinforcing material.
In an enclosure made in accordance with the present invention, when high pressures are generated within the enclosure during the operation of the high-voltage device, the flexible enclosure material flexes sufficiently under the stress imposed by the operation of the high-voltage device for the load produced to be transferred to the glass reinforcing material. In this manner, the enclosure will have the burst resistence afforded by the glass reinforcement while remaining resilient in those portions of the enclosure which are not glass reinforced.
In one application of the present invention, the enclosure contains a conventional current-limiting fuse. The fuse includes a current responsive fusible element comprising one or more conductive filaments, a support member supporting the fusible element(s), and terminal assemblies electrically connected to opposite ends of the fusible element(s). Mounted around the fusible element support member is a subassembly housing. The subassembly housing may comprise a tubular member which is enclosed on each end by caps associated with the terminal assemblies. The subassembly housing is filled with arc-quenching material through a filling hole in the subassembly housing, and the arc-quenching material is then compacted in the subassembly by vibration or other suitable means.
Various techniques may be utilized to apply glass fiber or glass cloth reinforcing material around the high-voltage device in accordance with the present invention. The preferred method will depend, in part on constraints imposed by the particular high-voltage device to be housed. One embodiment of the present invention utilizes an open-weave, woven, or mat type reinforcing cloth, which is wrapped around the subassembly housing with the excess material folded over the ends of the subassembly housing.
In a first alternative embodiment, the glass fiber is wound around a form which is somewhat longer then the length of the subassembly housing. The glass fiber is wrapped around the tubular sides and ends of the form in a roving spiral manner and then lightly impregnated with an epoxy resin to bind the glass fiber into a molded housing capable of being handled. After the epoxy resin has cured, the molded housing is cut near its midpoint to create two cup-shaped members. The cup-shaped members are provided with openings or holes at the end to allow insertion of the mounting studs associated with the terminal assemblies. The cup-shaped members are installed over and encapsulate the subassembly housing, with the mounting studs passing through the holes in the cup-shaped members. The cup-shaped members telescope together and overlap near the midsection.
In a second alternative embodiment, glass filament is wrapped around the subassembly housing in a roving spiral manner much the same as that utilized in the manufacture of glass-reinforced pressure vessels.
After the glass reinforcing material has been applied via suitable means, such as those described above, a one-piece flexible enclosure is molded around the glass wrapped subassembly housing. The molded enclosure can be provided with skirts or other surface elongating means which are not reinforced, so that they will retain flexibility and thus be relatively immune to breakage by rough handling. Alternatively the molded enclosure may be fabricated without the use of surface elongating means.
Accordingly, it is a primary object of the present invention to provide an improved housing for a high-voltage device which permits easy, economical fabrication.
Another object of the present invention is to provide a high-voltage device with a one-piece glass-reinforced enclosure which can withstand the forces generated by operation of the device.
A further object of the present invention is to provide a high-voltage device with a one-piece glass-reinforced enclosure which is impervious to leakage.
A still further object of the present invention is to provide a high-voltage device having a glass-reinforced enclosure made of flexible material which effectively transfers the load produced by operation of the device to the glass reinforcing material.
These and other objects, advantages and features of the present invention shall hereinafter appear, and for the purposes of illustration, but not for limitation, exemplary embodiments of the present invention are illustrated in the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side, partially cross-sectional view of one embodiment of the high-voltage device in accordance with the present invention.
FIG. 2 is a side, partially cross-sectional view of one method of forming glass reinforcement around a subassembly of a high-voltage device in accordance with the present invention.
FIG. 3 is a perspective view of an alternative method of forming the glass reinforcement around a subassembly of a high-voltage device in accordance with the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
With reference to FIG. 1, the present invention is an improved housing for a high-voltage device. A typical application for the present invention is as a housing for a high-voltage fault limiter, as hereinafter described in detail. However, the present invention is equally applicable to a variety of other high voltage devices, as will be readily apparent to one familiar with the art.
High-voltage fault limiter 10 comprises a current responsive fusible element 12 that is helically wound around a support member 14. Mounted on each end of support member 14 are metallic terminators 16 which are electrically connected to the ends of fusible element 12. Terminators 16 are electrically connected to metal ferrules or end caps 22 by welding or other suitable means. First and second mounting studs 18 and 19 are electrically connected to the metal ferrules or end caps 22 by welding or other suitable means so that an electrical circuit is completed through the fuse. Fusible element 12 is formed of a material that fuses when a current in excess of a predetermined level is passed through it. Support member 14 and terminators 16 may be fabricated in any conventional manner. The fusible element, support member and the terminators illustrated herein are substantially the same as those disclosed in U.S. Pat. No. 4,010,438--Scherer and U.S. Pat. No. 4,057,775--Biller, which are assigned to the same assignee as the present invention.
Mounted around fusible element 12 and support member 14 is a tubular member 20 which is closed at each end by the end caps 22. Tubular member 20 may be formed from any electrically insulating material from which a thin-walled tube may be fabricated. A particularly suitable material for the fabrication of tubular member 20 is rolled paper tubing made from alpha cellulose paper or kraft paper and held together with high temperature glue or impregnated with high temperature resin.
Each of the end caps 22 can be formed with an indentation 32 to center the ends of tubular member 20. In an alternative embodiment, the end caps 22 may be glued to the tubular member 20 using a high temperature adhesive 24 to form a subassembly 26. The subassembly 26 is filled with a suitable arc-quenching material 28, such as quartz or silica sand, through a filling hole 30 in one of the end caps 22, and the arc-quenching material is then compacted by vibration or other suitable means. The subassembly 26 at this stage need only be sufficiently strong to contain the compacted arc-quenching material 28.
The preferred structure for the subassembly 26 in other applications will depend on the nature of the high-voltage device housed therewithin. For example, in applications of the present invention wherein the high-voltage device does not require an environment of arc-quenching material, a sleeve such as tubular member 20 may not be needed.
Various techniques for providing the glass reinforcement may be utilized in accordance with the present invention. As shown in FIG. 1, one embodiment utilizes an open-weave, woven or mat type, glass cloth 40 which is formed completely around the subassembly housing 26, with the excess material folded over the end caps 22 of the subassembly housing 26.
A first alternative embodiment of the glass reinforcing technique is illustrated in FIG. 2. In this embodiment, glass fiber 41 is wound around the sides and ends of a form which is somewhat longer than the length of the subassembly 26. The fiber is then lightly impregnated with an epoxy resin to bind the fiber into a molded housing capable of being handled. After the epoxy resin has cured, the molded housing is cut near its midpoint to create first and second cup-shaped members 46, 48.
The first and second cup-shaped members 46, 48 are provided with openings or holes 50, 52 for insertion of the first and second mounting studs 18, 19. The first cup-shaped member 46 is installed over and encapsulates one side of subassembly 26 with first mounting stud 18 passing through hole 50 in first cup-shaped member 46. Likewise, second cup-shaped member 48 is installed over and encapsulates the other side of subassembly 26 with second mounting stud 19 passing through hole 52 in second cup-shaped member 48. The first and second cup-shaped member 46, 48 telescope together and overlap near the midsection 54.
Advantageously, the form upon which the molded enclosure is formed may have a slightly enlarged band (not shown) near the midsection so that when the reinforcing body is cut into the first and second cup-shaped members 46, 48 either the first or second cup-shaped member will have a slightly enlarged diameter and thus allow the first and second cup-shaped members 46, 48 to telescope together with minimum effort.
Sufficient overlap of the first and second cup-shaped members 46, 48 at the midsection 54 is provided so that the subsequent steps of molding the flexibilized epoxy resin around the first and second cup-shaped members 46, 48 will produce an enclosure of the requisite longitudinal strength. Several wraps of glass fiber reinforcing strands around the midsection 54 may be used to increase the longitudinal strength of the enclosure.
A second alternative embodiment of the glass-reinforcing technique is illustrated in FIG. 3. In this embodiment, the preferred form of the subassembly 60 takes the form of a cylindrical sleeve 61 closed on both ends by first and second end cap assemblies 62, 63. End cap assembly 62 incorporates hemispherical cap 66, and terminal 68. Similarly, end cap assembly 63 incorporates hemispherical end cap 67 and terminal 69. Terminals 68 and 69 are electrically connected through the operative portion of the high-voltage device contained within sleeve 61. The sleeve 61 can be held in position with respect to end cap assemblies 62 and 63 by lips 70 and 71 respectively formed at the edges of end caps 66 and 67.
In this embodiment of the present invention, the glass-reinforcing material is applied to the subassembly 60 by winding a continuous glass filament 65 around the subassembly 60 in a roving spiral manner as shown in FIG. 3. This method of applying fiberglass reinforcement is particularly effective in improving both the longitudinal and radial burst resistance of the housing. It is also possible to wrap a glass filament around the subassembly in other patterns. For example, a series of longitudinal wraps combined with a series of transverse wraps would provide the requisite axial and radial burst resistance.
The completed housing, (shown only in FIG. 1) including the fiberglass reinforcement 40, 41, or 61 applied by any of the aforementioned techniques, is then molded within a flexible enclosure 34. Materials which can be used for the enclosure 34 include cycloaliphatic resin epoxy resin, polyester resin, phenolics, rubbers, EPDM, and urethanes. If these materials are unfilled, they will have sufficient flexibility to function in accordance with the present invention. If these materials are filled, the addition of flexibilizing material might be necessary in order for the housing 34 to have sufficient flexibility to load the glass fiber 40, 41, or 61 in accordance with the present invention as hereinafter described.
The principal characteristic necessary for suitable housing material is that the material be sufficiently flexible. In an enclosure made in accordance with the present invention, the housing material is molded around the glass-wrapped subassembly so that the enclosure material fills the interstices of the glass-reinforcing material. In this manner, the reinforcing layer and the enclosure become locked together. During operation of the device, the pressure generated will cause the enclosure to flex or deform sufficiently to load the glass fiber reinforcing layer in tension. In this manner, the high burst strength associated with fiberglass reinforced materials can be obtained without depriving the housing exterior of the resilience associated with unreinforced materials. Based upon presently available data, it appears that the housing material must have the ability to stretch at least 2% in order for the glass-reinforcing material to be operative in improving the burst resistance of the housing. Unfilled resins may be used in accordance with the present invention since reinforcing material has already been directly applied to the subassembly. In the alternative, resins filled with antitrack fillers may be used.
Completion of a reinforced enclosure 34 in accordance with the present invention proceeds by placing the glass reinforced subassembly 26 inside a mold cavity. A suitable material such as epoxy resin would be injected into the mold cavity to enclose the subassembly and impregnate the glass-reinforcing material. When the resin has cured, the fault limiter is complete. As shown in FIG. 1, the molded enclosure 34 encloses subassembly housing 26, and partially encloses mounting studs 18 and 19. Mounting studs 18 and 19 may be provided with recesses 25, which help insure water-tight integrity between the mounting studs 18 and 19 and the molded enclosure 34.
As also shown in FIG. 1, the molded enclosure 34 can be provided with skirts or other surface elogating means 36 which are not reinforced, so that they will remain flexible and will therefore be relatively immune to breakage caused by rough handling. Alternatively, the molded enclosure 34 may be fabricated without the use of such skirts 36.
In an alternative embodiment of the present invention, the glass-reinforced subassembly can be enclosed by a compression molding technique. In compression molding, the glass-wrapped subassembly would be placed in a heated molded along with a liquid resin. The liquid resin would then be compressed around the subassembly to form the finished housing. In this alternative embodiment, it may be possible to take advantage of the high pressure associated with compression molding to assist in compaction of arc-quenching material within the subassembly housing. This result can be achieved by using a flexible material to serve as the tubular member 20, in accordance with the teachings of co-pending application Ser. No. 8,424 filed Feb. 1, 1979 in the name of Guleserian, and assigned to the same assignee as the present invention.
It should be understood that various changes, alterations, and modifications described herein can be made without departing from the scope and spirit of the present invention as set forth in the following claims. | An improved housing for a high-voltage device which may be subjected to rough handling during installation and to high internal pressure during operation. A flexible, thick outer enclosure is molded about an inner, thin reinforcing layer which has interstices and high tensile strength. The molding locks the enclosure to the layer as the material of the former enters the interstices. The flexibility of the enclosure protects the housing and the device from the effects of rough handling. The flexibility of the enclosure also ensures that it is deformed or stretched sufficiently by high pressures accompanying device operation to ensure that the layer is loaded in tension. Loading the layer in tension ensures that the housing does not fracture or violently rupture. | 7 |
This application claims priority to U.S. Provisional Application Ser. No. 60/822,400, filed Aug. 15, 2006, and incorporated herein by reference in its entirety.
BACKGROUND
Networks, such as telecommunication networks, data transfer networks (including the Internet), and the like, are ubiquitous and increasingly relied upon in conducting a wide variety of activities. Businesses that maintain and operate these networks need to accurately analyze network operation, and need tools to plan for network growth. The ability to abstract the network into a virtual network environment such as a database, simulate traffic flows through the network, and analyze many aspects of the network's operation, allows network administrators to optimize existing networks, plan for future growth, increase reliability by simulating network failures, analyze network security, and ensure conformance with organizational policies and other rules regarding network operation.
Conventional network simulation includes creating a virtual network and simulating traffic flows through the virtual network according to predetermined routing protocols, to populate the virtual network nodes with routing and forwarding information such as forwarding tables. A virtual network is a data structure comprising virtual features (nodes and links) that represent corresponding features in a physical network. The physical network features may exist in an actual network, or, in the case of “what if” simulations such as planning for network growth, the virtual network may include virtual features that do not have an existing counterpart in an actual network. In either case, traffic flows may be simulated through the virtual network, and the simulated behavior monitored and analyzed.
To achieve high fidelity simulations, wherein simulated traffic behavior closely matches traffic behavior on an actual, physical network, the routing and forwarding information generated through the simulation should closely match that maintained at corresponding nodes in the physical network. However, if the virtual network is incomplete with respect to topology or configuration, the simulation may not have enough data to create accurate forwarding tables. Additionally, equipment vendors often create protocol behaviors that are not described in the standards for a particular protocol, in response to requests from their customers, or to differentiate their products in the marketplace. These deviations from the standard protocol may not be reflected in the simulation, which models the standards. Accordingly, the forwarding tables generated through the simulation may differ significantly from those that are created in the actual, physical network.
SUMMARY
According to one or more embodiments disclosed and claimed herein, a hybrid approach to populating forwarding tables in a virtual network obtains forwarding data both by simulating routing protocol behavior in the virtual network to build forwarding tables, and by importing operational forwarding data from corresponding physical nodes in a physical network. The use of operational forwarding data improves the fidelity of the simulation by closely conforming forwarding behavior in the simulation to that which occurs in the physical network.
One embodiment relates to a method of network analysis. A virtual network environment is provided, at least part of which represents physical network features. Operational forwarding data is obtained from one or more physical network nodes, and the operational forwarding data is applied to corresponding virtual network nodes. For one or more virtual network nodes, forwarding data is computed by simulating routing protocol behavior in the virtual network environment.
Another embodiment relates to a computer readable medium including one or more computer programs operative to cause a computer to perform network analysis. The computer programs are operative to cause the computer to perform the steps of providing a virtual network environment, at least part of which represents physical network features; obtaining operational forwarding data from one or more physical network nodes, and applying the operational forwarding data to corresponding virtual network nodes; and for one or more virtual network nodes, computing forwarding data by simulating routing protocol behavior in the virtual network environment.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a flow diagram of a method of network analysis.
FIG. 2 is a functional block diagram of a computer executing software operative to perform network simulation using operational forwarding data.
DETAILED DESCRIPTION
Network routing is the process of selecting paths in a network along which to send traffic, such as data packets in an IP network. For small networks, routing may be performed manually, by constructing routing tables prior to applying traffic to the network. Larger networks utilize dynamic routing, wherein routing tables are constructed automatically according to a routing protocol. Known routing algorithms include Distance Vector, Link-state, and Path Vector. Several well-defined routing protocols are known, such as the Link-state protocol Open Shortest Path First (OSPF), which uses Dijkstra's algorithm to calculate the shortest path tree inside each network area.
Dynamic routing protocols dynamically construct routing tables during a network learning process. The routing tables, maintained at network router nodes, include routes through the network to network destinations, which may be stored, for example, as network addresses (e.g., IP addresses). The routing tables may also include metrics associated with the routes, which may include bandwidth, delay, hop count, path cost, load, Maximum Transmission Unit (MTU), reliability, cost, and the like. Depending on the routing protocol, the routing table includes the entire network topology (link-state) or partial topology, such as the shortest paths to known destinations via all of its neighbors (distance vector).
Forwarding is the relaying of datagrams (such as IP packets) from one network segment to another by nodes in the network. Network nodes such as routers, bridges, gateways, firewalls, switches, and the like, forward packets by inspecting the packet header for a destination address, and looking up the destination address in a forwarding table. A forwarding table is a subset of a routing table, and includes the mapping of a next-hop address and an output interface to each destination network address (such as an IP address). The forwarding table thus tells each node which output interface to forward any packet towards. Forwarding tables are built at each node during a learning process that is independent of the forwarding process, by applying the routing protocol.
Forwarding tables are conventionally constructed in virtual networks by simulating the network learning process, and building forwarding tables at each network node prior to simulating traffic flow through the network. As discussed above, due to non-standard routing behavior, imperfect network topology or other information, or other factors, forwarding tables constructed by network simulation may not match the operational forwarding data maintained at actual, physical network nodes. As used herein, the term “operational forwarding data” refers to actual, real-world forwarding data constructed and maintained at physical nodes in an actual, physical network.
According to one or more embodiments of the present invention, operational forwarding data are extracted from a physical network and applied to corresponding virtual nodes in a virtual network for network simulation and analysis. The operational forwarding data may be obtained in several ways. In one embodiment, shell commands extract the forwarding table from each node in a physical network. In another embodiment, a user issues commands to a physical network node to export the forwarding table. This might yield a forwarding table including only the best path data. In yet another embodiment, a user issues a “data dump” command to obtain all forwarding information from a physical node, including secondary, tertiary, etc., path data. In this case, the user may extract a forwarding table from the resulting data via subsequent analysis.
Regardless of how the operational forwarding data is obtained, in one embodiment the operational forwarding data may be filtered to reduce the forwarding table size and obtain only data that is necessary for particular simulation purposes. For example, a service provider network node may include over 200,000 entries in a forwarding table. If a simulation will involve only a known set of address prefixes, the operational forwarding data may be filtered to remove the irrelevant entries.
Operational forwarding data may not always be available. For example, a particular physical network node may not report operational data, a user may lack administrator privilege or permission to obtain the data, or the like. In this case, according to one embodiment, operational forwarding data is obtained and applied to all virtual network nodes corresponding to the physical network nodes from which sufficient operational forwarding data is available. For other virtual network nodes, including those for which a corresponding physical network node does not exist, forwarding tables may be built conventionally, by simulating routing behavior in the virtual network. In one embodiment, partial operational forwarding data at a particular virtual network node may be supplemented by further building the forwarding table during simulation.
Once forwarding tables are obtained for all virtual network nodes, whether by obtaining and applying operational forwarding data or by simulating a routing protocol in the virtual network, a variety of simulations and analyses may be performed on the virtual network with the significant benefit of high simulation fidelity, with virtual network nodes more precisely simulating the behavior of physical network nodes due to the use of operational forwarding data.
One type of analysis is traffic and capacity analysis. There is constant growth in the network capacity requirements of most physical networks due to a combination of increased number of users of existing applications and the addition of new applications. A simulation may apply and analyze network traffic based on the model protocol behavior for a variety of types of traffic. For example, traffic having different burst characteristics or Quality of Service (QoS) constraints may be simulated to ascertain the network load, response, and the like. By using operational forwarding data, a more accurate traffic and capacity analysis is obtained.
Another type of analysis is security analysis, wherein various security policies may be applied to simulated network traffic, and the behavior of the security policies tested and validated. For example, the simulation and analysis may verify that certain traffic is blocked, and other traffic passes through the network. By using operational forwarding data, network managers may ensure that non-standard routing protocol behavior in network nodes does not thwart security policies.
A particularly powerful tool for understanding network traffic behavior is graphic visualization. According to one embodiment, a graphical representation of the network may be output to a display screen, printer, plotter, or the like. The screen display may be zoomed and panned, as known in the art. Based on network traffic simulations utilizing operational forwarding data, the graphical display may be annotated with a variety of information. For example, visual depictions of traffic flows may illuminate how any given device in the network learns to reach a particular network address.
A variety of network analyses may be performed on any of these types of high-fidelity simulations using operational forwarding data, and reports may be generated based on the analyses. These reports provide network managers with valuable information on network operation. For example, reporting on forwarding tables themselves is critical to ensuring proper network behavior, e.g., that the proper default routes appear in the forwarding tables. Since a network node will drop a packet for which it has not entry in the forwarding table, maintaining default routes in each forwarding table is important to prevent excessive data loss and retransmission.
As another example, the simulations may be analyzed for conformance to organizational policies. Network managers at various organizations may set policies and rules to ensure appropriate routing guidelines. For example, they may (or may not) allow multiple next hops to a destination, to cause (or avoid) asymmetric routing. Asymmetric routing can cause packets to arrive out-of-order at the destination, resulting in unpredictable latencies, which in turn can impact the performance of certain applications. The simulations may be analyzed for conformance to such policies, and reports generated to alert network managers to policy violations. Here again, the use of operational forwarding data ensures that non-standard routing protocol behavior does not thwart organizational policies.
FIG. 1 depicts a method 10 of network analysis, according to one or more embodiments of the present invention. The method begins by providing a virtual network environment, at least part of which represents physical network features (i.e., nodes and links) (block 12 ). The virtual network may include network features that do not exist in a physical network, such as when simulating projected growth or other “what if” simulations to assess the impact of adding features to a network. For virtual network nodes that do correspond to physical network nodes, operational forwarding data is obtained from the physical network nodes and applied to the corresponding virtual network nodes (block 14 ). For one or more other virtual network nodes (which may or may not correspond to physical network nodes), forwarding data are computed by simulating the learning process of a routing protocol behavior in the virtual network environment (block 16 ). This hybrid approach provisions nodes in the virtual network environment with forwarding tables, preparing them for network traffic simulations.
Depending on the simulations to be performed, traffic types may be defined (e.g., bursty), QoS constraints defined and applied, and security and/or organizational policies may be applied (block 18 ). Traffic flows are then simulated in the virtual network environment (block 20 ). The results of the simulation are analyzed (block 22 ), and annotated graphical network representations and/or analysis reports are generated and output to the user (block 24 ). If more simulations are to be performed (block 26 ), they are defined (block 18 ) and the process repeats. If no more simulations are to be performed in the virtual network environment provisioned with operational forwarding data (block 26 ), the method ends (block 28 ).
FIG. 2 depicts a functional block diagram of a computer 30 operative to execute one or more computer programs 38 implementing the method 10 . The computer 30 includes a processor 32 , which may comprise a general-purpose microprocessor, a digital signal processor, or custom hardware such as an FPGA or ASIC. The processor 32 is operatively connected in data flow relationship with memory 36 . The memory 36 includes, at least during its execution, software 38 operative to perform some or all of the method 10 of FIG. 1 . A non-volatile copy of the software 38 may reside on a fixed disk drive 40 . The software 38 may be initially loaded into the computer 30 from a computer-readable medium 46 , such as a CD-ROM or DVD, via a removable media drive 42 .
The computer 30 preferably includes a user interface 48 , comprising a keyboard, pointing device, and the like, and a graphic display 50 operative to display a graphical representation of a virtual network environment, annotated with information derived from a high-fidelity simulation using operational forwarding data. The graphic representation and/or reports of network simulation analyses may be output to a printer 52 , plotter (not shown), or other hard copy peripheral as known in the art. An input/output (I/O) interface 54 connects via a wired or wireless data channel 56 to a physical network 58 . Operational forwarding data is obtained from nodes in the physical network 58 , and applied by the software 38 to nodes in the virtual network environment prior to network traffic simulation.
One embodiment of the software 38 implementing the method 10 of network analysis using operational forwarding data is the OPNET SP Guru Release 12.0, available from OPNET Technologies, Inc. Although depicted as software 38 executing on a general-purpose computer 30 , implementations of the method 10 are not limited to this embodiment. In general, the method may be performed by any means known in the art, including any combination of software, dedicated hardware, firmware, or the like.
The present invention may, of course, be carried out in other ways than those specifically set forth herein without departing from essential characteristics of the invention. The present embodiments are to be considered in all respects as illustrative and not restrictive, and all changes coming within the meaning and equivalency range of the appended claims are intended to be embraced therein. | A hybrid approach to populating forwarding tables in a virtual network obtains forwarding data both by simulating routing protocol behavior in the virtual network to build forwarding tables, and by importing operational forwarding data from corresponding physical nodes in a physical network. The use of operational forwarding data improves the fidelity of the simulation by closely conforming forwarding behavior in the simulation to that which occurs in the physical network. | 7 |
CROSSS-REFERENCE TO RELATED APPLICATION
[0001] This patent application claims benefit of U.S. provisional patent application serial No. 60/290,234 filed May 11, 2001.
FIELD OF THE INVENTION
[0002] This invention relates to a four-stage process for producing high quality white oils particularly food grade mineral oils from mineral oil distillates. The process includes three separate hydrotreating stages and a sulfur sorbent stage.
BACKGROUND OF THE INVENTION
[0003] White mineral oils, called white oils, are colorless, transparent, oily liquids obtained by the refining of crude petroleum feedstocks. In the production of white oils, an appropriate petroleum feedstock is refined to eliminate, as completely as possible, oxygen, nitrogen, and sulfur compounds, reactive hydrocarbons including aromatics, and any other impurity which would prevent use of the resulting white oil in the pharmaceutical or food industry. White oils generally fall into two classes, technical grade and pharmaceutical grade. Technical grade white oils are those suitable for use in cosmetics, textile lubrication, bases for insecticides, and the like. The more highly refined pharmaceutical grade white oils are those suitable for use in drug compositions, foods, and for the lubrication of food handling machinery. The pharmaceutical grade white oils must be chemically inert and substantially without color, odor, or taste. Also, for these applications manufacturers must remove “readily carbonizable substances” (RCS) from the white oil. RCS are impurities that cause the white oil to change color when treated with strong acid. The Food and Drug Administration (FDA) and white oil manufacturers have stringent standards with respect to RCS, which must be met before the white oil can be marketed for use in food or pharmaceutical applications. In particular, the Code of Federal Regulations, 21 C.F.R. §172.878(1988) defines white mineral oil as a mixture of liquid hydrocarbons, essentially paraffinic in nature obtained from petroleum and refined to meet the test requirements of the United States Pharmacopoeia XX, pp. 532 (1980) for readily carbonizable substances and for sulfur compounds. The Ultraviolet Absorption Test generally measures the ultraviolet absorbance of an extract in the range of 260-350 nm, which absorbance is then compared with that of a naphthalene standard. This test sets forth limits for the presence of polynuclear compound impurities in the white oil.
[0004] White oil must also pass the Hot Acid Carbonizable Substances Test (ASTM D-565) to conform to the standard of quality required for pharmaceutical use. In order to pass this test the oil layer must show no change in color and the acid level is not darker than that of the reference standard colorimetric solution. From this test it will be seen that for purposes of interpreting test results, the art has recognized that a value of 16 or below on a standard test, the Hellige Amber C Color Wheel, is sufficient to pass the carbonizable substances test.
[0005] The present invention is primarily concerned with the production of pharmaceutical grade white oils. There are numerous processes in the prior art for the production of white oils of both grades. In general, the first step in the production of white oil is the removal of lighter fractions, such as gasoline, naphtha, kerosene, and gaseous fractions, from the feedstock by fractional distillation. In early processes, white oil was refined by treatment with sulfuric acid to remove unsaturated aromatic and unstable hydroaromatic compounds, which comprised most of the impurities present in the oil. Typically, the acid treated oil was subjected to adsorption refining to remove such impurities as carbon, coke, asphaltic substances, coloring matter and the like.
[0006] Conventional methods of making white oils with sulfuric acid however, have been subject to objection in recent years since acid treating is costly and gives rise to undesirable amounts of sludge. Because of objections to sulfuric acid treatments, other procedures were developed for the production of white oils from hydrocarbon feedstocks. Representative processes of these procedures can be found in U.S. Pat. Nos. 3,392,112; 3,459,656; 4,055,481; 4,251,347; 4,263,127; and 4,325,804. U.S. Pat. No 4,786,402 discloses a two-step catalytic hydrogenation process. Further, U.S. Pat. No 6,187,176 discloses a three-step catalytic hydrogenation process.
[0007] Hydrodesulfurization (HDS) is one of the fundamental processes of the refining and chemical industries. The removal of feed sulfur by conversion to hydrogen sulfide is typically achieved by reaction with hydrogen over non-noble metal sulfides, especially those of Co/Mo and Ni/Mo. The reaction is performed at fairly severe conditions of temperatures and pressures in order to meet product quality specifications, or to supply a desulfurized stream to a subsequent sulfur sensitive process. The latter is a particularly important objective because some processes are carried out over catalysts which are extremely sensitive to poisoning by sulfur. This sulfur sensitivity is sometimes sufficiently acute as to require a substantially sulfur free feed. In other cases environmental considerations and mandates drive product quality specifications to very low sulfur levels.
[0008] There is a well-established hierarchy in the ease of sulfur removal from the various organosulfur compounds common to refinery and chemical streams. Simple aliphatic, naphthenic, and aromatic mercaptans, sulfides, di- and polysulfides and the like surrender their sulfur more readily than the class of heterocyclic sulfur compounds comprised of thiophene and its higher homologs and analogs. Desulfurization reactivity decreases with increasing molecular structure and complexity within the generic thiophenic class. For example, the simple thiophenes are the more labile, or “easy” sulfur types. The other extreme, which is sometimes referred to as “hard sulfur” or “refractory sulfur,” is represented by the derivatives of dibenzothiophene, especially those mono- and di-substituted and condensed ring dibenzothiophenes bearing substituents on the carbon beta to the sulfur atom. These highly refractory sulfur heterocycles resist desulfurization as a consequence of steric inhibition precluding the requisite catalyst-substrate interaction. For this reason, these materials survive traditional desulfurization and they poison subsequent processes whose operability is dependent upon a sulfur sensitive catalyst. Destruction of these “hard sulfur” types can be accomplished under relatively severe high-pressure process conditions, but this may prove to be economically undesirable owing to the onset of undesirable side reactions. Also, the level of investment and operating costs required to drive the severe process conditions may be too great for the required sulfur specification.
[0009] A recent review (M. J. Girgis and B. C. Gates, Ind. Eng. Chem., 1991, 30, 2021) addresses the fate of various thiophenic types at reaction conditions employed industrially, e.g., 340-425° C. (644-799° F.), 825-2550 psig. The substitution of a methyl group into the 4-position or into the 4- and 6-positions decreases the desulfurization activity by an order of magnitude for dibenzothiophenes. These authors state, “These methyl-substituted dibenzothiophenes are now recognized as the organosulfur compounds that are most slowly converted in the HDS of heavy fossil fuels. One of the challenges for future technology is to find catalysts and processes to desulfurize them.”
[0010] M. Houalla et al, J. Catal., 61, 523 (1980) disclose activity debits of 1 to 10 orders of magnitude for similarly substituted dibenzothiophenes under similar hydrodesulfurization conditions. While the literature addresses methyl substituted dibenzothiophenes, it is apparent that substitution with alkyl substituents greater than methyl, e.g., 4,6-diethyldibenzothiophene, would intensify the refractory nature of these sulfur compounds. Condensed ring aromatic substituents incorporating the 3,4 and/or 6,7 carbons would exert a similar negative influence. Similar results are described by Lamure-Meille et al, Applied Catalysis A: General, 131, 143, (1995) based on similar substrates.
[0011] Mochida et al, Catalysis Today, 29, 185 (1996) address the deep desulfurization of diesel fuels from the perspective of process and catalyst designs aimed at the conversion of the refractory sulfur types, which “are hardly desulfurized in the conventional HDS process.” These authors optimize their process to a product sulfur level of 0.016 wt. %, which reflects the inability of an idealized system to drive the conversion of the most resistant sulfur molecules to extinction. Vasudevan et al, Catalysis Reviews, 38, 161(1996) in a discussion of deep HDS catalysis report that while Pt and Ir catalysts were initially highly active on refractory sulfur species, both catalysts deactivated with time on oil.
[0012] In light of the above, there is still a need for a desulfurization process that can convert feeds bearing the refractory, condensed ring sulfur heterocycles at relatively mild process conditions to products containing substantially no sulfur.
SUMMARY OF THE INVENTION
[0013] In accordance with the present invention there is provided a process for the preparation of pharmaceutical grade white oils from a mineral hydrocarbon oil feedstock having a viscosity ranging from, about 70 to about 600 SUS at 37.8° C., by a four stage catalytic process, which process comprises: (1) hydrotreating the mineral oil feedstock in a first reaction stage containing a hydrotreating catalyst and a hydrogen-containing treat gas under hydrotreating conditions, thereby resulting in a first stage reaction product which is at least partially hydrogenated and desulfurized; (2) hydrotreating the reaction product of the first reaction stage in a second reaction stage in the presence of: (i) a hydrodesulfurization catalyst comprised of a Group VIII metal on bound M41S support, (ii) a hydrogen containing treat gas, wherein the second reaction stage is operated at temperatures from about 150° C. to 500° C. and pressures from about 500 to 3,000 psig (3549 to 20,786 kPa); (3) treating hydrotreated product from stage 2 with a reduced metal hydrogen sulfide sorbent material in stage 3, and (4) hydrogenating the reaction product from reaction stage 3 in a fourth reaction stage in the presence of a Group VIII based catalyst, thereby producing a white oil.
[0014] In a preferred embodiment of the present invention, the Group VIII metal (Periodic Table by Fisher Scientific Co.) is a noble metal selected from Pt, Pd, Ir, and mixtures thereof supported on bound MCM-41.
[0015] In still another preferred embodiment of the present invention the initial feedstock is a solvent extracted lubricating oil having a viscosity ranging from about 70 to 600 SUS at 37.8° C.
[0016] In another preferred embodiment of the present invention, the hydrogen sulfide sorbent is selected from supported reduced non-noble Group VII metal.
[0017] The white oil product from the present process meets pharmaceutical requirements and has a hot acid number (ASTM D-565) of less than about 16 on the Hellige Amber C Color Wheel and an ultraviolet absorbance value of less than 0.1.
DETAILED DESCRIPTION OF THE INVENTION
[0018] The process of the present invention is applicable to removing sulfur from all sulfur bearing mineral hydrocarbon oil feedstocks. The process is particularly suitable for the desulfurization of the least reactive, most highly refractory sulfur species, especially the class derived from dibenzothiophenes, and most especially the alkyl, aryl, and condensed ring derivatives of this heterocyclic group, particularly those bearing one or more substituents in the 3-, 4-, 6-, and 7-positions relative to the thiophenic sulfur. The process of the present invention will result in a product stream having substantially no sulfur. For purposes of this invention, the term, “substantially no sulfur”, depends upon the overall process being considered, but can be defined as a value less than about 1 wppm, preferably less than about 0.5 wppm, more preferably less than about 0.1 wppm, and most preferably less than about 0.01 wppm as measured by existing, conventional analytical technology.
[0019] The initial feedstocks suitable for use in the practice of the present invention are any petroleum hydrocarbon fraction capable of yielding a product of the desired purity range by treatment in accordance with the process steps of the present invention. When the desired final product of the present invention is a white mineral oil, or other oil in the lubricating range of viscosities, the charge to the first stage is preferably a light to heavy lubricating distillate which generally has viscosities ranging from about 70 SUS to 600 SUS at 37.8° C. For pharmaceutical grade white oil production, the charge stock is preferably a raffinate resulting from solvent treatment of a light to heavy neutral distillate oil with a selective solvent, i.e., a distillate fraction which has been extracted. For the production of technical grade white oils, a non-solvent extracted distillate oil may be used as the starting material. When the final product is charcoal lighter fluid, the charge stock can comprise alkylate bottoms such as materials obtained from sulfuric acid or hydrogen fluoride alkylation processes boiling above the gasoline range. When the final product is petrolatum, the chargestock can be paraffin slack wax, microcrystalline waxes, oils and the like. For producing pharmaceutical waxes, paraffin wax obtained by solvent dewaxing of a waxy lubrication distillate is suitable.
[0020] First stage hydrotreating catalysts are conventional hydrotreating catalysts such as those containing Group VIB metals (based on the Period Table published by Fisher Scientific), and non-noble Group VIII metals, i.e., iron, cobalt and nickel and mixtures thereof These metals or mixtures of metals are typically present as oxides or sulfides on refractory metal oxide supports. Preferred catalysts are those containing Co/Mo, Ni/Mo and Ni/W. The first stage hydrotreating conditions include temperatures of from 250-400° C., pressures of from 1000-3000 psig (6996-20,786 kPa), liquid hourly space velocities (LHSV) of from 0.1-5 and treat gas rates of from 1000-5000 scf/B (178-890 m 3 /m 3 ).
[0021] Catalysts suitable for use in stage 2 of the present invention are those comprised of at least one noble or non-noble metal of Group VIII of the Periodic Table of the Elements supported in a highly dispersed and substantially uniformly distributed manner on bound M41 S support.
[0022] The bound stage 2 catalyst is a crystalline mesoporous material belonging to the M41S class or family of catalysts. The M41S family have high silica contents and are described in J. Amer. Chem. Soc., 1992, 114, 10834. Members of the M41S family include MCM-41, MCM-48 and MCM-50. A preferred member of this class is MCM-41 whose preparation is described in U.S. Pat. No. 5,098,684. MCM-41 is characterized by having a hexagonal crystal structure with a unidimensional arrangement of pores having a cell diameter greater than about 13 Angstroms. The physical structure of MCM-41 is like a bundle of straws wherein the opening of the straws (the cell diameters of the pores) ranges from about 13 to 150 Angstroms. MCM-48 has a cubic symmetry and is described for example in U.S. Pat. No. 5,198,203. MCM-50 has a layered or lamellar structure and is described in U.S. Pat. No. 5,246,689.
[0023] Group VIII noble metals that may be used for the hydrodesulfurization and partial hydrogenation catalysts of the present invention include Pt, Pd, and Ir; preferably Pt, Pd. Preferred bimetallic noble metal catalysts include Pt-Ir, Pd-Ir, and Pt-Pd; Pt-Ir and Pt-Pd are more preferred. These mono- and bimetallic noble metal catalysts may contain a promoter metal, preferably at least one of Re, Cu, Ag, Au, Sn, Zn, and the like, for stability and selectivity improvement
[0024] Suitable binding materials for the bound M41S include inorganic, refractory materials such as alumina, silica, silicon carbide, amorphous and crystalline silica-aluminas (zeolites), silica-magnesias, aluminophosphates boria, titania, zirconia, and mixtures and cogels thereof. Preferred supports include alumina and low acidity crystalline or amorphous materials.
[0025] The metals may be loaded onto these supports by conventional techniques known in the art. Such techniques include impregnation by incipient wetness, by adsorption from excess impregnating medium, and by ion exchange. The metal bearing catalysts of the present invention are typically dried, calcined, and reduced; the latter may either be conducted ex situ or in situ as preferred. The catalysts need not be presulfided because the presence of sulfur is not essential to hydrodesulfurization activity and activity maintenance.
[0026] Total metal loading for stage 2 catalysts of the present invention is in the range of about 0.01 to 5 wt. %, preferably about 0.1 to 2 wt. %, and more preferably about 0.15 to 1.5 wt. %. For bimetallic noble metal catalysts similar ranges are applicable to each component; however, the bimetallics may be either balanced or unbalanced where the loadings of the individual metals may either be equivalent, or the loading of one metal may be greater or less than that of its partner. The loading of stability and selectivity modifiers ranges from about 0.01 to 2 wt. %, preferably about 0.02 to 1.5 wt. %, and more preferably about 0.03 to 1.0 wt. If present, chloride levels range from about 0.3 to 2.0 wt. %, preferably about 0.5 to 1.5 wt. %, and more preferably about 0.6 to 1.2 wt. %. Sulfur loadings of the noble metal catalysts approximate those produced by breakthrough sulfiding of the catalyst and range from about 0.01 to 1.2 wt. %, preferably about 0.02 to 1.0 wt. %.
[0027] Reaction conditions in Stage 2 include temperatures of from 150 to 500° C., preferably 250 to 400° C., pressures of from 500 to 3000 psig (3549 to 20,786 kPa), preferable 1000 to 2000 psig (6996 to 13,891 kPa), a LHSV of from 0.1 to 10, preferably 0.1 to 3 and a treat gas rate of from 500 to 10,000 scf/B (89 to 1780 m 3 /m 3 ), preferably 1000 to 5000 scf/B (178 to 890 m 3 /m 3 ).
[0028] The hydrogen sulfide sorbent of this invention may be selected from several classes of material known to be reactive toward hydrogen sulfide and capable of binding same in either a reversible or irreversible manner. Metals in their reduced state are useful in this capacity and may be employed supported on an appropriate support material such as an alumina, silica, or a zeolite, or mixtures thereof. Representative metals include those of the metals from Groups IA, IIA, IB, IIB, IIIA, IVA, VB, VIB, VIIB, VIII of the Periodic Table of the Elements. Representative elements include Zn, Fe, Ni, Cu, Mo, Co, Mg, Mn, W, K, Na, Ca, Ba, La, V, Ta, Nb, Re, Zr, Cr, Ag, Sn, and the like. The metals or their respective oxides may be employed individually or in combination. The preferred metals are those of Co, Ni, and Cu.
[0029] A preferred class of hydrogen sulfide sorbents are those which are regenerable as contrasted to those which bind sulfur irreversibly in a stoichiometric reaction. Active hydrogen sulfide sorbents regenerable through the sequential action of hydrogen and oxygen include iron, cobalt, nickel, copper, silver, tin, rhenium, molybdenum, and mixtures thereof. These regeneration reactions may be facilitated by the inclusion of a catalytic agent that facilitates the oxidation or reduction reaction required to restore the sulfur sorbent to its initial, active condition.
[0030] These regeneration processes operate over a temperature range of 200-700° C., preferably 250-600° C., and more preferably 275-500° C. at pressures of from 100 to 5000 psig (791 to 34,576 kPa).
[0031] The stage 4 catalysts have a high activity for hydrogenation and aromatic saturation. The catalysts include Group VIII metals on a support. Preferred metals are Ni, Pt and Pd, especially Ni. These metals are on the support in the reduced state, i.e., as metals. Typical supports include silica, alumina and M41S, especially MCM-41. Stage 4 reactions conditions include temperatures of from 150 to 300° C., pressures of 1000 to 3000 psig (6996 to 20,786 kPa), LHSV of 0.1 to 5 and treat gas rates of 500 to 5000 scf/B (89 to 890 m 3 /m 3 ).
[0032] Various catalyst bed configurations may be used in the practice of the present invention. However, the preferred configuration is a stacked configuration, where the three components are layered sequentially with a HDS/ASAT (aromatic saturation) catalyst occupying the top position, the hydrogen sulfide sorbent the middle, and the stand-alone Group VIII-based hydrogenation catalyst the bottom zone. While the three component systems may occupy a common reactor, these systems may utilize a multi reactor train. This arrangement offers increased process flexibility permits operating the two reactor sections at different process conditions, especially temperature, and imparts flexibility in controlling process selectivity and/or product quality. Alternatively, each component could occupy separate reactors. This would allow process conditions for each component as well as facilitate frequent or continuous replacement of the hydrogen sulfide sorbent material. The HDS/ASAT catalyst and the preferred stand-alone Ni-based hydrogenation catalyst may or may not be the same material.
[0033] Noble metal catalysts can simultaneously provide HDS and aromatic saturation (ASAT) functions. The ASAT activity of the catalyst can be maintained if said catalyst is intimately mixed with a hydrogen sulfide sorbent. The mixed bed configuration, as described above, allows operation in this mode. If this configuration is employed, the use of a preferred stand-alone Ni-based hydrogenation catalyst after the mixed bed is optional, and said use would be dictated by specific process conditions and product quality objectives. If employed, the stand-alone Ni-based hydrogenation catalyst downstream may or may not be the same material as the HDS/ASAT catalyst used in the mixed bed. ASAT activity can also be maintained in a stacked bed configuration, but activity will generally be at a lower level than the mixed bed configuration.
[0034] Materials can also be formulated which allow one or more of the various catalytic functions of the instant invention (i.e., HDS, ASAT) and the hydrogen sulfide sorbent function to reside on a common particle. In one such formulation, the HDS/ASAT and hydrogen sulfide sorbent components are blended together to form a composite particle. For example, a finely divided, powdered Pt on alumina catalyst is uniformly blended with zinc oxide powder and the mixture formed into a common catalyst particle, or zinc oxide powder is incorporated into the alumina mull mix prior to extrusion, and Pt is impregnated onto the zinc oxide-containing alumina in a manner similar to that described in U.S. Pat. No. 4,963,249, which is incorporated herein by reference.
[0035] The composition of the sorbent bed is independent of configuration and may be varied with respect to the specific process, or integrated process, to which this invention is applied. In those instances where the capacity of the hydrogen sulfide sorbent is limiting, the composition of the sorbent bed must be consistent with the expected lifetime, or cycle, of the process. These parameters are in turn sensitive to the sulfur content of the feed being processed and to the degree of desulfurization desired. For these reasons, the composition of the guard bed is flexible and variable, and the optimal bed composition for one application may not serve an alternative application equally well. In general, the weight ratio of the hydrogen sulfide sorbent to the HDS/ASAT catalyst may range from 0.01 to 1000, preferably from 0.5 to 40, and more preferably from 0.7 to 30. For three component configurations the ranges cited apply to the mixed zone of the mixed/stacked arrangement and to the first two zones of the stacked/stacked/stacked design. The Group VIII-based hydrogenation catalyst present in the final zone of these two configurations is generally present at a weight equal to, or less than, the combined weight compositions of the upstream zones.
[0036] The process of this invention is operable over a range of conditions consistent with the intended objectives in terms of product quality improvement and consistent with any downstream process with which this invention is combined in either a common or sequential reactor assembly. It is understood that hydrogen is an essential component of the process and may be supplied pure or admixed with other passive or inert gases as is frequently the case in a refining or chemical processing environment. It is preferred that the hydrogen stream be sulfur free, or substantially sulfur free, and it is understood that the latter condition may be achieved if desired by conventional technologies currently utilized for this purpose. In general, the conditions of temperature and pressure are significantly mild relative to conventional hydroprocessing technology, especially with regard to the processing of streams containing the refractory sulfur types as herein previously defined.
EXAMPLES
[0037] This invention is illustrated by, but not limited to, the following examples which are for illustrative purposes only.
Example 1
[0038] In this example two hydrotreated white oil feedstocks (350N) were used. The feedstock had a density of about 0.867 g/cc at 15° C., and sulfur content of approximately 2.1 and 4.8 wppm, and an aromatic UV adsorption at 274 nm of approximately 27.2 and 70 in a 1 cm cell. These feedstocks were processed over a Pt-Pd alumina bound MCM-41, at 220° C. temperature, over a space velocity range of 0.6 to 3.5 h-, a pressure of 2,000 psig (13,891 kPa) and treat gas rate of 2,500 SCF/B (445 m 3 /m 3 ). The product was analyzed for aromatic content by UV spectroscopy and trace sulfur by the Houston-Atlas technique (ASTM D-4045). The results are reported in Table I.
TABLE I UV @ Aromatic Sulfur Sulfur Reduction LHSV 274 nm Reduction (%) (wppm) (%) Feed 1 27.2 — 2.4 — 0.6 0.56 97.9 N/A 1.2 0.68 97.5 N/A 1.8 0.90 96.7 N/A 3.5 2.2 91.9 N/A Feed 2 70 — 4.7 — 0.63 0.78 98.9 1.0 79 1.20 2.14 96.9 2.8 40. 2.36 4.32 93.8 3.0 36 2.97 5.30 92.4 3.2 32
[0039] These results demonstrate that sulfur and aromatic levels of hydrotreated dewaxed raffinates are decreased by hydroprocessing over Pt-Pd/MCM-41(Al 2 O 3 ). Pt-Pd supported on alumina bound MCM-41 is highly effective at reducing aromatics even when processing higher sulfur containing feedstock. Secondly, the catalyst was also found to have a reasonable HDS activity.
Example 2
[0040] This example illustrates the superior HDS and hydrogenation activity of alumina bound MCM-41. The MCM-41 based catalyst is compared with amorphous silica-alumina support. Pt-Pd loading was kept similar for both catalysts. The feedstocks were a hydrotreated solvent raffinate (150 and 600N), ranging from 10 to 250 wppm sulfur, and aromatics content ranging from 72 to 80 wt %.
[0041] Operating temperatures between 230° C. and 316° C., a space of 2.0 LHSV, a pressure of 1,800 psig (12,512 kPa) and a treat gas rate of 2,500 SCF/B (445 m 3 /m 3 ). The effluent products were analyzed for aromatic content by clay gel and trace sulfur by Houston-Atlas technique. The results shown in Table II below.
TABLE II Grade/Sulfur % HYDROGENATION % HYDRODESULFURIZATION (ppm) 240° C. 250° C. 260° C. 275° C. 300° C. 316° C. 240° C. 250° C. 260° C. 275° C. 300° C. 316° C. MCM-41 150/25 98.0 98.6 99.0 99.3 45 62 150/74 65.4 96.0 97.0 98.0 99.0 38 39 56 79 150/190 96.0 98.4 98.9 41 78 90 600/10 96.3 97.9 98.4 99.0 600/25 95.4 96.4 97.2 98.3 38 50 600/64 92.0 93.1 94.2 95.7 98.0 46 52 67 78 SiAl 150/22 95.5 97.2 97.3 35 46 54 600/10 97.8 98.4 98.6 600/20 98.5 98.4 99.0 600/64 84.9 85.6 89.9 93.8 19 23 40 59
[0042] These results demonstrate that Pt-Pd/MCM-41 (Al 2 03) has superior hydrogenation and HDS activity than Pt-Pd/SiAl [1800 psig, LHSV 2.0 h-1]
Example 3
[0043] In this example the feedstock is a hydrotreated white oil feedstock (350N). The feedstock contained about 4.8 wppm, sulfur and has an aromatic UV adsorption at 275 nm of approximately 70 in a 1 cm cell. The feedstock was processed over a stacked bed of a reduced 20% Ni/alumina acting as the sulfur sorbent and a highly selective Ni based hydrogenation catalyst. The space velocity ranged from 0.6 to 1.0 h-, a pressure was 2,000 psig and treat gas rate 2,500 SCF/B. The product was analyzed for aromatic content by UV spectroscopy and trace sulfur by the Houston-Atlas technique. The results are reported in Table III and the Figure.
TABLE III Hours on LHSV UV @ % Configuration Oil (h − 1) 275 nm Hydrogenation Feed — — 70 — S sorbent/Ni 12 0.61 0.30 99.6 52 0.63 99.1 76 0.75 0.67 99.0 116 1.07 98.4 140 1.0 1.80 97.4 160 1.93 97.2 180 2.27 96.7
Example 4
[0044] In this example The Pt-Pd/MCM-41(Al2O3) catalyst was placed in front of the catalyst system described in example 3. The product and gas effluent from the MCM-41 based catalyst were directly cascaded to the sulfur sorbent and the Ni hydrogenation catalyst without further treatment. The operating conditions were maintained similar to those in example 3. Comparison with Example 3 reveals an improvement in the hydrogenation activity maintenance by exhibiting a lower deactivation rate when adding the MCM-41 based catalyst to the system.
TABLE IV Hours on LHSV UV @ % Configuration Oil (h − 1) 275 nm Hydrogenation PtPdMCM41/ 200 1.0 1.43 97.9 S sorbent/Ni 240 1.42 97.9
[0045] By comparing the results from Tables III and IV, it can bee seen that PtPd/MCM-41(Al2O3) reduces Ni hydrogenation catalyst deactivation when run in a stacked bed configuration. | A four stage process for producing high quality white oils, particularly food or medicinal grade mineral oils from mineral oil distillates. The first reaction stage employs a sulfur resistant hydrotreating catalyst and produces a product suitable for use as a high quality lubricating oil base stock. The second reaction stage employs a hydrogenation/hydrodesulfurization catalyst. The third stage employs a reduced metal sulfur sorbent producing a product stream which is low in aromatics and which has substantially “nil” sulfur. The final reaction stage employs a selective hydrogenation catalyst that produces a product suitable as a food or medicinal grade white oil. | 2 |
This application is a continuation of application Ser. No. 11/161,912, filed Aug. 22, 2005 (now U.S. Pat. No. 8,411,194), the entirety of which is hereby incorporated by reference.
BACKGROUND
Disclosed embodiments relate to handheld devices, and more particularly to combining image capture and image projection functions within a single device. Small, handheld electronic devices such as personal digital assistants (PDAs) and cell phones have incorporated still and/or video camera capabilities, and the trend is expanding. However, these devices have limited display capabilities because of their small size. Consequently, the small display size limits a user's ability to view or share pictures and/or videos with others.
SUMMARY
New and efficient light sources such as light emitting diodes (LEDs) have made it possible to construct very small projectors with digital light processing (DLP™) technology that can project images that are large enough and bright enough for small groups of people to share. Combining image projection and image capture functions in very small handheld devices will thereby overcome the direct-view display size limitation, and allow users to make small group presentations or put on family slideshows or videos.
Described are handheld devices with combined image capture and image projection functions. The disclosed handheld devices are operable to both project and capture images, thereby overcoming the direct-view display size limitation. One embodiment of the handheld device includes a light source projecting a light beam along a first optic path and being modulated along a second optic path by a reflective light modulator. An image sensor may then capture an image reflected from the second optic path back along the first optic path by the reflective light modulator. In another embodiment, the reflective light modulator and the image sensor may be situated on a mechanical structure that is operable to switch between providing the reflective light modulator for image projection and providing the image sensor for image capture. In yet another embodiment, the reflective light modulator and the image sensor may be formed on the same semiconductor substrate, with the image sensor operable to capture an image reflected from multiple optic paths by the reflective light modulator.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagram of an optical projection system; and
FIG. 2 is a diagram of an optical projection/camera system with a presently disclosed image sensor embodiment;
FIGS. 3A-3B are diagrams of an optical projection/camera system with a presently disclosed mirror/prism embodiment;
FIGS. 4A-4B are diagrams of an optical projection/camera system with a presently disclosed mechanical structure embodiment;
FIGS. 5A-5B are diagrams of an optical projection/camera system with a presently disclosed circular turret-like structure embodiment;
FIGS. 6A-6B are diagrams of an optical projection/camera system with another presently disclosed mechanical structure embodiment;
FIGS. 7A-7B are diagrams of an optical projection/camera system with a presently disclosed support structure embodiment;
FIGS. 8A-8B are diagrams of an optical projection/camera system with a presently disclosed projection/imaging lens embodiment;
FIG. 9 is a diagram of an optical projection/camera system with a presently disclosed dual lens embodiment;
FIG. 10A illustrates a top-down view of a 3×3 array of digital micromirror device cells; and
FIG. 10B is a diagram of an optical projection/camera system with a presently disclosed integrated image sensor embodiment.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 is a diagram of the various devices and components of an optical projection system 100 generally starting with a light source 102 , such as light emitting diodes (LEDs) or lasers. The beams of light from the light source 102 are processed by optical devices 104 , including but not limited to color separation elements such as color filters and color wheels, optics such as condensing, shaping, and relay lenses, and integrating elements such as an integrator. These optical devices 104 may substantially align, shape, configure, filter, or orient the beams of light. The processed light is then modulated by a spatial light modulator (SLM) 106 such as a digital micromirror device (DMD). The features and functions of SLMs and DMDs are further described in a commonly owned U.S. Pat. No. 6,038,056 entitled “Spatial light modulator having improved contrast ratio,” Ser. No. 09/354,838, filed Jul. 16, 1999, which is incorporated herein by reference in its entirety for all purposes. The SLM or DMD 106 substantially modulates and aligns the light before it is focused and projected by projection optics 108 onto an image plane such as a screen 110 .
FIG. 2 illustrates a presently disclosed embodiment integrating an image-capturing device such as a charge-coupled device (CCD) image sensor 112 within an optical projection system 100 . A complementary metal oxide semiconductor (CMOS) image sensor 112 may also be used. Both the CCD and the CMOS image sensors 112 digitally capture images by converting light into electric charge and processing the charge into electronic signals. The electronic signals may then be stored on an image processing electronics (not shown). Additionally, the image processing electronics (not shown) of the image sensor 112 may be integrated with the processing electronics of the DLP chip 106 . As illustrated, the CCD image sensor 112 resides within an optic path of the optical devices 104 between the light source 102 and the DMD 106 . In image capture or camera mode, an incoming image 114 may be collected by the projection optics 108 and focused upon the DMD 106 . The projection lens 108 is acting like a camera lens 108 whereby the lens 108 may refocus or shift as necessary to capture the image 114 at an optimal focal length 116 .
Because of the DMD's 106 mirror-like surface, the incoming image 114 may be reflected toward the same optic path as that of the optical devices 104 and the CCD image sensor 112 . The CCD image sensor 112 records and stores the incoming image 114 as it reflects off the DMD 106 and into the common optic path. One of the benefits of the presently disclosed embodiment is that alternating between projection mode and camera mode may be accomplished by sliding the CCD image sensor 112 into or out of the optic path of the optical devices 104 . In this and in subsequent described embodiments, a mechanical actuator such as a motor, a relay, or other electromechanical devices may be provided to meet the mechanical movements. Additional advantages include the ability to match the size and resolution of the CCD image sensor 112 with the DMD 106 by matching the magnification between image projection and image capture. In another embodiment, depending on whether the DMD 106 mirrors are turned to the “on-state” or the “off-state,” the incoming image 114 may be directed to an alternate optic path 118 .
FIGS. 3A-3B illustrate another embodiment in which a CCD image sensor 112 is incorporated within an optical projection system. As illustrated, the CCD image sensor 112 is situated at 90 degrees relative to the DMD 106 . A single mirror or prism 120 may be positioned parallel with and in front of the CCD image sensor 112 . The single mirror or prism 120 actuates to one of two positions. In FIG. 3A projection mode 122 , the single mirror 120 remains parallel with the CCD image sensor 112 thereby allowing light from the DMD 106 to be focused by the projection lens 108 and projected out onto a screen 110 . In FIG. 3B camera mode 124 , however, the single mirror 120 extends or flips out into the optic path between the DMD 106 and the camera lens 108 . As a result, an incoming image 114 may be focused by the camera lens 108 , reflected by the single mirror or prism 120 , and captured by the CCD image sensor 112 .
FIGS. 4A-4B illustrate another embodiment whereby a CCD image sensor 112 can slide into position depending on the mode of operation. As illustrated, a CCD image sensor 112 may be positioned parallel with and in front of the DMD 106 . In FIG. 4A projection mode 122 , the CCD image sensor 112 resides off the optic path thereby allowing light from the DMD 106 to be focused by the projection lens 108 and projected out onto a screen 110 . In FIG. 4B camera mode 124 , however, the CCD image sensor 112 rotates or translates into the optic path between the DMD 106 and the camera lens 108 . As a result, an incoming image 114 is focused by the camera lens 108 and captured by the CCD image sensor 112 . The lens 108 may automatically or manually refocus to compensate for optimal focal length 116 as necessary. Alternatively, the CCD image sensor 112 could be fixed and the DMD 106 could be the device that is switched in or out of the optic path.
FIGS. 5A-5B illustrate another embodiment whereby a CCD image sensor 112 may be adjacent to a DMD 106 with their backs (non-functional surfaces) to each other on a circular turret-like structure 126 . Also, the turret-like structure 126 need not be circular as long as it can substantially rotate about at least one axis. Alternatively, the CCD image sensor 112 and the DMD 106 may be flip-chip packaged together to a common substrate or circuit board. The CCD image sensor 112 and the DMD 106 may also be formed on the same semiconductor substrate. In FIG. 5A projection mode 122 , the DMD 106 is blocking the CCD image sensor 112 thereby allowing light from the DMD 106 to be focused by the projection lens 108 and projected out onto a screen 110 . In FIG. 5B camera mode 124 , the circular turret-like structure 126 rotates thereby exposing the CCD image sensor 112 to the optic path rather than the DMD 106 . As a result, an incoming image 114 may be focused by the camera lens 108 and captured by the CCD image sensor 112 . The camera lens 108 may not have to refocus the incoming image 114 because the CCD image sensor 112 and the DMD 106 may be situated at the same focal length 116 . Alternatively, the circular turret-type structure 126 may make full or partial rotations.
FIGS. 6A-6B illustrate another embodiment whereby a CCD image sensor 112 may be placed adjacent to a DMD 106 on a rectangular structure 128 . The rectangular structure 128 need not be rectangular as long as the structure 128 can substantially translate about an axis. Additionally, the CCD image sensor 112 and the DMD 106 may be formed next to each other on the same semiconductor substrate or mounted together to a common substrate or circuit board in a multi-chip module. In FIG. 6A projection mode 122 , the rectangular structure 128 translates in one direction (in this case upward as is shown in the figure) so that only the DMD 106 is exposed to the optic path thereby allowing light from the DMD 106 to be focused by the projection lens 108 and projected out onto a screen 110 . In FIG. 6B camera mode 124 , the rectangular structure 128 translates in the opposite direction (downward) thereby exposing only the CCD image sensor 112 to the optic path. As a result, the camera lens 108 focuses the incoming image 114 to be captured and stored by the CCD image sensor 112 . No refocusing of the lens 108 may be necessary because the CCD image sensor 112 and the DMD 106 may be situated at the same focal length 116 . Alternatively, the rectangular structure 128 may translate along more than one axis.
FIGS. 7A-7B illustrate another embodiment whereby a CCD image sensor 112 and a DMD 106 are each supported by a support structure 130 . The CCD image sensor 112 and the DMD 106 may also be formed next to each other on the same semiconductor substrate, and maintained together as a single unit by a single support structure 130 . In FIG. 7A projection mode 122 , the support structure 130 for the DMD 106 is at the 12 o'clock position while the support structure 130 for the CCD image sensor 112 is at the 2 o'clock position. In this mode, the DMD 106 support structure 130 lines up the DLP chip 106 to the optic path thereby allowing light from the DMD 106 to be focused by the projection lens 108 and projected out onto a screen (not shown). The optic path is normal (coming out of the paper) to the DMD 106 while the projection lens 108 is parallel with the DMD 106 and is illustrated as being on top of the DMD 106 . In FIG. 7B camera mode 124 , the DMD 106 support structure 130 moves or rocks from the 12 o'clock position (in projection mode 122 ) to the 10 o'clock position (in camera mode 124 ), thereby taking the DLP chip 106 out of the optic path. Additionally, the camera lens 108 support structure 130 moves or rocks from the 2 o'clock position (in projection mode 122 ) to the 12 o'clock position (in camera mode 124 ) thereby lining up the CCD image sensor 112 to the optic path and allowing an incoming image (not shown) to be focused by the camera lens 108 and captured and stored by the CCD image sensor 112 . Alternatively, the support structures 130 may “rock” optical devices 106 , 112 into position (into an optic path) by various switching mechanisms including translating, rotating, or combinations thereof. Also, the degree or amount of moving or rocking need not have a fixed magnitude (from 12 o'clock to 10 o'clock), but may vary depending on design and device constraints.
FIGS. 8A-8B illustrate another embodiment whereby a lens 108 switches back and forth between FIG. 8A projection mode 122 and FIG. 8B camera mode 124 . As illustrated, a CCD image sensor 112 is adjacent to a DMD 106 . The two devices 112 , 106 may also be formed on the same semiconductor substrate or mounted to a common substrate or circuit board. Furthermore, the processing electronics (not shown) for the two optical devices 112 , 106 may be integrated. In FIG. 8A projection mode 122 , a projection lens 108 resides within an optic path of the DMD 106 thereby allowing light from the DMD 106 to be focused by the projection lens 108 and projected out onto a screen 110 . In FIG. 8B camera mode 124 , a camera lens 108 resides within an optic path of the CCD image sensor 112 thereby allowing an incoming image 114 to be focused by the camera lens 108 and captured and stored by the CCD image sensor 112 . The lens 108 switches back and forth depending on the mode of operation 122 , 124 , and may also automatically or manually refocus to compensate for optimal focal length 116 as necessary. The various switching mechanisms may include translating, rotating, or combinations thereof.
FIG. 9 illustrates another embodiment whereby two lenses 108 are provided within an optical projection system. As illustrated, a projection lens 108 resides in a DMD's 106 optic path during projection mode 122 , and a camera lens 108 resides in a CCD image sensor's 112 optic path during camera mode 124 . The two lenses 108 need not be the same and may be optimized based on the type of optical devices 112 , 106 that are used. The lenses 108 may also have different magnification and resolution depending on the size of the DMD 106 and the size of the CCD image sensor 112 . In addition, although the CCD image sensor 112 is adjacent to the DMD 106 , the two devices 112 , 106 may be formed on the same semiconductor substrate or mounted to a common substrate or circuit board. Furthermore, the processing electronics (not shown) of the two devices 112 , 106 may be integrated. In projection mode 122 , light from the DMD 106 may be focused by the projection lens 108 and projected out onto a screen 110 , while in camera mode 124 , an incoming image 114 is focused by the camera lens 108 and captured and stored by the CCD image sensor 112 . The two lenses 108 may also allow images to be captured and projected simultaneously.
FIGS. 10A-10B illustrate yet another embodiment whereby a CCD or a CMOS image sensor 112 may be integrated with a DMD 106 on the same semiconductor substrate. FIG. 10A illustrates a top-down view of a 3×3 array of DMD cells 107 . There may be thousands or millions of these DMD cells or pixels 107 within a DMD chip 106 . Because of the nature of the DMD chip 106 , there are areas 132 on the die surface that are not completely covered by the pixel mirrors 107 . These uncovered areas 132 are spacings or gaps between the DMD pixels 107 that must exist in order for the pixels 107 to actuate or tilt. For a typical DMD chip 106 today, the unused area 132 is approximately equivalent to a pixel cell area for a CCD or a CMOS image sensor 112 . Therefore, it is feasible to add camera functionality to the semiconductor substrate of the DMD chip 106 in these unused areas 132 thereby providing dual functionality in a single chip without degrading the function or utility of either. Furthermore, with the coming of wafer-level packaging of DMD chips 106 , there will be other large areas (not shown) of unused silicon around the perimeter of a DMD chip 106 that could also be used to include the imaging CCD or CMOS circuitry 112 .
FIG. 10B further illustrates additional advantages of integrating a CCD or a CMOS imaging sensor 112 with a DMD chip 106 on the same semiconductor substrate. The 3×3 array of DMD cells 107 of FIG. 10B is similar to that of FIG. 10A except that the DMD mirrors 107 in FIG. 10B are actuating to one side, as is illustrated by the slight tilting of the DMD mirrors 107 . Depending on whether the DMD mirrors 107 are operating in an “on” or “off” state, they will tilt to a certain angle. As a result, additional light may be captured or collected by a CCD or CMOS image cell 112 within an optical projection system 100 . As is shown in the system 100 , the top and the bottom of the DMD mirrors 107 may be deposited with the same material, typically aluminum or some other reflective metallic material. As an incoming light or image 114 is collected by a camera lens 108 and is being focused upon the DMD mirrors 107 , it is once reflected by the top surface of the DMD mirror 107 towards an adjacent or neighboring DMD mirror 107 . The once-reflected light 134 can then be twice reflected by the bottom surface of the neighboring DMD mirror 107 . The twice-reflected light 136 is then captured or collected by the CCD or CMOS image cell 112 that lies between unused areas 132 of a DMD chip 106 . In other words, when the DMD mirrors 107 substantially actuate in one direction such that the electronic device is being used in camera mode, they form a rhomboid reflector or periscope action which helps to guide more light to be captured or collected by the CCD/CMOS cells 112 situated underneath the DMD mirrors 107 . Additionally, there may be multiple reflections (not shown) before the CCD/CMOS cells 112 capture the additional light. Also, the CCD/CMOS cells 112 may capture an incoming light directly without any reflection by the DMD mirrors 107 .
Other advantages that could result in low cost by adding functionality due to sharing of many components, especially electronics and optics, may include multi-functional use of the common optics including integrating projector and camera image processing electronics on a single chip. Furthermore, additional functionalities may include sharing a single dynamic random access memory (DRAM) chip to store images from the projector and the camera, sharing a system control microprocessor, or sharing FLASH memory for programming both camera control operations and projector control operations. Also, power supply and battery, as well as universal serial bus (USB) ports and other input/output (I/O) ports may also be shared. In addition, a new digital signal processing (DSP) chip integrating many of these functions may also be added to the electronic device.
It will be appreciated by those of ordinary skill in the art that the invention can be embodied in other specific forms without departing from the spirit or essential character thereof. For example, although an image-capturing device such as a CCD or CMOS image sensor may be integrated within an optical projection system, an image-projecting device such as a DMD or a DLP chip may be integrated within an optical imaging system like a digital camera or camcorder or even with a cellular phone or hand-held gaming device. In addition, although several embodiments have been illustrated, other orientations of the image sensor (CCD or CMOS) and image projector (DMD and DLP) not shown may nevertheless work encompassing the same or similar concepts of the presently disclosed embodiments. The presently disclosed embodiments are therefore considered in all respects to be illustrative and not restrictive. The scope of the invention is indicated by the appended claims rather than the foregoing description, and all changes that come within the meaning and ranges of equivalents thereof are intended to be embraced therein.
Additionally, the section headings herein are provided for consistency with the suggestions under 37 C.F.R. §1.77 or otherwise to provide organizational cues. These headings shall not limit or characterize the invention(s) set out in any claims that may issue from this disclosure. Specifically and by way of example, although the headings refer to a “Technical Field,” the claims should not be limited by the language chosen under this heading to describe the so-called technical field. Further, a description of a technology in the “Background” is not to be construed as an admission that technology is prior art to any invention(s) in this disclosure. Neither is the “Summary” to be considered as a characterization of the invention(s) set forth in the claims found herein. Furthermore, any reference in this disclosure to “invention” in the singular should not be used to argue that there is only a single point of novelty claimed in this disclosure. Multiple inventions may be set forth according to the limitations of the multiple claims associated with this disclosure, and the claims accordingly define the invention(s), and their equivalents, that are protected thereby. In all instances, the scope of the claims shall be considered on their own merits in light of the specification, but should not be constrained by the headings set forth herein. | Described are handheld devices with combined image capture and image projection functions. One embodiment includes modulating and capturing a light beam along the same optic path. In another embodiment, the optical components are operable to switch between projection and capture modes. In yet another embodiment, the optical components may be formed on the same semiconductor substrate thereby increasing functionality. | 7 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority from U.S. Provisional Patent Application Ser. No. 61/252,241 filed on Oct. 16, 2009, the entirety of which is expressly incorporated by reference herein.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to hunting and wildlife accessories and, more particularly, to deer attracting aids.
2. Discussion of the Related Art
It is well known that hunting and observing deer are popular activities. It is also known that to see deer, stalking techniques in which the hunter or observer tries to approach the deer is extremely difficult since deer have keen senses for detecting predators.
It is therefore often desirable to try luring deer or attracting them to a predetermined location for hunting or observing. Naturally attracting deer by providing, for example, a food plot near a hunting blind or observation blind is one common technique. However, food plots are typically large and a hunter or observer may not be able to readily see deer in certain portions of plots that are furthest from a blind.
Attempts have been made to attract deer to more specific locations than to general locations like food plots in order to increase the likelihood that the hunter or observer will have a clear line of sight to the deer at such specific location. These attempts include providing bait, minerals, and artificial scents to attract the deer to specific locations. These techniques can be expensive, time consuming, and may not be permitted in certain hunting or observing jurisdictions.
SUMMARY OF THE INVENTION
The present inventor has recognized that regular replenishing activities for maintaining baits, minerals, and artificial scents, at particular locations creates predator-like pressures upon the deer. The present inventor recognized that deer may react to these pressures by reducing activity and at times even temporarily fleeing or “bumping” to different locations. The present inventor has further recognized that over time, deer will learn the schedule of the hunter's or observer's regular replenishing activities. The deer may then start patterning the hunter's or observer's own schedules for replenishing activities and “bump” to other locations or reduce activity levels accordingly.
The present inventor has therefore developed a device for attracting deer to a specific location that is minimally invasive to deer habitat, is easily portable and can be quickly assembled, and which requires very little human maintenance and replenishing over time. The device capitalizes on a deer's curiosity to initially attract it near the device and then further capitalizes on a deer's olfactory sensitivity to entice it to investigate a scent on the device once it is near. The deer may be further enticed to leave its own scent on the device by scent marking, licking, or otherwise. This may encourage other deer to do the same, whereby with a nominal amount of human activity or presence, the device may function as an auto-regenerating communal scent post for the deer.
Specifically, in accordance with an aspect of the invention, at least one of these desires is fulfilled by providing a deer attracting device that includes a base that is supported from below by a ground surface and a lock that is connected to the base. The lock defines a locked position and an unlocked position. A visual lure is removably held by the lock and extends upwardly from the base so that it can be viewed by deer. When the lock is in the locked position, the visual lure is retained in the device. When the lock is in the unlocked position, the visual lure can be readily withdrawn or removed from the device. This modular configuration may enhance portability and ease of assembly and dissemble of the device. This could be desirable because the device may have to be transported relatively far distances into a woods, field, or other suitable location for use.
In accordance with another aspect of the invention, the visual lure may be at least one of a tree, a portion of a tree, a replica of a tree, and a replica of a portion of a tree. Such configuration may provide a substantially natural appearance to the visual lure, so as to not appear overly-foreign and perhaps startling to the deer. Correspondingly, by placing the device so that it is sufficiently spaced from other trees, the visual lure may be visually conspicuous and easily recognizable by the deer.
In accordance with another aspect of the invention, the visual lure is configured to and/or capable of receiving a scent carrier emitting a deer attracting scent. The visual lure can maintain the scent carrier thereon for extended periods of time, for example, four hours, eight hours, twelve hours, or more. While the scent carrier is maintained on the visual lure, the scent carrier continues to emit the deer attracting scent to an extent that is detectable by the deer. The scent carrier may resemble or be made from at least one of a glandular secretion, a pheromone, a foodstuff, which may entice deer to scent mark upon or lick the visual lure. Doing so leaves the deer's own scent in addition to and/or in place of that of the scent carrier. This may encourage further investigation of the visual lure by other deer. Such other deer may also be enticed into scent marking and/or licking the visual lure. This activity may continue so that the device serves as, for example, an auto-regenerating communal scent post.
In accordance with another aspect of the invention, the device includes a column that extends upwardly from the base and interconnects the base and the lock. The column may be transversely flexible in a manner that allows the visual lure to bend toward the ground and restore to its initial upright position. The column may be a coil spring that concentrically accepts an end of the visual lure therein to hold the visual lure in the upright position. By spacing the lock from the base with the column, the visual lure can be supported through a relatively large supporting interface between it and the rest of the device, which may enhance stability.
In accordance with another aspect of the invention, the lock includes a collar having a longitudinally extending central bore. A width of the collar bore may be about three-inches or less to accommodate relatively small trees, if trees are being used as the visual lures. A setscrew may extend through the collar and being radially movable into and out of the collar bore. In such configuration, (i) the locked position of the lock is defined when the setscrew is moved inwardly into the collar bore, and (ii) the unlocked position of the lock is defined when the setscrew is moved outwardly from the collar bore. The setscrew may be configured for tool-less operation by, for example, having a thumbscrew configuration or a knob at its outer end that can be turned by hand. The tool-less operation of the lock may shorten the amount of time required to assemble and disassemble the device.
In accordance with another aspect of the invention, the device includes at least one stake that extends downwardly from the base and inserts into the ground, so as to hold the base in a fixed location upon the ground. The stake may have a length that is at least two-times that of the column and which may be at least one-half of an overall length or height of the device. The stake may have an irregular outer surface that interlocks with the ground when the stake is inserted into the ground. The irregular outer surface of the stake may be defined by ribs that extend outwardly from the stake and are spaced from each other along the length of the stake. In some implementations, each stake may be made from a piece of rebar typically used for reinforcing concrete or masonry, or from similar stock and of similar size. The stake may have a substantially flat cap welded or otherwise affixed to its upper end. The cap may prevent the stake from pulling through the base during use. The substantial length and irregular outer surface characteristics of the stake can provide a stronger gripping interface between the stake and the ground, enhancing the anchoring function of the stake.
In accordance with another aspect of the invention, the device may be part of a kit for attracting deer to a particular location. The kit may include the device itself and the corresponding visual lure and also the scent carrier that emits a deer attracting scent, allowing a user to set up the device as an auto-regenerating communal scent post for deer. The kit may be used to attract deer to a particular location for observation by a hunter or a wildlife watcher. Or, the kit may be used to attract deer to a particular location so as to discourage their presence at other locations, for example to attract deer away from ornamental sapling trees or other decorative landscaping that the deer might otherwise bother.
Various other features, embodiments, and alternatives of the present invention will be made apparent from the following detailed description taken together with the drawings. It should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration and not limitation. Many changes and modifications could 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 DRAWINGS
Preferred exemplary embodiments of the invention are illustrated in the accompanying drawings, in which like reference numerals represent like parts throughout, and in which:
FIG. 1 is a pictorial view of a deer attracting kit in accordance with the present invention; and
FIG. 2 is a side elevation view of a variant of the deer attracting device of the kit of FIG. 1 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following detailed description is of the best currently contemplated modes of carrying out exemplary embodiments of the invention. The description is not to be taken in a limiting sense, but is made merely for the purpose of illustrating the general principles of the invention, since the scope of the invention is best defined by the appended claims.
Referring initially to FIGS. 1 and 2 , the drawings illustrate exemplary embodiments of deer attracting systems of the invention, shown as kits 5 . Each kit 5 has a deer attracting device 10 and one or more scent carriers 12 , 14 . The deer attracting device 10 is visually conspicuous to deer and visually entices the deer into approaching the device 10 . After approaching the device 10 , the scent carriers 12 , 14 further entice the deer into applying their own scent to the device 10 by scent marking or licking, explained in greater detail elsewhere herein.
Referring now to FIG. 1 , deer attracting device 10 of this embodiment includes a base 20 that is supported from below by a ground surface and a lock 50 that removably holds a visual lure 80 so that it stands upright and can be easily seen by deer. Base 20 is substantially planar and has a lower surface that sits directly on the ground surface and an upper surface that faces away from the ground. The dimensions of base 20 are selected to provide a lower surface area that correspondingly gives a footprint against, or interface with, the ground. This large surface area helps the base 20 resist puncturing into the ground due to, e.g., the weight of the overall device 10 and also gives tipping-negating stability to the device 10 . In one embodiment, the lower surface of base 20 has a surface area of at least about thirty-six square inches, more preferably at least about fifty square inches. In one embodiment, the base 20 has a square perimeter shape with dimensions of about six inches by six inches with a thickness dimension of about ¼ inch or ⅛ inch.
Still referring to FIG. 1 , in this embodiment, two mounting holes 22 extend through the entire thickness of base 20 , on opposing sides of the base 20 . The mounting holes 22 are provided near the perimeter edge of the base 20 , for example, each being within two inches or preferably within one inch of the perimeter edge. The particular configuration of mounting holes 22 is based on characteristics of the stakes 30 that extend through the holes 22 to anchor the base 20 to the ground. For example, a single mounting hole 22 may be provided for versions of base 20 that use only a single stake 30 , whereas more that two mounting holes 22 are provided for versions of base 20 that use more than two stakes 30 . The inside diameter (ID) of the holes 22 is large enough to accommodate the stakes 30 therethrough, preferably only having about a ⅛ inch clearance between the ID surface of the mounting holes 22 and the stakes 30 to prevent or reduce sloppiness in the joint and/or stake-to-base rattling sounds during use. In another embodiment, no mounting holes 22 are provided in the base 20 and instead the stake(s) 30 is fixed, attached, or joined to the base 20 .
Still referring to FIG. 1 , stake 30 is an elongate pin that is driven into and anchors the base 20 to the ground. The dimensions of stakes 30 are selected to provide a substantial amount of surface area against the abutting ground surface to create a large amount of withdrawal-preventing friction therebetween. In one embodiment, stake 30 has a length that is at least two-times that of portion of the device 10 that sits above the ground, whereby the stake 30 is at least one-half of the overall length or height of the entire device 10 . In one embodiment, the stake 30 is at least about 16 inches long and has a width or diameter of at least about ½ inch, which provides sufficient surface area for anchoring most implementations of the device 10 to the ground.
Referring still to FIG. 1 , stake 30 may have an irregular or discontinuous outer surface to enhance its anchoring characteristics. In this embodiment, the irregular outer surface of the stake 30 is defined by ribs 32 that extend outwardly from its shaft portion and are spaced from each other along its length. In one embodiment, the stake 30 is made from a piece of reinforcing bar (rebar) stock that is commonly used to reinforce concrete or masonry, and that is cut to length and ground to a point or sharpened on its lower end. At its upper end, a cap 35 is fixed to the shaft of the stake 30 . Cap 35 is wider than the ID of the corresponding mounting hole 22 . Preferably the cap 35 is thin, rising less than about ⅛ inch from the upper surface of the base 20 when the stake 30 is fully inserted into the ground.
Referring yet further to FIG. 1 , in this embodiment, a column 40 extends between the base 20 and the lock 50 , elevating the lock 50 with respect to the base 20 . Column 40 is in the form of a cylindrical tube that is fixed to and extends generally orthogonally upward from the middle of the upper surface of the base 20 .
Referring now to FIG. 2 , column 40 of this embodiment is transversely flexible, relative to its longitudinal axis, in a manner that allows the visual lure 80 to bend toward the ground and then restore to its initial upright position. The column 40 of this embodiment is a coil spring, shown here as a compression spring. It is noted that while a compression spring is shown, in some embodiments, the flexible versions of column 40 may be tension springs, non-coiled springs, or other suitably flexible, preferably resiliently flexible, structures that can attach the base 20 and lock 50 to each other while providing restorative forces to return the visual lure 80 to an upright position after being bent downwardly.
Referring now to FIGS. 1 and 2 , lock 50 , which sits at the top of the column 40 of these embodiments, defines a locked position and an unlocked position. In the locked position, lock 50 retains the visual lure 80 in it, whereas in the unlocked position, the visual lure 80 can be removed from the lock 50 . In the embodiment shown in FIG. 1 , the lock 50 includes a collar 55 and setscrews 60 that extend through the collar 55 into a longitudinally extending bore of the collar 55 . In one embodiment, the diameter of the collar bore is about three inches or less, although the particular dimensions and configurations of the collar 50 and setscrews 60 are selected to correspond to the configuration of the end of the visual lure 80 that inserts into the collar 50 .
In the embodiment of FIG. 1 , the lower end of the visual lure 80 is placed on the upper surface of the base 20 , and the lock 50 is then engaged with the visual lure 80 at a location above the lower end of the visual lure 80 . The column 40 thus serves to rigidly secure the bottom of the visual lure 80 in position on the base 20 . The lower end of the visual lure 80 may be secured similarly in the embodiment of FIG. 2 . In this instance, the spring that forms the column 40 simply serves to rigidly support the lower end of the visual lure 80 , since engagement of the lower end of the visual lure 80 with the bottom of the spring column 40 stiffens the spring column 40 and prevents it from flexing. Alternatively, the visual lure 80 may be positioned such that its lower end is spaced above the upper surface of the base 20 by any desired distance. When visual lure 80 is secured in this manner, the length of the spring column 40 above the base 20 and below the lower end of the visual lure 80 provides a degree of flexibility to the mounting of the visual lure 80 . In this manner, the visual lure 80 will “give” when the deer in engages it, which provides an added degree of stimulation or movement that can hold a deer's interest. To provide a relatively small degree of flexibility of the visual lure 80 , the lower end of the visual lure 80 is positioned relatively close to the upper end of the base 20 . To increase the amount of flexibility of the visual lure 80 , the lower end of the visual lure 80 is moved outwardly away from the base 20 and toward the lock 50 . The length of the visual lure 80 contained within the spring column 40 functions to stiffen the spring column 40 , such that the stiffness of the spring column 40 is controlled by the closeness of the lower end of the visual lure 80 to the upper surface of the base 20 .
Still referring to FIGS. 1 and 2 , the locks 50 of these embodiments are configured for tool-less operation. In these particular embodiments, the setscrews 60 are shown as being thumbscrews that can be tightened and loosened by hand. In another embodiment, the setscrews 60 have knobs that can be tightened and loosened by hand. In yet other embodiments, the lock 50 includes a cam-lock, a constricting band, or other suitable hardware, that is used to selectively secure the visual lure 80 into the lock 50 . The lock 50 may also include collar 55 and nails or screws are driven through the holes of the collar and into the visual lure 80 to retain it in the device 10 .
Still referring to FIGS. 1 and 2 , in the complete assemblage of these embodiments, a lower end of the visual lure 80 is held concentrically in the lock 50 . The visual lure 80 preferably stands substantially upright and has any desired height, which may be least about four feet tall. The particular height of the visual lure 80 is selected based on the end-use location of the device 10 . For example, when the device 10 is placed in an open field and relatively far from, e.g., trees or other tall habitat structures, the visual lure 80 may be relatively taller to ensure that is can be seen from far distances. When the visual lure 80 is placed within a tree-crowded woods habitat and near a deer trail, the visual lure 80 can be relatively shorter because the deer will not have to see it from such far distances. In this situation, a shorter visual lure 80 amongst tall trees may blend in less with the surrounding trees, thereby making the visual lure 80 more visually conspicuous in this particular setting.
Referring now to FIG. 2 , in this embodiment, the visual lure 80 is a sapling or tree, noting that in other embodiments, a tree-like version of the visual lure 80 is a branch or other portion of a tree, a replica of a tree, and a replica of a portion of a tree. Preferably, the trees or portions of trees have been recently cut and are fresh, for example still having their leaves.
Referring again to FIGS. 1 and 2 , regardless of the particular configuration of the visual lure 80 , it serves as not only visually enticing deer to approach it, but also as a holding substrate for the scent carrier 12 , 14 . In use, the scent carrier 12 , 14 is applied to the lure 80 so that the scent carrier 12 , 14 and lure 80 cooperate with each other to present a scent that is detectable and intriguing to deer for an extended period of time. The period of time is preferably, for example, four hours, eight hours, twelve hours, or more, depending on the particular composition of the scent carrier 12 , 14 .
Still referring to FIGS. 1 and 2 , in some embodiments, the scent carrier 12 , 14 may resemble or be made from deer-specific tissues, secretions, or fluids. These may include deer glandular secretions, pheromones, urine, and/or others. In other embodiments, the scent carrier 12 , 14 may resemble or be made from a non-deer-specific materials. For example, the scent carrier 12 , 14 may be or resemble the scent of a foodstuff that is either native or alternatively foreign to the particular habitat in which the device 10 is being used. Regardless, the scent carrier 12 , 14 is configured to encourage deer to leave their own scent(s) scent marking and/or licking the scent carrier 12 , 14 from the visual lure 80 . This may encourage further investigation of the visual lure 80 by other deer. Such other deer may also be enticed into scent marking and/or licking the visual lure. This activity may continue over time so that the device 10 serves as, for example, an auto-regenerating communal scent post.
It should be understood, of course, that the foregoing relates to exemplary embodiments of the invention and that modifications may be made without departing from the spirit and scope of the invention as set forth in the following claims.
Various alternatives and embodiments are contemplated as being within the scope of the following claims particularly pointing out and distinctly claiming the subject matter regarded as the invention. | A deer attracting device and/or a kit incorporating the same facilitates luring deer to a specific location. The device includes a base that is supported from below by an underlying ground surface and a lock that holds a visual lure in an upright position, extending away from the base, so that deer can easily see the visual lure. A scent carrier may be applied to the visual lure and is configured to entice deer to apply their own scent(s) to the visual lure by scent marking or licking the lure. This encourages other deer to do the same after being visually drawn close enough to the visual lure to detect the scent. Correspondingly, the deer maintain or replenish the scent of the lure mitigating the need for a human to artificially do the same. The visual lure is maintained in position on the base be a column within which a lower end of the visual lure is received, and a lock that maintains the visual lure within the column. | 0 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application relates to and claims priority from U.S. Prov. Ser. No. 61/877,370 filed Sep. 13, 2014, the entire contents of which are incorporated fully by reference.
FIGURE SELECTED FOR PUBLICATION
[0002]
FIG. 1
BACKGROUND OF THE INVENTION
[0003] 1. Field of the Invention
[0004] The present invention relates to multi-functional compacts for cosmetics and the like. More particularly, the present invention relates to a parallelepiped-type (generally 6-sided-type) multi-functional compact with a magnifying mirror in which the compact has upper and lower housing portions that open in a clam-like manner about a hinge, wherein the upper portion houses the magnifying mirror and the lower portion houses one or more cosmetic products.
[0005] For illustration purposes, the present invention is described herein as embodied in compacts for cosmetics, it being understood, however, that its broader aspects the invention is not limited thereto but may also be embodied in compacts for containing other types of materials.
[0006] 2. Description of the Related Art
[0007] Compacts are commonly referred to as portable containers for housing many cosmetics materials, including face powders, foundations, eye shadows, blushes, and some lipsticks and mascaras. Conventional compacts include a base formed as a tray with one or more upwardly open recesses for holding the cosmetic material in compressed or like stable condition, and a cover for overlying the base and enclosing the tray to prevent the contents from drying out, becoming contaminated, spilling, or soiling outside objects. One or more brushes, pads such as powder puffs or other implements for applying the cosmetics may also be placed within the compact between the base and cover.
[0008] Typically, the base and cover are molded of plastic or formed of metal, and are hinged together along one side of the compact, a manually operable latch being provided on the other side to hold them in closed position. The compact is dimensioned to be held in the hand, and may be square, rectangular, oval, circular, or of other regular or irregular shape. To apply the contained cosmetics, the user opens the compact, draws an applying implement (or a finger) across the cosmetic material held in a recess of the base tray to pick up some of the material, and conveys it on the implement to the appropriate facial area.
[0009] Generally, a compact comprises a flat non-magnifying portable mirror which allows a user, particularly, a woman, views his/her face while making up the face indoors or outdoors, and thereby has a small size to be easily carried by the user within a handbag, a suitcase, or a pocket of a garment. Conventionally, a mirror is provided within the inwardly facing surface of the cover so as to be visible by a user when the compact is open and the user is applying the cosmetic material to the face. Thus, the user can easily and accurately apply the cosmetic when no external mirror is available. The disposition of the mirror within the compact cover is an important feature of convenience in that it enables the user to hold and position both the exposed body of cosmetic material and the mirror in one hand while employing the other hand to manipulate the applicator.
[0010] When a user needs to view partial areas of his/her face, such as the eyebrows, while magnifying the partial areas of the face during making up the face, the user wants to use a convex mirror. However, the conventional convex mirrors are produced at high costs, and are provided separately—typically with a separate handle, wall mount or counter-support mount, thus increasing the production costs of such items and rendering them unusable in ‘compact form.’ Typically it is known that conventional compact mirror cases and/or the cases of a variety of makeup compacts, such as pressed powder compacts, powder blusher compacts, cake mascara compacts, and eyeshadow compacts.
[0011] Moreover, because the conventional compact mirror cases and the conventional cases of the variety of makeup compacts are small-sized to be easily carried by users and are typically equipped with plane mirrors, the users only view their faces on the limited reflection surfaces of the plane mirrors. Thus, the conventional compact mirror cases and the conventional cases of the variety of makeup compacts are not multifunctional.
[0012] In conventional compacts containing mirrors, the plane mirrors installed have limited sizes of reflection surfaces, thus forcing a user to place the mirror at a position relatively far away from his/her face when the user needs to view his/her entire face reflected on the mirror. However, the user cannot clearly view the face since the image of the face focused on the mirror is too small.
[0013] Thus, when the user paints and/or powders partial areas of his/her face, such as the eye rims, the eyebrows or the lips, the user needs to view the partial areas of the face on the mirror while magnifying the partial areas to carefully make up the partial areas. In such a case, the user must repeatedly and alternately place the mirror at positions close to a partial area of the face to clearly view the partial area to be painted or powdered and at positions relative far away from the face to view the entire face to check the painted or powdered partial area with the other areas of the face, or alternatively divert their gaze to a conventional magnifying mirror-in a wall, counter, or floor mount type. The conventional compact mirror cases and the conventional cases of the variety of makeup compacts are thus inconvenient to use.
[0014] Also, it is often desirable to package a compact in a manner enabling retail customers to view the contained cosmetic material at the point of sale without exposing the material to contamination such as can occur if a compact is opened at a store by a prospective purchaser. Accordingly, the compact may be sealed in a transparent plastic film, e.g., in a blister package, with the cover opened to lie flat with the base so that the contents of the compact are clearly visible through the blister film.
[0015] Accordingly, there is a need in the art for an improved multi-functional, multilayered cosmetic compact case that overcomes the detriments seen in the known prior compact cases. There is a further need for an improved multi-functional, multilayered cosmetic compact case having a dual-layer base construction with a pull out side drawer including only a single magnifying mirror and a lie flat hinge assembly. There is also a need for an improved multi-functional, multilayered cosmetic compact case that has multiple compartments or wells for housing a plurality of products, and having a secure snap-fit mechanism for securely closing the compact when not in use.
ASPECTS AND SUMMARY OF THE INVENTION
[0016] According to the preferred embodiment of the invention, provided is a compact for holding cosmetic products comprising a base having a first product housing region for housing one or more cosmetic products, a cover hingedly connected to the base, and a side drawer slidably mounted in the base, wherein the side drawer comprises a second product housing region, wherein the cover has an inner surface and an outer surface, and wherein the cover carries an inwardly-facing mirror removably mounted on the inner surface by a removable frame member. The compact according to the invention has a cover carrying a detent that engages a protrusion positioned on the base to secure the base and the cover in a closed position, wherein the detent comprises at least one rib formed integrally with the cover to lock the cover in a closed position when the cover is moved from an open position into the closed position. Preferably, the minor is a single magnifying mirror and the compact has a generally square configuration. The cover has an extended closure member with a recess for engaging a corresponding protrusion on the base for securing the compact in a closed position. Also, the first and/or second product housing regions may comprise more than one rectangular or other shaped product wells. Also preferably, at least one of the cover portion and the base portion is made of a material selected from a transparent plastic, an opaque plastic, a metal, a wood, a composite, a polymer, or a ceramic. Optionally, the cover may comprise a window through which the cosmetic product can be viewed when the cover and the base are in a closed position.
[0017] In another embodiment of the invention provided is a compact comprising a case body having an inner frame to form a fitting groove to hold a first product well for containing a first cosmetic product, a cover having an inner mirror frame to form a fitting groove to hold a mirror, and a hinge assembly for movably interconnecting the cover to the case body, the hinge assembly coupled at both ends thereof to hinge shafts of the case body to form a hinged joint around which the cover is opened or closed relative to the case body. Preferably, at least one of the cover portion and the base portion is made of a material selected from a transparent plastic, an opaque plastic, a metal, a wood, a composite, a polymer, or a ceramic. Also, the case body is preferably provided at each side thereof with a hinge holder each spaced apart from one another to define a space between the hinge holders, with hinge shafts provided on inside surfaces of the hinge holders extending toward each other and inserted into both ends of a hinge hole formed in the upper housing member, and forming a hinge joint around which the cover portion is opened or closed relative to the base portion.
[0018] The present invention provides a compact for holding cosmetics in a square shape, including one or more wells for cosmetics and/or tools for application of same. The compact according to the present invention preferably opens and closes in a clam-like manner having a hinge assembly at the back end thereof and preferably a snap-fit closure at the front end thereof. Optionally, rectangle shapes having square-like corners may also be used. The cosmetic container according to the present invention preferably has only one magnifying mirror recessed in the top cover or upper housing portion. Depending on the product, e.g., eye, lip or face make-up, multiple product wells or areas may be used, but not more than one simple magnifying mirror. Preferably, the singular magnifying mirror has a magnification strength of approximately 2-3 times the normal. Of course, lesser or greater strength mirrors may also be used in conjunction with the present invention. Room exists left in the upper portion to expand to a greater strength mirror. The simple mirror compact assembly and system improves upon complicated prior systems that include interchangeable mirrors or multiple mirrors, which make manufacturing and distribution very difficult and expensive. Modification of the compact from the prior complex multi-mirror systems to a simple compact with a singular mirror allows for greater flexibility with respect to the choice of cosmetic products provided. Preferably, in one embodiment of the cosmetic compact according to the present invention provides a square single layer compact, for example, for use with blush or wet foundation.
[0019] In another embodiment of the cosmetic compact according to the present invention provides a dual (or double) layer cosmetic compact case bottom or lower portion having a pull-out drawer position therein for housing additional cosmetic product(s), for example, for use with concealing foundation with an applicator sponge.
[0020] In yet another embodiment of the cosmetic compact according to the present invention provides a square single layer compact having multiple product wells therein (i.e., 2, 3 or more smaller rectangular wells), for example, for use with 2-color eyebrow or 2 color concealer pack, or 3 shades of eye shadow, or even 4 or more.
[0021] In another embodiment of the cosmetic compact according to the present invention provides a dual (or double) layer cosmetic compact case bottom or lower portion having a pull-out drawer position therein for housing additional cosmetic product(s) each of the layers having multiple product wells therein (i.e., 2, 3 or more smaller rectangular wells), for example, for use with 2-color eyebrow or 2 color concealer pack, or 3 shades of eye shadow, or even 4 or more.
[0022] As shown and described herein, the cosmetic compact according to the preferred embodiment of the invention comprises a deep base closure to facilitate a longer top (male/female) closure. Preferably, the compact is configured in a square shape with slightly rounded edges to prevent cracking, although other rectangular-base shapes may be used. Within the base or lower portion of the cosmetic compact, there is provided a semi-permanently attached cosmetic well for housing a cosmetic product. There is also provided a deep internal return system within the upper well or frame of the compact to allow for the upper magnifying mirror having a slight concave configuration and a mirror frame. Preferably, there is provided an extended top closure portion on the upper housing portion for secure closing of the upper portion with the lower portion in view of the extra deep mirror portion and product base or lower housing portion. Preferably, the inner frames for securing the mirror and product wells appear invisible to allow for securing the magnifying mirror and/or product wells as well as making rounded edges still appear square. There is provided a cut out hinge system that allows for clam-like opening and closing of the cosmetic compact according to the invention. Preferably, the lower interior frame aligns the product well with the compact's upper portion. Also preferably, a pull out side drawer is provided for housing additional cosmetic product(s). This is an improvement over the existing compacts in that rather than a bottom drawer, which is very difficult and cumbersome to use while applying makeup, a side drawer provides simple and convenient access to the product positioned therein. Such a drawer will have a square shape finish such that its corners will match the corners of the upper and lower housing portions of the compact to essentially hide the drawer therein.
[0023] Accordingly, an object of the invention is to provide a new and improved cosmetic material container of the type comprising a compact. A particular object is to provide such a container providing a size or area of inwardly-facing simple mirror on the cover of the compact providing a significant mirror-magnification to allow efficient and accurate make-up application. Another object is to provide an improved multi-functional, multilayered cosmetic compact case having a dual-layer base construction with a pull out side drawer including only a single magnifying mirror, a lie flat hinge assembly, multiple compartments or wells for housing a plurality of products, and a secure snap-fit mechanism for securely closing the compact when not in use.
[0024] To these and other ends, the present invention broadly contemplates the provision of a compact for holding cosmetics or the like, including a base for containing a quantity of cosmetic material, and a cover hingedly connected to the base and having an extended area with an inner surface and an outer surface, disposed in a first portion of the extended area, and an inwardly-facing magnifying mirror, mounted on the inner surface. As a further feature of the invention, in currently preferred embodiments, the cover carries a latch mechanism that engages a receiving portion on a second lower housing portion or base to retain the cover in a closed position. The detent may comprise at least one rib formed integrally with the cover or lower housing portion or base.
[0025] The present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide a multifunctional compact mirror case, of which an upper case body seats, in a frame seating well thereof, a mirror frame having upper and lower portions, and in which the upper surface and a lower surface are concave and convex to form a concave lens part and a convex lens part, or convex or concave to form a convex lens part and a concave lens part, respectively, thus allowing a user to use a concave mirror function formed by both the concave lens part, and which allows the user to view his/her face on the upper plane mirror when the lid is open from the case body. This is thus efficiently used by the user outdoors while traveling, such as traveling on business, or indoors, such as in an office room. In the compact according to the invention, a transparent window may optionally be provided in the cover to enable point-of-purchase viewing of the contents of the compact with the compact in a closed position, while a replaceable mirror, initially underlying the cosmetic product, for example, leaves the window unobstructed, can be readily installed upon first use of the compact. A magnifying mirror use in combination with the construction is the most commonly envisioned use of the present invention, but nothing herein will so limit the invention to that most common use.
[0026] To achieve the above objects, according to a preferred embodiment of the present invention, there is provided a multi-functional and/or multi-layered cosmetic compact mirror case, comprising a base having a first product housing region for housing one or more cosmetic products, a cover hingedly connected to the base, and a side drawer slidably mounted in the base, wherein the side drawer comprises a second product housing region, wherein the cover has an inner surface and an outer surface, and wherein the cover carries an inwardly-facing mirror removably mounted on the inner surface by a removable frame member.
[0027] The compact described herein provides improved magnification with simplified design and fewer components. These characteristics are particularly advantageous in a variety of compacts for a variety of reasons, including, but not limited to, having a dual-layer base construction with a pull out side drawer including only a single magnifying mirror, having a lie flat hinge assembly, having multiple compartments or wells for housing a plurality of products, and having a secure snap-fit mechanism for securely closing the compact when not in use.
[0028] It is an aspect of the present invention to provide a compact that addresses the concerns and deficiencies in prior designs, and which is still functional, practical and aesthetically pleasing.
[0029] The above and other aspects, features and advantages of the present invention will become apparent from the following description read in conjunction with the accompanying drawings, in which like reference numerals designate the same elements.
BRIEF DESCRIPTION OF THE DRAWINGS
[0030] A further understanding of the present invention can be obtained by reference to a preferred embodiment set forth in the illustrations of the accompanying drawings. Although the illustrated preferred embodiment is merely exemplary of methods, structures and compositions for carrying out the present invention, both the organization and method of the invention, in general, together with further objectives and advantages thereof, may be more easily understood by reference to the drawings and the following description. The drawings are not intended to limit the scope of this invention, which is set forth with particularity in the claims as appended or as subsequently amended, but merely to clarify and exemplify the invention.
[0031] For a more complete understanding of the present invention, reference is now made to the following drawings in which:
[0032] FIG. 1 shows a perspective view of a dual-layer cosmetic compact depicted in an open configuration in accordance with the preferred embodiment of the present invention;
[0033] FIG. 2A shows a bottom plan view of the cosmetic compact shown in FIG. 1 depicted in a closed configuration according to the preferred embodiment of the present invention;
[0034] FIG. 2B shows a front plan view of the cosmetic compact shown in FIG. 1 depicted in a closed configuration according to the preferred embodiment of the present invention;
[0035] FIG. 2C shows a back plan view of the cosmetic compact shown in FIG. 1 depicted in a closed configuration according to the preferred embodiment of the present invention;
[0036] FIG. 3 shows a top right front perspective view of the cosmetic compact shown in FIG. 1 depicted in a closed configuration according to the preferred embodiment of the present invention;
[0037] FIG. 4 shows a front plan view of the cosmetic compact shown in FIG. 1 depicted in a closed configuration according to the preferred embodiment of the present invention;
[0038] FIG. 5 shows a left side plan view of the cosmetic compact shown in FIG. 1 depicted in a closed configuration according to the preferred embodiment of the present invention;
[0039] FIG. 6 shows a right side plan view of the cosmetic compact shown in FIG. 1 depicted in a closed configuration according to the preferred embodiment of the present invention;
[0040] FIG. 7 shows a back plan view of the cosmetic compact shown in FIG. 1 depicted in a closed configuration according to the preferred embodiment of the present invention;
[0041] FIG. 8 shows a bottom right front perspective view of the cosmetic compact shown in FIG. 1 depicted in a closed configuration according to the preferred embodiment of the present invention;
[0042] FIG. 9 shows a perspective view of a single-layer cosmetic compact depicted in an open configuration in accordance with an alternative embodiment of the present invention;
[0043] FIG. 10A shows a bottom plan view of the cosmetic compact shown in FIG. 9 depicted in a closed configuration according to an alternative embodiment of the present invention;
[0044] FIG. 10B shows a front plan view of the cosmetic compact shown in FIG. 9 depicted in a closed configuration according to an alternative embodiment of the present invention;
[0045] FIG. 10C shows a back plan view of the cosmetic compact shown in FIG. 9 depicted in a closed configuration according to an alternative embodiment of the present invention;
[0046] FIG. 11 shows a top right front perspective view of the cosmetic compact shown in FIG. 9 depicted in a closed configuration according to an alternative embodiment of the present invention;
[0047] FIG. 12 shows a front plan view of the cosmetic compact shown in FIG. 9 depicted in a closed configuration according to an alternative embodiment of the present invention;
[0048] FIG. 13 shows a left side plan view of the cosmetic compact shown in FIG. 9 depicted in a closed configuration according to an alternative embodiment of the present invention;
[0049] FIG. 14 shows a right side plan view of the cosmetic compact shown in FIG. 9 depicted in a closed configuration according to an alternative embodiment of the present invention;
[0050] FIG. 15 shows a back plan view of the cosmetic compact shown in FIG. 9 depicted in a closed configuration according to an alternative embodiment of the present invention; and
[0051] FIG. 16 shows a bottom right front perspective view of the cosmetic compact shown in FIG. 9 depicted in a closed configuration according to an alternative embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0052] As required, a detailed illustrative embodiment of the present invention is disclosed herein. However, techniques, systems, compositions and operating structures in accordance with the present invention may be embodied in a wide variety of sizes, shapes, forms and modes, some of which may be quite different from those in the disclosed embodiment. Consequently, the specific structural and functional details disclosed herein are merely representative, yet in that regard, they are deemed to afford the best embodiment for purposes of disclosure and to provide a basis for the claims herein which define the scope of the present invention.
[0053] Reference will now be made in detail to several embodiments of the invention that are illustrated in the accompanying drawings. Wherever possible, same or similar reference numerals are used in the drawings and the description to refer to the same or like parts or steps. The drawings are in simplified form and are not to precise scale. For purposes of convenience and clarity only, directional terms, such as top, bottom, up, down, over, above, below, etc., or motional terms, such as forward, back, sideways, transverse, etc. may be used with respect to the drawings. These and similar directional terms should not be construed to limit the scope of the invention in any manner.
[0054] Referring first to FIG. 1 , shown is a perspective view of the multi-layer or dual-layer compact 100 in accordance with the preferred embodiment of the present invention, depicted in an open configuration. As illustrated, compact 100 is of a generally square (or rectangular) plan configuration, dimensioned to be held in a user's hand, for holding a cosmetic material such as powder, blush, mascara, foundation, or the like, for application to the face. The compact 100 includes a base 11 preferably formed or provided with a side drawer 13 that houses a product well or housing region 14 , and a cover 5 is hingedly connected to the base 11 and has an extended area 8 with opposed inner and outer surfaces, i.e., surfaces respectively facing toward and away from the interior of the compact 100 when the cover 5 is in closed position overlying the base 11 . The cover 5 may optionally carry a transparent window (not shown) disposed in the top surface 19 of the cover 5 to enable a prospective end user to view the color (shade) of the contained cosmetic, e.g. at a point-of-purchase display, without opening the compact, and an inwardly facing magnifying mirror 6 , mounted in the inner frame 9 on the inner surface of the cover 5 . More particularly, in the compact of FIGS. 1-8 the base 11 and cover 5 are of identical square (or rectangular) plan diameter (though they may differ in depth), interconnected along one edge portion by a hinge assembly 10 and provided on an opposite edge portion with a latch assembly (comprising cover extended portion 8 having a recess or detent, and base closure portion 1 having a protrusion 15 ) for securing the cover 5 in closed position on the base 11 . The hinge and latch may be entirely conventional in structure, function and location.
[0055] The base 11 and cover 5 are substantially rigid and are self-sustaining in shape. They may be fabricated in a generally conventional manner of materials conventionally used for such purposes, such as, transparent plastic, opaque plastic, metal, wood, composite, polymer, and ceramic. Conveniently, the cover 5 is a molded element, with an optional aperture in which a window (itself typically a molded transparent plastic member) is fixedly assembled so as to constitute an effectively integral part of the cover for enclosing the cosmetic-containing interior of the compact. The base is also an element molded of opaque plastic. Optionally, such a window may comprise a two-way mirror (i.e., substantially reflective in a first direction and substantially transparent in a second direction.
[0056] In accordance with the invention, the cosmetic-holding well or portion 3 of the base 11 may include a molded plastic element or inner frame 17 fixedly mounted, for example, by snap fitting in the interior of the base 11 to define well 3 , opening upwardly within the interior of the compact, for holding a quantity of cosmetic material or other product. Alternatively, the base 11 may be a single-piece base which has no holding well 3 but rather is capable to hold the cosmetic material. Also, since the compact is ordinarily carried by a user with the cover member 5 closed and latched over the base member 11 so as to enclose the contained cosmetics, the compact 100 must be opened to expose the cosmetic-holding recess 3 to allow access to the cosmetic material. Thus, the user then removes a portion of a the contained cosmetic material with, for example, an applicator tool (e.g., a powder puff or like pad, brush or other implement), or a finger, and applies the cosmetic to his/her face. To facilitate such operation, the hinge assembly 10 permits the cover 5 to move, in opening, through an angle of at least about 90° relative to the base 11 . Preferably, however, the cover 5 is movable to a full-open position at an angle of 180° relative to the base 11 .
[0057] The cover 5 , as seen in FIGS. 1-8 , preferably has the shape of a shallow square inverted pan with a planar lip or edge flange extending inwardly (i.e., toward the interior of the compact 100 ) entirely around the circumference of the cover 5 . Thus, the cover 5 may be considered to have a recessed planar inner surface facing the interior of the compact 100 . The inwardly facing mirror 6 occupies substantially the entire area of the inner surface of the cover 5 . The proximate edges of the mirror 6 lie along a line parallel to the width of the cover 5 . It will be appreciated that these specific features of configuration and arrangement are merely illustrative and are nonlimiting. Advantageously, one or more ribs may be molded into the extended portion 8 of the cover 5 to engage and lock the cover 5 with the base 11 in a closed position.
[0058] For the initial use of the compact 100 , the user unlatches and opens the compact 100 , exposing the interior of the cover 5 and base 11 as shown in FIG. 1 . In a generally extended position, the reflective surface of the magnifying mirror 6 faces inwardly so that substantially the entire inner surface area of the cover 5 of compact 100 becomes a usable mirror. That is to say, once cover 5 has been rotated into an extended position, the area of the mirror 6 is viewable to constitute the mirror area available for use in applying the contained cosmetic. While the mirror 6 is preferably a magnifying mirror, it may nonetheless be, for example, an ordinary (non-magnifying) mirror.
[0059] According to the preferred embodiment of the invention, provided is compact 100 comprising a base 11 having a first product housing region 3 for housing one or more cosmetic products, a cover 5 hingedly connected to the base 11 , and a side drawer 13 slidably mounted in the base 11 , wherein the side drawer 13 comprises a second product housing region 14 , wherein the cover 5 has an inner surface and an outer surface, and wherein the cover 5 carries an inwardly-facing mirror 6 removably mounted on the inner surface by a removable frame member 9 . The cover 5 of compact 100 according to the invention has a detent that engages a protrusion 15 positioned on the base 11 to secure the base 11 and the cover 5 in a closed position, wherein the detent optionally comprises at least one rib formed integrally with the cover 5 to lock the cover 5 in a closed position when the cover 5 is moved from an open position into the closed position.
[0060] Preferably, the mirror 6 is a single magnifying mirror and the compact 100 has a generally square configuration. The cover 5 has an extended closure member 8 with a recess for engaging a corresponding protrusion 15 on the base 11 for securing the compact 100 in a closed position. Also, the first and/or second product housing regions 3 / 14 may comprise more than one rectangular or other shaped product wells. Also preferably, at least one of the cover portion 5 and the base portion 11 is made of a material selected from a transparent plastic, an opaque plastic, a metal, a wood, a composite, a polymer, or a ceramic. Optionally, the cover 5 may comprise a window through which the cosmetic product can be viewed when the cover 5 and the base 11 are in a closed position.
[0061] As can be seen in FIGS. 2A-2C , which show bottom, front and side plan views of the compact shown in FIG. 1 in a closed configuration according to the preferred embodiment of the present invention, side drawer portion 13 is preferably of a size and shape consistent with the size and shape of the base 11 . Alternatively, more than one side drawer 13 may be used, either vertically one on top of the other, or horizontally side by side with each other. Preferably, side drawer 13 has ends 12 for ease in opening and closing drawer 13 during use.
[0062] Turning next to FIGS. 3-8 , shown are various views of the compact 100 shown in FIG. 1 in a closed configuration according to the preferred embodiment of the present invention. As can be seen, cover 5 and base 11 are preferably consistent in size and shape. It is preferred that the overall shape of the compact 100 is square but that each cover corner 7 and base corner 2 are rounded and matching for easy and safe handling of the compact 100 .
[0063] Referring now to FIGS. 9-10 , shown is a perspective view of a single-layer compact 110 in accordance with an alternative embodiment of the present invention, depicted in an open configuration. As illustrated, alternative compact 110 is also of a generally square (or rectangular) plan configuration, dimensioned to be held in a user's hand, for holding a cosmetic material such as powder, blush, mascara, foundation, or the like, for application to the face. The compact 110 includes a base 11 preferably formed or provided with a product well or housing region 3 , and a cover 5 that is hingedly connected to the base 11 . As with compact 100 , the alternative compact 110 has an extended area 8 with opposed inner and outer surfaces, i.e., surfaces respectively facing toward and away from the interior of the compact 110 when the cover 5 is in closed position overlying the base 11 . The cover 5 may optionally carry a transparent window (not shown) disposed in the top surface 19 of the cover 5 , and an inwardly facing magnifying mirror 6 , mounted in the inner frame 9 on the inner surface of the cover 5 . More particularly, in the compact of FIGS. 9-16 the base 11 and cover 5 are of identical square (or rectangular) plan diameter (though they may differ in depth), interconnected along one edge portion by a hinge assembly 10 and provided on an opposite edge portion with a latch assembly (comprising cover extended portion 8 having a recess or detent, and base closure portion 1 having a protrusion 15 ) for securing the cover 5 in closed position on the base 11 . The hinge and latch may be entirely conventional in structure, function and location.
[0064] In this alternative embodiment of the present invention provided is a compact 110 comprising a case body 11 having an inner frame 17 to form a fitting groove to hold a first product well 3 for containing a first cosmetic product, a cover 5 having an inner mirror frame 9 to form a fitting groove to hold a mirror 6 , and a hinge assembly 10 for movably interconnecting the cover 5 to the case body 11 . The hinge assembly 10 is preferably coupled at both ends thereof to hinge shafts 4 of the case body 11 to form a hinged joint around which the cover 5 is opened or closed relative to the case body 11 . Preferably, at least one of the cover portion 5 and the base portion 11 of compact 110 is made of a material selected from a transparent plastic, an opaque plastic, a metal, a wood, a composite, a polymer, or a ceramic. Also, the case body 11 is preferably provided at each side thereof with a hinge holder each spaced apart from one another to define a space between the hinge holders, with hinge shafts 4 provided on inside surfaces of the hinge holders extending toward each other and inserted into both ends of a hinge hole formed in the upper housing member, and forming a hinge joint around which the cover portion 5 is opened or closed relative to the base portion 11 .
[0065] Lastly, referring to FIGS. 11-16 show various views of the compact 110 shown in FIG. 9 but in a closed configuration according to an alternative embodiment of the present invention. As can be seen, cover 5 and base 11 of the alternative compact 110 are preferably consistent in size and shape. It is preferred that the overall shape of the compact 110 is square but that each cover corner 7 and base corner 2 are rounded and matching for easy and safe handling of the compact 110 .
[0066] In yet a further alternative and adaptive system (not shown in the drawings) a lip makeup assembly is provided, in the form of a lipstick tube (rectangular or circular container for lipstick cosmetic makeup), one side may be provided with a magnifying mirror as discussed herein. Such a magnifying mirror on the side of a lipstick tube assembly may be on the lipstick cap-cover portion of such a system or alternatively on the holding-non-cap-cover portion of such a system. Preferably, and while not departing from the scope of the present invention, the magnifying mirror would be on the cover-cap portion of the lipstick tube assembly so that a user may position the cover-cap portion with one hand, while applying the lipstick cosmetic using the other hand (holding the non-cap-cover portion. This embodiment is not shown in the figures, but one of skill in the art will readily appreciate the same without need to refer to a drawing. In another alternative lip cosmetic embodiment, a rectangular lipstick cosmetic cover is formed as a parallel piped, having a magnifying mirror on one side extending substantially all of one side and substantially flush therewith for convenience (but not limited thereto).
LISTING OF REFERENCE NUMERALS
[0000]
1 base closure portion
2 base corner or lower housing portion corner
3 first product well or portion
4 hinge rod
5 upper housing portion or cover
6 magnifying mirror
7 cover corner or upper housing portion corner
8 extended top closure
9 mirror inner frame
10 hinge assembly
11 lower housing portion or base
12 drawer end portion
13 side drawer
14 second product well or portion
15 latch or protrusion
16 product inner frame
17 product inner frame
18 bottom surface
19 top surface
20 product well outline
21 mirror outline
100 dual-layer cosmetic compact
110 single-layer cosmetic compact
[0090] In the claims, means or step-plus-function clauses are intended to cover the structures described or suggested herein as performing the recited function and not only structural equivalents but also equivalent structures. Thus, for example, although a nail, a screw, and a bolt may not be structural equivalents in that a nail relies on friction between a wooden part and a cylindrical surface, a screw's helical surface positively engages the wooden part, and a bolt's head and nut compress opposite sides of a wooden part, in the environment of fastening wooden parts, a nail, a screw, and a bolt may be readily understood by those skilled in the art as equivalent structures.
[0091] Having described at least one of the preferred embodiments of the present invention with reference to the accompanying drawings sufficient to enable one of ordinary skill in the art to practice the invention, and to provide the best mode of practicing the invention presently contemplated by the inventor, it is to be understood that such embodiments are merely exemplary and that the invention is not limited to those precise embodiments, and that various changes, modifications, and adaptations may be effected therein by one skilled in the art without departing from the scope or spirit of the invention as defined in the appended claims. Accordingly, the disclosed embodiments are not mutually exclusive combinations of features; rather, the invention may comprise a combination of different individual features selected from different individual embodiments, as understood by persons of ordinary skill in the art. The scope of the invention, therefore, shall be defined solely by the appended claims.
[0092] Further, while there is provided herein a full and complete disclosure of the preferred embodiments of this invention, it is not desired to limit the invention to the exact construction, dimensional relationships, and operation shown and described. Various modifications, alternative constructions, changes and equivalents will readily occur to those skilled hi the art and may be employed, as suitable, without departing from the true spirit and scope of the invention. Such changes might involve alternative materials, components, structural arrangements, sizes, shapes, forms, functions, operational features or the like, it will be apparent to those of skill in the art that numerous changes may be made in such details without departing from the spirit and the principles of the invention. It should be appreciated that the present invention is capable of being embodied in other forms without departing from its essential characteristics. | A multi-functional, multi-layer compact for cosmetics, including a base for holding cosmetic material and a cover hingedly connected to the base in clam-shell manner with an inwardly facing mirror mounted in a portion of the cover so as to provide a convex magnifying lens. The compact mirror case provides a convex mirror function. In the multifunctional compact mirror of the invention, the plane mirror is set in a mirror frame within an upper housing and facing opposite the cosmetic product. The upper housing or cover is coupled to the lower portion or base at a hinged joint and has a fastener to secure the upper and lower housing portions in a closed position. Preferably, the multi-functional compact of the invention is also multi-layered having one or more side drawers positioned therein for housing additional cosmetic products. In addition, each product well or area may comprise multiple rectangular wells or areas to increase the variety of cosmetics available for use in a single compact. | 0 |
BACKGROUND OF THE INVENTION
Lamps used in display lighting commonly include a bulb contained within a generally frustoconical glass envelope. The interior of the envelope is metallized to define a reflector. To provide a whiter light throughout its life, the bulb is filled with gases including halogen gas. When such a lamp burns out, it is simply discarded and replaced with a new one. When used in retail stores and other commercial installations, these lamps are on many hours of each day. Thus, they must be replaced frequently. The combination of the cost of the bulb-within-an-outer-envelope construction and the frequency of replacing the lamp used in display lighting makes such lamps expensive to use.
Outdoor lamps are not as expensive because they do not have an inner bulb and they are not on as many hours in a day. Nevertheless, whenever they burn out, outdoor lamps must be discarded in their entirety. Most vehicle headlamps must also be discarded when the bulb therein burns out.
SUMMARY OF THE INVENTION
It is therefore an important object of the present invention to reduce the cost of using the type of lamp having an outer envelope, such as a reflector and a bulb.
It is another object of the present invention to accomplish such cost reduction by permitting the reuse of the outer envelope, the lens and other elements, and replacing only the bulb. Another object is to enable ready removal of the bulb in such lamps and to enable ready replacement thereof.
In summary, there is provided a lamp comprising an outer envelope having a rear portion and an opening therethrough, mounting means on the rear portion and including a hole, a removable member including a threaded base and a socket, the socket protruding through the hole and into the space defined by the reflector, means for retaining together the mounting means and the removable member on the mounting means, and a replaceable bulb capsule including a male element which is removably mated with the socket.
The invention consists of certain novel features and a combination of parts hereinafter fully described, illustrated in the accompanying drawings, and particularly pointed out in the appended claims, it being understood that various changes in the details may be made without departing from the spirit, or sacrificing any of the advantages of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS For the purpose of facilitating an understanding of the invention, there is illustrated in the accompanying drawings a preferred embodiment thereof, from an inspection of which, when considered in connection with the following description, the invention, its construction and operation, and many of its advantages should be readily understood and appreciated.
FIG. 1 is a side elevation view of a lamp constructed in accordance with the features of the present invention;
FIG. 2 is an exploded view of the several portions of the lamp;
FIG. 3 is a side elevational view of the removable member and the removable bulb capsule applied thereto;
FIG. 4 is a view in section taken along the line 4--4 of FIG. 3;
FIG. 5 is a fragmentary view of the mounting shell showing the transverse wall;
FIG. 6 is a sectional view of the removable member assembled to the mounting shell taken on the line 4--4, in the position where the removable member can be installed or removed; and
FIG. 7 is a view like FIG. 6 but with the removable member in the position where it cannot be removed.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Turning now to the drawings and more particularly to FIG. 1 thereof, there is depicted a lamp 10 constructed in accordance with the present invention. The lamp includes an outer envelope which, in the embodiment depicted, is generally frustoconical in shape. Its interior is metallized to provide a reflector 11 for the light created by the bulb therein. Attached to the front portion 13 of the reflector 11 is a light-transmitting plate or lens 14. The reflector 11 and the lens 14 are modified standard items. The principles of the present envelope could be utilized with other types of outer envelopes.
Attached at the rear portion 12 (FIG. 2) of the reflector 11 is a mounting shell 20 to which is removably attached a removable member 30 having a threaded base 31. As will be described, a replaceable bulb capsule is plugged to the member 30, which capsule is located in the space defined by the reflector 11. The lamp 10 is utilized in the usual way. Its base is threaded into a standard lamp socket and when the socket is energized, the lamp 10 will emit light through the lens.
Turning now to FIG. 2, further details of the lamp 10 will be described. In the embodiment shown, the mounting shell 20 is constructed of brass sheet, stamped into the shape shown. It includes a skirt 21 matching the shape of the rear portion 12 of the reflector 11. The shell 20 also includes a frustoconical wall 21a a which extends to a transversely extending wall 22. In the wall 22 is a hole 23, the periphery of which has formations thereon. Referring also to FIG. 5, these formations include a pair of diametrically opposed tongues 24 extending into the hole 23 and toward each other. Also, there is a pair of diametrically opposed notches 25 and a pair of diametrically opposed guide edges 26, each edge 26 being located between a tongue 24 and the associated notch 25.
The removable member 30 includes a body 30a of generally cylindrical shape having an end portion 30b, a central portion 30c and a head 32. The head may be composed of ceramic or thermoplastic, for example. In a preferred embodiment, the body 30a is longitudinally split in half to provide two mating pieces. Within the portion 30a is a diode 36 and wiring to connect the socket to the threaded base 31. The portion 30a fits into the base 31 and is permanently attached thereto. In the head 32, there is a pair of longitudinally extending openings within which are located socket terminals 33 that are generally parallel to each other. The head 32 also has a pair of longitudinally extending grooves 34 and a pair of circumferentially extending grooves 35 between the central portion 30c and the head 32.
The removable member 30 also includes a pair of latching elements 40, each having one an attachment end 41, the other end being bent to form a finger engagement portion 42, the part between the two ends defining a camming portion 43. The ends 41 of the latching elements 40 are attached to the head 32 adjacent the forward end thereof and at diametrically opposed points on the sidewall thereof. The sidewall of the head is longitudinally recessed to accommodate the elements 40. Each latching element 40 is movable between a latching position wherein the engagement portion 42 is away from the head 32 to an unlatching position wherein it is depressed into the longitudinal recess.
The lamp 10 further comprises a replaceable bulb capsule 50 having a base 51 which is generally rectangular in cross section and a pair of pins 52. The pins 52 are generally parallel to each other. The bulb capsule 50 also includes the bulb 53 which contains gases including halogen, for example. The base 51 may be hollow and it may be made of ceramic or thermoplastic for example. The leads of the halogen bulb are inserted into the pins 52 and then the base 51 is potted.
The capsule 50 is first mounted on the removable member 30 by inserting the pins 52 into the socket terminals 33. Then the combination of the removable member 30 and the replaceable bulb capsule 50 are mounted on the mounting shell 20. This is accomplished as follows. The two longitudinally extending grooves 34 are respectively aligned with the mounting tongues 24. At the same time the camming portions 43 of the two latching elements 40 are aligned with the edges 26 on the mounting shell 20. These latching elements 40 are biased outwardly as previously explained. The removable member 30 is then forcibly pushed forwardly, whereby the edges 26 automatically deflect the latching elements 40, and specifically the camming portions 43 thereof, inwardly, toward the head 32. When the portion 30c of the head 32 is seated against the wall 22 of the shell 20, the removable member 30 is rotated clockwise while the camming portions 43 ride on the edges 26, respectively, until they reach the notches 25. The outward bias of the latching elements 40 cause them to snap outwardly, whereupon the camming portions 43 become located within the notches 25, respectively. As this rotation is taking place, the tongues 24 enter the circumferentially extending grooves 35, whereby axial movement of the removable member 30 is no longer possible. With the camming portions 43 in the notches 25, further rotation of the removable member 30 is not possible and the removable member is retained in place.
With assembly completed, the lamp 10 will assume the condition depicted in FIG. 1 and it can be used in the usual way. When the bulb 53 burns out, the removable member 30 is disassembled to enable the replaceable bulb capsule 50 to be replaced. This removal is accomplished in the following manner. While holding the reflector 11 and the mounting shell 20 fixedly attached thereto, one grips the engagement portions 42 of the latching elements 40 with the thumb and forefinger, pushing them toward the head 32, against the outward biasing action of these latching elements. This causes the camming portions 43 to be located outside of the notches 25. Now the latching elements 40 are again in their unlatching positions and the removable member 30 may be rotated counterclockwise while the camming portions 43 engage the edges 26, respectively. This rotation causes the tongues 24 to be located outside of the circumferentially extending grooves 35, thereby enabling the removable member 30 to be withdrawn from the mounting shell 20.
The replaceable bulb capsule 50 is then exposed and can be pulled out of the socket terminals 33 and replaced with a fresh capsule. The removable member 30 with the fresh capsule can then be reinstalled as above described.
It may be seen that the lamp 10 includes keeper structure in the form of the tongues 24 on the mounting shell 20 and keeper structure in the form of circumferentially extending grooves 35 on the removable member 30. This keeper structure is constructed and arranged to releasably prevent removal of the removable member 30. Also, the lamp 10 includes latching structure on the mounting shell 20 in the form of the notches 25 and latching structure on the removable member 30 in the form of the latching elements 40. This locking structure ensures that the removable element cannot be rotated into the position where it can be withdrawn. The keeper structure and the locking structure enable the mounting shell to releasably retain the removable member 30.
In the past when lamps of the general type and character depicted in FIG. 1 are used, and they burn out, the entire lamp must be replaced. However, by utilizing the invention described above, all that needs to be replaced is the replaceable bulb capsule 50, thereby making it more economical to use such lamps. Also, because of the construction, the lamp 10 has a shape and dimension substantially the same as currently available lamps. In other words, it can be used in the same kind of lighting devices.
The sizes of the head 32 and the capsule 50 are such that the filament of the bulb 53 will be located at the optically correct spot within the reflector 11 to attain maximum light output.
Despite the existence of the hole 23 in the mounting shell 20, the light output unexpectedly and surprisingly exceeds that from currently available lamps that do not have a replaceable bulb capsule. This is thought to be true because the filament of the bulb 53 can be positioned more rearwardly and, therefore, at a better point in respect to the metallized reflector 11.
The tolerances of manufacture are not as severe as are necessary with a permanent bulb.
What has been described therefor is an improved lamp utilizing a removable member to enable the bulb capsule to be readily replaced. While a particular embodiment of this invention has been described, it is to be understood that changes can be made in such embodiment without departing from the spirit or scope of the invention as defined in the claims. | The lamp has a frustoconical reflector with a mounting shell attached to its small end. A removable member includes a threaded base and socket. The socket protrudes through the hole in the mounting shell and into the reflector. It removably receives a replaceable bulb capsule. Means are provided for retaining the removable member to the mounting means. | 5 |
STATEMENT OF GOVERNMENT INTEREST
The present invention may be manufactured and used by or for the Government of the United States of America for governmental purposes without the payment of any royalties thereon or therefor.
BACKGROUND OF THE INVENTION
(1) Field of the Invention
This invention relates to the placing of bones under tension during healing.
(2) Description of the Prior Art
Under certain circumstances, broken bones need tension applied to them during the healing process. Depending on the bone involved, current methods require drilling a hole into the bone to allow a pin to be inserted. Cables are then connected to the pin to facilitate the application of appropriate tension.
This use of pins, however, has serious drawbacks. One of the greatest risks is that of infection, the risk increasing with the time of fixation. Skin and soft tissue necrosis, and bone necrosis at the pin contact point, are also problems. Additionally, chronic osteitis of the bone is a possibility. A non-invasive alternative could substantially eliminate these health risks.
External clamps with cables attached would suffice for the application of tension, but the ensuing restriction of circulation to the flesh in contact with the clamp could result in gangrene, tissue damage and, among other complications, infection. This is because the flesh directly in contact with a static clamp, i.e., the flesh near the surface of the skin, experiences restricted blood flow. It is this surface flesh that can become gangrenous. Such a clamp should of course never be so tight as to completely restrict blood flow to the rest of the limb.
SUMMARY OF THE INVENTION
The principal object of this invention is a non-invasive body clamp to provide tension on a body member to facilitate healing without risking gangrene, tissue damage, infection and other clamp induced complications. In accord therewith, a first movable collar is connected to a second movable collar, the ensemble being attached to a means for generating tension. In further accord therewith, the collars are cyclically moved in such manner that one collar is always in a state that is in embracing relation with the body part under tension while the other collar is in a state that is in circulation allowing relation to the same body part. As the first and second collars cyclically alternate between their respective states, the ensemble always has one collar gripping the body member so that tension remains applied to the body part under tension while permitting the free circulation of the same body part.
In the preferred embodiment, the collars are mechanically actuable cuffs connected by a rigid link, the rigid link serving both as an attachment anchor to the means for generating tension to the body part and as a spacer holding the cuffs in spaced-apart relation about the body part.
BRIEF DESCRIPTION OF THE DRAWINGS
Other features, objects and benefits of the invention can be more clearly understood with reference to the following description thereof, and to the drawings, in which:
FIG. 1 is a perspective view of a body limb provided with the novel non-invasive body clamp of the invention; and
FIG. 2 is a perspective view of a presently preferred embodiment of the non-invasive body clamp of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
With reference now to FIG. 1, a body limb generally designated schematically at 10 is shown with the clamp assembly generally designated 12 of the invention in position around the limb 10. The limb 10 may be a leg or any other body part to which it is necessary or desirable to apply tension during healing of the same or another body part. The clamp assembly 12 is fabricated in sizes that accommodate differently sized and shaped body parts.
The clamp assembly 12 includes a first clamp 14 connected to a second clamp 16 by link 18. The clamps 14, 16 may be any clamp capable of assuming a first body-part-embracing condition adapted to grip the body limb 10 in such manner as to firmly embrace the same, and a second body-part-circulation-permitting condition adapted to allow the free circulation of the body limb 10. The surface area and interface characteristics of the clamp members 14, 16 are selected to provide the intended first and second conditions thereof. To minimize the clamping pressure for a given tension, it is presently preferred that the interface of each clamp exhibit a maximum amount of friction between the clamp and the limb for a given clamping pressure. Any suitable mechanical, pneumatic or other clamping member, mechanism or device that may be caused to cyclically embrace so as to substantially immovably grip the body part and not to embrace so as to allow circulation to the flesh directly in contact therewith may be employed without departing from the inventive concept.
The link 18 preferably is rigid, and serves two primary functions. The one is to connect the first clamp 14 to the second clamp 16 so as to maintain them in intended orientation, and the second is to provide a connecting point for cable 19 which is attached to a means for generating tension 20. While in the illustrated embodiment two (2) clamps 14, 16 and a single rigid link 18 are preferred, it is envisaged that the link may have a different number of link members, and that a different number of clamps may be used.
A control unit 22 is relayed to both clamps 14 and 16 by control wires 24. The clamps 14, 16 are operated by the control unit 22 to coordinate the opening and closing of clamps 14 and 16 in an alternating fashion so that clamp 14 is caused to be constricted about the body part 10 while clamp 16 is caused to be loose enough to permit the flow of blood to the area which was directly in contact with clamp 16, and vice versa. After a predetermined period, such as fifteen minutes, the clamp 16 is then signaled to tighten. When clamp 16 is tight, clamp 14 is then signaled to loosen. This alternating cycle continues as long as desired to further the healing process. The body clamp 12 in this fashion thus allows a substantially constant tension to be applied to body part 10 without either penetrating the skin, tissues, and bone or cutting off the circulation thereto.
Referring now to FIG. 2, which illustrates one presently preferred embodiment of the non-invasive body clamp of the invention, a clamp assembly generally designated 25 is shown about the body part schematically illustrated by phantom cylinder 25a and includes two movable arcuate cuffs generally designated 26 and 28, each cuff 26, 28 having an articulation 30 pivotally joining one pair of cuff ends, and each having a threaded bolt 32 joining the other ends. A foam insert 34 lines the interior of the cuffs 26, 28 to protect the skin along the surface of contact. The surface of the foam preferably exhibits a large coefficient of friction when in contact with both the cuff and the skin of the body part 25a. The cuff ends remote from the pivot 30 of each of the cuffs 26, 28 terminate in flanges 26a, and 28a respectively. The bolt 32 is fastened to flange 28a at one of its ends and is received through an opening provided therefor in flange 26a at the other of its ends for each of the cuffs 26, 28. A nut 33 is journaled at 35 to flange 26a of cuff 26 to the inside of which the corresponding bolt 32 is threadably engaged. A motor 36 drives gear 36a that is coupled to and rotatably drives nut 33 of each of the cuffs 26. In response to signals from control unit 22, the motors 36 and cooperative gears 36a cause the nuts 33 threaded to the bolts 32 of each of the cuffs 26, 28 to rotate relative to the corresponding flange 26a, the threads of which engage the threads of the bolts 32, thereby pushing apart or pulling together the opposing ends of the cuff ends of the corresponding cuffs 26 and 28 in dependance on the sense of rotation of the motors 36. A compression spring 38 mounted between flanges 26a, 28a is used to assist the cuffs 26, 28 to move to their open conditions.
Again, the control unit 22 is operative as described above in connection with the description of the FIG. 1 to so actuate the motors 36 that the cuffs are cyclically driven between their respective body-embracing and circulation allowing conditions and in such a way that one is always in its closed condition while the other is either being actuated to its open condition or already in its open condition. The mechanism of FIG. 2 is of course to be understood as solely exemplary, other embodiments being quite readily possible on the basis of the present invention. Further, changes are possible to the FIG. 2 mechanism, such as, to give one example, the replacement of the stationary bolt 32 with one that is journaled for rotation to the cuffs.
These and other examples of the concept of the invention illustrated above are intended by way of example and the actual scope of the invention is to be determined solely from the following claims. | The present invention discloses a means for providing tension to bones dug the healing process that is non-invasive. In the preferred embodiment, the disclosed means for placing bones under tension comprises a first collar and a second collar. Each collar is controllably moved cyclically between a body member embracing condition and a body member releasing condition in such manner that when one collar is in one condition the other is in the other condition. A firm grip is therewith always maintained on the body member while allowing the circulation thereof. | 0 |
FIELD OF THE INVENTION
This invention relates to an improved apparatus and method for the measurement of grain in imaging systems and more particularly to an improved ruler for comparing ruler patches against an image generated by a reference system and a method for making the ruler.
BACKGROUND OF THE INVENTION
In designing an image capture and reproduction system, it is important to be able to determine the magnitude of the level of image degradation to be expected in the final image as viewed by the observer. Understanding the magnitude of the image degradations due to grain is also important to the use of the image reproduction system and can have a major impact on the selection of key elements for use in the imaging chain. For example, in a photographic system, the selection of a film speed, film format, and film type are determined by the image to be captured and the end use of the final image. The film grain also becomes important depending on the degree of enlargement anticipated for the final print.
In a photographic system, the variations in otherwise uniform responses to exposing light are referred to as grain. These variations in the density can be observed through physical measurement by measuring the optical density of photographic materials, such as film or paper, with a microdensitometer. The root mean square (rms) value or standard deviation is used as a measure of the variation in density of an otherwise uniform area. This value is referred to as the granularity. A photographic image is perceived by an observer and the perception of these unwanted, random fluctuations in optical density are called graininess. Thus, the physically measured quantity of granularity is perceived by the observer as a level of graininess.
The first grain slide or ruler was designed and fabricated by Thomas Maier et al. (See for example, T. O Maier and D. R. Miller, "The Relationship Between Graininess and Granularity" SPSE's 43 Annual Conference Proceedings, SPSE, Springfield, Va. pp207-208, (1990)). The fundamental relationship relating the granularity and graininess was determined by C. James Bartleson (See for example, C. J. Bartleson, The Journal of Photographic Science, 33, pp117-126, (1985)). He determined the following relationship between the graininess G i and the granularity σ v
G.sub.i =a*log(σ.sub.v)+b Eq. (1)
where a and b are constants. He also determined that the perceived graininess did not depend on the color of the image, thus graininess was found to be strictly a function of the achromatic channel of the visual system.
Maier et al. produced a series of uniform neutral patches of grain at the same average density with increasing amounts of grain using a digital simulation instrument. They then used microdensitometer measurements and the fundamental psychophysical relationship to relate the graininess to the rms granularity. This was accomplished by assuming that a 6% change in granularity would correspond to a 2 unit change in graininess, or grain index. As a result of this assumption, the constant multiplying the lead term must be 80 since the log range of the ruler patches was 1.2 or about 48 times log of (1.06). They then assumed the lowest patch was grainless and assigned it an arbitrary value of 25. The following equation resulted
G.sub.i =80*log(σ.sub.v)-28.64 Eq. (2)
Then a series of 18 uniform neutral samples of increasing grain were assigned train index numbers in 17 unequal steps from 25 to 120 depending on the measured granularity. The final grain ruler consisted of two scales printed on black and white photographic paper mounted on a rigid backing material.
The resulting grain ruler was then used as a scaling tool to evaluate the graininess in other photographic materials. Such other materials consisted primarily of photographic materials with either uniform areas or images printed on them. In the form described above the grain ruler suffers from several significant deficiencies.
In use on contemporary photographic materials, the ruler led to widely divergent measurements by individual users. Measurements on colored photographic materials led to the most widely varying results. Since most current photographic materials are colored in nature, this is a serious deficiency. The non uniform scale of the original ruler, the arbitrary range of sample grain levels, and the layout as two separate rulers led to further difficulties in use. In addition, the method of generating the ruler failed to take into account the different look that grain has in different imaging systems, and did not address how one might model or display the impact grain would have in images rendered in media and materials other than silver halide photographic materials. The display of grain rendered in video and other modern optoelectronic output devices was also not addressed.
SUMMARY OF THE INVENTION
The present invention is directed to overcoming one or more of the problems set forth above. Briefly summarized, according to one aspect of the present invention a generalized grain ruler incorporating a plurality of uniform patches representing a range of granularities, each patch being a perceptually distinct representation of graininess spaced at perceptually uniform intervals and recorded in an increasing sequence of graininess
According to another aspect of the present invention there is provided a method for producing a generalized grain ruler for the measurement by comparison of grain in a reference imaging system generated image, comprising, the steps of:
a) generating a set of random numbers for each image component;
b) filtering each set of random numbers to alter the Wiener spectrum to result in a filtered set of random numbers that look as if they were generated by the reference photographic system; and
c) delivering the filtered set of random numbers to an output device that renders them into an image which is the generalized grain ruler.
The above and other objects of the present invention will become more apparent when taken in conjunction with the following description and drawings wherein identical reference numerals have been used, where possible, to designate identical elements that are common to the Figures.
ADVANTAGEOUS EFFECTS OF THE INVENTION
The present invention has the following advantages: It provides a more precise measurement apparatus for photographic materials and a method and means for producing a ruler. Furthermore, the method and means of producing the ruler need not be limited to conventional photographic materials, but can be applied generally to any image rendering system including optoelectronic systems. It does allow for production using colored photographic materials, measurement of colored photographic materials, a perceptually uniform scale, and a range of graininess levels relevant to current photographic products.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of an improved grain ruler in accordance with a preferred embodiment of the invention showing the arrangement of the uniform neutral patches containing specified amounts of grain;
FIG. 2 is a flow chart illustrating the method used to produce the improved grain ruler apparatus of FIG. 1;
FIG. 3 illustrates a functional arrangement of a color negative photographic enlarging system;
FIGS. 4A, 4B, and 4C demonstrate, for the case of a high quality enlarging lens, the behavior of the lens MTF with respect, to the color channel and printing magnifications of 4x, 8x, 12x, 16x, and 20x;
FIGS. 5A, 5B, and 5C are graphs illustrating the measured Wiener Spectrum in each of the three color channels, respectively, for selected ruler steps.
FIG. 6 is a schematic diagram of a generalized grain ruler in accordance with an alternate embodiment of the invention showing the arrangement of the uniform patches containing specified amounts of grain; and
FIG. 7 is a flowchart illustrating the method used to produce the generalized grain ruler apparatus of FIG. 6.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1, an improved grain ruler 10 in accordance with a preferred embodiment of the invention consists of a plurality of uniform neutral patches 12 1 . . . 12 n on a color reflection print material 14 which is mounted onto a rigid backing material 16. Each patch 12 is a uniform neutral area containing a prescribed amount of photographic grain. The patches are selected to span the levels of graininess from the lowest levels of image grain to the highest usable level of image grain currently present in the trade. In other words, the patches are selected based on their proposed use. At any point in time film producers manufacture a range of films each having a different granularity. Patches would be selected to include the granularities of those films. In addition, these films will be subjected to different magnification factors when the films are printed or electronically displayed. For maximum ruler utility the patches should represent the range of available film granularity and the range of magnifications that are used in the film processing industry. In addition, these patches should be spaced at perceptually uniform intervals. In accordance with Eq. 1, perceptually uniform intervals (an arithmetic sequence) of graininess correspond to constant geometrical changes in granularity. The spacing of the patches should be chosen to be large enough so that nearly all observers agree that the patches represent distinct levels of graininess, while at the same time small enough that observers can use the ruler to determine the graininess of a test sample with adequate precision.
In the preferred embodiment, Eq. 1 is used to establish a numerical scale relating the perceived graininess of each patch to the measured granularity of each patch. The constant "a" multiplying the lead term of Eq. 1 is selected to be 80, so that a 2 unit change in graininess corresponds to a 6% change in granularity. It is known that a 6% change in granularity is perceived as a just noticeable change in graininess by 80% of observers in a forced choice paired comparison (see D. M. Zwick and D. L. Brothers, "RMS Granularity: Determination of Just-Noticeable Differences", SMPTE, 86, pages 427-1430, 1977). In the preferred embodiment, the ruler patches are set at intervals of 5 graininess units, to optimize the precision of the ruler as described above. The constant "b" in Eq. 1 is assigned a value of -25. This aligns the numerical scale to the industry standard scale (see "Print Grain Index-An Assessment of Print Graininess for Color Negative Films", Kodak Publication No. E-58, CAT 887 5809, 1994).
The patches 12 are sorted in an ascending order of perceived graininess and are labeled with a numerical value indicating the graininess of each patch, and are abutted so as to form a scale of graininess. The scale of graininess proceeds from the lowest level in the upper left corner number 15, to moderate levels in the upper right corner 60, and lower right corner 65, to the highest level in the lower left corner 110.
Referring to FIG. 2, the process used to produce the grain ruler 10 of FIG. 1 commences with a random noise generator 20 and includes the use of spatial filters 22, 24, and 26, an output device 28, a film negative 30, and a contact printing apparatus 32.
The random noise generator 20 is used to create three sets of 16 bit random numbers representing the red, green, and blue (R, G, and B) pixel components in the patches 12. These three sets of numbers represent the red, green and blue photographic grain patterns to be manipulated and transferred to the grain ruler scale. The random numbers have the following properties:
1. The mean value of the R, G and B numbers is such that the resulting uniform area on the grain ruler can be made substantially neutral, with a visual density of 0.8.
2. The standard deviation of the R, G, and B numbers is such that the prescribed amount of photographic grain is produced in the resulting uniform area on the grain ruler.
3. The R, G, and B numbers are normally distributed.
4. The R, G, and B numbers are spatially uncorrelated, such that each number in the sequence is independent of those preceding and following.
5. The R, G, and B numbers are substantially independent of each other.
The R, G, and B numbers are subsequently modified by spatial filters 22, 24, and 26, using well known techniques of discrete convolution, to produce sets of random numbers R', G', and B'. This process is repeated for each patch of the grain ruler. For each patch, the standard deviation of the R, G, and B numbers is selected. The spatial filters 22, 24, and 26 are chosen such that the resulting grain pattern has a particular look (appearance). An important feature of the invention is that the particular look of the grain patterns on the grain ruler is substantially the same as the look of the grain patterns produced by the imaging system whose grain the grain ruler is intended to measure. This is accomplished by adjusting the modulation transfer function (MTF) of the image generation process, so that the MTF of said image generation process matches the MTF of the imaging system whose grain the grain ruler is intended to measure. For instance, the MTF of the image generation process is substantially determined by the MTF associated with the spatial filters 22, 24, and 26, the output device 28, the film negative 30, the contact printer 32, and the color reflection print material 14 on which the grain ruler is recorded. The system MTF is a function of spatial frequency and color channel. For example, the MTF of the image generation process for the red channel may be written:
MTF.sub.R (f)=(MTF.sub.22 (f))(MTF.sub.28,R (f))(MTF.sub.30,R (f)) (MTF.sub.32,R (f))(MTF.sub.14,R (f)) Eq. (3)
where f is the spatial frequency in cycles/mm on the grain ruler. Analogous equations can be written for the blue and green channels.
In the preferred embodiment, the imaging system whose grain the grain ruler is intended to measure, termed the reference system, is a color negative photographic system. Referring to FIG. 3, the reference system is composed of a color negative film 36 which is magnified by an enlarging lens 38 onto a color reflection print material 40. The look of the photographic grain produced by the reference system is substantially determined by the MTF of the enlarging lens and the MTF of the color reflection print material. The MTF of the red channel of the reference system may be written:
MTF.sub.reference,R (f)=(MTF.sub.38,R (f))(MTF.sub.40,R (f))Eq. (4)
Analogous equations may be written for the green and blue channels. The spatial filters 22, 24, and 26 are used to accomplish the match of the MTF of the reference system with that of the image generation system. The spatial frequency response of the filters is determined by combining the above equations and solving for the desired spatial filter MTF. For example, the MTF of the spatial filter 22 is given by: ##EQU1## In the preferred embodiment of the invention the MTF of the color reflection print material has been eliminated from Eq. 5, since the same print material is used in both the reference system and the image generation process. If this is not the case, separate terms representing the MTF of the relevant reflection print material must be retained.
It will be appreciated, upon inspection of Eq. 5, that once an image generation system is chosen, so that the MTF associated with components 28, 30, and 32 is fixed, the MTF of the spatial filters 22, 24, and 26 is substantially determined by the MTF associated with the enlarging lens of the reference system.
FIGS. 4A, 4B, and 4C illustrate by way of graphs the behavior of a high quality lens MTF with respect to the R, G, and B, color channels and printing magnifications of 4x, 8x, 12x, 16x, and 20x. The spatial frequency axes refers to the spatial frequency on the print. Two significant trends are evident: first, that the lens MTF becomes poorer as the magnification increases from 4x to 20x, and second, that the MTF varies between the color channels, being substantially poorer for the red channel compared to the blue and green channels.
In the preferred embodiment, the look of the grain ruler grain patterns will change from the lowest patch to the highest patch, such that the grain patterns will appear to be blurred to an increasing degree as the overall graininess increases. This is in accord with the behavior of the enlarging lens, whose MTF becomes poorer as the magnifications increases, and the fact that most low graininess prints will be made at low magnifications, while most high graininess prints are made at high magnification. In the preferred embodiment, the grain ruler grain patterns should exhibit a gradual change in sharpness from patch to patch.
The response curves of FIGS. 4A, 4B, and 4C were interpolated to produce a series of 20 MTF curves for each color channel, ranging from the best MTF curve at 4x magnification, corresponding to the lowest graininess patch on the grain ruler, to the poorest MTF at 20x magnification, corresponding to the highest graininess patch on the grain ruler.
Referring back to FIG. 2, the random numbers representing R', G', and B' corresponding to each patch of the grain ruler are sent to an output device 28, which produces a film negative 30 of substantially uniform density, on which an image of computer generated photographic grain patterns has been recorded. The film negative 30 is then placed in a contact printing apparatus 32, which produces a grain ruler 34 on color reflection print material 14. The contact printing apparatus 32 is adjusted so that the uniform areas on the grain ruler 10 are substantially neutral in appearance, with a corresponding average visual density of 0.8.
To verify that the grain ruler 10 meets the specifications, each patch was scanned using a reflection microdensitometer with nominal ANSI Status M red, green, and blue spectral responses, and the WS of each patch was estimated using standard techniques. For example see, J. C. Dainty and R. Shaw, "Image Noise Analysis and the Wiener Spectrum", Image Science, Academic Press, New York, Chapter 8, (1974).
FIG. 5A shows the red WS for ruler patches 15, 40, and 90. FIG. 5B shows the green WS, and FIG. 5C shows the blue WS for the same patches. As expected, the WS level increases faster at the lower spatial frequencies than at the higher spatial frequencies, in accordance with the graphs shown in FIGS. 4A, 4B, and 4C. Also, the red WS is lower in the higher spatial frequencies than the green or blue.
An alternate embodiment of the invention is shown in FIG. 6. A generalized grain ruler 42 consists of a plurality of uniform patches 44 1 . . . 44 n on a display medium 46. The display medium 46 on which the generalized grain ruler 42 is rendered may include, but is not limited to:
1. color negative photographic paper
2. color reversal photographic paper
3. black and White photographic paper
4. color reversal transmission material
5. color negative transmission material
6. color electrophotographic material
7. black and White electrophotographic material
8. color thermal print paper
9. color video monitor
10. motion picture projection screen
11. color slide projection screen
Each patch 44 is a uniform area containing a prescribed amount of grain. The range of grain levels spanned by the patches is selected based on their proposed use. As described earlier, the precision of the ruler is optimized when the patches are spaced at perceptually uniform grain intervals, said intervals as small as possible, but large enough that the patches remain perceptually distinct. The patches 44 are sorted in an ascending order of perceived grain, are labelled with a numerical value indicating the perceived grain of each patch, and are abutted so as to form a scale of perceived graininess. The patches shown in FIG. 6 are labelled in the same manner as those shown in FIG. 1; any labelling method that is consistent with Eq. 1 is acceptable.
FIG. 7 illustrates the method for the construction of the generalized grain ruler 42. The process again commences with the random number generator 20, and includes the use of spatial filters 50 1 , 50 2 . . . 50 m , and an output system 52. The random number generator 20 is used to create m sets of 16-bit random numbers, denoted 1, 2, . . . m, representing the pixel components in the patches 44. The number m is commensurate with the number of chromatic channels pertaining to the system whose grain the generalized grain ruler is intended to measure. For example, a generalized grain ruler intended for use with a single channel (black and white) imaging system may require the use of only one set of random numbers. Or, in another example, a generalized grain ruler intended for use with certain thermal print systems may require the use of four sets of random numbers, corresponding to cyan, magenta, yellow and black (CMYK) channels. The m sets of numbers represent the grain patterns to be manipulated and transferred to the generalized grain ruler scale. The random numbers have the following properties:
1. The mean value of each set of numbers is such that the resulting uniform area on the generalized grain ruler can be made to the desired average density.
2. The standard deviation of each set of numbers is such that the prescribed amount of grain is produced in the resulting uniform area on the generalized grain ruler.
3. The random numbers 1, 2, . . . m follow a prescribed unimodal distribution.
4. The random numbers, 1, 2, . . . m are spatially uncorrelated, such that each number in the sequence is independent of those preceding and following.
5. The sets of random numbers 1, 2, . . . m are mutually independent.
The random numbers 1, 2 . . . m are subsequently modified by spatial filters 50 1 . . . 50 m , using well known techniques of discrete convolution, to produce sets of random numbers 1', 2'. . . m'. This process is repeated for each patch of the generalized grain ruler. For each patch, the standard deviation of the numbers 1, 2 . . . m is selected. The spatial filters 50 1 . . . 50 m are chosen such that the resulting grain pattern has a particular look (appearance). Again, the MTF of the image generation process is adjusted so that the MTF of said image generation process matches the MTF of the imaging system whose grain the ruler is intended to measure. Referring to FIG. 7, the MTF of the image generation process for the first channel may be written:
MTF.sub.1 (f)=(MTF.sub.50,1 (f))(MTF.sub.52,1 (f))(MTF.sub.46,1 (f))Eq. (6)
where MTF 50 ,1 (f) denotes the MTF of spatial filter 50 1 . Analogous equations can be written for the remaining chromatic channels. In this embodiment, the reference system can be any imaging system which can be described by a Modulation Transfer Function. The MTF of the spatial filter 50 1 is given by: ##EQU2## Analogous equations can be written for the remaining spatial filters. Referring to FIG. 7, the random numbers 1', 2' . . . m' corresponding to each patch of the generalized grain ruler are sent to an output system 52, which renders the generalized grain ruler 42 on the display medium 46, at the desired uniform density. In this embodiment the output system 52 is presumed to include such components as necessary to produce the desired rendition on the display medium 46.
Parts List
______________________________________10 grain ruler12.sub.1 . . . 12.sub.n patches14 color reflection print material16 backing material20 random noise generator22 red spatial filter24 green spatial filter26 blue spatial filter28 output device30 film negative32 contact printer36 color negative film38 enlarging lens40 color reflection print material42 generalized grain ruler44.sub.l . . . 44.sub.n patches46 display medium50.sub.l . . . 50.sub.m spatial filters52 output system______________________________________ | A generalized grain ruler incorporating a plurality of uniform patches representing a range of granularities, each patch being a perceptually distinct representation of graininess spaced at perceptually uniform intervals and recorded in an increasing sequence of graininess. A method for producing a generalized grain ruler for the measurement, by comparison of, grain in a reference imaging system generated image, comprising, the steps of:
a) generating a set of random numbers for each image component;
b) filtering each set of random numbers to alter the Wiener spectrum to result in a filtered set of random numbers that look as if they were generated by the reference photographic system; and
c) delivering the filtered set of random numbers to an output device that renders them into an image which is the generalized grain ruler. | 6 |
FIELD OF THE INVENTION
[0001] The present invention relates to the field of dispensing of liquid products, and in particular, relates to a method and apparatus for the dispensing of liquid dairy products having a selectable range of fat and milk solid content.
BACKGROUND OF THE INVENTION
[0002] Milk is an oil-in-water emulsion of fat globules which is dispersed in a continuous skim milk phase. As such, milk comprises water, fat (also termed as “milk fat” or “butter fat”), and milk solids such as proteins, minerals, ash, and the like. If left to stand, the fat globules will agglomerate and rise to the top of the skim milk phase where they can be separated from the skim milk phase. As such, it is common practice in the dairy industry to be able to produce a wide range of liquid dairy products, based on milk, ranging from, for example skim milk (with little or no fat globules) to creams having up to, for example 45 to 50% fat dispersed in a skim milk phase. A wide range of dairy products with different fat contents are readily available, and commonly used. These can include common liquid dairy products having fat contents of 0% (skim milk), 1%, 2%, 3.25%, 10%, 18%, 35%, or even higher depending on the amount of fat desired in a milk or a cream material.
[0003] As such, there are a wide range of liquid dairy products available which are commonly used for different purposes, or as a result of different consumer preferences. For the purposes of the present application, the term milk is used interchangeably with the term “dairy” to include all liquid products produced from milk.
[0004] In a retail setting, such as for example, a restaurant or a coffee shop, it is frequently necessary to have a variety of dairy products available to meet the preferences of the consumer, or for different applications. Some of these applications may be low volume, while others might be much higher volume. As such, the owner of the retail outlet must maintain a supply of all of the necessary liquid dairy products, and maintain adequate inventories of each product to cover their use of the selected dairy product.
[0005] Also, with low volume materials, it may be necessary to discard product since dairy products typically have a limited shelf life.
[0006] Further, it is known in the retail and industrial environments, that beverages can be made from individual components which are generally mixed together and dispensed by a dispensing system. These dispensing systems may be manual or automatic and may operate continuously or in discrete dispensation steps. Liquid dispensation systems typically involve at least a liquid receptacle for holding the liquid and a pump for dispensing the liquid into a consumable portion. This can include mixing water with a flavoured concentrate to produce a soft drink, reconstituting a juice drink by the addition of water to a juice concentrate, or various other techniques. A variety of these types of liquid dispensing systems are commercially available. Systems are also known which provide gas, or carbonation to liquid materials by the addition of, for example, fluid CO 2 to a liquid material.
[0007] In some circumstances, two liquids may be dispensed together by the same apparatus. Typically, an apparatus that allows mixing of two liquids results in effectively a better mixed consumer beverage product. As an example, two liquids can be dispensed using a dual liquid dispenser package, as disclosed in U.S. Pat. No. 4,774,057 to Uffenheimer et al. This patent discloses a dispenser package containing two separate liquid dispensing chambers, two liquid reservoirs, and liquid supply channels connecting the reservoirs to the chambers. However, this device is primarily direct to a dispenser which is adapted to provide two reagent liquids to automated liquid analysis system.
[0008] Other dispensing systems include U.S. Pat. No. 3,987,715 to Muller which provides an apparatus for mixing a solid or powdered material such as a powdered soup, to a hot liquid, and mixing the two to provide a liquid soup for dispensing.
[0009] Similarly, Vanderhoff et al., in U.S. Pat. No. 4,177,177 describe an apparatus for producing an aqueous polymer emulsion from an insoluble polymer phase by use of a suitable emulsifier.
[0010] U.S. Pat. No. 4,923,093 to Gerber describes a flavour dispensing device wherein a liquid flavour component can be added to a solid frozen material, such as for example, ice cream.
[0011] Additionally, U.S. patent Publication No. 2001/0026821 A1, published Oct. 4, 2001, also describes a two container apparatus for blending two different materials together (optionally with water as a third diluent) in order to form a final product. This system is primarily concerned with blending coffee components together in order to form a coffee product which more closely simulates freshly brewed coffee.
[0012] Further, PCT patent publication No. WO2004/004523 published Jan. 15, 2004 provides a method for the addition of steam to a milk in order to produce a hot beverage.
[0013] With respect to the milk/dairy industry, methods are also known for the modification of the milk solids and fat content of a liquid dairy product by combination of various milk products. For example, Bell in U.S. Pat. No. 4,651,898 provides a method for simply combining two different liquid milk products.
[0014] Further, O'Keefe, in U.S. Pat. No. 4,144,804 provides a milk processing system wherein heat treated milk is separated in high fat and low fat milk components and then mixed together to form milk products having a desired fat content. Similarly, Zettier et al. in U.S. Pat. No. 5,260,079 provide a method for controlling the fat content in milk by separation of the milk into a cream and a skim milk component. The two streams are then recombined in a desired ratio to provide a milk having the desired fat level. However, these patents are directed to the industrial production of milk products and is not suitable for retail use, or the like, where rapid changes of milk fat content on small samples is required.
[0015] U.S. patent publication No. 2001/0026825, published Oct. 4, 2001, and U.S. patent publication No. 2003/0054079, both provide high concentration milk products which can be chemically stabilized, and which can be mixed with water to produce various milk products. However, there is no mechanism to vary the ratio of milk solids to fat, or to produce a liquid dairy product having no fat content.
[0016] Accordingly, none of these approaches address all of the difficulties encountered with the provision of liquid dairy products, and in particular, the provision of a wide range of liquid dairy products in potentially very small volumes, in a retail environment. As such, the prior art devices do not allow for the rapid dispensing of liquid dairy products having selected milk fat ratios, which have been produced from various liquid dairy components, in order to provide the small volumes of the wide variety of liquid dairy products, which are commonly used in retail establishments.
[0017] Also, the prior art references do not address the issue of providing an intimate mixture of dairy products to produce the taste, texture, appearance, mouth “feel”, and “whitening” ability, of a wide range of commonly used dairy products, and thereby produce liquid dairy products having a quality which dairy product consumers have come to expect. Further, none of the references address the ability to provide small amounts of liquid dairy products in a sanitary or hygienic fashion, with the ability to rapid switch from one type of liquid dairy product to another.
[0018] As an example, it would be desirable to provide an apparatus to the retail market that would provide the ability to rapidly switch from dispensing 250 ml of 2% milk fat (M.F.) milk, to dispensing 15 ml of 35% M.F. cream and then to dispensing 30 ml of skim milk (0% M.F.), and provide the various products quickly, and without any significant blending between the final products, and without the need for a specific cleaning of the dispensing equipment between the dispensing of each product.
[0019] While it is also noted that the above named U.S. Pat. No. 3,987,715 does address the issue of cleaning of an ultrasonic mixing device by spraying water on the mixing device, this patent is directed to the cleaning of a device in a vending machine where a liquified product, such as soup or the like, is produced from water and a solid or powdered material. Accordingly, its use is primarily directed to a system to avoid build-up of solids or powdered material within the mixing chamber.
[0020] As such, it would be beneficial to provide an apparatus which is capable of dispensing a wide variety of liquid dairy products, in potentially small volumes, which would be able to provide some or all of the advantageous features described hereinabove.
SUMMARY OF THE INVENTION
[0021] The advantages set out hereinabove, as well as other objects and goals inherent thereto, are at least partially or fully provided by the liquid dairy product dispensation system of the present invention, as set out hereinbelow.
[0022] Accordingly, it is a principal advantage of the present invention to provide a liquid dairy product dispensation device which will provide a wide range of liquid dairy products from two or more base components.
[0023] Accordingly, in one aspect, the present invention provides a liquid dairy dispensation system for providing a liquid dairy product comprising:
[0024] a packaging assembly configured and designed for storing at least a first and a second dairy component product, and preferably, a first and second liquid dairy products, in separate compartnents, wherein the dairy component and/or liquid dairy products are capable of forming a resultant liquid dairy product after being combined;
[0025] a mixing chamber having a mixer for mixing said first and second dairy component product, and preferably said first and second liquid dairy product, together to form said resultant liquid dairy product;
[0026] a component delivery assembly, preferably comprising a pump, for transferring said first and second dairy component product, and preferably said liquid dairy products, from said packaging assembly to said mixing chamber, and
[0027] a dispensing assembly for dispensing said resultant liquid dairy product from said mixing chamber
[0028] In a further aspect, the present invention also provides a liquid dairy product dispensation apparatus comprising a packaging assembly adapted to receive at least a first and a second dairy component product, and preferably, a first and second liquid dairy product,
[0029] a mixing chamber having a mixer for mixing a first and a second dairy component product, and preferably, said first and second liquid dairy product, together to from a resultant liquid dairy product;
[0030] a component delivery assembly, preferably comprising a pump, for transferring said first and second dairy component products and preferable said liquid dairy products to said mixing chamber; and
[0031] a dispensing assembly for dispensing said resultant liquid dairy product from said mixing chamber.
[0032] Optionally, the dispensation system or dispensation apparatus described hereinabove with respect to the present invention, can additionally comprise a water delivery system which is capable of adding water to said mixing chamber for dilution of said first or said second dairy component products, such as said first or second liquid dairy product, as well as for dilution of said resultant liquid dairy product. The water might also be used for cleaning of said mixing chamber and/or said dispensing assembly.
[0033] As such, the optional inclusion of a water component allows for a wider variety of liquid dairy products to be produced. The water might also be used to assist in cleaning of the mixing assembly and the dispensing assembly.
[0034] In a still further aspect, the present invention also provides containers for said fist and said second dairy component product, and preferably said first and second liquid dairy products, which containers are adapted to be placed within said packaging assembly.
[0035] In a yet still further aspect, the present invention also provides a method for the dispensation of a liquid dairy product prepared from at least two dairy component products, and preferably at least two liquid dairy product components, comprising:
[0036] providing and retaining at least a first and a second different liquid dairy products in separate compartments of a packaging assembly;
[0037] withdrawing a selected amount of each of said first and said second liquid dairy products from said compartments, and feeding the withdrawn liquid dairy products to a mixing chamber;
[0038] intimately mixing said first and second liquid dairy products together to form a resultant liquid dairy product; and
[0039] dispensing said resultant liquid dairy product from said mixing chamber.
[0040] In a preferred embodiment, the system, apparatus, and methods of the present invention provide a resultant liquid dairy product which has acceptable levels of water, milk solids and fat, which meet with various government and other regulatory bodies guidelines or regulations, in order to be treated as standard dairy products.
BRIEF DESCRIPTIONS OF THE DRAWINGS
[0041] Embodiments of this invention will be described, by way of example only, in association with the accompanying drawings in which:
[0042] FIG. 1 is an exploded schematic of the elements of a preferred dispensation system;
[0043] FIG. 2 is a diagrammatic view of a preferred mixing chamber;
[0044] FIG. 3 is a perspective view of a preferred dispensation apparatus;
[0045] FIG. 4 is a schematic view of the dispensing apparatus;
[0046] FIG. 5 is a component flow diagram for the production of 21 ml of 2% milk;
[0047] FIG. 6 is a component flow diagram for the production of 21 ml of 18% milk; and
[0048] FIG. 7 is a schematic representation of the apparatus of FIG. 4 , which has been adapted to undergo a cleaning procedure.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0049] The novel features which are believed to be characteristic of the present invention, as to its structure, organization, use and method of operation, together with further objectives and advantages thereof, will be better understood from the following drawings in which a presently preferred embodiment of the invention will now be illustrated by way of example only. In the drawings, like reference numerals depict like elements,
[0050] It is expressly understood, however, that the drawings are for the purpose of illustration and description only and are not intended as a definition of the limits of the invention.
[0051] Further, in the present application, the term “dairy component product” is used to describe a product that can be used to contribute either milk solids or fat to a resultant dairy product. As such, the dairy component product preferably has at a combination of milk solids and fat, but can also provide a range of products including skim milk comprised of essentially only milk solids, to a semi-solid material known as “butter oil” having essentially 100% butter fat. Preferably, however, the dairy component product is a “liquid dairy product” which term is used to refer to liquid products made from milk. This would include products ranging in fat from 0% (skim milk) to up to about 50% or more of fat.
[0052] Further, the skilled artisan will be aware that this term might also apply to products not made of milk, per se, and thus can include liquid or liquefiable dairy products such as edible oil products or the like, which can be made as milk substitutes. As such the terms “dairy component products” and “liquid dairy products” can include products made from products such as soy oil, or the like.
[0053] Further, while most “dairy component product” and/or “liquid dairy products” would be expected to be produced from the milk from cows, in this application, the term is also intended to cover milk from other non-cow sources, such as for example goats or the like. Accordingly, while the present application is described with particular reference to the milk product from cows, the skilled artisan would be aware that the present application is equally applicable in other applications.
[0054] Also, any or all of the liquid dairy products may be a conventional milk product having a standard milk fat concentration (such as skim, 1%, 2%, 3.25%, 10%, 18% or 35%). However, since the present invention operates by blending of the two products, the range of resultant dairy products can be limited by the composition of the starting materials. Accordingly, it is preferred that the two liquid dairy products are selected from: 1) a skim milk base having little or no milk fats, and preferably a concentrated skim milk base having up to 4 or 5 times the standard amount of milk solids normally present in a typical, prior art liquid dairy product only; and, 2) a high milk fat liquid dairy product, such as for example, a 35%, 45% or even 60%, fat product.
[0055] As such, one of the two liquid dairy components is preferably skim milk having essentially no fat, and containing only water and milk solids. Typically, skim milk will have an MSNF (milk solids non fat) concentration of 8.5 to 9.5%, by volume, and this might be used if there is no water for dilution. However, If water is used as a diluent, than a stabilized, skim milk concentrate having an MSNF concentration of, for example of greater than 20%, more preferably of between 20 and 50%, and most preferably, between 25 to 47% can be employed. A preferred skim milk concentrate would be 3 to 5 times the normal concentration of skim milk, and thus would have a MSNF concentration of between 25.5 to 46.5%.
[0056] To prepare the stabilized skim milk concentrate, or in more general terms, any of the dairy component products, various stabilizers, emulsifiers, thickeners, buffering agents, colourants and the like, can be added to dairy component product. For example, buffering salts such as sodium hexametaphosphate (SHMP) might be added since the phosphate aids in delaying gelation, or kappa carrageenan can be added to provide improved viscosity or added “body” in a product considered to be too “thin”. Use of materials for modification of the dairy product properties is known to the skilled artisan.
[0057] Also, if desired, fat in the amount of up to, say, 0.3% by volume can be added to the skim milk concentrate in order to provide a liquid dairy product which, depending on the local government regulations, would fall within the “skim milk” classification, once diluted. This added fat, preferably in the form of butterfat, will aid in the processing of the skim milk concentrate by reducing foaming, reducing protein gelation, and increase whitening.
[0058] When designing the apparatus of the present invention, it is desirable to include at least one skim milk component (or a component having a very low fat content) in order to be able to supply skim milk as one of the resultant liquid dairy products available.
[0059] The second dairy component is preferably a liquid dairy product component having a fat content of greater than 25%, more preferably between 25 and 50% fat, and most preferably between 30 and 45% fat. This high fat component can be formed on an industrial scale by skimming a high fat cream portion from the milk of a separator, and then adding milk or milk solids in order to provide a desired milk fat content. Again, various stabilizers and the like can be added to the high fat component to aid in the stability of the product.
[0060] The second dairy component might also include a liquid or liquefiable butter oil product described hereinabove having essentially 100% fat However, while this type of material might reduce the amount of water shipped as part of one of the dairy component products, it would typically require a higher amount of milk solids to be contributed by using higher amounts of, for example, skim milk.
[0061] As such, the second dairy component is preferably a liquid dairy product which comprises between 25 and 50% fat, and more preferably, a liquid dairy product having between 35 and 45% fat. It should be noted, however, that for stability of the fat content of the fat-containing materials, it is also preferred to have a milk solids component present. Accordingly, when preparing a desired, resultant liquid dairy product, the amount of milk solids from the second dairy component would be included in the calculation (as would any fat content from the skim milk).
[0062] By combinations of these materials, a wide variety of products can be prepared having the desired milk fat content, as well as the necessary and/or desired milk solids content. Also, with the optional addition of water, the amount of water which must be transported as part of the component dairy products is reduced
[0063] While a combination of say 2% and 25% milk fat materials, might be used, in a preferred arrangement, a mixture of skim milk, and a high solids cream of say 45%, together with a method to provide additional water as required, would be used. Without being restricted to this particular embodiment, the invention will hereinafter be described with respect to this particular combination. However, the skilled artisan would be aware that other component arrangements are possible.
[0064] It should also be noted that the viscosities of the various dairy component products may vary. For example, cream is typically more viscous than skim milk. However, by use of appropriate pumps, as discussed below, the relative viscosities of the materials is largely irrelevant Typically, at the temperatures commonly encountered (eg. 2° to 25° C.), the products preferably have a viscosity of between about 0.1 cPs to 10,000 cPs, and more preferably, between about 200 cPs to 7,500 cPs.
[0065] The apparatus used in the practice of the present invention is able to provide a wide range of volumes depending on the various components selected for use. As such, the apparatus could dispense as little as 1 ml of resultant liquid dairy product, or it might be adapted to provide a continuous flow of resultant liquid dairy product until at least one of the component containers was empty. Preferably, however, the apparatus will typically dispense between 5 ml and 500 ml of resultant liquid dairy product, and more preferably between 10 and 100 ml of product. Still more preferably, the apparatus would be designed to dispense between 15 and 30 ml of resultant liquid dairy product.
[0066] The resultant dairy product would preferably be considered by the consumer to be essentially equivalent to a “fresh” milk product The term “fresh” as applied to milk herein means characteristics normally associated with fresh, pasteurized milk, whether it is in the categories of Fat Free, or skim (less than 0.21% fat), Low Fat (1% fat), Reduced Fat (2% fat), or Full Fat (3.25% fat). When purchased at a store, a consumer who recognize these materials as being fresh. In contrast, consumers would not recognize as being fresh those products sold as, for example, canned or condensed milk, reconstituted powdered milk, or the like. Other tests for “freshness” usually evaluate the major sensory characteristics of fresh milk which include (a) the presence or absence of visual defects, whether it has visibly separated or coagulated, or changed in color, (b) the aroma and taste, which together contribute to the flavor, (c) the texture and mouth feel, i.e., free of milk defects which may be described as watery, thin, coagulated, sandy, gritty, or separated, and (d) the ability of the product to suitably “whiten” a darker liquid such as coffee, tea or the like.
[0067] The dairy component products and/or liquid dairy products may require refrigeration in order to maintain their stability, and maintain their freshness. As such, transportation means, and the storage means for these products may require refrigeration capabilities. Further, the packaging assembly may be refrigerated and/or insulated to preserve the materials when in use in the method and/or apparatus of the present invention.
[0068] Preferably, however, the dairy component products have an extended shelf life (ESL), such as ESL pasturized, or are pasturized, or most preferably are “aseptic” so as to eliminate the need for refrigeration; particularly during transportation or storage. The aseptic product might, however, still be refrigerated prior to, or in use in order to suit the consumer's preferences for a cold dairy product.
[0069] Preferably, the aseptic product will be able to provide a shelf life of at about 180 days, meaning that the liquid dairy product is able to produce a product after 180 days which has an property profile similar to that of fresh product. This type of product is hereinafter referred to as “aseptic” or aseptically packaged” liquid dairy product.
[0070] Referring to FIG. 1 , a liquid dairy dispensation system 10 for providing a liquid dairy product of use in the practice of the present invention is shown in an exploded schematic view.
[0071] System 10 has two containers 12 , 14 for holding a first and second liquid dairy products. In this embodiment container 12 holds a skim milk concentrate (hereinafter “skim milk component”) having 3 times the normal MSNF components of skim milk (e.g. the concentrate has 0% fat, and 26% milk solids). Container 14 holds a concentrated dairy product (hereinafter the “cream component”) having 35% fat, and 8.5% milk solids.
[0072] Containers 12 and 14 can be identically shaped, and can have the same volume and the like. Alternatively, the containers can be different sizes in order to differentiate the skim milk component from the cream component. However, in order to differentiate the higher fat content container from the lower fat content container, it is preferred that the containers have projections, grooves and the like to prevent accidental misplacement of the container in a wrong compartment of the system apparatus.
[0073] The container might also contain some method to identify the contents of the container. For example, the container might be colour-coded, or the like in order to group similar products in like groups. In a preferred embodiment, containers 12 and 14 will each contain a RFID chip 60 and 61 , respectively, or some other identification markings, which will specifically identify the container, and/or which can provide specific information on the dairy product component of the specific container. This feature will assist in control of the system of the present invention, as discussed further hereinbelow.
[0074] Also, while containers 12 and 14 are shown as being two separate containers, it should be noted that they might also be two separated portions of a single container, with each portion having a separate outlet.
[0075] Further, the capacities of each container may vary greatly, depending on a number of factors, e.g., such as the concentration of the product, the overall size of the apparatus, or the relative amount of material expected to be used. For example, in applications where mostly cream is used, the size of the cream component container could be larger, whereas in a situation where mostly 2% milk was used, the size of the skim milk component might be larger. In one embodiment, the containers hold between about 50 ml and 10 litres, preferably between about 100 ml and 5 litres, and more preferably between about 200 ml and 4 litres. In a preferred embodiment, the ratio of the size of each container falls within the range of between about 5:1 and 1:1. Most preferably, the size of each container is essentially the same.
[0076] Containers 12 and 14 can merely be solid plastic containers which are adapted to fit within the apparatus. However, they may also be collapsible and/or disposable pouches made from, for example, barrier films which are able to keep water vapor, oxygen, and light transmission to a minimum. Suitable barrier films are commercially available, for example, containing laminated layers of polyester/aluminum/polyethylene, or the like.
[0077] The skim milk component and the cream component from containers 12 and 14 are each pumped from their respective containers using a component delivery assembly. The component delivery system in this embodiment consisting of tubes 16 and 18 which take product from containers 12 and 14 respectively, pumps 20 and 22 , and tubes 24 and 26 through which the output of pumps 20 and 22 are fed to mixing chamber 30 .
[0078] It is to be noted that tubing 16 and 18 , and all tubing used herein, are preferably flexible tubes which are suitable for use with food products, and in particular, dairy products. These types of tubes are well known in the industry, and can include tubes of flexible polymeric materials, which are commonly used for contacting and dispensing consumable beverages. Examples of suitable piping include food grade plastics, such as PTFE, PE, HDPE, PP, PVC, silicones, and the like. For example, tubing sold under the trade marks “Tygon” and “Norprene” are examples of the type of tubing that might be utilized.
[0079] Further, tubes 16 and 18 preferably connect to containers 12 and 14 using releaseable, and preferably, aseptic couplings (not shown) which would allow containers 12 and 14 to be rapidly replaced, when needed. In a preferred arrangement, the coupling used on tube 16 will be different from the coupling on tube 18 , and thus, a incorrect connection to containers 12 and 14 can be avoided.
[0080] Pumps 20 and 22 can be eliminated from the component delivery system if gravity feed is used, or if a pressurized system is used to move the liquid components. However, for accurate control and ease of use, it is preferred that pumps 20 and 22 be present. Any suitable pump can be used. A preferred type of pump, however, is a positive displacement pumps, and most preferably, the pump is a peristaltic pump. Peristaltic pumps are preferred since they can be accurately controlled (with respect to delivery timing and volume), and since, in this type of pump, the liquid dairy product components will not contact the pump components, per se, but remain within the tubing. This assists in minimizing the need for any cleaning of the pump, and minimizes the possibility of contamination of the dairy products from the pump components.
[0081] In a peristaltic pump, the liquid is moved by the action of the squeezing of the tube by the action of rollers or “fingers” on the tubing. The motor for the pump is preferably a “stepper” motor which can be accurately controlled to dispense a precise amount of liquid.
[0082] In the embodiment described herein, water is taken from a pressurized water supply, such as a city potable water supply, through tube 32 to a water treatment device 34 . While treatment of the water may not be required, it is shown in this embodiment to acknowledge that some water supplies are required to be treated for either health concerns, for taste preferences, or for similar reasons. The water treatment device can include devices such as filters, activated carbon filters, reverse osmosis (RO) membranes, water softeners, UV sterilizers, pressure valves, and the like, but in this example, water treatment device 34 is simply an RO membrane.
[0083] The water treatment can be done prior to feeding the water to the apparatus used in the present invention, or alternatively, various water treatment components can be included as part of the apparatus of the present invention.
[0084] Water exiting treatment device 34 is fed, as a result of the city water pressure, through tube 36 to mixing chamber 30 . Valve 38 on tube 36 is used to control the flow of water to the mixing chamber 30 , while pumps 20 and 22 are used to control the amount of product from containers 12 and 14 which flows into mixing chamber 30 . Alternatively, valve 38 can be replaced by a third pump which will pump precisely controlled amounts of water into the mixing chamber.
[0085] Mixing chamber 30 is a hollow cylindrical shell, which is shown in a cut-away view in FIG. 1 , and is shown in greater detail in FIG. 2 . Suitable mixing chambers can be any suitable vessels which might be used to mix the dairy component products, and optionally water, and can be made of any suitable material. Preferably, however, it is made of made of a material which would be suitable for food applications, and could include materials such as glass, stainless steel, glass lined products, or the like.
[0086] The mixing chamber is preferably a closed system in that the only ready access to the mixing chamber is through the tubes used to pump the dairy component products into the chamber, the water inlet (if used), and the resultant product outlet. As such, foreign objects or liquids will not fall into the mixing chamber, and thus, contamination of the resultant product in the mixing chamber is avoided. Further, however, the mixing chamber is preferably easily disassembled with the proper tools, in order to facilitate inspection, or routine intensive cleaning.
[0087] Once the dairy product components, and optionally water, have been introduced into mixing chamber 30 , they are preferably mixed using a mixing device. A variety of mixing devices might be utilized, and these can include a wide variety of mechanical mixers, including rotating mixing blades, static mixers, and the like. However, in order to provide a resultant liquid dairy product have good properties similar to a fresh dairy product, it is particularly preferred that the mixing device be an ultrasonic mixing device, which is placed within the mixing chamber.
[0088] In the preferred embodiment, shown in FIG. 1 , and in more detail in FIG. 2 , the ultrasonic mixing device is preferably a rod-shaped “sonotrode” 40 which is inserted into a cylindrically shaped mixing chamber 30 so as to provide intimate contact between the sonotrode and the components added to the mixing chamber.
[0089] A preferred type of mixing chamber, with a sonotrode as a mixing device, is commercially available from Hielscher GMBH and sold under the “UIP” trade mark, although other ultrasonic mixers might also be used. The ultrasonic mixers are available with a variety of power consumption ranges, and the skilled artisan will be able to select a power range appropriate for the size of mixing chamber to be utilized in the apparatus.
[0090] Without being bound by theory, it is believed that the ultrasonic mixer provides a small area of intense turbulence and cavitation which acts to intimately mix the dairy components on a molecular level. As a result of this intense mixing, the resultant dairy product is not only reconstituted, it is recombined.
[0091] In a “reconstituted” dairy product, the milk solids and the fat components are both present in the skim milk phase, but there is little intimate nixing, on a molecular level, of the milk solid content, and specifically, the proteins and minerals present, present in the skim milk phase, with the fat globules. As such, they are prone to “phase separation” of one component from another, by, for example, settling, agglomerating, aggregating, solidifying, liquefying, forming a precipitate, forming another liquid phase, or in some other way causing an unevenly or non-uniformly mixed product to result. This can occur at any time after the components are mixed together and/or any time after the component mixture is dispensed.
[0092] In a “recombined” dairy product however, the proteins from the milk solids component are intimately mixed, and forms bonds with and/or around the fat globules. As a result of this recombination, the intimate inclusion of the protein in the fat globules assists in stabilizing the fat globule within the aqueous skim milk phase. As such, the recombined liquid dairy product has improved stability over other dairy products which have merely been reconstituted, and provides a material which more closely resembles a fresh dairy product.
[0093] Accordingly, mixing with an ultrasonic mixer assists in reestablishing a recombined dairy product since it is able to mix the component materials together, in a non-destructive manner, in a more effective manner than other types of commonly used mixing methods. This is done, in the present invention, on a small scale, in order to rapidly produce a variety of different liquid dairy products from concentrated components, all of which have properties similar to traditional dairy products.
[0094] Thus, an ultrasonic mixer is preferred since with this type of ultrasonic mixer in the mixing chamber, the degree of homogenization, that is, the degree to which the fat globules have been dispersed in the skim milk phase approaches that of homogenized milk products with respect to the size and the consistency of the size of the fat globule dispersion. By approaching the same degree of homogenization of homogenized milk products, the colour, taste, appearance, feel, whitening ability, and the like, of the resultant product will more closely approximate fresh milk.
[0095] As such, the resultant material will preferably have a degree of homogenization which will be approximately equal to that of commercial milk products having a similar fat content. The following properties with respect to its degree of homogenization:
[0096] Mixing chamber 30 also has a series of openings to allow the water and the skim milk and/or the cream components to enter the mixing chamber, where they are mixed together, and/or mixed with the water. Sonotrode 40 is adapted to fit into mixing chamber 30 so as to leave a small gap between the interior wall of the shell of the mixing chamber 30 , and the exterior wall of the sonotrode 40 . As such, with the sonotrode 40 inserted in place, the mixing chamber 30 typically holds a volume of approximately 5 ml, although larger or smaller mixing chambers can be used depending on the particular application, and the expected flow rates and volumes.
[0097] With respect to the design of the mixing chamber, the size of the orifices of the openings in the mixing chamber, as well as the size of the tubing used throughout, and the pump sizes, can be varied according to various factors such as the viscosity, desired flow rate, and expected total amounts of the component(s) to be used, as well as the relative ratio of the components to be used Proper selection of these design configurations would be clearly understood by those skilled in the art.
[0098] At the bottom of sontrode 40 is a “sonic membrane” 44 which acts to transmit the ultrasonic frequencies used for mixing of the liquids. As such, liquids enter the mixing chamber 30 in the vicinity of sonic membrane 44 , and are mixed together by ultrasonic mixing. After mixing, the liquids are propelled up between the walls of the sonotrode and the mixing chamber shell, and then exit chamber 30 through tube 42 .
[0099] Tubes 24 , 26 and 36 are all shown separately entering mixing chamber 30 . This arrangement is preferred in order to minimize “contamination” of the skim or cream components prior to entry into mixing chamber 30 . However, it will be clear to the skilled artisan that any or all of these delivery tubes can joined to one another outside of the mixing chamber 30 . All of these tubes enter the mixing chamber 30 , at or near the bottom of the chamber.
[0100] Tube 42 , which carries the resultant dairy product, exits from mixing chamber 30 at or near the top of the mixing chamber in order to promote an upward flow of liquid in the mixing chamber 30 , and thus further assists in mixing of the liquids by maintaining a level of liquid within the mixing chamber. The amount of liquid held in the mixing chamber can vary depending on its size and design, but typically will have a volume which ranges from 1 ml to 25 ml, preferably from 2 to 10 ml, and more preferably, from 4 to 6 ml.
[0101] Between uses, mixing chamber 30 may contain a small amount of residual liquid, but this would be a small amount, and in a preferred embodiment, will likely be essentially water, as will be explained hereinbelow.
[0102] After the components are mixed, the resultant product exits mixing chamber 30 through tube 42 . While tube 42 may additionally contain a valve to contain the output from mixing chamber 30 , preferably, the resultant product flows freely from mixing chamber 30 though tube 42 .
[0103] Also, while a pump or a pressurized system might be connected to tube 42 to move the resultant product from mixing chamber 30 , preferably, the resultant product flows out of mixing chamber 30 merely by the force of the incoming liquids, and then flows through tube 42 as a result of the force of gravity. As such, tube 42 preferably slopes downward from mixing chamber 30 to the terminal point of tube 42 . When the resultant dairy product exits tube 42 , it is ready for collection and use as the final dairy product.
[0104] In FIG. 3 a representative view of the outside of an apparatus 50 for operation of the dispensation system 10 of the present invention is shown, and in particular, the face 51 of the apparatus. Apparatus 50 has two sets of selection buttons 52 and 54 which provide control over the volume of liquid dairy products to be produced 52 , and the butter fat content of the liquid dairy product 54 . A start button 56 is also provided, as well as the terminal, output end of tube 42 . In operation, the user would select the type of dairy product desired using button set 54 , and then select the volume of liquid dairy product using button set 52 . Once these controls have been set, the user merely hits start button 56 to dispense the liquid dairy product.
[0105] In will be clear however, that other arrangements can be provided in order to select the appropriate type and amount of product. For example, buttons could be pre-programmed to provide a set volume of a selected type of liquid dairy product (e.g. 21 ml of 2% milk).
[0106] Latch 58 is shown on the side of apparatus 50 which allows the front panel to be moved in order to gain access to the interior of apparatus 50 in order to change containers 12 and 14 , or to conduct maintenance, cleaning, or the like. Finally, a tray section 59 is shown to collect any spilt materials.
[0107] While the apparatus of use in the system of the present invention might operate solely by use of mechanical linkages and other arrangements, it is preferred that the various components are controlled by a computerized system. In FIG. 4 , a schematic representation of a computerized control system is show, which would be of use in the system 10 shown in FIG. 1 .
[0108] In FIG. 4 , sensors 160 and 161 are located in the apparatus near to the location of RFID chips 60 and 61 , respectively, and are thus are able to read the information from chips 60 and 61 . Preferably, sensors 160 and 161 are able to read the information without needing to be directly connected to chips 60 and 61 .
[0109] The information from chips 60 and 61 is passed to a central, computerized controller 110 . This information can include such information as the level of fat, the level of milk solids, a product expiry date, or the like, and this information can be used by the controller to extract the exact amount of the cream or skim milk components necessary, and to ensure that the components are still acceptable for use. By using the information from chips 60 and 61 , the central controller is able to precisely calculate the ratios of the water and dairy component products needed to exactly match the desired resultant liquid dairy product. This system also permits for a variety of dairy product component concentrations to be used, and thus minimizes the need for exact control of their concentration.
[0110] Sensors 152 and 154 are connected to button sets 52 and 54 respectively, and are used to determine the desired amount of material, and type of dairy product to be produced. Again these sensors are linked to central controller 110 so that this information can be provided to controller 110 . Also, central controller 110 is linked to start button 56 in order to activate the system, when required.
[0111] Pump controllers 120 and 122 are used to accurately time when pumps 20 and 22 are switched on and off, and, optionally, the flow rate at which pumps 20 and 22 will operate. Pumps 20 and 22 may require “calibration” in order to ensure that precise volumes are being dispensed. This calibration could be controlled by pump controllers 120 and 122 , or by central controller 110 .
[0112] Valve controller 138 is connected to valve 38 and is used to control the timing, amount, and optionally the flow rate, of the water entering the mixing chamber. Again, valve controller 138 is linked to central controller 110 , and may require calibration, or calibration controls.
[0113] Finally central controller 110 is also linked to a sonotrode controller 140 , which turns sonotrode 40 on and off at appropriate times.
[0114] In operation, buttons in button sets 52 and 54 are set to their desired position, and this information is provided to central controller 110 using sensors 152 and 154 , so that central controller knows the type of dairy product desired, and the amount desired. Once start switch 56 is activated, central controller calculates the amount of each of the water, and the skim milk and cream components from containers 12 and 14 . This calculation is based on the information taken from chips 60 and 61 collected by sensors 160 and 161 .
[0115] Once the formulation for preparing the desired product has been calculated, central controller activates pump controllers 120 and 122 , and water valve controller 138 in order to provide a mixture of 2 or 3 of the components in the mixing chamber. Once liquid is in the mixing chamber, sonotrode 40 is activated using sonotrode controller 140 in order to mix the components together.
[0116] By way of example, in the practice of the present invention, in order to provide a consumer with skim milk, the skim milk concentrate would be diluted with water, and no milk fat component needs to be added. For example, 2 parts by volume of water would be mixed with 1 part by volume of a 25.5% MSNF concentrate of skim milk to product a resultant skim milk product having milk solids of 8.5%. However, a small amount of the high fat content material might be added to provide some property enhancements (such as colour enhancement, or the like), while still meeting the government guidelines or regulations for skim milk fat levels.
[0117] In order to prepare a non-skim milk type product, the high fat content component is also mixed with the skim milk component and optionally water to produce a liquid dairy product having the desired milk fat content, and the necessary Or desired milk solid content. For example, to produce a 2% milk product, 20.6% of a 3 times (3×) concentration of skim milk would be combined with 5.7% of a 35% cream material, and 73.7% water (all by weight), in order to produce the desired resultant 2% milk product. This mixture would be added to the mixing chamber using controllers 120 , 122 and 138 , and the sonotrode 40 would be activated using controller 140 .
[0118] Use of the computerized system described in FIG. 4 allows for precise timing of the addition of liquids to the mixing chamber. In a preferred method, the timing of the addition of these components is controlled in order to provide the ability to maintain a sanitary and hygienic environment in the mixing chamber, the component delivery assembly, and/or the dispensing assembly, and preferably, in all three of these areas.
[0119] This is preferably achieved by controlling the timing of the addition of the water to the mixing chamber in order to provide a rinse of the mixing chamber at the end of each dispensing cycle.
[0120] For example, in FIG. 5 , a flow diagram for the production of 21 ml of 2% milk is shown from a mixture of an aseptic, 3 times concentrate of skim milk component (having 25.5% MSNF), an aseptic 35% fat cream component, and an appropriate amount of water, in an apparatus as shown and discussed in FIGS. 1 to 4 .
[0121] In FIG. 5 , the bottom axis shows the timing of the addition of the component, and in this example, the resultant dairy product is produced over a 3 second period. The left axis shows the flow rate of the addition of the components to the mixing chamber in ml/sec while the right axis is used to show the total volume of liquid added to the mixing chamber. The mixing chamber has a volume of 5 ml, and thus has a residual volume of essentially clean water from a previous cycle. This residual water content will vary in amount depending on the location of the exit location of tube 42 on the mixing chamber.
[0122] Once start button 56 is pressed, the skim milk component and the cream component are added to the mixing chamber, and the sonotrode ultrasonic mixer is activated to mix the liquids together in order to form a recombined dairy product. As liquid enters the mixing chamber, liquid also begins to exit the chamber starting first with the residual water, and followed by the recombined dairy product. After 1.5 seconds, a combined total of 6 ml of skim milk component and cream component have been added to the chamber and mixed to form the recombined dairy product.
[0123] Over the next 1.5 seconds, 15 ml of water is added to the mixing chamber, and preferably, the sonotrode ultrasonic mixer continues to operate in order to dissolve any dairy components remaining in the mixer in the incoming water stream. As such, near the end of the water addition, virtually all of the dairy components have been flushed from the chamber and have exited through the dispensing tube. All of the liquid exiting the mixing chamber is collected in order to form the desired dairy product.
[0124] After the total 3 second period, a mixture has been dispensed which accurately simulates the desired dairy product. The water exiting the mixing chamber at or near the end of the cycle easily mixes with the recombined milk product which has previously exited the mixing chamber.
[0125] On completion of the cycle, the mixing chamber is again filled with approximately 5 ml of clean residual water and is ready for production of the next dairy product.
[0126] The skilled artisan would be aware that the size of the mixing chamber can be varied in order to provide acceptable residual volumes of water. For example, an apparatus used to prepare 250 mls of a milk material would tolerate a higher residual volume in the mixing chamber than an apparatus designed to provide 15 ml of material at a time.
[0127] Also, the skilled artisan would be aware that devices such as check valves can be used to prevent, or better control the flow of liquids within the apparatus.
[0128] In FIG. 6 , a similar flow diagram for the production of 21 ml of 18% milk is shown, which could be produced immediately following the production of the 2% material described with respect to FIG. 5 . In FIG. 6 , increased amounts of the skim milk component, and in particular, the cream component are added to the mixing chamber, with its residual water content, and mixed in the first 1.8 seconds. The total amount of dairy products added is approximately 14 ml. In the final 1.2 seconds, 7 ml of water is added to the mixing chamber in order to flush the dairy product from the mixing chamber, and leave essentially clean residual water in the mixing chamber.
[0129] Those skilled in the art will appreciate that the amount of residual water, the flow rates of product addition, and the like can all be varied by minor modification of the mixing chamber design, and the like. The flow rate of the water and the dairy product components can vary greatly, depending on any of the previously stated conditions or properties, such as those indicated above. In a preferred embodiment, however, each volumetric flow rate is from about 0.1 ml/min to 100 ml/min, preferably from about 0.5 ml/min to 50 ml/min, and even more preferably about 2 ml/min to 35 ml/min. However, it will be clear that the flow rates will vary depending on the design parameters of the apparatus.
[0130] Also, those skilled in the art will also appreciate that further components can be added so as to include more than 2 dairy components, and thus, increase the flexibility of the apparatus. Also, the beverage product to be dispensed may include other materials, such as flavouring, or other components which are desired to give the resultant dairy product additional properties. Further, while it is preferred that the resultant dairy product meet the local requirements for substitution of regular dairy products, this is not essential. Instead, customized dairy “blends” could be produced having relatively higher or lower fat levels and fat level to milk solids ratios.
[0131] Still further, the skilled artisan will also appreciate that the dispensing apparatus might also contain other non-essential features which provide some functional or aesthetic benefits, such as, for example, a hot or cold water taps, component level indicators, alarms, digital displays of the apparatus settings and conditions such as temperature, reminders concerning pump or valve calibration or the timing of routine intensive cleaning, and the like.
[0132] Yet still further, the skilled artisan will be aware that the volume of the mixing chamber might be adjusted in an apparatus by various means. These might include relative movement of the sonotrode within the mixing chamber to reduce or enlarge the area between the sonotrode and the mixing chamber. This might also be accomplished by changing the wall positions of the mixing chamber using a moveable section wherein, for example, the “floor” of the mixing chamber could be raised to decrease the volume of the mixing chamber, or the like.
[0133] Also, the skilled artisan will be aware that, although routine use of the apparatus will maintain a sanitary environment, regular cleansing of the apparatus would likely also be desirable. This can be accomplished by, for example, the configuration shown in FIG. 7 . In FIG. 7 , a schematic representation of the system of the present invention is shown in which, inter alia, a separate cleaning tank 80 is also provided Tank 80 can be positioned within apparatus 50 after containers 12 and 14 have been temporarily removed, and tubes 16 and 18 , both, or individually, are connected to tank 80 . Also, dispensing tube 42 is connected to extension tube 82 which passes through a heater module 84 , and a then meets with ree-way valve 86 . The liquid passing though tube 82 can then be sent via tube 88 to the top of tank 80 , or can be sent to a drain by tube 90 by movement of valve 86 .
[0134] In use, containers 12 and 14 are disconnected from the system, and tank 80 is connected to tubes 16 or 18 , but preferably to both tubes 16 and 18 . Tank 80 is preferably of a size where it can be placed within the space vacated by containers 12 and 14 . Tank 80 is filled with rinse water, and preferably a cleaning solution. Pumps 20 and 22 are then operated in a continuous mode to pull cleaning solution from tank 80 through tubes 16 and 18 , and then sent it to mixing chamber 30 , and then through dispensing tube 42 . An initial portion of cleaning solution can be sent to drain through tube 90 .
[0135] After this initial rinse period, heater module 84 is engaged to heat the cleaning solution to a suitable temperature such as 90° C. Also, valve 86 is moved so that the heated cleaning solution is recycled and returned to tank 80 . The heated liquid can be sent to the tubes and mixing chamber components in order to sanitize these components.
[0136] After a sufficient period of time, heater module 84 is turned off, and valve 86 is turned so that the heated cleaning solution is drained from the system through tube 90 . Tank 80 is then filled with clean, cool rinse water, and pumps 20 and 22 are used to circulate the clean water throughout the system, and to cool the system. This rinsing operation may be repeated in order to remove any traces of the cleaning solution from apparatus 50 .
[0137] The skilled artisan will also be aware that residence time in the mixing chamber will ultimately determine the degree of homogenization of the resultant product. However, it is preferred that the mixing chamber, with mixer, be designed so that homogenization of the product is accomplished essentially instantaneously as the components preferably flow continuously through the mixing chamber. Thus, the residence time in the mixing chamber will preferably average less than 10 seconds, more preferably less than 5 seconds, and most preferably, be less than 2 seconds.
EXAMPLES
Example 1
[0138] A 2% M.F. product was prepared in accordance with the present invention from a 3× concentration mixture of skim milk, and a 35% cream material. Sufficient water was added to produce the desired resultant product.
[0139] This product was compared to a control mixture that had been simply hand blended under low shear conditions. In general, the product prepared using the method and apparatus of the present invention provided scores 5% closer to standard milk with respect to colour (namely “L, a, b” scores) than did the control mixture. Further the product prepared using the method and apparatus of the present invention provided a particle size distribution that was 22% closer to standard milk than did the control.
[0140] Finally, on standing in a pyrex beaker, the product prepared using the method and apparatus of present invention did not leave a skim solids line on the beaker after standing, similar to the performance of regular milk. However, the control mixture left a substantial skin solids line on the beaker surface.
Example 2
[0141] A first 2% milk sample was prepared from a blend of 3× skim milk concentrate, 35% cream and water (Formula A) in a second dispersion apparatus. A second 2% milk sample was prepared from regular skim milk, 35% cream and water (Formula B). These samples were compared to a commercial 2% milk sample (Target), and a hand blended control sample (Control) with respect to colour and particle size. The products were also compared for their ability to colour coffee in a 2% milk blend in coffee. The results are shown in Table 1.
TABLE 1 Particle Size Colour Mean Spec. Surface Sample L a b Diameter (μm) Area (m 2 /ml) Target 77.89 −2.37 2.62 0.86 10.06 Control 74.22 −2.56 0.57 2.46 7.46 Formula A 78.61 −2.39 1.41 0.91 11 Formula B 79.40 −2.73 2.40 0.83 14.6 Coffee & 44.56 2.45 13.8 Target Coffee & 39.69 1.57 10.7 Control Coffee and 44.97 2.55 13.96 Formula A Coffee and 45.27 2.58 13.62 Formula B
[0142] The results show that the recombined and reconstituted products, which have been prepared in accordance with the present invention, have properties significantly improved over a simple hand blended mixing procedure, and have final properties which approach that of traditional standard milk products.
[0143] Thus, it is apparent that there has been provided, in accordance with the present invention, a liquid dairy product dispensation system which fully satisfies the goals, objects, and advantages set forth hereinbefore. Therefore, having described specific embodiments of the present invention, it will be understood that alternatives, modifications and variations thereof may be suggested to those skilled in the art, and that it is intended that the present specification embrace all such alternatives, modifications and variations as fall within the scope of the appended claims.
[0144] Additionally, for clarity and unless otherwise stated, the word “comprise” and variations of the word such as “comprising” and “comprises”, when used in the description and claims of the present specification, is not intended to exclude other additives, components, integers or steps.
[0145] Moreover, the words “substantially” or “essentially”, when used with an adjective or adverb is intended to enhance the scope of the particular characteristic; e.g., substantially planar is intended to mean planar, nearly planar and/or exhibiting characteristics associated with a planar element.
[0146] Further, use of the terms “he”, “him”, or “his”, is not intended to be specifically directed to persons of the masculine gender, and could easily be read as “she”, “her”, or “hers”, respectively, and, the term “about,” as used herein with respect to a range of values, should be understood to modify either value stated in the range, or both.
[0147] Also, while this discussion has addressed prior art known to the inventor, it is not an admission that all art discussed is citable against the present application. | A multi-component liquid dairy product dispensing system is provided which preferably utilizes an ultrasonic mixing chamber to essentially instantaneously combine and reconstitute liquid dairy product streams of various concentrations, with or without water, into a single homogeneous final liquid dairy product. Depending on the ratio of the liquid dairy products, a resultant liquid dairy product is provided which possess the same quality and attributes of the traditional liquid dairy products known by consumers, and can meet the regulatory standards for identification for various milk and cream products with respect to milk solids and fat content percentages. The liquid dairy product streams are preferably aseptic products in order to increase their shelf-life and stability. The resultant liquid dairy product dispensing system provides a system which is capable of rapidly providing a variety of liquid dairy products. | 1 |
BACKGROUND OF THE INVENTION
This invention relates to gas turbine engines, and deals more particularly with the construction of a nozzle assembly for supplying fluent materials to a burner can and with the manner in which a plurality of such nozzle assemblies are combined with a single burner can and with associated parts of the engine to facilitate removal of various parts from the engine for cleaning, repair or replacement or to provide repair or inspection access to other less easily removed engine parts.
The nozzle construction and arrangement of this invention may be used with various different models of gas turbine engines each having a compressor section, a combustion section, and a turbine section and each being of the type wherein the combustion section includes a plenum containing at least one burner can receiving air from the plenum and to which one or more fuels or other fluent materials are supplied to support combustion with the air in the can. In the following description and the accompanying drawings, however, the engine to which the invention is applied is taken to be one similar to that shown in U.S. Pat. Nos. 3,991,562, 4,009,569 and 4,016,718, all assigned to the assignee of this application, to which reference is made for further details of the engine construction not repeated in this application.
In the operation of a gas turbine engine it is often necessary or desirable, when changing from one mode of operation to another, to vary the injection of fuel or other fluent material into the burner cans. For example, during starting it may be desirable to inject one fuel and during normal running to inject another or an additional fuel. Or, during starting it may be desirable to have the fuel injected into the burner can in one spray pattern and during normal running of the engine to have it injected with a different spray pattern. Along with the fuel or fuels it may also be desirable to inject water, steam, or other materials to enhance combustion or to reduce the amount of pollutants in the exhaust gases. Also, the nozzle heads of any nozzle assemblies used in a gas turbine usually require frequent inspection since they are subject to clogging due to coking or the catching of foreign particles contained in the fluent material passing therethrough.
The general object of this invention is, therefore, to provide a nozzle assembly for a gas turbine engine whereby a number of different fluent materials may be supplied, at separate times or simultaneously, to the nozzle head for injection into an associated burner can and/or by means of which different spray patterns may be obtained, the nozzle head nevertheless being relatively easily removable from the engine for inspection and for cleaning, repair, or replacement, if necessary.
Another object of this invention is to provide a plurality of nozzle assemblies of the foregoing character for each burner can of the engine and which plurality of nozzle assemblies is so arranged relative to the other parts of the engine and to the associated supply manifolds as to permit removal of the central liner of the associated burner can without disturbing the nozzle assemblies and their supply manifolds.
A still further object of this invention is to provide a plurality of nozzle assemblies which are mounted on a removable wall member of the engine and which may be entirely removed from the engine along with the wall member for inspection or repair and to provide a relatively large access opening for reaching other parts of the engine located in the combustion section.
Other objects and advantages of the invention will be apparent from the drawings and from the following description.
SUMMARY OF THE INVENTION
The invention resides in a nozzle assembly for supplying fluent materials to an associated burner can of a gas turbine engine, the assembly having a tubular housing extending between a wall of the engine and the burner can and also having an elongated tubular feeder with an inboard and an outboard portion. At its free end the inboard portion of the feeder carries a nozzle head slidably received in the tubular housing and positioned to spray fluent material supplied to it into the burner can. The outboard end of the feeder extends outwardly from the wall and is connected with a supply of fluent material. Intermediate its length the feeder includes a flange or other means sealing the associated opening in the wall and releasably connected to the wall, so that when the flange or similar means is released from the wall the feeder and the associated nozzle head may be removed from the engine by sliding the feeder endwise away from the wall, thereby withdrawing the nozzle head from its tubular housing.
The invention also resides in the feeder being comprised of two concentric pipes providing two separate feeder passageways for conducting fluent material to the nozzle head, and it also resides in a means for supplying fluent material to the annular passage defined between the tubular housing and the feeder, the nozzle head having a means permitting such fluent material to flow past the nozzle head from the passage to the burner can.
The invention further resides in there being a plurality of nozzle assemblies for a burner can with the assemblies being arranged in an annular array and with their fluent material supply manifolds being of an annular shape so as to permit the central liner of the burner can to be removed from the engine without disturbing the nozzle assemblies and their supply manifolds.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a fragmentary sectional view taken on a plane passing through the longitudinal axis of a gas turbine engine embodying this invention and showing a portion of the combustion section of said engine.
FIG. 2 is a view partly in longitudinal section and partly in side elevation showing in more detail one of the nozzle assemblies of FIG. 1.
FIG. 3 is an enlarged longitudinal sectional view of the left hand end portion of the nozzle assembly shown in FIG. 2.
FIG. 4 is an enlarged view taken on the line 4--4 of FIG. 1.
FIG. 5 is a sectional view taken on the line 5--5 of FIG. 1.
FIG. 6 is a reduced scale view generally similar to to FIG. 2 but showing the feeder and nozzle head removed from the tubular housing of the nozzle assembly.
FIG. 7 is a sectional view taken on the line 7--7 of FIG. 6.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Turning to the drawings and first considering FIG. 1, this figure shows a portion of the combustion section of a gas turbine engine, the illustrated parts of the engine including an annular diffuser-burner case 10 and an annular plenum cover 12 defining part of an annular plenum 14. The plenum 14 receives high pressure air delivered to it by an annular duct 16 forming a diffuser for the compressor section of the engine, the illustrated stator vanes 18, 18 being part of the last compressor stage, and contains a number of burner cans, such as the one indicated at 20. Air from the plenum enters the burner cans and is there burned with fuel to provide combustion gases delivered to the turbine section of the engine located to the right of the parts shown in FIG. 1.
As disclosed by the aforementioned patents, the instant engine has eight burner cans similar to the illustrated can 20 and each of these cans together with the associated parts shown in FIG. 1 are generally identical to one another.
As shown in FIG. 1, the illustrated burner can 20 is associated with a dormer portion 22 of the diffuser-burner case 10 with the dormer portion providing a relatively large aperture 24 communicating with the plenum 14. The aperture 24 is closed by a recessed or cup-shaped aperture cover 26 which is releasably fastened to the diffuser-burner case by a plurality of threaded fasteners such as the one shown at 28. The cover 26 has a cylindrical side wall 30 and a bottom wall 32.
Fastened to the wall 32 are a plurality of nozzle assemblies, indicated generally at 34, 34, which extend between the wall 32 and the burner can 20 and serve to supply fuel and/or other fluent materials to the burner can to support the combustion process which occurs therein. Also connected to the bottom wall 32, by a plurality of threaded fasteners 35, 35 as shown in FIG. 4, is a cover plate 36 which normally seals a central opening 38 in the wall. Supportingly fixed to the cover plate 36 is a supporting structure 40 which extends between the plate and the center tube or liner 42 of the burner can 20. The liner 42 is connected to the supporting structure 40 and unconnected to other parts of the burner can 20 so that when the threaded fasteners 35, 35 are removed from the cover plate 36, the supporting structure 40 and the liner 42 may be removed from the engine by moving the plate 36 to the left in FIG. 1 thereby sliding the supporting structure and the liner out of the engine through the opening 38 in the bottom wall 32.
Referring to FIGS. 2 and 3, each nozzle assembly 34 has a tubular housing 44 which is fixed to the bottom wall 32 of the cover 26 and which extends between that wall and an associated opening in the burner can 20 defined by an annular socket 46 fixed to the can. The tubular housing 44 is comprised of a relatively thick walled tubular section 48 welded to the wall 32, as indicated at 50, a relatively thin walled tubular section 52, and a tubular nose section 54. The sections 48 and 52 are connected to one another by a set of flanges and threaded fasteners, as indicated at 56, and the sections 52 and 54 are connected to one another by welding. The nose section 54 is slidably received in the associated burner can socket 46 and has a plurality of spacing fins 58, 58 which, as seen best in FIG. 7, center the nose section 58 in the socket 46 while permitting air to flow from the plenum 14 into the burner can 20 between the socket and the nose section. Mounted on the very end of the nose section 54 is a swirler ring 60 for swirling the air which does enter the burner can 20 through the socket 46.
The tubular housing 44 of the nozzle assembly, as shown in FIG. 2, at its left hand end is aligned with and surrounds an opening 62, in the wall 32, aligned with the burner can opening provided by the socket 46. Passing through the opening 62 is an elongated feeder 63 which supplies fluent material to a nozzle or spray head 64 received in the nose section 54 of the tubular housing adjacent the burner can 20. The feeder 63 has an inboard portion 66 received in the tubular housing 44 and an outboard portion 68 extending outwardly of the wall 32 in the direction away from the plenum 14. The feeder also includes a radially extending flange 70 which normally seals the opening 62 in the wall 32 and is releasably connected to the wall by three headed screws 72, 72 passing through the flange and threaded into the wall 32. Releasably connected to the outboard end of the outboard portion 68 of the feeder is a first fuel manifold, indicated generally at 74, which, as explained in more detail hereinafter, separately supplies fluent material to two different passageways extending through the feeder from the manifold 74 to the nozzle head 64.
The nozzle head 64 is slidably received in the tubular housing 44 and has a maximum outside diameter less than the minimum inside diameter of the tubular housing and less than the diameter of the opening 62 in the wall 32 so that when the manifold 74 is removed from the feeder and the screws 72, 72 are removed from its flange 70, the feeder and the attached nozzle head 64 may be removed from the engine by shifting the feeder end-wise to the left in FIG. 2 to thereby withdraw the inboard feeder portion 66 and the nozzle head 64 from the tubular housing as shown in FIG. 6.
The feeder 63, as best shown in FIGS. 2 and 3, preferably consists of two concentric pipes 80 and 82. The inner pipe 80 is a unitary member extending the full length of the feeder from the nozzle head 64 to the manifold 74; and the outer pipe 82 is comprised of an inboard member 84, extending from the wall 32 to the nozzle head 64, and an outboard member 86 connected to the inboard member 84, providing the flange 70 and extending from the wall 32 to the manifold 74. The bore 88 of the inner pipe 80 provides one passageway from the manifold 74 to the nozzle head and the annular space 90 between the inner pipe 80 and the outer pipe 82 provides a second such passageway.
The manifold 74 includes a primary supply line or conduit 92 and a secondary supply line or conduit 94. These supply lines are connected individually to the two passageways in the feeder as shown in FIG. 3. More particularly, for each nozzle assembly the supply manifold 74 includes a connector body 96 threadably connected to the outer end of the feeder by a union nut 98. The connector body 96 has a bore, concentric with the bores of the feeder pipes 80 and 82, defining an outer chamber 100 connected to the primary supply line 92 and an inner chamber 102 connected to the secondary supply line 94. Between the outer chamber 100 and the inner chamber 102 the connector body bore has a cylindrical seal section 104 which slidably receives a conforming cylindrical head 106 on the outer end of the inner pipe 80, thereby sealing the outer chamber 100 from the inner chamber 102 and causing the chamber 100 to communicate exclusively with the bore 88 of the inner pipe 80 and the inner chamber 102 to communicate exclusively with the annular passageway 90.
The internal structure of the nozzle head 64 may vary widely without departing from the invention and is not shown in detail. It will be understood, however, that the bore 88 of the inner tube 80 communicates with one set of discharge ports in the free or right hand end of the nozzle head to cause the material supplied to the nozzle head by the bore 88 to be sprayed into the burner can with one type of spray pattern and that the annular passageway 90 of the feeder communicates with another set of discharge ports in the free or right hand end of the nozzle head to cause the material supplied to the nozzle head by the annular passageway 90 to be sprayed into the burner can with another spray pattern. The manifold 74 may supply the same or different material through the two passageways 88 and 90, and at different times in the operation of the engine either one or the other or both of the passageways may be used to supply material to the burner can. Generally, the fluent material supplied by either the passageway 88 or the passageway 90 will be a fuel such as fuel oil.
In addition to the fluent material supplied to the nozzle head by the passageways 88 and 90 the nozzle assembly 34 also may inject a third fluent material supplied by a toroidal supply manifold 108 to the annular passage 110 between the outside of the outer pipe 82 of the feeder and the inside of the tubular housing 44. The nozzle head 64 includes means, such as grooves or flutes on its outside surface, permitting the fluid in the annular passage 110 to flow past it into the burner can 20 and the nose portion 54 of the tubular housing may also include vanes or the like cooperating with the nozzle head 64 to impart a desired spray pattern to this fluent material. This fluent material may be any one of a wide variety of materials, but is preferably steam which acts to enhance the combustion occurring in the burner and to also reduce the amount of pollutants contained in the exhaust gases.
As shown in FIG. 4 there are eight nozzle assemblies 34,34 associated with illustrated burner can 20 of FIG. 1 all of which are attached to the bottom wall 32 of the recessed aperture cover 26 by their flanges 70, 70 and attachment screws 72, 72. The eight nozzle assemblies are further arranged in an annular array around the cover plate 36 and have their longitudinal axes parallel to one another and parallel to the central axis of the cover plate 36 and of the center tube or liner 42 of the burner can. As shown in FIG. 5, the manifold 108 for supplying steam or other fluent material to the passages 110, 110 of the nozzle assemblies is a toroidal member having a central opening 110 large enough to accommodate the burner tube liner 42 and its supporting structure 40. Each nozzle assembly has the thick walled part 48 of its tubular housing passing through the toroidal member as shown in FIG. 5. Each part 48 is welded to the manifold 108, as shown in FIG. 2 and indicated at 114, and each part 48 has at least one opening 116 providing communication between the bore of the manifold 108 and the associated passage 110.
The supply manifold 74, as shown in FIG. 4, is also annular in shape, so as to surround the cover plate 36. It includes the primary supply line 92, made of a number of tubular segments extending between the various connector bodies 96, 96 of the nozzle assemblies, and the secondary supply line 94, also made of a number of tubular segments extending between the various connector bodies 96, 96. The primary supply line has an inlet fitting 120 and the secondary supply line 94 has an inlet fitting 122. A supply conduit 124 is fixed to the recessed aperture cover 26, passes through its bottom wall 32, and is connected to the manifold 108 as shown in FIG. 5 to supply fluent material to that manifold.
From the foregoing, it will, therefore, be understood that the construction and arrangement of the nozzle assemblies 34, 34 is such that the center tube or liner 42 of the burner can and its supporting structure 40 may be removed from the engine without disturbing the nozzle assemblies or their manifolds 74 and 108 by removing the screws 35, 35 from the cover plate 36 and by then shifting the cover plate to the left in FIG. 1 to withdraw the supporting structure and the liner 42 through the hole 38 in the bottom wall 32. Also, the feeder 63 and nozzle head 64 of each nozzle assembly may be removed from the engine by loosening all eight union nuts 98, 98 and removing the supply manifold 74, by removing the screws 72, 72 holding the nozzle feeder in place, and by then shifting the feeder to the left in FIG. 2 to withdraw the feeder and the nozzle head 64 from the tubular housing 44 as shown in FIG. 6. Still further, if desired, the fasteners 28, 28 holding the recessed aperture cover 26 in place may be removed, after which the cover 26 may be shifted to the left to withdraw it, the tubular housings 44, 44 of the nozzle assemblies and the toroidal supply manifold 108 from the engine, making the nozzle assemblies 34, 34 available in their entirety for cleaning, inspection, repair, etc., and also providing, by way of the dormer opening 24, a relatively large access area to reach other internal parts of the engine. | An axial flow gas turbine engine has a combustion section with a number of nozzle assemblies for injecting fluent materials, such as fuel, combustion enhancers, or pollutant reducers, into a burner which is supplied with air from the combustion section plenum. The nozzle assemblies are carried by a wall separating the plenum from the outside of the engine and extend from the wall to associated openings in the burner can. The nozzle head and an associated feeder tube is easily removable from the remainder of each nozzle assembly for cleaning, repair or replacement of the nozzle head, or for other purposes. The nozzle assemblies and their supply manifolds are further arranged so that a central liner of the burner can may be removed through the wall without disturbing the nozzle assemblies or the supply manifolds. Also, the wall is provided by a member removably attached to the engine case or frame and supporting the nozzle assemblies and the burner can liner, so that by a more complete procedure all of the nozzle assemblies, and the burner can liner, may be entirely removed from the engine, if desired. | 5 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims benefit of U.S. Provisional Patent Application Ser. No. 60/883,686, filed on Jan. 5, 2007, which application is incorporated herein by reference in its entirety.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] Embodiments of the present invention generally relate to methods and apparatus for destroying tissues in the body. Particularly, embodiments of the present invention generally relate to methods and apparatus for removing prostatic tissue. More particularly, embodiments of the present invention generally relate methods and apparatus for surgical enlargement of the urethra lumen with minimal while conserving the natural inner lining of the urethra.
[0004] 2. Description of the Related Art
[0005] Benign prostatic hyperplasia (“BPH”) is a common medical condition experienced by men over 50 years old. BPH arises from the benign replication and growth of cells in the prostate. Hyperplastic enlargement of the prostate gland often leads to compression of the urethra, resulting in obstruction of the urinary tract and the subsequent development of symptoms including frequent urination, decrease in urinary flow, pain, discomfort, and dribbling.
[0006] Traditional treatments of BPH include non-surgical and surgical treatments. Treatment with medication is usually recommended for mild cases of BPH. For more severe cases, surgery to resect the prostate is usually performed. Transurethral resection of the prostate (“TURP”) is commonly performed to remove a large portion of the prostate. In order to enlarge the diameter of the urethra, TURP removes the inner lining of the urethra and the surrounding prostatic tissue. Due the procedure's aggressive nature, one drawback of TURP is that too much tissue is removed, thereby causing cavitation. Another drawback is that substantial bleeding may occur from destruction of the inner lining, thereby causing formation of blood clots.
[0007] Laser surgery is another common procedure performed to remove portions of the prostate. Although laser surgery causes less bleeding, it delivers light energy to the prostatic tissue by burning through the inner lining of the urethra. Another disadvantage of laser surgery is that it may not efficiently remove the desired volume of resection. For example, a typical laser may have a 1 mm diameter. In order to make a 1 cm diameter cut, a substantial number of laser fires must be executed.
[0008] There is a need, therefore, for methods and apparatus for removing prostatic tissue with minimal damage to the inner lining of the urethra.
SUMMARY OF THE INVENTION
[0009] Embodiments of the present invention generally relates to methods and devices for treating prostatic tissues. In one embodiment, a method of treatment includes removing prostatic tissues adjacent the urethra and enlarging the lumen of the urethra, whereby the treatment conserves a natural wall of the urethra.
[0010] In another embodiment, a method of removing tissue of a prostate proximate a urethra having an inner lining. The method includes positioning a catheter in the urethra; inserting a mechanical debrider through the catheter; positioning the mechanical debrider in the prostate proximate the tissue to be removed; rotating the mechanical debrider against the tissue; and removing the prostatic tissue, thereby forming a cavity adjacent the inner lining of the urethra.
[0011] In another embodiment, a medical device includes a catheter having a first channel and a second channel; a first medical tool positioned in the first channel; and a mechanical debrider positioned in the second channel, wherein the debrider includes an outer tube and a tissue removal member.
[0012] In yet another embodiment, a medical device includes a catheter; an endoscope positioned in the catheter; and a mechanical debrider extending out of the catheter, wherein the debrider includes an outer tube and a tissue removal member.
[0013] Embodiments of medical devices and treatment method disclose herein are particularly useful for treating benign prostate hyperplasia (BPH). However, it must be noted that the devices and treatment methods are suitable to remove other tissues such as tumor cells and cancer cells. Moreover, it is further contemplated that the devices and treatment methods may be used to treat other bodily tissues and is not limited to the prostate.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
[0015] FIGS. 1 and 1A illustrate an enlarged prostate constricting the urethra.
[0016] FIGS. 2 and 2A illustrate a surgical device inserted into the urethra according to one embodiment.
[0017] FIGS. 3A-B illustrate an embodiment of the surgical device.
[0018] FIGS. 4 and 4 A-B illustrate operation of the surgical device. As shown in FIGS. 4 and 4A , a guide needle extends out of a side port of a catheter of the surgical device. FIG. 4B illustrates another embodiment wherein the guide needle extends out of the front end of the catheter.
[0019] FIGS. 5 and 5A illustrate operation of the surgical device. As shown, a removal device is inserted through the cannula.
[0020] FIGS. 6A-E illustrate operation of the surgical device. FIGS. 6A-B illustrates operation of the removal device. FIGS. 6C-E illustrate a multi-step process of forming a cavity.
[0021] FIGS. 7 and 7 A-B illustrate removal of tissue around the urethra.
[0022] FIGS. 8 and 8A illustrate an embodiment of a rotation controller.
[0023] FIGS. 9A-C illustrate inflation of a balloon in the lumen.
[0024] FIGS. 10 and 10A illustrate enlargement of the lumen after the procedure.
[0025] FIGS. 11A-C illustrate the process of positioning a stent in the lumen.
[0026] FIGS. 12A-C illustrate different views of a polyethylene urethral stent.
[0027] FIGS. 13A-B illustrate views of the lumen of the urethra before and after the surgical procedure.
[0028] FIGS. 14A-B illustrate views of the lumen of the urethra before and after the surgical procedure with placement of a stent.
[0029] FIGS. 15A-E illustrate views of another embodiment of a debrider.
[0030] FIGS. 16A-C illustrate the expansion process of the blades of the debrider shown in FIGS. 15A-E .
[0031] FIGS. 17A-D illustrate views of another embodiment of a debrider. FIGS. 17B-D illustrate the expansion process of the blades of the debrider shown in FIG. 17A .
[0032] FIG. 18 illustrates an embodiment of a debrider with a built in RF probe.
[0033] FIGS. 19 , 20 , 21 A-B illustrate operation of the debrider of FIG. 18 .
[0034] FIG. 22A illustrates expansion of the lumen using a balloon. FIG. 22B illustrates implantation of a stent in the enlarged lumen.
[0035] FIG. 23 illustrates a stent positioned in a lumen.
[0036] FIGS. 24A-D illustrates an embodiment of a device and process of removing a stent from the urethra.
DETAILED DESCRIPTION
[0037] FIG. 1 shows an enlarged prostate 10 constricting the lumen 20 of the urethra 15 . The prostate 10 attaches near the bladder neck, and the urethra 15 extends from the bladder 25 and through the prostate 10 . FIG. 1A is an exploded view of the constricted urethra 15 .
[0038] Embodiments of the present invention provide methods and apparatus for removal of prostatic tissue to alleviate the constriction on the urethra 15 . In one embodiment, the method begins with inserting a surgical device 100 into the urethra 15 and positioning the surgical device 100 at a desired location, see step 1 as illustrated in FIGS. 2 and 2A . The surgical device 100 includes an expandable member such as an inflatable balloon 105 fitted to the outer surface of the front end of the device 100 . The balloon 105 may be inflated using a fluid such as air, water, and combinations thereof. The balloon 100 may be made from polyurethane or other suitable expandable material. The balloon 100 may be inflated to facilitate the exchange, insertion, or removal of a probe or other tools. In this respect, the balloon 100 may act as a dilator to expand the urethra 15 to the desired diameter.
[0039] Referring now to FIGS. 3A and 3B , the surgical device 100 includes a catheter 110 having at least two channels 111 , 112 . A first channel 111 may be a central channel extending through the front end of the catheter 110 . The central channel 111 may be used to deliver a tool such as an endoscope. The endoscope may be used for visualization during the procedure. A second channel 112 in the catheter 110 exits the catheter through a side port 114 . The second channel 112 may be used to deliver a tool such as a cannula 120 . In one embodiment, the cannula 120 is fitted with a guide needle 125 for insertion into the prostatic tissue. Suitable materials for the guide needle 125 include a flexible memory metal. As shown, the tip 127 of the guide needle 125 may be angled to direct a tool, such as a debrider, in the desired direction when it leaves the guide needle 125 . The degree of the angle may be any desired angle such that the tool may be advanced in the proper direction. For example, the tip 127 may have an angle such that the debrider may turn sufficiently after leaving the cannula 120 and proceed in a direction substantially parallel to the catheter 110 . FIG. 3A shows the guide needle 125 retracted in the second channel 112 . FIG. 3B shows the guide needle 125 in the advanced position. In another embodiment, the cannula 120 may be rotatable. In this respect, the angle of departure of the debrider may be controlled and adjusted. In yet another embodiment, the needle tip 127 may be straight for a straightforward advancement in the prostate 10 . In yet another embodiment, the second channel 112 in the catheter 110 may be angled such that the guide needle 125 is already positioned in the proper direction when it exits the catheter 110 . It must be noted that additional channels (central or side channels) may be provided in the catheter to accommodate additional tools or other requirements. For example, one or more channels may be used to deliver a fluid to operate a tool.
[0040] Step 2 of the procedure includes advancing the guide needle 125 through the side port 112 and at least partially into the prostatic tissue, as illustrated in FIGS. 4 and 4A . It can be seen that the guide needle 125 only creates a small hole in the urethral wall. The cannula 120 and the guide needle 125 are now in position to deliver another tool. In another embodiment, the guide needle 125 may exit the catheter 110 through the front end, as illustrated in FIG. 4B . The guide needle 125 may be inserted through a second central channel adjacent the central channel 111 housing the endoscope, or the central channel housing the endoscope after the endoscope is retrieved.
[0041] In Step 3 , a debrider 130 is inserted through the guide needle 125 and into the prostatic tissue 10 , as illustrated in FIGS. 5 and 5A . The direction of the debrider's movement is dictated by the angle of the tip 127 of the guide needle 125 . The distance of travel of the debrider 130 may be controlled by an operator at the other end of the catheter 110 . In one embodiment, the debrider 130 is a mechanical debrider that is operated to remove prostatic tissue in its path. Other suitable debriders include, but not limited to, laser, RF catheter probe, mechanical aspirator, microwave probe, and combinations thereof.
[0042] In step 4 , the debrider 130 is actuated to remove portions of the prostatic tissue. Referring now to FIGS. 6A-B , an embodiment of the debrider 130 includes a longitudinal body 132 disposed inside an outer tube 135 . The longitudinal body 132 may have an auger portion 137 disposed on an outer surface and a removal member such as a blade 140 that is slidable in the outer tube 135 . The debrider 130 may be equipped with one or more blades 140 . To actuate the debrider 130 , the tube 135 is initially inserted through the guide needle 125 to a desired distance. Thereafter, the blade 140 and the auger portion 137 are extended out of the outer tube 135 . The longitudinal body 132 is then rotated to apply torque to the blade 140 and the auger portion 137 . Rotation and advancement of the free end of the blade 140 removes prostatic tissue in its path of rotation to form a cavity 150 . In this respect, the debrider 130 may be operated to remove portions of the prostatic tissue adjacent the urethra 15 . The blade 140 may be advanced to any distance to form the desired cavity size 150 . During operation, a groove in the auger portion 137 pulls some of the loosened tissue into the outer tube 135 for removal. Additionally or alternatively, the longitudinal body 132 may be reciprocated back and forth to remove the loosened tissue. In another embodiment, the guide needle 125 may be provided with aspiration and/or suction to facilitate tissue removal.
[0043] In one embodiment, the balloon 105 is inflated during the operation of the debrider 130 . Expansion of the balloon 105 forces additional prostatic tissue toward the debrider 130 and into the path of rotating blade 140 , see FIGS. 6A-B . In this respect, maximum tissue removal may be achieved because some of the prostatic tissue that would not have been in the path of the rotating blade 140 may now be removed.
[0044] In another embodiment, the prostatic tissue may be removed in multi-step fashion. Referring now to FIGS. 6C-E , the debrider 130 is initially used to form a small cavity 151 in the prostate 10 . Then, the debrider 130 and the guide needle 125 are retrieved. The surgical device 100 is advanced a short distance such that the successive cavity 152 will overlap with the previous cavity 151 . The guide needle 125 is then inserted through the urethral wall followed by the debrider 130 . The second cavity 152 is then formed. Thereafter, the guide needle 125 and the debrider 130 are retrieved. This process may be repeated until the desired length of cavity is formed, for example, to form a third cavity 153 .
[0045] At step 5 , the surgical device 100 may be used to form one or more cavities 151 adjacent the urethra 15 . FIG. 7 shows one embodiment of multiple tubular cavities 151 formed around the urethra 15 . FIG. 7A is a close up view of the tubular cavities 151 . FIG. 7B is a cross-sectional view of FIG. 7 taken at the urethra 15 . Although the Figures show the tubular cavities 151 are positioned circumferentially, it must be noted that any suitable number or combination of tubular cavities may be formed. For example, tubular cavities 151 may be formed at 0, 90, 180, and 270 degrees around the urethra 15 . In another example, two or more tubular cavities 151 may be spaced circumferentially around the urethra 15 .
[0046] FIGS. 8 and 8A show the control end 108 of the surgical device 100 . In one embodiment, the control end 108 is equipped with a rotation controller 155 adapted to rotate the catheter 100 to the proper position for insertion of the guide needle 125 into the prostate 10 . The controller 155 may be marked with numbers to indicate the angle of rotation. The rotation controller 155 may be used to facilitate formation of one or more tubular cavities 151 around the urethra 15 .
[0047] After the desired quantity of prostatic tissue has been removed, the guide needle 125 and the debrider 130 are retracted back into the side passage 112 . At step 6 , the balloon 105 is then inflated to enlarge the lumen 20 of the urethra 15 . This process is shown in FIGS. 9A-C . The inflated balloon 105 helps to maintain the urethra 15 in a dilated state. During debriding of the prostatic tissue, bleeding may occur within that cavity 151 . One added benefit of the balloon inflation is that the balloon 105 may tamponage the bleeding. Thus, one embodiment of the present invention includes inflating a balloon 105 to tamponage bleeding.
[0048] At step 7 , the surgical device 100 is removed from the urethra 15 , as illustrated in FIGS. 10 and 10A . It can be seen now that the constricted portion of the urethra 15 has been enlarged and dilated. Additionally, because the cavities 151 are formed adjacent the urethra 15 , the procedure preserved the inner lining of the urethra 15 . Further, the cavities 151 reduce the compression pressure from the prostate 10 previously acting on the urethra 15 to help maintain the lumen 20 of the urethra 15 in the enlarged state.
[0049] In another embodiment, an optional urethral stent 160 may be installed in the urethra 15 to maintain the dilated state. Potential bleeding caused by the debrider 130 may push the enlarged portion of the lumen 20 back, thereby constricting it. The urethral stent 160 may be temporarily installed to prevent the enlarged lumen 20 from constriction by the bleeding. An exemplary stent suitable for use is a mesh tube. In FIG. 11A , the urethral stent 160 is positioned around the front end of the surgical device 100 and the balloon 105 for insertion into the urethra 15 . Thereafter, the balloon 105 is inflated to expand the urethral stent 160 against the inner wall of the urethra 15 , as shown in FIG. 11B . After expansion, the balloon 105 is deflated and the surgical device 100 is removed, leaving behind the expanded urethral stent 160 , as shown in FIG. 11C . In one embodiment, the temporary stent 160 may be installed for 1-14 days; preferably, about 2-8 days; more preferably, 3-5 days. The stent 160 may be expanded to a size that is larger than the constricted diameter. Other suitable stents include nitinol stents and polyethylene urethral stent. FIGS. 12A-B show the polyethylene urethral stent 165 positioned in the enlarged lumen 20 of the urethra 15 . FIG. 12C shows a close up view of the polyethylene urethral stent 165 . In one embodiment, the polyethylene urethral stent 165 has tapered ends 166 to facilitate insertion or removal.
[0050] FIGS. 13A-B illustrate the prostate 10 before and after the surgical procedure. It can be seen in FIG. 13B that the surgical procedure according to one embodiment has enlarged the lumen 20 of the urethra 15 while conserving the natural wall 22 of the urethra 15 .
[0051] FIGS. 14A-B illustrate the prostate 10 before and after the surgical procedure according to another embodiment. It can be seen in FIG. 14B that the surgical procedure has successfully enlarged the lumen 22 , installed a stent 160 , and conserved the natural wall 22 of the urethra 15 .
[0052] FIGS. 15A-E illustrate another embodiment of a mechanical debrider 230 . The debrider 230 includes a longitudinal body 232 movably disposed within an outer tube 235 . The outer tube 235 may be inserted through the cannula 120 and the guide needle 125 . The longitudinal body 232 includes a passage 236 extending therethrough and an auger shaped outer portion 237 . A removal member such as a blade 240 may be inserted through the passage 236 of the longitudinal body 232 . As shown, the removal member includes four blades 240 connected at the front end using a pointed tip 242 . As shown in the cross-sectional view of FIG. 15D , at least one angle edge 245 may be formed on one side of the blade 240 for cutting through the tissue. The blades 240 may be manufactured from flexible memory metal. The blades 240 are adapted to flex radially outward after exiting the passage 236 . As shown in FIGS. 16A-C , the diameter of the removal member 240 may be adjusted to control the volume of tissue cavity to be created. In one embodiment, the diameter of the removal member 240 is determined by the length of the blades 240 extending beyond the passage 236 . In FIG. 16B , a short blade extension L 1 expands the removal member 240 to a small diameter. In FIG. 16C , a longer extension L 2 expands the removal member 240 to a larger diameter. During operation, the diameter of the removal member 240 may be increased in a stepwise fashion to gradually increase the size of the tissue cavity, or the diameter of the removal member 240 may be constant and the removal member is advanced forward to increase the size of the tissue cavity, or combinations thereof.
[0053] FIGS. 17A-D show another embodiment of a mechanical debrider 330 . The debrider 330 includes a longitudinal body 332 movably disposed within an outer tube 335 . The outer tube 335 may be inserted through the cannula 120 and the guide needle 125 . The longitudinal body 332 includes a passage 336 extending therethrough and an auger shaped outer portion 337 . The removal member includes four blades 340 connected to the longitudinal body 332 at one end and the pointed tip 342 at another end. A cable 345 extending through the passage 336 is inserted between the blades 340 and connected to the pointed tip 342 . The diameter of the removal member 340 may be adjusted by extending or retracting the cable 345 . In FIG. 17B , the entire length of the blades 340 is extended beyond the outer tube 335 . To expand the removal member 340 , the cable 345 is retracted relative to the longitudinal body 332 to pull the pointed tip 342 towards the outer tube 335 is shown in FIG. 17C . The retraction causes the blades 340 to expand radially. As shown in FIG. 17D , when more cable 345 is retracted, the expansion increases. Thus, the diameter of the removal member 340 may be controlled by controlling the extent of the cable 345 retraction. In another embodiment, a shaft or other conveying member may be used instead of a cable to control the expansion.
[0054] In another embodiment, a radio frequency (RF) probe 430 with a built-in aspiration device may be used to remove the prostatic tissue around the urethra 15 . FIG. 18 shows an exemplary RF probe 430 suitable for use with the various embodiments the surgical procedure described herein. The RF probe 430 is connected to a RF generator 438 and includes a longitudinal probe body 432 and a probe head 434 having an outer auger portion 437 . The longitudinal body 432 is movable within an outer tube. In FIG. 19 , the RF probe 430 is inserted into the prostate 10 through the cannula 120 . As shown, the probe head 434 has extended out of the outer tube 435 . After insertion, RF energy 439 is transmitted through the probe body 432 to the probe head 434 to treated the prostatic tissue, as shown in FIG. 20 . At the same time, the RF probe 430 may be rotated 433 to activate the auger portion 437 . Rotation 433 of the auger portion 437 draws the treated tissue into the outer tube 435 , thereby creating the tissue cavity. FIG. 21A shows the zone 410 of tissue that may be affected by the RF energy 439 . FIG. 21B shows the cavity 450 that may be created.
[0055] FIG. 22A shows the RF probe 430 retracted into the surgical device 400 . After the cavity 450 has been created, a balloon 405 may be inflated to enlarge the lumen 20 of the urethra 15 . In FIG. 22B , a urethral stent 465 may be implanted, at least temporarily, to maintain the enlarged lumen 20 .
[0056] In another embodiment, the mechanical debrider and an energy probe may be used in combination. For example, after the mechanical debrider has created a cavity, a RF probe, a laser probe, or other suitable energy deliverable probe may be inserted into the prostate to apply RF, heat, or other suitable energy to treat the targeted tissue. The energy applied may assist with the control of hemostasis. In another example, the energy probe may be inserted before the mechanical probe to apply energy to the prostatic tissue. Then, the mechanical debrider may be inserted to remove the heat treated tissue. In yet another embodiment, energy may be applied before and after deployment of the mechanical debrider. Additionally, energy may also be applied during operation of the debrider. In yet another embodiment, the mechanical debrider may be attached to a RF energy source such that RF energy may be applied through the debrider. In yet another embodiment, the debrider may be fitted with a laser probe such that heat energy may be delivered from the debrider.
[0057] FIGS. 23-24 illustrate a method and device for removing a temporary stent 565 . FIG. 23 illustrates a stent positioned in the enlarged lumen 20 of the urethra 15 . In FIG. 24A , a stent removal device 570 is inserted into the urethra 15 and the front end is positioned just before the stent 570 . The stent removal device 570 includes a catheter 510 having an expandable member such as a balloon 505 positioned at its front end. The device 570 further includes a second balloon 575 that is delivered by a conveying member 580 such as a cannula, as shown in FIG. 24B . After the first balloon 505 is properly positioned, the second balloon 575 is transported through the stent 565 and positioned behind the stent 565 . Thereafter, both balloons 505 , 575 are inflated to enlarge the lumen 20 of the urethra 15 , as shown in FIG. 24C . In FIG. 24D , the second balloon 575 is pulled toward the first balloon 505 , which also pulls the stent 565 toward the first balloon 505 . After the stent 565 makes contact with the first balloon 505 , the two balloons 505 , 575 and the stent 565 may be retrieved and removed together from the urethra 15 .
[0058] Several advantages of the embodiments of the present invention may be readily apparent to one of ordinary skill in the art. One advantage of the devices and treatment methods disclosed herein is conservation of the inner lining of the urethra, which minimizes bleeding, improves the recovery process, reduces post-operative pain, and eliminates the potential for post-surgical scar which may lead constriction of the urethra. Another advantage of the disclosed embodiments is increased tissue reduction. Yet another advantage is the treatment methods would be suitable for outpatient treatment, wherein the patient may return home after the procedure is completed. As a result of less tissue destruction, a temporary stent may be implanted to maintain the lumen and allow the patient to control urination after the surgical procedure. The potential for less post-operative complication also increases likelihood for use as an outpatient procedure.
[0059] In one embodiment, a method of removing a tissue of a prostate proximate a urethra having an inner lining includes positioning a catheter in the urethra; inserting a mechanical debrider through the catheter; positioning the mechanical debrider in the prostate proximate the tissue to be removed; rotating the mechanical debrider against the tissue; and removing the prostatic tissue, thereby forming a cavity adjacent the inner lining of the urethra.
[0060] In another embodiment, the method of removing tissue includes applying thermal energy to the tissue. In yet another embodiment, the thermal energy is applied before rotation of the debrider. In yet another embodiment, the thermal energy is applied after rotation of the debrider. In yet another embodiment, the thermal energy is applied during rotation of the debrider. In yet another embodiment, the method includes positioning an energy probe in the tissue to apply the thermal energy. In yet another embodiment, the thermal energy comprises one of RF energy, laser, and combinations thereof. In yet another embodiment, the thermal energy is applied through the debrider.
[0061] In yet another embodiment, the method includes expanding an expandable member in the urethra. In yet another embodiment, the expandable member is expanded during rotation of the mechanical debrider. In yet another embodiment, the expandable member is expanded after removing the prostatic tissue. In yet another embodiment, the expandable member is also expanded during rotation of the mechanical debrider. In yet another embodiment, the expandable member comprises an inflatable balloon.
[0062] In another embodiment, a medical device includes a catheter; an endoscope positioned in the catheter, and a mechanical debrider extending out of the catheter, wherein the debrider includes an outer tube and a tissue removal member.
[0063] In one or more of the embodiments described herein, the catheter includes an inflatable balloon.
[0064] In one or more of the embodiments described herein, the debrider further includes a spiral groove disposed on a outer portion.
[0065] In one or more of the embodiments described herein, rotation of the spiral groove draws a loosened tissue into the outer tube.
[0066] In one or more of the embodiments described herein, the removal member includes one or more blades for cutting a tissue.
[0067] In one or more of the embodiments described herein, the one or more blades comprise a flexible metal.
[0068] In one or more of the embodiments described herein, the one or more blades are adapted to flex radially outward.
[0069] In one or more of the embodiments described herein, a medical device includes an expandable member. In yet another embodiment, the expandable member comprises an inflatable balloon. In yet another embodiment, the medical device includes a third channel for supplying a fluid to the expandable member.
[0070] In one or more of the embodiments described herein, a medical device includes a tissue removal member having an adjustable diameter. In another embodiment, the debrider further includes a conveying member having a central passage. In another embodiment, the tissue removal member is movable in the central passage. In another embodiment, a length of the tissue removal member extending out of the central passage is controllable to adjust the diameter of the tissue removal member. In another embodiment, the medical device includes a cable attached to an end of the removal member. In another embodiment, the cable is retractable within the central passage to adjust a diameter of the tissue removal member. In another embodiment, the conveying member includes an auger portion.
[0071] While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. | Methods and apparatus for medical treating prostatic tissues are provided. In one embodiment, the method includes removing prostatic tissues adjacent the urethra and enlarging the lumen of the urethra, whereby the treatment conserves a natural wall of the urethra. | 0 |
This is a continuation of co-pending application Ser. No. 07/136,559, filed on 12/22/87, now abandoned.
BACKGROUND OF THE INVENTION
The present invention relates to a process for the separation of sulfuric acid (H 2 SO 4 ) from aqueous mixtures of paraffin-sulfonic acids.
SUMMARY OF THE INVENTION
The present invention is a process for removing sulfuric acid (H 2 SO 4 ) from a paraffin-sulfonic solution. The process comprises (a) admixing with the paraffin sulfonic solution at least one halogenated solvent selected from the group consisting of methane, ethane, and ethylene halogenated derivatives of the following formulas: ##STR1## wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 , each independently, is halogen or hydrogen, with at least one of R 1 , R 2 , R 3 , R 4 is halogen, at a temperature of from 10° of an to 80° C., thereby forming a two-phase mixture consisting of an organic phase containing paraffin-sulfonic acids dissolved therein and an aqueous phase substantially containing sulfuric acid;
(b) separating the organic phase from the aqueous phase;
(c) optionally admixing the organic phase with sulfuric acid, thereby forming a two phase mixture consisting of an organic phase containing paraffin-sulfonic acids dissolved therein and an aqueous phase substantially containing sulfuric acid, separating the organic phase from the aqueous phase, and
(d) removing the halogenated solvents from the separated organic phase.
The object of the present invention is to provide a process to remove excess H 2 SO 4 from a refined mixture of paraffin-sulfonic acids free or substantially free, from paraffins.
The residual mixtures from which H 2 SO 4 must be separated according to the present invention are those which derive from the sulfoxidation of (C 12 -C 18 )-n-paraffin with sulfur dioxide (SO 2 ) and oxygen (O 2 ) in the presence of water (H 2 O) and ultra-violet light, at a temperature between 25° to 50° C. These residual mixtures undergo one of the following extraction treatments after the removal of n-paraffins (which separate spontaneously) and excess SO 2 .
a) The residual mixture is dehydrated until the residual mixture becomes cloudy (due to the formation of a two phase system). The cloudy mixture or the supernatant phase of the two phase system is then extracted with CO 2 under supercritical conditions to separate the non-sulfoxidated paraffins from the dehydrated residual mixture at a temperature between 32° to 80° C., a pressure between 75 to 350 bars, and with a CO 2 to paraffin-sulfonic acids weight ratio of 1/1 to 50/1 so as to obtain a refined mixture.
b) H 2 SO 4 is added to the residual mixture until at least the residual mixture becomes cloudy (due to the formation of a two-phase system). The cloudy mixture or the supernatant phase of the two phase system is then extracted with CO 2 under supercritical conditions, to separate the residual paraffins from the residual mixture at a temperature between 32° to 80° C., a pressure between 75 to 350 bars, and with a CO 2 to paraffin-sulfonic acids weight ratio of 1/1 to 50/1 so as to obtain a refined mixture.
c) An aliphatic alcohol containing a number of carbon atoms up to about 4, preferably isopropanol, is added to the residual mixture until a two phase system is formed. The two phase system is then extracted with CO 2 under supercritical conditions to separate the residual paraffins from the mixture at a temperature between 32° to 80° C., a pressure between 75 to 350 bars and with a CO 2 to paraffin-sulfonic acids weight ratio of from 1/1 to 50/1 so as to obtain a refined mixture.
The refined mixture of paraffin-sulfonic acids free, or substantially free, from paraffins, obtained by means of the above treatments still contains, besides the paraffin-sulfonic acids, a considerable amount of H 2 SO 4 .
The composition of the refined mixtures of paraffin-sulfonic acids obtained by the above methods, i.e., (a) to (c), are the following:
1) (C 12 -C 18 )-Paraffin-sulfonic acids: from 3 to 83% by weight;
2) H 2 O: from 79 to 8.5% by weight;
3) H 2 SO 4 , from 18 to 8.5% by weight and
4) (C 12 -C 18 )-Paraffins: less than 1% by weight, relative to the weight of (C 12 -C 18 ) paraffin-sulfonic acids
The starting mixture, even if it is obtained in the above three ways, i.e., (a) to (c), can be obtained in other ways too, so that the present invention should not be considered as being limited to the way in which the starting mixture with the above reported composition is obtained. The process of the invention can be applied to any mixtures, in whatever way they are obtained, having the above compositions.
DETAILED DESCRIPTION OF THE INVENTION
The process is carried out at a temperature between 10° to 80° C., preferably between 20° to 50° . The refined mixture of paraffin-sulfonic acids is mixed with one or more of the above halogenated solvents.
In the two phase mixture, which is formed, the aqueous phase constitutes H 2 SO 4 and H 2 O and the residual refined phase contains paraffin-sulfonic acids dissolved therein. The residual refined phase is separated from the aqueous phase. Optionally it is mixed with H 2 SO 4 ranging from an aqueous H 2 SO 4 having a minimum concentration of 70% by weight of H 2 SO 4 to concentrated H 2 SO 4 , or oleum, or even SO 3 , at a temperature between 10° C. to 80° C., preferably between 20° C. to 50° C., in such a way that a second phase is formed. The second phase, which constitutes H 2 SO 4 and H 2 O, is then separated from the residual refined phase. The halogenated solvent is separated from the residual refined phase. In particular, the separation is carried out by distillation at a temperature below 100° C., preferably lower than 60° C., and more preferably at least partially under vacuum.
Among the halogenated solvents preferred are methylene chloride, chloroform, carbon tetrachloride and dichloroethane. The amount of halogenated solvent(s) added depends on the type of solvent used and the composition of the refined mixture of paraffin-sulfonic acids. The amount used should make it possible to separate the largest amount of H 2 SO 4 possible.
The amount of H 2 SO 4 optionally added can be, in the case of 96% concentrated H 2 SO 4 , up to 200% by weight, preferably from 50% to 150% by weight, relative to the weight of the paraffin-sulfonic acids contained in the refined mixture.
A practical embodiment of the process of the present invention is to mix the halogenated solvent(s) and H 2 SO 4 simultaneously with the refined mixture of paraffin-sulfonic acids in a single processing step.
If any residual H 2 SO 4 is present before the application of the process according to the present invention, can be removed by being converted into an insoluble product by means of the addition of carbonates, hydroxides or oxides of alkaline-earth metals, particularly, by calcium carbonate, calcium hydroxide or calcium oxide.
Some examples are now given for the purpose of better illustrating the invention. It is understood that the invention is not to be limited to or by the Examples.
EXAMPLE 1
The upper-phase of a raw mixture (from which Decantable n-paraffins and SO 2 have been removed) of paraffin-sulfonic acids obtained by sulfoxidation of (C 12 -C 18 ) n-paraffins, and having the following composition:
Paraffin-sulfonic acids: 24.74% by weight
(C 12 -C 18 )-n-paraffins: 26.46% by weight
H 2 O: 40.94% by weight
H 2 SO 4 : 7.86% by weight
was extracted with CO 2 under supercritical conditions, so as to separate the residual paraffins after the addition of 20% by weight of H 2 SO 4 at 96% by weight, referred to the weight of said raw mixture.
The upper phase of the raw mixture was extracted with CO 2 under the following conditions:
CO 2 /paraffinsulfonic acid ratio: 15.5
Extraction pressure: 150 bar
Extraction temperature: 45° C.
Extraction time: 1 hour
Analysis of the upper phase of the paraffin-sulfonic acids after extraction showed the following composition:
Paraffinsulfonic acids: 59.95% by weight
(C 12 -C 18 )-n-paraffins: 0.22% by weight
H 2 O: 28.73% by weight
H 2 SO 4 : 11.11% by weight
Then 20.47 g of the upper phase after extraction was mixed with 30.69 g of CH 2 Cl 2 (methylchloride) in a tightly sealed glass separator funnel.
The separator funnel was thoroughly shaken for a few minutes, and two phases were allowed to separate. After 3 hours of standing at 22° C., the two separated phases were taken away from each other, and analyzed. The lower phase was constituted of:
H 2 O: 55.44% by weight
H 2 SO 4 : 44.02% by weight
CH 2 Cl 2 : traces
In the upper phase, all charged paraffin-sulfonic acids were present, together with minor amounts of H 2 O, H 2 SO 4 , n-paraffins, and CH 2 Cl 2 . In particular, the content of H 2 SO 4 , as referred to the present paraffin-sulfonic acids, decreased from 18.5% by weight (before the treatment with CH 2 Cl 2 ) to 8.36% by weight. Also the H 2 O content, still referred to paraffin-sulfonic acids, decreased from 47.9% by weight to 31.7% by weight.
Aliquots of the upper phase, obtained by means of the treatment with CH 2 Cl 2 , had the composition of:
Paraffin-sulfonic acids: 25.92% by weight
(C 12 -C 18 )-n-paraffins: 0.094% by weight
H 2 O: 8.21% by weight
H 2 SO 4 : 2.168% by weight
CH 2 Cl 2 : the balance to 100
were extracted, inside a separator funnel, with different amounts of H 2 SO 4 at 96% by weight to form a lower phase at 22° C. The lower phase was constituted by H 2 SO 4 and H 2 O and separated from the upper phase.
The values obtained for each phase are reported in Table 1.
TABLE 1__________________________________________________________________________ Added H.sub.2 SO.sub.4 / H.sub.2 SO.sub.4 / H.sub.2 O/paraffin - paraffin- Analysis of the upper phase Analysis of the lower paraffin- sulphonic ac- sulphonic Paraffin- Paraffin- sulphonic ids ratio in CH.sub.2 Cl.sub.2 Added acids % sulphonic H.sub.2 O, H.sub.2 SO.sub.4, sulphonic H.sub.2 O, H.sub.2 SO.sub.4, ratio in the upperTest Phase H.sub.2 SO.sub.4 ratio, by acids, % % by % by acids, % % by % by upper phase, phase,No. Charge, g at 96%, g weight by weight weight weight by weight weight weight % by weight % by__________________________________________________________________________ weight1.1 10.2143 1.0944 41.33 28.64 2.74 1.364 0 35.28 63.64 4.76 9.571.2 10.3137 1.5468 57.87 28.51 1.94 1.268 0 30.37 68.69 4.45 6.801.3 10.6545 2.0810 75.3 29.91 1.46 1.292 0 27.50 71.08 4.14 4.88__________________________________________________________________________
EXAMPLE 2
217.8 g of the upper phase mixture of paraffin-sulfonic acids after extraction as in Example 1, was mixed with 652.9 g of CH 2 Cl 2 in a tightly sealed separator funnel. The separator funnel was thoroughly shaken and two phases were allowed to separate. After standing 24 hours at 22° C., the two separated phases were taken away from each other, and analyzed.
The lower phase was constituted by:
H 2 O: 50.73% by weight
H 2 SO 4 : 44.03% by weight
CH 2 Cl 2 : small amount
In the upper phase, all charged paraffin-sulfonic acids were present, together with minor amounts of H 2 O, H 2 SO 4 , n-paraffins and CH 2 Cl 2 . In particular, the content of H 2 SO 4 , referred to the present paraffin-sulfonic acids, decreased from 18.5% by weight (before the treatment with CH 2 Cl 2 ) to 7.49% by weight. Also the H 2 O content, still referred to the present paraffin-sulfonic acids, decreased from 47.9% by weight to 30.0% by weight.
Aliquots of the upper phase, obtained by means of the treatment with CH 2 Cl 2 , had the composition of:
Paraffin-sulfonic acids: 16.535% by weight
(C 12 -C 18 )-n-paraffins: 0.060% by weight
H 2 O: 4.96% by weight
H 2 SO 4 : 1.238% by weight
CH 2 Cl 2 : the balance to 100
were extracted inside a separator funnel, with different amounts of H 2 SO 4 at 96% by weight at 22° C., to form a second phase or lower phase. The lower phase was constituted by H 2 SO 4 and H 2 O and separated from the upper phase. The values obtained for each phase are reported in Table 2.
TABLE 2__________________________________________________________________________ Added H.sub.2 SO.sub.4 / H.sub.2 SO.sub.4 / H.sub.2 O/paraffin - paraffin- Analysis of the upper phase Analysis of the lower paraffin- sulphonic ac- sulphonic Paraffin- Paraffin- sulphonic ids ratio in CH.sub.2 Cl.sub.2 Added acids % sulphonic H.sub.2 O, H.sub.2 SO.sub.4, sulphonic H.sub.2 O, H.sub.2 SO.sub.4, ratio in the upperTest Phase H.sub.2 SO.sub.4 ratio, by acids, % % by % by acids, % % by % by upper phase, phase,No. Charge, g at 96%, g weight by weight weight weight by weight weight weight % by weight % by__________________________________________________________________________ weight2.1 23.8090 3.5494 90.2 16.60 0.499 0.496 0 24.41 72.84 2.99 3.012.2 24.1925 5.9650 149.1 16.49 0.176 0.594 0 19.42 79.73 3.60 1.072.3 24.1608 8.3762 209.7 16.52 0.118 0.914 0 15.55 83.12 5.53 0.714.1 17.7698 1.2404 45.15 16.28 1.306 0.586 0 33.43 65.66 3.60 8.024.2 19.0743 2.0422 69.25 16.46 0.801 0.511 0 28.06 71.515 3.10 4.874.3 17.9379 2.5976 93.67 16.40 0.498 0.502 0 25.02 74.18 3.06 3.04__________________________________________________________________________
EXAMPLE 3
22.45 g of the upper phase mixture of paraffin-sulfonic acids after extraction as in Example 1, was mixed with 224.35 g of CH 2 Cl 2 in a tightly sealed separator funnel. The separator funnel was thoroughly shaken and two phases were allowed to separate. After standing 24 hours at 22° C., the two separated phases were taken away from each other, and analyzed.
The lower phase was constituted by:
H 2 O: 53.51% by weight
H 2 SO 4 : 42.48% by weight
CH 2 Cl 2 : minor amounts
In the upper phase, all charged paraffin-sulfonic acids were present, together with minor amounts of H 2 O, H 2 SO 4 , n-paraffins and CH 2 Cl 2 . In particular, the content of H 2 SO 4 , referred to the present paraffin-sulfonic acids, decreased from 18.5% by weight (before the treatment with CH 2 Cl 2 ) to 6.36% by weight. Also the H 2 O content, still referred to the present paraffin-sulfonic acids, has decreased from 47.9% by weight to 33.0% by weight.
Aliquots of the upper phase, obtained by means of the treatment with CH 2 Cl 2 , had the composition of:
Paraffin-sulfonic acids: 5.584% by weight
(C 12 -C 18 )-n-paraffins: 0.020% by weight
H 2 O: 1.840% by weight
H 2 SO 4 : 0.355% by weight
CH 2 Cl 2 : the balance to 100
were extracted, inside a separator funnel, with different amounts of H 2 SO 4 at 96% by weight at 22° C., to form a second phase or lower phase. The lower phase was constituted by H 2 SO 4 and H 2 O and separated from the upper phase. The obtained values of each phase are reported in Table 3.
TABLE 3__________________________________________________________________________ Added H.sub.2 SO.sub.4 / H.sub.2 SO.sub.4 / H.sub.2 O/paraffin - paraffin- Analysis of the upper phase Analysis of the lower paraffin- sulphonic ac- sulphonic Paraffin- Paraffin- sulphonic ids ratio in CH.sub.2 Cl.sub.2 Added acids % sulphonic H.sub.2 O, H.sub.2 SO.sub.4, sulphonic H.sub.2 O, H.sub.2 SO.sub.4, ratio in the upperTest Phase H.sub.2 SO.sub.4 ratio, by acids, % % by % by acids, % % by % by upper phase, phase,No. Charge, g at 96%, g weight by weight weight weight by weight weight weight % by weight % by__________________________________________________________________________ weight3.1 38.6158 1.9658 91.2 5.809 0.139 0.091 0 25.14 71.30 1.57 2.393.2 38.1813 3.7011 173.6 5.806 0.0317 0.123 0 17.84 79.05 2.12 0.553.3 38.2163 1.3300 62.32 5.720 0.260 0.106 0 29.15 68.00 1.85 4.553.4 38.0728 0.7079 33.30 5.640 0.491 0.152 0 36.63 61.26 2.70 8.713.5 27.9606 1.9132 122.6 5.804 0.080 0.142 0 21.35 76.47 2.45 1.38__________________________________________________________________________
EXAMPLE 4
16.1 g of the upper phase mixture of paraffin-sulfonic acids after extraction as in Example 1, was mixed with 48.6 g of CH 2 Cl 2 in a tightly sealed separator funnel. The separator funnel was thoroughly shaken and placed inside an oven maintained at the controlled temperature of 40° C. After 30 minutes, the separator funnel was thoroughly shaken once more inside the oven. Two phases were allowed to separate. After standing 16 hours at 40° C., the lower phase was removed, with the separator funnel being kept inside the oven. The funnel containing the upper phase was removed from the oven, and was cooled to room temperature. The two phases were analyzed.
The lower phase was constituted by:
H 2 O: 53.47% by weight
H 2 SO 4 : 42.90% by weight
CH 2 Cl 2 : minor amounts
In the upper phase, all charged paraffin-sulfonic acids were present, together with minor amounts of H 2 O, H 2 SO 4 , n-paraffins and CH 2 Cl 2 . In particular, the content of H 2 SO 4 , referred to the present paraffin-sulfonic acids, decreased from 18.55% by weight (before the treatment with CH 2 Cl 2 ) to 5.58% by weight. Also the H 2 O content, still referred to the present paraffin-sulfonic acids, decreased from 47.9% by weight to 27.22% by weight.
Aliquots of the upper phase, obtained by means of the treatment with CH 2 Cl 2 , had the composition of:
Paraffin-sulfonic acids: 15.98% by weight
(C 12 -C 18 )-n-paraffins: 0.058% by weight
H 2 O: 4.35% by weight
H 2 SO 4 : 0.892% by weight
CH 2 Cl 2 : the balance to 100
were extracted, inside a tightly sealed separator funnel that can withstand moderate pressure, with different amounts of H 2 SO 4 at 96% by weight, by operating at 40° C. inside an oven, to form a second phase or lower phase.
After the phases separated, at 40° C., the lower phase was removed, inside the oven. The lower phase was constituted by H 2 SO 4 and H 2 O.
The separator was then removed from the oven, and was cooled to room temperature. The two phases were then analyzed. The values obtained for each phase are reported in Table 4.
TABLE 4__________________________________________________________________________ Added H.sub.2 SO.sub.4 / H.sub.2 SO.sub.4 / H.sub.2 O/paraffin - paraffin- Analysis of the upper phase Analysis of the lower paraffin- sulphonic ac- sulphonic Paraffin- Paraffin- sulphonic ids ratio in CH.sub.2 Cl.sub.2 Added acids % sulphonic H.sub.2 O, H.sub.2 SO.sub.4, sulphonic H.sub.2 O, H.sub.2 SO.sub.4, ratio in the upperTest Phase H.sub.2 SO.sub.4 ratio, by acids, % % by % by acids, % % by % by upper phase, phase,No. Charge, g at 96%, g weight by weight weight weight by weight weight weight % by weight % by__________________________________________________________________________ weight6.1 11.4404 1.0814 59.2 17.005 0.860 0.497 0 29.71 69.57 2.92 5.066.2 12.7039 2.0280 99.9 17.090 0.355 0.447 0 24.60 75.7 2.62 2.086.3 10.9668 2.2819 130.2 16.890 0.243 0.570 0 21.32 78.88 3.37 1.44__________________________________________________________________________
EXAMPLE 5
23.0 g of the upper phase mixture of paraffin-sulfonic acids after extraction as in Example 1, were mixed with 142.6 g of CH 2 Cl 2 in a tightly sealed separator funnel that can withstand moderate pressure. The separator funnel was thoroughly shaken. The separator funnel was then placed inside an oven maintained at the controlled temperature of 40° C. After 1 hour, the separator funnel was thoroughly shaken once more inside the oven. The phases were allowed to separate. After standing 26 hours at 40° C., the lower phase was removed from the interior of the oven. The funnel containing the upper phase was removed from the oven, and was allowed to cool down to room temperature. The two phases were analyzed.
The lower phase (4.4391 g) was constituted of:
H 2 O: 56.66% by weight
H 2 SO 4 : 43.08% by weight
CH 2 Cl 2 : minor amounts
In the upper phase (160.8172 g), all of the charged paraffin-sulfonic acids were present, together with minor amounts of H 2 O, H 2 SO 4 , n-paraffins, and CH 2 Cl 2 . In particular, the content of H 2 SO 4 , referred to the present paraffin-sulfonic acids, decreased from 18.5% by weight (before the treatment with CH 2 Cl 2 ) to 4.84% by weight. Also the H 2 O content, still referred to the present paraffin-sulfonic acids, decreased from 47.9% by weight to 28.11% by weight.
11.5 g of H 2 SO 4 at 96% by weight was charged into a separator funnel resistant to moderate pressures, with 148.1 g of the upper phase. The separator funnel was thoroughly shaken, and placed inside an oven maintained at the controlled temperature of 40° C. After 1 hour, the separator funnel was thoroughly shaken once more and then left standing for 4 hours at 40° C. The lower phase (15.2294 g) was removed inside the oven. The separator containing the upper phase (143.9 g) was removed from the oven, and allowed to cool down to room temperature. The two phases were then analyzed.
The lower phase was constituted of:
H 2 O: 25.5% by weight
H 2 SO 4 : 73.6% by weight
CH 2 Cl 2 : the balance to 100%
The lower phase did not contain paraffin-sulfonic acids.
The upper phase had the following composition:
Paraffin-sulfonic acids: 9.07% by weight
(C 12 -C 18 )-n-paraffins: 0.033% by weight
H 2 O: 0.230% by weight
H 2 SO 4 : 0.198% by weight
CH 2 Cl 2 : the balance to 100
The H 2 SO 4 /paraffin-sulfonic acids ratio was 2.18% and the H 2 O/paraffin-sulfonic acids ratio was 2.54%. 134 g of the upper phase was fed, in continuous mode, to a rotary evaporator operating under a slight vacuum (120-130 mm Hg ), and with the temperature of the heating bath being between 50° to 55° C. When all of the product had been fed, and approximately the total amount of CH 2 Cl 2 has evaporated, the vacuum was increased up to 700 mm Hg . The whole process step lasted about 1 hour.
The residual product remaining inside the kettle of the rotary evaporator after all the CH 2 Cl 2 had evaporated, was a thin liquid essentially constituted by paraffin-sulfonic acids, with 1.585% by weight of H 2 O, 2.182% by weight of H 2 SO 4 and 0.360% by weight of (C 12 -C 18 )-n-paraffins.
The distribution of monosulfonic, disulfonic and trisulfonic acids found in the concentrated residual product resulted to be the same as found in the raw mixture of paraffin-sulfonic acids downstream from the sulfoxidation reactor.
EXAMPLE 6
By operating at 22° C., and using the same mixture of paraffin-sulfonic acids as used in Example 1, tests of purification of the paraffin-sulfonic acids from H 2 SO 4 using different solvents, were carried out.
The results obtained are shown in Table 5. It can be observed how only the halogenated solvents supply interesting results.
TABLE 5__________________________________________________________________________ Grams of Separated Separated Ratio, by weight, Ratio, by weight, paraffin- organic aqueous of H.sub.2 SO.sub.4 /paraffin- of H.sub.2 O/paraffin-Test Type of Grams of sulphonic phase, phase, sulphonic acids in sulphonic acids inNo. solvent solvent mixture g g organic phase, % organic phase, REMARKS__________________________________________________________________________1 CHCl.sub.3 3.4815 3.2700 6.0640 0.5247 4.12 32.22 CCl.sub.4 2.5884 3.4649 5.7156 0.3264 7.79 38.33 CH.sub.2 Cl--CH.sub.2 Cl 3.0531 3.4600 5.1625 0.4214 10.2 35.4 Also present in the intermediate phase of CH.sub.2 Cl--CH.sub.2 Cl4 CCl.sub.2 =CH.sub.2 2.6188 3.4609 5.6313 0.4488 10.99 33.75 (C.sub.2 H.sub.5).sub.2 O 1.7001 3.3640 4.9189 0.0810 16.26 40.66 CH.sub.3 COOC.sub.2 H.sub.5 2.3794 3.4308 Single phase7 Petroleum ether, 1.9217 3.3102 Single phase 40-70° C.__________________________________________________________________________
EXAMPLE 7
7.4428 g of the upper phase mixture of paraffin-sulfonic acids after extraction as in Example 1, was mixed with 14.7382 g of CHCl 3 in a tightly sealed test tube. The test tube was thoroughly shaken, left standing at 23° C. for 6.5 hours, and then centrifuged to favor the phase separation of the two phases that have formed. The two phases were taken away from each other and were analyzed.
The lower phase (1.3330 g) was essentially constituted by H 2 O (57.5% by weight) and H 2 SO 4 (42.46% by weight).
The upper phase (20.7284 g), was constituted of all the charged paraffin-sulfonic acids, together with minor amounts of H 2 O, H 2 SO 4 , n-paraffins, and CHCl 3 . In particular, the content of H 2 SO 4 , referred to the present paraffin-sulfonic acids, decreased from 18.5% by weight (before the treatment with CHCl 3 ) to 5.74% by weight. The H 2 O content, still referred to the present paraffin-sulfonic acids, decreased from 47.9% by weight to 29.35% by weight.
To 10.5305 g of the beforehand separated upper phase, 2.0448 g of H 2 SO 4 at 96% by weight was charged. The test tube was thoroughly shaken, and was left standing at 23° C. After 7 hours, two phases formed and were taken away from each other and analyzed.
The lower phase contained H 2 O (25.08% by weight), H 2 SO 4 (73.44% by weight), together with a small amount of CHCl 3 , and did not contain paraffin-sulfonic acids.
The upper phase had the following composition:
Paraffin-sulfonic acids: 22.75% by weight
(C 12 -C 18 )-n-paraffins: 0.082% by weight
H 2 O: 0.80% by weight
H 2 SO 4 : 0.686% by weight
CH 2 Cl 2 : the balance to 100
The H 2 SO 4 /paraffin-sulfonic acids ratio was 3.02% and the water/paraffin-sulfonic acids ratio resulted to be 3.52%. | The purpose of the process of the present invention is to remove excess sulfuric acid from a mixture of paraffin-sulfonic acids free or substantially free, from paraffins.
In order to remove said sulfuric acid, according to the process of the present invention, the paraffin-sulfonic acid mixture is mixed with one or more halogenated solvent(s), possibly in mixture with sulfuric acid to form a two phase mixture consisting of an organic phase containing paraffin-sulfonic acids dissolved therein and an aqueous phase substantially containing sulfuric acid. The organic phase is then treated with sulfuric acid and the organic phase and aqueous phase are then separated and the organic phase is submitted to evaporation, for the removal of the halogenated solvent(s), and with the concentrated paraffin-sulfonic acids being obtained. | 2 |
CROSS REFERENCE TO RELATED APPLICATIONS
This invention is related to subject matter disclosed in my copending U.S. applications Ser. Nos. 800,641 800,656, and 800,644, all filed on May 26, 1977. All of the aforesaid applications are also my inventions and are assigned to the same assignee as the assignee of this application. All of the disclosures referenced above are incorporated herein in their entirety by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to quinone-coupled polyphenylene oxides having an average hydroxyl group per molecule value greater than the average hydroxyl group value associated with polyphenylene oxide reactants employed in the reaction with quinones.
2. Description of the Prior Art
Self-condensation reactions of certain phenols employing oxygen in combination with an effective oxidative coupling catalyst system to form prior art polyphenylene oxides, i.e., polyphenylene oxides having an average hydroxyl group per molecule of 1.0 or less, are described in various U.S. patent applications including Hay's U.S. Pat. Nos. 3,306,879; 3,914,266; application Ser. No. 540,473, filed Jan. 13, 1975, now U.S. Pat. No. 4,028,341 a continuation-in-part of Ser. No. 441,295, filed Feb. 11, 1974, now abandoned; and Olander's U.S. Pat. Nos. 3,956,442; 3,965,069; 3,972,851; and Ser. No. 582,910, filed June 2, 1975, now U.S. Pat. No. 4,054,553. All of the Hay and Olander disclosures referenced above are incorporated herein in their entirety by reference.
Cooper's U.S. Pat. No. 3,496,236 discloses the equilibration of polyphenylene oxide and certain phenols in the presence of phenoxy radical carried out under oxidizing reacting conditions. My U.S. Pat. No. 3,367,978 discloses the preparation of novel compositions of matter resulting from the reaction of a phenol and a polyphenylene oxide under equilibration reaction conditions, i.e., carried out under oxidizing reaction conditions. All of the Cooper and my disclosures referenced above are incorporated herein in their entirety by reference.
Heretofore, quinone reaction product species known to be most deleterious to the color of polyphenylene oxides have been separated therefrom by precipitating the polymer from a solvent system in which the quinone species are soluble. Heretofore, multiple solvent precipitation and/or extraction techniques have been employed to remove significant amounts of quinone, e.g., up to one percent of quinone based on the weight of polymers, prior to isolation of prior art polyphenylene oxides as a solid reaction product suited to further processing to form a suitable commercial end product.
Unexpectedly and advantageously I have found that quinones can be reacted with polyphenylene oxides to form novel quinone-coupled polyphenylene oxides having an average hydroxyl group value greater than the hydroxyl group value associated with the polyphenylene oxide reactants. The resulting quinone-coupled polyphenylene oxides are new compositions of matter substantially free of quinone color entities, which are suited to the manufacture of thermoplastic compositions having improved chemical and physical properties.
DESCRIPTION OF THE INVENTION
This invention embodies new quinone-coupled polyphenylene oxides having an average hydroxyl group per molecule value greater than the average hydroxyl group value associated with the polyphenylene oxide reactant.
Broadly, a presently preferred quinone-coupled polyphenylene oxides are illustrated by the formula: ##STR1## wherein independently each --OZO-- is a divalent quinone residue, Z is a divalent arene radical, either a or b is at least equal to 1, the sum of a plus b is preferably at least equal to 10, and more preferably 40 to 500, even more preferably 125 to 250, R' is hydrogen, a hydrocarbon radical, a halohydrocarbon radical having at least 2 carbon atoms between the halogen atoms and phenol nucleus, a hydrocarbonoxy radical, or a halohydrocarbonoxy radical having at least two carbon atoms between the halogen atoms and phenol nucleus, R" being the same as R' and, in addition, halogen. A presently preferred quinone-coupled polyphenylene oxide is of formula (I) above wherein independently each R' is hydrogen, a hydrocarbon radical, a halohydrocarbon radical, and even more preferably is a methyl radical, R" being hydrogen.
Representative of the classes of substituents, such as R' and R" which can be associated with a quinone-coupled polyphenylene oxide of formula (I) above are any of the substituents associated and positioned in analogous locations relative to the hydroxyl group of any of the phenol reactants described by Hay and Olander in their U.S. patents and applications referred to hereinbefore. Accordingly, the descriptions of representative substituents as described by Hay and Olander as set out in the aforesaid patents and applications are hereby incorporated herein in their entirety by reference.
Broadly, the quinone-coupled polyphenylene oxides can be prepared by reacting polyphenylene oxides containing quinones under any reaction conditions, e.g., time, temperature and pressure, which facilitates reaction of at least a portion, and preferably all of any quinone species of polyphenylene oxides, subject to the proviso that the reaction is carried out in a reaction medium substantially free of (1) any monophenol reactant and (2) any active oxidative coupling catalyst system known to those skilled in the art which promotes self-condensation of monophenols to form polyphenylene oxides.
Accordingly, any prior art quinone containing polyphenylene oxide reaction product can be employed including, illustratively, those of Hay and Olander referred to herein, subject to the proviso that the reaction products be separated from substantially all of the active catalyst system as well as substantially all of any unreacted phenol prior to reacting the quinone with the polyphenylene oxide. Separation of the active catalyst system from the Hay and Olander prepared prior art polyphenylene oxides can be carried out by any means, e.g., by purging oxygen from the reaction medium via inert gas displacement by argon, nitrogen, etc., whereby substantially all of the oxygen or air employed in the oxidative coupling process is separated from the polymer; by centrifuging the reaction products whereby substantially all of any copper or manganese component of the active catalyst system and/or any unreacted monophenol contained within the aqueous phase reaction products is separated from the organic phase which comprises substantially all of the polyphenylene oxide and quinone plus minor amounts of any primary, secondary or tertiary amines employed in the prior art catalytic processes.
The organic phase as separated from the oxidative coupling catalyst system and phenol reactant can be employed without further refinement. In the reaction of quinone with polyphenylene oxide, substantially all of the quinone entrained by the polyphenylene oxide reaction products is integrated into the polymer backbone in a nonextractable form. Not limiting my invention to any theory, I believe that the quinone entities are coupled with individual polymer entities in accordance with the following postulated theoretical reaction mechanism: ##STR2## where n=number average degree of polymerization and
m=0, 1, 2, 3, . . . etc.
In general, any reaction temperature can be employed. Presently, temperatures of from 0° C. to 150° C. or even higher, preferably 50° C. to 100° C. are used. In a preferred embodiment of this invention, the quinone containing polyphenylene oxide is prepared in accordance with Hay's process described in U.S. application Ser. No. 540,473, employing the hydrolytically stable catalyst system described in Hay's U.S. Pat. No. 3,914,266, since the quinone containing polyphenylene oxide reaction products associated with the aforementioned process after separation from the oxidative coupling catalyst system can be reacted with the quinone at elevated temperatures, e.g., in excess of 50° C. without deleteriously affecting the intrinsic viscosity of the quinone-coupled polyphenylene oxides, i.e. without decreasing by 10-50% the value of the intrinsic viscosity associated with polyphenylene oxide charged to the reaction medium.
Any polyphenylene oxide can be employed regardless of intrinsic viscosity or the amount of quinone contained within the polyphenylene oxide charged to the reaction medium prepared according to any of the prior art method of Hay or Olander.
Broadly, the polyphenylene oxides of Hay and Olander that can be employed are illustrated by the formula ##STR3## wherein independently each a is at least equal to 10, preferably 40 to 170, R', R" are as defined hereinbefore with respect to formula (I).
Preferably, the polyphenylene oxides employed in the quinone-coupling reaction is a polyphenylene oxide which contains quinone limited to 1% or less by weight based on the weight of polymer and more preferably contains less than 1% by weight of quinone as well as less than 2% and more preferably less than 11/2% by weight of any primary or secondary or tertiary amine.
Polymers prepared herein having enhanced hydroxyl content and being free of known species which are deleterious to polymer color characteristics can be advantageously coupled and/or capped as described in my related U.S. Pat. No. 4,156,770 issued May 29, 1979 and U.S. Pat. No. 4,165,422 issued Aug. 21, 1979 to further enhance their molecular weight and/or color stability, respectively. The resulting quinone-coupled polyphenylene oxide polymer reaction products can be employed in conjunction with other polymers such as high impact polystyrene, etc., prepared polymer blends as taught by Cizek in U.S. Pat. No. 3,383,435 in the preparation of polyphenylene oxide resin combinations well known to those skilled in the art as Noryl® resins "Encyclopedia of Polymer Science and Technology", entitled Phenols, Oxidative Polymerization, Vol. 10, published by Interscience Publishers (1969).
EXAMPLE I
(A) Polymer Preparation
A 2.5 gallon stainless steel polymerization reactor equipped with stirrer, heating and cooling coils, thermocouples, monomer inlet tube, oxygen/nitrogen inlet tube, reflux condenser and an external circulation loop with pressure gauge to monitor viscosity was charged with 5.18 l. toluene, 255.9 g. N,N-dibutylamine, 67.2 g. methanol, 6.64 g. cupric chloride, 10.17 g. sodium bromide and 1.5 g. Aliquat® 336, i.e. tricaprylylmethylammonium chloride. Oxygen was bubbled through the stirred mixture and 1600 g. 2,6-xylenol, also known as 2,6-dimethylphenol, dissolved in 1800 ml. toluene was added over a 40 minute period. The initial heat of reaction brought the temperature up to 40° C. which temperature was maintained during the course of the reaction.
(B) Catalyst Deactivation
After a total reaction time of 85 minutes, the oxygen flow was replaced with nitrogen and 69.5 g. of an aqueous 38% trisodium EDTA solution was added. Analysis of the reaction mixture showed a poly(2,6-dimethyl-1,4-phenylene oxide) having an intrinsic viscosity [η] equal to 0.62 dl./g. as measured in chloroform as 25° C., and a hydroxyl end group infrared absorption at 3610 cm. -1 of 0.043 units based on a 2.5% solution in CS 2 over a 1 cm. path calibrated against CS 2 in a matched cell. Spectrophotometric analysis of the reaction mixture (diluted with benzene and measured over a 1 cm. path at 422 nm.) showed 1% by weight of 2,6-xylenol had been converted to 3,3',5,5'-tetramethyl-1,4-diphenoquinone (TMDQ).
(C) Quinone Coupling
(1) The TMDQ containing reaction mixture during a two hour period was diluted with toluene to a 10% solids level, heated at 50° C., washed with an equal volume of water and passed through a Westphalia liquid-liquid centrifuge to remove the aqueous phase which contained copper salts and a portion of the amine. Methanol (2.5 volumes) was added to half of the centrifuged reaction mixture to precipitate the polymer. The polymer was collected on a filter, washed with methanol and dried in a circulating air oven at 80° C. Polymer analysis showed: [η] equal to 0.55 dl./g., an OH absorbance of 0.090 units, a nitrogen content of 1051 ppm, and a TMDQ content of less than 0.01% by weight based on the weight of 2,6-xylenol TMDQ.
(2) The remaining half of the TMDQ containing mixture was precipitated by spraying with steam through a nozzle into water at 95° C. at a rate sufficient to provide rapid azeotropic removal of toluene and other volatiles, such as amines and methanol. The steam precipitated solid polymer was collected on a filter, washed with additional water and dried at 90° C. in a circulating air oven. Polymer analysis showed a yellow pelletized material, an [η] equal to 0.55 dl./g., a OH absorbance of 0.25 units, a nitrogen content of 1136 ppm, and a TMDQ content of 0.1% based on the weight of 2,6-xylenol.
A summary of polymer processing and results is set out in Table I.
TABLE I______________________________________ Reac- tion OH Temp. [η] AbsorbanceProcess Step(s) °C. dl./g. @ 2610 cm..sup.-1______________________________________(A) Polymer Preparation, plus(B) Catalyst Deactivation 40 0.62 0.043(C) Quinone Coupling(1) Methanol precipitation 40-50 0.55 0.090(2) Steam precipitation 95 0.55 0.250______________________________________
EXAMPLE II
(A) Polymer Preparation
A 2.5 gallon stainless steel reactor equipped with an air-driven paddle stirrer, oxygen inlet tube, and water-cooled coil and jacket was charged with 5.48 l. toluene, 121.2 ml. of a stock catalyst solution, i.e. (29.5 ml. bromine added slowly to a chilled solution of 7.76 g. cuprous oxide and 132.0 g. 2,6-xylenol in methanol, then diluted to 1.0 l.), 4.51 g. N,N'-di(t-butyl)ethylenediamine (DBEDA), 26.5 g. N,N-dimethylbutylamine (DMBA), and 16.0 g. di(n-butyl)amine (DBA). Oxygen was bubbled into the resulting admixture at a rate of 10 SCFH while vigorously agitating the admixture, 1600 g. of 2,6-xylenol dissolved in 1.8 l. toluene was pumped into the reactor over a 30 minute period. Summarily, the reaction parameters relative to molar ratios of 2,6-xylenol:Cu:DBEDA:DMBA:Br:DBA were as follows: 1000:1:2:20:8:9.4. The reaction temperature was maintained at 25° C. throughout the monomer addition, and was increased to and maintained at 40° C. until the reaction was terminated.
(B) Catalyst Deactivation
The reaction was terminated after 58 minutes (measured from start of monomer addition) by replacing oxygen with nitrogen and the addition of 16.0 ml. 38% Na 3 EDTA in water. Polymer analysis showed an [η] equal to 0.59 dl./g. and an OH absorbance of 0.042 units.
(C) Quinone Coupling
The resulting TMDQ containing reaction mixture was heated under nitrogen at 50° to 60° C. for 30 minutes and then at 95° C. for 15 minutes. At this point the mixture no longer exhibited the characteristic TMDQ color. Polymer analysis after methanol precipitation, washing and drying as described in Example I(C)(1) showed an [η] equal to 0.53 dl./g., and an OH absorbance of 0.139 units.
A summary of polymer processing and results are set out in Table II.
TABLE II______________________________________ Reac- tion OH Temp. [η] AbsorbanceProcess Step(s) °C. dl./g. @ 2610 cm..sup.-1______________________________________(A) Polymer preparation, and(B) Catalyst Deactivation 25-40 0.59 0.042(C) Quinone Coupling 50-95 0.53 0.139______________________________________
EXAMPLE III
The (A) Polymer Preparation and (B) Catalyst Reactivation processes of Example II, described above, were repeated.
(C) Quinone Coupling
The reaction temperature was 60° C. Polymer analysis showed an [η] equal to 0.55 dl./g., and an OH absorbance of 0.055 units.
A summary of polymer processing and results are set out in Table III.
TABLE III______________________________________ Reac- tion OH Temp. [η] AbsorbanceProcess Step °C. dl./g. @ 2610 cm..sup.-1______________________________________(A) Polymer Preparation, plus(B) Catalyst Deactivation 40 0.60 0.017(C) Quinone Coupling 60 0.55 0.055______________________________________
EXAMPLE IV
(A) Polymer Preparation
A reactor equipped as in Example II was charged with 4.0 l. toluene, 240 g. 2,6-xylenol, 24.0 g. di(n-butyl)amine, 64 g. 50% NaOH in 200 ml. methanol, and 900 ml. methanol. Oxygen was bubbled through the stirred mixture at 10 SCFH. After 5 minutes, a solution of 3.97 g. benzoin oxime and 1.10 g. manganese chloride in 100 ml. methanol was added. A solution containing 2.89 kg. 2,6-xylenol in 1.8 l. toluene was added at the rate of 96 ml./min. An additional 445 ml. toluene was added to wash in any residual reagents. The reaction temperature was maintained at 28° C.
(B) Catalyst Deactivation and Partial Quinone Coupling
After 90 minutes the oxygen flow was replaced with nitrogen, the temperature was raised to 40° C., an equal volume of water was added, and the aqueous phase was separated during a two-hour liquid-liquid centrifugation step.
(C) Additional Quinone Coupling
Partial quinone coupling occurred during the centrifugation step. The resulting polymer solution was further quinone reacted by heating at 60° C. for 15 minutes and then 90° C. for 10 minutes. The final reaction mixture was divided into two portions, one for isolation by the addition of two volumes of methanol, the other for isolation by steam precipitation. A summary of product analysis at the various stages of this Example is set out hereafter:
TABLE IV__________________________________________________________________________ OH Reaction [η] AbsorbanceProcess Step Temp.°C. Isolation dl./g. @ 2610 cm..sup.-1__________________________________________________________________________(A) Polymer Preparation 28 Methanol Ppt. 0.65 0.036(B) Catalyst Deactivation, plus Partial Quinone Coupling 40 Methanol Ppt. 0.57 0.058(C) Additional Quinone Coupling 60 Methanol Ppt. 0.55 0.085 Additional Quinone Coupling 90 Methanol Ppt. 0.53 0.106 Additional Quinone Coupling 90 Steam Ppt. 0.52 0.163__________________________________________________________________________
EXAMPLE V
(A) Polymer Preparation, and (B) Catalyst Deactivation
A 2.5 gallon stainless steel reactor equipped with an air-driven paddle stirrer, oxygen inlet tube, and water-cooled coil and jacket was charged with 4.6 l. toluene, a catalyst premix composed of 6.28 g. of cupric chloride, 9.62 g. of sodium bromide, 6.84 g. of Aliquat® 336, 33.1 g. N,N-dimethylbutylamine (DMBA), and 42.3 g. di-n-butylamine (DBA). Oxygen was bubbled through the reaction medium at a rate of 10 SCFH with vigorous mixing of the reaction mixture. 2000 g. 2,6-xylenol in 2.4 l. of toluene was pumped into the reactor over a 30-minute period. The temperature of the reaction mixture rose to 45° C. and was maintained at 45° C. until after a total reaction time of 70 minutes, the polymer portion was precipitated with methanol containing 0.5% acetic acid, filtered and washed, dried in a circulating air oven at 80° C. Polymer analysis showed an intrinsic viscosity [η] equal to 0.24 dl./g. and a TMDQ content less than 0.01% based on the weight of 2,6 -xylenol. Summarily, the reaction parameters relative to molar ratios of 2,6-xylenol: Cu:DMBA:Br:DBA were as follows: 350:7:7:2:1. The resulting polymer was employed in a series of reactions described hereafter where TMDQ was added to the polymer on a controlled weight percent basis to evaluate the increases in hydroxyl--[OH] content as well as any changes in the intrinsic viscosity of the resulting quinone reacted polymer.
(C) Quinone Coupling
A series of reactions were carried out according to the procedure employed in Run No. 5 set out in Table V hereafter. The procedure employed in Run No. 5 was as follows:
A solution of 10 g. of poly(2,6-dimethyl-1,4-phenylene oxide) having an intrinsic viscosity of 0.31 dl./g. dissolved in 80 ml. of toluene at 80° was charged with 3 g. 3,3',5,5'-tetramethyl-4,4'-diphenoquinone (TMDQ) and stirred under positive nitrogen pressure. After 34 minutes the TMDQ had dissolved completely to form a clear orange colored solution. After a total reaction time of one hour the solution was cooled, 400 ml. methanol was added slowly with stirring to precipitate the polymer, the polymer was washed with methanol, and dried at 80° C. in a vacuum oven.
A summary of polymer processing and results is set out in Table V.
TABLE V__________________________________________________________________________Summary of a Series of Reactions of Low Molecular Weight [η] 0.31dl./g. Poly(2,6-dimethyl-1,4-phenylene oxide)s With TMDQ Time for OH React. React. TMDQ to Absorb-Run TMDQ Temp. Time Dissolve Yield [η] ence GPCNo. (%).sup.1 (° C.) (min.) (min.) (%).sup.1 (dl./g.) at 3610 --M.sub.w /--M.sub.n__________________________________________________________________________1 0 80 60 n.a. 98.9 .31 .22 2.02 0.5 80 30 <5 98.8 .32 .27 3.93 1.0 80 30 10 99.3 .28 .33 2.84 1.5 80 60 30 101.0 .31 .36 2.15 3 80 60 34 99.4 .32 .48 2.36 6 80 60 .sup.2 98.5 .35 .60 2.67 12 80 60 .sup.2 102.5 .34 .57 2.68.sup.3 12 80 60 .sup.2 103.7 .33 .51 2.69 12 80 15 .sup.2 104.9 .35 .67 2.210 12 80 30 .sup.2 104.9 .30 .48 2.411 12 80 120 .sup.2 99.3 .31 .40 2.712 1.5 80 2 .sup.2 98.8 .34 .37 2.613 1.5 80 5 .sup.2 98.8 .31 .31 2.314 1.5 80 15 .sup.2 99.5 .29 .35 3.715 1.5 80 30 30 99.0 .31 .36 3.916 1.5 80 120 30 99.4 .31 .37 4.117 1.5 50 30 .sup.2 98.2 .35 .22 2.118 1.5 110 30 <1 99.0 .30 .40 2.819 3 50 60 .sup.2 98.2 .35 .23 2.120 3 110 60 <10 99.4 .27 .43 2.221 12 50 60 .sup.2 106.5 .31 .27 1.822 12 110 60 50 94.0 .25 1.0 3.0__________________________________________________________________________ .sup.1 = Based on weight of initial PPO. .sup.2 = Not completely dissolved at end of reaction period. .sup.3 = Benzene was the solvent. n.a. = Nonapplicable.
EXAMPLE VI
(A) Polymer Preparation and (B) Catalyst Deactivation
A series of poly(2,6-dimethyl-1,4-phenylene oxide)s were polymerized by procedures similar to those described in Examples I, II and V and were separated by methanol precipitation, washed with methanol and dried in a circulating oven at 80° C. The resulting polymers were employed in a series of reactions described hereafter where TMDQ was added to the various polymers on a controlled weight percent basis to evaluate the increases in the hydroxyl content as well as any changes in the intrinsic viscosities of the resulting quinone reacted polymer.
(C) Quinone Coupling
A series of reactions were carried out according to the general procedure described by Run No. 5 in Example V above.
A summary of the polymer processing and results is set out in Example VI.
TABLE VI______________________________________Summary of a Series of Reactions of High Molecular Weight [η]0.44 to 1.0 dl./g. Poly(2,6-dimethyl-1,4-phenylene oxide)sWith TMDQ [η] OH React. React. (dl./g.) 3610 cm..sup.-1Run TMDQ Time Temp. Yield Ini- Fi- AbsorbanceNo..sup.1(%) (min.) (° C.) (%).sup.3 tial nal Initial Final______________________________________1.sup.31.5 60 80 101 .44 .41 .12 .302.sup.33 60 80 101 .44 .38 .12 .403.sup.36 60 80 97 .44 .44 .12 .474.sup.43 120 80 98 .50 .38 .03 .285.sup.43 120 130 97 .50 .38 .03 .286.sup.53 120 80 99β .60 .49 .08 .257.sup.53 120 80 99 1.00 .89 .03 .22______________________________________ .sup.1 = Solvent was toluene in Run Nos. 1-5, 7 and 8. Solvent was chlorobenzene in Run No. 6. .sup.2 = Yield was based on initial weight of polymer = 100%. .sup.3 = Polymer prepared by a procedure similar to one as set out in Example V. .sup.4 = Polymer prepared by a procedure similar to one as set out in Example I except with diethylamine instead of dibutylamine. .sup.5 = Polymer prepared by a procedure similar to one as set out in Example II except for the omission of the dibutylamine.
EXAMPLE VII
(A) Polymer Preparation and (B) Catalyst Deactivation
A series of poly(2,6-dimethyl-1,4-phenylene oxide)s were polymerized as described in Example V and were separated by methanol precipitation, washed with methanol and dried in a circulating oven at 80° C. The resulting polymers were employed in a series of quinone coupling reactions described hereafter where TMDQ and basic as well as acetic additives were added to the various polymers on a controlled weight percent basis to evaluate the increases in the hydroxyl content as well as any changes in the intrinsic viscosities of the resulting quinone reacted polymer.
(C) Quinone Coupling
A series of reactions were carried out according to the general procedure described by Run No. 5 in Example V above.
A summary of the polymer processing and results is set out in Example VII hereafter.
TABLE VII__________________________________________________________________________Summary of a Series of Reactions at 80° C. of Low MolecularWeightPoly(2,6-dimethyl-1,4-phenylene oxide)in the Presence of Basic and Acidic Additives Quantity Time for of React. TMDQ to OHSample Additive.sup.a TMDQ Time Dissolve Yield [η] Absorbance GPC NitrogenNo. Additive (%) (%).sup.a (min) (min) (%).sup.a dl/g at 3610 --M.sub.w /--M.sub.n (ppm)__________________________________________________________________________1 None 0 0 60 -- 98.9 .31 .22 2.0 5302 " 0 1 30 10 99.3 .28 .33 2.8 5343 Dibutylamine .3 1 30 15 95.8 .28 .33 1.6 7454 " 5 1 30 10 96.6 .29 .34 1.5 7975 " 10 1 30 8 96.0 .29 .34 1.7 8006 " 1 1.5 30 <10 100.0 .20 .38 3.3 11407 " 5 1.5 30 <10 100.4 .22 .40 4.4 10418 " 10 1.5 30 17 96.2 .26 .38 1.6 9949 " 5 2 30 20 94.4 .22 .41 1.6 113010 " 10 2 60 10 100.4 .23 .45 1.8 98411 " 10 30 60 20 100.8 .19 .54 1.7 115012 Butyldimethylamine 5 1.5 30 <10 99.8 .26 .38 4.2 64813 " 10 1.5 30 15 96.2 .26 .39 1.8 64514 " 5 3 30 15 92.6 .30 .44 2.3 59915 " 10 3 60 30 100.7 .21 .56 2.1 85916 Acetic acid 10 3 60 30 98.9 .19 .62 1.7 .sup.c17 Sulfuric acid 10 3 60 <1 98.6 .32 .25 2.0 .sup.c18 50% aq. NaOH 4 3 60 .sup.b 98.9 .30 .34 2.9 .sup.c__________________________________________________________________________ .sup.a Based on weight of initial PPO. .sup.b A green precipiate forms which does not dissolve completely during the reaction period. .sup.c Not determined.
As illustrated by the foregoing examples, quinones can be reacted effectively with polyphenylene oxides to form novel quinone-coupled polyphenylene oxide having an average hydroxyl group values greater than the average hydroxyl group value associated with the polyphenylene oxide reactant. Analogous results are obtained wherein any prior art polyphenylene oxide is employed in the preparation of quinone-coupled polyphenylene oxides which can contain quinone species of the general formula: ##STR4## wherein R' and R" are as defined hereinbefore, which are other than those employed in the Examples such as TMDQ.
Other modifications and variations of the present invention are possible in light of the above teachings. | Quinones and polyphenylene oxides are reacted to provide quinone-coupled polyphenylene oxides having an average hydroxyl group per molecule value greater than the average hydroxyl group value associated with polyphenylene oxide reactants. The resulting new polymers have improved color and in combination with styrene resins provide thermoplastic compositions having improved chemical and physical properties. | 2 |
PRIORITY CLAIM
This application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Application Ser. No. 62/052,296, filed Sep. 18, 2014, which is expressly incorporated by reference herein.
BACKGROUND
The present disclosure relates to polymeric materials that may be formed to produce a container, in particular polymeric materials that insulate. More particularly, the present disclosure relates to morphology and crystalline structure of cellular polymeric material that may be transformed into usable articles, such as insulated containers.
SUMMARY
An insulated container in accordance with the present disclosure, which may be a drink cup or a food-storage cup (e.g.), is manufactured from a sheet extrudate or tubular extrudate produced in an extrusion process. In illustrative embodiments, the extrudate is a cellular polymeric material.
In illustrative embodiments, an insulative container in accordance with the present disclosure is manufactured from a tubular extrudate produced in an extrusion process. In illustrative embodiments, the extrudate is an insulative cellular polypropylene-based material configured to crease and/or wrinkle during cup convolution or shaping.
In illustrative embodiments, the cell morphology of an extruded sheet of insulative cellular polypropylene-based material in accordance with the present disclosure is a function of the extrusion angle, which has an effect on the quality of an article, such as an insulative container, formed therewith. In particular, cell morphology is affected by the angle at which a polypropylene-based material in accordance with the present disclosure exits an enclosed die volume through extruder die lips, and is related to deep creasing and/or wrinkling in the formed article.
In illustrative embodiments, the cell morphology of an extruded sheet of insulative cellular polypropylene-based material in accordance with the present disclosure is a function of formulation and process conditions, which conditions have an effect on the quality of an article, such as an insulative container, formed therewith. In particular, the effects of such conditions on cell density and cell dimensional attributes, and ultimately on creasing/wrinkling, results in a wrinkle prediction model based on power law regression.
In illustrative embodiments, the cell aspect ratio of insulative cellular polypropylene-based material in accordance with the present disclosure has an effect on the wrinkling of that material during mechanical convolution. Parameters such as cell density and aspect ratio ultimately determine control limits that result in a wrinkling model for a mechanically convoluted container.
In illustrative embodiments, the circumferential direction cell aspect ratio of an extruded sheet of insulative cellular polypropylene-based material in accordance with the present disclosure has a greater effect than the cell aspect ratio in the axial direction on the wrinkling of that material during mechanical convolution.
In illustrative embodiments, the orientation of an extruded sheet of insulative cellular polypropylene-based material in accordance with the present disclosure has an effect on the wrinkling of that material during mechanical convolution. In particular, when formed into a circular article, the sheet may be oriented such that the circumference of the circular article represents −45° to +45° perpendicular to the direction of flow for the material of the sheet. The effects of parameters such as sheet orientation in formed circular articles affect the cell morphology of articles, and the cell morphology of the articles ultimately influence their tendency to wrinkle.
Additional features of the present disclosure will become apparent to those skilled in the art upon consideration of illustrative embodiments exemplifying the best mode of carrying out the disclosure as presently perceived.
BRIEF DESCRIPTIONS OF THE DRAWINGS
The detailed description particularly refers to the accompanying figures in which:
FIG. 1 is a perspective view of an insulative cup in accordance with the present disclosure showing that the insulative cup includes a side wall and a floor coupled to the sidewall to define an interior region formed in the insulative cup and that the side wall of the cup extends around the interior region in a circumferential direction (along the circumference of the side wall) and between a brim included in the insulative cup and the floor in an axial directions (up and down);
FIG. 2 is an enlarged view of an axial portion of an insulative cup from the circled region of FIG. 1 showing that the insulative cup is made from an insulative sheet including an outer skin made from a polymeric film and a strip of insulative cellular non-aromatic polymeric material;
FIG. 3 is a diagrammatic and perspective view of a material-forming process in accordance with the present disclosure showing that the material-forming process includes, from left to right, a formulation of insulative cellular non-aromatic polymeric material being placed into a hopper that is fed into a first extrusion zone of a first extruder where heat and pressure are applied to form molten resin and showing that a blowing agent is injected into the molten resin to form an extrusion resin mixture that is fed into a second extrusion zone of a second extruder where the extrusion resin mixture exits and expands to form an extrudate which is slit to form a strip of insulative cellular non-aromatic polymeric material and suggesting that a side-wall blank (in phantom) is oriented on the strip to cause an eventual circumference of an insulative cup formed using the side-wall blank to be oriented perpendicular to the direction of extrusion;
FIG. 4 is a plan view of a side-wall blank cut from the strip of insulative cellular non-aromatic polymeric material showing the circumferential direction and the axial direction;
FIG. 5 is a microscopy image of an axial portion of an insulative cup made from a 44°-extruded sheet strip from an insulative cellular polypropylene-based material of the present disclosure used to quantify dimensional morphology of cell length and width;
FIG. 6 is a microscopy image of cell wall measurement for a portion of an insulative cup made from a 44°-extruded sheet strip from an insulative cellular polypropylene-based material of the present disclosure used to quantify dimensional morphology;
FIG. 7 is a microscopy image of a portion of an insulative cup made from a 90°-extruded sheet strip from an insulative cellular polypropylene-based material of the present disclosure used to quantify dimensional morphology;
FIG. 8 is an image showing cells with an aspect ratio of about 2.32 and cell density of about 1,216,000 cells/in 3 , which cells were taken from the axial direction of an insulative cup that did not demonstrate micro-creasing and macro-creasing behavior;
FIG. 9 is an image showing cells with an aspect ratio of about 3.25 and cell density of about 1,159,000 cells/in 3 , which cells were taken from the axialdirection of an insulative cup that demonstrated micro-creasing and macro-creasing behavior;
FIG. 10 is an image showing cells with an aspect ratio of about 1.94 and cell density of about 1,631,000 cells/in 3 , which cells were taken from the circumferential direction of an insulative cup that did not demonstrate micro-creasing and macro-creasing behavior;
FIG. 11 is an image showing cells with an aspect ratio of about 3.63 and cell density of about 933,000 cells/in 3 , which cells were taken from the circumferential direction of an insulative cup that demonstrated micro-creasing and macro-creasing behavior;
FIG. 12 is a graph with a power law regression fit of cell density vs. cell length in an x-y plot for insulative cups made from insulative cellular polypropylene-based materials of the present disclosure where the power law equation for predicting cell length with respect to cell density is y=999,162,715.083x −2613 and R 2 =0.972;
FIG. 13 is a graph with a power law regression fit of cell density vs. cell length in a log-log plot for the axial directions of insulative cups made from insulative cellular polypropylene-based materials of the present disclosure where the power law equation for predicting cell length with respect to cell density is y=999,162,715.083x −2.613 and R 2 =0.972;
FIG. 14 is a graph with a power law regression fit of cell density vs. cell width in an x-y plot for the axial directions of insulative cups made from insulative cellular polypropylene-based materials of the present disclosure where the power law equation for predicting cell width with respect to cell density is y=287,106,186.479x −3.295 and R 2 =0.974;
FIG. 15 is a graph with a power law regression fit of cell density vs. cell width in a log-log plot for the axial directions of insulative cups made from insulative cellular polypropylene-based materials of the present disclosure where the power law equation for predicting cell width with respect to cell density is y=287,106,186.479x −3.295 and R 2 =0.974;
FIG. 16 is a graph with a power law regression fit of cell density vs. cell wall thickness in an x-y plot for the axial directions of insulative cups made from insulative cellular polypropylene-based materials of the present disclosure where the power law equation for predicting cell wall thickness with respect to cell density is y=448,002.648x −3.053 and R 2 =0.973;
FIG. 17 is a graph with a power law regression fit of cell density vs. cell wall thickness in a log-log plot for the axial directions of insulative cups made from insulative cellular polypropylene-based materials of the present disclosure where the power law equation for predicting cell wall thickness with respect to cell density is y=448,002.648x −3.053 and R 2 =0.973;
FIG. 18 is a graph with a power law regression fit of cell density vs. cell length in an x-y plot for the axial directions of insulative cups made from insulative cellular polypropylene-based materials of the present disclosure where the power law equation for predicting cell length with respect to cell density is y=1,243,388,528.484x −2.626 and R 2 =0.945;
FIG. 19 is a graph with a power law regression fit of cell density vs. cell width in an x-y plot for the axial directions of insulative cups made from insulative cellular polypropylene-based materials of the present disclosure where the power law equation for predicting cell width with respect to cell density is y=426,736,129.761x −3.417 and R 2 =0.939;
FIG. 20 is an x-y plot of cell density vs. circumferential direction cell aspect ratio illustrating the effect of circumferential direction cell morphology on creasing;
FIG. 21 is an x-y plot of cell density vs. axial direction cell aspect ratio illustrating the effect of axial direction cell morphology on creasing;
FIG. 22 is an elevation view of an extrusion nozzle in accordance with the present disclosure with portions enlarged to show an inner die lip angle X and an outer die lip angle Y;
FIG. 23 illustrates sampling for microscopy and X-Ray analysis for which samples were cut from the side of an insulative cup side wall and analyzed in two perpendicular directions: View A from top to bottom of the cup and view B looking sideways;
FIG. 24 shows a View A microscopy image of the insulative cup side wall from the cup of Example 5 (with printed film laminated to the foam), where OET is outside of the insulative cup, illustrating that the insulative cup side wall collapsed in compression during cup formation leading to crease formation with crease depth of 0.23 mm; and
FIG. 25 shows a View A microscopy image of the insulative cup side wall from an insulative cup that is without a laminated printed film and that a black marker was used to eliminate light reflection for a clearer image, where OET is outside of the insulative cup, again illustrating that creasing/deep wrinkles formed on the inside of the insulative cup in the same way as in FIG. 24 .
DETAILED DESCRIPTION
One feature of of an extruded sheet of insulative cellular polypropylene-based material in accordance with the present disclosure is the ability of the sheet to form a surface with noticeable creases and wrinkles when curved to form a round article, such as an insulative cup. The surface may be wrinkled inside the cup, where compression forces may cause material to crush and/or crease easily, especially for low density material with a large cell aspect ratio. In exemplary embodiments, the surface profile of a cup made from an extruded sheet of insulative cellular polypropylene-based material as detected by microscopy is such that there is at least one indentation (i.e., creases and/or wrinkles) that is about 5 microns or more naturally occurring in the outside and/or inside of the cup surface when it is subject to extension and compression forces during cup forming. In one exemplary embodiment, the surface profile may include indentations of about 50 microns or more. In another exemplary embodiment, the surface profile may include indentations of about 100 microns or more. At a depth of about 10 microns and less, micro-wrinkles and/or creases on a cup surface are ordinarily not visible to the naked eye.
In one exemplary embodiment, an insulative cup formed from a sheet comprising a skin and a strip of insulative cellular polypropylene-based material in accordance with the present disclosure had typical creases (i.e., deep wrinkles) about 200 microns deep extending from the top of the cup to the bottom of the cup. In another exemplary embodiment, an insulative cup formed from a sheet comprising a strip of insulative cellular polypropylene-based material only (without a skin) in accordance with the present disclosure had typical creases about 200 microns deep extending from the top of the cup to the bottom of the cup. Such creases with depths from about 100 microns to about 500 microns are typically formed inside of a cup undergoing compression. Creases may form in instances where sheets include a skin or exclude a skin.
It was unexpectedly found that the cell morphology of an extruded sheet of insulative cellular polypropylene-based material in accordance with the present disclosure has an effect on the quality of the formed article, such as an insulative cup. The effects of cell morphology on a tendency of insulative cellular polypropylene-based material to wrinkle during convolution may be illustrated through examining the effect of varying the angle of the extruder die lips. In exemplary embodiments, the angle at which insulative cellular polypropylene-based material in accordance with the present disclosure exits an enclosed volume may affect the material's tendency to wrinkle. It was found that for a specified formulation of insulative cellular polypropylene-based material and specified cup forming conditions, different die exit angles lead to noticeably different levels of creasing and/or wrinkling in article surfaces during extruded sheet convolution. The two geometric exit angles selected for examination in the present disclosure are those commonly used in polyethylene foam production, i.e., an exit angle of 90°, and in polystyrene foam production, i.e., an exit angle of 44° (see, Example 1).
In exemplary embodiments, insulative cellular polypropylene-based material in accordance with the present disclosure may be extruded as sheet. Microscopy images show that distinct cell morphology exists, i.e., cell structure distinctions, within insulative cups made from such extruded sheets when one sheet is produced with a higher curvature die exit angle and the other with a lower curvature die exit angle. Insulative cups may be made by cutting the sheets such that the resulting circumference of the insulative cup is aligned to be perpendicular or parallel to the direction the sheets are extruded. The difference in cell morphology between cups cut in the two directions may be detected by examining portions cut from the axial sides of the cups under a microscope.
Direct evidence of polymer cell structure is provided by microscopy studies. There is a close relationship between the regularity of molecular structure and malleability. Cell morphology describes polymer cell density, cell structure, cell wall thickness, cell shape, and cell size distribution of cells. Polymer cell structures may have the same general shape and appearance, being composed predominantly of ovular cells, and the same lognormal cell distribution, but possess a different cell aspect ratio and cell wall thickness. Illustratively, cell aspect ratio is the ratio between lengths of the ovular polymer cells to widths of the ovular polymer cells. Illustratively, cell wall thickness is the solid polymeric distance between individual polymer cells.
In one exemplary embodiment, an extruded sheet of insulative cellular polypropylene-based material in accordance with the present disclosure may exit from an enclosed die volume at an angle of 90°. In another exemplary embodiment, an extruded sheet of insulative cellular polypropylene-based material may exit from an enclosed die volume at an angle of 44°. Illustratively, an extruded sheet of insulative cellular polypropylene-based material may exit from an enclosed die volume at an angle between 44° and 90°. Two such sheets, one produced at an exit angle of 44° and the other at an exit angle of 90°, may be prepared as strips either in the machine direction or in the cross direction and analyzed with digital microscopy. Cell density, cell distribution, cell shape, cell aspect ratio, and cell wall thickness of an extruded sheet may be held constant when extrusion parameters such as recipe, temperature, and cooling rate are the same. In the present disclosure, formation of wrinkled material was found to occur when the exit angle of curvature increased from 44° to 90° (see, Example 1, FIGS. 5-7 ). Without wishing to be bound by theory, one plausible explanation may be that cell density and dimensional morphology are a function of enclosed die volume exit angle, i.e., cell density and dimensional morphology may be altered upon exit from different enclosed die volume exit angles, thereby creating wrinkled material.
The disclosure herein provides methods of producing an insulative cellular material. In an embodiment, the insulative cellular material is polypropylene based. In an embodiment, the insulative cellular material produces wrinkles and/or creases during mechanical convolution. In an embodiment, a method of producing an insulative cellular material includes extruding a formulation as disclosed herein through an extruder die lips at an exit angle from about 0° to about 60°. In an embodiment, the formulation is extruded through die lips at an angle of about 0° to about 10°, about 10° to about 20°, about 20° to about 30°, about 30° to about 40°, about 40° to about 50°, about 50° to about 60°, about 40° to about 45°, 0° to about 20°, 0° to about 30°, 0° to about 40°, 0° to about 50°, about 10° to about 60°, about 10° to about 50°, about 10° to about 40°, about 10° to about 30°, about 20° to about 60°, about 20° to about 50°, about 20° to about 40°, about 30° to about 60°, about 30° to about 50°, or about 40° to about 60°. An embodiment includes the method wherein the die exit angle may be about 10°, 20°, 30°, 40°, 41°, 42°, 43°, 44°, 45°, 46°, 47°, 48°, 49°, 50°, or 60°.
In an embodiment of a method of producing an insulative cellular material, wherein the formulation comprises i) a first polymer material comprising at least one high melt strength polypropylene homopolymer, and ii) a second polymer material comprising at least one polymer selected from the group consisting of crystalline polypropylene homopolymer, impact polypropylene copolymer, and mixtures thereof. In an embodiment, the formulation further comprises at least one nucleating agent. In an embodiment, the formulation further comprises at least one slip agent. In an embodiment of a method of producing an insulative cellular material, cell dimensional attributes are according to y=Ax K , wherein either x or y is cell density of the insulative cellular polypropylene-based material and the non-cell density variable is cell length, cell width, or cell wall thickness of the insulative cellular polypropylene-based material.
It was unexpectedly found that cell morphology, especially cell density, of an extruded sheet of insulative cellular polypropylene-based material in accordance with the present disclosure has an effect on the quality of the formed article, such as a cup, formed therewith. The effects of cell density and dimensional attributes on wrinkling in insulative cellular polypropylene-based material may be illustrated through examining cell morphology data from different formulations and process conditions, thus creating a wrinkling prediction model based on power law regression.
In exemplary embodiments, the cell density of insulative cellular polypropylene-based material in accordance with the present disclosure may affect the material's tendency to wrinkle during mechanical convolution. In other exemplary embodiments, the total number of cells of insulative cellular polypropylene-based material may affect the material's tendency to wrinkle during mechanical convolution. In other exemplary embodiments, the cell aspect ratio in the circumferential direction 10 of an insulative cup 12 , may affect the material's tendency to wrinkle during mechanical convolution. In other exemplary embodiments, the cell aspect ratio in the axial direction 20 of an insulative cup 12 , may affect the material's tendency to wrinkle during mechanical convolution.
As shown in FIG. 1 , insulative cup 12 includes includes a body 14 having a sleeve-shaped side wall 16 and a floor 18 as shown in FIG. 1 . Floor 18 is coupled to body 14 and cooperates with side wall 16 to form an interior region 22 therebetween for storing food, liquid, or any suitable product. Body 14 also includes a rolled brim 24 coupled to an upper end of side wall 16 and a floor mount 26 coupled to a lower end of side wall 16 and to floor 18 as shown in FIG. 1 . Side wall 16 is arranged to extend around an axis 28 in circumferential direction 10 . Side wall 16 is arranged to extend along axis 28 in axial direction 20 as shown in FIGS. 1 and 2 . Side wall 16 is spaced apart from axis 28 in a radial direction 30 as shown in FIGS. 1 and 2 . U.S. application Ser. No. 13/491,007, filed Jun. 7, 2012 is hereby incorporated by reference in its entirety for disclosure relating to an insulative cup.
Insulative cup 12 includes a sheet of insulative cellular non-aromatic polymeric material made according to a material-forming process 100 as shown in FIG. 3 . Material-forming process 100 begins with a polypropylene-based formulation 121 in accordance with the present disclosure which is used to produce strip 82 of insulative cellular non-aromatic polymeric material as shown in FIG. 3 . Formulation 121 is heated and extruded in two stages to produce a tubular extrudate 124 that can be slit to provide strip 82 of insulative cellular non-aromatic polymeric material as illustrated, for example, in FIG. 3 . A blowing agent in the form of a liquefied inert gas is introduced into a molten resin 122 in the first extrusion zone. As an example, material-forming process 100 uses a tandem-extrusion technique in which a first extruder 111 and a second extruder 112 cooperate to extrude strip 82 of insulative cellular non-aromatic polymeric material.
As shown in FIG. 3 , a formulation 121 of insulative cellular non-aromatic polymeric material is loaded into a hopper 113 that is coupled to first extruder 111 . Formulation 121 of insulative cellular non-aromatic polymeric material is moved from hopper 113 by a screw 114 included in first extruder 111 . Formulation 121 is transformed into a molten resin 122 in a first extrusion zone of first extruder 111 by application of heat 105 and pressure from screw 114 as suggested in FIG. 3 .
In exemplary embodiments, a physical blowing agent may be introduced and mixed into molten resin 122 after molten resin 122 is established. In exemplary embodiments, as discussed further herein, the physical blowing agent may be a gas introduced as a pressurized liquid via a port 115 A and mixed with molten resin 122 to form a molten extrusion resin mixture 123 as shown in FIG. 3 .
Extrusion resin mixture 123 is conveyed by screw 114 into a second extrusion zone included in second extruder 112 as shown in FIG. 7 . There, extrusion resin mixture 123 is further processed by second extruder 112 before being expelled through an extrusion die 116 coupled to an end of second extruder 112 to form an extrudate 124 . As extrusion resin mixture 123 passes through extrusion die 116 , gas comes out of solution in extrusion resin mixture 123 and begins to form cells and expand so that extrudate 124 is established. The extrudate 124 may be formed by an annular extrusion die 116 to form a tubular extrudate 124 . A slitter 117 then cuts extrudate 124 to establish strip 82 of insulative cellular non-aromatic polymeric material as shown in FIG. 3 . U.S. application Ser. No. 14/462,073, filed Aug. 18, 2014 is hereby incorporated by reference in its entirety for disclosure relating to formulations of insulative cellular non-aromatic polymeric material.
A blank 200 used to form a portion of insulative cup 10 is shown in phantom in FIG. 3 and in FIG. 4 . In one example, blank is oriented on strip 82 such that circumferential direction 10 is aligned with a machine direction 101 as shown in FIGS. 3 and 4 . As a result axial direction 20 is aligned with a cross direction 102 as shown in FIGS. 3 and 4 . U.S. application Ser. No. 13/526,444, filed Jun. 18, 2012 is hereby incorporated by reference in its entirety for disclosure relating to processes for forming an insulative cup 10 using a blank. Blank 200 may be oriented in any direction. Blank 200 orientation may influence cell morphology.
In other exemplary embodiments, the cell length of insulative cellular polypropylene-based material may affect the material's tendency to wrinkle during mechanical convolution. When cells are measured in the circumferential direction 10 , cell length is the circumferential distance in the circumferential direction 10 . When cells are measured in the axial direction 20 , cell length is the axial distance in the axial direction 20 .
In other exemplary embodiments, the cell width of insulative cellular polypropylene-based material may affect the material's tendency to wrinkle during mechanical convolution. Cell width is the maximum radial distance measured in a radial direction. In other exemplary embodiments, the cell wall thickness of insulative cellular polypropylene-based material may affect the material's tendency to wrinkle during mechanical convolution. In other exemplary embodiments, cell dimensional attributes may follow a power law that is independent of formula and processing conditions (see, Example 2, FIGS. 12-19 ). The present disclosure also provides process know how and a basis for predicting a tendency for an insulative cellular polypropylene-based material to wrinkle during mechanical convolution that is independent of material formula and processing conditions.
The insulative cellular polypropylene-based material of the present disclosure may be formed into an article, such as an insulative cup, that includes the features of a tendency to wrinkle and/or crease during mechanical convolution as described herein, and may include many, if not all, of the features of insulative performance, recyclability, puncture resistance, frangibility resistance, and microwavability, which features are described in U.S. patent application Ser. Nos. 13/491,007 and 13/491,327 both of which are incorporated herein by reference in their entirety.
Nucleating agent means a chemical or physical material that provides sites for cells to form in a molten formulation mixture. Nucleating agents may include chemical nucleating agents and physical nucleating agents. The nucleating agent may be blended with the formulation that is introduced into the hopper of the extruder. Alternatively, the nucleating agent may be added to the molten resin mixture in the extruder.
Suitable physical nucleating agents have desirable particle size, aspect ratio, and top-cut properties. Examples include, but are not limited to, talc, CaCO3, mica, and mixtures of at least two of the foregoing. One representative example is Heritage Plastics HT6000 Linear Low Density Polyethylene (LLDPE) Based Talc Concentrate.
Suitable chemical nucleating agents decompose to create cells in the molten formulation when a chemical reaction temperature is reached. These small cells act as nucleation sites for larger cell growth from a physical or other type of blowing agent. In one example, the chemical nucleating agent is citric acid or a citric acid-based material. One representative example is HYDROCEROL™ CF-40E (available from Clariant Corporation), which contains citric acid and a crystal nucleating agent.
A blowing agent refers to a physical or a chemical blowing agent (or combination of materials) that acts to expand nucleation sites. Blowing agents may include only chemical blowing agents, only physical blowing agents, combinations thereof, or several types of chemical and physical blowing agents. The blowing agent acts to reduce density by forming cells in the molten formulation at the nucleation sites. The blowing agent may be added to the molten resin mixture in the extruder.
Chemical blowing agents are materials that degrade or react to produce a gas. Chemical blowing agents may be endothermic or exothermic. Chemical blowing agents typically degrade at a certain temperature to decompose and release gas. One example of a chemical blowing agent is citric acid or citric-based material. One representative example is HYDROCEROL™ CF-40E (available from Clariant Corporation), which contains citric acid and a crystal nucleating agent. Here, the citric acid decomposes at the appropriate temperature in the molten formulation and forms a gas which migrates toward the nucleation sites and grows cells in the molten formulation. If sufficient chemical blowing agent is present, the chemical blowing agent may act as both the nucleating agent and the blowing agent.
In another example, chemical blowing agents may be selected from the group consisting of azodicarbonamide; azodiisobutyro-nitrile; benzenesulfonhydrazide; 4,4-oxybenzene sulfonylsemicarbazide; p-toluene sulfonyl semi-carbazide; barium azodicarboxylate; N,N′-dimethyl-N,N′-dinitrosoterephthalamide; trihydrazino triazine; methane; ethane; propane; n-butane; isobutane; n-pentane; isopentane; neopentane; methyl fluoride; perfluoromethane; ethyl fluoride; 1,1-difluoroethane; 1,1,1-trifluoroethane; 1,1,1,2-tetrafluoro-ethane; pentafluoroethane; perfluoroethane; 2,2-difluoropropane; 1,1,1-trifluoropropane; perfluoropropane; perfluorobutane; perfluorocyclobutane; methyl chloride; methylene chloride; ethyl chloride; 1,1,1-trichloroethane; 1,1-dichloro-1-fluoroethane; 1-chloro-1,1-difluoroethane; 1,1-dichloro-2,2,2-trifluoroethane; 1-chloro-1,2,2,2-tetrafluoroethane; trichloromonofluoromethane; dichlorodifluoromethane; trichlorotrifluoroethane; dichlorotetrafluoroethane; chloroheptafluoropropane; dichlorohexafluoropropane; methanol; ethanol; n-propanol; isopropanol; sodium bicarbonate; sodium carbonate; ammonium bicarbonate; ammonium carbonate; ammonium nitrite; N,N′-dimethyl-N,N′-dinitrosoterephthalamide; N,N′-dinitrosopentamethylene tetramine; azodicarbonamide; azobisisobutylonitrile; azocyclohexylnitrile; azodiaminobenzene; bariumazodicarboxylate; benzene sulfonyl hydrazide; toluene sulfonyl hydrazide; p,p′-oxybis(benzene sulfonyl hydrazide); diphenyl sulfone-3,3′-disulfonyl hydrazide; calcium azide; 4,4′-diphenyl disulfonyl azide; p-toluene sulfonyl azide; and combinations thereof.
In an illustrative embodiment, a nucleating agent may be about 0.1% to about 20% (w/w), about 0.25% to about 20%, about 0.5% to about 20%, about 0.75% to about 20%, about 1% to about 20%, about 1.5% to about 20%, about 2% to about 20%, about 2.5% to about 20%, about 3% to about 20%, about 3% to about 20%, about 4% to about 20%, about 4.5% to about 20%, about 5% to about 20%, about 0.1% to about 10%, about 0.25% to about 10%, about 0.5% to about 10%, about 0.75% to about 10%, about 1.0% to about 10%, about 1.5% to about 10%, about 1.0% to about 10%, about 2.0% to about 10%, about 2.5% to about 10%, about 3.0% to about 10%, about 3.5% to about 10%, about 4.0% to about 10%, about 4.5% to about 10%, about 5.0% to about 10%, about 0.1% to about 5%, about 0.25% to about 5%, about 0.5% to about 5%, about 0.75% to about 5%, about 1% to about 5%, about 1.5% to about 5%, about 1% to about 5%, about 2% to about 5%, about 2.5% to about 5%, about 3% to about 5%, about 3.5% to about 5%, or about 4% to about 5%, or about 4.5% to about 5%. In an embodiment, a nucleating agent may be about 0.5%, about 1%, about 1.5%, about 2%, about 2.5%, about 3%, about 4%, or about 5% (w/w). In an embodiment, the polymeric material lacks a nucleating agent. In an embodiment, the polymeric material lacks talc.
In an illustrative embodiment, a chemical blowing agent may be about 0 to about 5% (w/w), about 0.1% to about 5% (w/w), about 0.25% to about 5%, about 0.5% to about 5%, about 0.75% to about 5%, about 1% to about 5%, about 1.5% to about 5%, about 2% to about 5%, about 3% to about 5%, about 4% to about 5%, 0 to about 4% (w/w), about 0.1% to about 4% (w/w), about 0.25% to about 4%, about 0.5% to about 4%, about 0.75% to about 4%, about 1% to about 4%, about 1.5% to about 4%, about 2% to about 4%, about 3% to about 4%, 0 to about 3% (w/w), about 0.1% to about 3% (w/w), about 0.25% to about 3%, about 0.5% to about 3%, about 0.75% to about 3%, about 1% to about 3%, about 1.5% to about 3%, about 2% to about 3%, 0 to about 2%, about 0.1% to about 2% (w/w), about 0.25% to about 2%, about 0.5% to about 2%, about 0.75% to about 2%, about 1% to about 2%, about 1.5% to about 2%, 0 to about 1%, about 0.1% to about 1%, about 0.5% to about 1%, or about 0.75% to about 1%. In an illustrative embodiment, a chemical blowing agent may be about 0.1%, 0.5%, 0.75%, 1%, 1.5% or about 2%. In one aspect of the present disclosure, where a chemical blowing agent is used, the chemical blowing agent may be introduced into the material formulation that is added to the hopper.
One example of a physical blowing agent is nitrogen (N 2 ). The N 2 is pumped into the molten formulation via a port in the extruder as a supercritical fluid. The molten material with the N 2 in suspension then exits the extruder via a die where a pressure drop occurs. As the pressure drop happens, N 2 moves out of suspension toward the nucleation sites where cells grow. Excess gas blows off after extrusion with the remaining gas trapped in the cells formed in the extrudate. Other suitable examples of physical blowing agents include, but are not limited to, carbon dioxide (CO 2 ), helium, argon, air, pentane, butane, other alkanes, mixtures of the foregoing, and the like.
In one aspect of the present disclosure, at least one slip agent may be incorporated into the formulation to aid in increasing production rates. Slip agent (also known as a process aid) is a term used to describe a general class of materials which are added to the formulation and provide surface lubrication to the polymer during and after conversion. Slip agents may also reduce or eliminate die drool. Representative examples of slip agent materials include amides of fats or fatty acids, such as, but not limited to, erucamide and oleamide. In one exemplary aspect, amides from oleyl (single unsaturated C-18) through erucyl (C-22 single unsaturated) may be used. Other representative examples of slip agent materials include low molecular weight amides and fluoroelastomers. Combinations of two or more slip agents may be used. Slip agents may be provided in a master batch pellet form and blended with the resin formulation. One example of a suitable slip agent is Ampacet 102823 Process Aid PE MB LLDPE.
In an embodiment, a slip agent may be about 0% to about 10% (w/w), about 0.5% to about 10% (w/w), about 1% to about 10% (w/w), about 2% to about 10% (w/w), about 3% to about 10% (w/w), about 4% to about 10% (w/w), about 5% to about 10% (w/w), about 6% to about 10% (w/w), about 7% to about 10% (w/w), about 8% to about 10% (w/w), about 9% to about 10% (w/w), about 0% to about 9% (w/w), about 0.5% to about 9% (w/w), about 1% to about 9% (w/w), about 2% to about 9% (w/w), about 3% to about 9% (w/w), about 4% to about 9% (w/w), about 5% to about 9% (w/w), about 6% to about 9% (w/w), about 7% to about 9% (w/w), about 8% to about 9% (w/w), about 0% to about 8% (w/w), about 0.5% to about 8% (w/w), about 1% to about 8% (w/w), about 2% to about 8% (w/w), about 3% to about 8% (w/w), about 4% to about 8% (w/w), about 5% to about 8% (w/w), about 6% to about 8% (w/w), about 7% to about 8% (w/w), about 0% to about 7% (w/w), about 0.5% to about 7% (w/w), about 1% to about 7% (w/w), about 2% to about 7% (w/w), about 3% to about 7% (w/w), about 4% to about 7% (w/w), about 5% to about 7% (w/w), about 6% to about 7% (w/w), about 0% to about 6% (w/w), about 0.5% to about 6% (w/w), about 1% to about 6% (w/w), about 2% to about 6% (w/w), about 3% to about 6% (w/w), about 4% to about 6% (w/w), about 5% to about 6% (w/w), about 0% to about 5% (w/w), about 0.5% to about 5% (w/w), about 1% to about 5% (w/w), about 2% to about 5% (w/w), about 3% to about 5% (w/w), about 4% to about 5% (w/w), about 0% to about 4% (w/w), about 0.5% to about 4% (w/w), about 1% to about 4% (w/w), about 2% to about 4% (w/w), about 3% to about 4% (w/w), about 0% to about 3% (w/w), about 0.5% to about 3% (w/w), about 1% to about 3% (w/w), about 2% to about 3% (w/w), about 0% to about 2% (w/w), about 0.5% to about 2% (w/w), about 1% to about 2% (w/w), about 0% to about 1% (w/w), or about 0.5% to about 1% (w/w). In an embodiment, a slip agent may be about 0.5%, about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, or about 10% (w/w). In an embodiment, the formulation lacks a slip agent.
In an embodiment, a colorant may be about 0% to about 20% (w/w), about 0% to about 15% (w/w), about 0% to about 10% (w/w), about 0% to about 5% (w/w), about 0% to about 4% (w/w), about 0.1% to about 4%, about 0.25% to about 4%, about 0.5% to about 4%, about 0.75% to about 4%, about 1.0% to about 4%, about 1.5% to about 4%, about 2.0% to about 4%, about 2.5% to about 4%, about 3% to about 4%, about 0% to about 3.0%, about 0% to about 2.5%, about 0% to about 2.25%, about 0% to about 2.0%, about 0% to about 1.5%, about 0% to about 1.0%, about 0% to about 0.5%, about 0.1% to about 3.5%, about 0.1% to about 3.0%, about 0.1% to about 2.5%, about 0.1% to about 2.0%, about 0.1% to about 1.5%, about 0.1% to about 1.0%, about 1% to about 5%, about 1% to about 10%, about 1% to about 15%, about 1% to about 20%, or about 0.1% to about 0.5%. In an embodiment, a formulation lacks a colorant.
In one exemplary embodiment, a formulation used to produce the cellular polymeric material includes at least one polymeric material. The polymeric material may include one or more base resins. In one example, the base resin is polypropylene. In an illustrative embodiment, a base resin may include Borealis WB140 HMS polypropylene homopolymer. In another illustrative embodiment, a base resin may include Braskem F020HC polypropylene homopolymer. In an embodiment, a base resin may include both Borealis WB140 HMS polypropylene homopolymer and Braskem F020HC polypropylene homopolymer.
In embodiments with more than one polypropylene copolymer base resin, different polypropylene copolymers may be used depending on the attributes desired in the formulation. Depending on the desired characteristics, the ratio of two polypropylene resins may be varied, e.g., 10%/90%, 20%/80%, 25%/75%, 30%/70%, 35%/65%, 40%/60%, 45%/55%, 50%/50%, etc. In an embodiment, a formulation includes three polypropylene resins in the base resin. Again, depending on the desired characteristics, the percentage of three polypropylene resins may be varied, 33%/33%/33%, 30%/30%/40%, 25%/25%/50%, etc.
In illustrative embodiments, a polymeric material includes a primary base resin. In illustrative embodiments, a base resin may include polypropylene. In illustrative embodiments, an insulative cellular non-aromatic polymeric material comprises a polypropylene base resin having a high melt strength and a polypropylene copolymer or homopolymer (or both). In one example, the polypropylene base resin has a drawdown force greater than about 15 cN. In another example, the polypropylene base resin has a drawdown force greater than about 20 cN. In another example, the polypropylene base resin has a drawdown force greater than about 25 cN. In another example, the polypropylene base resin has a drawdown force greater than about 35 cN.
In an embodiment, a formulation of the polymeric material comprises about 50 wt % to about 100 wt %, about 70 wt % to about 100 wt %, about 50 wt % to about 99 wt %, 50 wt % to about 95 wt %, about 50 wt % to about 85 wt %, about 55 wt % to about 85 wt %, about 80 wt % to about 85 wt %, about 80 wt % to about 90 wt %, about 80 wt % to about 91 wt %, about 80 wt % to about 92 wt %, about 80 wt % to about 93 wt %, about 80 wt % to about 94 wt %, about 80 wt % to about 95 wt %, about 80 wt % to about 96 wt %, about 80 wt % to about 97 wt %, about 80 wt % to about 98 wt %, about 80 wt % to about 99 wt %, about 85 wt % to about 90 wt %, or about 85 wt % to about 95 wt % of the primary base resin. In an embodiment, a colorant may be about 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or 100%.
As defined hereinbefore, any suitable primary base resin may be used. One illustrative example of a suitable polypropylene base resin is DAPLOY™ WB140 homopolymer (available from Borealis A/S) which is a high melt strength structural isomeric modified polypropylene homopolymer.
In illustrative embodiments, a polymeric material includes a secondary resin, wherein the secondary resin may be a polypropylene copolymer or homopolymer (or both). In another embodiment, a secondary resin may be about 0 wt % to about 50 wt %, about 0 wt % to about 30 wt %, about 0 wt % to about 25 wt %, about 0 wt % to about 20 wt %, about 0 wt % to about 15 wt %, about 10 wt % to about 50 wt %, about 10 wt % to about 40 wt %, about 10 wt % to about 30 wt %, about 10 wt % to about 25 wt %, about 10 wt % to about 20 wt %, or about 10 wt % to about 15 wt % of a secondary resin. In an embodiment, a polymeric material includes about 0 wt %, about 10 wt %, about 15 wt %, about 20 wt %, about 25 wt %, or about 30 wt %. In an embodiment, a polymeric material does not have a secondary resin. In an embodiment, a secondary resin may be a high crystalline polypropylene homopolymer, such as F020HC (available from Braskem) or PP 527K (available from Sabic). In an embodiment, a polymeric material lacks a secondary resin.
The term die exit angle means the angle subtended by the central axis of the torpedo mandrel and the outer surface of the torpedo mandrel adjacent the exit lip of an extrusion apparatus. Such an angle may be referred to as an inner lip angle, and is commonly understood to be angle X as shown in FIG. 22 . The die exit angle may be an angle as disclosed in any of the following numbered lines 1-15:
1.) 1-60°
2.) 10-60°
3.) 20-60°
4.) 30-60°
5.) 30-58°
6.) 32-58°
7.) 35-58°
8.) 35-56°
9.) 37-54°
10.) 40-54°
11.) 40-52°
12.) 40-50°
13.) 40-48°
14.) 42-48°
15.) 42-46°
In particular embodiments of the disclosure, the die exit angle may be formed by an inner lip angle identified as X in FIG. 22 and an outer lip angle identified as Y in FIG. 22 . Outer lip angle Y is the angle subtended by the lip of the extrusion apparatus and the central axis of a torpedo mandrel. Inner lip angle X is the angle subtended by the central axis of the torpedo mandrel and the outer surface of the torpedo mandrel adjacent the lip of the extrusion apparatus as shown in FIG. 22 . Angles X and Y may be configured as disclosed in any of the following numbered lines 16-22:
16.) X is 45-60° and Y is 35-55°
17.) X is 47-58° and Y is 37-50°
18.) X is 47-56° and Y is 37-48°
19.) X is 47-54° and Y is 39-46°
20.) X is 48-54° and Y is 40-45°
21.) X is 49° and Y is 41°
22.) X is 53° and Y is 41°
In an embodiment, the process comprises extruding a formulation at any of the angles disclosed in numbered lines 1-22 above, wherein the formulation comprises:
50-100 wt % of a primary base resin
0-50 wt % of a secondary resin
0-5 wt % of a chemical blowing agent
0.1-20 wt % of a nucleating agent
0-20 wt % of a colorant
0-10 wt % of a slip agent
In an embodiment, the process comprises extruding a formulation at any of the angles defined in numbered paragraphs 1-22 above, wherein the formulation comprises:
50-100 wt % of a primary base resin
0-50 wt % of a secondary resin
0-2 wt % of a chemical blowing agent
0-20 wt % of a physical nucleating agent
0-20 wt % of a colorant
0-10 wt % of a slip agent
In an embodiment, the process comprises extruding a formulation at any of the angles disclosed in the numbered lines 1-22 above, wherein the formulation comprises:
75-85 wt % of a primary base resin
10-20 wt % of a secondary resin
0-0.1 wt % of a chemical blowing agent
0.1-3 wt % of a nucleating agent
0-2 wt % of a colorant
0-4 wt % of a slip agent
In an embodiment, the process comprises extruding a formulation at any of the angles disclosed in the numbered lines 1-22 above, wherein the formulation comprises:
50-99.65 wt % of the primary base resin
0-50 wt % of the secondary resin
0-10 wt % of the slip agent
0-10 wt % of the colorant
0.35-1.5 wt % of nucleating agent
In an embodiment, the process comprises extruding a formulation at any of the angles disclosed in the numbered lines 1-22 above, wherein the formulation comprises:
50-95 wt % of the primary base resin
0-50 wt % of the secondary resin
0-10 wt % of the slip agent
0-10 wt % of the colorant
0.4-1.2 wt % of nucleating agent
In an embodiment, the process comprises extruding a formulation at any of the angles disclosed in the numbered lines 1-22 above, wherein the formulation comprises:
55-85 wt % of the primary base resin
0-50 wt % of the secondary resin
0-10 wt % of the slip agent
0-10 wt % of the colorant
0.45-1.25 wt % of nucleating agent
In an embodiment, the process comprises extruding a formulation at any of the angles disclosed in the numbered lines 1-22 above, wherein the formulation comprises:
50-99.69 wt % of the primary base resin
0-50 wt % of the secondary resin
0-10 wt % of the slip agent
0-10 wt % of the colorant
0.01-1.5 wt % of the primary nucleating agent
0.3-1.7 wt % of the secondary nucleating agent
In an embodiment, the process comprises extruding a formulation at any of the angles disclosed in the numbered lines 1-22 above, wherein the formulation comprises:
50-95 wt % of the primary base resin
0-50 wt % of the secondary resin
0-10 wt % of the slip agent
0-10 wt % of the colorant
0.02-1.0 wt % of the primary nucleating agent
0.4-1.5 wt % of the secondary nucleating agent
In an embodiment, the process comprises extruding a formulation at any of the angles disclosed in the numbered lines 1-22 above, wherein the formulation comprises:
55-85 wt % of the primary base resin
0-50 wt % of the secondary resin
0-10 wt % of the slip agent
0-10 wt % of the colorant
0.03-0.7 wt % of the primary nucleating agent
0.45-1.25 wt % of the secondary nucleating agent
In an embodiment, the process comprises extruding a formulation at any of the angles disclosed in the numbered lines 1-22 above, wherein the formulation comprises:
78-83 wt % of a primary base resin
14-16 wt % of a secondary resin
0-0.05 wt % of a chemical blowing agent
0.25-2 wt % of a nucleating agent
1-2 wt % of a colorant
1.5-3.5 wt % of a slip agent
In the preceding embodiments, the primary base resin may comprise polypropylene. In another illustrative embodiment, the primary base resin comprises at least one of Borealis WB140 HMS polypropylene homopolymer and Braskem F020HC polypropylene homopolymer. In another embodiment, the primary base resin is Borealis WB140 HMS polypropylene homopolymer.
In the preceding embodiments, the secondary resin may comprise at least one polypropylene copolymer or polypropylene homopolymer. In another embodiment, the secondary resin comprises at least one of Braskem F020HC polypropylene homopolymer and PP 527K (available from Sabic). In another embodiment, the secondary resin is Braskem F020HC polypropylene homopolymer.
In the preceding embodiments, the chemical blowing agent may comprise citric acid, or a citric acid-based material. In an illustrative embodiment the chemical blowing agent is Hydrocerol™ CF-40E (available from Clariant Corporation).
In the preceding embodiments, the nucleating agent may comprise talc, CaCO 3 , mica, or mixtures thereof. In an illustrative embodiment, the nucleating agent is one or more of HT4HP talc (available from Heritage Plastics), HT6000 Linear Low Density Polyethylene (LLDPE) (available from Heritage Plastics), and Techmer PM PPM 16466 Silica. In another embodiment, the nucleating agent is HT4HP talc (available from Heritage Plastics) or Techmer PM PPM 16466 Silica. A primary nucleating agent may be defined as a chemical blowing agent or chemical foaming agent, itself comprising a nucleating agent. In another embodiment, a primary nucleating agent is Hydrocerol™ CF-40E™ (available from Clariant Corporation). In an illustrative embodiment, a secondary nucleating agent is selected from HPR-803i fibers (available from Milliken) or talc
In the preceding embodiments, the colorant may comprise at least one of Colortech 11933-19 TiO 2 PP or Cell Stabilizer. In another embodiment, the colorant is Colortech 11933-19 TiO 2 PP.
In the preceding embodiments, the slip agent may comprise one or more amides of fats or fatty acids, such as erucamide and oleamide. The slip agent may also comprise one or more low molecular weight amides and fluoroelastomers. In an embodiment, the slip agent is Ampacet 102823 Process Aid PE MB LLDPE.
The method of any of the preceding embodiments may also comprise adding CO 2 to the formulation prior to extrusion at a rate of 1-4 lbs/hr. In an embodiment, the CO 2 is added at a rate of 2-3 lbs/hr. In another embodiment, the CO 2 is added at a rate of 2.2-2.8 lbs/hr. Such practice may also be referred to as adding a physical blowing agent.
EXAMPLES
The following examples are set forth for purposes of illustration only. Parts and percentages appearing in such examples are by weight unless otherwise stipulated.
Example 1: Formulation, Extrusion, and Sheet Formation
An Exemplary Formulation Used to Illustrate the Present Disclosure is presented below and is described in U.S. Provisional Application Ser. No. 61/719,096, the disclosure of which is hereby incorporated herein by reference in its entirety:
DAPLOY™ WB140 polypropylene homopolymer (available from Borealis A/S) was used as the polypropylene base resin. F020HC, available from Braskem, a polypropylene homopolymer resin, was used as the secondary resin. The two resins were blended with: Hydrocerol™ CF-40E™ as a chemical blowing agent, talc as a nucleation agent, CO 2 as a blowing agent, a slip agent, and titanium dioxide as a colorant. Percentages were:
81.45% Primary resin: high melt strength polypropylene Borealis WB140 HMS 15% Secondary resin: F020HC (Braskem) homopolymer polypropylene 0.05% Chemical blowing agent: Clariant Hyrocerol CF-40E™ 0.5% Nucleation agent: Heritage Plastics HT4HP Talc 1% Colorant: Colortech 11933-19 TiO 2 PP 2% Slip agent: Ampacet™ 102823 Process Aid LLDPE (linear low-density polyethylene), available from Ampacet Corporation
The formulation described above was added to an extruder hopper. The extruder heated the formulation to form a molten resin mixture. To this mixture was added 2.2 lbs/hr CO 2 , which was injected into the resin blend to expand the resin and reduce density. The mixture thus formed was extruded through a die head into a sheet as described in U.S. application Ser. No. 13/491,007, the disclosure of which is hereby incorporated herein by reference in its entirety.
High resolution microscopy may be used to determine the dimensional properties of insulative cellular non-aromatic polymeric material. The Keyence VHX-1000 Digital Microscope was used to determine the dimensional properties of insulative cellular polypropylene-based material cells of the present disclosure. In one exemplary embodiment, cell length may be the dimensional property denoting maximum distance from top to bottom of cells running parallel to the circumferential direction 10 of an insulative cup made from insulative cellular non-aromatic polymeric material. In another exemplary embodiment, cell length may also be the dimensional property denoting maximum distance from top to bottom of cells running parallel to the axial direction 20 of an insulative cup made from insulative cellular non-aromatic polymeric material. In yet another exemplary embodiment, cell width may be the dimensional property denoting maximum distance from top to bottom of cells running in the radial direction of an insulative cup made from insulative cellular non-aromatic polymeric material. In still another exemplary embodiment, cell wall thickness may be the dimensional property denoting maximum distance between separated cell voids across a line running perpendicular to the circumferential and axial direction.
In order to assess the effect of cell morphology of an extruded sheet of insulative cellular polypropylene-based material on the quality of an article formed therewith, such as an insulative cup, a minimum of 700 measurement points were chosen for each of the length and width dimensional properties in order to verify consistency throughout a strip of the material. A minimum of 200 measurement points were chosen for cell wall thickness as a dimensional property in order to verify consistency throughout the strip of insulative cellular polypropylene-based material. In one exemplary embodiment, a sheet of insulative cellular polypropylene-based material may be extruded from an enclosed die volume at an angle of 44°. In another exemplary embodiment, a sheet of insulative cellular polypropylene-based material may be extruded from an enclosed die volume at an angle of 90°. A sheet of insulative cellular polypropylene-based material extruded at an angle of 44° is referred to herein as Material C. A sheet of insulative cellular polypropylene-based material extruded at an angle of 90° is referred to herein as Material D. Strips of insulative cellular polypropylene-based material from 44° and 90° exit angles were quantitatively compared as shown in FIGS. 5-7 .
Example 1: Test Method
The typical testing method used for cell morphology measurement was as follows:
1.) Cut a side wall blank for an insulative cup as shown in FIG. 4 from a strip of insulative cellular polypropylene-based material as suggested by FIG. 3 or at any other orientation. 2.) Make an insulative cup using the side wall blank by the method disclosed in U.S. patent application Ser. No. 13/526,454 filed on Jun. 18, 2004, the disclosure of which is hereby incorporated by reference herein in its entirety. 3.) Cut a strip of the side wall of the insulative cup along the axial direction and circumferential direction. 4.) Hold the material with a flat clamp and use a razor blade to perform a fine shave. 5.) Focus the microscope at 100× and adjust lighting onto the material. 6.) Perform length and width measurements of each unique cell in the axial direction and circumferential direction orientation and record values as suggested by FIG. 5 . 7.) Perform cell wall thickness measurements across 3-4 tangent lines to overall length of each unique cell in the axial and circumferential orientation and record the values as suggested by FIG. 6 . 8.) Move microscope visual field so the bottom of the most upper incomplete cell is touching the bottom of the screen. 9.) Repeat steps 6-7 on each new unique cell until at least 0.500″ of the strip is measured.
A sheet of insulative cellular polypropylene-based material produced as described herein typically possessed a density of about 0.1615 g/cm 3 and material thickness of about 0.066 inches (1.6764 mm).
Example 1: Test Results
The cell morphology of an extruded sheet of insulative cellular polypropylene-based material exiting the enclosed die volume at angles of 44° and 90° differed greatly in terms of cell height, cell width, cell aspect ratio, and cell wall thickness as shown in Table 1. In the circumferential direction, Material C had an average length of 19.54 mils (49.63 mm), an average width of 8.53 mils (21.67 mm), an average cell wall thickness of 1.02 mils (2.59 mm), and average aspect ratio of 2.29. In the circumferential direction, Material D had an average length of 17.01 mils (43.21 mm), an average width of 5.22 mils (13.26 mm), an average cell wall thickness of 0.77 mils (1.96 mm), and average aspect ratio of 3.26.
In the axial direction, Material C had an average length of 18.45 mils (46.86 mm), an average width of 8.28 mils (21.03 mm), an average cell wall thickness of 0.96 mils (2.44 mm), and average aspect ratio of 2.23. In the axial direction, Material D had an average length of 16.43 mils (41.73 mm), an average width of 5.30 mils (13.46 mm), an average cell wall thickness of 0.84 mils (2.13 mm), and average aspect ratio of 3.10.
Moreover, formation of wrinkled insulative cellular polypropylene-based material was found to occur when the exit angle of curvature increased from 44° to 90° as suggested by Example 1, FIGS. 5-7 . Based on these results, it may be concluded that die exit angles from enclosed die volumes create different material morphology, with differing tendencies to wrinkle and/or crease, when recipe and process conditions are held constant. In one exemplary embodiment, insulative cellular polypropylene-based material with a tendency to wrinkle during convolution may be created concomitantly with a decrease in die exit angle. The higher the angle of die exit, the easier it is to increase the cell aspect ratio, thus enabling preparation of a sheet of insulative cellular polypropylene-based material that possesses relatively high cell aspect ratios. In one example, the relatively high cell aspect ratio is greater than about 2.5. In another example, the relatively high cell aspect ratio is greater than about 3.
In exemplary embodiments, die exit angles within an inclusive range of 50°-60° may produce insulative cellular polypropylene-based material with a tendency to wrinkle during convolution. In other exemplary embodiments, die exit angles within an inclusive range of 40°-50° may produce insulative cellular polypropylene-based material with a tendency to wrinkle during convolution. In other exemplary embodiments, die exit angles within an inclusive range of 30°-40° may produce insulative cellular polypropylene-based material with a tendency to wrinkle during convolution. In other exemplary embodiments, die exit angles within an inclusive range of 20°-30° may produce insulative cellular polypropylene-based material with a tendency to wrinkle during convolution. In other exemplary embodiments, die exit angles within an inclusive range of 10°-20° may produce insulative cellular polypropylene-based material with a tendency to wrinkle during convolution. In other exemplary embodiments, die exit angles within an inclusive range of 0°-10° may produce insulative cellular polypropylene-based material with a tendency to wrinkle during convolution. The lower the angle of die exit, the further from 1 the cell aspect ratio becomes, especially in the direction parallel to the flow of insulative cellular polypropylene-based material. Without wishing to be bound by theory, higher cell aspect ratios may increase local stress concentrations that are experienced during convolution of insulative cellular polypropylene-based material, thus leading to material with a greater tendency to wrinkle during convolution.
TABLE 1
Circumferential Direction and Axial Direction Dimensional
Attributes of Material C and Material D
44°
90°
Cells dimensions
Material
Material
[milli inches]
C
D
Circumferential
Cell length
19.54
17.01
Direction
Cell width
8.53
5.22
Circumferential
2.29
3.26
Direction Cell Aspect
Ratio
Cell Wall Thickness
1.02
0.77
Axial Direction
Cell length
18.45
16.43
Cell width
8.28
5.30
Axial Direction Cell
2.23
3.10
Aspect Ratio
Cell Wall Thickness
0.96
0.84
Example 2: Formulation, Extrusion, and Sheet Formation
High resolution microscopy may be used to determine the dimensional properties of insulative cellular non-aromatic polymeric materials. The Keyence VHX-1000 Digital Microscope and Keyence VHX-2000 Digital Microscope were used to determine the dimensional properties of insulative cellular polypropylene-based material cells from the present disclosure.
Nine specified formulations with dissimilar processing conditions as shown in Table 2 produced cell dimensional properties that were found to follow a power law model with high accuracy and produce material that may possess a tendency to wrinkle during convolution. The following variables were held constant throughout iterations 1-18: 1° extruder temperature, 2° temperature, extruder speed, sheet pull rate, cooling mandrel diameter, cooling mandrel temperature, and overall die temperature as shown in Table 3A. The following variables were altered throughout the aforementioned trial iterations: formula, exit die pressure, die lip angle, die air ring cooling [l/min], and orientation as shown in Table 3A. The following variables were held constant throughout iterations 19-45: 1° extruder temperature, extruder speed, sheet pull rate, cooling mandrel diameter, cooling mandrel temperature, and overall die temperature as shown in Table 3B. The following variables were altered throughout the aforementioned trial iterations: 2° temperature, exit die pressure, die air ring cooling [l/min], CO 2 %, and orientation as shown in Table 3B. Iterations 46-50 were conducted in a manner similar to iterations 1-45 in order to investigate the occurrence of creasing during convolution of insulative cellular polypropylene-based material into a circular article (see, Table 3C).
Axial direction and circumferential direction dimensional attributes of 50 different iterations with nine specified formulations were incorporated in the analysis in order to produce data sufficient for high accuracy and precision, as shown in FIGS. 5-7 . The specific formulation described above for Example 1 as well as eight other formulations were used to illustrate this aspect of the present disclosure as shown in Table 2.
TABLE 2
Formulations and Processing Conditions
CO 2
Chemical
(Lbs/Hr)
Blowing
Additive
Additive
Additive
Additive
[Table
Formula #
1° Resin
2° Resin
Agent
#1
#2
#3
#4
3B]
1
81.5%
15%
None
0.5% Heritage
1%
2%
None
2.2-2.3
Borealis
Braskem
Plastics HT4HP
Colortech
Ampacet ™
WB140
F020HC
Talc
11933-19
102823
HMS
TiO 2 -PP
Process Aid
2
82.5%
15%
None
0.5% Techmer
None
2%
None
2.2-2.3
Borealis
Braskem
PM PPM16466
Ampacet ™
WB140
F020HC
Silica
102823
HMS
Process Aid
3
82.5%
15%
None
0.5% Techmer
None
2%
None
2.2-2.3
Borealis
Braskem
PM PPM16464
Ampacet ™
WB140
F020HC
Silica
102823
HMS
Process Aid
4
82.5%
15%
None
0.5% Heritage
None
2%
None
2.2-2.3
Borealis
Braskem
Plastics HT4HP
Ampacet ™
WB140
F020HC
Talc
102823
HMS
Process Aid
5
81.5%
15%
None
0.5% Heritage
1%
2%
None
2.2-2.3
Borealis
Braskem
Plastics HT4HP
Cell
Ampacet ™
WB140
F020HC
Talc
Stabilizer
102823
HMS
Process Aid
6
81.45%
15%
0.05%
0.5% Heritage
1%
2%
None
2.2-2.4
Borealis
Braskem
Clariant
Plastics HT4HP
Colortech
Ampacet ™
WB140
F020HC
Hydrocerol
Talc
11933-19
102823
HMS
CF-
TiO 2 -PP
Process Aid
40E ™
7
81.45%
15%
0.05%
0.5% Techmer
1%
2%
None
2.2-2.4
Borealis
Braskem
Clariant
PM PPM16466
Colortech
Ampacet ™
WB140
F020HC
Hydrocerol
Silica
11933-19
102823
HMS
CF-
TiO 2 -PP
Process Aid
40E ™
8
79.95%
15%
0.05%
2% Heritage
1%
2%
None
2.8
Borealis
Braskem
Clariant
Plastics HT4HP
Colortech
Ampacet ™
WB140
F020HC
Hydrocerol
Talc
11933-19
102823
HMS
CF-
TiO 2 -PP
Process Aid
40E ™
9
77.95%
15%
0.05%
2% Heritage
1%
2%
2%
2.8
Borealis
Braskem
Clariant
Plastics HT4HP
Colortech
Ampacet ™
Techmer
WB140
F020HC
Hydrocerol
Talc
11933-19
102823
PM
HMS
CF-
TiO 2 -PP
Process Aid
PPM164
40E ™
66 Silica
TABLE 3A
Trial Iterations
Iteration
Formula
#
#
Orientation
Wrinkle
1
8
Axial Direction
No
2
1
Circumferential
Yes
Direction
3
9
Axial Direction
No
4
9
Circumferential
No
Direction
5
6
Axial Direction
Yes
6
6
Circumferential
Yes
Direction
7
6
Axial Direction
No
8
6
Circumferential
No
Direction
9
7
Axial Direction
No
10
7
Circumferential
No
Direction
11
3
Circumferential
Yes
Direction
12
3
Circumferential
Yes
Direction
13
2
Circumferential
Yes
Direction
14
2
Circumferential
Yes
Direction
15
4
Circumferential
Yes
Direction
16
4
Circumferential
Yes
Direction
17
5
Circumferential
Yes
Direction
18
5
Circumferential
Yes
Direction
TABLE 3B
Trial Iterations (continued)
Secondary
Iteration
Formula
Extruder
#
#
Temp
CO2 %
Orientation
Wrinkle
19
1
335
2.2
Axial Direction
No
20
1
335
2.2
Axial Direction
No
21
1
335
2.2
Axial Direction
No
22
1
335
2.2
Axial Direction
No
23
1
335
2.2
Axial Direction
No
24
1
330
2.2
Axial Direction
Yes
25
1
330
2.2
Circumferential
Yes
Direction
26
1
330
2.2
Circumferential
No
Direction
27
1
330
2.2
Axial Direction
No
28
1
330
2.2
Circumferential
No
Direction
29
1
330
2.6
Axial Direction
Yes
30
1
330
2.6
Circumferential
Yes
Direction
31
1
330
2.6
Axial Direction
No
32
1
330
2.6
Circumferential
No
Direction
33
1
350
2.2
Axial Direction
Yes
34
1
350
2.2
Circumferential
Yes
Direction
35
1
350
2.2
Axial Direction
No
36
1
350
2.2
Circumferential
No
Direction
37
1
350
2.2
Circumferential
No
Direction
38
1
350
2.2
Circumferential
No
Direction
39
1
350
2.2
Circumferential
No
Direction
40
1
350
2.2
Axial Direction
Yes
41
1
350
2.2
Axial Direction
Yes
42
1
350
2.6
Axial Direction
Yes
43
1
350
2.6
Circumferential
Yes
Direction
44
1
350
2.2
Axial Direction
No
45
1
350
2.2
Circumferential
No
Direction
TABLE 3C
Trial Iterations (continued)
Iteration
Formula
Orientation
Wrinkle
46
1
Circumferential
No
Direction
47
1
Circumferential
No
Direction
48
1
Circumferential
Yes
Direction
49
1
Axial Direction
Yes
50
1
Circumferential
No
Direction
Example 2: Test Method
The typical testing method used for cell morphology measurement was as follows:
1.) Cut a side wall blank for an insulative cup as shown in FIG. 4 from a strip of insulative cellular polypropylene-based material as suggested by FIG. 3 or at any other orientation. 2.) Make an insulative cup using the side wall blank by the method disclosed in U.S. patent application Ser. No. 13/526,454 filed on Jun. 18, 2004, disclosure of which is hereby incorporated by reference herein in its entirety. 3.) Cut a strip of the side wall of the insulative cup along the axial direction and circumferential direction. 4.) Hold the material with a flat clamp and use a razor blade to perform a fine shave. 5.) Focus the microscope at 100× and adjust lighting onto the material. 6.) Perform length and width measurements of each unique cell in the axial direction and circumferential direction orientation and record values as suggested by FIG. 5 . 7.) Count the number of measured unique cells and record the values as suggested by FIG. 5 . 8.) Perform cell wall thickness measurements across 3-4 tangent lines to overall length of each unique cell in the axial direction and circumferential orientation and record the values as suggested by FIG. 6 . 9.) Perform three overall strip thickness measurements starting from the bottom of the first measured cell group, to the middle of the cell group, to the top of the cell group as suggested by FIG. 7 . 10.) Perform an overall length measurement starting from the lowest complete cell to the highest complete cell as suggested by FIG. 7 . 11.) Move microscope visual field so the bottom of the most upper incomplete cell is touching the bottom of the screen. 12.) Repeat steps 6-11 on each new unique cell until about 0.200″ to 0.800″ of the strip is measured. Ensure that the overall length and cell composition does not overlap. Each overall length measurement after the first measurement is taken from the top of the previous highest complete cell to the top of the current highest complete cell.
A sheet of insulative cellular polypropylene-based material produced as described herein typically possessed a density of about 0.1615 g/cm 3 and material thickness of about 0.066 inches (1.6764 mm).
Example 2: Test Analysis
All cell measurements were performed on over 7500 unique cell units from 50 different samples produced in various ways as described above. Although the maximum window view range of the Keyence digital microscope was 100 mils by 100 mils, careful attention was paid to ensure that each cell was unique and that the overall height and width of the measured strip was an average of values. A total of six (6) different dimensional parameters were measured for iterations 1-18.
In one exemplary embodiment, dimensional parameters of overall strip length (L), overall strip thickness (T), and total numbers of cells in the measured strip area (n) may be classified as bulk properties because they describe an overall cell property. In another exemplary embodiment, dimensional parameters of cell length (l), cell width (w), and cell wall thickness (t) may be classified as cell properties because they describe each cell unit.
A total of five (5) different dimensional parameters were measured for iterations 19-50. In one exemplary embodiment, dimensional parameters of overall strip length (L), overall strip thickness (T), and total numbers of cells in the measured strip area (n) may be classified as bulk properties because they describe an overall cell property. In another exemplary embodiment, dimensional parameters of cell length (l) and cell width (w) may be classified as cell properties because they describe each cell unit.
Each set of dimensional values was separately analyzed to ascertain a correlation between bulk properties and cell properties. Cell density (p) was used to normalize each cell number value because each of the 50 iterations possessed a different number of cells per area (cells/m 2 ) due to different strip geometries. Cell density is calculated as the total number of cells in a given strip (n) divided by the overall strip length (L) and overall strip thickness (T), raised to the 3/2 power, as shown in Equation 1. Cell aspect ratio (A) is calculated as the average cell length (l) divided by the average cell width (w) of given iterations, as shown in Equation 2.
p =( n/TL ) 3/2 Equation 1:
A =( l/w ) Equation 2:
Equation 1 transforms the units from cells per unit area (cells/in 2 ) into cells per unit volume (cells/in 3 ). Through mathematical manipulation of the denominator, the area (m 2 ) is raised to the 3/2 power to transform the dimensional property into volume with correct units (m 3 ). The same correlative effect is applied to the number of cells for consistency. Therefore, cell density is independently measured and calculated from the average bulk properties, as shown in Table 4 and Table 5. Cell properties such as cell length, cell width, and cell wall thickness are also independently measured and the average is calculated, also as shown in Table 4 and Table 5. By comparing independent values, quantitative correlations may be established to predict the occurrence of wrinkling during mechanical convolution of a material based solely on comparison of independent variables.
TABLE 4
Test Analysis Data From Iterations 1-18
Number
of Cells
Strip
Strip
Cell
Cell
Cell
Cell Wall
Cell
in Strip
Length
Thickness
Density
Length
Width
Thickness
Aspect
Iteration #
(cells)
(mils)
(mils)
(cells/in 3 )
(Mils)
(Mils)
(Mils)
Ratio
1
265
654.48
59.05
5.68 × 10 5
14.22
7.33
0.96
1.94
2
101
521.43
84.41
1.10 × 10 5
34.28
10.87
1.83
3.15
3
398
693.10
60.79
9.18 × 10 5
11.94
6.70
0.78
1.78
4
290
635.96
68.79
5.40 × 10 5
19.78
6.56
0.93
3.02
5
500
759.73
70.83
8.96 × 10 5
16.43
5.30
0.84
3.10
6
457
692.33
69.96
9.16 × 10 5
17.01
5.22
0.77
3.26
7
281
752.03
66.41
4.22 × 10 5
18.45
8.28
0.96
2.23
8
276
754.69
69.28
3.84 × 10 5
19.54
8.53
1.02
2.29
9
402
833.86
62.49
6.78 × 10 5
8.09
5.92
0.88
1.37
10
421
833.37
70.72
6.04 × 10 5
9.99
6.17
0.9
1.62
11
39
828.50
50.75
2.82 × 10 4
60.77
14.81
2.40
4.10
12
53
807.00
55.43
4.08 × 10 4
51.27
12.85
2.75
3.99
13
37
931.48
55.28
2.28 × 10 4
68.52
16.36
2.27
4.19
14
29
802.19
58.33
1.54 × 10 4
70.44
20.80
3.12
3.39
15
21
817.08
64.75
7.91 × 10 3
86.75
24.36
3.43
3.56
16
36
830.59
77.76
1.32 × 10 4
65.06
19.97
2.63
3.26
17
31
825.61
64.22
1.41 × 10 4
65.00
22.00
2.99
2.95
18
28
832.65
61.00
1.29 × 10 4
63.30
20.71
3.56
3.06
TABLE 5
Test Analysis Data from Iterations 19-50
Cell
Iteration
Cell
Cell
Cell
Aspect
#
Length
Width
Density
Ratio
19
14.73
5.60
6.007E+05
2.63
20
20.72
7.16
4.407E+05
2.89
21
22.04
5.92
4.791E+05
3.72
22
17.95
5.95
6.545E+05
3.02
23
18.41
6.20
5.602E+05
2.97
24
17.02
5.93
910587
2.87
25
17.48
5.29
971383
3.30
26
13.04
5.92
1230737
2.20
27
13.97
6.34
1260693
2.20
28
13.08
6.6
1420564
1.98
29
18.1
5.45
1099014
3.32
30
20.74
6.53
728556
3.18
31
13.2
6.45
1167341
2.05
32
11.72
5.87
1851158
2.00
33
16.08
5.48
1179837
2.93
34
25.03
6.35
683270
3.94
35
14.02
6.05
1215786
2.32
36
11.54
5.94
1544317
1.94
37
10.59
5.46
1630729
1.94
38
10.71
5.52
1650454
1.94
39
10.78
6.1
1713915
1.77
40
16.14
5.43
1061618
2.97
41
19
5
911612
3.80
42
17.07
5.26
1159422
3.25
43
20.36
5.61
933041
3.63
44
14.81
6.51
1006006
2.27
45
12.57
6.05
1405602
2.08
46
12.99
6.38
1345104
2.04
47
13.5
6.03
1355593
2.24
48
21.82
6.69
751112.4
3.26
49
15.74
5.24
1005240
3.00
50
11.07
5.31
1962021
2.08
Example 2: Test Results
By correlating cell density bulk property to cell length, cell width, and cell wall thickness cell properties, a strong correlation was found that may predict dimensional properties with respect to cell density, and subsequently cell area. The coefficient of determination (R 2 ) values produced by Microsoft Excel 2010 power law regression fit demonstrates a high degree of accuracy with regard to the validity of the fitted power law-based model. The power law has an equation form of two dependent variables, x and y, and two independent variables or constants, A and K, as shown in Equation 3 and Equation 4:
y=Ax K Equation 3:
x =( y/A ) l/K Equation 4:
In exemplary embodiments, cell density may predict cell length, cell width, and cell wall thickness with R 2 values of 0.945, 0.939, and 0.973 as shown in FIG. 18 , FIG. 19 and FIG. 16 , respectively. The closer the R 2 value is to 1, the more accurate the model fit. It is generally accepted that a regression fit value greater than 0.85 demonstrates a strong quantitative correlation between two independent variables, which, in this case, are represented by bulk properties and cell properties.
In exemplary embodiments, the equation for predicting cell length with respect to cell density may be y=1,243,388,528.483x −2.626 , wherein the power law constants for predicting cell length with respect to cell density are A=1,243,388,528.483 and K=−2.626. In other exemplary embodiments, the equation for predicting cell width with respect to cell density may be y=426,736,129.761x −3417 wherein the power law constants for predicting cell width with respect to cell density are A=426,736,129.761 and K=−3.417. In other exemplary embodiments, the equation for predicting cell wall thickness with respect to cell density may be y=448,002.648x −3653 wherein the power law constants for predicting cell wall thickness with respect to cell density are A=448,002.648 and K=−3.053.
The data also illustrate a satisfactory range where insulative cellular polypropylene-based material possesses wrinkles, as defined by Wrinkles and Minimal Wrinkles, where Wrinkles means the cup possesses wrinkles and/or creases and Minimal Wrinkles means wrinkles and/or creases are not present. As shown in FIG. 20 and FIG. 21 , the data may be organized in both the circumferential direction and axial direction. From interpretation of the data in FIG. 20 , it may be seen that the aspect ratio of cells that run parallel to the circumference (i.e., in the circumferential direction) may not only play an important role in determining a tendency to wrinkle during convolution, but a more important role than that of either cell density or the aspect ratio of cells running perpendicular to the circumference (i.e., in the axial direction, as shown in FIG. 21 ).
In exemplary embodiments as suggested by FIG. 20 , insulative cellular polypropylene-based material that possesses a cell aspect ratio of less than about 2.75 in the circumferential direction of an article, such as an insulative cup, may not wrinkle when convoluted into the article. Illustratively, insulative cellular polypropylene-based material that possesses a cell aspect ratio of 2.5 or less in the circumferential direction of an article, such as an insulative cup, may not wrinkle when convoluted into the article. In other exemplary embodiments as suggested by FIG. 21 , insulative cellular polypropylene-based material that possesses a cell aspect ratio of less than about 2.75 in the axial direction of an article, such as an insulative cup, may not wrinkle when convoluted into the article. Illustratively, insulative cellular polypropylene-based material that possesses a cell aspect ratio of 2.5 or less in the axial direction of an article, such as an insulative cup, may not wrinkle when convoluted into the article. In other exemplary embodiments as suggested by FIG. 21 , insulative cellular polypropylene-based material that possesses a cell aspect ratio of about 2.75 to about 4.00 in the axial direction of an article, such as an insulative cup, and a cell density of about 300,000 cells/in 3 to about 900,000 cells/in 3 may not wrinkle when convoluted into the article. In other exemplary embodiments as suggested by FIG. 20 , insulative cellular polypropylene-based material that possesses a cell aspect ratio of about 2.75 to about 3.5 in the circumferential direction of an article, such as an insulative cup, and a cell density of about 300,000 cells/in 3 to about 700,000 cells/in 3 may not wrinkle when convoluted into the article.
The cell prediction model accurately describes cell growth in the cell width, cell length, and cell wall thickness category and possesses power law functionality, similarly to that seen in many natural phenomena. By taking on a log-log plot form, the correlation is unexpectedly a straight line that penetrates near or through all data points with accuracy. This development provides further evidence for power law correlation and subsequently the ability to model and predict cell growth, as shown in FIGS. 12-17 .
As presaged by the cell morphology versus micro-creasing/macro-creasing results shown in FIGS. 12-15 , and as summarily illustrated in FIG. 20 and FIG. 21 , the present disclosure permits the identification of a control range with respect to cell aspect ratio and cell density, which range permits the manufacture of insulative cups that wrinkle and/or crease. FIG. 20 illustrates cell densities in a (cup) convolution process as a function of cell aspect ratio in the circumferential direction, whereas FIG. 21 illustrates cell densities in a (cup) convolution process as a function of cell aspect ratio in the axial direction. In FIG. 20 and FIG. 21 , cell densities that have Minimal Wrinkles are not tolerated because of the lack of wrinkling and/or creasing during cup convolution. Conversely, cell densities in FIG. 20 and FIG. 21 that are associated with wrinkling and/or creasing during cup convolution, i.e., that Wrinkles, result in micro-creasing and/or macro-creasing, where micro-creasing and/or macro-creasing are defined as follows:
Micro-Creasing defines small creases inside the cup found in the middle, top, and especially bottom areas; they are generally ¼″ to ½″ in length and near invisible to the eye unless you look for them.
Macro-Creasing defines large creases inside the cup that run all the way from the bottom to top or tangent to the cup; they are generally cup-length and very visible to the eye. | A formulation of material includes a polymeric material, a nucleating agent, and a surface active agent. The formulation of material may be polymeric materials that relate morphology and crystalline structure of cellular polymeric material that may be used to form usable articles, such as an insulated container useful for containing food or liquid. | 2 |
BACKGROUND OF THE INVENTION
This invention relates generally to a spring as used in a door hinge to bias the door to a closed position as well as to securely maintain the door in one or more open positions, and is particularly directed to a vehicle door hinge such as used in automobiles and trucks.
A door hinge used in a vehicle such as an automobile or a truck generally includes a resilient spring element for controlling the position of the door. For example, the spring typically biases the door to the closed position when the door is only slightly open. In addition, the spring ensures that the door remains in one or more open positions to prevent the door from closing upon a vehicle operator or passenger upon entering or exiting the vehicle. Generally, the spring maintains the door in a stable manner in the full open position as well as in an intermediate position between the full open and closed positions. The resilient spring typically engages a portion of the hinge attached to the door for urging the door to a given position or securely maintaining the door in a desired orientation. The force exerted by the spring upon the door can be overcome by the application of sufficient force upon the door by one entering or exiting the vehicle.
Referring to FIG. 1, there is shown a perspective view of a vehicle, in this case a pickup truck, 22 incorporating a door hinge 20 in which the spring of the present invention is intended for use. The door hinge 20 pivotally couples a door 24 of the vehicle to the vehicle's frame 26. The hinge 20 allows the door 24 to be pivotally displaced about a generally vertical axis as the door is opened and closed.
Referring to FIGS. 2 and 3, there are shown two views of a door hinge 20 incorporating a prior art spring 32. The prior art spring 32 is also shown in FIG. 4. The door hinge 20 is comprised of a first hinge member 28 pivotally coupled to a second hinge member 30 by means of a pivot pin 46. The first hinge member 28 includes a plurality of apertures (not shown) therein through which first and second mounting bolts 34 and 36 are inserted for attaching the first hinge member to a vehicle frame member 26a. Each of the mounting bolts 34, 36 engages a respective threaded nut 34a, 36a attached to an inner surface of the frame member 26a. A third nut and inverted sems bolt with captive washer combination 37 is also typically provided for securely mounting the first hinge member 28 to the vehicle frame 26a. The second hinge member 30 is comprised of upper and lower portions which are coupled together by means of an intermediate hinge portion 30b. Each of the upper and lower portions of the second hinge member 30 includes one or more apertures 30a through which a mounting bolt (not shown) may be inserted for securely attaching the second hinge member to a vehicle door (also not shown for simplicity).
The upper and lower ends of the pivot pin 46 coupling the first and second hinge members 28 and 30 are each configured to engage a respective portion of the second hinge member to prevent the removal of the pivot pin from the door hinge 20. This may be accomplished by any one of a number of processes such as crimping, notching, or otherwise deforming the ends of the pivot pin 46 so as to prevent its removal from the hinge. Positioned in a spaced manner along the length of the pivot pin 46 and adjacent to respective ends thereof are upper and lower bushings 47, 48. The upper and lower bushings 47, 48 are inserted through respective apertures in the first hinge member 28 and facilitate rotation of the pivot pin 46 and the second hinge member 30 with respect to the first hinge member.
A generally S-shaped spring 32 includes a first semicircular end 32a, a linear, elongated intermediate section 32b, and a double 90° bent second end 32c. The intermediate section 32b of the spring 32 is positioned within aligned notches 28a and 28b in upper and lower portions of the first hinge member 28 on a first side thereof. The distal portion of the first end 32a of the spring 32 is provided with a recess 32d for engaging a notch 28c in an upper portion of the first hinge member 28 on a second side thereof. Similarly, the distal portion of the second end 32c of spring 32 is adapted for positioning within another notch 28d in a lower portion of the first hinge member 28 on the second side thereof. Thus, the respective ends of the spring 32 are positioned within notches 28c and 28d on one side of the first hinge member 28, while the intermediate section 32b of the spring is positioned within aligned notches 28 a and 28b on the other facing side of the first hinge member. The configuration and dimensions of the spring 32 are such that the spring is maintained under tension due to torsion applied to the intermediate section 32b of the spring along the length thereof. Thus, the spring 32 must be distorted in order to mount it upon the first hinge member 28 and it is this spring distortion which maintains the spring securely in position thereon. Because of the high strength of the spring 32 used in most vehicle door hinges, a special tool is required for mounting the spring in the hinge 20.
First and second notched, or segmented, striker rollers 38 and 40 are respectively positioned upon first and second mounting pins 42 and 44 which, in turn, are mounted to and extend from a lower portion of the second hinge member 30. Positioned between the end of each of the first and second mounting pins 42, 44 and the first and second notched rollers 38, 40 is a respective corrugated washer for maintaining a notched roller in position upon a mounting pin and providing resistance to its free rotation thereon. As the vehicle door (not shown), and thus the second hinge member 30, is rotationally displaced relative to the first hinge member 28 from the closed to the full open position, the second notch roller 40 first engages the second end 32c of the spring 32 and displaces this portion of the spring. Continued opening of the door results in the second spring end 32c being positioned generally between the first and second notched rollers 38, 40 which then function to securely maintain the vehicle door in an intermediate open position. Continued outward displacement of the door causes the first notched roller 38 to engage the second spring end 32c and to deflect this portion of the spring. Further displacement of the second hinge member 30 and door combination allows the second spring end 32c to assume its original position whereupon the vehicle door is biased to the full open position. The door may be closed by reverse rotational displacement of the second hinge member 30 relative to the first hinge member 28 and the successive engagement of the first and second notched rollers 38, 40 with the second spring end 32c. As the second spring end 32c is engaged and deflected by a respective notched roller, a torque is applied to the spring 32 about the longitudinal axis of its intermediate section 32b and the spring is thus subjected to a torsional force. When the spring 32 is repeatedly subjected to this torsional force over an extended period of time, it tends to break due to structural fatigue. The prior art spring 32 generally breaks in the area of the 90° bend junctures in its second end 32c after extended use.
Installation of the spring 32 requires the application of a large force thereto in order to configure it to fit the first hinge member 28 as previously described. This requires a specially designed machine or a unique tool when installation is performed by a worker. In addition, in order to ensure safety of the worker during spring installation a shield is generally positioned between the worker and the hinge. Because of the need for a special tool or machine to apply the required force to the spring and the danger involved in such an operation, failure of the spring requires replacement of the entire hinge assembly. This is an expensive repair for the vehicle owner not only because of the cost of the hinge assembly itself, but also because this removal and installation procedure requires approximately 11/2 man-hours.
The present invention avoids the aforementioned limitations of the prior art by providing a door hinge spring which is easily and safely installed and does not require complete hinge replacement upon spring failure. The door hinge spring of the present invention also affords longer operating lifetime by reducing the torsional force per unit length applied to the spring during opening and closing of the door. The biasing force applied by the spring upon the door may also be varied in several embodiments of the inventive spring in order to establish the magnitude of the force required to move the door at a desired value.
OBJECTS OF THE INVENTION
Accordingly, it is an object of the present invention to provide an improved spring for use in a door hinge.
It is another object of the present invention to provide a hinge spring particularly adapted for use in a vehicle which is capable of biasing the door of the vehicle to a closed position as well as maintaining the door in a stable manner in one or more open positions.
Yet another object of the present invention is to provide a door hinge spring which affords improved spring resilience while reducing the torsion per unit length applied to the spring during displacement of a door mounted to and supported by the hinge.
A further object of the present invention is to facilitate and make safer the installation of a resilient spring in a door hinge such as used in a vehicle.
A still further object of the present invention is to provide a door hinge spring such as used in an automobile or a truck which can be easily mounted to existing hinge hardware without modification to the hinge or additional hardware in an arrangement which provides improved door control and longer spring operating life.
Another object of the present invention is to provide an arrangement for a door hinge spring in which spring tension and thus the force applied by the spring to maintain the door securely in one or more open positions may be adjusted as desired over a wide range of values.
Still another object of the present invention is to provide an installation arrangement for a door hinge spring wherein the torque applied to a spring mounting bolt establishes the force applied by the spring to the hinge in maintaining the door securely in one or more open positions as well as in biasing the door to the closed position.
A still further object of the present invention is to provide an inexpensive spring for use in a vehicle door hinge which is easily and safely installed in existing hinge arrangements yet offers substantial advantages over currently available door hinge springs.
BRIEF DESCRIPTION OF THE DRAWINGS
The appended claims set forth those novel features which characterize the invention. However, the invention itself, as well as further objects and advantages thereof, will best be understood by reference to the following detailed description of a preferred embodiment taken in conjunction with the accompanying drawings, where like reference characters identify like elements throughout the various figures, in which:
FIG. 1 is a perspective view of a pickup truck illustrating the location of a door hinge in which the spring of the present invention is intended for use;
FIG. 2 is a planar view shown partially in phantom of a door hinge incorporating a prior art spring;
FIG. 3 is a sectional view of the door hinge of FIG. 2 taken along sight line 3--3 therein;
FIG. 4 is a side view of the prior art spring used in the door hinge of FIG. 2;
FIG. 5 is a planar view of a door hinge incorporating a spring in accordance with the present invention;
FIG. 6 is a sectional view of the door hinge of FIG. 5 taken along sight line 6--6 therein;
FIG. 7 is a lateral view shown partially in phantom of a door hinge spring in accordance with one embodiment of the present invention;
FIGS. 8 and 9 illustrate two views of the mirror image of the door hinge spring illustrated in FIGS. 5, 6 and 7, wherein one spring configuration is used on one side of the vehicle and the other spring configuration is used on the other, facing side of the vehicle;
FIGS. 10-13 are bottom planar views of the hinge illustrated in FIG. 5 showing the displacement and relative orientation of various hinge components as the door is opened;
FIGS. 14 and 15 illustrate two views of another embodiment of a door hinge spring in accordance with the present invention;
FIGS. 16 and 17 illustrate two views of still another embodiment of a door hinge spring in accordance with the present invention which makes use of spring tension varying means;
FIG. 18 illustrates still another embodiment of a door hinge spring in accordance with the present invention;
FIGS. 19a and 19b illustrate two different shapes for the coiled portion of the spring of FIG. 18 as well as the direction of displacement of adjacent coiled spring portions upon application of a torsional force thereto;
FIG. 20 illustrates a hook-shaped door hinge spring and a mounting arrangement therefore which makes use of spring tension varying means in accordance with the present invention;
FIG. 21 is a front planar view shown partially in phantom of a mounting arrangement for a door hinge spring in accordance with the present invention;
FIG. 22 is a sectional view of the door hinge spring installation arrangement of FIG. 21 taken along sight line 22--22 therein; and
FIG. 23 illustrates a resilient mounting arrangement for coupling the various embodiments of the spring of the present invention to a door hinge.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 5, there is shown a door hinge 52 incorporating a spring 50 in accordance with the principles of the present invention. The hinge 52 illustrated in FIG. 5 is identical in configuration to the hinge 20 illustrated in FIG. 2, with common identification numbers assigned to the same elements in these figures. A sectional view taken along sight line 6--6 in FIG. 5 of the door hinge 52 illustrated therein is shown in FIG. 6, while FIG. 7 is a lateral end-on view of the spring used in the door hinge of FIGS. 5 and 6.
As in the case of the door hinge illustrated in FIG. 2, the door hinge 52 illustrated in FIGS. 5 and 6 includes first and second hinge members 28 and 30 coupled by means of a pivot pin 46. The first hinge member 28 is adapted for secure mounting to a portion of a vehicle door frame 26b by means of first and second mounting bolts 34 and 36. The second hinge member 30 is similarly adapted for secure mounting to a lateral edge of a door (not shown) by means of mounting bolts (also not shown) inserted through respective apertures 30a in the upper and lower portions of the second hinge member. Respective ends of the pivot pin 46 are provided with an upper and a lower bushings 47 and 48 to facilitate rotational displacement of the pivot pin as well as the second hinge member 30 relative to the first hinge member 28.
The spring 50 includes a first circular end 50a, a coiled intermediate section 50b and a U-shaped second end 50c. First and second mounting bolts 34, 36 in combination with respective washers, are inserted through respective apertures in the first hinge member 28 and the vehicle frame 26b and threadably engage first and second threaded nuts 34a and 36a which are securely mounted to the facing surface of the vehicle frame. In this manner, the hinge 52 may be securely mounted to the vehicle frame 26b. The first mounting bolt 34 is also inserted through the first circular end 50a of the spring 50 for attaching the spring to the first hinge member 28. As shown in FIG. 5, the portion of the spring 50 between its coiled intermediate section 50b and its second U-shaped end 50c is positioned within a first slot 28b in a lower angle of the first hinge member 28. The distal end of the U-shaped second end 50c of the spring 50 is similarly positioned within a second slot 28d in the first hinge member 28. Slots 28b and 28d are on facing surfaces of the first hinge member 28. With the first mounting bolt 34 inserted through the circular first end 50a of the spring 50, the first end of the spring may be drawn tightly up against and in contact with the first hinge member 28 causing the spring 50 to be rotationally displaced about the axis X-X illustrated in FIG. 5. This causes the distal portion of the second U-shaped end 50c of the spring to securely engage the second slot 28d in the first hinge member 28. Torsion is not applied to the spring 50 until the first mounting bolt 34 is tightened. A flat washer ensures secure engagement between the circular first end 50a of the spring 50 and the head of a mounting bolt 34.
First and second notched or segmented striker rollers 38 and 40 are rotationally positioned upon respective first and second mounting pins 42 and 44 which are mounted to and extend downward from the second hinge member 30. As previously described, a corrugated washer is positioned between each of the notched rollers and a respective end of its associated mounting pin to securely maintain the roller on the mounting pin and to inhibit roller rotation for more securely maintaining a door attached to the second hinge member 30 in one or more open positions.
Referring to FIGS. 10-13, the operation of the door hinge spring 50 in biasing a door to the closed position as well as securely maintaining the door in one or more open positions will now be described. FIG. 10 illustrates the relative positions of the first and second hinge members 28, 30 as well as that of a door 35 securely bolted to the second hinge member, with the door in the closed position. With the door closed, neither of the first or second notched rollers 38, 40 engages the spring 50. As the door 35 is opened and the second hinge member 30 is pivotally displaced about the pivot pin 46 relative to the first hinge member 28, the second segmented roller 40 initially engages and deflects the distal portion of the second U-shaped end 50c of the spring 50 as shown in FIG. 11. This causes a torsion to be applied to the spring 50 not only about that portion of the spring disposed along the axis X--X, but this torsion is also applied to the coiled intermediate portion 50b of the spring forcing adjacent coiled portions of the spring apart. Continued opening of the door 35 results in positioning of the distal portion of the second U-shaped end 50c of the spring 50 between the first and second notched rollers 38, 40 as shown in FIG. 12. With the door hinge spring 50 thus positioned, the first and second notched rollers 38, 40 securely maintain the door 35 in an open position intermediate the closed and full open positions.
Continued opening of the door 35 results in engagement of the first notched roller 38 with the distal end portion of the second U-shaped end 50c of the spring 50 causing deflection of this portion of the spring and the application of a torsional force along the linear and coiled sections of the intermediate portion 50b of the spring. After the first notched roller 38 has been displaced over the distal portion of the second U-shaped end 50c of the spring 50 and the spring is allowed to resume its original and natural configuration, spring tension maintains the door 35 securely in the full open position as shown in FIG. 13. A key aspect of the present invention is an increase in the length of the spring 50 provided by its coiled intermediate portion 50b which distributes the torsional force applied to the spring over a greater effective spring length and reduces the stress per unit length applied to the door hinge spring. This reduction in per unit length stress on the door hinge spring 50 increases the operating life of the spring.
Another primary advantage of the door hinge spring 50 of the present invention is the manner in which it is mounted to the hinge 52. The distal end portion of the second U-shaped end 50c of the spring is first positioned in the second slot 28d, followed by positioning of the linear intermediate portion of the spring in the first slot 28b. The aperture in the circular first end 50a of the spring 50 is then aligned with a corresponding mounting aperture (not shown) in the first hinge member 28 and the first mounting bolt 34 is then inserted in this aperture for threaded engagement with threaded nut 34a. A washer positioned over the circular first end 50a of the spring 50 ensures that the head of the first mounting bolt 34 does not pass through the aperture in the spring's first end. This mounting procedure for the door hinge spring 50 allows the spring to be initially positioned in the hinge in a torsion-free state and for torsion to be gradually applied to the spring as the first mounting bolt 34 is tightened. Thus, once the door hinge spring 50 is secured to the first hinge member 28 by means of the first mounting bolt 34, the spring is not free to become separated from the hinge regardless of the torsional force applied to the spring as the first mounting bolt is tightened. This prevents the spring from injuring a worker installing the spring and requires only the tightening of a single bolt for spring installation. Thus, mounting and installation of the door hinge spring 50 of the present invention avoids the danger of prior art spring mounting and installation wherein improper securing of the spring under tension to the hinge frequently resulted in sudden release of spring tension and injury to the spring installer.
Referring to FIGS. 8 and 9, there is shown a door hinge spring 56 which is the mirror image of the door hinge spring 50 illustrated in FIGS. 5, 6 and 7. These mirror image springs are intended for use on opposite sides of the vehicle to accommodate reverse, or reciprocal, hinge installations. As in the case of the door hinge spring previously described, the door hinge spring 56 illustrated in FIGS. 8 and 9 includes a first generally circular end 56a, a coiled intermediate portion 56b, and a second U-shaped end 56c.
Referring to FIGS. 14 and 15, there is shown another embodiment of a door hinge spring 66 in accordance with the principles of the present invention. In the embodiment illustrated in FIGS. 14 and 15, the spring 66 also includes a first generally circular end 66a, a coiled intermediate portion 66b, and a generally U-shaped second end 66c. The circular first end 66a of the spring 66 is adapted to receive the second mounting bolt 36 illustrated in FIGS. 5 and 6 for mounting of the spring to the first hinge member 28 illustrated in these figures. Thus, the door hinge spring embodiments of FIGS. 5 through 7 and 14 and 15 allow for mounting of the door hinge spring to the first hinge member using either the first or second mounting bolts 34, 36 previously described. It should be noted that the hinge spring arrangement illustrated in FIGS. 14 and 15 requires the use of a stronger mounting bolt than that required for the spring of FIGS. 5-7. The second mounting bolt 36 used in mounting the door hinge spring 66 illustrated in FIGS. 14 and 15 is more likely to break than the first mounting bolt 34 used in the mounting of the spring embodiment illustrated in FIGS. 5 through 7 apparently because in the former arrangement the secured ends of the spring are disposed on the same side of the axis X--X of the linear intermediate portion of the spring. The symmetrical engagement about the torsion axis X--X of the first circular end 50a and the second U-shaped end 50c of the door hinge spring 50 results in the application of less force on the first mounting bolt 34 than that applied to the second mounting bolt in the spring arrangement of FIGS. 14 and 15.
Referring to FIGS. 16 and 17, there are shown two views of yet another embodiment of a door hinge spring 60 in accordance with the present invention. The door hinge spring 60 includes a first circular end 60a with an aperture therein, an angled intermediate portion 60b, and a second generally U-shaped end 60c. The intermediate angled portion 60b of the spring provides an offset, or riser, to accommodate the 90° angle formed in the lower edge of the first hinge member 28. The circular first end 60a of the door hinge spring 60 is adapted to receive the first mounting bolt 35, described above, for attaching the door hinge spring to the first hinge member 28. One or more cone spring washers 64 may be positioned on the first circular end 60a of the door hinge spring 60 in a stacked manner to provide additional resiliency for the spring. Various numbers of spring washers 64 may be disposed between the head of mounting bolt 35 and the first circular end 60a of the spring 60 to provide the desired resiliency in the mounting of the door hinge spring. Adjacent pairs of cone spring washers 64 may be positioned on the mounting bolt 35 in reverse orientation wherein the respective concave or convex surfaces are in facing relation in order to further increase the tension applied to the door hinge spring 60 in the manner in which it is mounted. It is this tension which is applied to the spring 60 which determines its resilience upon impact with the movable member of the hinge in which it is used. Finally, where the intermediate portion 60b of the door hinge spring 60 does not include a riser, but rather is in a straight or linear configuration, a spacer bushing 63 may be positioned between the circular end 60a of the spring and the hinge assembly in order to accommodate the 90° edge angle formed in the first hinge member.
Referring to FIG. 18, there is shown another embodiment of a door hinge spring 70 in accordance with the principles of the present invention. The door hinge spring 70 includes a first circular end 70a with an eyelet therein as well as a generally U-shaped second end 70b. Disposed along the length of the door hinge spring 70 between the respective ends thereof is a coiled intermediate portion 70c which is oriented generally transversely relative to the first and second ends of the spring. When a force is applied to the U-shaped end 70b of the spring in the direction indicated by the arrow in FIG. 18, the coils at a contact point in the intermediate portion 70c of the spring are forced apart under the load to utilize the full capability of the spring's resilience as shown by the direction of the arrows in FIG. 19a. The coiled portions of the door hinge spring 70 would typically be forced apart under a load when opening the vehicle door. By forcing the adjacent coil portions of the door hinge spring 70 apart upon the application of a force to one end thereof, the effective length of the spring with respect to the applied torque is increased so as to more evenly distribute the applied torque over the spring's entire length and provide the spring with increased effective resiliency.
Referring to FIG. 19b, there is shown another embodiment of a door hinge spring 70' similar to that illustrated in FIGS. 18 and 19a wherein the spring includes an intermediate portion 74 having a double 45° bend therein. The double 45° bend in the intermediate section 74 of the spring 70' provides a riser or offset to facilitate proper installation on a door hinge. In the case of the door hinge spring 70' illustrated in FIG. 19b, a force applied to the distal portion of the U-shaped end 70b' will apply pressure to intermediate spring portion 74 in the direction of the arrows forcing adjacent coiled spring portions together. The door hinge spring 70 illustrated in FIGS. 18 and 19a also incorporates an offset provided by an approximately 60° bend in the juncture between the spring's first circular end 70a and its coiled intermediate portion 70c. The eyelets included in the respective first circular end portions 70a of the springs 70 and 70' illustrated in FIGS. 19a and 19b are adapted to receive a mounting bolt (not shown) for securely mounting the door hinge spring to a hinge member as previously described.
Referring to FIG. 20, there is shown another embodiment of a door hinge spring 80 in accordance with the present invention. The door hinge spring 80 is generally J-shaped and includes a circular first end 80a with an eyelet or aperture therein, an elongated, linear intermediate section 80b, and a generally U-shaped second end 80c. In this embodiment, an L-shaped bracket 84 is securely mounted to the first hinge member (not shown) by means of a first mounting bolt 86. A second mounting bolt 82 is inserted through a second aperture in the L-shaped bracket 84 and is further inserted through the eyelet in the spring's first circular end 80a. A compression spring 90 in combination with a pair of flat washers 87 and 88 each positioned in contact with a respective end thereof are positioned on the second mounting bolt 82. The combination of compression spring 90 and flat washers 87 and 88 is maintained in position on the second mounting bolt 82 by means of a self-locking nut 83. The torque applied to the self-locking nut 83 establishes the compression exerted on the first circular end 80a of the spring 80. In this manner, the resiliency of the spring installation as well as the force applied to the vehicle door in maintaining it in one or more open positions may be fixed as desired in accordance with the torque applied to the self-locking nut 83 in mounting the spring to the hinge. When installed in a hinge, the distal portion of the second U-shaped end 80c of the spring 80 is contacted and displaced by the notched rollers in the vehicle door hinge.
Referring to FIG. 21, there is shown yet another resilient mounting arrangement for a J-shaped door hinge spring 94 having a first circular end 94a, an elongated, linear intermediate section 94b, and a second U-shaped end 94c. FIG. 22 is a sectional view of the door hinge spring mounting arrangement of FIG. 21 taken along sight line 22--22 therein.
A dowel pin 98 is firmly affixed to a flat spring 98, with one end of the dowel pin positioned in contact with the hinge 104. The first circular end 94a of the spring 94 is positioned over the dowel pin 98. The outer diameter of the dowel pin 98 is less than the inside diameter of the first circular end 94a of the spring 94 and provides free torsional flexibility for the spring yet securely engages and maintains the door hinge spring in its proper position and orientation during displacement of the vehicle door. The resilient flat spring 96 is positioned adjacent to the first circular end 94a of the door hinge spring 94 for maintaining it in position upon the dowel pin 98. The flat spring 96 is, in turn, maintained in position upon and is coupled to the door hinge 104 by means of a pair of spaced shoulder bolts 100 and 102 respectively inserted through elongated slots 96a and 96b in the flat spring. Each of the shoulder bolts 100 and 102 is inserted within and threadably engages a respective threaded nut 106, 108 which are welded to the hinge 104. The shoulder bolts 100 and 102 are then tightened with a torque appropriate for the respective grade and size of the flat spring 96. The non-threaded, or shoulder, portion of the shoulder bolts 101, 102 may be provided in various incremental lengths to facilitate matching the tension to which these bolts are tightened with the grade and size of the flat spring 96. Thus, with the shoulder bolts tightened to a standard torque value, a longer shoulder portion of the bolt may be used with a stronger, more rigid flat spring while the length of the shoulder portion of the bolt may be shortened for more resilient flat springs in order to provide a standard spring mounting tension value. The force exerted on the first circular end 94a by the flat spring 96 provides the door hinge spring 94 with a resilient tension at the point where it is contacted by the segmented rollers of the hinge, i.e., adjacent to the distal portion of the U-shaped second end 80c of the spring. It is this portion of the J-shaped door hinge spring 94 which is engaged and deflected by the notched rollers in the vehicle door hinge. The elongated slots 96a and 96b in the flat spring provide free linear expansion and contraction of the flat spring when opening and closing the vehicle door and afford additional resiliency for the J-shaped door hinge spring 94. An inverted sems bolt typically is used to mount the hinge 104 to a support frame such as that of a vehicle as described earlier, although this is not shown in FIGS. 21 and 22 for simplicity.
Referring to FIG. 23, there is shown a resilient mounting arrangement adapted for use in the mounting of any of the above described embodiments of the spring of the present invention to a door hinge. The mounting arrangement of FIG. 23 includes a cap screw 109 inserted through an eyelet portion of any of the above described door hinge springs of the present invention for engaging a hinge-mounted threaded nut in mounting the spring to the hinge. Positioned along the length of the cap screw 109 and disposed between the screw head and the door hinge spring which it mounts to a hinge is the combination of two flat washers 110 and a resilient bushing 111 disposed therebetween. The resilient bushing 111 is comprised of a compressible material which provides another means for controlling the tension on the spring in its mounting to a door hinge. The two flat washers 110 separate the resilient bushing 111 from the cap screw head as well as from the eyelet portion of the door hinge spring and protect the compressible material of the resilient bushing from damage by spring movement. The compressibility of the resilient bushing 111 as well as the torque at which the cap screw 109 is tightened may be selected to provide a desired mounting tension for the door hinge spring.
There has thus been shown a door hinge torsion spring which allows the force applied to an open door mounted to the hinge to be varied as desired in maintaining the door in one or more fixed open positions. A resilient mounting arrangement is used for applying a force to the spring which can be varied over a wide range of values for increasing or decreasing the resiliency of the spring installation. In one embodiment in which spring mounting tension is not varied, an intermediate portion of the spring is provided with various shapes in order to increase the effective length of the spring and reduce the torsional force per unit length applied to the spring when the door is opened. By thus spreading the torsional force applied to the spring over a greater portion of its length and increasing the effective length of the spring, door hinge spring operating lifetime is increased. The various door hinge spring arrangements of the present invention are easily and safely installed using a single mounting bolt in most cases.
FIG. 24 no. 112 cross section of a J spring assembly attached to the vehicle hinge by capscrew no. 113.
The elastomer or resilient material no. 115 provides a torsional means for the spring. This material is bonded to the top end of the J spring as well as the metal, attaching component member no. 114. This can be square or hex to resist the torsional force.
FIG. 25 top view as follows:
No. 112 J spring
No. 113 Capscrew
No. 114 Metal attaching means
No. 115 Elastomer or resilient material
While particular embodiments of the present invention have been shown and described, it will be obvious to those skilled in the art that changes and modifications may be made without departing from the invention in its broader aspects. Therefore, the aim in the appended claims is to cover all such changes and modifications as fall within the true spirit and scope of the invention. The matter set forth in the foregoing description and accompanying drawings is offered by way of illustration only and not as a limitation. The actual scope of the invention is intended to be defined in the following claims when viewed in their proper perspective based on the prior art. | A door hinge torsion spring fixedly mounted at a first end thereof to one hinge member is engaged and deflected at a second end thereof by a second hinge member when the two hinge members are pivotally displaced relative to one another. An intermediate section of the spring is configured in the form of a coil for increasing the length of the spring and reducing the torque applied to the spring per unit length without increasing the mounting space required for the spring, while allowing the spring to be mounted to and operate with existing hinge configurations. The door hinge spring is particularly adapted for use in the door hinge of a vehicle such as a truck, wherein the second hinge member is provided with a pair of spaced, notched rollers for successively engaging the second end of the spring as the door is opened to either bias the door to the closed position or securely maintain the door in either a fully open position or in an intermediate position between full open and closed. The spring is comprised of a strong, resilient material such as steel and is configured for mounting to the hinge using existing hardware. Alternative embodiments make use of cone spring washers or a compression spring in mounting the door hinge spring to increase its resiliency. | 8 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser. No. 13/578,340, filed Oct. 24, 2012, which is the U.S. National Phase entry under 35 U.S.C. §371 of International Application No. PCT/GB2011/000200, filed Feb. 14, 2011, designating the United States and published in English on Aug. 25, 2011, as WO2011/101620, which claims priority to United Kingdom Application No. 1002616.9, filed Feb. 16, 2010, each of which is incorporated by reference in its entirety.
FIELD
[0002] The invention relates to heat transfer compositions, and in particular to heat transfer compositions which may be suitable as replacements for existing refrigerants such as R-134a, R-152a, R-1234yf, R-22, R-410A, R-407A, R-407B, R-407C, R507 and R-404a.
BACKGROUND
[0003] The listing or discussion of a prior-published document or any background in the specification should not necessarily be taken as an acknowledgement that a document or background is part of the state of the art or is common general knowledge.
[0004] Mechanical refrigeration systems and related heat transfer devices such as heat pumps and air-conditioning systems are well known. In such systems, a refrigerant liquid evaporates at low pressure taking heat from the surrounding zone. The resulting vapour is then compressed and passed to a condenser where it condenses and gives off heat to a second zone, the condensate being returned through an expansion valve to the evaporator, so completing the cycle. Mechanical energy required for compressing the vapour and pumping the liquid is provided by, for example, an electric motor or an internal combustion engine.
[0005] In addition to having a suitable boiling point and a high latent heat of vaporisation, the properties preferred in a refrigerant include low toxicity, non-flammability, non-corrosivity, high stability and freedom from objectionable odour. Other desirable properties are ready compressibility at pressures below 25 bars, low discharge temperature on compression, high refrigeration capacity, high efficiency (high coefficient of performance) and an evaporator pressure in excess of 1 bar at the desired evaporation temperature.
[0006] Dichlorodifluoromethane (refrigerant R-12) possesses a suitable combination of properties and was for many years the most widely used refrigerant. Due to international concern that fully and partially halogenated chlorofluorocarbons were damaging the earth's protective ozone layer, there was general agreement that their manufacture and use should be severely restricted and eventually phased out completely. The use of dichlorodifluoromethane was phased out in the 1990's.
[0007] Chlorodifluoromethane (R-22) was introduced as a replacement for R-12 because of its lower ozone depletion potential. Following concerns that R-22 is a potent greenhouse gas, its use is also being phased out.
[0008] Whilst heat transfer devices of the type to which the present invention relates are essentially closed systems, loss of refrigerant to the atmosphere can occur due to leakage during operation of the equipment or during maintenance procedures. It is important, therefore, to replace fully and partially halogenated chlorofluorocarbon refrigerants by materials having zero ozone depletion potentials.
[0009] In addition to the possibility of ozone depletion, it has been suggested that significant concentrations of halocarbon refrigerants in the atmosphere might contribute to global warming (the so-called greenhouse effect). It is desirable, therefore, to use refrigerants which have relatively short atmospheric lifetimes as a result of their ability to react with other atmospheric constituents such as hydroxyl radicals or as a result of ready degradation through photolytic processes.
[0010] R-410A and R-407 refrigerants (including R-407A, R-407B and R-407C) have been introduced as a replacement refrigerant for R-22. However, R-22, R-410A and the R-407 refrigerants all have a high global warming potential (GWP, also known as greenhouse warming potential).
[0011] 1,1,1,2-tetrafluoroethane (refrigerant R-134a) was introduced as a replacement refrigerant for R-12. However, despite having no significant ozone depletion potential, R-134a has a GWP of 1300. It would be desirable to find replacements for R-134a that have a lower GWP.
[0012] R-152a (1,1-difluoroethane) has been identified as an alternative to R-134a. It is somewhat more efficient than R-134a and has a greenhouse warming potential of 120. However the flammability of R-152a is judged too high, for example to permit its safe use in mobile air conditioning systems. In particular it is believed that its lower flammable limit in air is too low, its flame speeds are too high, and its ignition energy is too low.
[0013] Thus there is a need to provide alternative refrigerants having improved properties such as low flammability. Fluorocarbon combustion chemistry is complex and unpredictable. It is not always the case that mixing a non-flammable fluorocarbon with a flammable fluorocarbon reduces the flammability of the fluid or reduces the range of flammable compositions in air. For example, the inventors have found that if non-flammable R-134a is mixed with flammable R-152a, the lower flammable limit of the mixture alters in a manner which is not predictable. The situation is rendered even more complex and less predictable if ternary compositions are considered.
[0014] There is also a need to provide alternative refrigerants that may be used in existing devices such as refrigeration devices with little or no modification.
[0015] R-1234yf (2,3,3,3-tetrafluoropropene) has been identified as a candidate alternative refrigerant to replace R-134a in certain applications, notably the mobile air conditioning or heat pumping applications. Its GWP is about 4. R-1234yf is flammable but its flammability characteristics are generally regarded as acceptable for some applications including mobile air conditioning or heat pumping. In particular, when compared with R-152a, its lower flammable limit is higher, its minimum ignition energy is higher and the flame speed in air is significantly lower than that of R-152a.
[0016] The environmental impact of operating an air conditioning or refrigeration system, in terms of the emissions of greenhouse gases, should be considered with reference not only to the so-called “direct” GWP of the refrigerant, but also with reference to the so-called “indirect” emissions, meaning those emissions of carbon dioxide resulting from consumption of electricity or fuel to operate the system. Several metrics of this total GWP impact have been developed, including those known as Total Equivalent Warming Impact (TEWI) analysis, or Life-Cycle Carbon Production (LCCP) analysis. Both of these measures include estimation of the effect of refrigerant GWP and energy efficiency on overall warming impact.
[0017] The energy efficiency and refrigeration capacity of R-1234yf have been found to be significantly lower than those of R-134a and in addition the fluid has been found to exhibit increased pressure drop in system pipework and heat exchangers. A consequence of this is that to use R-1234yf and achieve energy efficiency and cooling performance equivalent to R-134a, increased complexity of equipment and increased size of pipework is required, leading to an increase in indirect emissions associated with equipment. Furthermore, the production of R-1234yf is thought to be more complex and less efficient in its use of raw materials (fluorinated and chlorinated) than R-134a. So the adoption of R-1234yf to replace R-134a will consume more raw materials and result in more indirect emissions of greenhouse gases than does R-134a.
[0018] Some existing technologies designed for R-134a may not be able to accept even the reduced flammability of some heat transfer compositions (any composition having a GWP of less than 150 is believed to be flammable to some extent).
[0019] A principal object of the present invention is therefore to provide a heat transfer composition which is usable in its own right or suitable as a replacement for existing refrigeration usages which should have a reduced GWP, yet have a capacity and energy efficiency (which may be conveniently expressed as the “Coefficient of Performance”) ideally within 10% of the values, for example of those attained using existing refrigerants (e.g. R-134a, R-152a, R-1234yf, R-22, R-410A, R-407A, R-407B, R-407C, R507 and R-404a), and preferably within less than 10% (e.g. about 5%) of these values. It is known in the art that differences of this order between fluids are usually resolvable by redesign of equipment and system operational features. The composition should also ideally have reduced toxicity and acceptable flammability.
SUMMARY
[0020] The subject invention addresses the above deficiencies by the provision of a heat transfer composition consisting essentially of from about 82 to about 88% by weight trans-1,3,3,3-tetrafluoropropene (R-1234ze(E)) and from about 12 to about 18% by weight of 1,1-difluoroethane (R-152a). These will be referred to hereinafter as the binary compositions of the invention, unless otherwise stated.
[0021] By the term “consist essentially of”, we mean that the compositions of the invention contain substantially no other components, particularly no further (hydro)(fluoro)compounds (e.g. (hydro)(fluoro)alkanes or (hydro)(fluoro)alkenes) known to be used in heat transfer compositions. We include the term “consist of” within the meaning of “consist essentially of”.
[0022] All of the chemicals herein described are commercially available. For example, the fluorochemicals may be obtained from Apollo Scientific (UK).
[0023] As used herein, all % amounts mentioned in compositions herein, including in the claims, are by weight based on the total weight of the compositions, unless otherwise stated.
[0024] In a preferred embodiment, the binary compositions of the invention consist essentially of from about 83 to about 87% by weight of R-1234ze(E) and from about 13 to about 17% by weight of R-152a, or from about 84 to about 86% by weight of R-1234ze(E) and from about 14 to about 16% by weight of R-152a.
[0025] For the avoidance of doubt, it is to be understood that the upper and lower values for ranges of amounts of components in the binary compositions of the invention may be interchanged in any way, provided that the resulting ranges fall within the broadest scope of the invention. For example, a binary composition of the invention may consist essentially of from about 82 to about 86% by weight of R-1234ze(E) and from about 14 to about 18% by weight of R-152a, or from about 84 to about 87% by weight of R-1234ze(E) and from about 13 to about 16% by weight of R-152a.
[0026] In another embodiment, the compositions of the invention from about 2 to about 20% by weight R-152a, from about 5 to about 60% R-134a, and from about 5 to about 85% by weight R-1234ze(E). These will be referred to herein as the (ternary) compositions of the invention.
[0027] The R-134a typically is included to reduce the flammability of the compositions of the invention, both in the liquid and vapour phases. Preferably, sufficient R-134a is included to render the compositions of the invention non-flammable.
[0028] Preferred compositions of the invention comprise from about 5 to about 20% by weight R-152a, from about 10 to about 55% R-134a, and from about 30 to about 80% by weight R-1234ze(E).
[0029] Advantageous compositions of the invention comprise from about 10 to about 18% by weight R-152a, from about 10 to about 50% R-134a, and from about 32 to about 78% by weight R-1234ze(E).
[0030] Further preferred compositions of the invention comprise from about 12 to about 18% by weight R-152a, from about 20 to about 50% R-134a, and from about 32 to about 70% by weight R-1234ze(E).
[0031] Further advantageous compositions of the invention comprise from about 15 to about 18% by weight R-152a, from about 15 to about 50% R-134a, and from about 32 to about 70% by weight R-1234ze(E).
[0032] Preferably, the compositions of the invention which contain R-134a are non-flammable at a test temperature of 60° C. using the ASHRAE 34 methodology.
[0033] The compositions of the invention containing R-1234ze(E), R-152a and R-134a may consist essentially (or consist of) these components.
[0034] For the avoidance of doubt, any of the ternary compositions of the invention described herein, including those with specifically defined amounts of components, may consist essentially of (or consist of) the components defined in those compositions.
BRIEF DESCRIPTION OF THE DRAWINGS
[0035] FIG. 1 is a chart with the vertices representing pure air, fuel and diluent with the point on the interior of the triangle representing mixtures of air, fuel and diluent.
DETAILED DESCRIPTION
[0036] Compositions according to the invention conveniently comprise substantially no R-1225 (pentafluoropropene), conveniently substantially no R-1225ye (1,2,3,3,3-pentafluoropropene) or R-1225zc (1,1,3,3,3-pentafluoropropene), which compounds may have associated toxicity issues.
[0037] By “substantially no”, we include the meaning that the compositions of the invention contain 0.5% by weight or less of the stated component, preferably 0.1% or less, based on the total weight of the composition.
[0038] The compositions of the invention may contain substantially no:
[0039] (i) 2,3,3,3-tetrafluoropropene (R-1234yf),
[0040] (ii) cis-1,3,3,3-tetrafluoropropene (R-1234ze(Z)), and/or
[0041] (iii) 3,3,3-tetrafluoropropene (R-1243zf).
[0042] The compositions of the invention have zero ozone depletion potential.
[0043] Preferably, the compositions of the invention (e.g. those that are suitable refrigerant replacements for R-134a, R-1234yf or R-152a) have a GWP that is less than 1300, preferably less than 1000, more preferably less than 500, 400, 300 or 200, especially less than 150 or 100, even less than 50 in some cases. Unless otherwise stated, IPCC (Intergovernmental Panel on Climate Change) TAR (Third Assessment Report) values of GWP have been used herein.
[0044] Advantageously, the compositions are of reduced flammability hazard when compared to the individual flammable components of the compositions, e.g. R-152a. Preferably, the compositions are of reduced flammability hazard when compared to R-1234yf.
[0045] In one aspect, the compositions have one or more of (a) a higher lower flammable limit; (b) a higher ignition energy; or (c) a lower flame velocity compared to R-152a or R-1234yf. In a preferred embodiment, the compositions of the invention are non-flammable. Advantageously, the mixtures of vapour that exist in equilibrium with the compositions of the invention at any temperature between about −20° C. and 60° C. are also non-flammable.
[0046] Flammability may be determined in accordance with ASHRAE Standard 34 incorporating the ASTM Standard E-681 with test methodology as per Addendum 34p dated 2004, the entire content of which is incorporated herein by reference.
[0047] In some applications it may not be necessary for the formulation to be classed as non-flammable by the ASHRAE 34 methodology; it is possible to develop fluids whose flammability limits will be sufficiently reduced in air to render them safe for use in the application, for example if it is physically not possible to make a flammable mixture by leaking the refrigeration equipment charge into the surrounds. We have found that the effect of adding R-1234ze(E) to flammable refrigerant R-152a is to modify the flammability in mixtures with air in this manner.
[0048] It is known that the flammability of mixtures of hydrofluorocarbons, (HFCs) or hydrofluorocarbons plus hydrofluoro-olefins, is related to the proportion of carbon-fluorine bonds relative to carbon-hydrogen bonds. This can be expressed as the ratio R=F/(F+H) where, on a molar basis, F represents the total number of fluorine atoms and H represents the total number of hydrogen atoms in the composition. This is referred to herein as the fluorine ratio, unless otherwise stated.
[0049] For example, Takizawa et al, Reaction Stoichiometry for Combustion of Fluoroethane Blends, ASHRAE Transactions 112(2) 2006 (which is incorporated herein by reference), shows there exists a near-linear relationship between this ratio and the flame speed of mixtures comprising R-152a, with increasing fluorine ratio resulting in lower flame speeds. The data in this reference teach that the fluorine ratio needs to be greater than about 0.65 for the flame speed to drop to zero, in other words, for the mixture to be non-flammable.
[0050] Similarly, Minor et al (Du Pont Patent Application WO2007/053697) provide teaching on the flammability of many hydrofluoroolefins, showing that such compounds could be expected to be non-flammable if the fluorine ratio is greater than about 0.7.
[0051] It may be expected on the basis of the art, therefore, that mixtures containing R-152a (fluorine ratio 0.33) and R-1234ze(E) (fluorine ratio 0.67) would be flammable except for limited compositional ranges comprising almost 100% R-1234ze(E), since any amount of R-152a added to the olefin would reduce the fluorine ratio of the mixture below 0.67.
[0052] Surprisingly, we have found this not to be the case. In particular, we have found that binary blends of R-152a and R-1234ze(E) having a fluorine ratio of less than 0.7 exist that are non-flammable at 23° C. As shown in the examples hereinafter, the binary compositions of the invention are non-flammable even though they have a fluorine ratio as low as about 0.58.
[0053] In one embodiment, the compositions of the invention have a fluorine ratio of from about 0.57 to about 0.61, such as from about 0.58 to about 0.60.
[0054] By producing non-flammable R-152a/R-1234ze(E) blends containing surprisingly small amounts of R-1234ze(E), the amount of R-152a in such compositions is increased. This is believed to result in heat transfer compositions exhibiting, for example, increased cooling capacity, decreased temperature glide and/or decreased pressure drop, compared to equivalent composition containing higher amounts (e.g. almost 100%) R-1234ze(E).
[0055] Thus, the compositions of the invention exhibit a completely unexpected combination of non-flammability, low GWP and improved refrigeration performance properties. Some of these refrigeration performance properties are explained in more detail below.
[0056] Temperature glide, which can be thought of as the difference between bubble point and dew point temperatures of a zeotropic (non-azeotropic) mixture at constant pressure, is a characteristic of a refrigerant; if it is desired to replace a fluid with a mixture then it is often preferable to have similar or reduced glide in the alternative fluid. In an embodiment, the compositions of the invention are zeotropic.
[0057] Conveniently, the temperature glide (in the evaporator) of the compositions of the invention is less than about 10K, preferably less than about 5K, advantageously less than 3K.
[0058] Advantageously, the volumetric refrigeration capacity of the compositions of the invention is at least 85% of the existing refrigerant fluid it is replacing, preferably at least 90% or even at least 95%.
[0059] The compositions of the invention typically have a volumetric refrigeration capacity that is at least 90% of that of R-1234yf. Preferably, the compositions of the invention have a volumetric refrigeration capacity that is at least 95% of that of R-1234yf, for example from about 95% to about 120% of that of R-1234yf.
[0060] In one embodiment, the cycle efficiency (Coefficient of Performance, COP) of the compositions of the invention is within about 5% or even better than the existing refrigerant fluid it is replacing
[0061] Conveniently, the compressor discharge temperature of the compositions of the invention is within about 15K of the existing refrigerant fluid it is replacing, preferably about 10K or even about 5K.
[0062] The compositions of the invention preferably have energy efficiency at least 95% (preferably at least 98%) of R-134a under equivalent conditions, while having reduced or equivalent pressure drop characteristic and cooling capacity at 95% or higher of R-134a values. Advantageously the compositions have higher energy efficiency and lower pressure drop characteristics than R-134a under equivalent conditions. The compositions also advantageously have better energy efficiency and pressure drop characteristics than R-1234yf alone.
[0063] The heat transfer compositions of the invention are suitable for use in existing designs of equipment, and are compatible with all classes of lubricant currently used with established HFC refrigerants. They may be optionally stabilized or compatibilized with mineral oils by the use of appropriate additives.
[0064] Preferably, when used in heat transfer equipment, the composition of the invention is combined with a lubricant.
[0065] Conveniently, the lubricant is selected from the group consisting of mineral oil, silicone oil, polyalkyl benzenes (PABs), polyol esters (POEs), polyalkylene glycols (PAGs), polyalkylene glycol esters (PAG esters), polyvinyl ethers (PVEs), poly (alpha-olefins) and combinations thereof.
[0066] Advantageously, the lubricant further comprises a stabiliser.
[0067] Preferably, the stabiliser is selected from the group consisting of diene-based compounds, phosphates, phenol compounds and epoxides, and mixtures thereof.
[0068] Conveniently, the composition of the invention may be combined with a flame retardant.
[0069] Advantageously, the flame retardant is selected from the group consisting of tri-(2-chloroethyl)-phosphate, (chloropropyl) phosphate, tri-(2,3-dibromopropyl)-phosphate, tri-(1,3-dichloropropyl)-phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminium trihydrate, polyvinyl chloride, a fluorinated iodocarbon, a fluorinated bromocarbon, trifluoro iodomethane, perfluoroalkyl amines, bromo-fluoroalkyl amines and mixtures thereof.
[0070] Preferably, the heat transfer composition is a refrigerant composition.
[0071] In one embodiment, the invention provides a heat transfer device comprising a composition of the invention.
[0072] Preferably, the heat transfer device is a refrigeration device.
[0073] Conveniently, the heat transfer device is selected from group consisting of automotive air conditioning systems, residential air conditioning systems, commercial air conditioning systems, residential refrigerator systems, residential freezer systems, commercial refrigerator systems, commercial freezer systems, chiller air conditioning systems, chiller refrigeration systems, and commercial or residential heat pump systems. Preferably, the heat transfer device is a refrigeration device or an air-conditioning system.
[0074] Advantageously, the heat transfer device contains a centrifugal-type compressor.
[0075] The invention also provides the use of a composition of the invention in a heat transfer device as herein described.
[0076] According to a further aspect of the invention, there is provided a blowing agent comprising a composition of the invention.
[0077] According to another aspect of the invention, there is provided a foamable composition comprising one or more components capable of forming foam and a composition of the invention.
[0078] Preferably, the one or more components capable of forming foam are selected from polyurethanes, thermoplastic polymers and resins, such as polystyrene, and epoxy resins.
[0079] According to a further aspect of the invention, there is provided a foam obtainable from the foamable composition of the invention.
[0080] Preferably the foam comprises a composition of the invention.
[0081] According to another aspect of the invention, there is provided a sprayable composition comprising a material to be sprayed and a propellant comprising a composition of the invention.
[0082] According to a further aspect of the invention, there is provided a method for cooling an article which comprises condensing a composition of the invention and thereafter evaporating said composition in the vicinity of the article to be cooled.
[0083] According to another aspect of the invention, there is provided a method for heating an article which comprises condensing a composition of the invention in the vicinity of the article to be heated and thereafter evaporating said composition.
[0084] According to a further aspect of the invention, there is provided a method for extracting a substance from biomass comprising contacting the biomass with a solvent comprising a composition of the invention, and separating the substance from the solvent.
[0085] According to another aspect of the invention, there is provided a method of cleaning an article comprising contacting the article with a solvent comprising a composition of the invention.
[0086] According to a further aspect of the invention, there is provided a method for extracting a material from an aqueous solution comprising contacting the aqueous solution with a solvent comprising a composition of the invention, and separating the material from the solvent.
[0087] According to another aspect of the invention, there is provided a method for extracting a material from a particulate solid matrix comprising contacting the particulate solid matrix with a solvent comprising a composition of the invention, and separating the material from the solvent.
[0088] According to a further aspect of the invention, there is provided a mechanical power generation device containing a composition of the invention.
[0089] Preferably, the mechanical power generation device is adapted to use a Rankine Cycle or modification thereof to generate work from heat.
[0090] According to another aspect of the invention, there is provided a method of retrofitting a heat transfer device comprising the step of removing an existing heat transfer fluid, and introducing a composition of the invention. Preferably, the heat transfer device is a refrigeration device or (a static) air conditioning system. Advantageously, the method further comprises the step of obtaining an allocation of greenhouse gas (e.g. carbon dioxide) emission credit.
[0091] In accordance with the retrofitting method described above, an existing heat transfer fluid can be fully removed from the heat transfer device before introducing a composition of the invention. An existing heat transfer fluid can also be partially removed from a heat transfer device, followed by introducing a composition of the invention.
[0092] In another embodiment wherein the existing heat transfer fluid is R-134a, and the composition of the invention contains R134a, R-1234ze(E) and R-152a (and optional components as a lubricant, a stabiliser or a flame retardant), R-1234ze(E), R-152a, etc, can be added to the R-134a in the heat transfer device, thereby forming the compositions of the invention, and the heat transfer device of the invention, in situ. Some of the existing R-134a may be removed from the heat transfer device prior to adding the R-1234ze(E), R-152a, etc to facilitate providing the components of the compositions of the invention in the desired proportions.
[0093] Thus, the invention provides a method for preparing a composition and/or heat transfer device of the invention comprising introducing R-1234ze(E) and R-152a, and optional components such as a lubricant, a stabiliser or a flame retardant, into a heat transfer device containing an existing heat transfer fluid which is R-134a. Optionally, at least some of the R-134a is removed from the heat transfer device before introducing the R-1234ze(E), R-152a, etc.
[0094] Of course, the compositions of the invention may also be prepared simply by mixing the R-1234ze(E) and R-152a, optionally R-134a (and optional components such as a lubricant, a stabiliser or a flame retardant) in the desired proportions. The compositions can then be added to a heat transfer device (or used in any other way as defined herein) that does not contain R-134a or any other existing heat transfer fluid, such as a device from which R-134a or any other existing heat transfer fluid have been removed.
[0095] In a further aspect of the invention, there is provided a method for reducing the environmental impact arising from operation of a product comprising an existing compound or composition, the method comprising replacing at least partially the existing compound or composition with a composition of the invention. Preferably, this method comprises the step of obtaining an allocation of greenhouse gas emission credit.
[0096] By environmental impact we include the generation and emission of greenhouse warming gases through operation of the product.
[0097] As mentioned above, this environmental impact can be considered as including not only those emissions of compounds or compositions having a significant environmental impact from leakage or other losses, but also including the emission of carbon dioxide arising from the energy consumed by the device over its working life. Such environmental impact may be quantified by the measure known as Total Equivalent Warming Impact (TEWI). This measure has been used in quantification of the environmental impact of certain stationary refrigeration and air conditioning equipment, including for example supermarket refrigeration systems (see, for example, http://en.wikipedia.org/wiki/Total_equivalent_warming_impact).
[0098] The environmental impact may further be considered as including the emissions of greenhouse gases arising from the synthesis and manufacture of the compounds or compositions. In this case the manufacturing emissions are added to the energy consumption and direct loss effects to yield the measure known as Life-Cycle Carbon Production (LCCP, see for example http://www.sae.org/events/aars/presentations/2007papasavva.pdf). The use of LCCP is common in assessing environmental impact of automotive air conditioning systems.
[0099] Emission credit(s) are awarded for reducing pollutant emissions that contribute to global warming and may, for example, be banked, traded or sold. They are conventionally expressed in the equivalent amount of carbon dioxide. Thus if the emission of 1 kg of R-134a is avoided then an emission credit of 1×1300=1300 kg CO2 equivalent may be awarded.
[0100] In another embodiment of the invention, there is provided a method for generating greenhouse gas emission credit(s) comprising (i) replacing an existing compound or composition with a composition of the invention, wherein the composition of the invention has a lower GWP than the existing compound or composition; and (ii) obtaining greenhouse gas emission credit for said replacing step.
[0101] In a preferred embodiment, the use of the composition of the invention results in the equipment having a lower Total Equivalent Warming Impact, and/or a lower Life-Cycle Carbon Production than that which would be attained by use of the existing compound or composition.
[0102] These methods may be carried out on any suitable product, for example in the fields of air-conditioning, refrigeration (e.g. low and medium temperature refrigeration), heat transfer, blowing agents, aerosols or sprayable propellants, gaseous dielectrics, cryosurgery, veterinary procedures, dental procedures, fire extinguishing, flame suppression, solvents (e.g. carriers for flavorings and fragrances), cleaners, air horns, pellet guns, topical anesthetics, and expansion applications. Preferably, the field is air-conditioning or refrigeration.
[0103] Examples of suitable products include a heat transfer devices, blowing agents, foamable compositions, sprayable compositions, solvents and mechanical power generation devices. In a preferred embodiment, the product is a heat transfer device, such as a refrigeration device or an air-conditioning unit.
[0104] The existing compound or composition has an environmental impact as measured by GWP and/or TEWI and/or LCCP that is higher than the composition of the invention which replaces it. The existing compound or composition may comprise a fluorocarbon compound, such as a perfluoro-, hydrofluoro-, chlorofluoro- or hydrochlorofluoro-carbon compound or it may comprise a fluorinated olefin
[0105] Preferably, the existing compound or composition is a heat transfer compound or composition such as a refrigerant. Examples of refrigerants that may be replaced include R-134a, R-152a, R-1234yf, R-410A, R-407A, R-407B, R-407C, R507, R-22 and R-404A. The compositions of the invention are particularly suited as replacements for R-134a, R-152a or R-1234yf.
[0106] Any amount of the existing compound or composition may be replaced so as to reduce the environmental impact. This may depend on the environmental impact of the existing compound or composition being replaced and the environmental impact of the replacement composition of the invention. Preferably, the existing compound or composition in the product is fully replaced by the composition of the invention.
[0107] The invention is illustrated by the following non-limiting examples.
EXAMPLES
Flammability
[0108] The flammability of R-152a in air at atmospheric pressure and controlled humidity was studied in a test flask apparatus as described by the methodology of ASHRAE standard 34. The test temperature used was 23° C.; the humidity was controlled to be 50% relative to a standard temperature of 77° F. (25° C.). The diluent used was R-1234ze(E), which was found to be non flammable under these test conditions. The fuel and diluent gases were subjected to vacuum purging of the cylinder to remove dissolved air or other inert gases prior to testing.
[0109] The results of this testing are shown in FIG. 1 , where the vertices of the chart represent pure air, fuel and diluent. Points on the interior of the triangle represent mixtures of air, fuel and diluent. The flammable region of such mixtures was found by experimentation and is enclosed by the curved line.
[0110] It was found that binary mixtures of R-152a and R-1234ze(E) containing at least 70% v/v (about 80% w/w) R-1234ze(E) were non-flammable when mixed with air in all proportions. This is shown by the solid line on the diagram, which is a tangent to the flammable region and represents the mixing line of air with a fuel/diluent mixture in the proportions 70% v/v diluent to 30% v/v fuel.
[0111] Using the above methodology we have found the following compositions to be non-flammable at 23° C. (associated fluorine ratios are also shown).
[0000]
Non-flammable mixture
composition (volumetric
Fluorine ratio
Composition on a
basis)
R = F/(F + H)
weight/weight basis
R-152a 30%, R-1234ze(E)
0.567
R-152a 19.9%, R-
70%
1234ze(E) 80.1%
R-152a 27.5%, R-
0.575
R-152a 18%, R-1234ze(E)
1234ze(E) 72.5%
82%
R-152a 20%, R-1234ze(E)
0.600
R-152a 12.6%, R-
80%
1234ze(E) 87.4%
R-152a 10%, R-1234ze(E)
0.633
R-152a 6.1%, R-
90%
1234ze(E) 93.9%
[0112] It can be seen that non flammable mixtures comprising R-152a and R-1234ze(E) can be created if the fluorine ratio of the mixture is greater than about 0.57.
[0000] Performance of R-152a/R-1234ze and R-152a/R-1234ze/R-134a Blends
[0113] The performance of selected binary and ternary compositions of the invention was estimated using a thermodynamic property model in conjunction with an idealised vapour compression cycle. The thermodynamic model used the Peng Robinson equation of state to represent vapour phase properties and vapour-liquid equilibrium of the mixtures, together with a polynomial correlation of the variation of ideal gas enthalpy of each component of the mixtures with temperature. The principles behind use of this equation of state to model thermodynamic properties and vapour liquid equilibrium are explained more fully in The Properties of Gases and Liquids (5 th edition) by B E Poling, J M Prausnitz and J M O'Connell pub. McGraw Hill 2000, in particular Chapters 4 and 8 (which is incorporated herein by reference).
[0114] The basic property data required to use this model were: critical temperature and critical pressure; vapour pressure and the related property of Pitzer acentric factor; ideal gas enthalpy, and measured vapour liquid equilibrium data for the binary system R-152a/R-1234ze(E).
[0115] The basic property data (critical properties, acentric factor, vapour pressure and ideal gas enthalpy) for R-152a and R-134a were derived from literature sources including: NIST REFPROP 8.0 (which is incorporated herein by reference). The critical point and vapour pressure for R-1234ze(E) were measured experimentally. The ideal gas enthalpy for R-1234ze(E) over a range of temperatures was estimated using the molecular modelling software Hyperchem 7.5, which is incorporated herein by reference.
[0116] Vapour liquid equilibrium data for the binary mixtures was regressed to the Peng Robinson equation using a binary interaction constant incorporated into van der Waal's mixing rules as follows. Vapour liquid equilibrium data for R-152a with R-1234ze(E) was modelled by using the equation of state with van der Waals mixing rules and optimising the interaction constant to reproduce the known azeotropic composition of approximately 28% by weight R-1234ze(E) at −25° C. Vapour liquid equilibrium data for R-152a with R-134a was taken from the literature, notably the references cited in the NIST REFPROP code, and the data used to regress a value of interaction constant. Vapour liquid equilibrium data for R-134a with R-1234ze(E) was measured in an isothermal recirculating still over the range −40 to +50° C. and the resulting data were also fitted to the Peng Robinson equation. No azeotrope was found to exist between R-134a and R-1234ze(E) in this temperature range.
[0117] The refrigeration performance of selected compositions of the invention were modelled using the following cycle conditions.
[0000]
Condensing temperature (° C.)
60
Evaporating temperature (° C.)
0
Subcool (K)
5
Superheat (K)
5
Suction temperature (° C.)
15
Isentropic efficiency
65%
Clearance ratio
4%
Duty (kW)
6
Suction line diameter (mm)
16.2
[0118] The refrigeration performance data of these compositions are set out in the following tables.
[0119] The binary compositions offer non-flammability and enhanced energy efficiency compared to R-1234yf, and offer significantly enhanced capacity compared to R-1234ze(E) alone. The suction line pressure drop is also more favourable than R-1234ze(E) and for most of the compositions the pressure drop is also more favourable than for R-1234yf. The practical effect of this will be that in a real system the effective capacity of the compositions as compared to R-1234yf will be somewhat higher than that predicted by theory, since the effect of reducing suction pressure drop is to increase the effective throughput capability of the system compressor. This is especially true for automotive air conditioning or heat pump systems.
[0120] The ternary compositions of the invention offer further increased cooling capacity as compared to R-1234ze(E) while reducing further the flammability of the mixture. Surprisingly, it is possible to achieve performance close to that expected from non-flammable mixtures of R-152a and R-134a at a significantly lower GWP for the fluid.
[0000]
TABLE 1
Theoretical Performance Data of R-152a/R-1234ze(E) Compositions of the Invention
R152a
% b/w
12
13
14
15
16
17
18
R1234ze(E)
% b/w
88
87
86
85
84
83
82
Calculation results
134a
R1234yf
R1234ze(E)
12/88
13/87
14/86
15/85
6/84
17/83
18/82
Pressure ratio
5.79
5.24
5.75
5.71
5.71
5.70
5.70
5.70
5.69
5.69
Volumetric
83.6%
84.7%
82.8%
83.3%
83.3%
83.4%
83.4%
83.4%
83.5%
83.5%
efficiency
condenser glide
K
0.0
0.0
0.0
0.4
0.4
0.4
0.4
0.4
0.4
0.5
Evaporator glide
K
0.0
0.0
0.0
0.3
0.3
0.3
0.3
0.3
0.3
0.3
Evaporator inlet
° C.
0.0
0.0
0.0
−0.1
−0.1
−0.1
−0.1
−0.1
−0.1
−0.1
temperature
Condenser exit
° C.
55.0
55.0
55.0
54.8
54.8
54.8
54.8
54.8
54.8
54.8
temperature
Condenser pressure
bar
16.88
16.46
12.38
13.16
13.22
13.28
13.33
13.38
13.43
13.48
Evaporator pressure
bar
2.92
3.14
2.15
2.31
2.32
2.33
2.34
2.35
2.36
2.37
Refrigeration effect
kJ/kg
123.76
94.99
108.63
119.92
120.86
121.81
122.77
123.72
124.68
125.63
COP
2.03
1.91
2.01
2.04
2.04
2.05
2.05
2.05
2.05
2.05
Discharge
° C.
99.15
92.88
86.66
90.80
91.13
91.46
91.79
92.12
92.44
92.77
temperature
Mass flow rate
kg/hr
174.53
227.39
198.83
180.13
178.71
177.32
175.94
174.59
173.25
171.93
Volumetric flow
m 3 /hr
13.16
14.03
18.29
16.81
16.71
16.61
16.51
16.42
16.33
16.24
rate
Volumetric capacity
kJ/m 3
1641
1540
1181
1285
1293
1301
1308
1316
1323
1330
Pressure drop
kPa/m
953
1239
1461
1247
1232
1217
1203
1189
1176
1163
Gas density at
kg/m 3
13.26
16.21
10.87
10.71
10.70
10.68
10.66
10.63
10.61
10.59
evaporator exit
Gas density at
kg/m 3
86.37
99.16
67.78
66.54
66.39
66.24
66.09
65.93
65.77
65.60
condenser inlet
GWP (AR4)
1430
4
6
20
21
23
24
25
26
27
GWP (TAR)
6
20
21
22
23
24
25
27
F/(F + H)
0.667
0.603
0.598
0.594
0.589
0.584
0.580
0.575
Capacity relative
106.6%
100.0%
76.7%
83.5%
84.0%
84.5%
85.0%
85.4%
85.9%
86.4%
to 1234yf
Relative COP
106.0%
100.0%
105.3%
106.8%
106.9%
107.0%
107.1%
107.2%
107.3%
107.4%
Relative pressure
76.9%
100.0%
117.9%
100.6%
99.4%
98.2%
97.1%
96.0%
94.9%
93.8%
drop
[0000]
TABLE 2
Theoretical Performance Data of Selected R-152a/R-1234ze(E)/R-134a Blends
containing 12% b/w R-152a
R-152a (% b/w)
12
12
12
R-134a (% b/w)
10
15
20
R-1234ze(E) (% b/w)
78
73
68
COMPARATIVE DATA
Calculation results
134a
R1234yf
R1234ze(E)
12/10/78
12/15/73
12/20/68
Pressure ratio
5.79
5.24
5.75
5.70
5.69
5.68
Volumetric efficiency
83.6%
84.7%
82.8%
83.4%
83.4%
83.5%
condenser glide
K
0.0
0.0
0.0
0.7
0.7
0.7
Evaporator glide
K
0.0
0.0
0.0
0.4
0.4
0.4
Evaporator inlet
° C.
0.0
0.0
0.0
−0.2
−0.2
−0.2
temperature
Condenser exit
° C.
55.0
55.0
55.0
54.7
54.6
54.6
temperature
Condenser pressure
bar
16.88
16.46
12.38
13.74
14.01
14.27
Evaporator pressure
bar
2.92
3.14
2.15
2.41
2.46
2.51
Refrigeration effect
kJ/kg
123.76
94.99
108.63
120.82
121.29
121.78
COP
2.03
1.91
2.01
2.04
2.04
2.04
Discharge temperature
° C.
99.15
92.88
86.66
91.93
92.49
93.04
Mass flow rate
kg/hr
174.53
227.39
198.83
178.77
178.08
177.36
Volumetric flow rate
m 3 /hr
13.16
14.03
18.29
16.10
15.78
15.49
Volumetric capacity
kJ/m 3
1641
1540
1181
1342
1369
1395
Pressure drop
kPa/m
953
1239
1461
1187
1160
1135
GWP (TAR BASIS)
6
149
214
278
F/(F + H)
0.667
0.604
0.604
0.604
Capacity relative to
106.6%
100.0%
76.7%
87.1%
88.9%
90.6%
1234yf
Relative COP
106.0%
100.0%
105.3%
106.7%
106.6%
106.6%
Relative pressure drop
76.9%
100.0%
117.9%
95.8%
93.7%
91.6%
R-152a (% b/w)
12
12
12
12
12
12
R-134a (% b/w)
25
30
35
40
45
50
R-1234ze(E) (% b/w)
63
58
53
48
43
38
Calculation results
12/25/63
12/30/58
12/35/53
12/40/48
12/45/43
12/50/38
Pressure ratio
5.68
5.67
5.67
5.67
5.67
5.67
Volumetric efficiency
83.6%
83.6%
83.7%
83.7%
83.8%
83.8%
condenser glide
K
0.7
0.7
0.6
0.5
0.5
0.4
Evaporator glide
K
0.4
0.4
0.3
0.3
0.2
0.2
Evaporator inlet
° C.
−0.2
−0.2
−0.2
−0.1
−0.1
−0.1
temperature
Condenser exit
° C.
54.6
54.7
54.7
54.7
54.8
54.8
temperature
Condenser pressure
bar
14.52
14.76
14.99
15.21
15.41
15.60
Evaporator pressure
bar
2.56
2.60
2.64
2.68
2.72
2.75
Refrigeration effect
kJ/kg
122.31
122.87
123.49
124.16
124.90
125.71
COP
2.04
2.04
2.04
2.04
2.04
2.04
Discharge temperature
° C.
93.60
94.16
94.73
95.31
95.91
96.52
Mass flow rate
kg/hr
176.60
175.79
174.91
173.97
172.94
171.82
Volumetric flow rate
m 3 /hr
15.21
14.95
14.71
14.49
14.29
14.10
Volumetric capacity
kJ/m 3
1420
1445
1468
1491
1512
1532
Pressure drop
kPa/m
1111
1089
1067
1047
1028
1009
GWP (TAR BASIS)
343
408
473
537
602
667
F/(F + H)
0.605
0.605
0.605
0.606
0.606
0.606
Capacity relative to
92.2%
93.8%
95.4%
96.8%
98.2%
99.5%
1234yf
Relative COP
106.5%
106.5%
106.5%
106.5%
106.5%
106.5%
Relative pressure drop
89.7%
87.9%
86.1%
84.5%
82.9%
81.4%
[0000]
TABLE 3
Theoretical Performance Data of Selected R-152a/R-1234ze(E)/R-134a Blends
containing 13% b/w R-152a
R-152a (% b/w)
13
13
13
R-134a (% b/w)
10
15
20
R-1234ze(E) (% b/w)
77
72
67
COMPARATIVE DATA
Calculation results
134a
R1234yf
R1234ze(E)
13/10/77
13/15/72
13/20/67
Pressure ratio
5.79
5.24
5.75
5.69
5.69
5.68
Volumetric efficiency
83.6%
84.7%
82.8%
83.4%
83.5%
83.5%
condenser glide
K
0.0
0.0
0.0
0.6
0.7
0.7
Evaporator glide
K
0.0
0.0
0.0
0.4
0.4
0.4
Evaporator inlet
° C.
0.0
0.0
0.0
−0.2
−0.2
−0.2
temperature
Condenser exit
° C.
55.0
55.0
55.0
54.7
54.7
54.7
temperature
Condenser pressure
bar
16.88
16.46
12.38
13.78
14.05
14.31
Evaporator pressure
bar
2.92
3.14
2.15
2.42
2.47
2.52
Refrigeration effect
kJ/kg
123.76
94.99
108.63
121.78
122.26
122.76
COP
2.03
1.91
2.01
2.04
2.04
2.04
Discharge temperature
° C.
99.15
92.88
86.66
92.26
92.81
93.37
Mass flow rate
kg/hr
174.53
227.39
198.83
177.37
176.67
175.95
Volumetric flow rate
m 3 /hr
13.16
14.03
18.29
16.01
15.70
15.41
Volumetric capacity
kJ/m 3
1641
1540
1181
1349
1376
1402
Pressure drop
kPa/m
953
1239
1461
1174
1148
1123
GWP (TAR BASIS)
6
150
215
280
F/(F + H)
0.667
0.599
0.599
0.600
Capacity relative to
106.6%
100.0%
76.7%
87.6%
89.3%
91.0%
1234yf
Relative COP
106.0%
100.0%
105.3%
106.8%
106.7%
106.7%
Relative pressure drop
76.9%
100.0%
117.9%
94.7%
92.6%
90.6%
R-152a (% b/w)
13
13
13
13
13
13
R-134a (% b/w)
25
30
35
40
45
50
R-1234ze(E) (% b/w)
62
57
52
47
42
37
Calculation results
13/25/62
13/30/57
13/35/52
13/40/47
13/45/42
13/50/37
Pressure ratio
5.67
5.67
5.67
5.67
5.67
5.67
Volumetric efficiency
83.6%
83.7%
83.7%
83.8%
83.8%
83.8%
condenser glide
K
0.7
0.6
0.6
0.5
0.4
0.4
Evaporator glide
K
0.4
0.4
0.3
0.3
0.2
0.2
Evaporator inlet
° C.
−0.2
−0.2
−0.2
−0.1
−0.1
−0.1
temperature
Condenser exit
° C.
54.7
54.7
54.7
54.7
54.8
54.8
temperature
Condenser pressure
bar
14.56
14.79
15.02
15.23
15.43
15.62
Evaporator pressure
bar
2.57
2.61
2.65
2.69
2.72
2.75
Refrigeration effect
kJ/kg
123.30
123.88
124.51
125.20
125.96
126.79
COP
2.04
2.04
2.04
2.04
2.04
2.04
Discharge temperature
° C.
93.93
94.49
95.06
95.65
96.24
96.86
Mass flow rate
kg/hr
175.18
174.36
173.48
172.52
171.49
170.36
Volumetric flow rate
m 3 /hr
15.14
14.89
14.65
14.44
14.24
14.05
Volumetric capacity
kJ/m 3
1427
1451
1474
1496
1517
1537
Pressure drop
kPa/m
1100
1078
1057
1037
1018
999
GWP (TAR BASIS)
344
409
474
538
603
668
F/(F + H)
0.600
0.600
0.601
0.601
0.601
0.602
Capacity relative to
92.7%
94.2%
95.7%
97.2%
98.5%
99.8%
1234yf
Relative COP
106.6%
106.6%
106.6%
106.6%
106.6%
106.6%
Relative pressure drop
88.8%
87.0%
85.3%
83.7%
82.1%
80.7%
[0000]
TABLE 4
Theoretical Performance Data of Selected R-152a/R-1234ze(E)/R-134a Blends
containing 14% b/w R-152a
R-152a (% b/w)
14
14
14
R-134a (% b/w)
10
15
20
R-1234ze(E) (% b/w)
76
71
66
COMPARATIVE DATA
Calculation results
134a
R1234yf
R1234ze(E)
14/10/76
14/15/71
14/20/66
Pressure ratio
5.79
5.24
5.75
5.69
5.68
5.68
Volumetric efficiency
83.6%
84.7%
82.8%
83.5%
83.5%
83.6%
condenser glide
K
0.0
0.0
0.0
0.6
0.7
0.7
Evaporator glide
K
0.0
0.0
0.0
0.4
0.4
0.4
Evaporator inlet
° C.
0.0
0.0
0.0
−0.2
−0.2
−0.2
temperature
Condenser exit
° C.
55.0
55.0
55.0
54.7
54.7
54.7
temperature
Condenser pressure
bar
16.88
16.46
12.38
13.83
14.10
14.35
Evaporator pressure
bar
2.92
3.14
2.15
2.43
2.48
2.53
Refrigeration effect
kJ/kg
123.76
94.99
108.63
122.74
123.23
123.75
COP
2.03
1.91
2.01
2.04
2.04
2.04
Discharge temperature
° C.
99.15
92.88
86.66
92.58
93.14
93.69
Mass flow rate
kg/hr
174.53
227.39
198.83
175.98
175.28
174.55
Volumetric flow rate
m 3 /hr
13.16
14.03
18.29
15.93
15.62
15.34
Volumetric capacity
kJ/m 3
1641
1540
1181
1356
1382
1408
Pressure drop
kPa/m
953
1239
1461
1161
1135
1111
GWP (TAR BASIS)
6
151
216
281
F/(F + H)
0.667
0.594
0.595
0.595
Capacity relative to
106.6%
100.0%
76.7%
88.1%
89.8%
91.5%
1234yf
Relative COP
106.0%
100.0%
105.3%
106.9%
106.8%
106.8%
Relative pressure drop
76.9%
100.0%
117.9%
93.7%
91.6%
89.7%
R-152a (% b/w)
14
14
14
14
14
14
R-134a (% b/w)
25
30
35
40
45
50
R-1234ze(E) (% b/w)
61
56
51
46
41
36
Calculation results
14/25/61
14/30/56
14/35/51
14/40/46
14/45/41
14/50/36
Pressure ratio
5.67
5.67
5.67
5.67
5.67
5.67
Volumetric efficiency
83.6%
83.7%
83.7%
83.8%
83.8%
83.9%
condenser glide
K
0.7
0.6
0.6
0.5
0.4
0.3
Evaporator glide
K
0.4
0.4
0.3
0.3
0.2
0.2
Evaporator inlet
° C.
−0.2
−0.2
−0.2
−0.1
−0.1
−0.1
temperature
Condenser exit
° C.
54.7
54.7
54.7
54.8
54.8
54.8
temperature
Condenser pressure
bar
14.59
14.82
15.05
15.25
15.45
15.63
Evaporator pressure
bar
2.57
2.62
2.66
2.69
2.73
2.76
Refrigeration effect
kJ/kg
124.30
124.89
125.54
126.24
127.02
127.87
COP
2.04
2.04
2.04
2.04
2.04
2.04
Discharge temperature
° C.
94.25
94.82
95.39
95.98
96.58
97.19
Mass flow rate
kg/hr
173.78
172.95
172.06
171.10
170.05
168.92
Volumetric flow rate
m 3 /hr
15.08
14.83
14.60
14.39
14.19
14.01
Volumetric capacity
kJ/m 3
1433
1457
1479
1501
1522
1542
Pressure drop
kPa/m
1088
1067
1046
1027
1008
990
GWP (TAR BASIS)
345
410
475
540
604
669
F/(F + H)
0.595
0.596
0.596
0.597
0.597
0.597
Capacity relative to
93.1%
94.6%
96.1%
97.5%
98.9%
100.1%
1234yf
Relative COP
106.8%
106.7%
106.7%
106.7%
106.7%
106.8%
Relative pressure drop
87.8%
86.1%
84.4%
82.9%
81.4%
79.9%
[0000]
TABLE 5
Theoretical Performance Data of Selected R-152a/R-1234ze(E)/R-134a Blends containing
15% b/w R-152a
R-152a (% b/w)
15
15
15
R-134a (% b/w)
10
15
20
R-1234ze(E) (% b/w)
75
70
65
COMPARATIVE DATA
Calculation results
134a
R1234yf
R1234ze(E)
15/10/75
15/15/70
15/20/65
Pressure ratio
5.79
5.24
5.75
5.69
5.68
5.68
Volumetric efficiency
83.6%
84.7%
82.8%
83.5%
83.6%
83.6%
condenser glide
K
0.0
0.0
0.0
0.6
0.7
0.7
Evaporator glide
K
0.0
0.0
0.0
0.4
0.4
0.4
Evaporator inlet
° C.
0.0
0.0
0.0
−0.2
−0.2
−0.2
temperature
Condenser exit
° C.
55.0
55.0
55.0
54.7
54.7
54.7
temperature
Condenser pressure
bar
16.88
16.46
12.38
13.88
14.14
14.39
Evaporator pressure
bar
2.92
3.14
2.15
2.44
2.49
2.54
Refrigeration effect
kJ/kg
123.76
94.99
108.63
123.71
124.21
124.73
COP
2.03
1.91
2.01
2.05
2.04
2.04
Discharge temperature
° C.
99.15
92.88
86.66
92.91
93.46
94.02
Mass flow rate
kg/hr
174.53
227.39
198.83
174.60
173.90
173.17
Volumetric flow rate
m 3 /hr
13.16
14.03
18.29
15.85
15.55
15.27
Volumetric capacity
kJ/m 3
1641
1540
1181
1363
1389
1415
Pressure drop
kPa/m
953
1239
1461
1148
1123
1099
GWP (TAR BASIS)
6
153
217
282
F/(F + H)
0.667
0.590
0.590
0.590
Capacity relative to
106.6%
100.0%
76.7%
88.5%
90.2%
91.9%
1234yf
Relative COP
106.0%
100.0%
105.3%
107.0%
106.9%
106.9%
Relative pressure drop
76.9%
100.0%
117.9%
92.7%
90.6%
88.7%
R-152a (% b/w)
15
15
15
15
15
15
R-134a (% b/w)
25
30
35
40
45
50
R-1234ze(E) (% b/w)
60
55
50
45
40
35
Calculation results
15/25/60
15/30/55
15/35/50
15/40/45
15/45/40
15/50/35
Pressure ratio
5.67
5.67
5.67
5.67
5.67
5.67
Volumetric efficiency
83.7%
83.7%
83.8%
83.8%
83.9%
83.9%
condenser glide
K
0.6
0.6
0.5
0.5
0.4
0.3
Evaporator glide
K
0.4
0.3
0.3
0.2
0.2
0.1
Evaporator inlet
° C.
−0.2
−0.2
−0.1
−0.1
−0.1
−0.1
temperature
Condenser exit
° C.
54.7
54.7
54.7
54.8
54.8
54.8
temperature
Condenser pressure
bar
14.63
14.86
15.07
15.28
15.47
15.65
Evaporator pressure
bar
2.58
2.62
2.66
2.70
2.73
2.76
Refrigeration effect
kJ/kg
125.29
125.90
126.57
127.29
128.09
128.95
COP
2.04
2.04
2.04
2.04
2.04
2.04
Discharge temperature
° C.
94.58
95.15
95.72
96.31
96.91
97.53
Mass flow rate
kg/hr
172.39
171.56
170.66
169.69
168.64
167.50
Volumetric flow rate
m 3 /hr
15.01
14.77
14.55
14.34
14.15
13.97
Volumetric capacity
kJ/m 3
1439
1462
1485
1506
1527
1546
Pressure drop
kPa/m
1077
1056
1036
1017
998
981
GWP (TAR BASIS)
347
411
476
541
605
670
F/(F + H)
0.591
0.591
0.592
0.592
0.592
0.593
Capacity relative to
93.5%
95.0%
96.4%
97.8%
99.2%
100.4%
1234yf
Relative COP
106.9%
106.8%
106.8%
106.8%
106.9%
106.9%
Relative pressure drop
86.9%
85.2%
83.6%
82.1%
80.6%
79.2%
[0000]
TABLE 6
Performance Data of Selected R-152a/R-1234ze(E)/R-134a Blends containing 16% b/w R-152a
R-152a (% b/w)
16
16
16
R-134a (% b/w)
10
15
20
R-1234ze(E) (% b/w)
74
69
64
COMPARATIVE DATA
Calculation results
134a
R1234yf
R1234ze(E)
16/10/74
16/15/69
16/20/64
Pressure ratio
5.79
5.24
5.75
5.68
5.68
5.67
Volumetric efficiency
83.6%
84.7%
82.8%
83.6%
83.6%
83.7%
condenser glide
K
0.0
0.0
0.0
0.6
0.6
0.6
Evaporator glide
K
0.0
0.0
0.0
0.4
0.4
0.4
Evaporator inlet
° C.
0.0
0.0
0.0
−0.2
−0.2
−0.2
temperature
Condenser exit
° C.
55.0
55.0
55.0
54.7
54.7
54.7
temperature
Condenser pressure
bar
16.88
16.46
12.38
13.92
14.18
14.43
Evaporator pressure
bar
2.92
3.14
2.15
2.45
2.50
2.54
Refrigeration effect
kJ/kg
123.76
94.99
108.63
124.68
125.18
125.72
COP
2.03
1.91
2.01
2.05
2.05
2.05
Discharge temperature
° C.
99.15
92.88
86.66
93.23
93.79
94.35
Mass flow rate
kg/hr
174.53
227.39
198.83
173.25
172.55
171.81
Volumetric flow rate
m 3 /hr
13.16
14.03
18.29
15.77
15.48
15.20
Volumetric capacity
kJ/m 3
1641
1540
1181
1370
1396
1421
Pressure drop
kPa/m
953
1239
1461
1136
1111
1088
GWP (TAR BASIS)
6
154
218
283
F/(F + H)
0.667
0.585
0.585
0.586
Capacity relative to
106.6%
100.0%
76.7%
89.0%
90.7%
92.3%
1234yf
Relative COP
106.0%
100.0%
105.3%
107.1%
107.1%
107.0%
Relative pressure drop
76.9%
100.0%
117.9%
91.7%
89.7%
87.8%
R-152a (% b/w)
16
16
16
16
16
16
R-134a (% b/w)
25
30
35
40
45
50
R-1234ze(E) (% b/w)
59
54
49
44
39
34
Calculation results
16/25/59
16/30/54
16/35/49
16/40/44
16/45/39
16/50/34
Pressure ratio
5.67
5.67
5.67
5.67
5.67
5.67
Volumetric efficiency
83.7%
83.8%
83.8%
83.9%
83.9%
83.9%
condenser glide
K
0.6
0.6
0.5
0.4
0.4
0.3
Evaporator glide
K
0.4
0.3
0.3
0.2
0.2
0.1
Evaporator inlet
° C.
−0.2
−0.2
−0.1
−0.1
−0.1
−0.1
temperature
Condenser exit
° C.
54.7
54.7
54.7
54.8
54.8
54.8
temperature
Condenser pressure
bar
14.66
14.89
15.10
15.30
15.49
15.67
Evaporator pressure
bar
2.59
2.63
2.67
2.70
2.73
2.76
Refrigeration effect
kJ/kg
126.30
126.92
127.60
128.34
129.16
130.04
COP
2.05
2.05
2.05
2.05
2.05
2.05
Discharge temperature
° C.
94.91
95.47
96.05
96.64
97.25
97.87
Mass flow rate
kg/hr
171.02
170.18
169.28
168.30
167.24
166.10
Volumetric flow rate
m 3 /hr
14.95
14.71
14.49
14.29
14.10
13.93
Volumetric capacity
kJ/m 3
1445
1468
1490
1512
1532
1551
Pressure drop
kPa/m
1066
1046
1026
1007
989
972
GWP (TAR BASIS)
348
412
477
542
607
671
F/(F + H)
0.586
0.587
0.587
0.588
0.588
0.588
Capacity relative to
93.8%
95.4%
96.8%
98.2%
99.5%
100.7%
1234yf
Relative COP
107.0%
107.0%
107.0%
107.0%
107.0%
107.1%
Relative pressure drop
86.1%
84.4%
82.8%
81.3%
79.8%
78.5%
[0000]
TABLE 7
Theoretical Performance Data of Selected R-152a/R-1234ze(E)/R-134a Blends containing
17% b/w R-152a
R-152a (% b/w)
17
17
17
R-134a (% b/w)
10
15
20
R-1234ze(E) (% b/w)
73
68
63
COMPARATIVE DATA
Calculation results
134a
R1234yf
R1234ze(E)
17/10/73
17/15/68
17/20/63
Pressure ratio
5.79
5.24
5.75
5.68
5.68
5.67
Volumetric efficiency
83.6%
84.7%
82.8%
83.6%
83.7%
83.7%
condenser glide
K
0.0
0.0
0.0
0.6
0.6
0.6
Evaporator glide
K
0.0
0.0
0.0
0.4
0.4
0.4
Evaporator inlet
° C.
0.0
0.0
0.0
−0.2
−0.2
−0.2
temperature
Condenser exit
° C.
55.0
55.0
55.0
54.7
54.7
54.7
temperature
Condenser pressure
bar
16.88
16.46
12.38
13.97
14.22
14.46
Evaporator pressure
bar
2.92
3.14
2.15
2.46
2.51
2.55
Refrigeration effect
kJ/kg
123.76
94.99
108.63
125.65
126.17
126.71
COP
2.03
1.91
2.01
2.05
2.05
2.05
Discharge temperature
° C.
99.15
92.88
86.66
93.56
94.11
94.67
Mass flow rate
kg/hr
174.53
227.39
198.83
171.91
171.20
170.46
Volumetric flow rate
m 3 /hr
13.16
14.03
18.29
15.69
15.40
15.14
Volumetric capacity
kJ/m 3
1641
1540
1181
1377
1402
1427
Pressure drop
kPa/m
953
1239
1461
1123
1100
1077
GWP (TAR BASIS)
6
155
219
284
F/(F + H)
0.667
0.580
0.581
0.581
Capacity relative to
106.6%
100.0%
76.7%
89.4%
91.1%
92.7%
1234yf
Relative COP
106.0%
100.0%
105.3%
107.2%
107.2%
107.1%
Relative pressure drop
76.9%
100.0%
117.9%
90.7%
88.7%
86.9%
R-152a (% b/w)
17
17
17
17
17
17
R-134a (% b/w)
25
30
35
40
45
50
R-1234ze(E) (% b/w)
58
53
48
43
38
33
Calculation results
17/25/58
17/30/53
17/35/48
17/40/43
17/45/38
17/50/33
Pressure ratio
5.67
5.67
5.66
5.67
5.67
5.68
Volumetric efficiency
83.8%
83.8%
83.9%
83.9%
83.9%
84.0%
condenser glide
K
0.6
0.5
0.5
0.4
0.4
0.3
Evaporator glide
K
0.3
0.3
0.3
0.2
0.2
0.1
Evaporator inlet
° C.
−0.2
−0.2
−0.1
−0.1
−0.1
−0.1
temperature
Condenser exit
° C.
54.7
54.7
54.8
54.8
54.8
54.9
temperature
Condenser pressure
bar
14.69
14.91
15.12
15.32
15.51
15.68
Evaporator pressure
bar
2.59
2.63
2.67
2.70
2.74
2.76
Refrigeration effect
kJ/kg
127.30
127.94
128.64
129.40
130.23
131.14
COP
2.05
2.05
2.05
2.05
2.05
2.05
Discharge temperature
° C.
95.23
95.80
96.38
96.97
97.58
98.20
Mass flow rate
kg/hr
169.67
168.82
167.91
166.92
165.86
164.71
Volumetric flow rate
m 3 /hr
14.89
14.66
14.44
14.24
14.06
13.89
Volumetric capacity
kJ/m 3
1451
1474
1496
1516
1536
1555
Pressure drop
kPa/m
1056
1035
1016
998
980
963
GWP (TAR BASIS)
349
414
478
543
608
672
F/(F + H)
0.582
0.582
0.583
0.583
0.584
0.584
Capacity relative to
94.2%
95.7%
97.1%
98.5%
99.8%
101.0%
1234yf
Relative COP
107.1%
107.1%
107.1%
107.1%
107.1%
107.2%
Relative pressure drop
85.2%
83.6%
82.0%
80.5%
79.1%
77.7%
[0000]
TABLE 8
Theoretical Performance Data of Selected R-152a/R-1234ze(E)/R-134a Blends containing
18% b/w R-152a
R-152a (% b/w)
18
18
18
R-134a (% b/w)
10
15
20
R-1234ze(E) (% b/w)
72
67
62
COMPARATIVE DATA
Calculation results
134a
R1234yf
R1234ze(E)
18/10/72
18/15/67
18/20/62
Pressure ratio
5.79
5.24
5.75
5.68
5.67
5.67
Volumetric efficiency
83.6%
84.7%
82.8%
83.6%
83.7%
83.7%
condenser glide
K
0.0
0.0
0.0
0.6
0.6
0.6
Evaporator glide
K
0.0
0.0
0.0
0.4
0.4
0.4
Evaporator inlet
° C.
0.0
0.0
0.0
−0.2
−0.2
−0.2
temperature
Condenser exit
° C.
55.0
55.0
55.0
54.7
54.7
54.7
temperature
Condenser pressure
bar
16.88
16.46
12.38
14.01
14.26
14.50
Evaporator pressure
bar
2.92
3.14
2.15
2.47
2.51
2.56
Refrigeration effect
kJ/kg
123.76
94.99
108.63
126.62
127.15
127.71
COP
2.03
1.91
2.01
2.05
2.05
2.05
Discharge temperature
° C.
99.15
92.88
86.66
93.88
94.44
94.99
Mass flow rate
kg/hr
174.53
227.39
198.83
170.59
169.88
169.13
Volumetric flow rate
m 3 /hr
13.16
14.03
18.29
15.61
15.33
15.07
Volumetric capacity
kJ/m 3
1641
1540
1181
1383
1409
1433
Pressure drop
kPa/m
953
1239
1461
1112
1088
1066
GWP (TAR BASIS)
6
156
221
285
F/(F + H)
0.667
0.576
0.576
0.577
Capacity relative to
106.6%
100.0%
76.7%
89.8%
91.5%
93.1%
1234yf
Relative COP
106.0%
100.0%
105.3%
107.3%
107.3%
107.2%
Relative pressure drop
76.9%
100.0%
117.9%
89.7%
87.8%
86.0%
R-152a (% b/w)
18
18
18
18
18
18
R-134a (% b/w)
25
30
35
40
45
50
R-1234ze(E) (% b/w)
57
52
47
42
37
32
Calculation results
18/25/57
18/30/52
18/35/47
18/40/42
18/45/37
18/50/32
Pressure ratio
5.67
5.66
5.66
5.67
5.67
5.68
Volumetric efficiency
83.8%
83.8%
83.9%
83.9%
84.0%
84.0%
condenser glide
K
0.6
0.5
0.5
0.4
0.3
0.3
Evaporator glide
K
0.3
0.3
0.2
0.2
0.2
0.1
Evaporator inlet
° C.
−0.2
−0.1
−0.1
−0.1
−0.1
−0.1
temperature
Condenser exit
° C.
54.7
54.7
54.8
54.8
54.8
54.9
temperature
Condenser pressure
bar
14.73
14.94
15.15
15.34
15.52
15.69
Evaporator pressure
bar
2.60
2.64
2.67
2.71
2.74
2.76
Refrigeration effect
kJ/kg
128.32
128.97
129.68
130.46
131.31
132.24
COP
2.05
2.05
2.05
2.05
2.05
2.05
Discharge temperature
° C.
95.56
96.13
96.71
97.31
97.91
98.54
Mass flow rate
kg/hr
168.33
167.48
166.56
165.57
164.50
163.35
Volumetric flow rate
m 3 /hr
14.83
14.60
14.39
14.20
14.02
13.85
Volumetric capacity
kJ/m 3
1457
1479
1501
1521
1541
1559
Pressure drop
kPa/m
1045
1025
1006
988
971
955
GWP (TAR BASIS)
350
415
479
544
609
674
F/(F + H)
0.577
0.578
0.578
0.579
0.579
0.580
Capacity relative to
94.6%
96.1%
97.5%
98.8%
100.1%
101.3%
1234yf
Relative COP
107.2%
107.2%
107.2%
107.2%
107.3%
107.3%
Relative pressure drop
84.4%
82.8%
81.2%
79.8%
78.4%
77.1% | The invention provides a heat transfer composition consisting essentially of from about 82 to about 88% by weight of trans-1,3,3,3-tetrafluoropropene (R-1234ze(E)) and from about 12 to about 18% by weight of 1,1-difluoroethane (R-152a). The invention also provides a heat transfer composition comprising from about 5 to about 85% by weight R-1234ze(E), from about 2 to about 20% by weight R-152 a, and from about 5 to about 60 by weight 1,1,1,2-tetrafluoroethane (R-134a). | 8 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an improved premelted synthetic slag for ladle desulfurizing molten steel and more particularly to a premelted synthetic slag having an elevated magnesium oxide content and to the method for desulfurizing steel which employs the premelted synthetic slags and more particularly to a premelted synthetic slag for desulfurizing molten steel which synthetic slag is obtained as a co-product from vanadium and ferrovanadium processing.
2. Description of the Prior Art
Molten steel ladle metallurgical practices employ synthetic slag for desulfurization for a number of reasons. Synthetic slags provide a thermal insulation for the molten metal top surface and protect the molten metal from atmospheric oxidation. The synthetic slag ladle processing requires little additional equipment or additional capital costs. Synthetic slag ladle processing practices can achieve desulfurization as low as 0.005% (wt.) residual sulfur content and can remove 50% and more of the molten metal sulfur content. Such synthetic slags heretofore have had a high calcium oxide content and have included aluminum oxide, and occasionally calcium fluoride (as a flux), silicon dioxide and metallic aluminum or aluminum alloys. Improvements in the synthetic slag ladle processing of molten steel results when the synthetic slag is premelted to reduce the porosity and tendency to absorb moisture prior to use. Typically equal weights of calcium oxide and aluminum oxide are mixed and premelted together to form calcium aluminate. The premelted calcium aluminate is added to the ladle, either by itself, or with lime, fluorspar (to supply calcium fluoride) and occasionally some metallic aluminum.
Note that the premelted synthetic slag should be distinguished from prefused synthetic slag. The distinction is that prefused slag is created by a solid state reaction occurring at a temperature below the melting temperature of the slag. The resulting prefused synthetic slag tends to be porous and non-uniform. The premelted synthetic slag is obtained by actually melting the synthetic slag ingredients above their melting temperature to establish a liquid mixture which is allowed to cool to form the premelted synthetic slag.
To reduce the temperature required for melting synthetic slags, calcium fluoride as a fluxing agent frequently is added to the synthetic slag mixture. The presence of fluoride in the resulting slag tends to increase the wear on the refractory linings of molten steel ladles which are typically fabricated from cast dolomitic lime and/or high alumina ceramics and/or high MgO ceramics. Existing ladle practices encourage loss of magnesium oxide from the ladle lining into the ladle slag. Said loss requires frequent ladle lining replacement. The MgO loss can be detected by the increase of MgO content of the slag. Any process which lowers loss of MgO from the ladle lining will reduce the number of relinings and reduce the downtime needed to replace ladle linings.
Ferrovanadium Process
Vanadium is obtained by an exothermic reaction of metallic aluminum with vanadium concentrates. The ferrovanadium process is conducted in a crucible containing the vanadium concentrates and metallic aluminum. The reaction system is ignited by a thermite process comprising the combination of a metal such as aluminum or magnesium with an oxidizing agent. The ferrovanadium process comprises exothermic reaction of the metallic aluminum with the vanadium oxide to generate aluminum oxide as slag above a pool of molten vanadium. It is customary for the operator to add calcium oxide to the crucible to lower the slag melting temperatures and to promote separation of the molten metal.
Ferrovanadium slag tends to be high in MgO content. The MgO source is the ladle lining in most instances.
The three ferrovanadium slag products described herein as I, II and III were obtained from separate ferrovanadium slag processes wherein the operators provided differing quantities of calcium oxide.
STATEMENT OF THE PRESENT INVENTION
In its broadest aspect, the present invention provides premelted synthetic slag compositions having substantial quantities (9 to 20% by weight) of magnesium oxide. By including the magnesium oxide in a calcium aluminate slag, a reduced eutectic melting temperature for the ternary system (calcium oxide, aluminum oxide, magnesium oxide) can be achieved at temperatures corresponding to the calcium oxide/aluminum oxide eutectic temperature, e.g., 1400-1700 degrees C. Moreover the use of the magnesium oxide further avoids the ladle lining deterioration in ladle linings which contain MgO. A still further advantage is that magnesium oxide is less likely to absorb water of hydration than calcium oxide. Improved ladle processing can be expected from the avoidance of water in the ladle process.
In a further preferred embodiment of the present invention, the premelted synthetic slag is obtained directly as a by-product from the production of vanadium or ferrovanadium. Typical slags include 0.1 to 3.0 weight percent of vanadium oxides, possess low melting temperatures and possess relatively high magnesium oxide content.
By including magnesium oxide in a calcium aluminate slag, several advantages are obtained. The magnesium oxide replaces some of the calcium oxide and thereby retards magnesium oxide migration from the ceramic ladle linings into the slag. In addition, the magnesium oxide is less likely to absorb water of hydration than calcium oxide. Improved ladle processing can be expected from avoiding water in the ladle process.
However the presence of magnesium oxide increases the eutectic temperature of the ternary system: calcium oxide, magnesium oxide, aluminum oxide; hence increased MgO content in synthetic slags is counter-indicated, because of the need to have low melting temperature slag.
The presence of small quantities of vanadium oxide in the synthetic slag appears to provide lower eutectic temperatures in the ternary system: calcium oxide, magnesium oxide, aluminum oxide. Accordingly in a prepared embodiment of the present invention, small quantities of vanadium oxide (0.1-3.0% by weight) are included in the synthetic slag to achieve heretofore unappreciated low eutectic temperatures.
In the preferred embodiment of the invention, the synthetic slag which will be employed for ladle desulfurizing molten steel is a slag obtained as a waste product from processing ferrovanadium. Such ferrovanadium slags include calcium oxide and aluminum oxide along with elevated quantities (9-20% by weight) of magnesium oxide and small but effective quantities of vanadium oxide (0.1-3.0 by weight).
A typical high magnesium oxide premelted synthetic slag has the following composition:
______________________________________Al.sub.2 O.sub.3 44-85% by weightCaO 3-35% by weightMgO 9-20% by weightSiO.sub.2 0.1-3.0% by weightIron oxides 0.05-1% by weightMetals, oxides and <3% by weightinerts______________________________________
The preferred premelted synthetic slags are obtained as the slag by-product from production of vanadium and ferrovanadium and include typically
Ferrovanadium slag I (melting temperature approximately 1540 degrees C.):
______________________________________ Al.sub.2 O.sub.3 65% MgO 10-15% CaO 20-25% SiO.sub.2 1-3% Fe.sub.2 O.sub.3 0.3% V.sub.2 O.sub.5 0.1-1% L.O.I.* <.1%______________________________________ *L.O.I. means Loss on Ignition at 1000 degrees C., a customary test procedure.
Ferrovanadium slag II (melting temperature 1372 degrees C.):
______________________________________Al.sub.2 O.sub.3 45-55%MgO 15-20%CaO 30-35%SiO.sub.2 2-4%V.sub.2 O.sub.5 0.2-1%MnO.sub.2 0.2%Fe.sub.2 O.sub.3 0.3%L.O.I.* None detected______________________________________ *L.O.I. means Loss on Ignition at 1000 degrees C., a customary test procedure.
Ferrovanadium slag III (melting temperature greater than 1717 degrees C.*):
______________________________________ Al.sub.2 O.sub.3 85% MgO 9% CaO 3% SiO.sub.2 2% V.sub.2 O.sub.5 0.5-1% Fe.sub.2 O.sub.3 0.5% L.O.I. <0.1% B <10 ppm Mn 100 ppm Mo 50 ppm Ti 100 ppm Zr 30 ppm______________________________________
For comparison, a typical commercial premelted synthetic slag (melting temperature of 1398 degrees C.) has the following composition:
______________________________________ Al.sub.2 O.sub.3 51% CaO 48.0% MgO 0.2% SiO.sub.2 0.5% Fe.sub.2 O.sub.3 0.3%______________________________________
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic illustration of a typical ladle steel processing installation which can utilize the synthetic slag of this invention.
FIG. 2 is a ternary diagram of the system MgO, CaO, Al 2 O 3 .
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1, there is illustrated an electric furnace 10 containing approximately 150 tons of molten steel 11 covered by a layer of slag 12. After the molten steel in the electric furnace 10 is in condition for further treatment, the molten steel is discharged into a ladle 13 having a ceramic lining 14 which is usually magnesium oxide and/or alumina and/or fused dolomitic lime. Usually a small part of the molten slag 12 from the electric furnace will accompany the molten steel 11 into the ladle 13. Within the ladle 13 the molten steel is identified by the numeral 15 and frequently constitutes about 150 tons of molten metal. The molten metal is covered by a synthetic slag 16 in accordance with the present invention.
The molten slag 16 is formulated by materials which may be added to a hopper 17 and delivered through a downspout 18 directly into the ladle 13. Alternatively slag-forming ingredients and metal treating reagents may be supplied from a charge bucket 19 and containing an inventory 20 of slag-forming and metal treating ingredients. Typically the charge bucket contains up to about 2.5 tons of materials.
EXAMPLE 1
The premelted synthetic slag herein described has been employed in a commercial steel ladle desulfurization process as follows:
In manufacturing 4118 grade steel in an electric furnace 10, the molten steel had a carbon content of 0.06 weight percent and a sulfur content of 0.034 weight percent. The ladle charge was approximately 250 tons of molten steel 15 together with approximately 4000 to 5000 pounds of carryover slag 16.
The charging bucket 19 contained 1000 pounds of desulfurizing mix including an 85% lime (balance powdered aluminum and fluorspar); 1000 pounds calcium-magnesium aluminate (described herein as Ferroaluminum slag II; and about 500 pounds of notchbar aluminum metal. All of the ingredients in the charge bucket 20 were introduced into the ladle and the ladle was transferred to a ladle refining station where additional heat was introduced into the ladle and aluminum dross containing about 40% metallic aluminum (balance aluminum oxide) was added to the ladle together with alloying ingredients (manganese, chrome). Argon gas was bubbled through the heat from the base of the reactor to facilitate desulfurization for about 35 minutes. The temperature of the metal within the ladle refining station was approximately 2900 degrees F. The sulfur content reduced from 0.034 to 0.016 weight percent.
Prior heats in the same installation without using the Ferrovanadium slag II utilized an additional 1000 pounds of desulfurization composition (85% lime, balance fluorspar and aluminum); an additional 150 pounds of notchbar aluminum; and and additional 1000 pounds of lime; and an additional 150 pounds of fluorspar. The cost effectiveness of using the Ferrovanadium slag II was established.
By conducting magnesium oxide measurements on the slag, it was determined that less magnesium oxide was leached out of the ladle ceramic liner when the Ferrovanadium slag II was employed than in prior heats which did not use the Ferrovanadium slag II.
EXAMPLE 2
In an electric furnace 10 containing 150 tons of molten steel, the contents were tapped into a ladle 13 having a fused cast dolomite refractory lining. Carryover slag 16 from the electric furnace 10 was about 3000 to 4000 pounds. While the molten metal was tapping from the electric furnace 10 into the ladle 13, a supply (500 to 600 pounds of Ferrovanadium slag III passing through a one inch screen) was introduced through a downspout 18 into the ladle. No other ingredients were added. The ladle was transferred for further treatment consisting of bubbling argon gas through the ladle and subsequently vacuum degassing the ladle contents.
Improved desulfurization of the molten metal was observed. Reduced refractory attack on the lining of the ladle was observed. The slag viscosity appeared to be lower when the Ferrovanadium slag III was employed.
This process of Example 2 has been employed with a number of different grades of steel under a variety of conditions.
Ternary Oxide Systems
FIG. 2 is a ternary graph of the system CaO, MgO, Al 2 O 3 which appears in J. Am. Chem. Soc. 38, 568 (1916). It will be observed that the minimum melting temperature, approximately 1400 degrees C., occur at 50/50 CaO/Al 2 O 3 composition with negligible MgO. It will be further observed that the melting temperatures for the ternary system containing 9-20 weight percent MgO ranges from about 1500 degrees C. to 1850 degrees C.
The presence of small amounts of vanadium oxide in the three component system has an unpredictable and surprising effect in reducing the melting temperatures to values of 1540 degrees C. (Slag 1), 1372 degrees C. (Slag II) and 1717 degrees C. (Slag III). It will be observed that Slag III has an Al 2 O 3 content of 85% which indicates according to FIG. 2 melting temperatures above 2000 degrees.
The presence of at least 0.1 weight percent vanadium oxide in the ternary system CaO, MgO, Al 2 O 3 appears to lower the eutectic temperatures of the system below the eutectic which is presented in the absence of the vanadium oxide. | A premelted synthetic slag for ladle desulfurizing molten steel and a related method for desulfurizing molten steel employ high MgO content calcium-aluminate synthetic slag. A preferred slag composition contains 0.1-3.0% by weight of vanadium oxide. A particularly preferred composition is the slag obtained from production of vanadium or ferrovanadium by aluminum reduction of vanadium oxides. | 2 |
BACKGROUND OF THE INVENTION
The present invention relates to methods for melting glass, in particular, to the first stage of melting, i.e., rendering batch materials to a liquefied state. The invention is applicable to all types of glass melting, including flat glass, container glass, fiber glass and sodium silicate glass.
Continuous glass melting processes conventionally entail depositing pulverulent batch materials onto a pool of molten glass maintained within a tank type melting furnace and applying thermal energy until the pulverulent materials are melted into the pool of molten glass.
The conventional tank type glass melting furnace possesses a number of deficiencies. A basic deficiency is that several operations, not all of which are compatible with one another, are carried out simultaneously within the same chamber. Thus, the melter chamber of a conventional furnace is expected to liquefy the glass batch, to dissolve grains of the batch, to homogenize the melt, and to refine the glass by freeing it of gaseous inclusions. Because these various operations are taking place simultaneously within the melter, and because different components of the glass batch possess different melting temperatures, it is not surprising that inhomogeneities exist from point to point within the melter.
In order to combat these inhomogeneities, a melting tank conventionally contains a relatively large volume of molten glass so as to provide sufficient residence time for currents in the molten glass to effect some degree of homogenization before the glass is discharged to a forming operation. These recirculating flows in a tank type melter result in inefficient use of thermal energy and maintaining the large volume of molten glass itself presents difficulties, including the need to heat such a large chamber and the need to construct and maintain such a large chamber made of costly and, in some cases, difficult to obtain refractory materials. Moreover, corrosion of the refractories introduces contaminants into the glass and requires rebuilding of the melter in a matter of a few years. Additionally, it is known that some components of the batch such as limestone, tend to melt out earlier than the sand and sink into the melt as globules, whereas higher melting temperature components, such as silica, tend to form a residual unmelted scum on the surface of the melt. This segregation of batch components further aggravates the problem of inhomogeneities.
Recent findings have indicated that a major rate limiting step of the melting process is the rate at which partly melted liquefied batch runs off the batch pile to expose underlying portions of the batch to the heat of the furnace. The conventional practice of floating a layer of batch on a pool of molten glass is not particularly conducive to aiding the runoff rate, due in part to the fact that the batch is partially immersed in the molten glass. It has also been found that radiant energy is considerably more effective at inducing runoff than is convective heat from the pool of molten glass, but in a conventional melter, only one side of the batch is exposed to overhead radiant heat sources. Similarly, conventional overhead radiant heating is inefficient in that only a portion of its radiant energy is directed downwardly towards the material being melted. Not only is considerable energy wasted through the superstructure of the furnace, but the resulting thermal degradation of the refractory roof components constitutes a major constraint on the operation of many glass melting furnaces. Furthermore, attempting to heat a relatively deep recirculating mass of glass from above inherently produces thermal inhomogeneities which can carry over into the forming process and affect the quality of the glass products being produced.
Many proposals have been made for overcoming some of the problems of the conventional tank type glass melting furnace, but none has found significant acceptance since each proposal has major difficulties in its implementation. It has been proposed, for example, that glass batch be liquefied on a ramp-like structure down which the liquid would flow into a melting tank (e.g., U.S. Pat. Nos. 296,227; 708,309; 2,593,197; 4,062,667; and 4,110,097). The intense heat and severely corrosive conditions to which such a ramp would be subjected has rendered such an approach impractical since available materials have an unreasonably short life in such an application. In some cases, it is suggested that such a ramp be cooled in order to extend its life, but cooling would extract a substantial amount of heat from the melting process and would diminish the thermal efficiency of the process. Also, the relatively large area of contact between the ramp and each unit volume of glass throughput would be a concern with regard to the amount of contaminants that may be picked up by glass. Furthermore, in the ramp approach, a transfer from a radiant source to the melting batch materials is in one direction only.
A variation on a ramp type melter is shown in U.S. Pat. No. 2,451,582 where glass batch materials are dispersed in a flame and land on an inclined ramp. As in other such arrangements, the ramp in the patented arrangement would suffer from severe erosion and glass contamination.
The prior art has also suggested melting glass in rotating vessels where the melting material would be spread in a thin layer on the interior surface of the vessel and would, more or less, surround the heat source (e.g., U.S. Pat. Nos. 1,889,509; 1,889,511; 2,006,947; 2,007,755; 4,061,487; and 4,185,984). As in the ramp proposals, the prior art rotary melters possess a severe materials durability problem and an undesirably large surface contact area per unit volume of glass throughput. In those embodiments where the rotating vessel is insulated, the severe conditions at the glass contact surface would indicate a short life for even the most costly refractory materials and a substantial contamination of the glass throughput. In those embodiments where the vessel is cooled on the exterior surface, heat transfer through the vessel would subtract substantial amounts of thermal energy from the melting process, which would adversely affect the efficiency of the process. In a rotary melter arrangement shown in U.S. Pat. No. 2,834,157 coolers are interposed between the melting material and the refractory vessel in order to preserve the refractories, and it is apparent that great thermal losses would be experienced in such an arrangement. In cyclone type melters, as shown in U.S. Pat. Nos. 3,077,094 and 3,510,289, rotary motion is imparted to the glass batch materials by gaseous means as the vessel remains stationary, but the cyclone arrangements possess all the disadvantages of the rotary melters noted above.
Some prior art processes conserve thermal energy and avoid refractory contact by melting from the interior of a mass of glass batch outwardly, including U.S. Pat. Nos. 1,082,195; 1,621,446; 3,109,045; 3,151,964; 3,328,149; and 3,689,679. Each of these proposals requires the use of electric heating and the initial liquefaction of the batch materials depends upon convective or conductive heating through the mass of previously melted glass. This is disadvantageous because radiant heating has been found to be more effective for the initial liquefaction step. Additionally, only the last two patents listed disclose continuous melting processes. In a similar arrangement disclosed in U.S. Pat. No. 3,637,365, one embodiment is disclosed wherein a combustion heat source may be employed to melt a preformed mass of glass batch from the center outwardly, but it, too, is a batchwise process and requires that melting be terminated before the mass of glass batch is melted through.
The following copending applications of the assignee relate to improving runoff of liquefied batch in a conventional tank type melter: U.S. application Ser. No. 155,802, filed June 2, 1980, by J. J. Hammel titled "METHOD OF IMPROVING GLASS MELTING BY ABLATION ENHANCEMENT"; U.S. patent application Ser. No. 159,528, filed June 16, 1980, by E. P. Savolskis and W. W. Scott titled "APPARATUS FOR IMPROVING GLASS MELTING BY PERFORATING BATCH LAYER"; and U.S. patent application Ser. No. 174,469, filed Aug. 1, 1980, by J. J. Hammel and J. D. McKenzie, titled "GLASS MELTING ENHANCEMENT BY TOROIDAL BATCH SHAPING."
SUMMARY OF THE INVENTION
In the present invention the initial process of liquefying batch material is isolated from the remainder of the melting process and is carried out in a manner uniquely suited to the needs of the particular step, thereby permitting the liquefaction step to be carried out with considerable economies in energy consumption and equipment size and cost. Central to the invention is the concept of employing glass batch itself as the support surface upon which liquefaction of glass batch takes place. It has been found that a steady state condition may be maintained in a liquefaction chamber by distributing fresh batch onto a previously deposited batch surface at essentially the same rate at which the batch is melting, whereby a substantially stable batch layer will be maintained beneath a transient batch layer, and liquefaction is essentially confined to the transient layer. Thus, the partially melted batch of the transient zone runs off the surface while contacting substantially only a batch surface, thus avoiding contaminating contact with refractories. Because glass batch is a good heat insulator, providing the stable batch layer with sufficient thickness protects any underlying support structure from thermal deterioration. Because the exterior of a furnace can thus be protected thermally, as well as from contact with corrosive molten materials, the materials requirements can be greatly relaxed, even permitting the use of mild steel as a furnace housing. The economies thus achieved in furnace construction can be substantial. Furthermore, because the furnace housing is protected by the insulating effect of the stable batch layer, no cooling of the support surface is required, thereby avoiding extraction of useful heat from the melting process.
The stable batch surface upon which liquefaction is carried out may be sloped in order expedite runoff of the liquefied batch. The slope may be the natural angle of repose of the glass batch, or the angle may be increased by providing a preformed batch layer or by centrifugal force in a rotating furnace vessel. The runoff surface is preferably free from obstacles to flow so as to permit free drainage of the liquid out of the liquefaction zone into a subsequent zone where additional melting operations may be performed on the liquid. The liquid leaving the liquefaction zone is by no means a completely melted glass, but is a foamy, opaque fluid including unmelted sand grains and the like. However, it has been found that the additional energy required to complete the dissolution and refining of this runoff liquid constitutes a very small portion of the total energy required to melt glass in a conventional tank type melting operation. Thus, the relatively efficient liquefaction process of the present invention replaces a major energy consuming portion of the conventional melting process. Additionally, it has been found that the runoff liquid is surprisingly uniform in temperature and composition, and therefore each increment of the liquid has essentially identical needs for subsequent processing. This minimizes the need for subsequent homogenization and permits precisely tailoring the subsequent process steps to the specific needs for converting the runoff liquid to molten glass finished to the degree required for the product being produced.
Liquefaction of the batch is brought on by melting of the lowest-temperature-melting components of the batch. Thus, the liquid begins to flow out of the liquefaction zone at a temperature considerably below the temperature required for complete melting of glass, thereby advantageously limiting the function of the liquefaction zone to the unit operation of liquefying the batch. Essentially no increment of the liquefied batch is heated in the zone to a temperature substantially above that corresponding to the onset of flowability. As a result, the fluid leaves the zone at a relatively low, uniform temperature, and the cavity temperature within the liquefaction zone also remains relatively low. This has advantages for the construction of the liquefaction chamber and for reducing heat losses therefrom. The ability to accomplish a major step in the melting process without wastefully overheating some increments of the melt also has positive implications for energy conservation and for suppressing volatilization of some relatively volatile components that are sometimes included in the batch (e.g., sulfur and selenium).
In preferred embodiments of the invention, the thermal efficiency of the liquefaction process is further increased by providing a stable batch layer that substantially encircles a radiant heat source. Typically the batch surface may constitute a surface of revolution (e.g., a cylinder or frustum). In this manner, radiant energy being emitted by the source will impinge directly upon batch being melted over a wide range of angles. Such an arrangement also permits an efficient use of high temperature heat sources, such as oxygen enriched flames, since much of the enhanced heat flux from such a source will productively impinge upon the surrounding batch surface. In the most preferred embodiments, the concept of encircling the heat source is combined with rotating the batch surface so as to increase the angle of repose.
The present invention may also be employed to improve the emissions of a glass melting furnace. Sulfates included in many glass batch formulas are known to contribute significantly to undesirable emissions from glass furnaces. A major purpose for including sulfates in a glass batch is to aid the initial liquefaction process in a conventional tank melter. But since the present invention is specifically adapted to liquefying glass batch, it has been found that efficient liquefaction can be achieved without the presence of sulfates in the batch. Thus, the present invention permits omitting sulfates from the batch, thereby eliminating the resultant emissions.
It has also been found that wetting the batch with water as is conventionally done in order to control dusting is not necessary with the present invention. Since vaporizing the water consumes energy in a melter, elimination of the water improves the energy efficiency. Even more significantly, the ability to use dry batch means that preheated batch may be fed to the process. If the batch is preheated by heat recovery from the exhaust gas stream, substantial energy savings can be attained. It is an advantage of the present invention that the process can accommodate preheated, dry, particulate batch, whereas prior art proposals to recover waste heat by preheating batch have usually been tied to the use of agglomerated batch. It has been found generally that the cost of agglomerating batch on a commercial scale virtually negates the potential energy savings.
Liquefying batch in accordance with the present invention is carried out in a relatively compact vessel rather than the conventional tank type melter which contains a pool of molten glass. Reducing the size saves substantial construction costs. Also, by eliminating the need for a large residual pool of glass, product changeovers are facilitated by the present invention.
The invention will be more fully understood in view of the detailed description of several specific embodiments which follows.
THE DRAWINGS
FIG. 1 is a vertical cross-section through a first embodiment of the present invention featuring an elevated batch pile surrounded by heat sources.
FIG. 2 is a vertical cross-section through a second embodiment of the present invention featuring a sloped batch surface.
FIG. 3 is a vertical cross-section of a third embodiment of the present invention featuring a compacted, sharply sloping batch surface.
FIG. 4 is a vertical cross-section through a fourth embodiment of the present invention featuring a frustoconical batch surface encircling a heat source.
FIG. 5 is a vertical cross-section of a fifth embodiment of the present invention wherein an inclined rotary kiln provides a cylindrical batch surface.
FIG. 6 is a vertical cross-section of a preferred embodiment of the present invention wherein a drum rotating about a vertical axis of rotation provides a batch surface which is a paraboloid surface of rotation about a heat source.
FIG. 7 is a vertical cross-section of a schematic representation of a combustion melting furnace adapted to cooperate with the batch liquefier of the embodiment of FIG. 6.
FIG. 8 is a vertical cross-section of a schematic representation of an electric melting furnace adapted to cooperate with the batch liquefier of the embodiment of FIG. 6.
DETAILED DESCRIPTION OF THE EMBODIMENTS
A number of embodiments incorporating the principles of the present invention will be described, but it should be understood that the practice of the invention is not limited to the specific structures disclosed. Also, since the invention relates to the initial step of liquefying glass batch, the descriptions of the embodiments will be limited to what would be only the initial portion of most glass melting operations. It should be understood that where the product requires, the inventive liquefaction step may be employed in combination with conventional means for further melting, refining, conditioning and forming the glass.
FIG. 1 represents a simplified version of the present invention wherein a liquefaction chamber is defined by a refractory brick enclosure 10. A refractory pedestal 11 rises above (or slightly below) the level of a pool of molten glass 12 within the enclosure. A mound of glass batch 13 supported on the pedestal 11 may be either a loose pile of batch or a molded, preshaped mass of batch in the form of a hemisphere, cone, pyramid, tetrahedron or the like. The contour of the batch mound 13 may be maintained substantially stable by continuously replenishing the batch by means of a falling stream of batch 14 fed from a screw feeder 15 or the like through an opening 16 in the roof of the enclosure 10. Heat for melting is provided by radiant energy sources 17 which may be combustion burners as shown in FIG. 1 or any other radiant source such as electric arc heaters. In this embodiment, the radiant energy sources are preferably arranged to provide substantially uniform heat to all sides of the batch mound 13. As the batch liquefies, a fluid layer 18 runs down the surfaces of the batch mound 13 and falls into the pool of glass 12. By controlling the relative amount of heat input and batch being fed in stream 14, a steady state condition may be maintained whereby the batch mound 13 remains substantially stable and the liquefaction is substantially confined to the transient layer 18 and the newly introduced batch stream 14. The partially melted runoff in pool 12 may be passed from the liquefaction chamber to a subsequent chamber 19 for completing the melting of any residual particles and for otherwise processing the glass by methods well known in the art.
In the arrangement shown in FIG. 2, a liquefaction chamber defined by a refractory enclosure 20 includes a shelf portion 21 on which rests a batch mound 22. The batch mound presents a surface sloping downwardly in substantially one direction and facing a radiant heat source such as a burner 23. As shown in the drawing, the batch mound may assume the natural angle of repose of the pulverulent batch material. A layer of liquefied batch 24 runs off the batch mound 22 and over a refractory lip 25 at a bottom exit opening 26 through which the liquid passes from the liquefaction chamber to subsequent processing stations, which may entail a pool of molten liquid 27 in a subsequent chamber 28. Since the batch itself acts as an insulator, the refactory material from which most of the shelf portion 21 of the enclosure is fabricated need not provide exceptional thermal durability, thereby permitting use of economic materials. Only at the small lip area 25, where the batch mound is relatively thin and where the molten material contacts the support refractories, is it advisable to provide a durable refractory material suitable for molten glass contact such as fused quartz or fused cast alumina. Beneath a layer of batch of about 3 centimeters or more, the thermal durability requirements for the underlying refractory are negligible. As shown in FIG. 2, exhaust combustion gases may escape from the liquefaction chamber by way of a flue 29. Alternatively, the combustion gases may pass through the exit opening 26 and into the downstream chamber 28 so as to expend more of its thermal energy there. In order to maintain a substantially fixed interface between the stable batch mound 22 and the transient liquid layer 24, batch is continuously fed to the melting area. Batch may be distributed over the melting area by any suitable mechanical means or, as shown, the incoming batch may be dispersed by the combustion flame. Batch may be fed by way of a screw conveyor 30 to a ceramic tube 31 extending into the interior of the liquefaction chamber and opening in the vicinity of the burner 23.
FIG. 3 depicts a variation on the embodiment of FIG. 2. A refractory enclosure 35 defines the liquefaction chamber wherein the batch layer 36 is supported on a steeply sloped surface 37 rather than on a horizontal shelf. The batch layer 36 is provided with a slope sharper than the angle of repose of loose batch by preforming the batch layer into a rigid slab. Glass batch may be preformed by molding batch which has been wetted with water. The batch layer 36 may be retained in place by a refractory lip piece 41 which is preferably a material suitable for molten glass contact of the type discribed above. An example of a radiant heat source illustrated in FIG. 3 is an electric arc produced by a pair of electrodes 38 and 39 extending into the liquefaction chamber. It should be understood that the liquefaction chamber of either FIG. 2 or FIG. 3 may include a plurality of radiant heat sources so as to permit the melting area to be extended. Loose batch is deposited onto the batch layer 36, becomes liquefied and runs off as a liquid layer 40 which passes through a bottom exit opening 42 from the liquefaction chamber and may be gathered in a molten pool 43 within a chamber 44 for subsequent treatment. The loose batch may be fed by means of a screw feeder 45 to an opening 46 through the top of the liquefaction chamber. The relatively steep slope of the melting surface in the FIG. 3 embodiment may be an advantage for accelerating the runoff of the liquefied batch as well as for simplifying distribution of incoming batch over the melting area. In some cases it may be desirable for the slope to be vertical or nearly vertical.
The embodiment of FIG. 4 has a preferred feature wherein the batch layer encircles the radiant heat source. Such an arrangement advantageously results in a greater portion of the radiant energy productively impinging upon the batch material and permits greater utilization of the insulative effect of the batch layer. Because the heat source is encircled by the insulating batch layer, refractory materials need not be employed for the sidewalls of the housing in the FIG. 4 embodiment. Thus, the housing may comprise a steel vessel 50 which may be provided with a frustoconical shape as illustrated, which may be generally parallel to the interior surface of the batch layer. However, the sloped surface of the batch layer need not correspond to the shape of the housing, and the housing may take any form such as a cylindrical or box shape. A cover 51 of ceramic refractory material may be provided to enclose the upper end of the liquefaction vessel. Batch 52 may be fed from a ring-type vibratory feeder 53 through an annular opening 54 in the cover 51 so that the batch enters the upper end of the vessel substantially evenly distributed around its upper periphery. A sloping, stable batch layer 55 lines the sides of the interior of the liquefaction vessel and may be comprised of loose batch or a preformed, molded lining. As shown in the drawing, the surface of the batch layer facing the heat source if preferably a surface of rotation, in this case a frusto-conical shape parallel to the shape of the housing 50. Paraboloid and cylindrical surfaces may also be employed. However, it should be understood that while surfaces of revolution are preferred for the shape of the batch layer for the sake of receiving uniform heat from a central heat source, other non-revolutionary shapes may be employed, such as inverted pyramidal or tetrahedral shapes. It may be also noted that the batch layer need not be of uniform thickness as long as the minimum thickness is sufficient to provide the desired degree of insulation. Because of the excellent insulating properties of glass batch, a stable batch layer whose minimum thickness is on the order of about 3 centimenters to 5 centimeters, has been found more than adequate to protect a steel housing from undue thermal deterioration. A refractory ceramic bushing 56 at the bottom of the liquefaction chamber helps to retain the batch layer 55 in place, and a central opening 57 in the bushing defines an exit opening from the liquefaction chamber. A source of radiant energy, such as a burner 58 provides heat within the liquefaction zone for melting the batch being fed into the chamber which forms the transient layer 59. The transient layer 59 becomes fluid and flows downwardly through the exit opening 57. The liquefied batch may be captured in a pool 60 contained by a chamber 61 for subsequent processing. Combustion gases from the liquefaction zone may also pass through the opening 57, whereupon they may be discharged from the chamber 61 through a flue 62. Alternatively, an exhaust opening may be provided through the cover 51. FIG. 4 shows a single heat source 58 centrally located on the axis of the liquefaction zone but it should be understood that a plurality of heat sources could be provided with oblique orientations.
Referring now to FIG. 5, there is shown an embodiment featuring a rotary liquefaction zone. High thermal efficiency is provided by encircling the heat source with the batch material being melted, and the transient batch layer being melted is distributed within the vessel by means of its rotation. The rotating vessel comprises an inclined steel cylinder 65 which may be rotated by way of a motor 66. Loose glass batch may be fed to the upper open end of the cylinder by means of a screw feeder 67. Before the vessel is heated, an insulating layer of batch 68 is built up within the vessel. During operating, the rate of feeding the batch and the rate of heating are balanced against one another so that the layer 68 remains stable and serves as the surface upon which newly fed batch is melted and runs toward the lower end of the cylinder. A radiant heat source such as a combustion burner 69 may be oriented along the axis of the cylinder from either end of the cylinder. As shown in FIG. 5, the burner 69 is mounted in a refractory housing 70 which closes the lower end of the cylinder 65. The combustion gases pass axially through the cylinder and escape through the upper end into an exhaust box 71 which encompasses the upper end of the cylinder. Exhaust gases may be passed from the box 71 to a stack 72. The lower end of the rotating cylinder may be provided with a refractory ceramic bushing 73 suitable for molten glass contact. A gap 74 between the burner housing 70 and the bottom inside edge of the cylinder is provided for escape of the liquefied batch 75 which may fall into a collecting pool 76 contained by a chamber 77 where the molten material may be subjected to subsequent processing. The angle of incline of the rotating cylinder will be determined by the rate at which it is desired for the liquefied batch to run out of the cylinder. The cylinder should rotate at a speed at which loose batch is held against the inside walls by centrifugal force. The minimum speed will depend upon the effective diameter of the cylinder. The following are calculated estimates:
______________________________________Diameter Revolutions per Minute______________________________________0.5 Meters 601.0 Meters 432.0 Meters 37______________________________________
The preferred embodiment is shown in FIG. 6 and is characterized by a liquefaction chamber rotating about the vertical axis, with glass batch encircling a central heat source. The rotary melter 80 of this embodiment includes a housing comprising a steel cylinder 81 and a steel floor 82. The housing is provided with vertical support by a plurality of rollers 83 which are affixed to a frame 84. A plurality of side rollers 85 maintain alignment of the housing. Rotation of the housing may be provided, for example, by driving one of the rollers 83 or 85 by motor means (not shown). A central opening in the floor 82 is provided with a refractory ceramic bushing 86 suitable for molten glass contact and having a central opening 87. Any suitable structure may be provided for supporting frame 84 but for purposes to be described hereinafter, it is preferred to make the entire liquefaction structure 80 relatively portable. Therefore, overhead hoist means may engage attachment means 88 affixed to upper portions of the frame 84. The upper end of the vessel may be closed by a refractory lid 90 which may be stationary and supported by the frame. The lid 90 is provided with a central bore 91 through which a burner 92 or other radiant heating means may be inserted. Alternatively, a plurality of heat sources may be employed. The lid is also provided with a feed opening 93 whereby batch may be fed from a screw feeder 94 or the like to the interior of the vessel. Before the vessel is heated, a stable layer of batch 95 is provided in the vessel by feeding loose batch while the housing is rotated. The loose batch assumes a generally paraboloid contour as shown in FIG. 6. The shape assumed by loose, dry batch is related to the speed of rotation as follows:
H=μR+(2π.sup.2 ω.sup.2 R.sup.2)/g
where:
H=the elevation of a point on the batch surface in the direction parallel to the axis of rotation;
R=the radial distance of that point from the axis of rotation;
μ=a friction factor;
ω=angular velocity; and
g=the acceleration of gravity.
The friction factor may be taken as the tangent of the angle of repose, which for dry glass batch is typically about 35°. The above equation may be employed to select suitable dimensions for the rotary vessel at a selected speed of rotation or, conversely, for determining a suitable speed of rotation for a given vessel. The relationship shows that steeper slopes, which are generally preferred, require faster rotational speeds, and that at zero velocity, the slope is determined solely by the angle of repose as in the FIG. 4 embodiment (assuming no preforming of the batch layer).
During heating, continuous feeding of batch to the vessel of FIG. 6 results in a falling stream of batch 96 that becomes distributed over the surface of the stable batch layer, and by the action of the heat becomes liquefied in a transient layer 97 that runs to the bottom of the vessel and passes through opening 87. The liquefied batch falls as globules 98 from the exit opening and may be collected in a pool 99 within a vessel 100 for further processing. Exhaust gases from the combustion within the liquefaction vessel may also pass through the opening 87 and may be exhausted through a flue 101. Alternatively, an exhaust opening may be provided through the lid 90.
In FIGS. 7 and 8, there are depicted combinations of the rotary melter 80 of the FIG. 6 embodiments combined with conventional means for completing the melting of the liquefied batch. In order to melt residual sand grains and to refine the liquefied batch emanating from the rotary melter 80, an overhead fired furnace 110 of conventional construction may be provided as shown in FIG. 7. The furnace contains a pool of the melt 111 and may be provided with one or more side ports 112 or an end port, as are well known in the art, from which flames may be directed above the melt for providing heat thereto. The furnace may include a conventional inlet extension portion 113, but rather than feeding batch at such a location, the output from one or more batch liquefiers may be fed to the furnace through an opening 114. Melted and refined glass may pass from the furnace to a forming operation by way of a conditioner or forehearth 115. The function of the furnace 110 is primarily to raise the temperature of the melt and to provide sufficient residence time for any residual sand grains to dissolve and for gaseous inclusions to evolve from the melt. These functions represent a minor portion of those carried out in a conventional melting furnace, and therefore the furnace 110 may be only a fraction of the size of a conventional furnace having the same throughput. In other words, it is estimated that the batch liquefaction means of the present invention may replace one-half to two-thirds of a conventional flat glass melting furnace with commensurate savings in construction costs and with more efficient energy usage. A single liquefaction vessel may be used to provide liquefied batch to the furnace of a large scale, commercial glass-making operation, but it is generally more economical to provide a plurality of smaller units. Thus, to supply a throughput on the order of several hundred tons per day, it may be preferred to employ about three or four liquefaction units. It is preferred that each liquefaction unit be made portable so that a unit in need of maintenance may be removed and a reserve unit inserted in its place, thereby minimizing disruption of the glassmaking operation. The use of a plurality of liquefaction units also provides an economical means for varying the throughput of the glassmaking operation by increasing or decreasing the number of units in operation.
FIG. 8 illustrates another arrangement for completing the melting and refining of the output from one or more rotary liquefaction units 80, employing electric heat rather than overhead combustion firing. The electric melter 120 may be comprised of a refractory vessel 121 into which are inserted a plurality of electrodes 122 by which thermal energy is imparted to the melt by means of Joule resistance heating. The liquefied batch from a liquefaction unit or units may enter the electric melter through an opening 123. Following elevation of the melt temperature by the electric heating, a stream of the melt may pass through a submerged throat 124 to a refining zone 125 where gaseous inclusions are permitted to escape from the melt. It should be understood that in the arrangements shown in FIGS. 7 and 8, the rotary liquefaction unit 80 is illustrated as the preferred embodiment, but that the other liquefaction units disclosed herein may be used in place thereof.
In a typical glass batch formula consisting primarily of sand, soda ash and limestone, the soda ash begins to melt first, followed by the limestone, and finally the sand. Physical melting is accompanied by the chemical interactions, in particular, the molten alkalis attack the sand grains to effect their dissolution at a temperature below the melting point of silica. At some intermediate point in this process, the liquid phase of the heterogeneous mixture of reacting and melting materials begins to predominate and the material becomes flowable as a fluid. The temperature at which the batch becomes flowable will depend upon the particular batch formula, especially the amount and melting temperature of its lowest melting temperature ingredients. The most common low temperature melting ingredient is soda ash, which melts at 1564° F. (851° C.). Theoretically, a batch having a sufficient amount of soda ash may become liquefied at the soda ash melting temperature, but experience with commercial batch formulas indicates that the temperature is somewhat higher--2000° F. (1090° C.) to 2100° F. (1150° C.) for a typical flat glass batch. This may be explained by the fact that batch melting is a complex series of interactions among the various ingredients, whereby the physical properties of the individual ingredients are not exhibited. It may also be that insufficient soda ash is present when melted to entrain by itself the remainder of the unmelted materials. Moreover, even though the present invention eliminates much of the overheating of conventional melters, the runoff temperatures observed with the present invention may not truly represent the initiation of liquefaction, but may include a small amount of heating after liquefaction. Other low temperature melting ingredients sometimes employed in glass batches, such as caustic soda and boric acid, have even lower melting temperatures than soda ash and may behave differently as runoff initiators. On the other hand, some types of glass other than flat glass require higher temperatures to melt. It is preferred to use the present invention with batch formulas that liquefy below 3000° F. (1650° C.). For many types of glasses made on a large scale commercially, the present invention would be expected to operate satisfactorily with liquefied batch draining from the liquefaction chamber at about 1600° F. (870° C.) to 2300° F. (1260° C.).
In the present invention, the liquefied batch drains from the liquefaction zone as soon as it reaches the fluid state, and therefore the fluid draining from the liquefaction zone has a nearly uniform temperature close to the liquefying temperature of the particular batch formula, typically about 2100° F. (1150° C.) in the case of conventional flat glass. Because heat is transported out of the liquefaction zone at the liquefying temperature, which is considerably lower than the temperatures attained in a conventional glass melter, the temperature of the liquefaction vessel may be maintained relatively low regardless of the temperature of the heat source. As a result, materials requirements may be reduced relative to a conventional melter, and use of high temperature heat sources is made possible. The greater heat flux afforded by high temperature heat sources advantageously increases the rate of throughput. An example of a high temperature heat source is a combustion burner supplied with oxygen as a partial or total replacement for combustion air. The use of oxygen is also advantageous in the present invention for the sake of reducing the volume of combustion gases, thereby decreasing any tendency of the fine batch materials to become entrained in the exhaust gas stream. This is particularly significant in the preferred practice of feeding the batch dry to the liquefaction vessel as opposed to the conventional practice of wetting the batch with water to inhibit dusting. Furthermore, the use of oxygen instead of air is believed to reduce the potentially for creating nitrogen containing bubbles in the glass.
An example of a batch formula employed in the commercial manufacture of flat glass is the following:
Sand--1000 parts by weight
Soda Ash--313.5
Limestone--84
Dolomite--242
Rouge--0.75
The above batch formula yields approximately the following glass:
SiO 2 --73.10% by weight
Na 2 O--13.75%
CaO--8.85%
MgO--3.85%
Al 2 O 3 --0.10%
Fe 2 O 3 --0.10%
The liquefied batch running out of the liquefaction zone of the present invention, when using the batch formula set forth above, is predominantly liquid (weight basis) and includes about 15% by weight or less of crystalline silica (i.e., undissolved sand grains). The liquid phase is predominantly sodium disilicate and includes almost the entire soda ash portion of the batch and most of the limestone and dolomite. The fluid, however, is quite foamy, having a density typically on the order of about 1.9 grams per cubic centimeter, as opposed to a density of about 2.5 grams per cubic centimeter for molten glass.
Although additional energy must be imparted to the liquid to convert it to a completely melted glass, it is estimated that a major portion of the overall energy consumption is spent in the batch liquefaction process, and that that portion of the process is carried out substantially more efficiently by the liquefaction methods of the present invention compared to a conventional tank-type melter. A theoretically derived value for the total energy required to completely melt glass is 2.5 million BTU's per ton (0.7 million kcal/metric ton) of glass produced. In order to complete the melting of the material leaving the liquefaction zone of the present invention, it is calculated that theoretically 0.36 million BTU's per ton (0.1 million kcal/metric ton) would be required, or about 14% of the total theoretical energy requirement. In a conventional overhead fired tank melting furnace operating at state-of-the-art efficiency, total energy consumption has been found to be typically about 6.25 million BTU's per ton (1.75 million kcal/metric ton) of glass produced. The liquefaction process of the present invention, on the other hand, has been found to consume, typically, about 4.5 million BTU's per ton (1.26 million kcal/metric ton). Accordingly, it can be seen that the liquefaction step performed in accordance with the present invention accomplishes about 86% of the melting while consuming about 72% of the energy required by a conventional melter. The total energy efficiency of the present invention will depend upon the efficiency of the particular process employed to complete the melting of the liquefied batch, but if the efficiency of the subsequent stage is no better than the efficiency of a conventional tank-type melter, it can be estimated that the overall energy consumption for melting glass in accordance with the present invention would be about 5.4 million BTU's per ton (1.5 million kcal/metric ton), or about 86% of the amount of energy used in the conventional melting process. In fact, it is contemplated that the energy efficiency of subsequent processing steps employed in conjunction with the batch liquefaction of the present invention would be better than that of the conventional melting process, since conditions may be provided that are particularly adapted to the specific tasks of melting residual sand grains and removing gaseous inclusions from the melt. Furthermore, the energy consumption figures employed above for the conventional melting process include heat recovery from the exhaust gases, whereas the figures for the liquefaction process of the present invention do not. Therefore, employing conventional heat recovery means with the process of the present invention may be expected to lower its energy requirements further.
A pilot scale trial of the embodiment of FIG. 6 employed a steel cylindrical drum 18 inches (46 centimeters) high and having an inside diameter of 25.25 inches (64 centimeters). Optimum rotation of the drum was found to be in the range of 42 to 48 revolutions per minute in order to form a stable layer of loose batch covering the inside wall of the drum. The bottom exit opening had an 8 inch (20 centimeter) diameter. The burner was fired with natural gas and oxygen in stoichiometric ratio and expended 4.3 million BTU's per ton (1.2 million kcal/metric ton) of liquefied batch produced. The maximum production rate attained was 2.8 tons per day of liquefied batch.
Other modifications and variations as would be obvious to those of skill in the art may be resorted to without departing from the scope of the invention as defined by the claims which follow. | The initial step of melting glass, converting particulate batch materials to a partially melted, liquefied state, is carried out on a support surface of batch. As liquefied batch is drained from the surface, additional batch is fed onto the surface to maintain the surface substantially constant.
The questions raised in reexamination request No. 90/000,701, filed Dec. 31, 1984 have been considered and the results thereof are reflected in this reissue patent which constitutes the reexamination certificate required by 35 U.S.C. 307 as provided in 37 CFR 1.570(e). | 2 |
BACKGROUND OF THE INVENTION
[0001] The present invention relates to a display apparatus, and particularly to a display apparatus having a rotational display panel rotating around at least two stationary units.
[0002] Conventionally, an electronic display panel is composed of a great number of light emitting pixels, each composed of single or multiple light bulb, light emitting diode (LED) or other light emitting elements. In the case of a 480×640 pixel matrix monochromatic display, it will require 307,200 pixels of single color light emitting elements. In the case of a full color display, each pixel further consists of three light emitting elements in red, green and blue color, and the total light emitting elements will be 921,600. In such a display, each pixel will either display the image information from each image frame constantly within its frame rate to gain maximum brightness; or partially to cut down the cost of driver, energy consumption and in some case, to prolong the lifetime of the light emitting elements. In the later method, a so-called ⅛ duty cycle scanning display mode, will group every 8 lines of the display panel together and each line within this grouping will display its content sequentially each using only one eighth of its predetermined display time within its frame rate, which is defined as the time duration each image frame will display.
SUMMARY OF THE INVENTION
[0003] The object of the present invention is to use the scanning display method to provide a display apparatus, which will use only a fraction of the required light emitting elements from the above mentioned conventional electronic display panel, and thus provide great saving on the cost of such a display apparatus.
[0004] One aspect of the present invention consists of at least two stationary rotating units, which are parallel and spaced apart from each other and housed in a rigid frame with at least one opening formed between these two stationary rotating units as a viewing window for the display. A flexible web is wrapped around these two rotating units, and carries by the two rotating unit to move around them, further forming at least one moving viewing plane in the opening of the rigid housing. There are at least one line of light emitting elements arranged parallel to the rotating units and travels constantly through the display opening as the rotating units carry the moving web to rotate around them with constant speed. A control unit inside the housing provides power, display data and control signal to the light emitting elements on the moving web; A communication unit provides the necessary link between the control unit and the moving web so that power, display data and control signal can be passed on to the light emitting elements causing them to display either text, or video image on the moving web, which can be viewed through the opening of the housing, thus creates a single-face display apparatus.
[0005] The second aspect of the present invention uses multiple W stationary rotating units, all parallel and spaced apart from each other with flexible web wrapping around them to provide W moving viewing planes to create a W-face display apparatus. Here W has to be any number greater or equal to two.
[0006] The third aspect of the present invention describes a scanning method by moving at least one line of light emitting elements through the moving web as described above to create text or video images on the moving viewing plane for viewing.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] [0007]FIG. 1: Simplified three-dimensional view of the present invention.
[0008] [0008]FIG. 2: Stationary rotating unit.
[0009] [0009]FIG. 3: Moving unit.
[0010] [0010]FIG. 4: Communication unit.
[0011] [0011]FIG. 5: Control unit
[0012] [0012]FIG. 6: Dead zones in the rotating moving planes:
[0013] [0013]FIG. 7: Basic building unit
DETAILED DESCRIPTION OF THE INVENTION
[0014] The display apparatus in FIG. 1 has two stationary rotating units 1 driven by motor 3 with bearing 4 to provide smooth and constant rotation. 2 is the moving web, which wraps around the two rotating units forming two moving viewing planes. 7 are the light emitting elements on the moving web. 5 is the control unit. 6 is the communication unit and 8 is the rigid frame with two openings for viewing. 9 ˜ 12 and 10 ˜ 11 define two moving viewing planes W 1 and W 2 that can be viewed through the two openings of the rigid housing 8 .
[0015] The rotating unit is moving with a speed of P in the direction as described with the arrow in FIG. 1. The line of light emitting elements 7 , preferably to be light emitting diodes, or known as LEDs, which has the ability to carry with it memory storage for at least one whole image frame of the required image display. When it travels to point 9 , the control unit will start downloading one page data to the memory buffer and it will be completed way before it reaches point 10 . When it reaches point 10 , the control unit will order it to display its data in a line-by-line fashion such that the whole page of data will be displayed while the LED line 7 travels from point 10 to point 11 . When line 7 travels between point 11 and 12 , the control unit can use this time to do any kind of data management and prepare for line 7 to display either the same page information, or a different format of the previous page information, or even downloading a different page information to be displayed between point 12 and point 9 . When the LED line 7 reaches point 9 again, it has completed the function of displaying one frame of information through each of the two openings of the present invention. In such an arrangement, in order to maintain the image quality, rotation of the moving web 2 should maintain a certain RPM, such that the human eye cannot perceive the alternation of the light emitting lines 7 and the light emitting elements being sequentially turned on and off. A human eye may perceive the corresponding information displayed on the rotating web 2 due to the persistence of vision. In order to achieve a steady picture without flickering, we need a minimum frame rate of 24. Assuming we want to achieve a frame rate of 100 for a 480×640 pixel matrix display, that means we have to show 100 display image frames consists of 480×640 pixels during a one-second interval. So the above-mentioned process will be repeated 100 times. All this is done within the 1-second interval by manipulating the speed P of the rotating unit and the diameter D of the stationary rotating units, so that this one line of light emitting elements can travel around the two stationary rotating units 100 times within 1 second to complete this task.
[0016] In FIG. 2, 1 is the stationary rotating unit. 3 is the motor providing constant speed to the rotating unit. 4 is the bearing in the rotating unit. 13 is the spikes used to carry the moving web to rotate around the two stationary rotating units and to maintain in a fix trajectory without wobbling. 14 are the imbedded metallic rings to receive power and controlling information from the communication unit and pass them on to the moving web, which has the same pattern of metallic strips that coincide with this ring pattern and can pick up information from them.
[0017] In FIG. 3, 2 is the rectangular flexible moving web. It is used to wrap around the two stationary rotating units to form moving viewing plane for viewing. 7 are the light emitting elements arranged in line form, spaced evenly between each other's through out the moving web 2 . It is arranged on the side not making contact with the rotating units 1 as described in FIG. 1. 7 can be any point source light emitting elements, such as light emitting diodes, or LEDs. 16 are the imbedded metallic strips forming on the side of the web, which is making contact with the rotating unit 1 as described in FIG. 1. Metallic strips pattern 16 matches with metallic rings pattern 14 on the rotating unit 1 and making constant contact with 14 as it moves around 1 forming two moving viewing planes facing opposite directions as described in FIG. 1. 17 is the means to transfer information received from the metallic strips pattern 16 to the line of light emitting elements situated on the other surface of the moving web 2 .
[0018] In FIG. 4, the communication unit 6 described in FIG. 1 has an elongate rod 18 made of insolating material and situated parallel to the stationary rotating unit. 19 are the conductive contacts formed in a pattern matching the pattern of the metallic rings imbedded on the rotating unit 1 . 19 can be made of any kind of conductive material, such as carbon, copper, etc. 19 is making constant contact with the metallic rings imbedded on rotating unit 1 . 20 is the means to receive electronic signals and power source from the control unit 5 as described in FIG. 1, to the communication unit. This can be done through direct wiring or wireless connection with infrared or RF technology.
[0019] In FIG. 5, the control unit 5 described in FIG. 1 has an electronic control unit 21 capable of generating all necessary electronic signals that will enable the lines of light emitting elements on moving web 2 to perform its scanning operation to generate the required display images on the moving viewing planes created by the moving web. 21 can be a custom control box or simply a PC with special display control cards. 22 is the power source that will provide the necessary power for the whole system to function. 23 is the means to distribute the power and electronic signals from the control unit to the communication unit 6 . This can be accomplished through direct wire connection or combines with wireless connection with infrared or radio frequency technology. The communication unit 6 will transmit the electronic signal and power source first using its conductive contacts 19 to the metallic rings pattern 14 on the rotating units 1 . Then all of these signals and power source are transmitted from 14 to 16 , which makes constant contact with the metallic ring pattern on rotating unit 1 . The line of light emitting elements makes connection to the metallic strips pattern 16 of the web through a simple through-hole connection with either solder, conductive paste, or silver paste.
[0020] Another way to do this is to stick with the current method to connect power source to line of light emitting elements, but use either infrared or RF technology to transmit the electronic signal to the line of light emitting elements wirelessly. Infrared and RF signal transmitter can be incorporated in the control unit 5 and infrared and RF signal receiver can be incorporated on the moving web and connected to the line of light emitting elements to directly receive signal from the control unit.
[0021] In FIG. 6, The darken area labels Z 1 ˜Z 9 are defined as Dead Zone, which means it cannot be seen by viewer through the viewing opening of the rigid housing. The number of moving viewing plane W is always equals to the number of rotating units in the present invention and the Dead Zone in each system regardless of how many rotating units or moving viewing planes it consists, is always equals to one circumference of the rotating unit.
[0022] In FIG. 7, R is the radius of the rotating unit. It is rotating in a constant speed of P. 24 is a basic display unit which is defined as the circumference of the stationary rotating unit. The length of 24 is L=2πR. One can use one, or multiple basic display units as the basic building unit of the system. To simplify the illustration, we will use one basic unit as the length of the basic building unit of the system.
[0023] The basic building unit is defined as the length in the moving web, which consists of at least one basic display unit and have at least one line of light emitting elements 7 arranged parallel to the two rotating units, and can provide n y number of scanning lines by moving the line of light emitting elements between the two rotating units within the length of the basic display unit. To simplify the illustration, here the number of light emitting elements 7 in each of the basic building unit is C, and here we set C=1.
[0024] [0024] 25 is the moving viewing plane as the W 1 defined in FIG. 1. 25 has the length, which can provide the total number of vertical scanning lines N y required to produce the image it needs to display on the moving viewing plane. Here the length is equal to three basic building units and each unit will require to produce N y /3 number of scanning lines by moving that one line of light emitting elements 7 through out the length of L=2πR. So we can see the distance of the scanning line, or the pitch of the display image can be calculated as D y =(2πR)/(N y /3). By fixing the value of R and N y , we can come up with the pitch of the display apparatus D y .
[0025] Each display apparatus under the present invention will have a multiple number of basic display units to be divided evenly through out the length of the moving web 2 . If there are M basic building units needed for a single-face display, then the total number of basic building units needed for the present invention will be equal to (MW+dead zone)=MW+1. Note here W is defined in FIG. 6 as the total number of moving viewing plane in the display apparatus. Also we had previously defined the basic building unit=the basic display unit to enable us to define the dead zone=1 basic building unit. So in this illustration, W=2 and M=3. So the total length of moving web needed will be equal to 7 basic building units.
[0026] Since the speed of the rotating unit is defined as turns per second. When there is only one line of light emitting elements within each of the basic building unit, or in this case, the basic display unit, so for P=1 turn/second, the 7 basic building unit each with its one line of light emitting elements together will complete the scanning of the total number of N y in the two moving planes. Or we can say one frame of the required display image has been scanned. Since the number of image scanned per second is defined as frame rate F. For F=100, P=100 also.
[0027] To simplify the illustration, let N y =480 lines, display line pitch D y =4 mm, F=P=100, we will need:
[0028] R=D y (N y /3)/2π=D y N y /6π=101.91 mm;
[0029] Number of basic building unit=3 per display face;
[0030] Line to be scanned in each basic building unit=N y /3=160;
[0031] Length of flexible web to form moving web=4479.96 mm;
[0032] Number of line of light emitting elements=7.
[0033] We also note that if everything stays the same. To increase the number of lines of light emitting elements C in each of the basic building unit will enable us to reduce the speed requirement of the rotating unit to P/C while we still maintain the fixed frame rate F. If we put in 4 lines of light emitting elements in each of the basic building unit, then to get a frame rate of 100, the rotating unit will only need 25 turns per second, as each line of light emitting elements will be require to scan the total of 480 lines with a delay of 40 lines, instead of 160 lines between each two of these lines. | A display apparatus comprises of at least two stationary rotating units, which are parallel and spaced apart from each other and housed in a rigid frame with at least one opening formed as a viewing window. A flexible web is wrapped around these two rotating units, forming at least one moving viewing plane in the opening of the rigid housing. There are at least one line of light emitting elements arranged parallel to the rotating units and travels constantly through the display opening. A control unit inside the housing provides power, display data and control signal to the light emitting elements on the moving web; A communication unit provides the necessary link between the control unit and the moving web so that power, display data and control signal can be passed on to the light emitting elements causing them to display either text, or video image on the moving web, which can be viewed through the opening of the housing, thus creates a single-face display apparatus. | 6 |
This is a division of application Ser. No. 439,846, filed Feb. 6, 1974, now U.S. Pat. No. 3,897,018.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to the continuous feeding of fiber materials, such as seed cotton, to fiber processing apparatus, such as a cotton gin.
2. Description of the Prior Art
Normally, cotton is picked by a mechanical harvester and collected in a large basket or bin on the harvester. When the basket is full, it is dumped into a wagon for transportation to a cotton gin. Since cotton is transported to the gin soon after being picked, the gins are operated at full capacity during the harvesting season. Accordingly, the gin is comparatively idle between ginning seasons.
The use of mechanical harvesters has decreased harvest season length and increased the rate of seed cotton flowing to the gin. This increased flow of seed cotton to the gin has required higher capacity, more efficient ginning operations.
High capacity gins present a difficult problem in obtaining an economical seed cotton unloading system. In an article by Oliver M. McCaskill and Eugene G. Columbus entitled "Mechanical Seed Cotton Unloading System", June 1968, United States Department of Agriculture, Agricultural Research Service, ARS, 42-144, several experimental gin feeding systems are disclosed which provide improved seed cotton feed rate. Generally, the authors describe a feeding system in which specially designed side dump trailers are loaded with seed cotton in the field. The side dump trailers empty into a hopper which is sized in accordance with the dimensions of the dump trailer. Cotton is conveyed from the hopper to breaker cylinders where it is fed to subsequent processing apparatus. One particular problem of these experimental systems discussed by McCaskill et al is that of an uneven feed rate of cotton from the hopper. The McCaskill et al article also summarizes many problems with prior art feeding devices.
U.S. Pat. No. 3,749,003, issued to Lambert H. Wilkes and Joseph K. Jones on July 31, 1973, discloses a mechanized seed cotton handling apparatus wherein seed cotton from mechanical harvesters is compacted onto a pallet. The pallet, with its compacted seed cotton, may be transported by conventional trucks to the cotton gin. In addition to reduced storage space required by compressed cotton, the pallet system makes possible high density feeding for cotton gins. Gin feeding systems, however, have not been designed to accommodate high density feeding made possible by the pallet system. Accordingly, the pallets have generally been unloaded by workmen manhandling the conventional suction pipe used to feed cotton gins.
The invention disclosed an efficient, relatively inexpensive apparatus for supplying fibers to fiber processing apparatus, especially seed cotton to cotton gins. Seed cotton, or the like, arrives at the gin on pallets which may be covered, for example, with tarpaulins and then stored for later use to effectively stretch out the high volume ginning season. Alternately, the seed cotton may be promptly fed to the gin and the inexpensive pallets returned to the field for reuse.
SUMMARY OF THE INVENTION
The process of this invention begins by translating cotton-laden pallets longitudinally along a generally horizontal supporting surface at a uniform continuous rate determined by the rate at which fibers are to be consumed by subsequent processing apparatus. The bulk of fibers on a pallet are removed and the pallet surface is then swept clean of remaining fibers. Fibers thus removed are piled upon a conveyor for movement to the subsequent processing apparatus.
The apparatus of this invention includes a generally horizontal bed along which fiber-laden pallets are translated from a loading zone to a discharge zone. The fibers on each pallet are engaged by rotary breakers which loosen and remove the bulk of the fibers from each pallet. Loosened fibers are dischared from the horizontal bed by a conveyor system to the subsequent processing apparatus.
BRIEF DESCRIPTION OF THE DRAWINGS
The detailed description of a preferred embodiment of this invention which follows includes reference to the drawings in which:
FIG. 1 is a longitudinal cross-sectional view of the apparatus;
FIG. 2 is a cross-sectional view along line 2--2 of FIG. 1 with the pallet removed for the sake of clarity;
FIG. 3 is a cross-sectional view along lines 3--3 of FIG. 1;
FIG. 4 is a cross-sectional view taken along line 4--4 of FIG. 3; and
FIG. 5 is a detail of the engagement between a pallet and the positioning conveyor.
DETAILED DESCRIPTION OF THE INVENTION
The general overall spatial relationship between the various elements of a fiber unloading apparatus is disclosed in FIG. 1. Fibers are fed to the apparatus on any suitable pallet such as that illustrated in FIG. 1. 1. Each pallet 20 may be fabricated from one or more sheets of plywood, for example, wood, metal or any other suitable material. The pallet 20 may be provided with a plurality of transversely-spaced longitudinal stiffening elements 22 as illustrated in FIG. 3. Each pallet 20 has been loaded with fibers 24 which are removed therefrom and fed to fiber processing apparatus by the fiber unloading apparatus. The fibers may be seed cotton which has been compressed for storage on pallet 20 by any suitable method. One example of a method whereby seed cotton may be compressed on a pallet for storage and subsequent handling is disclosed in U.S. Pat. No. 3,749,003, issued July 31, 1973, to Lamber H. Wilkes and Joseph K. Jones.
The apparatus herein disclosed is, of course, suitable for handling any fiber material which may be placed on pallets for storage and/or handling. It will be appreciated by those skilled in the art that the fibers 24 may or may not be compressed while stored on the pallets 20. Moreover, it will be appreciated from the following description that the pallets 20 need not be of a uniform length. The apparatus herein disclosed can readily accommodate pallets of different lengths with the same efficient operation.
The fiber unloading apparatus comprises a bed means such as a generally horizontal bed 32 on which the fiber-laden pallets 20 are longitudinally translated. The horizontal bed 32 disclosed in FIG. 1 comprises a pallet feeder 26, a pallet unloader 28, and a pallet stacker 30. The horizontal bed 32 is provided with a plurality of legs 34 which may be adjustable to obtain the generally horizontal alignment between the pallet feeder 26, the pallet unloader 28 and the pallet stacker 30. The horizontal bed 32 is provided with a loading zone at one end which zone receives pallets 20 one at a time and positions the pallet relative to previously loaded pallets. In addition, the horizontal bed 32 includes a discharge zone where empty pallets are removed.
The pallet feeder 26 of the apparatus includes a pair of longitudinal side rails 36 which are held in spaced relationship by suitable cross members such as 38. The pallet feeder 26 also includes a pair of interior longitudinal rails 40 which are spaced from one another as shown in FIG. 2. A plurality of short idling rollers 42 are disposed between each longitudinal side rail 36 and the interior longitudinal rail 40 adjacent thereto. Each of the short idling rollers 42 is supported at one end by a longitudinal side rail 36 and at the other end thereof by an interior longitudinal rail 40. Also disposed between the longitudinal side rails 36 and the interior longitudinal rails 40 are a plurality of short powered rollers 44. The short powered rollers 44 constitute a portion of a loading conveyor system which is driven at a first predetermined speed to translate pallets 20 longitudinally along the horizontal bed 32 and the pallet feeder 26. It will be noted from FIG. 2 that the short powered rollers 44 are positioned such that a pallet 20 engages the short powered rollers 44 only after it has been initially positioned on the short idling rollers 42 of the generally horizontal bed 32.
Since it is advantageous to move the pallets 20 along the generally horizontal bed 32 in a manner such that a continuous flow of fibers will be supplied to the fiber processing apparatus, it is desirable to maintain the pallets 20 in end-to-end abutting relationship. Accordingly, a positioning conveyor means is provided to position the pallets 20 on the pallet feeder 26. The positioning conveyor means includes an endless chain 46 which is driven by a powered sprocket 48. An idling sprocket 50 is also provided for support of the endless chain 46 at one end of the horizontal bed 32. Both the powered sprocket 48 and the idling sprocket are disposed in a space defined between the interior longitudinal rails 40. The endless chain 46 may be driven at a variable speed, to be described more fully hereinafter, to bring a pallet 20 into engagement with the loading conveyor system. The above-noted loading zone thus includes the positioning conveyor means, the short powered rollers 44 and the short idling rollers 42.
Each of the short powered rollers 44 is provided with a driving sprocket 52 at one end thereof. The rotational rate of the short powered rollers 44 is constrained to a uniform value by interconnecting the driving sprockets 52 thereof by a drive chain 54. To facilitate driving engagement between a short powered rollers 44 and the bottom surface of pallets 20, each of the short powered rollers 44 is provided with an engagement means such as a plurality of longitudinal ribs 56. It will be appreciated by one skilled in the art that any other suitable engagement means may be provided on the short powered rollers 44 to facilitate driving engagement with the bottom surface of pallets 20.
The pallet feeder 26 may also include a plurality of long idling rollers 58 which are supported on each end by the longitudinal side rails 36. In addition, the pallet feeder 26 includes a plurality of long powered rollers 60 which comprise a transition conveyor means. Each long powered roller 60 is provided with a driving sprocket 62 at one end thereof and may be provided with an engagement means 64 to facilitate driving engagement with the bottom surface of a pallet 20.
The driving sprockets 62 of the transition conveyer means are drivingly interconnected by chain 63. Chain 63 is in turn driven by a two-speed clutch 65. A handle 69 provided on clutch 65 permits the transition conveyor to move pallets 20 at a first predetermined speed or at a second predetermined speed. The first predetermined speed corresponds to the predetermined speed at which the loading conveyor moves pallets. The second predetermined speed is slower than the first predetermined speed to enable the positioning conveyor means, the loading conveyor means and the transition conveyor means to position pallets 20 in end-to-end abutting relationship with previously positioned pallets.
A pivotally mounted hook 66 is provided for each pallet 20. Each hook 66 is connected to a strap 67 provided therefor at one end of each pallet 20. The hook 66 is engaged by the endless chain 46 to facilitate the initial positioning of a pallet 20 on the pallet feeder 26. The relationship of hook 66 and chain 46 is best illustrated by FIG. 5.
When pallets 20 have been properly positioned on the horizontal bed 32 and are translating in the direction shown by arrow 68 of FIG. 1, pallets 20 leave the pallet feeder 26 and enter the pallet unloader 28 which includes a pair of longitudinal side rails 28 that are rigidly spaced in any suitable manner such as by cross members. A plurality of idling rollers 72 are rotatably supported at each end by one of the longitudinal side rails 70. Similarly, two or more powered rollers 74 are supported rotatably at each end by the longitudinal side rails. The powered rollers 74 are part of a feed conveyor means which translates pallets 30 in abutting relationship at the second predetermined speed. Generally, the powered rollers 74 are spaced adjacent to one another along the horizontal bed 32 and are provided with a driving sprocket 76 at one end. The driving sprockets 76 are drivingly interconnected by a chain 77.
The pallet unloader 28 includes a first vertical wall 78 which is attached to one of the longitudinal side rails 70. A second vertical wall 80 is connected at one end of the first vertical wall 78 and is transversely disposed between the pair of longitudinal side rails 70. A third vertical wall 82 is disposed parallel to the first vertical wall and is positioned on the second longitudinal side rail 70. The three vertical walls 78, 80, 82 define an entrance 86 through which fiber-laden pallets 20 enter a chamber 90 defined therebetween. The first vertical wall 78 is provided with a fiber egress opening 84. The second vertical wall 80 is spaced vertically above the horizontal bed 32 to define a pallet egress opening 88 as clearly seen in FIG. 1.
Disposed within chamber 90 is a breaker means which includes a plurality of rotary members 92. The rotary members 92 are suitably rotatably mounted at one end in vertical wall 78 and suitably rotatably mounted at the second end thereof in vertical wall 82. Each rotary member 92 is horizontal and is transverse to the horizontal bed 32. Moreover, each rotary member 92 is spaced vertically above the horizontal bed 32 and spaced vertically from the other rotary members. Each rotary member is provided with a spiral auger blade 94 and a plurality of spikes 96. The spikes 96 and auger blades 94 facilitate the removal of fibers 24 from a from a pallet 20 as will be described more fully hereinafter.
The positioning of horizontal adjustment slots 100 in vertical wall 78 is illustrated in FIG. 4. A similar arrangement of adjustment slots is provided in vertical wall 82. The slots 100 permit horizontal positioning of rotary members 92 while maintaining the vertical spacing therebetween. Each rotary member 92 has a driving sprocket 89 at one end thereof which is drivingly interconnected with driving sprockets 98 of the other rotary members 92 such that each rotary member 92 rotates at a uniform angular velocity.
Also disposed within chamber 90 is a rotary sweeper 102. The rotary sweeper 102 is transversely positioned with respect to the horizontal bed 32 and includes a plurality of radially-aligned sweeping blades 104 which engage the upper surface of each pallet 20 and remove any fibers 24 remaining thereof after the pallet 20 has passed under the plurality of rotary members 92. The rotary sweeper 102 rotates such that the lowermost sweeping blade 104 moves in a direction opposite to that of arrow 68.
A transverse conveyor 106 is also provided within chamber 90. In the preferred embodiment, the transverse conveyor 106 includes an endless belt 108 having an upper moving surface 110 and a lower moving surface 112. At this point it should be noted that the transverse conveyor might be comprised of other suitable conveying systems including an auger system or screw conveyor system. One end of the transverse conveyor 106 protrudes through the fiber egress opening 84 and into a suction chamber 114; the other end of transverse conveyor 106 protrudes slightly through wall 82. The continuously moving endless belt 108 conveys fibers 160, which pile thereupon, transversely with respect to the horizontal bed 32 and deposits the fibers in suction chamber 114 wherein a current of air entrains the fibers and conveys them to the subsequent fiber processing apparatus. The upper moving surface 110 of the endless belt 108 is disposed with the chamber 90 such that each pallet 20 passes between the upper moving surface 110 and the lower moving surface 112 after the pallet has been swept by rotary sweeper 102 and prior to leaving the chamber 90 through pallet egress opening 88.
As a pallet 20 emerges from chamber 90 through pallet egress opening 88, the pallet proceeds to a pallet stacker 30. The pallet stacker 30 stacks pallets 20 for subsequent reuse and may be any conventional apparatus suitable for the purpose. The pallet egress opening 88 and the pallet stacker 30 are thus parts of the above-mentioned pallet discharge zone.
It will be noted that although only three vertical walls 78, 80, 82 are provided, fibers loosened and removed by rotary members 92 are inhibited from spilling out of the top of chamber 90 by two effects. The first is gravity which creates a natural tendency for the fibers to descend through chamber 90 toward transverse conveyor 106. The second is the current of air which is sucked into suction chamber 114 through fiber egress opening 84. The suction in chamber 114 creates a flow of air generally downward through chamber 90 which engrains the fibers loosened by rotary members 92.
To drive the rotating parts of the pallet unloading apparatus herein described, a hydraulic pump and control system 116 may be attached, for example, to vertical wall 80. Suitable hydraulic motors may be provided as necessary to drive the rotating parts. For example, hydraulic motor 118 may be provided to drive rotary members 92, hydraulic motor 120 for the pallet sweeper 106 and hydraulic motor 122 for the transverse conveyor 106. Each of the short powered roller systems may be provided with a hydraulic motor 120 to drive each drive chain 54. Similarly, a hydraulic motor 128 may be provided to drive the endless chain 46. Likewise, hydraulic motor 130 is provided to drive the transition conveyor means through clutch 65 and hydraulic motor 132 is provided to drive feed conveyor means through drive chain 77. Suitable controls may be provided to separately control the hydraulic motors driving the positioning conveyor means, the loading conveyor means, the transition conveyor means and the feed conveyor means. The second predetermined speed is determined by the capacity of the fiber treatment apparatus to which the pallet unloading apparatus is connected by means of the suction chamber 114 and may be adjusted according to the type of fiber processing apparatus being supplied. Typically, the first predetermined speed may be on the order of 15 feet/minute and the second predetermined speed may be on the order of 2 feet/minute.
It would, of course, be possible to use electric motors with suitable transmissions or any other suitable power devices to drive the rotating portions of the apparatus herein described.
In addition, it would be possible to use the pallet unloading apparatus herein described in combination with fiber processing apparatus not fed by an air current having entrained fibers. In this situation, fibers carried from the chamber 90 by the transverse conveyor 106 might be deposited directly within the fiber inlet of fiber processing apparatus. In the case of seed cotton fed to a cotton gin, the seed cotton may be fed directly to the hot air stream of the gin.
In operation, the leading edge of a pallet 20 having fibers 24 disposed thereon is first engaged by the endless chain 46. Hook 66 of a pallet 20 is connected with endless chain 46 as shown in FIG. 5. The chain 46 is then driven to pull pallet 20 over short idling rollers 42 to the short powered rollers 44 of the loading conveyor means. When the short powered rollers 44 engage the newly-positioned pallet, the hook 66 is disconnected from the endless chain 46 which may then be used to position a subsequent pallet.
After the endless chain 46 has been used to position the pallet 20, the short powered rollers 44 convey the fiber-laden pallets at the first predetermined speed longitudinally along the horizontal bed 32 to the transition conveyor means which is operating at the first predetermined speed. When the pallet 20 is in abutment with a previously loaded pallet, clutch 65 permits the transition conveyor to change speed to the second predetermined speed. As pallet 20 advances to the feed conveyor, the speed of the transition conveyor may be changed back to position a subsequent pallet. The feed conveyor translates the pallet through the unloading portion 28.
The leading end 150 of fibers 24 disposed on a pallet 20 is first engaged by the plurality of vertically disposed, horizontal rotary members 92. The fibers 24 are then loosened from the advancing end 150 by the rotating spikes 96 and the spiral blades 94 of rotary members 92. The interaction of the rotating spikes 96 and spiral blades 94 eliminates aggregations of fibers. Loosened fibers 155 generally fall into a pile 160 on transverse conveyor 106. Any fibers 24 which are not loosened and removed from the pallet by the rotating members 92 are swept from the pallet surface by the rotary sweeper 102. The pallet passes below the upper moving surface 110 of the transverse conveyor 106 and thereby does not collect any of the loosened fibers 155. The loosened fibers 155 which have coalesced into a pile 160 on the endless belt 108 of transverse conveyor 106 are moved transversely of the horizontal bed 32 toward a suction chamber 114. An air current removes the fibers from the suction chamber 114 for subsequent processing. The pallet 10, having the fibers 24 removed therefrom, passes out of chamber 90 through pallet egress opening 88 and is stacked by pallet stacker 30 for subsequent use.
At this point it will also be apparent that the pallet feeder portion 26 may be used independently of the pallet unloader 28 if a conventional gin suction tube is used to unload pallets 20. In this case, the pallet feeder would permit economical feeding of a gin by eliminating the time wasted for trucks to off-load their cargo of fibers.
The fiber-laden pallet unloading system described above has numerous advantages not heretofore available.
One advantage is the accommodation of pallets which have different lengths. This advantage is made possible by the long horizontal bed that supports the pallets and the abutting end-to-end positioning of the pallets.
Another advantage is the continuous feeding of fibers at a constant rate to subsequent processing apparatus which results from the end-to-end abutting relationship between pallets and the constant translational speed of the pallets on the horizontal bed.
Another advantage is the reduction of the number of workmen otherwise required to feed apparatus such as a cotton gin. This reduction is made possible by the mechanized pallet unloading apparatus which eliminates manhandling of a gin feeder suction tube.
A further advantage is that fiber-laden pallets may be stored during peak harvesting periods and processed at a later time thereby effecting a more continuous, and effective, use of expensive fiber processing machinery. In addition, the capacity required in fiber processing apparatus is reduced as a result of the longer period of time during which fiber processing may now be conducted.
When seed cotton is compressed on pallets and removed therefrom for ginning, the above apparatus has an additional advantage in that the rotating augers cause strain on individual "locks" of cotton during the pallet unloading process and thus aids the ginning process.
The use of easily fabricated, inexpensive pallets provides a further advantage in that capital expenditures for specially designed truck bodies are substantially eliminated in contrast to some prior-air gin-feeding apparatus.
The foregoing description discloses the preferred embodiment of the invention but does not in any way comprise a limitation of the scope of the claims appended hereto. Accordingly, the scope of the invention is defined by the claims and all modifications and equivalents thereof are intended to be included within the scope of the claims. | A system is disclosed wherein fibers are mounted on pallets for ease in handling and storage. The system uses the pallets to provide a continuous, uniform rate of fiber feed to other apparatus for subsequent fiber processing. A positioning system arranges pallets in end-to-end abutting relationship to provide the uniform rate of fiber feed generally desired for fiber processing. A plurality of vertically spaced horizontally disposed rotating augers engage the advancing face of fibers on a pallet to remove the bulk of fibers therefrom. The pallet surface is subsequently engaged by a pallet sweeper which removes any fibers not removed by the rotating augers. The loosened fibers are deposited on a transverse conveyor which overlies the pallet surface and moves the fibers transversely of the pallet unloading apparatus for delivery to the fiber processing apparatus. | 3 |
BACKGROUND OF THE INVENTION
1. Field of the Invention:
This invention relates to a carton construction, and more particularly, a carton construction provided with an integral handle on the top thereof for carrying the carton and its contents.
Heretofore, it was common practice to affix a separate paper handle to the top of a carton construction, e.g., a carton filled with laundry detergent, so the carton and its contents could be conveniently carried out of a retail establishment by a purchaser.
Due to the slow speed of applying the combination paper and plastic handle to the carton during fabrication, cost of construction has become excessive. Users, therefore, have created a demand for a less costly handle system, which is required on such cartons because of its bulk and weight.
Accordingly, this invention provides a handle integrally affixed to the carton blank in such a manner so that it can be formed expediently along with the erection of carton blank. The handle is also provided with a reinforcement to tearing and rupture at its joinder to the carton. Since the handle is integrally formed with the carton blank, it is also conveniently available for use by the carton consumer, who need only bend it out of the plane of the top of the carton to a substantially upright condition ready for use.
A similar carton was disclosed in our copending application being filed concurrently herewith and entitled "Carton With Integral Carrying Handle". In that application, a paperboard blank is provided having front, back and side panels which are connected by and folded about vertical score lines to form a rectangular parallelopiped enclosure or carton. Each of the front, back, and side panels include upwardly and downwardly extending substantially rectangular flaps connected to the panels by horizontal score lines. When the flaps are folded, a bottom and top wall for the enclosure is provided.
Die-cut in the upwardly extending flaps connected to the front and back panels, respectively, are mating handle elements, which when glued together, form an integral handle with the top wall of the carton which can be pivoted from a stored or non-use position lying substantially flat on the carton top wall to a substantially upright position perpendicular thereto.
Each handle element is die-cut from the top edge of the upwardly extending flap along diverging lines towards the front and back wall portions of the front and back panels, respectively, of the blank. Then, the handle element is scored substantially parallel to the top edge of its respective front and back flap to form a hinge therefor. A rectangular portion is die-cut from the interior of each handle element, but the lowermost edge thereof is left intact with the remainder of the flap adjacent the score line.
During assembly, the upwardly extending flaps connected to the front and back panels are folded into overlapping condition. One of the handle elements on either the front or back flaps is bent back upon itself 180° about its joining score lines to present a complementary surface facing the other handle element. The facing surfaces, as well as the overlapping flaps including the rectangular die-cut portion, can then be glued together.
The secured handle elements will lie substantially flat on the top wall of the carton, but can be pivoted about the score lines to a substantially upright condition.
In order to reinforce the joinder of the handle to the top wall of the carton, a pressure sensitive type tape is applied in a continuous strip across the entire width of the carton so as to lie just below and parallel to the joinder score line hinges of each handle element. This aids in precluding the handle from tearing or rupturing from the carton when the weight of the carton and its contents are supported by the handle.
SUMMARY OF THE INVENTION
To further strengthen the integral handle structure just described, an additional handle element comprising the mirror image of one of the handle elements, may be joined by a score line hinge to the top edge of one of the two handle elements glued together. When the handle elements are joined, the additional handle element may be pivoted 180° to overly the joined handle elements to provide a thickener reinforcement element. A tab joined to the lower edge of the additional handle element by a score line is rotated 180° around the lower edges of all the overlying handle elements to join the additional handle element to the others, and serve as a finger guard when carrying the carton.
BRIEF DESCRIPTION OF THE DRAWINGS
Further objects and advantages of the invention will become apparent from the following description and claims, and from the accompanying drawings, wherein:
FIG. 1 is a fragmentary perspective view of a carton provided with the integral carrying handle of the present invention;
FIG. 2 is a plan view of a blank for forming the carton of FIG. 1;
FIG. 3 is a plan view of the top portion of the opposite side of the blank of FIG. 2;
FIGS. 4 to 7 are perspective views illustrating the manner of forming the carton of FIG. 1 from the blank of FIG. 2; and
FIG. 8 is a longitudinal cross-sectional view of the carton of FIG. 1.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawings in detail, wherein like numerals indicate like elements throughout the several views, a carton 20 having an integral carrying handle 22 is formed from a paperboard blank 24 having a front panel 26, a back panel 28, and a pair of side panels 30 and 32, which are connected by and folded about vertical score lines 34 to form a substantially rectangular parallelopiped enclosure.
Connected by a vertical score line 34 to the free edge of back panel 28 is an extension flap 35, provided with an adhesive surface 37. Flap 35 is bent about the free edge of side panel 32 and adhered thereto to maintain the rectangular configuration of carton 20. Alternatively, the opposite surface of flap 35 can be provided with adhesive and the flap connected to the interior surface of side panel 32.
Each of the front, back, and side panels includes a downwardly extending, substantially rectangular flap 36 connected to its respective panel by a horizontal score line 38. The flap 36 connected to back panel 28 has an adhesive surface 40. When flaps 36 are folded about score lines 38, the flaps connected to the front and back panels overlap the flaps connected to the side panels and each other to form a bottom wall 42 for carton 20. The surface 40 can be adhesively connected to the lower surface of the flap 36 connected to the front wall 26 to retain the bottom wall together.
Each of the front, back and side panels also includes an upwardly extending, substantially rectangular flap 44 connected to its respective panel by a horizontal, reinforced rib 46 extending the entire width of blank 24. Rib 46 serves as a reinforced hinge about which each of the flaps 44 can be bent and overlapped to form the top wall 48 of carton 20. When bent, one of the flaps 44 connected to the back or front panel completely overlies the flaps 44 connected to the side panels (as shown in FIGS. 4 to 7), while the other of the flaps 44 connected to the back or front panel overlaps the one flap 44 overlying the flaps connected to the side panels. To retain the flaps closed on the carton 20, each of the flaps 44 connected to the front and back panels has an adhesive surface 50; the adhesive surface on the one back or front flap 44 being secured to the top surface of the side flaps 44, while the other back or front flap 44 being secured to the top surface of the one back or front flap.
Die-cut in the upwardly extending flaps 44 connected to the back and front panels 28 and 26, respectively, are mating handle elements 52, which when glued together, form a portion of the integral handle 22 for carton 20, which can be pivoted from a stored or non-use position lying substantially flat on the carton top wall 48 to a substantially upright position perpendicular thereto, as shown in FIGS. 1, 7 and 8.
Each handle element 52 is die-cut from the top edge 54 of the upwardly extending flap 44 along spaced diverging lines 56 and 58 towards the front and back wall portions of the front and back panels 26 and 28, respectively, of the blank 24. Then, the handle element is scored substantially parallel to the top edge of its respective front and back flap at 60 and 62, to form a hinge therefor. A rectangular portion 64 is die-cut from the interior of each handle element, but the lowermost edge 66 thereof is left intact with the remainder of the flap 44 adjacent to and contiguous with the score lines 60 and 62.
As shown in FIGS. 4 to 7, inclusive, during assembly, the upwardly extending flaps 44 connected to the front and back panels are folded into overlapping condition. One of the handle elements 52 on either the front or back flaps 44 is bent back upon itself 180° about its joining score lines 60 and 62 to present a complementary surface facing the other handle element 52 (FIG. 5). The facing adhesive surfaces 50, as well as the remainder of the overlapping flaps 44 including the rectangular die-cut portions 64, can then be glued together.
The secured handle elements 52 can be pivoted together about their score lines 60 and 62 to a substantially upright condition, providing an aperture 69 to receive the fingers of a hand. The aperture 69 is formed by the non-pivotable portions 64 of each handle element being held rigidly adhered together on the top wall 48 of carton 20.
In order to reinforce the joinder of the handle 22 to the top wall 48 of the carton 20, a pressure sensitive type tape 68 is applied in a continuous strip across the entire width of the carton 20 on the outer surface of blank 24 before the flaps are cut, so as to lie just below and parallel to the joinder score line hinges 60 and 62 of each handle element 52. This aids in precluding the handle from tearing or rupturing from the carton when the weight of the carton and its contents are supported by the composite, integral handle 22. Alternatively, tape 68 may be applied across the entire width of the inner surface of blank 24 below and parallel to hinges 60 and 62 or if the paperboard of the blank is of a two-ply construction, the tape may be sandwiched between the plies adjacent hinges 60 and 62. The tape may have a mesh construction, if desired, and may in the laminated version be disposed along the entire length and width of the panels 44.
In lieu of a pressure sensitive or mesh tape, the reinforcement may be supplied by utilizing specially designed embossings or debossings on the blank which surround the handle structure. By incorporating such embossments or debossments, not only can reinforcement of the handle be achieved, but end panel dimensional disparity of the entire end flap configuration is reduced when the flaps are folded into their final configuration. Additionally, the embossing and debossing allows the end flaps to interlock thereby providing more positive glue adhesion and more resistance to breakage where the carton is subjected to dropping and lifting.
To further strengthen the integral handle structure, an additional handle element 52' comprising the mirror image of one of the handle elements 52, may be joined by a score line hinge 70 to the top edge of the handle element in blank 24. When the handle elements 52 are joined, the additional handle element 52' may be pivoted 180° about hinge 70, as illustrated in FIGS. 6 and 7, to overly the joined handle elements 52 to provide a thickener reinforcement element. A tab 74 joined to the lower edge of the additional handle element by a score line 76 may also be rotated 180° about score line 76 around the lower edges of the joined handle elements 52 to join the additional handle element 52' to the others, and serve as a finger guard when carrying the carton, precluding cutting of the fingers by the bottom of handle elements 52.
The secured handle elements 52, 52 and 52' can be pivoted about their score line hinges, if desired, to lie substantially flat on the top wall 48 of the carton 20, and thus be stored when not in use. | A carton provided with an integral, pivotable carrying handle on the top wall. The handle is a portion of a unitary blank of paperboard stock used to form the carton. When the carton is erected, the handle can be pivoted from a substantially flat stored position on the top wall to an upright use position for carrying the carton. The handle is formed from three overlapping panels after the blank is folded to provide a handle having superior strength. | 1 |
1.0 BACKGROUND OF THE INVENTION
1.1 Broadcast, VCRs
This invention is related to the field of broadcast television in all it's forms. This includes but is not limited to over-the-air broadcast, cable TV, and satellite TV. The primary focus is the broadcast paradigm, whereby programs are scheduled by the broadcaster and broadcast in real-time whereupon viewers may tune in to the program. This invention relates in particular to a device which allows users much greater flexibility in their reception and use of this programming. VCRs are one example of an earlier technology that relates to the use of broadcast programs. Using VCRs, viewers were able to record a program and play it back at their leisure, perhaps at another time. Additionally, for the first time viewers were offered limited control over the viewing. The user could pause, rewind, fast-forward and stop and re-start viewing at any time after the initial recording was complete. The broadcast program was essentially captured in an analog medium for later use. Some of the limitations of a VCR which the present invention addresses are: simultaneous record and playback from the same medium are not available; the device records only one, or at the most two, channels at a time; and a removable medium, namely magnetic tape, is required.
This invention relates in a similar fashion to the broadcast television industry but offers new and unique features not found in VCRs or any other video/audio-programming-based device.
2.0 OBJECTS OF THE INVENTION
The objects of the present invention include, but are not limited to the following. It is one object of the invention to facilitate recording of a program and allow viewing of the already-recorded material to take place while the program recording continues. It is another object of the invention to allow this simultaneous record/playback to take place on one or more channels simultaneously. It is another object of the invention to record using digital storage in many forms, using either internal or external mediums. It is another object of this invention to provide a ‘save’ function which incorporates semi-permanent digital storage of the recorded program as a function distinct from the simultaneous recording and playback of the program. It is another object of the invention to allow complete VCR-like control during playback. It is another object of this invention to allow the ‘save’ function to save edited versions of the program as defined by the playback commands used during viewing.
3.0 SUMMARY OF THE INVENTION
3.1 Overview
With the advent of digital video components, it is now possible to digitize, compress and store entire video programs using a variety of digital storage devices such as disk, digital tape, RAM, CD-ROM, DVD (Digital Versatile Disk or Digital Video Disk) and others. In the present invention, the system may be connected to a conventional video source such as broadcast TV, cable TV, satellite TV, VCR and so forth. In most cases, the video signal is in a standard RF-modulated analog format such as NTSC, PAL or SECAM. In the case of a modulated video source such as broadcast TV or cable TV, the signal is first demodulated to tune to a specific channel. This is performed by a conventional tuner such as those found in VCRs and TVs. The tuner may be used to tune into one or more channels simultaneously and more than one tuner may be included in the system. Digital inputs are also provided and will be described shortly. In the case of an incoming analog video signal, the signal is then digitized and optionally compressed using a conventional video capture board or video capture chip sets integrated into the system. This capture hardware accepts a video input, digitizes the video/audio program, optionally compresses the quantity of digital data and outputs a digital data stream which can be stored using any digital storage media. In variations of the preferred embodiment, the incoming video signal may already be in a digital format and thus not require digitization (such as a High-Definition Television (HDTV), Direct Broadcast Satellite (DBS) signal, or Internet-based broadcasts). Furthermore, the source digital signal or the digitized analog signal may or may not be compressed. The compression method used may vary and is of little consequence to the present invention which can use uncompressed digital data or compressed data. However, the current common compressed digital formats include MPEG and AVI formats. For the present invention, the selection of the video capture board or chip sets (and the compressed digital format it uses) is relevant only to the quality of the video playback and the corresponding amount of digital storage required. It is envisioned that the embodiments will vary depending on the desired quality and cost constraints for the storage media. In a relatively inexpensive consumer device, for example, a cost-efficient MEPG-1 and inexpensive four-Gigabyte hard drive might currently be used. On the other hand, a professional application might currently use MPEG-2 and RAM for very high quality along with very fast access. An important consideration regarding the selection of the video capture board and the storage media is that the data rate for writing to the digital storage must exceed the output rate of the video capture hardware. For example, if MPEG-1 is the selected compression method and the output rate of the capture/compression hardware is therefore 1.5 Mbits/second, then the sustained data rate for writing to digital storage must be greater than 1.5 Mbits/second or else data will be lost. Also, compression/decompression may take place via software algorithms implemented by the system's main CPU or in dedicated compression/decompression processors. Cable converter boxes, commonly known as “set-top” boxes provide decoding of compressed digital video streams. In such a case one embodiment of the present invention includes a provision for using the set-top box for providing the compression/decompression for the system.
3.2 Dual-Port Circular Buffer Storage
A key aspect of the present invention is it's use of FIFO dual-port storage. Digital storage systems are most commonly used in an off-line mode, that is, data is written and the data is read at some later time. For example, in a video compression and playback system, the compressed digital data would likely be written to disk during recording and, after the recording process has been completed, the data could be read for playback. In this sense, storage is used as an archive—even if the archive will be used moments later, the process of storing all the data must be completed before the data is used. In contrast, the present invention is designed to be dual-ported, that is, to be accessed for writing and reading simultaneously on the same media. In this manner, at any time after the process of capturing, optionally compressing and storage has begun, the program is also accessible for reading, decompression, playback and other functions. This can also occur while the recording process is continuing to store data using a separate and distinct section of the same storage medium. Additionally, the storage medium in the system is designed as a FIFO, which is a commonly-understood acronym in the art which stands for First In First Out. FIFO storage is essentially used as a circular buffer. The first data written into this circular buffer is the first data which is overwritten. For brevity, the terms ‘buffer storage’ or ‘buffer’ may be used herein, but the term always refers to this dual-port circular buffer storage unless otherwise noted.
In an example of the preferred embodiment, the use of this buffer storage is also taken a step further. In this embodiment, once the storage medium has been filled, the oldest data, which is the first data to have entered the FIFO, is pushed out—it is overwritten with the new data. In this manner, the buffer storage is constantly filled with the latest recorded material. The total amount of storage in the buffer determines the extants of VCR-like control for rewind and fast-forward. Alternatively, only a designated amount of the total storage may be used for recording, leaving storage available for other features of the system. In any case, this FIFO dual-port storage will be referred to herein as buffer storage. Buffer storage is always the storage used to provide direct access for the viewer to control playback of the recorded material.
3.3 Circular Buffer Example
In the example of the preferred embodiment, consider the scenario for 30 minutes of buffer storage and the viewer wishing to begin viewing of a two-hour program fifteen minutes after the scheduled broadcast start time of 8:00 p.m. At 8:00 p.m. the system begins recording the broadcast program. This may occur due to a timer previously set by the user or it may occur because the system is set to continuously record. Furthermore, the system may have been recording continuously for some time. However, in order to illustrate the nature of the dual-port circular buffer, in the present example we consider the case where the present invention has just been turned on and the buffer has been initially empty.
Recording of the broadcast program begins at 8:00 p.m. At 8:15 p.m. the user begins viewing the 8:00 p.m. material. Simultaneously, the present invention continues to record the currently-broadcast 8:15 material. At 8:30 the buffer storage is completely filled. Consequently, the oldest material, namely 8:00, is overwritten with the current 8:30 material. This process continues indefinitely, and effectively, the viewer has time-shifted their viewing by 15 minutes in the present example. (The user may time-shift up to the maximum buffer storage size configured in the system, which in the present example would be 30 minutes.)
Because of the aforementioned 15-minute time-shift the viewer may now exercise VCR-like control features on the already-recorded material. So in the present example, the viewer could fast-forward past commercials or any objectionable material. Pause, stop and rewind features are also available, enabling the viewer to re-watch a segment or to pause the playback for a phone call or other interruption.
3.4 Catching up to Live Broadcast
If the viewer were to fast-forward through the full buffer of recorded material, they would be caught up to the live broadcast. When this occurs, the present invention may switch directly to the live feed without processing the input video through the usual capture and compression. In a further embodiment, even the input video stream (which is the ‘live’ feed) may be processed through capture and compression if so desired. Note that In such a scenario only pause and rewind features would be available because no material is available in the buffer for fast-forwarding.
3.5 Do-Not-Overwrite Mode
In one use of the present invention, the user may be watching video playback at the same rate at which new data is being recorded. Assuming that in the time between initiating recording and playback, the buffer storage has not already been filled up, it will in fact never get filled up because data is being removed at the same rate at which it is being added.
However, in another scenario, the user may not watch video playback at all during the recording process. In one embodiment of the present invention, the buffer storage is simply allowed to fill up and the recording process stops. In such an embodiment, it is the user's responsibility to recognize the limited amount of buffer storage in the system and use the system accordingly.
Consider the embodiment whereby the system is designed to store two hours of video from one or more channels and is not set to overwrite any recorded data. In such a case, the recording process acts much like a conventional VCR—two hours of programming are recorded and when the storage media is filled, recording stops. However, the present invention, even in this particular embodiment has several unique advantages over a VCR. Programming viewing and control, by virtue of the digital data, is entirely random-access. The user may almost instantaneously skip to any desired portion of the program. Furthermore, even though the recording process stopped when storage was filled, once playback begins, the user may record new material while viewing the two hours of previously-recorded material.
3.6 Partial Summary of Unique Features
The aforementioned features in essence return control of viewing to the viewer, who is no longer forced to view objectionable broadcast material or to adhere strictly to the broadcast schedules. Complete control is returned to the viewer, especially for real-time broadcasts. To achieve this control, the viewer need only slightly delay their viewing from the normally-scheduled broadcast start time. Once the present invention's FIFO dual-port storage has recorded some portion of the programming, the viewer has complete VCR-like control over the slightly-delayed but real-time broadcast, without having to wait for the entire program to be recorded.
3.7 Multiple-Channel Device
To complete the paradigm shift into viewer-controlled broadcast television viewing, one embodiment of the present invention performs all of the aforementioned functions simultaneously on many channels. In this manner, the viewer may literally scan through, watch, or store one or more of the channels, with all of the aforementioned features. In such an embodiment, multiple video capture compression/decompression cards would be required, or cards that are designed to accommodate more than one video input stream. Multiple input streams may be realized through multiple tuners with multiple output streams to one or more storage devices or through a single tuner with multiple output streams to one or more storage devices. The total aggregate bandwidth of data to be stored might also require faster storage media. Certainly RAM-based systems could handle such bandwidths and write speeds. In a disk-based embodiment, high-speed disk drives such as RAID drives can accommodate the higher bandwidths. The total required bandwidth in any embodiment is determined by the output data rate of each video capture/compression card, chipset or software data stream. By varying the quality of the video, the compression method or the video resolution, the bandwidth may be adjusted to suit the application. In some cases, these and other parameters of the video capture/compression hardware or software are adjustable, thus allowing the output data rate to be adjusted. In other cases, this adjustment is made merely by the selection of the desired compression/decompression hardware or software versus another. In one embodiment this configurability is tied directly to the content provider. For example, certain movies may include a command which is recognized by the present invention and is used to set (at the user's discretion) the compression/decompression quality to a higher-than-usual level.
3.8 Archival and ‘Save’ Features
Another feature of the present invention is it's ability to off-load the buffer storage onto other more permanent media for either internal or external archival. For example, a RAM-only embodiment may also be configured with one or more other digital storage devices, such as hard-disk or recordable DVD. At any time, even automatically during recording and/or playback, the contents of the buffer storage may be selectively or continuously transferred or duplicated to these archive storage devices in order to retain a copy of the program. In some embodiments, the viewer will transfer the program to removable media such as DVD disc in order for it to be used in another device, including another of the present invention. In this manner, viewers can build a ‘library’ of recorded material much like is currently accomplished with conventional VCRs. Such archival may occur at any time, including before, during or after the viewing of the stored material. In one embodiment, archival occurs as a user-selected transfer from the main storage to archival storage. In another embodiment programming is continuously recorded on the larger archival storage in addition to the main storage.
The present invention, however, offers several additional advantages over the traditional analog-tape VCR library. First, due to the digital nature of the data, many different embodiments are envisioned utilizing different types of digital storage media. In some embodiments, multiple types of storage media may be used, offering different levels of off-line or on-line storage and allowing the user to account for the various cost and physical considerations of the stored media type. Archival storage may be implemented as distinct devices separate from the buffer storage or as an allocation of one large storage device, with one portion designated and used as buffer storage and another as archival storage.
Another unique feature of the storage characteristics of the present invention is that the aforementioned archival functions may be initiated at any time including after the program has been viewed in it's entirety from the buffer storage. For example, in a RAM-based embodiment, the user may elect to transfer the entire contents of the program from RAM to hard disk, while playback and recording continue, or the user may also elect to transfer after viewing from RAM is complete. The only caveat in this process is that the user must consider the overwriting, circular buffer nature of the buffer storage and that the oldest material is overwritten when the allocated amount of storage becomes full. For this reason, this overwriting feature as well as all features of the system may be user-configurable. Other examples of archival storage mediums, both internal and external, include but are not limited to: hard disk, removable hard disk, tape, optical disk, DVD or any other digital storage medium.
3.9 Save-with-Edits Feature
Another unique feature of the storage characteristics of the present invention is that the aforementioned archival functions may include interpretation of the playback control as edit events, thus modifying the copy of the program which is to be archived. For example, a user may record a TV movie, fast-forwarding past each commercial. Upon storing the viewed program, the user may elect to interpret the fast-forwarding or similar control in several ways. First, it may be taken literally, with the archived program including a control code for ‘fast-forward’. Upon playback, this control could be interpreted and executed by the playback control software, thereby resulting in the playback of the program exactly as the viewer watched it, fast-forwards and all. A second manner of interpreting the fast-forward could be as an edit point, the implication being that since the user fast-forwarded past a portion of the program they did not want to view it and therefore that portion of the program need not be archived at all. In such a mode, upon playback the video would seamlessly skip past the fast-forwarded portion of the program since it was not recorded in the archive at all. And in a third manner of interpreting the fast-forward or other playback controls, these controls may not be recorded in archive at all, i.e. they may be ignored, implying that the user desires to have brand-new control over the video at playback time.
3.10 Demographic and Viewing Habits Data Collection
A further feature of the present invention is that all of the aforementioned VCR-like control features may be stored as data representing the viewer control. In other words, all of the viewer control such as fast-forward, play and pause are captured as data. This viewer control data may be used in a number of ways, including storage along with the archived program as described previously. In another embodiment of the present invention, a modem is provided for communication to other similar devices or to computers via network communication channels, such as phone lines, cable modems, and satellite. In such an embodiment, at the election of the viewer, the viewer control data may be provided to a central computer for storage. The data may later be analyzed by advertisers, broadcasters, ratings companies and so forth to receive indirect feedback from viewers regarding viewing preferences. This same communication channel may be used to transmit software upgrades to the invention, remote diagnostics, billing data or pay-per-view locking/unlocking by the content provider. In another embodiment, the modem may be replaced by a faster communications device such as a satellite receiver, Internet connection or so forth.
3.11 Network-Controlled Configurability
The aforementioned network communication channels are also used in another unique way. Since these channels provide a link to other computers, possibly on the Internet, this connection may be used to automatically set the configuration of the system from these computers. For example, in an embodiment connected to the Internet, the system also includes basic computer components sufficient to interact with the World-Wide Web. Besides the network communications channel the system also includes a video graphics card and one or more user-interface devices which may include but are not limited to: a mouse, touchpad, keyboard, trackball, remote control or voice control. With this Web-based connection, content providers or third parties may link Web pages to interact with the present invention. For example, a third party may offer pay-per-view programs, wherein the program may be ordered via the Web, and data provided via the Web so the present invention can set parameters such as record timers, video quality settings, channel tuning and so forth. The Web site may provide additional data about the offered program to aid the users in selecting programs, such as plot summaries, ratings, casts and so forth.
Many of the aforementioned features may be implemented in various modes and in some cases selectable by the user to be automatic. For example, “continuous recording” may be a mode, whereby the preferred embodiment continuously records on one or more programming channels, overwriting the oldest data as previously described. But this mode is selectable for there might be situations where this is not desirable, such as setting a timer on the present invention to record a program at a specific time. Should the user arrive home much later than expected, the recorded program is still available, instead of being recorded over by the latest program. And as another example, the aforementioned editing capabilities are configurable by the user, such as the “archive as edited” mode, in which control functions dictate an edited form of the program for archival. These functions and configurable options are all controlled through any one of several user-interface methods. In one embodiment, a remote control and on-screen menus are used. In another embodiment, buttons on the device are used, also in conjunction with on-screen menus. These and other user-interfaces are implemented alone or in combination, thus providing access to all of the unique features described herein.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 —underlying context of functional advantages, example one
FIG. 2 —underlying context of functional advantages, example two
FIG. 3 —operational overview
FIG. 4 —block diagram
FIG. 1 illustrates the underlying context of the operation of the present invention. Timeline 130 is depicted illustrating a particular example from 8:00 to 10:00. Of course the times and durations of this example are for illustrative purposes only and any time or duration may be used. Random access viewing position 100 represents the current location within the recorded buffer from which viewing is taking place. Buffer storage 110 illustrates the use of a 30-minute buffer and once again, this is for illustrative purposes only and any duration may be used. Similarly, archive storage 120 illustrates archive storage of over two hours of recorded material. In the example of FIG. 1 , assume the viewer wishes to time-shift their viewing by 15 minutes. With recorded material illustrated as gray-shaded, FIG. 1 shows the case at 8:15, whereby half of buffer storage 110 has been filled with recorded material from 8:00 to 8:15. Only half the buffer is filled in this example because this figure depicts the situation soon after present invention was initially turned on. Once the buffer fills up it acts as a circular buffer, as described previously. The underlying context shown in FIG. 1 corresponds with the example set forth in section 3.3.
As depicted for buffer storage 110 , within this buffer the user has complete VCR-like control such as rewind and fast-forward. So the viewer may begin playback of the 8:00 material and immediately has the capability to fast-forward up to the contents of the current buffer which in the illustrative example is 8:15. Archive storage 120 maintains an archived copy of all the recorded material.
FIG. 1 is used to illustrate the use of buffer storage 100 and it's relationship to the current time. Recording continues simultaneously during any of these operations, continuing at the position of the current real time as depicted in the figure.
The unique functional advantages of the invention are shown in FIG. 2 . This example depicts the situation at 9:00. In this case, buffer storage 210 is now filled with material which was recorded from 8:30 until 9:00 and the viewer has full VCR-like control over this range of time. All components of this figure, timeline 230 random access viewing position 200 , buffer storage 210 , archive and storage 220 are functionally equivalent to the corresponding elements of FIG. 1 . FIG. 2 simply illustrates the conceptual use of the buffer storage at a later time than that of FIG. 1 . Also, the buffer storage and archive storage of both FIGS. 1 and 2 correspond directly to the storage in the block diagrams in FIGS. 3 and 4 .
FIG. 3 illustrates the operational overview of the preferred embodiment. Analog input video source 300 is connected to capture/compression card 320 which includes capture/compression hardware 330 and decompression playback hardware 340 . Storage input connection 340 illustrates the writing of the compressed program data to storage device 380 . Storage device 380 corresponds to the aforementioned buffer storage and may also be used as archival storage.
For playback, storage output connection 350 transfers data from storage device 380 to decompression/playback hardware 360 . During playback, via video out connection 310 , the program is transferred to a standard video device (not shown) such as a TV, monitor or VCR. Recording direction arrow 370 is included to conceptually illustrate the use of storage 380 as a circular buffer as explained previously.
FIG. 4 depicts a block diagram of the preferred embodiment. Housing 400 is an enclosure for the present invention, including necessary power supplies, casing, fans, buttons, power cord and connectors. These components are not depicted but are well-understood in the design and manufacture of consumer (or professional-grade) electronics. Contained within this housing in addition to the aforementioned basic components are: CPU 530 , capture/display hardware 500 , compression/decompression hardware 480 , output display switch 470 , network interface 550 , I/O controller 570 , system RAM 560 , system bus 510 , storage 580 , removable storage 590 , set-top-box switch 424 , tuner bypass switch 426 , capture bypass switch 460 , and input monitor switch 428 . Also depicted but not included as part of the present embodiment are external components set-top box 410 , content provider 420 , television 430 , monitor 340 , VCR 450 , telecommunications connection 520 , telecommunications cloud 490 , workstation 595 and set-top box bypass switch 422 .
Content provider 420 comprises, without limitation, over-the-air television broadcasters, cable TV operators, satellite-feed providers and direct broadcast satellite (DBS) broadcasters. In some cases, the program material as made accessible to the user via set-top box 410 instead of directly from content provider 420 . Set-top box 410 may be a common cable converter box or a digital video and user-interface box as used in upcoming cable and satellite services. The video format provided by both set-top box 410 and content provider 420 is most often a standard analog video signal and is routed to capture/display hardware 500 . However, in some cases a digital video signals is provided and therefore the capture (analog-to-digital conversion) ordinarily provided by capture/display hardware 500 is not needed. Capture input switch 560 is provided for such a circumstance and the input digital video is routed directly to compressor/decompressor 480 . This switching may be automatic by the system, automatically controlled by the content provider or set-top box or it may be user-selectable.
In the case of a analog video input signal, the program must first be converted to a digital format. Capture/display hardware 500 is a video capture and playback card. Alternatively, this may be implemented in a chipset form and integrated onto the main circuit board of the system. Capture/display boards are well-known in the art. Current examples include hardware MPEG capture/compression boards commonly used in computer systems. Such boards often integrate the compression element of the present invention, compressor/decompressor 480 , into the same board for a full capture, compression, decompression and playback functionality. Such components may be used in the present invention to implement both capture/display hardware 500 and compressor/decompressor 480 . Alternatively, separate boards may be used. However, any of the capture, compression, decompression and display elements may be incorporated directly onto the main circuit board of the invention.
The capture and compression of the incoming video program, or the automatic or user-selectable switching out of the capture element, are all managed under control of CPU 530 which is a conventional microprocessor. Software running on CPU 530 manages the capture, compression and storage of the program. In doing so, it controls system bus 510 , to which all major components are connected. In this manner, CPU 530 controls the I/O controller, which in turn is used to operate storage 580 and removable storage 590 . Storage 580 may be implemented by one or more digital storage devices for buffer storage and/or archive storage as discussed previously. System RAM 560 is used as needed by the system for software execution and temporary data storage. The software controlling capture/display 500 and compressor/decompressor 480 may use this as buffer memory. In another embodiment, compressor/decompressor 480 may be eliminated entirely, with CPU 530 performing the compression/decompression operations in software, in which case compressor/decompressor 480 uses system RAM 560 as buffer memory for such operations. In a similar embodiment, compressor/decompressor 480 may be eliminated with set-top box 410 performing compression/decompression. And in yet another embodiment, compressor/decompressor 480 and capture/display 500 may both be eliminated, with all of these functions being performed by set-top box 410 .
Storage 580 is implemented as any type of digital storage media. This includes, without limitation, internal or external versions of hard disk, optical disk, DVD, magnetic tape and semi-conductor storage. Similar storage solutions may be implemented for removable media 590 . Although only one storage device is depicted, more than one may be used.
Network interface 550 connects the device through network connection 520 to telecommunications cloud 490 . Telecommunications “cloud” is a term commonly used to denote a myriad of inter-connected telecommunications connection types and interfaces. It is essentially a superset of the Internet and may include networked computers, telephone lines, and other telephone company equipment such as satellite, microwave and so forth. The portion of telecommunications cloud 490 to which the present invention is connected determines the type of network connection 520 and network interface 550 . For example, in a home-based embodiment, network interface 550 is likely to be a modem and telecommunications connection would be a telephone line. Other examples include, without limitation, cable modems and cable networks, computer networks such as Ethernet and their associated interfaces, and satellite modems. The present invention is operatively connected through telecommunications cloud 490 to workstation 595 . Workstation 595 is any type of computer used by advertisers, broadcasters, ratings companies and so forth to receive indirect feedback from viewers regarding viewing preferences. Data about the user's viewing habits and use of the invention may, at the user's option, be transmitted via network interface 550 through the aforementioned operative link to workstation 595 .
Many options are available for implementing the simultaneous read and write of storage 580 . Commonly-available hard disks may be used, depending on the data rate of the compressed data stream of the capture/compression hardware. For example, if MPEG-1 video is used, one stream requires a data rate of 1.5 Mbits/sec. Therefore, to simultaneously read and write, storage 580 must be capable of sufficient throughput for one write stream and one read stream, totaling 3.0 Mbits/sec. Such input/output speeds are well within the realm of current hard drives, which can sustain data rates of over 10 Mbits/sec.
Other embodiments can use other solutions for storage 580 . For example, some embodiments will record many channels simultaneously and may even play back more than one channel simultaneously to provide a ‘picture-in-picture’ feature similar to current televisions. The total required bandwidth may exceed the sustained data rates for conventional disk drives. In such a case RAID (Redundant Array of Inexpensive Disks) systems may be used. These systems are disk array subsystems which use several disk drives in parallel to achieve faster overall throughput. Similarly, the present invention may simply incorporate individual drives for each tuned channel. RAM and other high-bandwidth storage solutions may be also be used.
The ultimate use of the recorded data is in the playback. As the user views programming through all the aforementioned features, the data is read from storage 580 or from removable media 590 . This compressed data is routed to compressor/decompressor 480 for decompression under control of CPU 530 . In some embodiments, the data may be in an uncompressed form and compressor/decompressor 480 may be bypassed. Once the data is uncompressed, it may be routed directly to monitor 440 for viewing on a digital monitor such as those used by computer systems. Set-top box 410 and/or television 430 may also be capable of accepting digital data in either a compressed or uncompressed form and consequently data may be routed there directly. In the preferred embodiment, the uncompressed digital data is routed to capture/display 500 for conversion to an NTSC, PAL, SECAM or other standard video signal for viewing on one or more of the display devices, TV 430 , monitor 440 or VCR 450 . | A system and method for time-shifted viewing of broadcast television programs is disclosed. Simultaneous recording and playback are provided by using buffer storage as the source and destination of compressed or uncompressed digital video/audio programs. Full VCR-like control is provided for all playback within the buffer storage. Playback and control of recorded programs may be initiated by the user at any time after initiation of the broadcast program with simultaneous continuous recording of the ongoing live broadcast. Larger archival storage and removable is also provided for storing and building a library of programs. Viewer playback control data may be stored as part of the program or used as edit points prior to archival. Numerous options are provided for features such as continuous automatic recording in a circular buffer fashion, program archival, editing, Internet interfaces, multiple-channel recording and more. | 7 |
This application is a continuation-in-part of application Ser. No. 167,067, filed Mar. 11, 1988, now abandoned.
BACKGROUND OF THE INVENTION
This invention relates to methods for producing proteins in microbial hosts, particularly fusion proteins. The invention also relates to cloning vehicles for transformation of microbial hosts.
It is well established that prokaryotic or enkaryotic proteins can be expressed in microbial hosts where such proteins are not normally present in such hosts (i.e. are "heterologous" to the cells). Generally, such protein expression is accomplished by inserting the DNA sequence which codes for the protein of interest downstream from a control region (e.g. a lac operon) is plasmid DNA, which plasmid is inserted into the cell to "transform" the cell so it can produce (or "express") the protein of interest.
Despite this conceptually straightforward procedure, there are a number of obstacles in getting a cell to synthesize a heterologous protein and subsequently, to detect and recover the protein. The heterologous gene may not be efficiently transcribed into messenger RNA (mRNA). The mRNA may be unstable and degrade prior to translation into the protein. The ribosome binding site (RBS) present on the mRNA may only poorly initiate translation. The heterologous protein produced may be unstable in the cell or it may be toxic to the cell. If no antibodies to the protein are available or if there is no other way to assay for the protein it may be difficult to detect the synthesized protein. Lastly, even if the protein is produced, it may be difficult to purify.
Fusion systems provide a means of solving many of the aforementioned problems. The "carrier" portion of the hybrid gene, typically found on the 5' end of the gene, provides the regulatory regions for transcription and translation as well as providing the genetic code for a peptide which facilitates detection (Shuman et al., J. Biol. Chem. 255, 168 (1980)) and/or purification (Moks et al., Bio/Technology 5, 379 (1987)). Frequently, potential proteolytic cleavage sites are engineered into the fusion protein to allow for the removal of the homologous peptide portion (de Geus et al., Nucleic Acids Res. 15, 3743 (1987); Nambiar et al., Eur. J. Biochem. 163, 67 (1987); Imai et al., J. Biochem. 100, 425 (1986)).
When selecting a carrier gene for a fusion system, in addition to detectability and ease of purification, it would be extremely advantageous to start with a highly expressed gene. Expression is the result of not only efficient transcription and translation but also protein stability and benignity (the protein must not harm or inhibit the cell host).
SUMMARY OF THE INVENTION
This invention is a process for making proteins where a fusion protein of an E. coli enzyme, CKS (CTP:CMP-3-deoxy-D-manno-octulosonate cytidylyl transferase or CMP-KDO synthetase), and a heterologous protein is expressed in cells transformed with a cloning vehicle which has a DNA insert coding for CKS and the heterologous protein. The level of expression of CKS fusion protein in cells transformed with such cloning vehicles is quite high, in some instances up to 50 percent of total cellular protein.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graphic representation of a plasmid cloning vehicle of this invention;
FIG. 2 is a graphic representation of a plasmid pTB201 containing a gene for CKS;
FIG. 3 is a schematic representation of the construction of pTB201 from pWM145;
FIG. 4 is the DNA sequence for a synthetic lacP-type promoter used in the cloning vehicles of this invention;
FIG. 5 is a coomassie brilliant blue-stained gel of various amounts of whose cell lysate from pTB201-containing JM103 cells. A corresponding gel scan/integration is also shown.
FIG. 6 shows immunoblots of CKS-producing and nonproducing cells used to optimize the titration of goat anti-CKS serum for identifying CKS fusion proteins. M is protein molecular weight markers; A, negative control JM103 whole cell lysate; B, positive control pTB201/JM103 whole cell lysate.
FIG. 7 is a graphic representation of a plasmid, pTB210, used to express HIV p41 fusion proteins.
FIG. 8 shows a representation of the various synthetic p41 genes relative to the native gene. A hydrophobicity plot of the protein is also indicated. Levels of expression of each clone are included.
FIG. 9 is a sequence of the synthetic p41 full-length gene with the carboxy terminus of p120. The broken line over the sequence indicates the sequence of pTB310B. The sequence of pTB310A is the same as pTB310B except for the deletion of an A (nt 813) indicated by the Δ. Plasmid pTB321 includes Insert 1 (nt 15-143) which encode the carboxy terminus of p120. Plasmid pTB322 contains Insert 2 (nt 610-720) which encodes the hydrophobic region of p41.
FIG. 10 illustrates the acid hydrolysate of the fusion protein expressed from pTB310. Coomassie brilliant blue-stained SDS-PAGE is pictured on the right. An immunoblot of an SDS-PAGE using human AIDS positive serum is shown on the left. Refer to text, Example 5B, for details.
FIG. 11 is a graphic representation of a plasmid pTB260 used as a cloning vehicle in this invention.
FIG. 12 is a graphic representation of a plasmid pTB270 used as a cloning vehicle in this invention.
FIG. 13 is a coomassie brilliant blue-stained SDS-PAGE gel. Approximately equal numbers of cells of each clone type were lysed and loaded on the gel. The lane marked "XL-1" is the cell lysate from the XL-1 Blue strain with no plasmid. "Unfused CKS" is lysate from XL-1 Blue cells containing the pTB201 CKS-expressing vector. "CKS/Active SPL (Val)" is lysate from an XL-1 cell line which contains the active region of the pVal lung surfactant gene in fusion with the kdsB gene on the pTB201 plasmid.
FIG. 14 presents the DNA and amino acid sequences of the synthetic HIV-2 TMP fragment including Hind III/Bgl II linker sequences located 5' and a Sal I linker sequence located 3' to the HIV-2 TMP fragment.
FIG. 15 is a schematic representation of the construction of pJC22 and pJC100.
FIG. 16 is a coomassie brilliant blue stained gel of clone pJC100 induced for the specified time in hours. M is protein molecular weight markers.
DETAILED DESCRIPTION
1. General
This invention involves the expression of a gene coding for a protein of interest using a DNA cloning vehicle which includes a control region, a region coding for the bacterial enzyme CKS (CMP-KDO synthetase), and a region coding for the protein of interest. The cloning vehicles of this invention are capable of expressing fusion proteins (i.e. CKS--heterologous protein fusions) at high levels. The invention is illustrated in FIG. 1 which shows generically the features of a plasmid of this invention. The plasmid of this invention includes a control region (e.g a lac-type promoter with a sequence for a synthetic ribosome binding site), followed by a gene encoding CKS, which is linked to a gene coding for a heterologous protein of interest.
While fusion proteins per se are well established in the art, the use of CKS as a fusion system is novel. In addition to facilitating detection and purification of heterologous proteins, the expression vector of this invention utilizes the kdsB gene (encoding CKS) which, with the appropriate control region, expresses at higher levels than any other gene in E. coli in our hands.
2. Control Region
The control region of this invention is shown in FIG. 4. It includes a modified lac promoter which is essentially native lacP from -73 to +21 with two modifications: 1) a deletion at 23 of one G/C base pair, and 2) a T-A substitution at the -9 position. The control region also includes a synthetic ribosome binding site (nt 31-39) which is homologous to the 3' end of the 16S rRNA (ribosomal ribonucleic acid) in E. coli. Following the ribosome binding site is a consensus spacer region which is followed by the ATG translation initiation codon, followed by the structural gene for CKS.
3. CKS Structural Gene
The sequence for the structural gene encoding CKS (the kdsB gene) is published in Goldman et al., J. Biol. Chem. 261:15831, 1986. The amino acid sequence for CKS derived from the DNA sequence is described in the same article.
The kdsB gene was obtained from Goldman's plasmid pRGl (J. Bacteriol. 163:256) (FIG. 3). The first step in the kdsB gene isolation was a HpaII digestion of pRGl. Digestion with HpaII cleaved 51 base pairs from the 5' end of the gene.
A DNA fragment including the base pairs from the BamHI site to the HpaII site of FIG. 4 was constructed by annealing synthetic oligonucleotides (Example 1). This DNA sequence included the ribosome binding site as well as the 51 base pairs for the 5' end of the kdsB gene. The BamHI-HpaII fragment was then ligated to the HpaII native kdsB gene containing fragment, as described in detail in Example 1. As can be seen, the ligation replaced the 51 base pairs lost to kdsB, and added the ribosome binding site for the control region.
4. Construction of CKS Expression Vector
The pWM145 plasmid containing the modified lac promoter located between the EcoRI and BamHI sites shown in FIG. 4A was digested with BamHI and HindIII to provide an insertion site for the BamHI-HindIII fragment containing the CKS structure gene. (FIG. 3 The kdsB containing fragment was then ligated into the pWM145 vector, assembling the control region containing the modified lac promoter and the ribosome binding site in the process. This produced plasmid pTB201 (FIGS. 2 and 3).
5. Insertion of Linker Allowing Cloning of Heterologous Genes
pTB201 is a fusion expression vector for heterologous genes which have the appropriate reading frame when cloned into the BglII or the BglII-HindIII sites (FIG. 2). However, the versatility of pTB201 can be improved by introducing other restriction endonuclease cloning sites. This is shown in FIG. 7 where a linker containing multiple restriction sites replaces the BglII-HindIII fragment of pTB201 to produce a new vector, pTB210. The linker also includes a sequence coding for Asp-Pro which allows for cleavage of the CKS protein from the heterologous protein fused to it.
The linker of FIG. 7 also includes stop codons in all three reading frames, placed downstream of the restriction sites. Thus, no matter what heterologous structural gene or portion thereof is inserted in the linker, translation will terminate immediately after the inserted gene.
6. Insertion of Heterologous Genes into pTB210
Insertion of heterologous genes into a plasmid of this invention can be accomplished with various techniques, including the techniques disclosed in European Patent Publication Number 253,193 entitled "Method for Mutagenesis By Oligonucleotide-Directed Repair of a Strand Break" and in Japanese Patent Application Number 002348/1990, laid open to public inspection Jan. 8, 1990, entitled "Method for Mutagenesis by Oligonucleotide-Directed Repair of a Strand Break" which are incorporated herein by reference.
7. Examples
The Examples below illustrate the concepts explained above. Example 1 described the construction of a plasmid pTB201 which contains a modified lac promoter and the kdsB gene. In Example 2, cells containing pTB201 are used to express the CKS protein to establish that the kdsB gene is functional. In Example 3, goat anti-CKS sera is raised to detect the fusion proteins such as the one produced in Example 4. In Example 4, a fusion protein of CKS and HIVI p41 is disclosed. In Example 5, fusion proteins of CKS and various permutations of synthetic HIVI p41 and p120 are disclosed. In example 6, a fusion protein of CKS and HSVII gG2 is disclosed. In Example 7, a fusion protein of CKS and the "kringle" region of tPA (tissue-plasminogen-activator) is prepared. In Example 8, two fusion proteins of CKS and SPL(pVal) are prepared. In Example 9, a fusion for CKS and SPL(phe) is prepared. In Example 10, a fusion for CKS and HIV-2 is prepared.
EXAMPLE 1
CKS Expression Vector
A. Construction and Preparation of pWM145
The plasmid, pWM145, is a derivative of the C5a expression vector, pWM111. (mandecki et al, Gene 43:131, 1986) Whereas the pWM111 vector contains a lacP-UV5-D24 promoter, the pWM145 vector contains a lacP-T9-D23 promoter. The changes were accomplished by replacing the promoter/operator region of pWM111 contained within an EcoRI-BamHI fragment with asynthetic fragment (FIG. 4A) containing the modifications. The following procedure was used.
Plasmid DNA (pWM111) was isolated from JM83 (ara, (lac-proAB), rpsL, o80, lacZ M15) cells using a standard alkaline extraction protocol followed by purification on a cesium chloride gradient and precipitated with three volumes of 70% ethanol at -20° C. for two hours followed by centrifugation. DNA was resuspended in distilled water to a concentration of 1 mg/ml.
One microgram of pWM111 DNA was digested for two hours concomitantly with ten units of EcoRI and ten units of BamHI in 20 ul of a buffer consisting of 50 mM Tris, pH7.5; 10 mM MgCl 2 ; and 100 mM NaCl. Following digestion, the three kilobase plasmid was purified by 5% (50:1 acrylamide:BIS) polyacrylamide gel electrophoresis (PAGE). The fragment was cut out and extracted by shaking overnight at 37° C. in 10 volumes of 500 mM ammonium acetate, 10 mM magnesium acetate, 1 mM EDTA, and 0.1% SDS. The DNA was precipitated by chilling it for two hours at -20° C. with 2.5 volumes of 100% ethanol, followed by centrifugation.
The EcoRI-BamHI promoter fragment was composed of four oligonucleotides (oligos 1 through 4 indicated by brackets in FIG. 4A) which were purified by 20% PAGE under denaturing conditions and annealed by mixing equal molar amount of the oligonucleotides together in ligation buffer (66 mM Tris, pH7.6; 6.6 mM MgCl 2 ; 50 ug/ml BSA; 10 mM dithiothreitol; 1 mM ATP), maintaining the mixture at 80° C. for five minutes, cooling the mixture slowly to 25° C., then refrigerating for one hour. A ten fold molar excess of annealedoligonucleotides was ligated together with approximately 50 ng of the purified EcoRI-BamHI digested vector and one unit T4 ligase in 20 ul volume ligase buffer at 16° C. overnight. One-fourth of the ligation mix was used to transform competent JM103 (supE, thi, (lac-proAB), endA, rpsL, sbcB15, [F', traD36, proAB, lacI q Z M15) using standard protocol (Mandel & Higa, J. Mol. Biol. 53:154,1970). Plasmid DNA from the transformants was prepared from 150 ml cultures as described above, and the DNA was sequenced using Sanger methodology (Proc. Natl. Acad. Sci. USA 24:5463,1977).
B. Construction and Preparation of pTB201
The kdsB gene from E. coli K-12, which encodes CTP:CMP-3-deoxy-D-manno octulosonate cytidylyltransferase (CMP-DKO synthetase), was isolated from pRGl. The gene is almost entirely contained within a HpaII fragment (FIG. 3). A linker was constructed to facilitate cloning kdsB into pWM145. The linker not only provided a BamHI site for subsequent cloning but also included a strong ribosome binding site, and the DNA sequence coding for 17 amino acids at the amino terminus of CKS (FIG. 4B). The procedure for construction, shown in FIG. 3, was as follows:
1a. Plasmid pRGl was digested with HpaII and dephosphorylated with bacterial alkaline phosphatase (BRL). The 1.7 kb kdsB gene fragment was isolated on a 5% (50:1) Acrylamide:BIS gel, eluted, and purified as described above.
1b. Oligonucleotides (shown in FIG. 4B) were synthesized, purified, labeled (using BRL T4 Kinase, with a 2X molar excess of ATP [1 part gamma [ 32 P]ATP to 9 parts nonradioactive ATP] and BRL recommended protocol) and annealed.
2. Ligation of the HpaII gene fragment with the synthetic fragment was carried out at 16° C. overnight. Ligase was heat inactivated (15 min at 65° C.) DNA was then phosphorylated (as above), phenol extracted (1X l vol buffer equilibrated phenol, 1X l vol chloroform:isoamyl alcohol), ethanol precipitated, and resuspended in medium salt buffer (50 mM Tris, pH 7.5, 10 nMM, Cl 2 , and 50 mM NaCl). Following simultaneous digestion with HindIII and BamHI, the DNA was purified from a 5% (50:1) acrylamide gel.
3. The pWM145 vector was digested with HindIII and BamHI, dephosphorylated, and purified from a 5% (50:1) acrylamide gel as above. The vector (15 ng) and insert (20 ng) were ligated overnight at 16° C. One half of the total ligation mix was used to transform competent JM103 cells. The pTB201 construct was verified by DNA sequencing.
EXAMPLE 2
Expression of kdsB Gene and Purification of CKS From pTB201/JM103 Cells
A. Cultivation of pTB201/JM103 cells
A 50 ml flask containing 10 ml LB broth with 50 ug/ml ampicillin was inoculated with a loopful of frozen stock pTB201/JM103 cells. The culture was incubated at 37° C. while shaking at 225 RPM. When the culture become turbid, the 10 ml were used to inoculate one liter of LB/Amp in a four liter flask. At an OD 600 =0.3, IPTG (isopropyl-thio-β-galactoside) was added to a final concentration of 1 mM, and the cells were incubated overnight. A typical SDS-PAGE of the whole cell lysate as well as a gel scan on the sample is shown in FIG. 5. The relative percentage of the CKSto the total cellular proteins is 50 to 75%.
B. Purification of CKS
Purification procedure was that described by Goldman and Kohlbrenner (J. Bacteriol. 163; 256-261) with some modifications. Cells were pelleted by centrifugation, resuspended in 50 mM potassium phosphate (pH 7.6), and lysed by two passages through a French Press (15,000 PSI). The lysate was spun at 30,000 X g for 30 minutes. The soluble fraction was treated with protamine sulfate and ammonium sulfate, and dialyzed as described (Ray et al, Methods Enzymol. 83:535 1982). The sample was passed for final purification through a BioRad DEAE-5 PW HPLC-ion exchange column and eluted with a 50-400 mM potassium phosphate (10% acetylnitrile) gradient.
EXAMPLE 3
Generation of Goat Anti-CKS Sera
A. Goat immunization and bleeding
A goat was immunized monthly in three general areas--inguinal (subcutaneously), auxillary (subcutaneously) and hind leg muscles. Initial inoculation consisted of 1 mg purified CKS in complete Freund'Adjuvant. Thereafter, the boosting inoculum consisted of 0.5 mg purified CKS in incomplete Freund's Adjuvant. Five-hundred milliliters of blood was collected from the goat two and three weeks post-inoculation starting after the second boost. The blood was allowed to clot overnight, and the serum was decanted and spun at 2500 RPM for thirty minutes to remove residual red blood cells.
B. Immunoblotting
The presence of anti-CKS antibodies in the goat serum was confirmed by immunoblotting (FIG. 6). Whole cell lysates of pTB201/JM103 (labeled "b" in FIG. 6) and JM103 (labeled "a") controls were run on a 12.5% SDS-polyacrylamide gel, and proteins were electrophoretically transferred (Towbin, et al, Proc. Natl. Acad. Sci. USA 76:4350) to nitrocellulose. The filter was cut into strips which were pre-blocked with immunoblot buffer (5% instant dry milt, 1 X TBS [50 mM Tris, pH 8.1; 150 mM NaCl], 0.01% Antifoam C Emulsion) for fifteen minutes with agitation. Strips were placed into separate containers with immunoblot buffer and various amounts of serum (from 1:100 to 1:3000) were added. After one and one-half hours of agitation, the buffer was poured off, and the strips were washed three times for five minutes with 1 X TBS. The second antibody, horseradish peroxidase-labeled rabbit anti-goat (BioRad), was added to the strips at a 1:1500 dilution in immunoblot buffer. Following one and one-half hours of agitation, the buffer was poured off, and the strips were washed as above. Blots were developed for 5-10 minutes with agitation after addition of the developing agent (0.5 mg/ml of 3,3'-diaminobenzidine tetrahydrochloride dihydrate, 0.1 ug/ml of H 2 O 2 in 1 X TBS). A 1:3000 dilution of the serum was optimal, giving strong positive bands and negligible background.
EXAMPLE 4
Fusion protein--CKS/HIVI p41 HaeIII-HindIII
As an example of expression of a hybrid gene, a portion of the HIVI (human immunodeficiency virus I) p41 (envelope) gene was cloned into the CKS expression vector. The resulting gene coded for a protein fusion which consisted of CKS (less nine residues at the carboxy terminus), a nine amino acid residue linker, and a major epitope of the HIVI virus (amino acid positions 548-646 based on the precursor envelope protein, p160, numbering by Ratner, et al. Nature 313:227, 1985) (refer to FIG. 8). In order to assure the proper reading frame of the HIVI portion of the gene, a linker was designed and cloned into the pTB201 plasmid. The linker and HIVI gene fragments were cloned as close to the distal end of the kdsB gene as conveniently possible. Our rationale was that maximizing the amount of kdsB gene would maximize the change of success for high level expression of the heterologous gene.
A. Construction of pTB210
The pTB210 plasmid, American Type Culture Collection Deposit Number ATCC 68297, deposited Apr. 10, 1990 (FIG. 7) was a derivative of the pTB201 plasmid (described above). pTB201 was digested with BglII and HindIII, and the 3.6 kb vector fragment was purified from a 5% (50:1) acrylamide gel. The linker, composed of two synthetic oligonucleotides with overhands compatible with BglII and HindIII ends, was ligated into the vector, and the ligation mixture was used to transform competent JM109 cells (recA1, endA96, thi, hsdR17, supE44, relA1, λ-, (lac-proAB), [F', traD36, proAB, lac I 1 Z M15]). DNA sequencing was used to confirm the construction.
B. Construction of pTB211
The pTB211 plasmid was the vector construction used to express the hybrid kdsB-HIVI p41 major epitope gene. The source of HIVI DNA was a plasmid which contained the p160 gene of HIVI (HTLVIIIB isolate from NIH) cloned as a KpnI fragment into pUC18. The plasmid was digested with HaeIII and HindIII and a 296 bp fragment was isolated from a 5% acrylamide gel. This fragment was ligated into PvuII-HindIII digested pTB210 vector followed by transformation into competent JM109 cells.
C. Screening of Transformants
The transformed cells were plated on LB/AMP plates. Following overnight incubation at 37° C., several colonies were picked from the plate and used to inoculate 2 ml of LB/Amp broth. Cultures were grown to an OD 600 of 0.3-0.5 then IPTG was added to a final concentration of 1 mM. Cultures were shaken at 37° C. for an additional three hours. The absorbance of the cultures at 600 nm was measured; cells from one milliliter of each culture were precipitated by centrifugation, and then resuspended to an OD 600 equivalent of ten in treatment buffer (63 mM Tris, pH 6.8, 2%SDS, 10% glycerol, 5% 2-mercaptoethanol). Following a 10 minute incubation in a boiling waterbath, an aliquot (10 ul) of each lysed culture was elecrophoresed on 12.5% SDS-polyacrylamide gels. A protein band corresponding to the proper molecular weight of the fusion protein could be visualized directly on gells stained with Commassie brilliant blue. Fusion protein could also be detected by immunoblots using the goat anti-CKS serum (method described in Example 3B.) and HIVI positive human serum (using human serum at 1:250 dilution and HRP conjugated goat anti-human antibodies at 1:1500). The fusion protein level in the cells after induction was 5-10% of the total cellular protein.
EXAMPLE 5
Fusion protein--CKS/synthetic HIVI envelope peptides
In this example, hybrids of the kdsB and portions of a synthetic p41 genes expressed and produced fusion proteins to a level of up to 20% of the total cellular protein. Additionally, this example demonstrates the use of an Asp-Pro dipeptide in the linker region as a chemical cleavage site for cleaving the CKS portion of the protein from the HIVI portion. Further examples are included which demonstrate that multiple fusions (CKS peptide plus p41 and a portion of pl20) were attainable. These are useful peptides for diagnostics.
A. Synthesis and cloning of the HIVI synp41d gene
The synp41d gene codes for a deletion mutant of the HIVI p41 protein which contains a 38aa hydrophobic region deletion (from Ala674 to Bal711 based on p160 numbering, refer to FIG. 8 plasmid, pTB310B). The gene was synthesized using the method of oligonucleotide directed double-standard break repair disclosed in European Patent Publication Number 253,193 and Japanese Patent Application Number 002348/1990, laid open to public inspection Jan. 8, 1990 which are incorporated herein by reference. The specific sequence is indicated by single-line overscore on FIG. 9. The synthetic gene contained flanking BamHI and KpnI sites to facilitate cloning into pTB210. The vector was digested with BglII and KpnI, and the BamHI-KpnI synthetic gene fragment was ligated into the vector. Following transformation into JM109 cells, clones were cultivated, induced, and screened for expression.
B. Characterization of fusion protein encoded by pTB301A
Upon the initial screening, a clone was discovered containing a plasmid (pTB310A) which had a A/T base deletion at nucleotide position 813 (based on FIG. 9 numbering) Although this mutation (which occurred in cloning the synthetic p41d gene) resulted in a truncation in the p41d portion of the fusion protein, the protein produced was characterized for its diagnostic potential.
PRODUCTION AND PURIFICATION
Ten ml of LB/Amp in a 100 ml flask was inoculated with 100 ul of an overnight pTB310A/JM109 culture. After shaking at 37° C. for one and one-half hours, IPTG was added to the culture to a concentration of 1 mM, and the cells were grown for four more hours. An aliquot (1 ml) of the culture was pelleted and lysed in a an appropriate volume of 1 X treatment buffer to give a final concentration of cells of 10 OD 600 absorbance units. This sample, referred to as WCL (whole cell lysate), was used to measure the amount of fusion protein relative to total cellular proteins. The remaining 9 ml of cell culture was centrifuged (five minutes, 5000 rpm) and the cells were resuspended in 10 mM Tris (400 ul), pH8.0, 1 mM EDTA with 2 mg/ml lysozyme. After fifteen minutes on ice, 10 ul of 20% Triton X-100 was added, and the cells were sonicated (6 X 30 sec). The lysate was spun in an Eppendorf centrifuge for five minutes. The supernatant was collected, and the pellet was resuspended in 8M urea (400 ul). The fusion protein present in the resuspended pellet fraction is about 75% pure based on Commassie stained gels.
WESTERN AND IMMUNOBLOTS
A sample (10 ul) of pTB310A/JM109 WCL was loaded on a 0.7 mm thick 12.5% SDS-polyacrylamide gel, along with prestained protein molecular weight standards, WCL from JM109 without plasmid, and WCL from JM109 containing pTB210 (unfused CKS). Gel was run at 150 volts and terminated when bromophenol blue sample loading dye had reached the bottom of the gel. Proteins were then electrophoretically transferred to nitrocellulose. Immunoblotting was carried out as described in Example 3B. AN example of pTB310A/JM109 WCL on a standard gel and immunoblot is shown in FIG. 10.
CHEMICAL CLEAVAGE OF FUSION PROTEIN
An aliquot (30 ul) of the urea soluble fraction was diluted with ten volumes of water, and the insoluble fusion protein was pelleted by centrifugation. The protein was then dissolved in 30 ul of 6M guanidine hydrochloride, and 70 ul 98% formic acid added (Digestion 1). In a parallel experiment, 70 ul 98% formic acid was added to an aliquot (30 ul) of the urea fraction directly (Digestion 2). Following two days incubation at 42° C., ten volumes of water were added, and the insoluble proteins were pelleted by centrifugation. The pellet was resuspended in 1X treatment buffer (100 ul), and 10 ul was used per well on 12.5% SDS-polyacrylamide gel. FIG. 10 shows a sample of the cleaved products (Digestion 1 and Digestion 2) both on a Commassie-stained gel and an immunoblot (using HIVI positive human serum as primary antibody). Only two major bands are visible on the Commassie-stained gel. These represent the products of cleavage at the unique Asp-Pro bond: the CKS portion, MW=26.5 kDa and the p41 portion, MW=23.5 kDa. Peptide sequencing confirmed that the lower molecular weight band was indeed the p41 peptide, and that the amino terminal residue was proline which results from expected cleavage between the Asp and Pro.
C. Characterization of the pTB310B/JM109 clone
The clone containing the correct gene for the CKS-p41d fusion, pT310B, was cultured and assayed for expression. The fusion protein represents 10-20% of the total cellular protein (dependent on growth and induction conditions).
D. Addition of the p120 carboxy terminal region
A synthetic DNA fragment which encoded the carboxy terminal 42 amino acids of HIVI p120 (Insert 1, FIG. 9) was inserted into the NarI site of pTB310A and pTB310B at nt 15. The resulting clones pTB319/JM109 and pTB321/JM109, respectively, expressed the triple fusion protein at levels of up to 20% total cellular protein.
EXAMPLE 6
Fusion protein--CKS/HSVII gG2
A 1.1 kb fragment containing the Herpes Simplex Virus II (HSVII) gG2 gene (encoding a major envelope glycoprotein) was isolated following digestion with AatII and XbaI. A synthetic linker was ligated to the XbaI end to generate an AatII end. Both ends were then made blunt by treating the 3' overhangs with T4 polymerase.
The vector in this example was pTB260 (FIG. 11). It was constructed by ligating a synthetic fragment with multiple restriction sites into the BglII site of pTB201. In cloning the fragment, the original BglII site from pTB201 was inactived and thus, the BglII site in the linker 8 fragment is unique.
To facilitate cloning the blunt-ended DNA fragment containing the gG2 gene and to put the gene in the proper reading frame of kdsB, the BglII digested pTB260 was made blunt-ended by filling in the overhangs using Lenow and dNTP's. Following ligation of the gG2 DNA with pTB260, the DNA was used to transform competent TB-1 cells. Whole cells lysate from transformants run on gels and immunoblotted with rabbit serum against HSVII proteins gave a visible band of the proper molecular weight.
EXAMPLE 7
Fusion protein--CKS/Kringle region of tPA
A gene coding for the "kringle" (Patthy, L., Cell, 41:657 (1985)) region of tissue-plasminogen-activator was synthesized and cloned as a 335 bp HindIII-KpnI fragment into pTB270 (Zablen, L. B., unpublished). The pTB270 vector (FIG. 12) was a derivation of pTB210 which was constructed by ligating a synthetic multi-cloning site linker into BglII-KpnI digested pTB210. The pTB270 plasmid was then digested with HindIII-KpnI and ligated with the Kringle-region gene fragment. Transformation was carried in competent XL-1 Blue cells (stratagene). Clones containing the proper insert were confirmed by DNA sequencing of the plasmids. The level of the fusion protein reached 30%-40% of the total cellular proteins.
The CKS/Kringle protein was extracted from a culture by lysing the cells as in Example 5B, precipitating the cellular debris, and collecting the supernatant which contained the soluble fusion protein. Further purification was accomplished by "salting out" the protein. Briefly, ammonium sulfate was added to 10% (w/v), and the insuluble proteins were pelleted by centrifugation. The pellet of this fraction, after assaying to demonstrate the absence of fusion protein, was discarded. Ammonium sulfate was added to the supernatent to a final concentration of 30%, and the insoluble proteins were pelleted. This pellet contained 70% of the starting fusion protein amount and was 75% pure.
EXAMPLE 8
Fusion protein--CKD/SPL(pVal)
A. A human lung surfactant gene, SPL(pVal) (International Publication No. WO88/03170 filed by Whitsett et al.), contained within an 820 bp EcoRI fragment was cloned into pTB210. The overhanging EcoRI ends were filled using Klenow and dNTP's. The blunt-ended fragment was then ligated into PvuII digested pTB210. Following transformation into competent XL-1 Blue cells (Stratagene), DNA was isolated from a number of transformants and mapped with restriction endonucleases to identify clones with the insert in proper orientation. Expression level of the fusion protein based on whole cell lysates was 3%. The protein could be purified to about 50% purity by cell lysis and pelleting as described in Example 5B. The fusion protein was used to generate antibodies against the SPL peptide by immunizing rabbits with gel purified product.
B. A hybrid gene containing kdsB with the 139 nt active region of pVal was constructed by cloning a BglII-HindIII-ended synthetic fragment encoding the active region (refer to patent) into BglII-HindIII digested pTB201. Assays of whole cell lysates indicated that expression levels of up to 40% of the total cellular protein were obtained (FIG. 13).
EXAMPLE 9
Fusion protein--CKS/SPL(phe)
A human lung surfactant gene, SPL(phe) (disclosed in the Whitsett patent application above), contained within a 1635 bp EcoRI-HindIII fragment was cloned into pTB210. The gene was originally isolated from a clone, Phe 7-1, as a 1945 bp EcoRI fragment, blunt-end filled using Klenow and dNTP's, then digested with HindIII. This fragment was ligated into Pvu-HindIII digested pTB210 and transformed into competent XL-1 Blue cells. The CKS/SPL(phe) fusion protein level was 9% of the total cellular protein. The fusion protein was 50% pure in the pellet following lysis of the cells (procedure described in Example 5B). Gel purified CKS/SPL(Phe) was used to immunize rabbits to generate antibodies against the SPL(Phe) portion of the protein.
While several Examples of this invention have been provided, modifications to these Examples will be apparent to those of ordinary skill in the art. Such modifications are to be included in this invention, unless the claims which follow expressly state otherwise.
EXAMPLE 10
Fusion protein--CKS/synthetic HIV-2 TMP Fragment
In this example, a synthetic DNA fragment containing a portion of the HIV-2 (human immunodeficiency virus II) transmembrane protein (TMP) was cloned into the CKS expression vector. The resulting gene coded for a protein fusion consisting of CKS (less nine residues at the carboxy terminus), a ten amino acid residue linker, and the major epitope of the HIV-2 virus (envelope amino acid positions 502-609, numbering by Guyader, et al., Nature 326:662, 1987) followed by another ten amino acid residue linker. Thus fusion protein was expressed to a level of up to 15% of the total cellular protein and proved useful in the detection of sera containing HIV-2 antibodies.
A. Synthesis and cloning of the HIV-2 TMP fragment
The HIV-2 TMP fragment codes for the amino terminal 108 amino acids of the HIV-2 TMP (from Tyr 502 to Trp 609) identified in FIG. 14. The gene fragment was synthesized using the method of oligonucleotide directed double-stranded break repair disclosed in European Patent Publication No. 253,193 by Mandecki which is incorporated herein by reference. The five DNA fragments comprising the TMP gene fragment were ligated together and cloned at the HindIII-SalI sites of pUC19 (FIG. 15). A clone, designated pJC22, was identified by restriction mapping and its primary nucleotide sequence confirmed. The clone pJC22 was digested with HindIII-Asp718 to release a 361 bp fragment containing the synthetic HIV-2 TMP gene fragment which was ligated into the HindIII-Asp718 sites of plasmid pTB210 and transformed into XL1 cells. A clone, designated pJC100, was isolated and restriction mapped to identify the hybrid gene of kdsB and HIV-2 TMP.
B. Characterization of fusion protein encoded by pJC100
Fifty-ml of LB/Amp in a 250 ml flask was innoculated with 500 l of an overnight culture of either pTB210/XL1 or pJC100/XL1 and allowed to shake at 37° C. until the OD 600 reached 0.5 absorbance units (1.5-2.0 hours) at which time IPTG was added to a final concentration of 1 mM. An aliquot (1.5 ml) of the culture was removed every hour for four hours and then a final aliquot taken at 18 hours post induction. These aliquots were pelleted and lysed in an appropriate volume of 1X treatment buffer to give a final concentration of cells of 10 OD 600 absorbance units. Aliquots of each timepoint (15 l) were electrophoresed on 12.5% SDS/PAGE gels and transferred electropohoretically to nitrocellulose. Immunoblotting was carried out as described in Example 3B using HIV-2 positive human sera or goat antibody directed against CKS. The HIV-2 positive human sera demonstrated no signal to the pTB210/XL1 culture and a strong signal to the pJC100/XL1 culture at the expected molecular weight. The goat antibody against CKS reacted strongly with both cultures at the expected molecular weights. A similar SDS/PAGE gel was run and Coomassie blue staining demonstrated that expression of the fusion protein peaked at 3-4 hours post induction at a level of 15% of total protein. FIG. 16 demonstrates the expression of the CKS/HIV-2 TMP fusion protein in a ten liter fermenter as seen by coomassie blue staining of a 12.5% SDS/PAGE gel of various time points before and after induction. A partial purification of the fusion protein was obtained by the method described in Example 5B with similar results. | Disclosed is a method of producing fusion proteins wherein one part of the fusion protein is formed from the bacterial protein CKS. | 2 |
[0001] This invention claims the benefit of U.S. Provisional Application No. 61/233,480 with the title, “Cosmetic and Dermatological Skin Treatment Device” filed on Aug. 12, 2009 and which is hereby incorporated by reference. Applicant claims priority pursuant to 35 U.S.C. Par 119 (e)(i).
FIELD OF THE INVENTION
[0002] The present invention relates to cosmetic and dermatological devices and methods. More specifically it is concerned with the applictaion of cold temperatures to the skin for therapeutic or cosmetic purposes, for example for the treatment of swelling and redness as is found in, but not limited to, acne.
[0003] U.S. Pat. No. 4,378,025 by Bontemps R. Gaston and U.S. Pat. No. 3,168,895 by Motoharu Okuhara are also incorporated by reference.
BACKGROUND
[0004] Acne vulgaris is a common dermatologic disorder with a high prevalence in teenagers and young adults, and especially in women. It consists of both inflammatory and non-inflammatory types of lesions; non-inflammatory lesions include open and closed comedones, while inflammatory lesions include papules, pustules, and cysts. Acne is widely believed to have a multi-factorial origin, and evidence suggests that elevated sebum secretion, follicular hyperkeratosis, bacterial proliferation (P. acnes) and inflammation may play roles to varying degrees. Other influences include sex hormones and psychological stressors. Current treatments of acne therefore focus on remedying one or more of these factors.
[0005] Cryotherapy, or short-term (approximately or less than 15 minutes) application of moderately cold temperature to the skin, is widely accepted as having an anti-inflammatory effect and has various applications in medicine. (This is to be distinguished from cryosurgery, which consists of locally applying extreme cold to an affected area with the intent of obliterating abnormal tissue.) Moderate cold temperature has been shown to cause localized vasoconstriction, decreased cellular permeability, decreased cellular metabolism, and to decelerate bacterial replication. These effects synergistically diminish the inflammatory biochemical cascade response to cellular injury.
[0006] U.S. Pat. No. 4,378,025 by Gaston R. Bontemps describes a cooling device in the form of deep-frozen blocks or cakes of cosmetic substances which are directly applicable to the skin. The vasoconstrictive action of the cold is added to the action of the cosmetic substance. Bontemps' invention, however, poses a risk to the user. If the blocks of cosmetics are frozen in a conventional household freezer, they may become contaminated with microorganisms from the freezer environment, which may infect the very sores that the user is treating. In addition, if the blocks are returned to the freezer after use, they may transfer organisms from the user to the food stored in the freezer. The cold temperature of the freezer would support the preservation of these contaminants for an extended period of time. In addition, since these frozen blocks cannot be easily cleaned after being applied to one sore, they may promote the transfer of microorganisms from one place on the skin to a different place or from one person to another.
[0007] This invention is not limited to the treatment of acne vulgaris; other ailments benefiting from localized cryotheraphy as recognized by the medical art may also benefit from this invention.
[0008] This invention solves the problems identified above. None of the prior art offers the economy and hygiene of the present invention. Further features, aspects, and advantages of the present invention over the prior art will be more fully understood when considered with respect to the following detailed description and claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] FIG. 1 is a perspective front view of the device.
[0010] FIG. 2 provides a cross-section view of the exploded device showing the device's layers including the tube, the insulation layer, the top layer and the tip. It also shows the ice pack and the cover.
[0011] FIG. 3 shows a cross-section view of the device in a fully assembled state.
[0012] FIG. 4 illustrates a cross section and exploded version of the device in which the tip is eliminated by merging it with the tube.
[0013] FIG. 5 shows a fully assembled view of the device in which the tip is eliminated by merging it with the tube.
[0014] FIG. 6 illustrates the heat flow control mechanism consisting of a screw type arrangement that allows the user to vary the amount of surface area between the cladding and the tube. This figure shows the maximum contact possible.
[0015] FIG. 7 illustrates the heat flow control mechanism consisting of a screw type arrangement that allows the user to vary the amount of surface area between the cladding and the tube. This figure shows an intermediate heat configuration.
[0016] FIG. 8 illustrates the heat flow control mechanism consisting of a screw type arrangement that allows the user to vary the amount of surface area between the cladding and the tube. This figure shows an exploded view of the device.
[0017] FIG. 9 shows a reversal in the sex of the screw and threaded opening that allows the cladding to be mounted on the tube.
[0018] FIG. 10 illustrates how the heat conductivity of the device can be gradually altered by sliding concentric cylinders arranged in the top of the tube into a matching set of concentric cylinders in the cladding part of the device.
SUMMARY OF THE INVENTION
[0019] This invention is a dermatological device for cooling of the skin. It comprises:
a) An ice pack; b) A heat conductive shield configured to operate as an aseptic separator between the skin and the ice pack and to conduct heat from the skin to the ice pack.
[0022] In one particular embodiment of this invention, the shield is configured as a tube open at its back end and closed at its front end. The ice pack is shaped to snugly fit inside the tube.
[0023] Heat flow is optimized by building most of the tube in aluminum or copper.
[0024] As an option, and even though stainless steel does not conduct heat as well as aluminum or copper, a stainless steel cladding can be used to cover the tube's front end to facilitate cleaning and provide an increased degree of asepsis. As yet another option, the tube can also be completely built of stainless steel.
[0025] Heat flow can also be channeled away from the front toward the back by tapering the thickness of the tube, thick at the front and thin at the back and by covering it with a thermal insulating layer to avoid heat transfer except at the front tip.
[0026] A thermally insulating cap can also be employed to cover the front of the tube, thereby minimizing heat flow when the device is not in use.
[0027] The ice pack can either be soft-walled or be hard-walled. It can include a handle for its easy removal from, or insertion into, the tube. The chemicals held by the ice pack may include but are not limited to water, alcohol, ethylene glycol, and super absorbent polymers.
[0028] The shield can be configured to have controllable heat conductivity by adjusting the amount of contact surface between the icepack and the shield or between internal components in the shield itself. This can be done by means of a screw arrangement whereby the stainless steel cladding and the aluminum or copper material comprising the tube have a variable amount of common surface in contact with each other.
[0029] The method of using this invention includes cooling the ice pack in a freezer or refrigerator. The aseptic shield is then applied to the skin and the ice pack is placed in contact with the shield, thereby cooling the skin. When the shield is configured as a tube, the ice pack is inserted inside the tube before the device is applied to the skin.
[0030] The method can also include controlling the heat flow by adjusting the screw between the cladding and the tube. Interpenetrating sets of concentric cylinders mounted on the tube and on the cladding allow the contact surface between the tube and the cladding to be changed and the heat conductivity of the device to be altered.
DETAILED DESCRIPTION
[0031] This invention comprises an ice pack and a thermally conductive and aseptic shield. The ice pack is applied to one side of the shield and the other side of the shield is put in contact with the skin thereby cooling the skin.
[0032] One of the preferred embodiments of the invention is illustrated in FIGS. 1 , 2 , 3 , 4 and 5 . The shield is embodied as a hollow tube 1 made of a material that conducts heat well such as aluminum, copper or stainless steel (even though stainless steel does not conduct heat as well as aluminum or copper, its surface quality makes it an attractive option). This tube 1 is open at the back end 2 and is closed at the front end 3 . The walls of the tube 1 are thicker in the front to promote heat conductivity from front to back. The thickness of the tube 1 can be made to increase gradually from the back end to the front end as it dovetails with the front end 3 .
[0033] The front end 3 of the tube 1 is tipped with a cladding 4 made with a material such as stainless steel that combines efficient heat conductivity with the ability for having a smooth and polished surface to facilitate cleaning, to reduce germ transmission and to provide an aseptic environment for the treatment of the skin condition. “Aseptic” describes techniques aimed at keeping patients as free from hospital micro-organisms as possible and at preventing contamination of wounds and other susceptible sites by organisms that could cause infection.
[0034] A thermal insulation layer 5 , cylindrical in shape covering the outer wall of the tube 1 . This layer can be made, for example, of material such as an air gel or Styrofoam®.
[0035] An outer layer 6 , cylindrical in shape, covering the thermal insulation layer 5 . This layer can be made, for example, of material such as plastic or rubber or a combination of these to provide the device with a desired look and feel.
[0036] In a first version of this invention, the removable ice pack 7 is comprised an essentially cylindrical soft-walled bag filled with water or a solution having a high heat of fusion and capable of being frozen into slush rather than into a hard solid. The advantage of the soft-wall bag and soft slush is that the ice pack can conform to the inside of the tube 1 . A back plate 9 comprising an insulation layer 10 and a mechanically supporting layer 11 is attached to the back end of this ice pack 7 to provide insulation when the ice pack 7 is inserted into the tube 1 . A handle 8 is affixed to the supporting layer 11 to facilitate the retrieval of the ice pack after it is inserted in the tube 1 .
[0037] The back plate 9 can include a screw type or latch type attaching device, with the complementary screw or latch being carried by the back end 2 of the tube 1 .
[0038] The solution inside the ice pack can be a slush when frozen to allow it to conform itself to the shape of the tube 1 when inserted into it. The solution may comprise any ratio of water to solute optimized for desired mechanical properties when frozen. Possible solutes include but are not limited to alcohol, superabsorbent polymer (such as EverCold® gel produced by ColdIce, Inc.) and propylene glycol.
[0039] Superabsorbent polymers (SAP) (also called slush powder) are classified as hydrogels. They are polymers that can absorb and retain extremely large amounts of aqueous solutions through hydrogen bonding with the water molecule.
[0040] A typical proportion might consist of 66% water and 34% alcohol. The greater the proportion of alcohol the softer the mixture will be when frozen. In addition to freezable solutions, it is also possible to construct disposable ice packs that comprise two compartments separated by an internal barrier that, when broken through a simple squeeze or snap, permits the contents in each compartment to come into contact and generate an endothermic reaction, as demonstrated by the Instant Cold Pack produced by Dynarex. A well-known example of such an endothermic reaction would include ammonium nitrate and water.
[0041] In a second version of the invention shown in FIGS. 4 and 5 , the removable ice pack 7 comprises a hard-wall container conforming to the inside shape of the tube 1 . The icepack 7 is filled with a solution having a high heat of fusion. Care must be taken not to fill the ice-pack completely, to allow for the expansion of the solution as it freezes. Since the frozen solution does not have to be as soft as the first version, a smaller proportion of alcohol may be used, or the solution may comprise a polymer-based gel such as the previously mentioned EverCold® gel produced by ColdIce, Inc.
[0042] As is known to those familiar with the art, there are a number of other ingredients which can be used to make the ice-pack solutions. These ingredients include but are not limited to guar gum and salt. Dyes can also be used to color the ice pack mixture.
[0043] In yet another version of the invention illustrated in FIGS. 4 , and 5 , the tube is constructed of stainless steel, thereby voiding the need to have a separate cladding 4 (as shown in FIG. 2 ) at the tip of the tube.
[0044] The device also comprises a cap 12 that includes an insulation layer 13 and a mechanically supporting top layer 14 . This cap 12 is configured to fit over the front end 3 of the tube 1 and the stainless steel cladding 4 . It can be screwed on or snapped on.
[0045] A locking or snap mechanism may also be included and configured to maintain the ice pack 7 snugly inside the tube 1 .
[0046] In another version of the device, the shield is configured to have a controllable heat conductivity to allow the user to apply the amount of cold as he desires. Heat transmission can be implemented by varying the contact surface between the cladding and the tube. There are several techniques for achieving this result. One possible approach is shown in FIGS. 6 , 7 and 8 . The cladding 4 is mounted on a screw 15 that fits into a threaded opening 16 configured at the front end of the tube 3 . The amount of contact between the cladding 4 and the tube 3 and, therefore, the heat transmission of the device, can be controlled by screwing the cladding in or out the tube.
[0047] Heat transmission control can also be implemented by providing the user with several claddings, each cladding having a different inherent heat transmission characteristic.
[0048] FIG. 9 illustrates a version wherein the screw 17 is mounted on the tube and the threaded opening 18 is mounted on the cladding 4 .
[0049] FIG. 10 illustrates how the heat conductivity of the device can be gradually altered by configuring the top of the tube as concentric cylinders 19 that slidingly fit into concentric cylinders 20 configured in the cladding part 4 .
[0050] Operation of the Device: To use this invention, the ice pack 7 is first placed in the freezer for several hours to allow its content to freeze. The ice pack is then snugly inserted inside the tube 1 thus making firm contact with the tube 1 . The insulator layers 5 , 10 and 13 restrict heat flow and allow the device to remain operable over an extended period of time, typically 1 to 4 hours. The duration of cooling is influenced by external conditions, including ambient temperature, skin temperature, amount of usage, and the starting temperature of the ice pack. To use the device, the cap 12 is removed and the stainless tip 4 of the device is wiped and/or cleaned with a disinfectant. The stainless steel cladding 4 at the tip of the device is cold and can be applied to the skin to obtain the therapeutic or cosmetic effects such as reduction of swelling and redness as may occur on skin of acne sufferers.
[0051] Variations. It is clear to persons having ordinary skill in the art, that many variations are possible under the basic theme of this invention. These are some possible variations:
a) The thickness of the tube 1 can be maintained constant as it progresses from the rear to the front. This can reduce manufacturing costs. b) The outer layer 6 could be omitted to reduce manufacturing costs. c) The cross-sectional shape of the tubes does not have to be circular. For example it could be oval or polygonal. The tip may be pyramidal with a rounded tip in order to decrease irritation to the surrounding skin. d) The stainless steel cladding 4 could be omitted leaving the tube 1 metal (Aluminum for example) making direct contact with the skin again to reduce manufacturing costs. e) The stainless steel cladding 4 could be omitted by constructing the tube 1 out of stainless steel for example.
[0057] While the above description contains many specificities, the reader should not construe these as limitations on the scope of the invention, but merely as exemplifications of preferred embodiments thereof. Those skilled in the art will envision many other possible variations within its scope. Accordingly, the reader is requested to determine the scope of the invention by the appended claims and their legal equivalents, and not by the examples which have been given. | A dermatological device for cooling the skin comprised of an ice pack and a heat conductive shield configured to operate as an aseptic separator between said skin and the ice pack and to conduct heat from the skin to the ice pack. This invention is also a method of cooling the skin which comprises cooling an ice pack, placing the ice pack over an aseptic shield and applying the other side of the shield to the skin. Heat flow is controlled by adjusting the contact surface between components within the shield. | 0 |
[0001] This application claims the priority of German application 10 2006 061 491.7, filed Dec. 23, 2006, the disclosure of which is expressly incorporated by reference herein.
BACKGROUND AND SUMMARY OF THE INVENTION
[0002] This invention relates to a housing having an expansion tent that can be connected to the housing.
[0003] A housing in the sense of this invention may be a container, such as a 20′ ISO standard container. Such containers are used as shelters for multiple applications, such as mobile hospital or command post applications.
[0004] A container of this type having an expansion tent is disclosed, for example, in European Patent Document EP 1 273 743 A1.
[0005] Particularly for medical applications, it is important to avoid contamination of the tent interior at any time, especially during erecting or dismantling of the expansion tent. Direct contact between the interior space and the exterior space should generally be avoided, so that the interior side remains on the inside and the exterior side remains on the outside (this is the so-called IN IN/OUT OUT effect).
[0006] It is an object of the invention to permit hermetic sealing-off of such an interior space with respect to the environment in all constructive conditions of the tent, particularly during tent erecting and dismantling, independently of the type of construction of the expansion tent.
[0007] This task is achieved by way of a bag-shaped cover, which, at its opening, is permanently connected to the housing, which forms an interior surface of the erected expansion tent, and which is suitable for hermetically sealing off interiors of the housing and the expansion tent with respect to the environment. These interiors are sealed off, in this manner, during all operating conditions, while erecting the tent, and while dismantling the tent. Advantageous embodiments are also claimed.
[0008] According to the invention, a bag-shaped cover is provided, which, by way of its opening, is permanently connected to the housing in all constructive conditions of the expansion tent. In the erected condition of the expansion tent, this bag-shaped cover forms the interior surface of the expansion tent. Together with the housing, the cover forms a closed boundary surface which separates the contaminated exterior space from the interior space to be kept clean. As a result, a hermetically tight interior space can also be maintained during tent erecting and dismantling.
[0009] The expansion tent may be constructed as one element; thus, it may be constructed in one piece with a tent surface. According to an embodiment of the invention, the expansion tent may also be divided in several tent segments, which together form the expansion tent. This is particularly useful when an expansion tent is required that has a fairly large floor space. The reason is that, because of its size and weight, handling would be difficult with a single-element construction. Erecting and dismantling would require additional devices, which increases the erecting and dismantling time. The present invention ensures that, with several tent segments, contact of the environment with the interior is avoided at any time.
[0010] To erect the expansion tent, the individual tent segments can first be erected and mutually connected. In the case of a single-element tent, the latter is erected. The bag-shaped cover connected to the housing opening can then be unfolded and fixed to the interior surface of the tent segments. The bag-shaped cover thereby forms the interior surface of the expansion tent over all tent segments.
[0011] In an advantageous embodiment, the bag-shaped cover is constructed such that it is self-supporting in the erected condition. It is also stable by itself, and does not have to be connected with the tent construction. For this purpose, fiberglass rods known from conventional camping tents may be used. During erection, these rods can be pushed, for example, into pockets existing in the cover. This embodiment has the additional advantage that a complete uncoupling of the tent and the cover is achieved. The tent can be erected or dismantled completely independently of the cover.
[0012] The invention has the following advantages.
[0013] The handling of fairly large tents (larger than 45 m 2 ) during erecting and dismantling, with a low personnel requirement, is permitted;
[0014] Hermetic sealing is provided during the erecting and dismantling operations;
[0015] Arbitrary commercially available tents of all types and construction principles can be used without adaptation or with only a slight adaptation; and
[0016] The bag-shaped cover and the housing connected thereto form a closed boundary surface providing a permanent separation between a contaminated exterior space and an interior space that is to be kept clean (the IN IN/OUT OUT effect).
[0017] The bag-shaped cover also provides an improvement to the thermal protection of the tent.
[0018] In an advantageous embodiment of the invention, one of the tent segments is permanently connected with the bag-shaped cover. In this case, the bag-shaped cover is already flatly arranged on the inward-facing surface of the corresponding tent segment, and does not have to be connected during erection. This is accelerates erecting (analogously, the cover does not have to be detached again from the tent segment when the tent is dismantled). In addition, during erection of this tent segment, the bag-shaped cover is thereby simultaneously at least partially unfolded. The remaining tent segments are connected in a detachable manner with the bag-shaped cover only when erecting the tent, and are separated from one another again during dismantling. This connection between the cover and the tent segment can be eliminated with a self-supporting cover.
[0019] In a particularly advantageous embodiment of the invention, the bag-shaped cover is permanently connected with the tent segment that forms the closing segment at the end of the expansion tent away from the container. In this case, while erecting this tent segment, which is oriented away from the container, the bag-shaped cover is guided through the already erected tent segments, which are closer to the housing. As soon as the tent segment away from the container has been erected, the bag-shaped cover will also be completely unfolded and only still has to be fixed to the tent segment or to the remaining tent segments.
[0020] For erecting the expansion tent according to this embodiment, the individual tent segments, with the exception of the segment provided at the end away from the container, can be erected first and then connected with one another. Subsequently, the erection of the tent segment at the end away from the container takes place, the erection of the latter tent segment taking place together with the unfolding of the bag-shaped cover, specifically through the erected remaining tent segments. This cover then only has to be fixed to the interior surfaces of the remaining tent segments.
[0021] In a further embodiment of the invention, one of the tent segments itself forms a section of the bag-shaped cover. In this case, the tent segment must consist of a gastight material. This tent segment advantageously is the segment that is situated at the end of the expansion tent away from the container. The bag-shaped cover, therefore, consists of the corresponding tent segment, which forms the end of the tent away from the container, as well as a tube-shaped section, which, on one side, is gastightly connected to the above-mentioned tent segment and, on the other side, is gastightly connected to the housing.
[0022] To erect the expansion tent according to this embodiment, the individual tent segments, with the exception of the tent segment provided at the end away from the container, can first be erected and connected with one another. Subsequently, erection of the tent segment at the end away from the container takes place. Erection of the latter tent segment coincides with unfolding of the bag-shaped cover. In this case, erection takes place through the already erected tent segments. The cover then only has to be fixed to the interior surfaces of the remaining tent segments.
[0023] In the transport condition of the expansion tent, the tent segments and the bag-shaped cover are situated in a packed condition. These segments and the cover, for example, may be folded and rolled up inside the housing. Thus, a compact form is achieved, which protects the flexible, and therefore easily damageable, components of the expansion tent.
[0024] The expansion tent may be an inflatable tent. The following construction principles may be used here.
[0025] Air cells: Joined-together air-filled tubes whose exterior sides form the outer wall of the tent and whose interior sides form the interior wall. The tubes are connected with one another in the center, so that a hermetically closed wall structure is created in the center. The excess pressure in the tubes permits the omission of a supporting structure (no framing is required).
[0026] High-pressure beams: Tubes having an internal pressure greater than 1 bar inside the tent cover and having the purpose of absorbing forces acting upon the tent (frame replacement).
[0027] Low-pressure beams: Tubes having an internal pressure lower than 0.7 bar inside the tent cover and having the purpose of absorbing the forces acting upon the tent (frame replacement).
[0028] Other tent constructions, such as those with a bearing structure that is formed by a rod assembly, can also be used.
BRIEF DESCRIPTION OF THE DRAWINGS
[0029] The invention is described by way of two concrete embodiments with reference to the drawings. FIGS. 1 to 6 are consecutive snapshots during erection of the first embodiment. FIG. 7 is a snapshot during erection of the second embodiment.
[0030] FIG. 1 a is a lateral view, and FIG. 1 b is a top view, of both tent segments still in the completely packed condition;
[0031] FIG. 2 a is a top view of the unfolded first tent segment;
[0032] FIG. 2 b is a lateral view of the unfolded first tent segment;
[0033] FIG. 3 a is a top view of the inflated first tent segment;
[0034] FIG. 3 b is a lateral view of the inflated first tent segment;
[0035] FIG. 3 c is a front view of the inflated first tent segment;
[0036] FIG. 4 a is a top view of the unfolded second tent segment;
[0037] FIG. 4 b is a lateral view of the unfolded second tent segment;
[0038] FIG. 5 a is a top view of the partially inflated second tent segment;
[0039] FIG. 5 b is a lateral view of the partially inflated second tent segment;
[0040] FIG. 6 a is a lateral view of the completely inflated second tent segment;
[0041] FIG. 6 b is a front view of the completely inflated second tent segment.
[0042] FIG. 7 is a lateral view of the partially inflated second tent segment in the second embodiment.
DETAILED DESCRIPTION OF THE INVENTION
[0043] FIG. 1 shows the initial condition (transport condition) during erection of the expansion tent of a housing, which is constructed here as an ISO standard container. The space formed by the tent and the container may be used, for example, for a mobile hospital or a command post.
[0044] The container 3 has the shape of a cuboid and has firm walls made, for example, of steel or plastic. A multilayer construction consisting of base and cover layers, with an intermediate layer made of an insulating material, is also conceivable, as known, for example, from German Patent Document DE 102 25 281 C2. An expansion tent is to be built onto one side of the container (here, the shorter side). In this embodiment, the tent consists of exactly two tent segments. The division of the expansion tent into individual tent segments takes place perpendicular to the ridge line. Each of the individual tent segments may be erected by itself, independently of the other tent segment. They are then coupled at their gable ends. The erection therefore takes place along a direction defined by the roof ridge.
[0045] In the initial condition according to FIG. 1 , the two tent segments 1 , 2 are housed in the container in the packed condition (folded and rolled up). The tent segment 1 is shown by broken line in this position (see FIG. 1 a ). The segments consist of a flexible material.
[0046] After opening the front flap 8 of the container, the first tent segment 1 , which is close to the container, is rolled out of the container. In the erected condition of the expansion tent, this tent segment is situated directly adjacent to the container. It is advantageously permanently connected to the container along the entire circumference of the container opening. However, this permanent linkage can also be omitted.
[0047] FIG. 2 shows a situation in which the tent segment 1 is completely rolled out and unfolded. Like the tent segment 2 , the tent segment 1 consists of individual tube-type parallel chambers (air cells), respectively adjacent air cells communicating with one another by way of openings.
[0048] In FIG. 3 , the first tent segment 1 is completely inflated. As illustrated in the front view according to FIG. 3 c, this first tent segment 1 is open toward the front, beyond the container. There, the second tent segment 2 , which is still situated in the container 3 , can be connected.
[0049] A bag-shaped cover 4 is provided according to the invention. It consists of a gastight flexible material. With respect to the size and the blank, the cover is adapted to the expansion tent such that, in the erected condition, it can form the closed and tight interior surface of the entire expansion tent. It has precisely one opening at which it is gastightly connected to the container 3 along the circumference of the container opening. Together with the walls of the container 3 , the cover 4 forms the boundary surface between the contaminated exterior area and the interior area to be kept clean.
[0050] In the illustrated advantageous embodiment, the cover 4 is permanently and flatly connected with the tent segment 2 away from the container, specifically on the surface which, in the erected condition of the tent segment 2 , forms the inward-facing surface. This fastening of the cover to the tent segment 2 has the effect that, as a result of the rolling-out and unfolding of the tent segment ( FIG. 4 ) away from the container, the cover 4 connected with the latter is also rolled out and unfolded. The rolling-out of the disassembled tent segment 2 , away from the container, together with the cover 4 arranged thereon, takes place through the already erected tent segment 1 close to the container.
[0051] In an embodiment not shown here, the bag-shaped cover is connected with none of the tent segments in the transport condition. In this case, the individual tent segments are first erected and mutually connected. Subsequently, the unfolding of the bag-shaped cover takes place in the interior of the tent over all tent segments, so that the cover forms the interior surface of the expansion tent.
[0052] In FIG. 5 , the tent segment 2 away from the container is partially inflated. The cover 4 is flatly connected with the tent segment 2 , specifically on its entire inward-facing side. It is also shown in FIG. 5 that, in the area of the tent segment 1 close to the container, the cover 4 is still hanging through—and is therefore, at this point in time of the erecting operation as well as generally in the transport condition, not yet connected with the tent segment close to the container.
[0053] In FIG. 6 , the exterior tent segment 2 is now also completely inflated and is connected with the tent segment 1 close to the container at the gable sides (for example, by tightening straps which, at the coupling point, reach around the mutually abutting air cells of the two tent segments 1 , 2 ). In the area of the tent segment 1 close to the container, the cover 4 is fastened to the interior side, for example, by means of a velcro fastener, a tightening strap, or other fastening device(s). The cover 4 can thereby also contribute to improved heat insulation. As illustrated in the front view according to FIG. 6 c, the tent segment 2 away from the container comprises an essentially vertical wall, which forms the face side of the expansion tent. An adapter 6 for the connection of another tent or as an emergency exit is provided at this face side. At a corresponding point, for example, a gastight zipper may be arranged at the bag-shaped cover 4 , which zipper provides the passage way.
[0054] FIG. 7 is a snapshot during the erection of a second embodiment of the expansion tent according to the invention on a container. It shows a situation which corresponds to FIG. 5 for the first embodiment. The tent 1 close to the container is already completely erected. The tent 2 away from the container is only partially inflated.
[0055] However, in the embodiment according to FIG. 7 , the tent segment 2 , which is away from the container, itself forms a part of the bag-type cover. For this purpose, the tent segment away from the container consists of a gastight material. At a gable side, it is gastightly connected over its entire cross-sectional circumference with a tube-shaped cover 4 a. At its other end, the tube-shaped cover 4 a is gastightly connected with the housing 3 . It is therefore situated inside the tent segment 1 close to the container. The bag-type cover, which prevents contamination of the interior in all constructive conditions, in this embodiment, is formed by the combination of the tent segment 2 away from the container and the tube-shaped section 4 a. The erection of this embodiment otherwise takes place as described in FIGS. 1 to 6 for the first embodiment.
[0056] The foregoing disclosure has been set forth merely to illustrate the invention and is not intended to be limiting. Since modifications of the disclosed embodiments incorporating the spirit and substance of the invention may occur to persons skilled in the art, the invention should be construed to include everything within the scope of the appended claims and equivalents thereof. | A housing has an expansion tent connectable thereto. A bag-shaped cover is present, and has an opening permanently connected to the housing. The cover forms the interior surface of the erected expansion tent, and is suitable for hermetically sealing off the interior of the housing and the expansion tent with respect to the environment. Sealing can be provided during all operating conditions, while erecting the tent, and while dismantling the tent. | 4 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a flush tank, and more particularly to a flush tank having an electromagnetic control device for easily controlling and actuating or operating the flush tank.
2. Description of the Prior Art
Various kinds of typical flush tanks have been developed and widely used nowadays, and comprise a float movable toward an outlet pipe, in order to control the water flushing of the flush tanks, and a coupling chain coupling the float to an actuating knob, in order to control the engagement or the disengagement of the float and the outlet pipe.
For example, U.S. Pat. No. 5,249,313 to Chang, U.S. Pat. No. 5,459,885 to Gaw, U.S. Pat. No. 5,524,297 to Harrison, and U.S. Pat. No. 5,924,143 to Harrison disclose four of the typical flush tanks and also comprise a float coupled to a coupling chain which may actuate the float toward and away from the outlet pipe.
In addition, for the typical flush tanks, the float may not suitably or solidly forced to block the outlet pipe when the gasket is aged, or when the water level within the water tank is not high enough, or the like.
Furthermore, the control devices for the typical flush tanks include a mechanical mechanism and is required to be provided and attached to the flush tank, and is required to be operated manually. The mechanical operation of the mechanical mechanism may make noised while in use.
The applicant has developed a typical flush tank having an electromagnetic control device for easily controlling and actuating or operating the flush tank, and disclosed in U.S. Pat. No. 6,237,165 to Chen et al. However, the typical electromagnetic control device for the flush tank is also required to be operated manually and includes a complicated configuration.
The present invention has arisen to mitigate and/or obviate the afore-described disadvantages of the conventional flush tanks.
SUMMARY OF THE INVENTION
The primary objective of the present invention is to provide a flush tank including an electromagnetic control device for easily and automatically controlling and actuating or operating the flush tank.
In accordance with one aspect of the invention, there is provided a flush tank comprising a receptacle for receiving water therein, an outlet pipe attached to the receptacle for discharging the water, a float disposed close to the outlet pipe to selectively block the outlet pipe, and to control an outward flowing of the water through the outlet pipe. A magnetically forcing device may further be provided for magnetically forcing the float to block the outlet pipe, and a detecting device may be used to detect users and to actuate the magnetically forcing device to release the float automatically without being depressed or operated or actuated by the users.
The magnetically forcing device includes an electromagnetic device disposed in the receptacle for acting with the float. The float includes at least one projection extended therefrom for acting with the electromagnetic device. The magnetically forcing device includes a frame disposed in the receptacle to support the electromagnetic device, and for acting with the float.
The frame includes a casing provided therein to receive the electromagnetic device. The frame includes at least one block provided thereon and made of magnetically attractable material, the float includes at least one extension extended therefrom and made of magnetically attractable material for acting with the block.
A stop may further be provided and attached to the frame, for engaging with the float and for limiting a movement of the float relative to the frame. The frame includes at least one post extended therefrom, the stop includes at least one leg extended therefrom and adjustably secured to the post. The stop includes a loop attached to the leg and to slidably receive the post.
The post includes a plurality of apertures formed therein, the stop includes a catch provided on the leg to selectively engage into either of the apertures of the post, to adjustably secure the leg of the stop to the post. The leg includes a spring blade provided thereon to support the catch. The leg includes a hand grip provided on the spring blade to move the spring blade to disengage the catch from the leg.
The electromagnetic device includes a core for acting with the float, and a coil disposed around the core, to move the core relative to the coil. The electromagnetic device includes a housing to receive the core and the coil. The electromagnetic device includes a duct to receive the core. The duct includes a cushioning member disposed therein to engage with and to cushion the core.
The electromagnetic device includes a container having a cavity formed therein to slidably receive the core. A knob may further be provided and attached to the receptacle, and a chain coupled between the knob and the float.
Further objectives and advantages of the present invention will become apparent from a careful reading of the detailed description provided hereinbelow, with appropriate reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a flush tank in accordance with the present invention;
FIG. 2 is a partial cross sectional view illustrating the control device of the flush tank;
FIG. 3 is a perspective view of the control device for the flush tank;
FIG. 4 is a partial exploded view of the control device for the flush tank;
FIG. 5 is a top plan view of the control device for the flush tank;
FIG. 6 is a partial side plan view of the control device for the flush tank;
FIG. 7 is a partial cross sectional view taken along lines 7 — 7 of FIG. 3 ;
FIG. 8 is a partial cross sectional view similar to FIG. 7 ; illustrating the operation of the control device for the flush tank; and
FIG. 9 is a partial cross sectional view similar to FIG. 2 ; illustrating the operation of the control device for the flush tank.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to the drawings, and initially to FIGS. 1 and 2 , a flush tank in accordance with the present invention includes a receptacle 10 normally attached to a wall member 11 , and disposed above the rear portion of a toilet 12 , for receiving water to flush the toilet 12 . The receptacle 10 comprises a usual actuating knob 14 attached thereto, for controlling the flushing of the toilet 12 .
As shown in FIGS. 2–4 and 9 , an outlet pipe 20 is normally attached or secured to the bottom portion of the receptacle 10 with one or more fasteners 21 , and includes a passage 22 formed therein for allowing the water contained in the receptacle 10 to flow out and to flush of the toilet 12 or for discharging the water. A usual overflow tube 23 is attached to the outlet pipe 20 to maintain a water level of the receptacle 10 .
A frame 30 is attached or secured to the receptacle 10 , such as secured to the outlet pipe 20 of the receptacle 10 with one or more stays 24 , and includes a space 31 formed therein to slidably receive a float 40 therein. The float 40 is disposed above or close to the outlet pipe 20 and includes a pad 41 attached to the bottom thereof, for engaging with the outlet pipe 20 , to control the water outward flowing through the outlet pipe 20 .
The frame 30 includes one or more, such as two blocks 32 provided thereon or extended therefrom, and made of metal or magnetic members or magnetically attractable materials for magnetically attracting purposes. The frame 30 further includes one or more, such as two blocks or casings 33 provided thereon or extended therefrom, and each having a chamber 34 formed therein ( FIGS. 5 , 7 , 8 ) to receive an electromagnetic device 50 therein.
As shown in FIGS. 7 and 8 , each of the electromagnetic devices 50 includes a container 51 engaged into the chamber 34 of the corresponding casing 33 and having a cavity 52 formed therein, such as formed in the upper portion thereof. A housing 53 is engaged in the container 51 and includes an orifice 54 formed in the upper portion thereof and communicating with the cavity 52 of the container 51 .
Each of the electromagnetic devices 50 includes a duct 55 disposed in the housing 53 , a core 56 slidably received in the duct 55 and having an upper portion movable or engageable into the cavity 52 of the container 51 , and a coil 57 engaged around the core 56 or the duct 55 , for actuating the core 56 to move relative to the duct 55 and the housing 53 or the container 51 .
It is preferable that a resilient or cushioning member 58 is disposed in the lower portion of the duct 55 , and includes a depression 59 formed therein, to slidably receive the lower portion of the core 56 , and to cushion the core 56 , and to prevent the core 56 from impacting or hammering into the housing 53 or the container 51 .
The float 40 includes one or more, such as two extensions 42 provided thereon or extended therefrom, and made of magnetic members or magnetically attractable materials or metal for magnetically attracting or acting with the corresponding blocks 32 of the frame 30 . However, the magnetically attracting force between the extensions 42 of the float 40 and the blocks 32 of the frame 30 is smaller than the floating force or the buoyancy of the float 40 .
The float 40 further includes one or more, such as two projections 43 provided thereon or extended therefrom, and made of magnetic members or magnetically attractable materials or metal, or having a magnet 44 , such as a permanent magnet 44 disposed therein for magnetically attracting or acting with the electromagnetic device 50 . For example, when the electromagnetic device 50 is not energized, the magnetic core 56 of the electromagnetic device 50 may act with or may attract the projections 43 or the magnets 44 of the float 40 ( FIG. 7 ).
When the magnetic core 56 of the electromagnetic device 50 is acted with or attracted the projections 43 of the float 40 , and when the extensions 42 of the float 40 are also acted with the blocks 32 of the frame 30 , the magnetically attracting force between the extensions 42 and the blocks 32 , and between the core 56 and the projections 43 is arranged to be greater than the floating force or the buoyancy of the float 40 , in order to force the float 40 downwardly to block the outlet pipe 20 ( FIG. 2 ).
The flush tank further includes a sensor or detecting device 60 ( FIG. 1 ) attached to the wall member 11 , and preferably disposed above or close to the rear portion of the toilet 12 , for detecting whether the users are using the toilet 12 or not. The detecting device 60 is electrically coupled to the electromagnetic devices 50 , with such as wires 61 ( FIGS. 3 , 4 ), for actuating the electromagnetic devices 50 .
For example, when the detecting device 60 has detected that a user is using the toilet 12 , the electromagnetic devices 50 may be actuated to force or to pull the core 56 into the duct 55 , and thus to separate the core 56 from the projections 43 or the magnets 44 of the float 40 ( FIG. 8 ). As shown in FIG. 5 , the frame 30 may include one or more pathways 35 formed therein to receive the wires 61 .
When the core 56 is separated from the projections 43 or the magnets 44 of the float 40 , the magnetically attracting force between the extensions 42 of the float 40 and the blocks 32 of the frame 30 is smaller than the floating force or the buoyancy of the float 40 , and is thus not good enough to force the float 40 downwardly to block the outlet pipe 20 . At this moment, the float 40 may float upwardly away from the outlet pipe 20 ( FIG. 8 ), to allow the water in the receptacle 10 to flow out through the outlet pipe 20 and to flush the toilet 12 ( FIG. 9 ).
It is preferable that the core 56 may be formed into different polarity from that of the magnet 44 when the core 56 is separated from the projections 43 or the magnets 44 of the float 40 , or when the core 56 is forced into the duct 55 by the coil 57 , in order to further force the magnet 44 and the float 40 upwardly away from the frame 30 and the electromagnetic devices 50 .
After the water flushing operation, the float 40 may move downwardly to block the outlet pipe 20 again. The electromagnetic devices 50 may be switched off or de-energized when the float 40 floats upwardly away from the outlet pipe 20 to conduct the water flushing operation. At this moment, the core 56 is not acted by the coil 57 , and may be attracted to the magnet 44 , to solidly retain the float 40 to the frame 30 , and to solidly block the outlet pipe 20 again.
As shown in FIGS. 2–4 , a usual pull chain 45 may further be provided and coupled between the float 40 and the actuating knob 14 ( FIG. 1 ), to allow the float 40 to be pulled and disengaged from the outlet pipe 20 manually by the users, and to allow the toilet 12 to be flushed by the water when the float 40 is pulled disengaged from the outlet pipe 20 .
As shown in FIGS. 3 and 4 , the frame 30 may further include one or more, such as two posts 37 extended therefrom and each having one or more apertures 38 formed therein, and may further include a stop 70 adjustably secured thereto. For example, the stop 70 includes one or more, such as two legs 71 extended therefrom and each having a loop 72 provided thereon to slidably receive the posts 37 , and to slidably secure the stop 70 to the frame 30 .
The stop 70 includes one or more, such as two spring blades 73 formed in the legs 71 thereof respectively, and each having a catch 74 extended therefrom ( FIG. 4 ), for engaging into the corresponding apertures 38 of the posts 37 , and thus to adjustably secure the stop 70 to the posts 37 of the frame 30 . Each of the spring blades 73 may include a hand grip 75 extended therefrom, for pushing the spring blades 73 to disengage the catches 74 from the apertures 38 of the posts 37 , and thus to allow the legs 71 of the stop 70 to be slid and adjusted up and down along the posts 37 .
The stop 70 includes an opening 77 formed therein for receiving the usual pull chain 45 , and includes an inner peripheral shoulder 78 formed therein ( FIGS. 2 , 9 ) for receiving the upper portion of the float 40 , and for limiting the movement of the float 40 relative to the frame 30 .
It is to be noted that the float 40 is allowed to be automatically floated or moved upwardly away from the outlet pipe 20 to allow the water in the receptacle 10 to flow out through the outlet pipe 20 and to flush the toilet 12 when the detecting device 60 has detected that a user is using the toilet 12 , such as when the user has been detected to use the toilet 12 and then moved away from the toilet 12 . The typical electromagnetic control devices for the flush tanks are still required to be operated manually.
In addition, the electromagnetic device 50 and the magnet 44 may be enclosed or shielded or covered or protected with plastic materials, to prevent the electromagnetic device 50 and the magnet 44 from being rusted. In addition, the core 56 is received in the container 51 and the housing 53 , and will not make noises while moving relative to the duct 55 . No typical flush tanks have a magnetically attracting device to force the float to block the outlet pipe.
Accordingly, the flush tank in accordance with the present invention includes an electromagnetic control device for easily and automatically controlling and actuating or operating the flush tank.
Although this invention has been described with a certain degree of particularity, it is to be understood that the present disclosure has been made by way of example only and that numerous changes in the detailed construction and the combination and arrangement of parts may be resorted to without departing from the spirit and scope of the invention as hereinafter claimed. | A flush tank includes an outlet pipe attached to a receptacle for discharging water, a float disposed close to the outlet pipe to selectively block the outlet pipe, and to control an outward flowing of the water through the outlet pipe. A magnetically forcing device may magnetically force the float to block the outlet pipe, and a detecting device may be used to detect users and to actuate the magnetically forcing device to release the float. The magnetically forcing device includes an electromagnetic device supported by a frame to act with the float. A stop may be attached to the frame to limit a movement of the float relative to the outlet pipe. | 8 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit under 35 U.S.C. §119 of the filing date of International Application No. PCT/US2012/057231, filed Sep. 26, 2012. The entire disclosure of this prior application is incorporated herein by this reference.
TECHNICAL FIELD OF THE INVENTION
[0002] This invention relates, in general, to equipment utilized and operations performed in conjunction with a subterranean well and, in particular, to a single trip, multi zone completion assembly having smart well capabilities and methods for use thereof.
BACKGROUND OF THE INVENTION
[0003] Without limiting the scope of the present invention, its background is described with reference to providing communication and sensing during a production operation within a subterranean wellbore environment, as an example. It is well known in the subterranean well completion and production arts that downhole sensors can be used to monitor a variety of parameters in the wellbore environment. For example, during production operations, it may be desirable to monitor a variety of downhole parameters such as temperatures, pressures, pH, flowrates and the like in a variety of downhole locations. Transmission of this information to the surface may then allow the operator to modify and optimize the production operations. One way to transmit this information to the surface is using energy conductors such as electrical wires, optical fibers or the like.
[0004] In addition or as an alternative to operating as an energy conductor, optical fibers may serve as a sensor. For example, an optical fiber may be used to obtain distributed measurements representing a parameter along the entire length of the fiber. Specifically, optical fibers have been used for distributed downhole temperature sensing, which provides a more complete temperature profile as compared to discrete temperature sensors. In operation, once an optical fiber is installed in the well, a pulse of laser light is sent along the fiber. As the light travels down the fiber, portions of the light are backscattered to the surface due to the optical properties of the fiber. The backscattered light has a slightly shifted frequency such that it provides information that is used to determine the temperature at the point in the fiber where the backscatter originated. As the speed of light is constant, the distance from the surface to the point where the backscatter originated can also be determined. In this manner, continuous monitoring of the backscattered light will provide temperature profile information for the entire length of the fiber.
[0005] Use of an optical fiber for distributed downhole temperature sensing may be highly beneficial during production operations. For example, a distributed temperature profile may be used in determining the location of water or gas influx. Likewise, a distributed temperature profile may be used in determining the location of a failed gravel pack. It has been found, however, that installation of a completion including downhole sensors and energy conductors in a multi zone well requires numerous trips into and out of the well. In addition, it has been found, that even after the sensors and energy conductors have been installed and are providing information relative to production, well intervention may be required to modify or optimize the production operations.
[0006] Therefore, a need has arisen for an improved completion assembly that is operable to monitor a variety of downhole parameters in a variety of downhole locations. A need has also arisen for such an improved completion assembly that does not require numerous trips into and out of the well for multi zone installations. Further, a need has arisen for such an improved completion assembly that does not require well intervention to modify or optimize the production operations following receipt of information from the downhole sensors.
SUMMARY OF THE INVENTION
[0007] The present invention disclosed herein is directed to a single trip, multi zone completion assembly having smart well capabilities and methods for use thereof. The completion assembly of the present invention is operable to monitor a variety of downhole parameters in a variety of downhole locations. In addition, the completion assembly of the present invention does not require numerous trips into and out of the well for multi zone installations. Further, the completion assembly of the present invention does not require well intervention to modify or optimize the production operations following receipt of information from the downhole sensors.
[0008] In one aspect, the present invention is directed to a completion assembly for operation in a subterranean well having first and second production zones. The completion assembly includes a lower completion assembly that is operably positionable in the well. The lower completion assembly includes first and second zonal isolation subassemblies. An upper completion assembly is operably positionable at least partially within the lower completion assembly to establish fluid communication between first and second fluid flow control modules of the upper completion assembly, respectively, with the first and second zonal isolation subassemblies. A first communication medium having a connection between the upper and lower completion assemblies extends through the first and second zonal isolation subassemblies. A second communication medium is operably associated with the first and second fluid flow control modules. In operation, production from the first production zone is controlled by operating the first fluid flow control module responsive to data obtained by monitoring at least one fluid parameter of fluid from the first production zone (1) exterior of the first zonal isolation subassembly, (2) between the first zonal isolation subassembly and the first fluid flow control module and (3) interior of the first fluid flow control module. In addition, production from the second production zone is controlled by operating the second fluid flow control module responsive to data obtained by monitoring at least one fluid parameter of fluid from the second production zone (1) exterior of the second zonal isolation subassembly, (2) between the second zonal isolation subassembly and the second fluid flow control module and (3) interior of the second fluid flow control module.
[0009] In one embodiment, the first and second zonal isolation subassemblies each include a sand control screen and a production sleeve. In some embodiments, the first and second fluid flow control modules each include a control assembly and a valve assembly. In certain embodiments, the first communication medium may be a distributed temperature sensor. In one embodiment, the upper completion assembly is retrievable from the lower completion assembly. In another embodiments, the upper completion assembly is installed within the well in a single trip. In further embodiments, the lower completion assembly is installed within the well in a single trip.
[0010] In one embodiment, the first communication medium carries data obtained from monitoring the at least one fluid parameter of fluid from the first production zone exterior of the first zonal isolation subassembly and data obtained from monitoring the at least one fluid parameter of fluid from the second production zone exterior of the second zonal isolation subassembly. In another embodiment, the second communication medium carries data obtained from monitoring the at least one fluid parameter of fluid from the first production zone between the first zonal isolation subassembly and the first fluid flow control module and data obtained from monitoring the at least one fluid parameter of fluid from the second production zone between the second zonal isolation subassembly and the second fluid flow control module. In a further embodiment, the second communication medium carries data obtained from monitoring the at least one fluid parameter of fluid from the first production zone interior of the first fluid flow control module and data obtained from monitoring the at least one fluid parameter of fluid from the second production zone interior of the second fluid flow control module.
[0011] In another aspect, the present invention is directed to a method for completing a subterranean well. The method includes positioning a lower completion assembly in the well, the lower completion assembly including first and second zonal isolation subassemblies with a lower portion of a first communication medium extending therethrough and coupled to a lower connector; engaging the lower completion assembly with an upper completion assembly to establish fluid communication between first and second fluid flow control modules of the upper completion assembly, respectively, with the first and second zonal isolation subassemblies, the upper completion assembly including a second communication medium operably associated with the first and second fluid flow control modules and an upper portion of the first communication medium coupled to an upper connector; and operatively connecting the upper and lower connectors to enable communication between the upper and lower portions of the first communication media.
[0012] The method may also include setting a first packer of the upper completion assembly uphole of the lower completion assembly; unlocking an expansion joint of the upper completion assembly uphole of the first packer; setting a second packer of the upper completion assembly uphole of the expansion joint; anchoring the upper completion assembly within the lower completion assembly; engaging seal assemblies of the upper completion assembly with seal bores of the lower completion assembly to isolate the fluid communication between the first fluid flow control module and the first zonal isolation subassembly and to isolate the fluid communication between the second fluid flow control module and the second zonal isolation subassembly; controlling production through the first zonal isolation subassembly by operating an interval control valve of the first fluid flow control module and controlling production through the second zonal isolation subassembly by operating an interval control valve of the second fluid flow control module; monitoring at least one fluid parameter exterior of the first zonal isolation subassembly via the first communication medium, monitoring the at least one fluid parameter between the first zonal isolation subassembly and the first fluid flow control module via the second communication medium and monitoring the at least one fluid parameter interior of the first fluid flow control module via the second communication medium; monitoring the at least one fluid parameter exterior of the second zonal isolation subassembly via the first communication medium, monitoring the at least one fluid parameter between the second zonal isolation subassembly and the second fluid flow control module via the second communication medium and monitoring the at least one fluid parameter interior of the second fluid flow control module via the second communication medium; and/or operating the first communication medium as a distributed temperature sensor.
[0013] In another aspect, the present invention is directed to a method of operating a completion assembly during production from a subterranean well. The method includes providing an upper completion assembly having first and second fluid flow control modules positioned in a lower completion assembly having first and second zonal isolation subassemblies that are, respectively, in fluid communication with the first and second fluid flow control modules and first and second production zones; providing a first communication medium having a connection between the upper and lower completion assemblies and extending through the first and second zonal isolation subassemblies; providing a second communication medium operably associated with the first and second fluid flow control modules; controlling production from the first production zone by operating the first fluid flow control module responsive to data obtained by monitoring at least one fluid parameter of fluid from the first production zone (1) exterior of the first zonal isolation subassembly, (2) between the first zonal isolation subassembly and the first fluid flow control module and (3) interior of the first fluid flow control module; and controlling production from the second production zone by operating the second fluid flow control module responsive to data obtained by monitoring at least one fluid parameter of fluid from the second production zone (1) exterior of the second zonal isolation subassembly, (2) between the second zonal isolation subassembly and the second fluid flow control module and (3) interior of the second fluid flow control module.
[0014] The method may also include operating a first valve assembly to control production from the first production zone and operating a second valve assembly to control production from the second production zone; operating a first interval control valve to control production from the first production zone and operating a second interval control valve to control production from the second production zone; monitoring the at least one fluid parameter of fluid from the first production zone exterior of the first zonal isolation subassembly and monitoring the at least one fluid parameter of fluid from the second production zone exterior of the second zonal isolation subassembly via the first communication medium; operating the first communication medium as a distributed temperature sensor; monitoring the at least one fluid parameter of fluid from the first production zone between the first zonal isolation subassembly and the first fluid flow control module and monitoring the at least one fluid parameter of fluid from the second production zone between the second zonal isolation subassembly and the second fluid flow control module via the second communication medium; and/or monitoring the at least one fluid parameter of fluid from the first production zone interior of the first fluid flow control module and monitoring the at least one fluid parameter of fluid from the second production zone interior of the second fluid flow control module via the second communication medium.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] For a more complete understanding of the features and advantages of the present invention, reference is now made to the detailed description of the invention along with the accompanying figures in which corresponding numerals in the different figures refer to corresponding parts and in which:
[0016] FIG. 1 is a schematic illustration of an offshore oil and gas platform installing an upper completion assembly into a well having a lower completion assembly disposed therein according to an embodiment of the present invention; and
[0017] FIGS. 2A-2H are cross sectional views of consecutive axial sections of a single trip, multi zone completion assembly including an upper completion assembly installed within a lower completion assembly during a production operation according to an embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0018] While the making and using of various embodiments of the present invention are discussed in detail below, it should be appreciated that the present invention provides many applicable inventive concepts, which can be embodied in a wide variety of specific contexts. The specific embodiments discussed herein are merely illustrative of specific ways to make and use the invention, and do not delimit the scope of the invention.
[0019] Referring initially to FIG. 1 , an upper completion assembly is being installed in a well having a lower completion assembly disposed therein from an offshore oil or gas platform that is schematically illustrated and generally designated 10 . A semi-submersible platform 12 is centered over submerged oil and gas formation 14 located below sea floor 16 . A subsea conduit 18 extends from deck 20 of platform 12 to wellhead installation 22 , including blowout preventers 24 . Platform 12 has a hoisting apparatus 26 , a derrick 28 , a travel block 30 , a hook 32 and a swivel 34 for raising and lowering pipe strings, such as a substantially tubular, axially extending tubing string 36 .
[0020] A wellbore 38 extends through the various earth strata including formation 14 and has a casing string 40 cemented therein. Disposed in a substantially horizontal portion of wellbore 38 is a lower completion assembly 42 that includes various tools such as an orientation and alignment subassembly 44 including a downhole wet mate connector, packer 46 , sand control screen assembly 48 , packer 50 , sand control screen assembly 52 , packer 54 , sand control screen assembly 56 and packer 58 . As described below, packer 46 , sand control screen assembly 48 and packer 50 may be referred to as a zonal isolation subassembly associated with zone 60 . Likewise, packer 50 , sand control screen assembly 52 and packer 54 may be referred to as a zonal isolation subassembly associated with zone 62 and packer 54 , sand control screen assembly 56 and packer 58 may be referred to as a zonal isolation subassembly associated with zone 64 . Extending downhole from orientation and alignment subassembly 44 are one or more energy conductors 66 that pass through packers 46 , 50 , 54 and are operably associated with sensors position on sand control screen assemblies 48 , 52 , 56 or within the gravel packs surrounding sand control screen assemblies 48 , 52 , 56 . Energy conductors 66 may be optical, electrical, hydraulic or the like and may be disposed within a flatpack control umbilical having, for example, one or more hydraulic conductor lines, one or more electrical conductor lines and one or more fiber optic conductor lines that is suitably attached to the exterior of lower completion assembly 42 . Energy conductors 66 may operate as communication media to transmit power, data and the like between the downhole sensors, downhole components and surface equipment. In certain embodiments, one or more of the energy conductors 66 may operate as a downhole sensor.
[0021] For example, if optical fibers are used as one or more of the energy conductors 66 , the optical fibers may be used to obtain distributed measurements representing a parameter along the entire length of the fiber such as distributed temperature or pressure sensing. In this embodiment, a pulse of laser light from the surface is sent along the fiber and portions of the light are backscattered to the surface due to the optical properties of the fiber. The slightly shifted frequency of the backscattered light provides information that is used to determine the temperature or pressure at the point in the fiber where the backscatter originated. In addition, as the speed of light is constant, the distance from the surface to the point where the backscatter originated can also be determined. In this manner, continuous monitoring of the backscattered light will provide temperature or pressure profile information for the entire length of the fiber.
[0022] Disposed in wellbore 38 at the lower end of tubing string 36 is an upper completion assembly 68 that includes various tools such as packer 70 , expansion joint 72 , packer 74 , fluid flow control module 76 and anchor assembly 78 including downhole wet mate connector 80 . Extending uphole of connector 80 are one or more energy conductors 82 that pass through packers 70 , 74 and extend to the surface in the annulus between tubing string 36 and wellbore 38 . Energy conductors 82 are preferably disposed within a flatpack control umbilical as described above that is suitable coupled to tubing string 36 . Energy conductors 82 may be optical, electrical, hydraulic or the like and are preferably of the same type as energy conductors 66 such that energy may be transmitted therebetween following a wet mate connection process between energy conductors 82 and energy conductors 66 . Upper completion assembly 68 also includes one or more energy conductors 84 that pass through packers 70 , 74 and extend to the surface in the annulus between tubing string 36 and wellbore 38 . Energy conductors 84 are preferably disposed within a flatpack control umbilical that is suitable coupled to tubing string 36 . Energy conductors 84 may be optical, electrical, hydraulic or the like and may operate as communication media to transmit power, data and the like between sensors associated with upper completion assembly 68 , downhole components of upper completion assembly 68 and surface equipment. In certain embodiments, one or more of the energy conductors 84 may operate as a downhole sensor such as a distributed temperature or pressure sensor.
[0023] Even though FIG. 1 depicts a horizontal wellbore, it should be understood by those skilled in the art that the apparatus according to the present invention is equally well suited for use in wellbores having other orientations including vertical wellbores, slanted wellbores, multilateral wellbores or the like. Accordingly, it should be understood by those skilled in the art that the use of directional terms such as above, below, upper, lower, upward, downward, uphole, downhole and the like are used in relation to the illustrative embodiments as they are depicted in the figures, the upward direction being toward the top of the corresponding figure and the downward direction being toward the bottom of the corresponding figure, the uphole direction being toward the surface of the well, the downhole direction being toward the toe of the well. Also, even though FIG. 1 depicts an offshore operation, it should be understood by those skilled in the art that the apparatus according to the present invention is equally well suited for use in onshore operations. Further, even though FIG. 1 depicts a cased hole completion, it should be understood by those skilled in the art that the apparatus according to the present invention is equally well suited for use in open hole completions.
[0024] Referring now to FIGS. 2A-2H , therein is schematically depicted successive axial sections of the completion assembly of the present invention including a lower completion assembly 100 and an upper completion assembly 200 . As described above, prior to installing upper completion assembly 200 , lower completion assembly 100 is positioned in the well. In the illustrated embodiment, the well includes casing 40 that has been perforated in three zones 60 , 62 , 64 . Lower completion assembly 100 will now be described from its uphole end to its downhole end. As best seen in FIG. 2B , lower completion assembly 100 includes an orientation and alignment subassembly 102 that is operable to receive and rotationally align upper completion assembly 200 within lower completion assembly 100 . Orientation and alignment subassembly 102 includes one or more downhole wet mate connectors 104 that are operable to connect the various energy conductors disposed within a plurality of flatpack control umbilicals 106 (two shown) with a mating connector of upper completion assembly 200 . Umbilicals 106 preferably contained energy conductors such as one or more hydraulic conductor lines, one or more electrical conductor lines and one or more fiber optic conductor lines. Umbilicals 106 are suitably attached to the exterior of lower completion assembly 100 .
[0025] As best seen in FIG. 2C , downhole of orientation and alignment subassembly 102 , lower completion assembly 100 includes a ported subassembly 108 having one or more fluid ports 110 for allowing fluid communication between the interior and the exterior of lower completion assembly 100 . Lower completion assembly 100 includes a packer assembly 112 having one or more elements 114 for establishing a sealing and gripping relationship with casing 40 . As best seen in FIG. 2D , downhole of packer assembly 112 , lower completion assembly 100 includes a sand control screen assembly 116 . In the illustrated embodiment, sand control screen assembly 116 includes two filter media 118 , 120 , a production sleeve 122 and a frac sleeve 124 . Production sleeve 122 and frac sleeve 124 may be operated mechanically, electrically, hydraulically or the like via local or remote operations to selectively allow or disallow fluid flow therethrough. Also, as illustrated, sand control screen assembly 116 has a plurality of sensors 126 that are operably associated with one or more of the energy conductors of umbilicals 106 . Sensors 126 may be of any suitable type for obtaining downhole information such as temperature, pressure, pH, flowrate or the like. Downhole of sand control screen assembly 116 , lower completion assembly 100 includes a seal bore subassembly 128 operable to provide an internal sealing surface. Downhole of seal bore subassembly 128 , lower completion assembly 100 includes a packer assembly 130 having one or more elements 132 for establishing a sealing and gripping relationship with casing 40 . Together, packer assembly 112 , sand control screen assembly 116 and packer assembly 130 may be referred to as a zonal isolation subassembly that is associated with zone 60 , which is depicted as being gravel packed.
[0026] As best seen in FIG. 2E , lower completion assembly 100 includes a seal bore subassembly 134 operable to provide an internal sealing surface. As best seen in FIG. 2F , downhole of seal bore subassembly 134 , lower completion assembly 100 includes a sand control screen assembly 136 . In the illustrated embodiment, sand control screen assembly 136 includes two filter media 138 , 140 , a production sleeve 142 and a frac sleeve 144 . Production sleeve 142 and frac sleeve 144 may be operated mechanically, electrically, hydraulically or the like via local or remote operations to selectively allow or disallow fluid flow therethrough. Also, as illustrated, sand control screen assembly 136 has a plurality of sensors 146 that are operably associated with one or more of the energy conductors of umbilicals 106 . Downhole of sand control screen assembly 136 , lower completion assembly 100 includes a seal bore subassembly 148 operable to provide an internal sealing surface. Downhole of seal bore subassembly 148 , lower completion assembly 100 includes a packer assembly 150 having one or more elements 152 for establishing a sealing and gripping relationship with casing 40 . Together, packer assembly 130 , sand control screen assembly 136 and packer assembly 150 may be referred to as a zonal isolation subassembly that is associated with zone 62 , which is depicted as being gravel packed.
[0027] As best seen in FIG. 2G , lower completion assembly 100 includes a seal bore subassembly 154 operable to provide an internal sealing surface. As best seen in FIG. 2H , downhole of seal bore subassembly 154 , lower completion assembly 100 includes a sand control screen assembly 156 . In the illustrated embodiment, sand control screen assembly 156 includes two filter media 158 , 160 , a production sleeve 162 and a frac sleeve 164 . Production sleeve 162 and frac sleeve 164 may be operated mechanically, electrically, hydraulically or the like via local or remote operations to selectively allow or disallow fluid flow therethrough. Also, as illustrated, sand control screen assembly 156 has a plurality of sensors 166 that are operably associated with one or more of the energy conductors of umbilicals 106 . Downhole of sand control screen assembly 156 , lower completion assembly 100 includes a seal bore subassembly 168 operable to provide an internal sealing surface. Downhole of seal bore subassembly 168 , lower completion assembly 100 includes a packer assembly 170 having one or more elements 172 for establishing a sealing and gripping relationship with casing 40 . Together, packer assembly 150 , sand control screen assembly 156 and packer assembly 170 may be referred to as a zonal isolation subassembly that is associated with zone 64 , which is depicted as being gravel packed.
[0028] Upper completion assembly 200 will now be described from its uphole end to its downhole end. As best seen in FIG. 2A , upper completion assembly 200 includes a packer assembly 202 having one or more elements 204 for establishing a sealing and gripping relationship with casing 40 . Downhole of packer assembly 202 , upper completion assembly 200 includes an expansion joint 206 , depicted in its fully contracted configuration, that is operable to extend or contract the length of upper completion assembly 200 as described below. Downhole of expansion joint 206 , upper completion assembly 200 includes a packer assembly 208 having one or more elements 210 for establishing a sealing and gripping relationship with casing 40 . As best seen in FIG. 2B , upper completion assembly 200 includes a fluid flow control module 212 . In the illustrated embodiment, fluid flow control module 212 may be a SCRAMS module from Halliburton that provides for surface controlled reservoir analysis and management in a fully integrated control and data acquisition system. Fluid flow control module 212 includes a plurality of internal sensors 214 and a plurality of external sensors 216 to provide, for example, real-time pressure and temperature data. In addition, fluid flow control module 212 includes an infinitely variable interval control valve 218 which is preferably actuated by hydraulic power routed to an interval control valve piston via solenoid valves (not pictured). Power and communication are provided to fluid flow control module 212 by energy conductors extending from the surface and disposed within a flatpack control umbilical 220 containing, for example, one or more hydraulic conductor lines, one or more electrical conductor lines and one or more fiber optic conductor lines.
[0029] Upper completion assembly 200 includes an anchor assembly 222 that is operable to be received in and oriented by orientation and alignment subassembly 102 of lower completion assembly 100 . Anchor assembly 222 includes wet mate connectors 224 that are operable to connect the various energy conductors disposed within a plurality of flatpack control umbilicals 226 (two shown) with wet mate connectors 104 of lower completion assembly 100 . Umbilicals 226 are suitably attached to the exterior of upper completion assembly 200 . Upper completion assembly 200 has a tubing string 228 that extends into lower completion assembly 100 . Umbilical 220 also extends into lower completion assembly 100 and is suitably attached to the exterior of tubing string 228 . As best seen in FIG. 2D , tubing string 228 includes a seal assembly 230 having one or more elements 232 for establishing a sealing relationship with the internal sealing surface of seal bore subassembly 128 . As best seen in FIG. 2E , tubing string 228 also includes a seal assembly 234 having one or more elements 236 for establishing a sealing relationship with the internal sealing surface of seal bore subassembly 134 . Downhole thereof, tubing string 228 includes a fluid flow control module 238 such as the SCRAMS module from Halliburton as described above. Fluid flow control module 238 includes a plurality of internal sensors 240 and a plurality of external sensors 242 to provide, for example, real-time pressure and temperature data. In addition, fluid flow control module 238 includes an infinitely variable interval control valve 244 . Power and communication are provided to fluid flow control module 238 by energy conductors extending from the surface and disposed within flatpack control umbilical 220 .
[0030] As best seen in FIG. 2F , tubing string 228 includes a seal assembly 246 having one or more elements 248 for establishing a sealing relationship with the internal sealing surface of seal bore subassembly 148 . As best seen in FIG. 2G , tubing string 228 also includes a seal assembly 250 having one or more elements 252 for establishing a sealing relationship with the internal sealing surface of seal bore subassembly 154 . Further downhole, tubing string 228 includes a fluid flow control module 254 such as the SCRAMS module from Halliburton as described above. Fluid flow control module 254 includes a plurality of internal sensors 256 and a plurality of external sensors 258 to provide, for example, real-time pressure and temperature data. In addition, fluid flow control module 254 includes an infinitely variable interval control valve 260 . Power and communication are provided to fluid flow control module 254 by energy conductors extending from the surface and disposed within flatpack control umbilical 220 . As best seen in FIG. 2H , tubing string 228 includes a seal assembly 262 having one or more elements 264 for establishing a sealing relationship with the internal sealing surface of seal bore subassembly 168 .
[0031] As illustrated, packer assembly 208 between upper completion assembly 200 and casing 40 , packer assembly 112 between lower completion assembly 100 and casing 40 , and seal assembly 230 between tubing string 228 and lower completion assembly 100 provide an isolated fluid path between sand control screen assembly 116 and fluid flow control module 212 . Likewise, seal assembly 234 and seal assembly 246 between tubing string 228 and lower completion assembly 100 provide an isolated fluid path between sand control screen assembly 136 and fluid flow control module 238 . Also, seal assembly 250 and seal assembly 262 between tubing string 228 and lower completion assembly 100 provide an isolated fluid path between sand control screen assembly 156 and fluid flow control module 254 . In this configuration, production represented by arrows 300 from zone 60 is controlled by fluid flow control module 212 , production from zone 62 represented by arrows 302 is controlled by fluid flow control module 238 and production from zone 64 represented by arrows 304 is controlled by fluid flow control module 254 .
[0032] The operation of installing upper completion assembly 200 into lower completion assembly 100 will now be described. After lower completion assembly 100 has been deployed in the well, preferably in a single trip, each of the zones 60 , 62 , 64 may be sequentially gravel packed. After removal of the gravel pack service tools, lower completion assembly 100 is ready to receive upper completion assembly 200 , which is lowered downhole as a single unit on the end of a tubular string as depicted in FIG. 1 . Preferably, expansion joint 206 is locked in its fully extended configuration during this portion of the installation operation. The lower end of tubing string 228 now enters lower completion assembly 100 as upper completion assembly 200 is lowered into lower completion assembly 100 until anchor assembly 222 engages orientation and alignment subassembly 102 . At this point, seal assemblies 230 , 234 , 246 , 250 , 262 should be aligned with seal bore assemblies 128 , 134 , 148 , 154 , 168 , respectively. In this configuration, seal assembly 234 and seal assembly 246 provide an isolated fluid path between sand control screen assembly 136 and fluid flow control module 238 . Likewise, seal assembly 250 and seal assembly 262 provide an isolated fluid path between sand control screen assembly 156 and fluid flow control module 254 .
[0033] Anchor assembly 222 is now anchored or locked within orientation and alignment subassembly 102 and wet mate connectors 224 of upper completion assembly 200 are coupled to wet mate connectors 104 of lower completion assembly 100 to establish communication between respective energy conductors in umbilicals 226 of upper completion assembly 200 and umbilicals 106 of lower completion assembly 100 . Preferably, the connection of wet mate connectors 224 with wet mate connectors 104 proceeds at a controlled speed in accordance with the teachings of U.S. Pat. No. 8,122,967, the entire contents of which is hereby incorporated by reference. In some embodiments, the connection of wet mate connectors 224 with wet mate connectors 104 may be via inductive coupling. Once the wet mate connections are made and communication via the energy conductors therein is tested and confirmed, packer assembly 208 of upper completion assembly 200 is set to establish a sealing and gripping relationship with casing 40 . In this configuration, packer assembly 208 , packer assembly 112 and seal assembly 230 provide an isolated fluid path between sand control screen assembly 116 and fluid flow control module 212 .
[0034] Once packer assembly 208 is set, expansion joint 206 may be unlocked to allow for telescoping of expansion joint 206 . This feature enables improved space out operations and setting of the wellhead without placing stress on the completion assembly. Once the wellhead is landed, packer assembly 202 of upper completion assembly 200 is set to establish a sealing and gripping relationship with casing 40 . Setting this additional packer assembly 202 above expansion joint 206 provides a redundant seal. In the case of a non sealing expansion joint 206 , packer assembly 202 seals off the annulus to prevent tubing fluid from comingling with annulus production and to prevent fluid from migrating up the annulus. In the case of a sealing expansion joint 206 , packer assembly 202 isolates the tubing string from expansion and compression forces exerted by expansion joint 206 . In some embodiments, expansion joint 206 my be omitted in which case, a logging tool may be used to located the wellhead relative to the landing anchor.
[0035] Production operations using the completion assembly of the present invention will now be described. As described above, once upper completion assembly 200 is installed in lower completion assembly 100 , production from zone 60 is controlled by fluid flow control module 212 , production from zone 62 is controlled by fluid flow control module 238 and production from zone 64 is controlled by fluid flow control module 254 . Specifically, this is achieved by monitoring various fluid parameters, such as temperature and pressure at multiple locations associated with production from each zone. For example, sensors 126 are used to obtain fluid parameter data from exterior and the interior of sand control screen assembly 116 . Alternatively or additionally, distributed fluid parameter data may be obtained via one or more of the energy conductors, such as an optic fiber, located in the gravel pack to the exterior of sand control screen assembly 116 . In either case, the data is transmitted to a surface processor for reporting and analysis via energy conductor in umbilicals 106 of lower completion assembly 100 and umbilicals 226 of upper completion assembly 200 . At the same time, additional fluid parameter data may be obtained by sensors 216 in the annulus between upper completion assembly 100 and casing 40 and by sensors 214 to the interior of upper completion assembly 100 . This data is transmitted to a surface processor for reporting and analysis via energy conductors in umbilical 220 of upper completion assembly 200 . The fluid parameter data associated with production from zone 60 is used to control production from zone 60 by making desired adjustments to the position of infinitely variable interval control valve 218 . For example, monitoring pressures to the exterior of sand control screen assembly 116 via certain sensors 126 as well as to the interior of sand control screen assembly 116 via other sensors 126 or via sensors 214 , 216 , enables monitoring of the pressure drop through the gravel pack and enables redundant measures to identify and diagnosis equipment problems. Commands for controlling the position of variable interval control valve 218 and receiving feedback from variable interval control valve 218 are sent via energy conductors in umbilical 220 of upper completion assembly 200 . In this manner, fluid production from zone 60 is controlled.
[0036] Regarding zone 62 , sensors 146 are used to obtain fluid parameter data from exterior and the interior of sand control screen assembly 136 . Alternatively or additionally, distributed fluid parameter data may be obtained via one or more of the energy conductors, such as an optic fiber, located in the gravel pack to the exterior of sand control screen assembly 136 . In either case, the data is transmitted to a surface processor for reporting and analysis via energy conductor in umbilicals 106 of lower completion assembly 100 and umbilicals 226 of upper completion assembly 200 . At the same time, additional fluid parameter data may be obtained by sensors 242 in the annulus between upper completion assembly 100 and lower completion assembly 200 and by sensors 240 to the interior of upper completion assembly 100 . This data is transmitted to a surface processor for reporting and analysis via energy conductors in umbilical 220 of upper completion assembly 200 . The fluid parameter data associated with production from zone 62 is used to control production from zone 62 by making desired adjustments to the position of infinitely variable interval control valve 244 . Commands for controlling the position of variable interval control valve 244 and receiving feedback from variable interval control valve 244 are sent via energy conductors in umbilical 220 of upper completion assembly 200 . In this manner, fluid production from zone 62 is controlled.
[0037] Regarding zone 64 , sensors 166 are used to obtain fluid parameter data from exterior and the interior of sand control screen assembly 156 . Alternatively or additionally, distributed fluid parameter data may be obtained via one or more of the energy conductors, such as an optic fiber, located in the gravel pack to the exterior of sand control screen assembly 156 . In either case, the data is transmitted to a surface processor for reporting and analysis via energy conductor in umbilicals 106 of lower completion assembly 100 and umbilicals 226 of upper completion assembly 200 . At the same time, additional fluid parameter data may be obtained by sensors 258 in the annulus between upper completion assembly 100 and lower completion assembly 200 and by sensors 256 to the interior of upper completion assembly 100 . This data is transmitted to a surface processor for reporting and analysis via energy conductors in umbilical 220 of upper completion assembly 200 . The fluid parameter data associated with production from zone 64 is used to control production from zone 64 by making desired adjustments to the position of infinitely variable interval control valve 260 . Commands for controlling the position of variable interval control valve 260 and receiving feedback from variable interval control valve 260 are sent via energy conductors in umbilical 220 of upper completion assembly 200 . In this manner, fluid production from zone 64 is controlled.
[0038] While this invention has been described with reference to illustrative embodiments, this description is not intended to be construed in a limiting sense. Various modifications and combinations of the illustrative embodiments as well as other embodiments of the invention will be apparent to persons skilled in the art upon reference to the description. It is, therefore, intended that the appended claims encompass any such modifications or embodiments. | A completion assembly for operation in a subterranean well having multiple production zones. The completion assembly includes a lower completion assembly operably positionable in the well. The lower completion assembly includes first and second zonal isolation subassemblies. An upper completion assembly is operably positionable at least partially within the lower completion assembly to establish fluid communication between first and second fluid flow control modules, respectively, with the first and second zonal isolation subassemblies. A first communication medium having a connection between the upper and lower completion assemblies extends through the first and second zonal isolation subassemblies. A second communication medium is operably associated with the first and second fluid flow control modules. Data obtained by monitoring fluid from the production zones is carried by the first and second communication media and is used to control production through the first and second fluid flow control modules. | 4 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] Not Applicable
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not Applicable
REFERENCE TO A “SEQUENCE LISTING,” A TABLE, OR A COMPUTER PROGRAM
[0003] Not Applicable
BACKGROUND OF THE INVENTION
[0004] (1) Field of the Invention
[0005] The present invention relates to a method and apparatus for the controlled actuation of a microscope, in general, and to controlled actuation of a laser scanning microscope having multiple light sources, in particular.
[0006] (2) Description of Related Art
[0007] Confocal microscopy is, among other things, the tool for defined controlled actuation of micro-objects. Based on that, numerous methods for examination and influencing of microscopic objects were proposed, thus, for instance, by Denk in U.S. Pat. No. 5,034,613, by Liu in U.S. Pat. No. 6,159,749, or by Karl Otto Greulich in “Micromanipulation by Light in Biology and Medicine” in 1999.
[0008] A combination comprising an image-forming point scanning or line scanning system and a “manipulator” system is increasingly finding more and more interest in the professional circles.
[0009] The interest in the observation and analysis of fast microscopic processes has brought forth new devices and methods (for example Carl Zeiss Line Scanner LSM 5 LIVE), which, in combination with the above mentioned methods of manipulation, lead to new insights. Thereby, the simultaneous microscopic observation of radiation-induced manipulation of the samples with spatial resolution by means of a suitable imaging system stands especially in the foreground (See for example U.S. Pat. No. 6,094,300 and DE 102004034987 A1). Therefore the modern microscopes attempt to offer as many flexible and optically equivalent decoupling and coupling ports as far as possible (See: DE 102004016433 A1).
[0010] The availability at the same time of at least two coupling ports for independent scan systems is thereby of special importance in order to avoid limitations in the temporal resolution due to the slowness of mechanical switching processes. Besides the tube interface, other coupling ports on the sides of the microscope stand are possible (preferably in the extended infinite space between the microscope objective and the tube lens; the so-called “sideports”) as well as on the rear side of the stand (typically optically modified incident light axis or transmitted light axis with suitable tube lens; the “rearports”) as well as on the bottom side (the “baseport”).
[0011] Thereby, arrangements with a common direction of the incident light (either reflected or transmitted light) or with a direction opposite to incident light (transmitted light and reflected light) are possible in principle. Apart from the viewpoint of the applicability, a common direction of incidence is frequently preferred from the device-technical viewpoint.
[0012] In that case, use of at least one element is necessary, which combines the beam paths of both devices in the space between the scanners of the scan systems that are to be operated simultaneously and the objective. Thereby, according to the state-of-the-art, a diverse variety of beam-combining elements are conceivable, such as, for example, the optomechanical components, like suitably coated beam combiner flat plates and beam combiner wedges, beam combiner cubes and polarization splitters. Conceivable are further beam combining acousto-optical modulators and deflectors.
[0013] In the following, reference is made in particular to DE 102004034987 A1, which is incorporated by reference herein as if reproduced in full and which forms a part of the subject matter of the present publication.
[0014] FIG. 1 a shows schematically the design of a device system, which enables simultaneous operation of a manipulating and an imaging scan module in a microscope stand. The modules provided with a common actuation control system (control system, PC) and the laser or the laser modules are connected optically and controllably with both the scan modules.
[0015] In FIG. 1 b , an embodiment with an inverse stand is shown by way of example.
[0016] In a preferred embodiment, the electronic actuation of the microscope stand and the coupled manipulation and the imaging module are suitably equipped using a real-time electronic control system with an integrated real-time computer for the processing of the high data rates. Thereby, such embodiments are conceivable in which the scan systems of the manipulations and the imaging modules coupled with the microscope stand can be actuated in synchronous or asynchronous manner. Thus simultaneous scan modes of both the modules are possible in which manipulation and imaging in the different regions of the sample (ROIs; “regions of interest” DE19829981 C2) with variable scanning rates takes place as in FIG. 1 c.
[0017] Both for the manipulating system as well as for the imaging system, the useful spectral range can be extended, depending on the respective application, from the ultraviolet to the infrared spectral range. Manipulation wavelengths typically found in the applications are, for instance, 351, 355 and 364 nm (photo-uncaging), 405 nm (photoconversion, Kaede, Dronpa, PA-GFP), 488 and 532 nm (photobleaching, FRET, FRAP, FLIP) as well as 780-900 nm (multiphoton bleaching, for example MPFRAP, 2-photon uncaging; and direct multiphoton stimulation).
[0018] Since in many applications, both the manipulating as well as the imaging system employ the same laser wavelengths, it is reasonable to feed both the scan modules with a common laser source. In DE 102004034987 A1 different suitable arrangements for variably adjustable division of the beam between two independent scan modules are described:
a. Laser-specific, variable beam splitting with a rotatable λ/2-plate and polarization beam splitters (ref. FIG. 2 ):
By using a motorized rotatable λ/2-plate before each laser and a polarization beam splitter cube in the combined beam path of all lasers, a variable, loss-free beam splitting into two illumination canals takes place. Thereby, by rotating the λ 2-plate by an angle Θ, the polarization of the incident polarized laser is rotated by angle 2Θ. The horizontally and the vertically polarized components of the field amplitude are split by the subsequent polarization beam splitter cube (Glan-Taylor prism). Thereby the horizontally polarized light is transmitted and the vertically polarized light is reflected. By rotating the λ/2-plate from 0° to 45° the polarization of the incident beam is rotated from 0° to 90° and the beam intensity is thus divided continuously and variably between the split partial beams. The intensity of the split laser beams can be modulated in any of the illumination canals individually with the help of an appropriate light modulator (for example graduated, acousto-optical modulators like Pockels cells). When different laser sources are used in which their beams are combined as in FIG. 2 , this method of variable beam splitting is particularly practicable, if the individual beam combiners of the laser module are largely independent of the polarization. In addition to that, the fact that a finite switching time is necessary for the rotation of the λ/2-plate must be taken into account. Therefore a limitation from the viewpoint of the applications arises in the case of this method precisely then, when the manipulation and the fast imaging take place sequentially at time intervals of less than this switching period for the same wavelength and, in addition to that, the sum of laser power required for both partial processes exceeds the total available. The described method can be employed with advantage especially then, when the same laser line can be used simultaneously in the manipulating as well as in the imaging system. This is true particularly in photobleaching applications, such as, for instance, FRET, FRAP and FLIP.
b. This application-related limitation can however be eliminated, if, in lieu of the rotatable λ/2-plate, fast electrooptic or magnetooptic polarization rotators (for example Pockels cells, Faraday rotators or LC retarders) are used, which have switching periods in the microsecond range or shorter ( FIG. 2 ). c. A variable, wavelength-specific beam splitting into two illumination canals can be done also with two AOTFs (acousto-optical tunable filter) arranged successively one after the other as in FIG. 3 , whereby, for instance, the 1st order of diffraction of the first AOTF is used for the coupling in the imaging system, whereas the 0th order of diffraction is coupled in through a second AOTF in the manipulator module ( FIG. 3 ).
The imaging should thereby not be impaired by switching over of the bleaching ROI. This method has the disadvantage in applications that in case of simultaneous manipulation and imaging, the second manipulator AOTF must be adjusted simultaneously through software control with the switching of the first AOTF (for example switching off of the laser power of the imaging system at the reversal points of the raster scan).
d. A variant of c. without functional limitations can be realized when an AOTF is exclusively used for variable beam splitting between two illumination canals and the laser power can be adjusted separately in both canals through two other AOTFs ( FIG. 4 ). e. A simple economical method for beam splitting can be realized with the help of a neutral graduating wheel with different positions or a continuously coated neutral filter wheel or a neutral slider (graduated filter).
[0028] FIG. 5 shows an embodiment of a microscope system by way of example, which enables real-time microscopic imaging with a line scanner (right) that takes place simultaneously with the manipulation of the sample (point scanner left). In this way, both of the independent scan systems use the laser sources A-D jointly, whereby the power is divided in a variably tunable ratio between these two modules according to method a described above. The unification of the optical axes of the manipulating and the imaging system takes place in the region of the finite space between the microscope objective and the tube lens by means of a beam combiner. A systematic description of numerous other embodiments can be found in DE102004034987 A1.
BRIEF SUMMARY OF THE INVENTION
[0029] The present invention relates to a method and apparatus for actuation control of a microscope, in particular of a Laser Scanning Microscope, in which, at least one first illumination light, preferably moving at least in one direction, as well as at least one second illumination light moving at least in one direction, illuminate a sample through a beam combination. A detection of the light coming from the sample takes place. At least one part of the illumination light is generated through the splitting of the light from a common illuminating unit. A common control unit accomplishes a controlled splitting of the illumination light into the first and the second illumination lights. The intensity of the first illuminating light, as specified by a user or specified automatically, is assigned a higher priority (is prioritized) compared to the specified value for the second illumination light, and an adjustment for the second illumination light takes place until a maximum value is obtained, which is determined by the value specified for the first illumination light.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0030] FIG. 1 a is a schematic diagram of system which enables simultaneous operation of a manipulating and an imaging scan module in a microscope stand;
[0031] FIG. 1 b is a schematic drawing of an inverse microscope stand;
[0032] FIG. 1 c is a schematic diagram illustrating regions of interest and variable scanning rates;
[0033] FIG. 2 is a schematic diagram of two independent scan modules with variable beam splitting.
[0034] FIG. 3 is a schematic diagram showing beam splitting using two AOTFs;
[0035] FIG. 4 is a schematic diagram of variable beam splitting using multiple AOTFs;
[0036] FIG. 5 is a schematic diagram of a microscope system which enable real-time microscopic imaging with sample manipulation;
[0037] FIG. 6 graphically shows a selection of spectrally possible properties of beam combiners;
[0038] FIGS. 7 a - c are flow charts illustrating implementation of actuation control;
[0039] FIGS. 8 a - c are schematic diagrams showing the derivation of a beam combiner design embodying the present invention;
[0040] FIG. 9 graphically illustrates the relationship between the P SV, mani, sample and the beam combiner reflectivity RSV;
[0041] FIG. 10 is a screenshot of a user interface for a user for the bleaching as the manipulation; and
[0042] FIG. 11 is a screenshot for the imaging process with an imaging scan module.
DETAILED DESCRIPTION OF THE INVENTION
[0043] In describing preferred embodiments of the present invention illustrated in the drawings, specific terminology is employed for the sake of clarity. However, the invention is not intended to be limited to the specific terminology so selected, and it is to be understood that each specific element includes all technical equivalents that operate in a similar manner to accomplish a similar purpose.
[0044] If the manipulating as well as imaging systems compete for the power of the laser line in such a manner that it is as high as possible in the simultaneous operation in this type of microscope system, it is an advantage if the power requirement of the imaging system has a higher priority compared to the manipulator module. In commercial laser scanning microscope systems with only one scan module, typically the laser power for the manipulation process and the subsequent imaging can in each case be adjusted through the operating interface of the control software. This takes place, for example, using the corresponding software slider. In contrast to that, in the methods for simultaneous, variably tunable division of a laser line between two independent scan systems, shown in FIG. 2, 3 and 4 , besides the specification of the power for the manipulating and the imaging systems, adjustment of the splitting ratio between the two split up branches of the beams is also necessary.
[0045] According to the invention, the beam-splitting ratio as well as the subsequent intensity modulation are so optimally adjusted that, on one hand, the laser power requirement of the imaging system is fulfilled (higher priority) and, on the other hand, the manipulating system also receives laser power that is as high as possible at the same time. This makes it necessary to provide a method for optimal management of the laser power that is as automatic as possible, in which the user of the device only needs to define the laser powers necessary for imaging and manipulation in the customary manner (as in LSM systems with only one scan module) and, against that, the control software takes care on its own of the optimal tuning of the components shown in FIGS. 2, 3 and 4 .
[0046] Implementation of this principle of the actuation control, shown in the flow charts in FIGS. 7 a - 7 c for the layouts for the variable splitting of the beam shown in FIGS. 2, 3 and 4 , solves the problem of the management of the laser power that is as automated and optimal as possible in the simultaneous operation of two independent scan modules.
[0047] This principle is explained as follows on the basis of the variable splitting of the beam by means of a rotatable λ/2-plate and intensity modulation of the two split partial beams by means of an AOM (acousto-optic modulator).
[0048] The AOMs correspond, for instance, to the attenuators in the beam paths to the manipulator or the line scanner shown in FIG. 2 and 5 , whereby the rotatable λ/2-plates are arranged behind the lasers and exercise influence in both paths.
[0049] The principle of the controlling actuation shown generally in FIGS. 7 a .- c . can thereby be employed in analogous manner, if the other elements as in FIGS. 2, 3 and 4 and the above described methods a. to e. are used for beam splitting and intensity modulation.
[0050] As already explained above, in most of the applications, the power for the light required by the imaging system has the first priority. The imaging system (for example the line scanner in FIG. 5 ) is therefore denoted also as the “Master” system following the nomenclature selected in FIG. 7 .
[0051] The software slider in the operating software represents (analogous to the software interface of “stand alone” LSM systems) the total power for the light demanded by the respective scan module (image forming as well as manipulating systems). Screenshots of a user interface for the user are shown in FIG. 10 for the bleaching (as the manipulation) and in FIG. 11 for the imaging process (with the imaging scan module as described above). Thereby, the power for the individual wavelengths, expressed as percent units, is given in each case by the user in the lower part (excitation). It comprises, as in the generalized FIG. 7 a , the quantity of light made available by the variable beam splitting (see box) (λ/2-plate & polarization beam splitter cube) and the AOM (beam modulation box):
P ideal , Master = R λ / 2 · T AOM , Master P actual , Slave = T λ / 2 · T AOM , Slave 1 ≥ P actual , Master + P actual , Slave 1 ≅ R λ / 2 + T λ / 2
whereby R λ/2 and T AOM represent the part of the light reflected by the polarization beam splitter cube and the part of the light transmitted by the AOM. Thereby the designations “Master” and “Slave” stand for the “imaging” or the “manipulating” scan system. The “Master” part of the imaging system after the polarization beam splitter (R λ/2 ) is obtained here from the angular position Θ of the λ/2-plate
R λ/2 =cos 2 (2θ)
[0052] In the present invention, the strategy for the control is so arranged as in FIG. 7 b that the λ/2-plate, as the beam splitting element, moves as little as possible:
IF P ideal, Master > P actual, Master then IF R N2 > P ideal, Master then USE T AOM, Master ELSEIF USE R N2 ENDIF ELSEIF (P ideal, Master < P actual, Master USE T AOM, Master ENDIF
[0053] Pideal is the value specified by the user, on response yes to the comparison in the first box, it goes to the next query, on response no, the attenuator (AOM) of the master part must be adjusted.
[0054] In the next comparison, on no, the lambda half plate of the master system is adjusted, on yes, the attenuator (AOM) of the master system.
[0055] However, in the control, the power demanded by the manipulating system (“Slave”) comes to an expression as in FIG. 7 c . That means that in principle the unused part of the remaining power (1-P ideal, Master ) is available to the “slave” system for the manipulation of the sample.
IF P ideal, Slave, > P actual Slave then IF T N2 > P ideal, Slave then USE T AOM, Slave ELSEIF USE T N2 , BUT T N2, MAX ≦ (1 − P ideal, Master ) USE T AOM, Master ENDIF ELSEIF (P ideal, Slave < P actual, Slave USE T AOM, Slave ENDIF
EXAMPLES
[0056] To illustrate the actuation control processes shown in FIGS. 7 a - c with reference to five different user settings, shown in succession, as they may be found in the applications of the systems shown in FIGS. 1 and 5 .
[0057] The examples 1)-5) follow successively one after the other, whereby the reaction without the manipulating system is described first (ref. FIG. 7 b ). After that, the final result taking into account the additional power requirement of the manipulator system as in FIG. 7 c is explained.
[0058] 1) Imaging 100%, manipulation 0%, →R λ/2 =1, T AOM,Master =1, T λ/2 =0
the λ/2-plate is set to R λ/2 =1, that is, the master (imaging) receives the entire laser energy when the transmission of the corresponding attenuator is maximum (T AOM,Master =1), the attenuator is arranged in sequence after the λ/2-plate;
[0060] 2) Imaging 50%, manipulation 40%
The imaging demands 50% of the available energy, thus a maximum of 50% remains for the manipulation However the manipulation asks for only 40%, so that the manipulation can also actually receive its 40% For that the λ/2-plate must be regulated, because at that moment all the energy flows in the direction of the imaging system R □/2 =1, the λ/2-plate is thereby regulated as little as possible and hence moves according to T □/2 =0.4→R λ/2 =0.6 (the total is 1). But now the imaging system receives too much energy (60% because R □/2 /2=0.6 and T AOM,Master =1), that is, it must now be slightly attenuated: T AOM,Master =0. 8 3
[0065] Final result: T λ/2 /2=0.4→R λ/2 =0.6→T AOM,Master =0. 8 3, T AOM,Slave =1.0
[0066] 3) Imaging 50%, manipulation 70%
The manipulation demands 70%, but can have only 50%, because the power requirement of 50% for the imaging system has a higher priority, that is, increase by 10% from 40% to 50% is possible, for that the λ/2-plate must be moved slightly, from Rλ/2=0.6 to R λ/2 =0.5; after that the attenuators of both systems are each adjusted to give 100% transmission.
[0068] Final result: T λ/2 =0.5→R λ/2 =0.5→T AOM,Master =1.0, T AOM,Slave =1.0, P Slave =0.5 (insted of 0.7)
[0069] 4) Imaging 10%, manipulation 40%
The λ/2-plate can remain as it is, only the attenuators must be readjusted, this is done fast: T AOM,Master =0.2, T AOM,Slave =0.8
[0071] Final result: T λ/2 =0.5→R λ/2 =0.5→T AOM,Master =0.2, T AOM,Slave =0.8, P Slave =0.4
[0072] 5) Imaging 10%, manipulation 70%
The imaging (master) demands 10% of the laser power, that is, the manipulation can receive 70%; for that the λ/2-plate must be moved: T λ/2 =0.7→R □/2 =0.3 After that the attenuators are adjusted so as to yield the total values of 10% and 70% respectively
[0075] Final result: T λ/2 =0.7→R λ/2 =0.3→T AOM,Master =0. 3 3, T AOM,Slave =1.0
[0076] The generalized principle of the control shown in FIG. 7 a - c describes a method for optimal management of light power with simultaneous operation of two independent scanning systems, whereby
at least one source of light can be divided with a variably adjustable ratio of R ST /T ST between two scanning systems by means of a beam splitting element ST; the power requirement of one scanning system (“Master”) is assigned higher priority than that of the other scanning system (“Slave”); suitable intensity modulators are provided for, if necessary, reducing the intensity of the transmitted light distributed between the two partial branches T Master and T Slave ; the user of the devices defines only the power required by the two scanning systems through the interface of the operating SW, and the control SW determines on its own the optimal settings for the variable beam splitting and for the intensity modulators of the master and the slave scan modules.
[0081] FIG. 6 shows a selection of the spectrally possible properties of beam combiner types relevant from the viewpoint of applications, whereby the manipulation wavelengths 355 nm, 405 nm, 488 nm and 532 nm can be used both in the direction of transmission as well as of reflection. Typically, different types of beam combiners are provided with motorized loading devices for exchanging, such as, for example, a motorized reflector revolver, or a reflector slider, in the region of the infinite space between the objective and tube lens.
[0082] Neutral combiners (for example T20/R80) can be employed universally as beam combiners for most diverse varieties of applications and, in addition to that, enable applications in a simple manner, in which the same laser wavelengths can be used in simultaneous operation, both of the imaging system as well as of the manipulation system (in particular photobleaching, FRET, FRAP, FLIP). On the other hand, neutral combiners often represent a compromise, especially when the same laser line is used simultaneously for the manipulation as well as for the imaging, between the branching ratio for the respective laser wavelength, on one hand, and maximizing the signal efficiency in the range of the detection wavelength, on the other hand. Therefore, this demands an optimal design for the beam combiner, which is explicitly optimized for simultaneous operation of a manipulating and an imaging system for the same laser wavelength.
[0083] It is evident from FIG. 6 that simultaneous manipulation of the sample and imaging can be realized without problems with the help of a suitable dichroic beam combiner, if both scanning systems use different laser wavelengths. Thus, for example, the beam combiner denoted by “T405” has transmission T>0.9 only within a narrow bandpass range of, for instance, 405 nm±5 nm, whereas ideally it has mirroring effect with R ≈1 in all the other spectral ranges. This beam combiner is thus exclusively suitable for the manipulation of the sample with 405 nm (for example in photoconversion of Dronpa, Kaede, PA-GFP), whereby the manipulating system is arranged in the direction of transmission. Against that, the imaging system is arranged in the reflection direction, and allows, in the case of this special beam combiner type, fluorescence excitation and detection for any wavelength outside the bandpass range of 405 nm±5 nm. In the present invention, there is the requirement of bringing together a laser source that is split between a manipulating system and an imaging system to a beam combiner, whereby the beam combiner design optimally supports the management of the laser power implied in FIGS. 7 a - c . Since both scanning systems thereby simultaneously fall back on the same source of laser wavelength, a dichroic beam-combiner is not suitable for such an application.
[0084] FIGS. 8 a - c elucidate the derivation of a beam combiner design, which is designed especially for simultaneous operation of a manipulating system and an imaging system with the same laser wavelength distributed with a variable ratio. In this way, a comparison is done with the ideal mirror ( FIG. 8 a .), on one hand, and with a neutral combiner ( FIG. 8 b .), on the other hand. FIG. 8 a shows a microscope system, which is equipped only with an imaging system, which is arranged in the reflection direction (90° arrangement) with respect to the optical axis of the objective. The beams with the fluorescence excitation light of wavelength λ and the Stokes-shifted fluorescence light of wavelength λ FL generated in the sample are incident through an idealized mirror, with the reflectivity being R=1 in the entire spectral range under consideration. In order to generate a suitable fluorescence signal in this imaging system, the normalized relative laser power must be P 0,imag <1. The total available power of the source of light is 1. In the following considerations, the power P 0,imag is taken as the reference value in each case.
[0085] FIG. 8 b shows a microscope system, which enables simultaneous use of a manipulator arranged in the direction of transmission and an imaging system arranged in the direction of reflection. In use, the laser wavelength λ, split variably between the two scanning systems, is used both for the manipulation of the sample as well as for the fluorescence excitation, whereby the total laser power of the common source of light is again 1. In use, the superposition, accurate to the pixel, of the optical axes of the two scanning systems take place by means of a neutral beam splitter, which exhibits a constant reflectivity R NV <1 in the spectral range of interest. Thus, in the imaging, both the excitation light of wavelength λ as well as Stokes-shifted fluorescence signal of wavelength λ FL is reduced in each case by factor R NV . The power requirement of the imaging “Master” system (See FIG. 7 ) follows from the requirement that the same fluorescence signal intensity is detected after the neutral beam combiner as the combiner is arranged in the measurement setup shown in FIG. 8 a . The reduction in the intensity on the excitation and the emission side taking place in the neutral beam combiner can thereby each be compensated by a factor R NV , whereby, compared to the system in FIG. 8 a , laser power that is greater by a factor 1/(R NV ) 2 is incident on the neutral combiner. In order to detect the same fluorescence signal intensity as in the arrangement in FIG. 8 a , the power requirement of the imaging “Master” module is P NV,imag =P 0,imag /(R NV ) 2
[0086] The remaining laser power (1−P NV,imag ) of the common source of light of wavelength λ is thus available to the manipulating “Slave” system according to the actuation control schema in FIG. 7 , whereby, of this remaining manipulation laser power, again only the part (1−R NV ) is transmitted in the neutral combiner. The resulting laser power for the manipulation, which can be maximally available in the object plane, thus amounts to
P NV, mani, sample =(1 −P NV,imag )*(1 −R NV )
[0087] The optimal reflectivity R NV of the neutral beam combiner is obtained by maximizing the resulting manipulating laser power in the object plane P NV, mani, sample for the same fluorescence signal intensity as in the layout in FIG. 8 a . Thus one obtains the following analytical expression for the optimal reflectivity:
R NV = { P 0 , imag + P 0 , imag 2 + ( P 0 , imag 3 ) 3 3 + P 0 , imag - P 0 , imag 2 + ( P 0 , imag 3 ) 3 3 }
Example: P 0,imag =0.08 (8% excitation power for the embodiment 8 a .) R NV =0.4939 P NV, mani, sample =0.3401
[0089] FIG. 8 c now shows a beam combiner design optimized compared to such a neutral combiner. Let this beam combiner have reflectivity R SV <1 for the manipulation and fluorescence excitation wavelength λ, whereas let the reflectivity be RFL in the fluorescence wavelength range λ FL , which is as nearly equal to 1 as possible. In the calculation of the power requirement of the imaging “Master” system, again let the losses appearing on the excitation and the emission side be taken into account, which are compensated by the correspondingly increased laser power P SV,imag of the imaging module. Thereby the laser power incident on the beam combiner is reduced by factor R SV , whereas the reverse fluorescence signal is reduced by factor R FL . Therefore, in order to detect the same fluorescence signal intensity as in FIG. 8 a , the imaging system in FIG. 8c requires the laser power:
P SV,imag =P 0,imag /( R SV *R FL )
[0090] The remaining power (1−P SV,imag ) of the common light source of wavelength λ is thus available to the “slave” manipulation system according to the actuation control principle shown in FIG. 7 , whereby, of that, only the part (1−R SV ) crosses the beam combiner. The resulting laser power for the manipulation, which can be maximally available in the object plane, is thus expressed by:
P SV, mani, sample =(1 −P SV,imag )*(1 −R SV )
[0091] The reflectivity R SV of the beam combiner for the excitation and manipulation wavelength λ is now to be so optimized that for a given fluorescence reflectivity R FL (in the ideal case as nearly equal to 1 as possible) and the same fluorescence signal intensity as in the embodiment 8 a , a highest possible manipulation laser power P SV, mani, sample in the object plane is obtained. Analytically one obtains the optimum for:
[ R SV ] opt =( P 0,imag /R FL ) 1/2
[0092] In FIG. 9 , the relationship between the P SV, mani, sample and the beam combiner reflectivity RSV is shown.
Example: P 0,imag =0.08 (8% excitation power for the embodiment 8 a .), R FL =0.85 R SV =0.3068 and P SV, mani, sample =0.4805
[0094] For the same fluorescence signal intensity in the imaging system, one thus obtains, using this beam combiner, about 30% higher manipulation laser power in the sample—compared to the optimized neutral combiner of the embodiment 8 b.
[0095] If in contrast to the devices shown in FIGS. 8 a - c , the manipulator is instead arranged in the direction of reflection and the imaging scan system is arranged in the direction of transmission, the aforementioned argument follows in analogous manner, whereby in the above mentioned equations the designations for the transmission T and the reflection R must then be mutually exchanged.
[0096] To generalize, an optimized beam combiner design for the superposition of the optical axes of two independent scanning systems is required, in which both the modules are operated with at least one common laser wavelength λ. Thereby, at least one of the two scanning systems is designed as an imaging system and its power requirement is assigned higher priority compared to the other scanning system in such a manner that the detected fluorescence signal intensity is comparable with the corresponding “stand alone” system. For the wavelength(s) λ commonly used by both the systems, the branching ratio of this beam combiner is so selected that for a given fluorescence signal intensity, which would correspond to the typical intensity in a “stand alone” scanning system for free passage of the beam without a beam combiner, laser power that is as high as possible in the sample plane is obtained for one scanning system. Outside the common wavelength(s) λ used by the two scanning systems, the beam combiner is so designed that it is either only reflecting or transmitting as far as possible. The optimized spectral design of this beam combiner corresponds therefore to a “bad” bandpass filter in transmission or reflection.
[0097] In other words, as the control variables for the method according to the invention serve the grade of the reflectivity (Rsv, Rfl) or the transmission of the corresponding beam combiner for the excitation beam and fluorescence beam in the imaging system with respect to the proportion of the manipulation system or if specific power is given, the selection of a suitable beam combiner is optimized as the control variable.
[0098] In FIG. 6 , two examples for such types of beam combiners are shown schematically. The beam combiner “T488-30%” is thereby so embodied that the imaging system is arranged in the direction of reflection and the manipulating system in the direction of transmission. The wavelength 488 serves thereby both the purpose of the manipulation of the sample as well as of the excitation of fluorescence. The beam combiner layout is so designed that the transmission of 488 nm manipulation light is 70% and the reflection of 488 nm fluorescence signal light is 30%.
[0099] Outside the bandpass range of 488 nm, the beam combiner is as reflecting as possible as in FIG. 6 , so as to enable efficient signal detection in the direction of reflection. This beam combiner layout is therefore designed for such imaging applications, which require relatively low fluorescence excitation power (P 0,imag approximately 8%) and, at the same time, the manipulation power is as high as possible for the wavelength 488 nm. In practice such requirements are of relevance especially in FRAP applications. Thus, in a special embodiment, beam combiners optimized especially for FRAP applications are required. In contrast to that, the beam combiner type “R488-30%,” which is schematically depicted in FIG. 6 , is optimized for an arrangement in which the imaging system is in the transmission direction and the manipulation system in the reflection direction.
[0100] The described invention relates in a general sense to any type of imaging and manipulating system. Besides the (confocal and partially confocal) point and line scanners, it can also be of relevance in particular in multifocal laser scanning systems (for example, those based on lens arrays, diode laser arrays, with any type of beam splitting arrangement) and spinning disk systems/Nipkow systems. Further, in the present invention, the sample can be scanned with a scanning method according to current state-of-the-art. Thereby, one of the following can be the underlying scanning principle of the device for the deflection of the beam in the imaging or the manipulating system:
Galvo mirror or guidable, in particular rotatable and tiltable mirrors, for example step motor driven deflecting mirrors polygon mirrors acousto-optical deflecting devices, in particular acousto-optical deflectors (AODs) movable aperture masks, in particular in the form of a Nipkow disk movable (monomode) fibers movable objectives or objective parts mechanical x- and y-adjustment of a suitable component or of the entire scanning system, for example by means of acousto-optical modulators
[0109] However, since both the scanning systems must be independent of each other in the sense of this invention, a mechanical x- and y-adjustment of the sample is not admissible.
[0110] Besides the use of microscope systems with coherent light sources (lasers) and confocal or partially confocal scan modules, an advantageous application of the invention in analogous manner is conceivable also in the simultaneous manipulation of the sample and/or the imaging with the help of (structured) wide-field illumination systems with incoherent light sources.
[0111] Modifications and variations of the above-described embodiments of the present invention are possible, as appreciated by those skilled in the art in light of the above teachings. It is therefore to be understood that, within the scope of the appended claims and their equivalents, the invention may be practiced otherwise than as specifically described. | Method for actuation control of a microscope, in particular of a Laser Scanning Microscope, in which, at least one first illumination light, preferably moving at least in one direction, as well as at least one second illumination light moving at least in one direction, illuminate a sample through a beam combination, a detection of the light coming from the sample takes place, whereby, at least one part of the illumination light is generated through the splitting of the light from a common illuminating unit, characterized in that, by means of a common control unit, a controlled splitting into the first and the second illumination light takes place, in which the intensity of the first illuminating light, specified by the user or specified automatically, is assigned a higher priority (is prioritized) compared to the specified value for the second illumination light, and an adjustment for the second illumination light takes place until a maximum value is obtained, which is determined by the value specified for the first illumination light. | 6 |
[0001] The present patent document is a 35 U.S.C. § 371 application of PCT Application Serial Number PCT/EP2006/063902 filed Jul. 5, 2006, designating the United States, which is hereby incorporated by reference. This patent document also claims the benefit of German Patent Application No. DE 10 2005 033 957.3 filed Jul. 20, 2005, which is hereby incorporated by reference.
BACKGROUND
[0002] The present embodiments relate to wireless transmission for a medical device.
[0003] With a medical diagnostic or therapy system, one or a number of medical devices are usually provided to treat a patient. The medical devices are operated by a control unit. For example, the device may be an x-ray diagnosis device or other device for medical purposes. For the doctor or the operating personal, it is often necessary to be able to operate the device from different spatial positions. Some of the devices have a remote control unit. To prevent damage from occurring as a result of the connecting cable between the remote control unit and the device, the control signals may be transmitted wirelessly. The control signals may be transmitted using infrared signals or radio signals.
[0004] The wireless transmission of control signals is reliably guaranteed within a defined region, for example, within an examination room. With the use of infrared signals, the transmission of the control signals through objects disposed between the infrared transmitter and the infrared receiver is prevented. Even with radio signals, the transmit signals can be negatively affected through objects disposed between the transmitter and receivers, since the transmission power may only be set up for limited coverage. An unintended actuation of the remote control unit, when the remote control unit is located outside the examination room, for instance, should not result in the device being operated. This is ensured with the use of infrared transmitters. When radio signals are used, an attempt is made to achieve this by limiting the transmit power. Limiting the transmit power can result in functional impairments also occurring within the room.
[0005] Measures of this type are not sufficient to ensure a safe and reliable operation and to exclude malfunctions. Wired operation continues to be employed for safety-critical operating functions.
[0006] WO 00/17737 A1 discloses a mobile control device for undertaking locally different control functions in the household. The device uses all acceleration sensor, for example, as a relative local sensor, to determine a current actual position of the control device, and to provide context-sensitive control information as a function of the actual position as well as to transmit context-sensitive control commands in a wireless fashion.
[0007] EP 1 429 217 A2 discloses a processing, measuring or transportation station. The station can be controlled wirelessly by a mobile control panel. The station includes a local connection facility that only allows the station to be controlled by the control panel when in an activated state. The local connection facility is activated when the signal emitted by the control panel is received with minimal signal strength by a receiver of the station.
[0008] EP 0 801 342 A2 discloses a user interface with a mobile data processing system. A geographic position of the data processing system is determined by acceleration sensors. One of these corresponding user environments is selected with the aid of the position determined and activated on the data processing system. The user interface is intended in particular for use in the medical field.
SUMMARY AND DESCRIPTION
[0009] The present embodiments may obviate one or more drawbacks or limitations inherent in the related art. For example, in one embodiment, a medical device may include a safe and reliable wireless operation.
[0010] In one embodiment, an apparatus (system) includes a mobile remote control unit (remote control) for the wireless transmission of control signals to a receiver.
[0011] An acceleration sensor is integrated into the remote control. The measurement signals of the remote control represent a measure for a translocation of the mobile remote control unit. The apparatus includes a control unit, which is integrated into the remote control. The control unit is designed to receive and evaluate measurement signals of the acceleration sensor.
[0012] The control unit is designed to determine the connection quality between the remote control and the receiver. The control unit evaluates the signal strength and bit error frequency in order to determine the connection quality. The bit error frequency is the relationship between the faulty and the non-faulty digital data. The evaluation of the connection quality allows a redundant safety to be achieved and an extended distance measurement.
[0013] The control unit is designed to determine a decision criterion on the basis of the measurement signals of the acceleration sensor and the connection quality. The decision criterion indicating whether the safety and reliability of the signals transmission is ensured. The control unit may block the transmission of control signals if it detects that the decision criterion has been exceeded, and that the safety and reliability of the signal transmission is no longer ensured.
[0014] The acceleration sensor may include a conventional micromechanical acceleration sensor, as is used in many technical fields. By integrating the acceleration sensor into the remote controller, a safety measure for ensuring the control function is developed with a minimal technical outlay. The transmission power can be safely set sufficiently high, No complex systems for position determination are required for the remote controller, for example, an expensive triangulation measurement with a number of base stations.
[0015] The acceleration sensor is embodied as a three-dimensional acceleration sensor, which detects the acceleration in all three spatial directions. The acceleration sensor system is designed such that rotational movements about the three spatial axes are detected.
[0016] The control unit is determines the current actual position of the remote controller in respect or a reference position, for example, in respect of the receiver or of a defined spatial position, from the measurement signals. The control unit determines, on the basis of the measurement values transmitted by the acceleration sensor, the actual position of the remote control unit within the room. A difference distance value is determined from the starting position as a inertial navigation. The current actual position is monitored so as to determine whether it lies within a permitted movement space.
[0017] To improve the accuracy of the position determination, an electronic compass is integrated into the remote control. The movement direction can be accurately determined with the electronic compass.
[0018] The remote control may include a memory for storing the actual position. The memory may make a reliable statement relating to the respective actual position at any time. The memory may ensure that a correct spatial starting point is used to determine the current actual position even after a rest phase and in the event of the remote control being moved again.
[0019] The remote control may include a reset element. The reset element can reset the current coordinates of the actual position, for example, to the coordinates of the reference position. As a result a readjustment is carried out. The reset element is a manual key, for example, which is actuated if the remote control is located in the reference position. Alternatively, the reset element can be realized in a control-specific fashion, if the remote control is plugged into a charging or base station at the site of the reference position, for example.
[0020] The connection quality between the remote control and the receiver can be evaluated (determined). To determine the connection quality, the signal strength and the bit error frequency is evaluated. The bit error frequency is the relationship between the faulty and the non-faulty digital data. A redundant safety is achieved by evaluating the connection quality and an extended distance determination is enabled if necessary.
[0021] The data for connection quality is expediently correlated with the measurement signals of the acceleration sensor. The value of the signal strength, such as the change in the signal strength, for example, the gradient, is used as data for the connection quality. An evaluation is carried out at the same time to determine whether the remote control is moving and whether a change in the signal strength occurs. In the case of the correlated evaluation, it is not necessary to determine the actual position of the remote control, but the actual position can be determined. The decision criterion, which, if exceeded, results in the transmission of the control signals being blocked, is determined in a first variant by the determined actual position or the distance value calculated from there to the reference position in combination with the connection value. In a second variant the decision criterion is determined by the correlation between the translocation and the connection quality and/or the change thereof. With the evaluation of the correlation between the translocation and the connection quality, the transmission of control signals is only blocked, for example, when a reduction in the connection quality is detected in conjunction with an impermissibly large translocation.
[0022] The transmission of the control signals are blocked if the current actual position is detected and a predetermined inventive value is exceeded. In other words, when a predetermined distance from the remote control to the reference position is exceeded the transmission of the control signals is blocked. This prevents any unintended control outside the permitted movement space for the remote control.
[0023] The transmission of at least selected control signals may be blocked when a predetermined connection value for the connection quality is not reached. The blocked transmission may prevent the device from failing as a result of a faulty signal transmission when the connection quality is poor. Provided adequate signal strength for clear signal evaluation still exists, the blockage may only occur at the same time if the predetermined distance value is exceeded. This measure allows operation within the permitted movement space even when the connection quality is negatively affected. Unlike safety which exclusively takes the connection quality as its measure, with this embodiment variant, the functionality is not impaired by objects which are located between the transmitter and the receiver.
[0024] The remote control may include a release element for the manual release of the blockage. The doctor or operating person has the freedom also to operate the device outside the permitted movement space. A conscious release is needed, so that an unintended operation can be excluded. The release element is a release button arranged on the remote control, for example, which has to be actuated and kept pressed during the operation. Alternatively, a time function is activated after brief activation of the release button or a release foot switch. The time function allows operation for a predetermined time span of 10 seconds, for example.
[0025] The device emits at least one warning signal. A number of different warning signals may be emitted. The warning signals make the operating person or the doctor aware of interferences or specific impermissible or critical situations. A first acoustic warning signal may be provided. The warning signal is emitted if the transmission is blocked and the remote control is simultaneously actuated in order to trigger specific, critical control signals. These control signals are in particular safety-relevant control signals. The acoustic warning signal allows the operating person to be made aware of the blockage immediately. The acoustic warning signal is expediently emitted exclusively with such critical, safety-relevant control signals.
[0026] A second warning signal may be provided. The second warning signal is emitted when a critical distance between the remote control unit and the receiver is achieved. The second warning signal is an optical signal, a flashing light on the remote controller, for example, in order to make the user aware of the connection quality being poor or the permitted movement space resulting therefrom.
[0027] A third warning signal is provided. The third warning signal may be acoustic. The third warning signal is emitted when the connection between the remote control and the receiver is interrupted. This prevents an unintended removal of the remote control unit.
[0028] The warning signals may be embodied such that the control person is made aware of non-critical situations by way of optical warning signals, for example, flashing light-emitting diodes. Acoustic warning signals are only emitted if the control person selects a blocked control function or takes the remote controller with them by mistake. This results in the entire safety mechanism being highly user-friendly.
[0029] In one embodiment, the control unit comprises a teaching (collaboration) function in order to determine the permitted movement space. Using the teaching function, the boundary of the permitted movement space is paced out with the remote control unit in order to define the permitted movement space and/or some selected boundary positions of the movement space are accepted with the remote control. By pressing a “Teach-in” key, for example, the current actual position is stored as a limit value of the movement space.
[0030] Using the acceleration sensor, extreme acceleration values are detected and registered. The extreme accelerations can be attributed to an impact or fall for instance. This information can be helpful in the case of guarantee claims, in order to be able to point to an inappropriate operation. The permanently stored acceleration values, which exceed a predetermined limit value, can be read out and evaluated with the aid of a diagnosis device which can be connected if necessary to an interface.
[0031] A method for the wireless operation is provided. The preferred embodiments and functions cited in respect of the device are transferred to the method. A method for wirelessly transmitting control signals to a receiver using a mobile remote control unit may be provided. The method may include detecting a translocation of the remote control unit with respect to a reference position using an acceleration sensor; determining the connection quality between the remote control unit and the receiver; determining a decision criterion on the basis of the translocation and the connection quality; and blocking the wireless transmission of the control signals if the decision criterion is exceeded.
BRIEF DESCRIPTION OF THE DRAWINGS
[0032] An exemplary embodiment is described in more detail below with reference to the drawings, in which;
[0033] FIG. 1 shows one embodiment of a block diagram illustration of an apparatus for the wireless operation of a medical device; and
[0034] FIG. 2 shows one embodiment of a medical treatment room.
DETAILED DESCRIPTION
[0035] Identical parts are provided with the same reference characters in the figures.
[0036] In one embodiment, as shown in FIG. 1 , a remote controller 2 (indicated by dashed line) has a control panel 4 embodied as a keyboard, a keyboard controller 6 , a control unit 8 , a 3D acceleration sensor 10 , an electronic compass 12 , and a first radio module 14 A embodied as a transmitter. In addition to operating keys 16 , the control panel 4 has a reset element embodied as a reset button 18 and a release element 20 . In the exemplary embodiment, an acoustic warning element embodied as a loudspeaker 22 and an optical warning element 24 embodied as an LED are integrated in the control panel 4 .
[0037] The control unit 8 includes a microprocessor 26 and a memory 28 .
[0038] The remote controller 2 allows a medical device 30 (indicated by a dashed line) to be actuated in a wireless fashion with the aid of radio signals. A second radio module 14 B, which is embodied as a receiver, and a device controller 32 are integrated into the device 30 . A component 34 of the device 30 , for example, a radiation source of an x-ray device or a patient support (couch), is activated by the device controller 32 .
[0039] For the remote controlled wireless operation of the device 30 , a control signal S is transferred to the keyboard controller 6 by activating one of the control keys 16 . A check is carried out (performed) in the keyboard controller 6 to determine whether a release signal A 1 is present from the control unit 8 . If the release signal A 1 is present, the control signal S is forwarded to the first radio module 14 A, which emits the control signal S as a radio signal. The radio signal is detected by the radio module 14 B and transmitted to the device controller 32 , which thereupon triggers a control function. The control function corresponds to the device controller 32 , for example, a height adjustment of a patient support (couch) or an activation of a radiation source.
[0040] The two radio modules 14 A, B are transmit and receive units. For example, the radio module 14 A used as a transmitter for the control signals S simultaneously also receives signals from the second radio module 14 B. The received signals are transmitted as input signals E 1 to the control unit 8 to evaluate the connection quality. The control unit 8 also obtains measurement or input signals E 2 to E 5 from the acceleration sensor 10 , electrical compass 12 , the reset button 18 , and the release element 20 .
[0041] Output signals A 1 to A 3 are emitted from the control unit 8 to the keyboard controller 6 , the optical warning element 24 , and the loudspeaker 22 . The output signal Al may correspond to the release signal.
[0042] As can be seen from FIG. 2 , the device 30 is arranged within a treatment room 36 , which is accessible by a door 38 and has a window 40 . The remote control 2 is also arranged in the treatment room 36 . An obstruction 42 is arranged between the remote controller 2 and the device 30 . With this constellation, a remote control using an infrared signal, would already not be possible. A permitted movement space 44 is shown in FIG. 2 by a rectangle. Operation by the remote control 2 is allowed within this movement space 44 . The permitted movement space 44 is adjusted in the exemplary embodiment to the floor surface of the treatment room 36 and a sub region additionally extends across the front side of the treatment room 36 , so that the device 30 can also be controlled from outside the treatment room 36 using eye contact through the window 40 , for example.
[0043] To ensure a safe and reliable operation of the device 30 by the remote control 2 , two control mechanisms that complement one another are provided. The first control mechanism detects the actual movement of the remote control 2 within the three-dimensional space, for example, both within the plane and in terms of height. With the aid of the second control mechanism, the connection quality between the two radio modules 14 A, B is monitored. The second control mechanism may be used in addition to the first control mechanism. The two control mechanisms optionally or in combination with one another allow the following method and/or monitoring methods to be used. In one alternative embodiment, the current actual position is used with the aid of the first control mechanism. The value of the connection quality may be used. In another embodiment, the relative translocation is only determined instead of the actual determination of the actual position and the connection quality is set in correlation with the connection quality, such as in correlation with the change, for example, the gradient. Finally, a combination of these two alternatives is possible. All data available may be used to obtain the most accurate evaluation possible.
[0044] The first control mechanism may include the control unit 8 , the acceleration sensor 10 , the electrical compass 12 , and a memory 28 .
[0045] The acceleration sensor 10 detects acceleration and a translocation of the remote controller 2 . In one alternative embodiment, the current actual position is determined herefrom with respect to a reference position R. Conclusions can be drawn both in respect of the reset paths as well as the proposed direction with the aid of signals E 2 transmitted by the acceleration sensor 10 , so that when the starting position is known, a current actual position I of the remote controller 2 is determined in each instance. In order to increase directional accuracy, the input signal E 3 of the electrical compass 12 is used to determine the actual position I. The current coordinates of the actual position I are stored in the memory 28 in each instance. The zero point of the coordinate system may be determined by the reference position R.
[0046] Provided the actual coordinates of the remote control 2 move within the coordinates of the permitted movement space 44 , the control unit 8 transmits the release signal A 1 to the keyboard controller 6 . If the control panel 16 is activated, the control signal S is transmitted directly to the device 30 .
[0047] As soon as the remote control 2 leaves the permitted movement space 44 ; however, the keyboard controller 6 is blocked, for example, the release signal A 1 is no longer present. The output signal A 2 is simultaneously emitted to the optical warning element 24 , so that the control person is optically made aware (notified) of the remote control 2 leaving the permitted movement space 44 . If one of the control panels 16 is activated, the control signal S is not forwarded. Provided this is a non-critical control function, nothing more is done. If however, a specific, essential or safety-relevant function has been executed, an acoustic warning signal is emitted by the loudspeaker 22 , in order to notify the operating personal that the remote control 2 is blocked. By activating the release element 20 , the control person is able to eliminate the blockage for a short period and operate the device 30 .
[0048] The reset button 18 is provided to adjust the actual position I in relation to the reference position R. For adjustment purposes, the remote control 2 is brought to the reference position R and the reset button 18 is activated. This resets of the actual coordinate values are to zero.
[0049] In order to freely define the permitted movement space 44 , the control unit 8 includes a teaching (calibration) function, In order to freely define the movement space 44 , the remote control 2 is brought to the corner points of the movement space 44 , for example, and a teaching button is actuated so that the current actual coordinates of the movement space 44 are determined and stored in the memory 28 .
[0050] In parallel to monitoring the movement using the first control mechanism, the connection quality is monitored continuously. If the remote control 2 is located within the movement space 44 , the release signal A 1 is also present when an assumption actually has to be made from one position of the remote controller 2 outside the movement space 44 on the basis of a decreasing connection quality. These measures stop negative effects, such as the obstruction 42 , for example, from impairing the functionality.
[0051] As soon as a safety-relevant connection quality is exceeded; however, certain operating functions are blocked, for example, provided safety-relevant functions are actuated by the remote controller 2 , these are not transmitted to counteract the risk of a faulty function on grounds of an inadequate data transmission. At the same time, the acoustic signal is emitted, so that the operating person is informed and is able to eliminate the blockage by the release element 20 . The poor connection quality is previously indicated by the optical warning element 24 .
[0052] The field or signal strength received by the radio module 14 A and/or the bit error frequency are used in order to monitor the connection quality.
[0053] If no signal or no significant signal from the radio module 14 B is detected by radio module 14 A, this is assessed as a break in the radio connection and an acoustic signal is emitted again. The device 30 can no longer be operated, since the remote control 2 is located outside the transmission range.
[0054] In order to make the operating person aware of different statuses, a distinction is made in each instance between the acoustic and optical warning signals.
[0055] The device 30 can be remotely controlled using the described apparatus in a reliable, safe and user-friendly fashion. The apparatus described here can be used for devices outside the medical field, but within the medical field, patients can as a result be treated in a safer fashion without risking their health
[0056] To be able to identify an inappropriate operation, acceleration values which exceed a predetermined limit value and indicate an extreme acceleration may be stored permanently in the memory 28 . Extreme acceleration values of this type indicate an inappropriate operation, for example, dropping the unit or other extreme acceleration values caused by impacts. These extreme acceleration values stored in the memory 28 can be read out by an interface and evaluated by a diagnosis device, for example, within the scope of routine-specific maintenance works. | Various embodiments described herein can be used alone or in combination with one another. The forgoing detailed description has described only a few of the many possible implementations of the present invention. For this reason, this detailed description is intended by way of illustration, and not by way of limitation. It is only the following claims, including all equivalents that are intended to define the scope of this invention. | 6 |
CROSS-REFERENCE TO RELATED APPLICATION
The present application claims priority to Korean Patent Application No. 10-2011-0132266 filed in the Korean Intellectual Property Office on Dec. 9, 2011, the entire contents of which is incorporated herein for all purposes by this reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an actuator of a clutch, and more particularly to an actuator for operating a clutch in a transmission of an electric vehicle.
2. Description of Related Art
Generally, an actuator converts electrical energy, hydraulic energy or pneumatic energy to a mechanical energy. The actuator is used to operate a clutch of a transmission.
In a case of a manual transmission, a clutch control system of a clutch release cylinder type or concentric sleeve cylinder type is used.
In the clutch release cylinder type, if a driver pushes a clutch pedal, hydraulic pressure is generated in a clutch master cylinder and a tappet of a clutch release cylinder is operated by the generated hydraulic pressure.
At this time, the tappet pushes a clutch release fork so as to move a clutch release bearing in an axial direction. After that, the clutch release bearing moved in the axial direction operates a clutch diaphragm spring.
In a case of an automatic transmission, a clutch actuator is adapted to engage and release the clutch automatically. The clutch actuator of the automatic transmission receives a signal from an electric control unit (ECU) so as to operate the clutch. The clutch actuator has a master cylinder, a device for converting a motion direction and a motor.
The master cylinder is connected to a slave cylinder disposed around a release device of the clutch. The device for converting a motion direction includes a rod, a worm wheel and a worm gear. The rod contacts with a piston of the master cylinder. The worm wheel is fixed to an end portion of the rod. The worm gear is coupled to the worm wheel and is fixed to a rotating shaft of a motor. That is, if the motor rotates, the worm wheel is rotated by rotation of the worm gear. Thereby, the rod is moved linearly and the piston of the master cylinder is operated. Therefore, the hydraulic pressure is supplied from the master cylinder to the slave cylinder, and the slave cylinder is adapted to operate the release device so as to engage or release the clutch.
However, since the number of the components including conventional clutch actuators is many, a cost may be increased and a spatial utility may be deteriorated.
The information disclosed in this Background of the Invention section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
BRIEF SUMMARY
Various aspects of the present invention are directed to providing an actuator for a clutch having advantages of reducing cost and increasing fuel economy and spatial utility.
In an aspect of the present invention, an actuator apparatus for a clutch that operates the clutch of a transmission according to operation of a motor, may include the motor including a stator and a rotator, wherein the rotator may have a drive shaft and a rotator core receiving the drive shaft therein, a lead screw engaged to the drive shaft of the motor and movable in a length direction thereof according to the operation of the drive shaft in the motor, a rod disposed apart from the lead screw, a slider connecting the lead screw with the rod, and a guide rail disposed to contact with the slider and guiding a linear motion of the slider.
The drive shaft of the motor is formed with a cylindrical shape having an interior circumference and an exterior circumference.
A screw thread is formed at an exterior circumference of the lead screw and a screw thread is formed at a portion of the interior circumference of the drive shaft to be engaged with the lead screw and to move the lead screw linearly in the length direction by rotation of the drive shaft.
The lead screw and the rod are coaxially disposed.
The actuator apparatus may further may include an elastic member that is disposed inside the drive shaft of the motor and elastically biases the lead screw.
The actuator apparatus may further may include a cam that is coupled to the lead screw positioned outside the motor.
The guide rail is disposed in the length direction of the lead screw.
The slider may include a side surface to which the lead screw is rotatably coupled, the other side surface coupled to the rod, and an upper surface and a lower surface connecting the side surface and the other side surface.
The guide rail is disposed to slidably contact with at least one of the upper surface and the lower surface of the slider.
The actuator apparatus may further may include a gap forming portion that is connected with the slider and the rod respectively and connects the slider and the rod with a space formed therebetween such that the rod moves upwardly or downwardly.
The methods and apparatuses of the present invention have other features and advantages which will be apparent from or are set forth in more detail in the accompanying drawings, which are incorporated herein, and the following Detailed Description, which together serve to explain certain principles of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of an actuator for a clutch according to an exemplary embodiment of the present invention.
FIG. 2 is a cross-sectional view of a motor according to an exemplary embodiment of the present invention.
FIG. 3 is a schematic diagram showing operation of an actuator for a clutch according to an exemplary embodiment of the present invention.
It should be understood that the appended drawings are not necessarily to scale, presenting a somewhat simplified representation of various features illustrative of the basic principles of the invention. The specific design features of the present invention as disclosed herein, including, for example, specific dimensions, orientations, locations, and shapes will be determined in part by the particular intended application and use environment.
In the figures, reference numbers refer to the same or equivalent parts of the present invention throughout the several figures of the drawing.
DETAILED DESCRIPTION
Reference will now be made in detail to various embodiments of the present invention(s), examples of which are illustrated in the accompanying drawings and described below. While the invention(s) will be described in conjunction with exemplary embodiments, it will be understood that the present description is not intended to limit the invention(s) to those exemplary embodiments. On the contrary, the invention(s) is/are intended to cover not only the exemplary embodiments, but also various alternatives, modifications, equivalents and other embodiments, which may be included within the spirit and scope of the invention as defined by the appended claims.
An exemplary embodiment of the present invention will hereinafter be described in detail with reference to the accompanying drawings.
FIG. 1 is a schematic diagram of an actuator for a clutch according to an exemplary embodiment of the present invention.
As shown in FIG. 1 , an actuator 10 for a clutch includes a motor 20 , a case 60 , a lead screw 30 , a rod 50 , a slider 40 and a guide rail 42 .
The motor 20 is adapted to generate power for operating the actuator 10 . That is, the actuator 10 is operated according to operation of the motor 20 .
Components such as the lead screw 30 , the slider 40 , the guide rail 42 and so on can be disposed in the case 60 . The case 60 is coupled and fixed to the motor 20 .
The lead screw 30 moves linearly in a length direction thereof according to the operation of the motor 20 . In addition, some portion of the lead screw 30 is coupled to the drive shaft of the motor 20 .
The rod 50 moves in the length direction together with the lead screw 30 . The rod 50 and the lead screw 30 are disposed on the same axis. Some portion of the rod 50 is disposed in the case 60 , and the other portion of the rod 50 is disposed at an outside of the case 60 .
And, a boot 70 is disposed on the rod 50 for protecting the rod 50 disposed at the outside of the case 60 . A first support portion 56 and a second support portion 62 are disposed apart from each other on the rod 50 in the length direction, and support both end portions of the boot 70 .
The slider 40 is adapted to guide the lead screw 30 and the rod 50 such that the lead screw 30 and the rod 50 easily move in the length direction. That is, the slider 40 is disposed between the lead screw 30 and the rod 50 and connects the lead screw 30 with the rod 50 . Therefore, the lead screw 30 , the slider 40 and the rod 50 integrally move according to the length direction of the lead screw 30 .
The slider 40 has a side surface coupled to the lead screw 30 , the other side surface coupled to the rod 50 , and an upper surface and a lower surface connecting the side surface and the other side surface.
The guide rail 42 is adapted to guide the slider 40 such that the slider 40 easily moves. The guide rail 42 can be fixedly provided at the upper surface and/or the lower surface of the slider 40 in the case 60 . That is, the guide rail 42 is adapted to contact with at least one of the upper surface and the lower surface of the slider 40 . The guide rail 42 is disposed in the length direction of the lead screw, and accordingly, the slider 40 moves in a moving direction of the lead screw according to the guide rail 42 .
A catching portion 32 is disposed on the lead screw 30 so as to prevent the slider 40 from being separated from the lead screw 30 . The catching portion 32 is coupled to the end portion of the lead screw 30 connected to the slider 40 .
FIG. 2 is a cross-sectional view of a motor according to an exemplary embodiment of the present invention.
As shown in FIG. 2 , the motor 20 generates a rotating force by a stator 21 formed with a ring shape and a rotator 25 including a drive shaft 22 disposed in the stator and a rotator core 23 disposed at an exterior circumference of the drive shaft 22 . The drive shaft 22 of the motor 20 is formed with a cylindrical shape having an interior circumference and an exterior circumference. In addition, a lead screw receiving hole 24 is a hole portion of the drive shaft 22 of the motor in which some portion of the lead screw 30 inserted.
A screw thread is formed at some portion of an interior circumference of the drive shaft 22 . In addition, a screw thread is formed at an exterior circumference of the lead screw 30 . Therefore, if the motor 20 is driven, the lead screw 30 moves in the length direction along the screw thread of the drive shaft according to the rotation of the drive shaft 22 . In addition, since the drive shaft 22 can rotate in both directions, the lead screw 30 can reciprocate linearly in the length direction.
An elastic member 26 is disposed in the lead screw receiving hole 24 . The elastic member 26 is connected to an end portion of the lead screw 30 . Therefore, the elastic member 26 can reduce a driving torque of the motor 20 and efficiently move the lead screw 30 linearly by using elastic force thereof.
A cam 34 is disposed at the other portion of the lead screw 30 that is not inserted in the motor 20 . And, since the cam 34 increases rotational inertia of the lead screw, the cam 34 can reduce the drive torque of the motor 20 .
FIG. 3 is a schematic diagram showing operation of an actuator for a clutch according to an exemplary embodiment of the present invention.
As shown in FIG. 3 , the rod 50 includes a connecting portion 54 and a gap forming portion 52 .
The connecting portion 54 is disposed at an end portion of the rod 50 . That is, the connecting portion 54 is formed at a portion of the rod which is not covered by the boot 70 and is disposed at the outside of the case 60 . And, the connecting portion 54 can contact with a connecting lever 82 coupled to a clutch 80 . That is, if the rod 50 moves linearly, the connecting portion 54 contacts with the connecting lever 82 and then moves the connecting lever. Accordingly, the clutch 80 is operated by the lever motion of the connecting lever 82 . Also, since the rod 50 can reciprocate linearly, the clutch 80 can be engaged or released.
The gap forming portion 52 is disposed at a portion where the rod 50 and the slider 40 are connected.
The gap forming portion 52 is respectively connected with the slider 40 and the rod 50 and connects the slider 40 and the rod 50 with a space formed therebetween such that the rod 50 moves upwardly or downwardly. The rod 50 pitches in a vertical direction to the length direction because of the lever motion of the connecting lever 82 rotating about a one point. Accordingly, the gap forming portion 52 compensates a pitch of the rod 50 .
According to an exemplary embodiment of the present invention, since the number of the components decreases, a cost may be reduced. Also, since the lead screw is used, a spatial utility may be improved. In addition, the clutch 80 needs not an additional energy for coupling. Therefore, fuel economy may be improved.
For convenience in explanation and accurate definition in the appended claims, the terms “upper”, “lower”, “inner”, “outer”, “forwards” and “backwards” are used to describe features of the exemplary embodiments with reference to the positions of such features as displayed in the figures.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the invention to the precise forms disclosed, and obviously many modifications and variations are possible in light of the above teachings. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and their practical application, to thereby enable others skilled in the art to make and utilize various exemplary embodiments of the present invention, as well as various alternatives and modifications thereof. It is intended that the scope of the invention be defined by the Claims appended hereto and their equivalents. | An actuator apparatus for a clutch that operates the clutch of a transmission according to operation of a motor, may include the motor including a stator and a rotator, wherein the rotator has a drive shaft and a rotator core receiving the drive shaft therein, a lead screw engaged to the drive shaft of the motor and movable in a length direction thereof according to the operation of the drive shaft in the motor, a rod disposed apart from the lead screw, a slider connecting the lead screw with the rod, and a guide rail disposed to contact with the slider and guiding a linear motion of the slider. | 5 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The invention, in general, relates to a plastic washing fluid container, hereafter sometimes referred to as a tub, for a washing machine and, more particularly, to a tub surrounding a cylindrical drum each end of which is provided with a closure cap at least one of which has an air trap for measuring the washing fluid level and which at its lower and upper ends is respectively provided with an opening and a nipple for receiving a hose.
[0003] 2. The Prior Art
[0004] Such well-know air traps are used for measuring the level of washing fluid which at different operational cycles of the washing machine is either plain water or water with a detergent dissolved therein, in a washing machine drum. As washing fluid rises within the air trap it causes the air entrapped therein to be compressed. The pressure of the compressed air is a measure of the level of washing fluid. Thus, German patent specification No.: DE 196 46 440 C2 to Thier et al. discloses an air trap at one of the caps of the washing fluid tub. The air trap disclosed by the German patent specification is a component mounted on the cap at a certain area thereof and requires an appropriate additional gasket or seal.
[0005] U.S. Pat. No. 5,115,651 to Nukaga et al. discloses an air trap formed on the cap of the washing fluid tub. In this case the housing is arranged at the exterior of the washing fluid tub and, therefore, necessitates additional means for connection with the internal chamber of the washing fluid tub.
[0006] European patent specification No.: 0,247,651 A1 to Grabarcsyk discloses an air trap mounted on the cylindrical container surrounding the drum, and U.S. Pat. No. 4,423,607 to Munimi discloses an air trap mounted on the washing fluid tub.
[0007] The disadvantage inherent in the devices of the mentioned prior art is not only that on the one hand the air traps are mounted as a separate components on the cap of the washing fluid container involving, on the other hand and particularly in the case of the air trap being mounted on the cylindrical drum, significant complexity if layout, design or geometry of detecting the air within the trap requires modification. In such cases it would be necessary to provide a complex injection molding tool to form the hollow body of the air trap.
OBJECT OF THE INVENTION
[0008] It is thus an object of the invention so to improve a plastic washing fluid container and, more particularly, the cap of such a container that the air trap may be structured at the cap of the washing fluid container such that it may be integrally formed by an injection molding tool.
[0009] In the accomplishment of these and other objects the invention provides for an air trap in a plastic washing fluid container of the kind referred to supra in which the air trap with its downwardly open housing and integral opening nipple is integrally formed in the wall of the washing fluid container cap in penetrating relationship therewith.
[0010] The advantages resulting from the arrangement in accordance with the invention are not least that the downwardly open housing with its attached opening nipple is an integral component of the cap of the washing fluid tub in penetrating relationship therewith such that the latter and the air trap are of unitary structure. This arrangement allows the air trap housing to be integrated into an injection molding tool so that both the air trap and the washing fluid container cap may be molded in a single operation. The result is an air trap which is fully integrated in the cap of the washing fluid container and which avoids the need for additional caps and seals or gaskets in the cap of the washing fluid container. In this manner the complexity of any alteration of the air trap in terms of tools otherwise required is minimized or at least reduced, because forming the hollow body of the air trap requires but one core in the injection molding tool for the cap of the washing fluid container. Moreover, the volume and the cross-section of the opening may be adjusted to existing air traps and significant changes or conversion procedures can be avoided.
[0011] In order to structure the injection molding tool in an advantageous manner as regards the directions of discharge from the mold, the housing with its opening nipple occupies a partial section of the outer wall surface of the washing fluid container cap with the opening nipple being formed to extend upwardly at an acute angle relative to the outer wall surface of the washing fluid container cap. Accordingly, the opening nipple is not only of a compact structure but it also is easily accessible for attaching a hose. As regards the inner wall surface, the housing is structured such that the housing of the air trap and its downwardly open section occupy a partial section of the inner wall surface of the washing fluid container cap, with the section of the opening being preferably also formed at a downwardly directed acute angle at the surface of the inner wall. In this manner it is possible to provide two mold discharge directions, one being disposed laterally and the other one in the direction of the angle of the air trap.
[0012] In an advantageous embodiment of the invention the partial section of the surface of the inner wall forming the housing of the air trap is offset in a step-like manner in order to enlarge the cross-section of the opening. Preferably, the step is inclined which advantageously affects the mold discharge process. The walls forming the housing are disposed parallel to each other which also affects the mold discharge process in an advantageous manner.
[0013] In accordance with another embodiment, more particularly in an upper section of the housing, the opening nipple for the hose is formed to extend into the interior of the housing. As a result of this structure, it is possible to operate with only one core in the mold for integrating the housing of the air trap. For securely attaching the hose to the downwardly extending opening nipple, the sleeve section of the nipple is provided with a collar or shoulder for arresting the hose.
[0014] In a useful embodiment the housing of the air trap is formed of a lower housing section and an upper housing section with the downwardly open lower housing section being integrally formed in, and penetrating through, the wall of the washing fluid container cap. The internal chamber of the air trap is thus accessible from the exterior because the upper housing section is mounted for movement relative to the lower housing section at the outer surface of the washing fluid container cap. Accordingly, the interior of the housing of the air trap is easily accessible for cleaning.
[0015] Advantageously, the upper housing section is integrally connected to the lower housing section by means of a hinge of flexible film or foil which makes possible the fabrication of both housing sections in one injection molding tool. In such an arrangement the upper housing section is pivotally connected to the lower housing section by the foil hinge so that the cap of the washing fluid container and the two housing sections may be molded in one piece. This yields two advantages: The air trap is integrally formed in the cap of the washing fluid container and as a result of the foil-hinge connection the interior of the air trap is rendered accessible.
[0016] In order to achieve an efficient integration of the air trap in the cap of the washing fluid container, the lower housing section occupies a partial section of the surface of the outer wall of the cap of the washing fluid container with the partial section being advantageously formed to extend upwardly from the outer surface at an acute angle in the manner of a wedge resulting, relative to the outer surface, in an opening of rectangular or square cross-section. However, to improve the sealing properties between the upper housing section and the lower housing section it may be useful so to shape the partial section formed in the wall to yield an opening of oval, elliptical or circular cross-section.
[0017] The downwardly open section of the lower housing section is offset in a step-like manner for enlarging the opening area, i.e. the water-inlet area. The step is inclined which facilitates its configuration. The lateral walls forming the housing are disposed parallel to each other which results in a rectangular channel-shaped housing, i.e. the internal chamber has a rectangular profile. In order to seal the upper section with respect to the lower section, the upper section is provided with a circumscribing groove for receiving a gasket. For opening or closing the upper housing section its outer wall is provided with lugs for securing it in a snap-like manner. Outwardly extending ribs are formed in the lateral walls of the lower housing section which occupies a partial section of the surface of the inner wall of the washing fluid container cap. Within the ribs there are provided bores or openings for receiving the lugs.
[0018] To provide for an easy or snap closure, the edges of the ribs are beveled or slanted which results in an incline. Thus, if the upper housing section is pivoted, the lugs thereof will initially engage the inclines, and the inclines will cause the ribs to be spread apart so that the lugs can more easily move relative to the bores.
DESCRIPTION OF THE SEVERAL DRAWINGS
[0019] The novel features which are considered to be characteristic of the invention are set forth with particularity in the appended claims. The invention itself, however, in respect of its structure, construction and lay-out as well as its manufacturing techniques, together with other advantages and objects thereof, will be best understood from the following description of preferred embodiments when read in connection with the appended drawings, in which:
[0020] FIG. 1 : is a sectional presentation of a first embodiment of an air trap inserted in a cap of a washing fluid container;
[0021] FIG. 2 : is a sectional presentation of a second embodiment of an air trap inserted in a cap of a washing fluid container;
[0022] FIG. 3 : is a detailed view of an opening nipple of the embodiment shown in FIG. 2 ;
[0023] FIG. 4 , 5 : depict an embodiment of an inserted air trap with a removable upper section; and
[0024] FIG. 6 : is a schematic presentation of a washing machine.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0025] FIG. 6 is a schematic lateral sectional view showing a washing machine 30 provided with a washing fluid container 1 . The washing fluid container 1 consist of a cylindrically structured receptacle 2 which surrounds a drum 31 . The cylindrical receptacle 2 is closed by at least one front wall or cap 3 .
[0026] FIGS. 1 and 2 depict a section of a washing fluid container 1 made of plastic. At each end of the receptacle 2 there is provided a structured washing fluid container cap 3 . As may be seen in FIGS. 1 and 2 , one of the washing fluid container caps 3 , which may have been retrofitted to the receptacle 2 , is provided with an air trap 4 for measuring the level of washing fluid. The air trap 4 has a housing 5 which opens in a downward direction and which at its upper end is provided with an opening nipple 6 for a measuring hose (not shown). As will be understood by those skilled in the art and as indicated supra, the hose is connected to a gage (not shown) or the like for deriving a measure of the level of washing fluid in the container as a function of the pneumatic pressure within the air trap 4 .
[0027] Looking at both FIGS. 1 and 2 , it will become apparent that the downwardly open housing 5 and its integral opening nipple 6 are fitted into the washing fluid container cap 3 , i.e. the cap 3 and the air trap 4 are fabricated as a one-piece molded component. In the embodiment shown, it is of particular advantage that the fully integrated air trap 4 can be fabricated by a single mold tool with only one additional core being required for molding the section of the hollow body of the housing 5 . The corresponding mold discharge directions have been indicated by arrows 13 , 14 and 15 .
[0028] In the embodiment of FIG. 1 , two cores are required for molding the housing 5 , the first core being indicated by mold discharge direction 13 and the second core being indicated by mold discharge direction 15 . The mold discharge direction 14 of the molding tool is away from the cap 3 . The embodiment according to FIG. 2 requires but one core for molding the air trap housing 5 . It is moved out of the lower section of the bore 8 in the direction of arrow 13 .
[0029] By looking at both FIGS. 1 and 2 it will become apparent that the housing 5 with its opening nipple 6 constitutes a part of the surface 7 of the outer wall of the washing fluid container cap 3 , the opening nipple 6 being preferably molded to extend in an upward direction and at an acute angle relative to the surface 7 of the outer wall. This area is formed by the single core, the arrow 15 representing it having been indicated to point in an upward direction. The other core serves to form the housing 5 with its downwardly opening section 8 which constitutes part of the inner wall surface 9 of the washing fluid container cap 3 . Preferably, the area 8 surrounding the lower opening of the air trap 4 extends downwardly at an acute angle relative to the inner wall 9 .
[0030] As will be understood, the housing 5 of the air trap is formed or molded in the area of the wall of the washing fluid container cap 3 when the cores (not shown) are in their inserted state. FIGS. 1 and 2 also show the partial section of the inner wall surface 9 within which the housing 5 is formed to be offset in a step-like manner so as to enlarge the section 8 of the opening. Step 10 is inclined to provide for a clean discharge from the mold. The walls 7 and 9 which form the housing 5 are disposed parallel to each other.
[0031] In accordance with the embodiment of FIG. 2 showing the opening nipple 6 for the hose to extend into the housing 5 , the opening nipple 6 may be molded by means of a single core within the molding tool. During manufacture the core is withdrawn in the discharge direction 13 from the inner chamber of the housing 5 .
[0032] FIG. 3 is a detailed view of the opening nipple 6 showing a sealing shoulder 12 formed in the sleeve section 11 of the inwardly directed opening nipple 6 . The shoulder 12 effectively secures or seals any hose (not shown) inserted into the nipple 6 .
[0033] The principles of manufacturing an air trap 4 in accordance with FIGS. 1 and 2 are such as not to require any additional components. Also, when modifying the pressure indicating air trap, there is no need for changing the molding tool for the washing fluid container. A changed tool for molding the cap and, possibly, a differently shaped core for forming the housing 5 are all that may be required.
[0034] FIGS. 4 and 5 depict separate presentations of an air trap 4 . The air trap is 4 arranged on a plastic washing fluid container, not shown in detail, of a washing machine. The container includes a cylindrical receptacle surrounding a drum. The air trap 4 is provided at the front surface of one of the caps 3 of the washing fluid container. FIG. 4 only depicts a partial section of the wall 103 of the washing fluid container cap 3 . The air trap 4 is used to measure the level of washing fluid within the washing machine 30 .
[0035] The housing of the air trap 4 consists of a lower housing section 104 which is open in a downward direction and an upper housing section 107 with an attached opening nipple 105 for a hose (not shown). The lower housing section 104 is integrally formed in, and penetrates through, the cap 3 of the washing fluid container.
[0036] As may be seen in FIG. 4 , the upper housing section 107 with its opening nipple 105 is pivotally connected to the lower housing section 104 by means of a foil hinge 108 . In this manner the washing fluid container cap 3 and the two housing sections 14 and 107 can be fabricated as a unitary component.
[0037] It will be understood, that in correspondence with the two mold discharge directions shown, that integration of the air trap 4 into the wall 103 of the washing fluid container cap 3 may be carried out by two cores. For discharging, at least one core is moved in an upward direction as shown by arrow 121 , and a further core may be moved downwardly as shown by arrow 120 . The mold is discharged in a substantially horizontal direction away from the outer surface of the wall 103 , as indicated by arrow 119 .
[0038] As shown in FIG. 4 , the lower housing section 104 occupies a partial section of the surface 109 of the outer wall of the washing fluid container cap 3 and protrudes in the manner of a wedge from the wall 103 in an upward direction at a preferably acute angle with respect to the surface 109 of th outer wall, resulting in an opening 110 of rectangular or square cross-section with respect to the outer surface.
[0039] Moreover, FIG. 4 shows that the downwardly directed section 111 of the lower housing section 104 occupies a partial section of the surface 112 of the inner wall of the washing fluid container cap 3 . The opening section 111 is preferably formed to extend downwardly at an acute angle relative to the surface 112 of the inner wall. The downwardly open section 111 of the lower housing section 106 is offset in a step-like manner in order to enlarge the section 110 of the opening. The step 113 extends at an incline.
[0040] As may be seen in FIGS. 4 and 5 , the lateral walls 106 . 1 and 106 . 2 forming the lower housing section 104 are disposed parallel of each other resulting in a rectangular profile over the extent of the housing interior. As shown in FIG. 4 in the opened state of the upper housing section 107 , the upper housing section 107 is provided with a circumferential groove 114 for receiving a gasket (not shown). It can also be seen that lugs 115 . 1 and 115 . 2 are provided at the outer wall of the upper housing section 107 to provide a snap-like or latched closure. To carry out the latched closure, the lateral side walls 106 . 1 and 106 . 2 of the lower housing section 104 are provided with ribs 116 . 1 and 116 . 2 extending beyond the opening range 110 . Within the ribs 116 . 1 and 116 . 2 there are provided bores 117 . 1 and 117 . 2 into which the lugs 115 . 1 and 115 . 2 penetrate in the closed state of the housing. The ribs 116 . 1 and 116 . 2 constitute a partial extension of the lateral walls 106 . 1 and 106 . 2 . Furthermore, FIG. 4 shows the outwardly directed edges of the ribs 116 . 1 and 116 . 2 to be inclined. Over their extent the two inclines are beveled inwardly. The beveling serves during pivoting of the upper housing section 107 when the lugs 115 . 1 and 115 . 2 contact the inner edge of the ribs 116 . 1 and 116 . 2 slightly to spread the ribs 116 . 1 and 116 . 2 outwardly which causes the lugs 115 . 1 and 115 . 2 to rub along the inner surface of the ribs 116 . 1 and 116 . 2 . As soon as the lugs 115 . 1 and 115 . 2 have arrived at the bores 117 . 1 and 117 . 2 they will snap into the bores, so that, as shown in FIG. 5 , the upper housing section 107 becomes firmly connected with the lower housing section 104 . It will be understood that the snap-fit takes place only after the seal engages the frame 110 of the opening. | A washing fluid container of substantially cylindrical configuration having at least one open end closed by a cover provided with an integrally formed air trap penetrating the cover at an acute angle with a first housing section extending at an acute angle upwardly of the surface of the cover outside of the container and a second housing section extending at an acute angle downwardly of the surface of the cover inside of the cover, the second housing section being adapted to receive washing fluid therein and the first housing section being provided with means responsive to washing fluid in the second housing section. | 3 |
BACKGROUND OF THE INVENTION
This invention relates to polyphosphazene homopolymers containing repeating ##STR3## units in the polymer chain in which dialkyl alkylene diamino substituents are attached to the phosphorus atom and to polyphosphazene copolymers containing a dialkyl alkylene diamino substituent and a substituted or unsubstituted alkoxy, aryloxy, amino or mercapto substituent. More particularly, the invention relates to polyphosphazene homopolymers containing substituents derived from dialkyl alkylene diamines and to copolymers derived from dialkyl alkylene diamines and substituted or unsubstituted aliphatic or aromatic alcohols, amines or mercaptans.
Polyphosphazene homo- and co- polymers containing repeating ##STR4## units in which various substituted or unsubstituted, saturated or unsaturated, alkoxy, aryloxy, amino or mercapto groups are attached to the phosphorus atom and their method of preparation are described in the prior art as illustrated in the publication "Phosphorus-Nitrogen Compounds", Academic Press, New York, New York 1972 by H. R. Allcock and "Poly(Organophosphazenes)", Chemtech, Sept. 19, 1975 by H. R. Allcock and in such U.S. Patents as Nos. 3,515,688; 3,702,833; 3,856,712; 3,974,242 and 4,042,561. When poly(dichlorophosphazene) is reacted with a phenylene diamine the poly(dichlorophosphazene) is crosslinked to an insoluble product, H. R. Allcock, W. J. Cook and D. P. Mack, Inorganic Chemistry, Vol. 11, 2584 (1972).
None of the aforementioned publications and patents or for that matter, none of the prior art of which applicants are aware, discloses or suggests polyphosphazene homopolymers and copolymers containing dialkyl alkylene diamino substituents attached to the phosphorus from or methods of preparing such polymers and copolymers.
SUMMARY OF THE INVENTION
In accordance with this invention, novel polyphosphazene homopolymers containing dialkyl alkylene diamino substituents and polyphosphazene copolymers containing dialkyl alkylene diamino as well as substituted or unsubstituted alkoxy, aryloxy, amino or mercapto substituents are prepared. The homopolymers contain repeating units represented by the formula: ##STR5## wherein X is ##STR6## in which R is an alkyl radical containing 1 to 8 carbon atoms, a is an integer of 2 to 8, and the polymer can contain from 20 to 50,000 of such units.
The copolymers of the invention contain units represented by the formulas: ##STR7## wherein X is ##STR8## in which R and a are as defined above and X' is selected from the group consisting of substituted or unsubstituted alkoxy, aryloxy, amino or mercapto radicals.
The homopolymers are prepared by reacting a poly(dichlorophosphazene) having the formula --(NPCl 2 ) n -- in which n is from 20 to 50,000 with a dialkyl alkylene diamine in the presence of a tertiary amine.
The homopolymers of the invention can be used to prepare films and may be utilized in applications such as molding, coatings, and the like.
The copolymers are prepared by reacting the poly(dichlorophosphazene) with a mixture of the dialkyl alkylene diamine and a substituted or unsubstituted aliphatic or aromatic alcohol, amino compound or mercaptan compound in the presence of a tertiary amine.
In the copolymer units represented by the above formulas, all X substituent groups may be the same or they may be mixed and all X' substituent groups may be the same or mixed. In the mixtures, the X substituent groups may be mixtures of different dialkyl alkylene diamino groups and the X' substituent groups may be mixtures of different alkoxy, aryloxy, amino and mercaptan groups or mixtures within each class.
The specific proportion of X to X' substituent groups incorporated in the copolymers of the invention may vary considerably depending upon chemical and physical properties desired in the copolymer and the particular end use application for which the copolymer is intended. Thus, for applications such as moldings, coatings, foams and the like, the copolymers should contain at least ten (10) percent by weight of the X substituent.
DETAILED DESCRIPTION OF THE INVENTION
The term "polymer" as used hereinafter throughout this specification and claims is employed in the broad sense and includes homopolymers, copolymers, terpolymers, tetrapolymers and the like.
As indicated heretofore, the polyphosphazenes of this invention are prepared by reacting a poly(dichlorophosphazene) polymer with a dialkyl alkylene diamine or a mixture of a dialkyl alkylene diamine and a compound capable of producing desired optional substituents.
Poly(dichlorophosphazene) polymers which are employed as starting materials in preparing the polymers of this invention are well known in the art as illustrated in U.S. Pat. Nos. 3,370,020; 4,005,171; and 4,055,520 and the aforementioned publications of H. R. Allcock, the disclosures of which are incorporated herein by reference.
These polymers have the general formula --(NPCl 2 ) n --, in which n may range from 20 to 50,000 or more. As described in the aforementioned references, the polymers are general prepared by the thermal polymerization of cyclic oligomers having the formula --(NPCl 2 ) n --, in which n is an integer of from 3 to 7, with the cyclic trimer and tetramer often comprising up to 90% of the oligomers.
The specific conditions of temperature, pressure and time employed in the thermal polymerization of the cyclic oligomers can vary considerably depending on whether or not the polymerization is catalyzed. Thus, temperatures may range from about 130° C. pressures may range from a vacuum of less than about 10 -1 Torr to superatmospheric and times may range from 30 minutes to about 48 hours.
A preferred process for preparing the poly(dichlorophosphazene) polymers used in the process of this invention is described in the aforementioned incorporated U.S. Pat. No. 4,005,171.
The dialkyl alkylene diamines which may be employed in forming the dialkyl alkylene diamino substituents of the polymers of the invention are those of the formula H 2 N--(CH 2 ) a --NR 2 wherein R is an alkyl group of 1 to 8 carbon atoms and a is an integer of 1 to 8. Representative suitable compounds of this type include N,N-diethyl propylene diamine, N,N-diethyl ethylene diamine, N,N-dimethyl ethylene diamine, N,N-dimethyl propylene diamine and N,N-dimethyl hexamethylene diamine and the like.
Preferred dialkyl alkylene diamines for use in forming the X substituent group are N,N-diethyl propylene diamine and N,N-dimethyl propylene diamine.
As indicated, the X' substituent group may be a substituted or unsubstituted alkoxy, aryloxy, amino or mercapto group.
The alkoxy groups (substituted or unsubstituted) may be derived from aliphatic alcohols having from 1 to 20 carbon atoms such as methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, hexane, dodecanol and the like; fluoroalcohols, especially those represented by the formula Z(CF 2 ) n CH 2 OH in which Z is hydrogen or fluorine and n is an integer from 1 to 10 as illustrated by trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,3,3,4,4,4-heptafluorobutanol; 2,2,3,3-tetrafluoro-propanol, 2,2,3,3,4,4,5,5-octafluoropentanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptanol and the like. In instances where it is desired to incorporate mixed X' substituent groups in the copolymers, mixtures of the foregoing alcohols may be employed.
The aryloxy groups (substituted or unsubstituted) may be derived from aromatic alcohols including among others phenol; alkylphenols such as cresols, xylenols, p-, o-, and m- ethyl and propyl phenols and the like; halogen-substituted phenols such as p-, o-, and m- chloro and bromo phenols and di- or tri-halogen substituted phenols and the like; and alkoxy-substituted phenols such as 4-methoxyphenol, 4-(n-butoxy)phenol and the like. Mixtures of the foregoing aromatic alcohols may also be employed.
The amino groups may be derived from any of the amino compounds heretofore employed in the polyphosphazene polymer art. Thus, the amino groups may be derived from aliphatic primary and secondary amines such as methylamine, ethylamine, dimethylamine, ethylmethylamine and the like are aromatic amines such as those described in U.S. Pat. No. 4,042,561 as illustrated by aniline, halogen-substituted anilines, alkyl-substituted anilines, alkoxy-substituted anilines and the like.
The mercapto groups may be derived from any of the mercaptan compounds heretofore employed in the polyphosphazene polymer art. Thus, for example, the mercaptan compounds described in U.S. Pat. No. 3,974,242 to Lanier at al may be utilized. Representative of suitable mercaptan compounds as described in the aforementioned patent are methyl mercaptan and its homologs ethyl, propyl, butyl, aryl and hexyl mercaptans, thiophenol, thionaphthols, benzyl mercaptan, cyclohexyl mercaptan and the like.
Particularly preferred substituent groups represented by X' for use in these polymers are substituted or unsubstituted alkoxy and aryloxy groups.
The use of a tertiary amine in preparing the polymers of the invention is a very important feature. Thus, the use of the tertiary amine minimizes undesirable side reactions and at the same time acts as an effective acid scavenger.
Tertiary amines which may be employed in preparing the polymers of the invention are those represented by the general structure: ##STR9## wherein R 1 , R 2 , and R 3 may each be alkyl containing from 1 to 8 carbon atoms. Thus, for example, the tertiary amine may be a trialkyl amine such as trimethylamine, triethylamine, tri-isopropylamine, tri-n-propylamine, tri-isobutylamine, tri-n-butylamine, and the like. In addition, tertiary amines such as pyridine, N,N,N',N'-tetramethylethylene diamine (TMEDA), dipipyridyl ethane, 1,4 diaza bicyclo (2.2.2) octane (DABCO), N-methyl pyrolle and N-methyl morpholine can also be utilized.
The preferred tertiary amines for use in preparing the polymers of the invention are triethylamine, N,N,N',N'-tetramethylethylene diamine and pyridine.
As indicated above, the polymers of the present invention are prepared by reacting the poly(dichlorophosphazene) polymer and a dialkyl alkylene diamine or a mixture of such dialkyl alkylene diamine with a substituted or unsubstituted aliphatic or aromatic alcohol, amino compound or mercaptan in the presence of a tertiary amine.
The specific reaction conditions and proportion of ingredients employed in preparing these polymers can vary somewhat depending on factors such as the reactivity of the specific compounds utilized, the particular tertiary amine employed, and the degree of substitution desired in the finished polymer. In general, reaction temperatures may range from about 25° C. to about 200° C. and times may range from 3 hours up to 7 days; lower temperatures necessitating longer reaction times and higher temperatures allowing shorter reaction times. These conditions are, of course, utilized in order to obtain the most complete reaction possible, i.e. in order to insure substantially complete conversion of the chlorine atoms in the polymer to the corresponding esters of the reactant compounds.
The above reaction is ordinarily carried out in the presence of a solvent. The solvent employed in the reaction should be a solvent for the poly(dichlorophosphazene) polymer, the dialkyl alkylene diamine reactant, other desired reactants and the tertiary amine. Examples of suitable solvents which may be employed include diglyme, triglyme, tetraglyme, toluene, xylene, cyclohexane, chloroform, dioxane, dioxalene, methylene chloride, tetrachloroethane, and tetrahydrofuran. The amount of solvent employed is not critical and any amount sufficient to solubilize the reaction mixture materials can be employed.
In addition, the materials in the reaction zone should be reasonably free of water. Preferably, the reaction mixture should contain less than about 0.01% by weight of water. The prevention of water in the reaction system is necessary in order to inhibit the reaction of the available chlorine atoms in the chloropolymer therewith.
In general, the amount of the dialkyl alkylene diamine compounds or mixture of such diamine compounds and other reactant compounds employed in the process should be at least molecularly equivalent to the number of available chlorine atoms in the polymer mixture. However, it is preferred that an excess of such compounds be employed in order to insure substantially complete reaction of all the available chlorine atoms.
Where the presence of crosslinking functionality is desired, in a polymer otherwise free of unsaturated crosslinking functionality, crosslinking functionality can be introduced in the polymer molecule through the use of ethylenically unsaturated substituent groups in addition to the groups X and X' set forth above. Examples of suitable crosslinking moieties and methods for their cure are set forth in U.S. Pat. Nos. 3,702,833; 3,844,983; 3,888,799; 4,055,520; and 4,061,606 which are hereby incorporated by reference and include unsaturated monovalent radicals such as --OCH═CH 2 ; ORCH═CH 2 ; ##STR10## --ORCF═CF 2 ; --OCH 2 RF═CF 2 and OR 1 R 2 in which R is an aliphatic or aromatic radical, R 1 is alkylene or arylene and R 2 is vinyl, allyl, crotyl or the like. Generally, when present, the moieties containing crosslinking functionality are usefully present in an amount between 0.1 mole % to about 50 mole % and usually between 0.5 mole % and about 10 mole % based on the replaceable chlorine in the starting poly(dichlorophosphazene).
The following examples are submitted for the purpose of further illustrating the nature of the present invention and are not intended as a limitation on the scope thereof. Parts and percentages referred to in the examples are by weight unless otherwise indicated.
EXAMPLE 1
Preparation of [((C 2 H 5 ) 2 N(CH 2 ) 3 NH) 2 PN] Polymer
To a dry nitrogen purged 28 ounce bottle were added 250 cc of tetrahydrofuran (hereinafter "THF") dried to less than 25 ppm water, 22.5 cc (210.4 millimoles) of N,N-diethyl propylene diamine (dried over calcium hydride), 19.8 cc of dry pyridine, and after cooling to 10° to 15° C., 120 gms. of a 7.94% solution of poly(dichlorophosphazene) of a degree of polymerization of about 2600. A rapid reaction was evident. The bottle was heated at 50° C. in a rotary bath for 68 hours. At the end of this time the solution was examined by infrared; the spectrum indicated presence of pyridine hydrochlorine but there were no bands attributable to P-Cl indicating good conversion.
The solid layer was isolated by decanting and washing with methanol. The resulting 16.6 gms. (66.6%) of polymer had a Tg of -58.5° C. and a peak melting temperature (T m ) of 145° C. Heating of the polymer at 300° F. in a forced air over for 10 days resulted in a weight loss of only 15.2%. Boiling 3 gms. of the polymer in 100 cc of water for 10 days resulted in a clear solution having a pH of 7.0. Analysis showed 15.2% chlorine indicating incomplete removal of pyridine hydrochloride.
EXAMPLE 2
Preparation of [((C 2 H 5 ) 2 N(CH 3 ) 3 NH)(CF 3 CH 2 O)PN] Polymer
To a 10 ounce beverage bottle were added 100 cc of dry THF, 6.02 cc (44 millimoles) of N,N-diethylpropylene diamine, 3.2 cc (44 millimoles) of dry trifluoroethanol, 12.3 cc (88 millimoles) of dry triethylamine, and 52.3 (4.62 gms., 39.8 millimoles) of a 8.83% solution of poly(dichlorophosphazene) of a degree of polymerization of 2600 in THF. The solution rapidly became opaque. After heating 68 hours at 80° C. the infrared spectrum of the resulting solution was obtained. There was no evidence of soluble phosphazene; the only bands were those attributable to triethylamine and triethylamine hydrochloride. Washing the salt layer with methanol gave 9.2 gms. (a yield of 84.6%) of copolymer with a Tg of -34° C. and a T m of 155° C.
An analysis of the polymer product showed the following results:
______________________________________ C H N P Cl______________________________________Calculated* (%) 41.16 7.89 16.33 12.46 5.50Actual (%) 41.16 7.89 16.32 12.46 5.50______________________________________ *Calculation based on a copolymer composition of 51.19 weight percent diethyl propylene diamine, and 32.24 weight percent trifluoroethanol with 3.83 weight percent of the poly(dichlorophosphazene) unreacted, 12.25% triethylamine hydrochloride and 5.36% hydrolysis of the chloropolymer.
EXAMPLE 3
This was prepared similar to Example 2 except for use of 12.04 cc (88 millimoles) of N,N-diethyl propylene diamine 18.4 cc (132 millimoles) of triethylamine, 3.2 cc (44 millimoles) of trifluoroethanol, and 13.7 gms. of a 33.9% cyclohexane solution of (Cl PN) x (44 millimoles of phosphazene) of a degree of polymerization of 1200. Reaction time was 20 hours at 120° C. The 3.2 cc (44 millimoles) of trifluoroethanol was added and heated to 120° C. for 4 additional hours. The I.R. showed no soluble phosphazene polymer. Methanol washing of the salt followed by vacuum drying at 80° C. gave 10.2 gms. of a rubbery, clear, yellow film.
EXAMPLE 4
Preparation of [((CH 3 ) 2 N(CH 2 ) 3 NH)(p-ClC 6 H 4 O)PN] Polymer
To a 10 oz. bottle was added 100 cc of THF, 5.35 cc (44 millimoles) of N,N-dimethyl propylene diamine, 4.43 cc (44 millimoles) of p-chlorophenol, 12.3 cc (88 millimoles) of triethylamine and 35.1 grams (39.4 millimoles) of a 13.0% solution of poly(dichlorophosphazene) of a degree of polymerization of about 2600 in cyclohexane. The bottle was heated at 120° C. for 20 hours. At the end of this time, the solution was examined by infrared and showed no P-Cl bands at 600 cm -1 indicating good conversion. The polymer product was isolated by coagulation with methanol. This procedure yielded 8.50 grams of a tan leathery polymer. | Polyphosphazene polymers are prepared which contain units represented by the formulas: ##STR1## wherein X is ##STR2## in which R is an alkyl group of 1 to 8 carbon atoms and a is an integer of 2 to 8 and wherein X' is the same as X for homopolymers and for copolymers X' is selected from the group consisting of substituted and unsubstituted alkoxy, aryloxy, amino or mercapto groups.
The polymers of the invention can be utilized to form protective films and may also be utilized in applications such as moldings, coatings and the like. | 2 |
CROSS REFERENCE TO RELATED APPLICATIONS
The present application is a continuation-in-part of U.S. application Ser. No. 11/283,382 filed Nov. 18, 2005, now abandoned, to which priority is claimed and which is herein incorporated by reference.
FIELD OF THE INVENTION
This invention is generally related to thermally insulating structures, and more particularly to a high thermal efficiency, insulated glass unit structure sealed with room temperature cured compositions having reduced permeability to gas, or mixtures of gases.
BACKGROUND OF THE INVENTION
Insulating glass units (IGU) commonly have two panels of glass separated by a spacer. The two panels of glass are placed parallel to each other and sealed at their periphery such that the space between the panels, or the inner space, is completely enclosed. The inner space is typically filled with air. The transfer of energy through an insulating glass unit of this typical construction is reduced, due to the inclusion of the insulating layer of air in the inner space, as compared to a single panel of glass. The energy transfer may be further reduced by increasing the separation between the panels to increase the insulating blanket of air. There is a limit to the maximum separation beyond which convection within the air between the panels can increase energy transfer. The energy transfer may be further reduced by adding more layers of insulation in the form of additional inner spaces and enclosing glass panels. For example three parallel spaced apart panels of glass separated by two inner spaces and sealed at their periphery. In this manner the separation of the panels is kept below the maximum limit imposed by convection effects in the airspace, yet the overall energy transfer can be further reduced. If further reduction in energy transfer is desired then additional inner spaces can be added.
Additionally, the energy transfer of sealed insulating glass units may be reduced by substituting the air in a sealed insulated glass window for a denser, lower conductivity gas. Suitable gases should be colorless, non-toxic, non-corrosive, non-flammable, unaffected by exposure to ultraviolet radiation, and denser than air, and of lower conductivity than air. Argon, krypton, xenon, and sulfur hexaflouride are examples of gases which are commonly substituted for air in insulating glass windows to reduce energy transfer.
Various types of sealants are currently used in the manufacture of insulated glass units including both curing and non-curing systems. Liquid polysulphides, polyurethanes and silicones represent curing systems, which are commonly used, while polybutylene-polyisoprene copolymer rubber based hot melt sealants are commonly used non-curing systems.
Liquid polysulphides and polyurethanes are generally two component systems comprising a base and a curing agent that are then mixed just prior to application to the glass. Silicones may be one component as well as two component systems. Two component systems require a set mix ratio, two-part mixing equipment and cure time before the insulating glass units can be moved onto the next manufacturing stage.
However, these sealant compositions are susceptible to permeability from the low conductivity energy transfer gases (e.g. argon) used to enhance the performance of insulated glass units. As a result of this permeability, the reduced energy transfer maintained by the gas between the panels of glass is lost over time.
There remains a need for sealants with superior barrier protection and even higher thermal insulation stability that overcomes the deficiencies described above, and is highly suitable for applications that are easy to apply and have excellent adhesion.
SUMMARY OF THE INVENTION
An insulated glass unit is provided herein which comprises at least two spaced-apart sheets of glass with a low thermal conductivity gas therebetween and a gas sealant element including a two-part curable sealant composition wherein:
Part 1 comprises (a) at least one silanol terminated first diorganopolysiloxane having a viscosity of from about 1,000 to 200,000 cps at 25 degrees C., and (b) a polymer exhibiting permeability to gas which is less than the permeability of the silanol terminated diorganopolysiloxane (a), and
Part 2 comprises (c) at least one trialkylsilyl terminated second diorganopolysiloxane, (d) an alkylsilicate crosslinker, and (e) a crosslinking catalyst.
The composition herein advantageously provides unexpectedly high adhesion to substrates.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional side view of a double glazed insulated glass unit (IGU).
FIGS. 2 and 3 are charts showing argon permeability data.
DETAILED DESCRIPTION OF THE INVENTION
The detailed embodiments of the present invention are disclosed herein. It should be understood, however, that the disclosed embodiments are merely exemplary of the invention, which may be embodied in various forms. Therefore, the details disclosed herein are not to be interpreted as limited, but merely as the basis for the claims and as a basis for teaching one skilled in the art how to make and/or use the invention. All composition percentages are by weight unless indicated otherwise. All ranges given herein are to be interpreted as including all subranges therein.
With reference to FIG. 1 an insulated glass unit 10 incorporating a curable sealant composition 7 providing separation of adjacent panes 1 , 2 and sealing of the gas impermeable space 6 therebetween is shown. Gases suitable for use in the invention include, for example, air, carbon dioxide, sulfur hexafluoride, nitrogen, argon, krypton, xenon, and mixtures thereof. As those skilled in the art will readily appreciate, the inventive concepts of the present curable sealant composition 7 may be applied in various manners without departing from the spirit of the present invention. For example, it is contemplated that the present curable sealant composition may be used in conjunction with other materials, for example, various types of glass, including, clear float glass, annealed glass, tempered glass, solar glass, tinted glass, and Low-E glass, acrylic sheets and polycarbonate sheets.
In accordance with the present invention, the curable sealant composition 7 is applied in the construction of an insulated glass unit with a double pane glass structure. The insulated glass unit, therefore, generally includes a first glass pane 1 and a second glass pane 2 separated by a continuous spacer 5 , a primary sealant 4 , and curable sealant composition 7 positioned between the first glass pane 1 and the second glass pane 2 . The use of curable sealant composition 7 in accordance with the present invention provides improved gas barrier characteristics and moisture leakage characteristics. As a result, the curable sealant composition 7 provides for longer in service performance of insulated glass units.
The dimensions of continuous spacer 5 will determine the size of the gas impermeable space 6 formed between the first glass 1 and second glass 2 when the sheets of glass are sealed to spacer 5 using primary sealant 4 and curable sealant composition 7 of the present invention. A glazing bead 8 , as known in the art, is placed between glass sheets 1 and 2 and window frame 9 .
The spacer 5 may be filled with a desiccant that will keep the sealed interior of the gas impermeable space 6 of the insulated glass unit dry. The desiccant should be one which will not adsorb the low thermal conductivity gas or other gases used if a gas mixture is used to fill the interior of the insulated glass unit.
The primary sealant 4 of the insulated glass unit may be comprised of polymeric materials as known in the art. For example, rubber base material, such as polyisobutylene, butyl rubber, polysulfide, EPDM rubber nitrile rubber, or the like. Other materials include, but are not limited to, compounds comprising polyisobutylene/polyisoprene copolymers, polyisobutylene polymers, brominated olefin polymers, copolymers of polisobutylene and para-methylstyrene, copolymers of polyisobutylene and brominated para-methylstyrene, butyl rubber-copolymer of isobutylene and isoprene, ethylene-propylene polymers, polysulfide polymers, polyurethane polymers, and styrene butadiene polymers.
As recited above, the primary sealant 4 can be fabricated of a material such as polyisobutylene, which has very good sealing properties. The glazing bead 8 is a sealant that is sometimes referred to as the glazing bedding and may be in the form of a silicone or butyl. A desiccant may be built into the continuous spacer 5 and is intended to remove moisture from the insulated glass or gas impermeable space between glass pane 1 and glass pane 2 .
The present invention unexpectedly provides adhesion about at least as good as standard sealant compositions. Moreover, the invention provides good adhesion to both glass and polyvinyl chloride (PVC) which is typically difficult to adhere to. The invention comprises a two-part formulation. Part 1 of the formulation includes
(a) a first diorganopolysiloxane or blend of diorganopolysiloxanes exhibiting a permeability to a gas or mixture of gases wherein each end of the polymer chain of each of the diorganopolysiloxanes is a silanol terminated, whereby the viscosity of the silanol terminated diorganopolysiloxanes can be from about 1,000 to 200,000 cps at 25 degrees C.; and (b) a polymer exhibiting permeability to the gas or mixture of gases that is less than the permeability of the silanol terminated diorganopolysiloxane (a). Part 2 of the formulation includes: (c) a second diorganopolysiloxane or blend or diorganopolysiloxanes wherein each end of the polymer chain of each of the second diorganopolysiloxanes is trialkylsilyl terminated; (d) an alkylsilicate crosslinker; and (e) a cross-linking catalyst.
Part 1 and 2 of the formulation are individually prepared and then combined in a weight ratio of Part 1/Part 2 preferably ranging from about 5:1 to about 20:1, more preferably from about 10:1 to about 15:1, and most preferably from about 12:1 to about 13:1.
The cured composition of the invention exhibits a low permeability to gases. The expression “low permability to gas(es)” as applied to the cured composition of this invention shall be understood to mean an argon permeability coefficient of not greater than about 900 barrer units (1 barrer=10 −10 (STP)/cm sec(cm Hg)) measured in accordance with the constant pressure variable-volume method at a pressure of 100 psi and temperature of 25° C. and more preferably not greater than 800 barrer units at a pressure of 100 psi and a temperature of 25° C.
The sealant composition of the present invention may further comprise an optional component, such as, filler, adhesion promoter, non-ionic surfactant, and the like and mixtures thereof.
Regarding Part 1 of the formulation, the silanol terminated diorganopolysiloxane polymer (a), generally has the formula:
M a D b D′ c
with the subscript a=2 and b equal to or greater than 1 and with the subscript c zero or positive where
M =(HO) 3-x-y R 1 x R 2 y SiO 1/2 ;
with the subscript x=0, 1 or 2 and the subscript y is either 0 or 1, subject to the limitation that x+y is less than or equal to 2, where R 1 and R 2 are independently chosen monovalent C1 to C60 hydrocarbon radicals; where
D =R 3 R 4 SiO 1/2 ;
where R 3 and R 4 are independently chosen monovalent C 1 to C 60 hydrocarbon radicals; where
D ′=R 5 R 6 SiO 2/2 ;
where R 5 and R 6 are independently chosen monovalent C 1 to C 60 hydrocarbon radicals. Silanol terminated diorganopolysiloxanes of the above formula which are useful in the invention are commercially available from Momentive Performance Materials under the designations CRTV941 (30,000 cps) and CRTV 942 (3000 cps).
The curable sealant composition 7 of the present invention further comprises at least one polymer (b) exhibiting permeability to a gas or mixture of gases that is less than the permeability of diorganopolysiloxane polymer (a).
Suitable polymers (b) exhibiting permeability to a gas or mixture of gases that is less than the permeability of diorganopolysiloxane polymer (a) include, inter alia, polyethylenes, such as, low density polyethylene (LDPE), very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE) and high density polyethylene (HDPE); polypropylene (PP), polyisobutylene (PIB), polyvinyl acetate (PVAc), polyvinyl alcohol (PVoH), polystyrene, polycarbonate, polyester, such as, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene napthalate (PEN), glycol-modified polyethylene terephthalate (PETG); polyvinylchloride (PVC), polyvinylidene chloride, polyvinylidene floride, thermoplastic polyurethane (TPU), acrylonitrile butadiene styrene (ABS), polymethylmethacrylate (PMMA), polyvinyl fluoride (PVF), polyamides (nylons), polymethylpentene, polyimide (PI), polyetherimide (PEI), polether ether ketone (PEEK), polysulfone, polyether sulfone, ethylene chlorotrifluoroethylene, polytetrafluoroethylene (PTFE), cellulose acetate, cellulose acetate butyrate, plasticized polyvinyl chloride, ionomers (Surtyn), polyphenylene sulfide (PPS), styrene-maleic anhydride, modified polyphenylene oxide (PPO), and the like and mixture thereof.
Polymer (b) of the curable sealant composition 7 can also be elastomeric in nature, examples include, but are not limited to ethylene-propylene rubber (EPDM), polybutadiene, polychloroprene, polyisoprene, polyurethane (TPU), styrene-butadiene-styrene (SBS), styrene-ethylene-butadiene-styrene (SEEBS), polymethylphenyl siloxane (PMPS), and the like.
These polymers can be blended either alone or in combinations or in the form of coplymers, e.g. polycarbonate-ABS blends, polycarbonate polyester blends, grafted polymers such as, silane grafted polyethylenes, and silane grafted polyurethanes.
In one embodiment of the present invention, the curable sealant composition 7 has a polymer selected from the group consisting of low density polyethylene (LDPE), very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), and mixtures thereof. In another embodiment of the invention, the curable sealant composition has a polymer selected from the group consisting of low density polyethylene (LDPE), very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), and mixture thereof. In yet another embodiment of the present invention, the curable sealant composition polymer is linear low density polyethylene (LLDPE).
In one embodiment of the present invention, the Part 1 of the curable sealant formulation contains from about 20 to about 99 weight percent of the silanol terminated diorganopolysiloxane polymer component (a) and from about 1 to about 80 weight percent polymer (b). In another embodiment of the present invention, Part 1 of the curable sealant composition contains from about 25 to about 70 weight percent diorganopolysiloxane polymer and from about 30 to about 75 weight percent polymer (b). In yet another embodiment of the present invention, Part 1 of the curable sealant composition contains from about 30 to about 60 weight percent diorganopolysiloxane polymer and from about 5 to about 35 weight percent polymer (b).
The blending method of diorganopolysiloxane polymer (a) with polymer (b) may be performed by those methods know in the art, for example, melt blending, solution blending or mixing of polymer powder component (b) in diorganopolysiloxane polymer (a).
Regarding Part 2 of the formulation, the trialkylsilyl terminated diorganopolysiloxane (c) generally has the formula:
M x D y D 1 z
with the subscript x=2 and y equal to or greater than 1 and with the subscript z zero or positive where
M =R a R b R c SiO 1/2 ;
wherein R a R b and R c can be the same or different and are each individually selected from C 1 to C 60 alkyl hydrocarbon radicals; where
D 1 ═R f R g SiO 1/2 ;
where R d and R e are independently chosen monovalent C 1 to C 60 hydrocarbon radicals; where
D 1 =R f R g SiO 2/2
where R f and R g are independently chosen monovalent C 1 to C 60 hydrocarbon radicals.
In one embodiment of the invention R a , R b and R c are each methyl. In another embodiment of the invention R a , R b and R c are each ethyl.
The trialkylsilyl terminated diorganopolysiloxane (c) can be present in Part 2 of the formulation in a range of from about 30% by weight to about 90% by weight, preferably from about 45% to about 75% by weight and more preferably by about 50% to about 70% by weight of the composition of Part 2 of the formulation.
Optionally, the trialkylsilyl terminated diorganopolysiloxane can also be a component of Part 1 of the formulation ranging from about 0% to about 20% by weight of Part 1.
Suitable cross-linkers (d) for the siloxanes of the curable sealant composition may include an alkylsilicate of the general formula:
(R 14 O)(R 15 O)(R 16 O)(R 17 O)Si
where R 14 , R 15 , R 16 and R 17 are independently chosen monovalent C 1 to C 60 hydrocarbon radicals.
Crosslinkers useful herein include, but are not limited to, tetra-N-propylsilicate (NPS), tetraethylortho silicate and methyltrimethoxysilane and similar alkyl substituted alkoxysilane compositions, and the like.
In one embodiment of the present invention, the level of incorporation of the alkylsilicate (crosslinker) ranges from about 0.1 weight percent to about 10 weight percent. In another embodiment of the invention, the level of incorporation of the alkylsilicate (crosslinker) ranges from about 0.3 weight percent to about 5 weight percent. In yet another embodiment of the present invention, the level of incorporation of the alkylsilicate (crosslinker) ranges from about 0.5 weight percent to about 1.5 weight percent of the total composition.
Suitable catalysts (e) can be any of those known to be useful for facilitating crosslinking in silicone sealant compositions. The catalyst may include metal and non-metal catalysts. Examples of the metal portion of the metal condensation catalysts useful in the present invention include tin, titanium, zirconium, lead, iron cobalt, antimony, manganese, bismuth and zinc compounds.
In one embodiment of the present invention, tin compounds useful for facilitating crosslinking in curable sealant compositions include: tin compounds such as dibutyltindilaurate, dibutyltindiacetate, dibutyltindimethoxide, tinoctoate, isobutyltintriceroate, dibutyltinoxide, solubilized dibutyl tin oxide, dibutyltin bis-diisooctylphthalate, bis-tripropoxysilyl dioctyltin, dibutyltin bis-acetylacetone, silylated dibutyltin dioxide, carbomethoxyphenyl tin tris-uberate, isobutyltin triceroate, dimethyltin dibutyrate, dimethyltin di-neodecanoate, triethyltin tartarate, dibutyltin dibenzoate, tin oleate, tin naphthenate, butyltintri-2-ethylhexylhexoate, and tinbutyrate, and the like. In still another embodiment, tin compounds useful for facilitating crosslinking in the curable sealant composition are chelated titanium compounds, for example, 1,3-propanedioxytitanium bis(ethylacetoacetate); di-isopropoxytitanium bis(ethylacetoacetate); and tetra-alkyl titanates, for example, tetra n-butyl titanate and tetra-isopropyl titanate. In yet another embodiment of the present invention, diorganotin bis β-diketonates is used for facilitating crosslinking in the curable sealant composition.
In one aspect of the present invention, the catalyst is a metal catalyst. In another aspect of the present invention, the metal catalyst is selected from the group consisting of tin compounds, and in yet another aspect of the invention, the metal catalyst is solubilized dibutyl tin oxide.
In one embodiment of the present invention, the level of incorporation of the catalyst, ranges from about 0.001 weight percent to about 1 weight percent of the total composition. In another embodiment off the invention, the level of incorporation of the catalyst, ranges from about 0.003 weight percent to about 0.5 weight percent of the total composition. In yet another embodiment of the present invention, the level of incorporation of the catalyst, ranges from about 0.005 weight percent to about 0.2 weight percent of the total composition.
The curable sealant composition of the present invention may further comprise an alkoxysilane or blend of alkoxysilanes as an adhesion promoter in Part 1 and/or Part 2 of the composition. In one embodiment, the adhesion promoter may be a combination blend of n-2-aminoethyl-3-aminopropyltrimethoxysilane and 1,3,5-tris(trimethoxysilylpropyl)isocyanurate. Other adhesion promoters useful in the present invention include but are not limited to n-2-aminoethyl-3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, aminopropyltrimethoxysilane, bis-γ-trimethoxysilypropypamine, N-Phenyl-γ-aminopropyltrimethoxysilane, triaminofunctionaltrimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldiethoxysilane, methacryloxypropyltrimethoxysilane, methylaminopropyltrimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxyethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)propyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, isocyanatopropyltriethoxysilane, isocyanatopropylmethyldimethoxysilane, β-cyanoethyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, 4-amino-3,3,-dimethylbutyltrimethoxysilane, and n-ethyl-3-trimethoxysilyl-2-methylpropanamine, and the like.
The level of incorporation of the alkoxysilane (adhesion promoter) ranges from about 0.1 weight percent to about 20 weight percent of the total compensation. In one embodiment of the invention, the adhesion promoter ranges from about 0.3 weight percent to about 10 weight percent of the total composition. In another embodiment of the invention, the adhesion promoter ranges from about 0.5 weight percent to about 2 weight percent of the total composition.
The curable sealant composition of the present invention may also comprise a filler in Part 1 and/or Part 2 of the composition. Suitable fillers of the present invention include but are not limited to ground, precipitated and colloidal calcium carbonates which is treated with compounds such as stearate or stearic acid; reinforcing silicas such as fumed silicas, precipitated silicas, silica gels and hydrophobized silicas and silica gels; crushed and ground quartz, alumina, aluminum hydroxide, titanium hydroxide, diatomaceous earth, iron oxide, carbon black and graphite or clays such as kaolin, bentonite or montmorillonite, and the like.
In one embodiment of the present invention, the filler is a calcium carbonate filler, silica filler or a mixture thereof. The type and amount of filler added depends upon the desired physical properties for the cured silicone composition. In another embodiment of the invention, the amount of filler is from 0 weight percent to about 80 weight percent of the total composition. In yet another embodiment of the invention, the amount of filler is from about 10 weight percent to about 60 weight percent of the total composition. In still another embodiment of the invention, the amount of filler is from about 30 weight percent to about 55 weight percent of the total composition. The filler may be a single species or a mixture of two or more species.
In a further embodiment of the present invention, the curable sealant composition contains in part 1 and/or Part 2 an inorganic substance from the general class of so called “nano-clays” or “clays.” “Organo-clays” are clays or other layered materials that have been treated with organic molecules (also called exfoliating agents) capable of undergoing ion exchange reactions with the cations present at the interlayer surfaces of the layers.
In one embodiment of the invention, the clay materials used herein include natural or synthetic phyllosilicates, particularly smectic clays such as montmorillonite, sodium montmorillonite, calcium montmorillonite, magnesium montmorillonite, nontronite, beidellite, volkonskoite, laponite, hectorite, saponite, sauconite, magadite, kenyaite, sobockite, svindordite, stevensite, talc, mica, kaolinite, as well as vermiculite, halloysite, aluminate oxides, or hydrotalcite, and the like and mixtures thereof. In another embodiment, other useful layered materials include micaceous minerals, such as illite and mixed layered illite/smectite minerals, such as rectorite, tarosovite, ledikite and admixtures of illites with the clay minerals named above. Any swellable layered material that sufficiently sorbs the organic molecules to increase the interlayer spacing between adjacent phyllosilicate platelets to at least 5 angstroms, or to at least 10 angstroms, (when the phyllosilicate is measured dry) may be used in the practice of this invention.
The aforementioned particles can be natural or synthetic such as smectite clay. This distinction can influence the particle size and for this invention, the particles should have a lateral dimension of between 0.01 μm and 5 μm, and preferably between 0.05 μm and 2 μm, and more preferably between 0.1 μm and 1 μm. The thickness or the vertical dimension of the particles can vary between 0.5 nm and 10 nm, and preferably between 1 nm and 5 nm.
In still another embodiment of the present invention, organic and inorganic compounds useful for treating or modifying the clays and layered materials include cationic surfactants such as ammonium, ammonium chloride, alkylammonium (primary, secondary, tertiary and quaternary), phosphonium or sulfonium derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines or sulfides. Such organic molecules are among the “surface modifiers” or “exfoliating agents” discussed herein. Additional organic or inorganic molecules useful for treating the clays and layered materials include amine compounds (or the corresponding ammonium ion) with the structure R 3 R 4 R 5 N, wherein R 3 , R 4 , and R 5 are C 1 to C 30 alkyls or alkenes in one embodiment, C 1 to C 20 alkyls or alkenes in another embodiment, which may be the same or different. In one embodiment, the organic molecule is a long chain tertiary amine where R 3 is a C 14 to C 20 alkyl or alkene. In another embodiment, R 4 and or R 5 may also be a C 14 to C 20 alkyl or alkene. In yet another embodiment of the present invention, the modifier can be an amine with the structure R 6 R 7 R 8 N, wherein R 6 , R 7 , and R 8 are C 1 to C 30 alkoxy silanes or combination of C 1 to C 30 alkyls or alkenes and alkoxy silanes.
Suitable clays that are treated or modified to form organo-clays include, but are not limited to, montmorillonite, sodium montmorillonite, calcium montmorillonite, magnesium montmorillonite, nontronite, beidellite, volkonskoite, laponite, hectorite, saponite, sauconite, magadite, kenyaite, sobockite, svindordite, stevensite, vermiculite, halloysite, aluminate oxides, hydrotalcite, illite, rectorite, tarosovite, ledikite, and mixtures thereof. The organo-clays of the present invention may further comprise one or more of ammonium, primary alkylammonium, secondary alkylammonium, tertiary alkylammonium quaternary alkylammonium, phosphonium derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines or sulfides or sulfonium derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines or sulfides. In one embodiment of the present invention, the organo-clay is an alkyl ammonium modified montmorillonite.
The amount of clay incorporated in the sealant composition of the present invention in accordance with embodiments of the invention, is preferably an effective amount to provide decrease the sealant's permeability to gas. In one embodiment of the present invention, the sealant composition of the present invention contains from 0 to about 50 weight percent nano-clay. In another embodiment, the compositions of the present invention have from about 1 to about 20 weight percent nano-clay The clays can be used alone or in combination with the low density linear polymers mentioned above.
The curable sealant composition of the present invention may optionally comprise in Part 1 and/or Part 2 a non-ionic surfactant compound selected from the group of surfactants consisting of polyethylene glycol, polypropylene glycol, ethoxylated castor oil, oleic acid ethoxylate, alkylphenol ethoxylates, copolymers of ethylene oxide (EO) and propylene oxide (PO) and copolymers of silicones and polyethers (silicone polyether copolymers), copolymers of silicones and copolymers of ethylene oxide and propylene oxide and mixtures thereof in an amount ranging from slightly above 0 weight percent to about 10 weight percent, more preferably from about 0.1 weight percent to about 5 weight percent, and most preferably from about 0.5 weight percent to about 0.75 weight percent of the total composition.
The curable sealant composition of the present invention may be prepared using other ingredients that are conventionally employed in room temperature vulcanizing (RTV) silicone compositions such as colorants, pigments and plasticizers, as long as they do not interfere with the desired properties.
Furthermore, these compositions can be prepared using melt, solvent and in-situ polymerization of siloxane polymers as known in the art.
Preferably, the methods of blending the diorganopolysiloxane polymers with polymers may be accomplished by contacting the components in a tumbler or other physical blending means, followed by melt blending in an extruder. Alternatively, the components can be melt blended directly in an extruder, Brabender or any other melt blending means.
The curable sealant composition of the invention is illustrated by the following non-limiting examples. The argon (Ar) permeability of the Examples was measured using a gas permeability set-up. The measurements were based on the variable-volume method at 100 psi and 25 degrees C. Measurements were repeated under identical conditions for 2-3 times to ensure their reproducibility. The variable-volume method measures Ar permeability in “barrer” units (0.0 to 1,200.0). All of the Examples of the invention exhibited barrer units below 900. The Ar permeability results are depicted in FIG. 2 .
Example 1 (Comparative)
The formation of this Example is a control and does not exemplify the invention, but is presented for purposes of comparison. Formulation 1 was prepared by combining a silanol terminated diorganopolysiloxane mixture of CRTV 941 (30,000 cps) and CRTV942 (3,000) cps, with stearic acid treated calcium carbonate in a 1:1 weight ratio (i.e., 50% of each component) to provide Part 1.
Part 2 was provided by combining 63.3% by weight of trimethylsilyl terminated diorganopolysiloxane, i.e., Viscasil® (10,000 cps) commercially available from Momentive Performance Materials, Inc., with 8% carbon black, 15% aminopropyl triethoxysilane, 13% tetra-N-propylsilicate and 0.7% solubilized dibutyltin oxide.
Parts 1 and 2 were then mixed in a static mixer in a Part 1/Part 2 weight ratio of 12.5:1. The composition of Formulation 1 is summarized below in Table 1.
Formulation 1 was then tested for adhesion using H-block test specimens composed of aluminum on one side and glass on the other side with the Formulation 1 sealant in between. More particularly, tensile adhesion data was generated using ASTM test C1135 using test panels comprising 1 inch×3 inch×0.25 inch anodized aluminum and glass substrates with a spacer therebetween forming a 0.5 inch×0.5 inch×2 inch sealant cavity. The sealant was cured at 23° and 50% humidity (RH) for 7 days. The test results for Formulation 1 included a cohesive failure of 100% (which indicates that the sealant broke before the bond to either the aluminum or glass substrates broke). The tensile strength was 111 psi elongation was 102% and the 50% modulus was 74 psi. The test data for Formulation 1 is summarized in Table 2 below. This formulation exhibited an Ar permeability of 539.00 barrer units.
Example 2
The formulation of this Example exemplifies the invention. Formulation 2 was prepared by combining 45.3 parts by weight of a silanol terminated diorganopolysiloxane mixture of CRTV941 and CRTV942; 50 parts by weight of a stearic acid treated calcium carbonate and 4.7 parts by weight of a linear low density polyethylene (LLDPE) in a continuous extrusion process to provide Part 1 of the formulation.
Part 2 of the formulation was provided with the same components and percentage composition as in Formulation 1 of Example 1.
Parts 1 and 2 of Formulation 2 were combined in a static mixer in Part 1/Part 2 weight ratio of 12.5:1 as in Example 1. The composition of Formulation 2 is summarized in Table 1 below.
Formulation 2 was tested for adhesion in the same manner as in Example 1. Formulation 2 exhibited a cohesive failure of 100%, a tensile strength of 111 psi, an elongation of 85%, and a 50% modulus of 86 psi. The test data for Formulation 2 is summarized in Table 2 below. This formulation exhibited an Ar permeability of 468.93 barrer units.
Example 3
The formulation of this Example exemplifies the invention. Formulation 3 was prepared by combining 40.0 parts by weight of the silanol terminated diorganopolysiloxane of Example 2, 50.0 parts by weight of the stearic acid treated calcium carbonate, and 10.0 parts by weight of the same linear low density polyethylene (LLPDE) as in Example 2 and in the same manner as in Example 2 to provide Part 1 of Formulation 3.
Part 2 of Formulation 3 was provided with the same components and percentage composition as in Formulation 1 of Example 1.
Parts 1 and 2 of Formulation 3 were combined in a static mixer in a Part 1/Part 2 weight ratio of 12.5:1 as in Example 1. The composition of Formulation 3 is summarized in Table 1 below.
Formulation 3 was tested for adhesion in the same manner as in Example 1. Formulation 3 exhibited a cohesive failure of 100%, a tensile strength of 107 psi, an elongation of 68%, and a 58% modulus of 96 psi. The test data for Formulation 3 is summarized in Table 2 below. This formulation exhibited an Ar permeability of 404.25 barrer units.
Example 4 (Comparative)
The formulation of this Example is a control and does not exemplify the invention. Formulation 4 was prepared with the same components and in the same percentage composition as Formulation 1 of Example 1. The composition of Formulation 4 is summarized in Table 1 below.
Formulation 4 was tested for adhesion in the same manner as Example 1 and exhibited a cohesive failure of 100%, a tensile strength of 106 psi, an elongation of 95%, and a 50% modulus of 72 psi. The test data for Formulation 4 is summarized in Table 2 below. This formulation exhibited an Ar permeability of 532.10 barrer units.
As can be seen from the above Examples 1 to 4, in comparison to the control Formulations 1 and 4, Formulations 2 and 3 of the invention show only minor differences in elasticity and only slightly higher modulus while tensile strength is substantially unchanged. More significantly, the adhesion to glass and aluminum is unchanged as reflected by the 100% cohesive failure rate, i.e. the sealant broke before the bond to the substrates. It is entirely unexpected that a polymer, such as those listed above for component (b) of the formulation, can be incorporated into the formulation while not reducing the adhesiveness of the sealant to the substrates.
TABLE 1
Formulation 1
Formulation 4
Ingredients (weight %)
(Control)
Formulation 2
Formulation 3
(Control)
Part 1
Silanol terminated diorganopolysiloxane
50.0
45.3
40.0
50.0
Stearic acid treated calcium carbonate
50.0
50.0
50.0
50.0
Linear low density polyethylene (LLDPE)
—
4.7
10.0
—
Part 2
Trimethylsilyl terminated diorganopolysiloxane
63.3
63.3
63.3
63.3
Carbon Black
8
8
8
8
Aminopropyltriethoxysilane
15
15
15
15
Tetra-N-propylsilicate
13
13
13
13
Solubilized Dibutylltin Oxide
0.7
0.7
0.7
0.7
TABLE 2
Cohesive
Tensile
Failure %
Strength
Elongation
50% Modulus
Formulation 1
100
111
102
74
Formulation 2
100
111
85
86
Formulation 3
100
107
68
96
Formulation 4
100
106
95
72
Example 5 (Comparative)
The formulation of this Example is a control and does not exemplify the invention but is presented for the purposes of comparison. Formulation 5 was prepared by combining 42.8 parts by weight of the silanol terminated diorganopolysiloxane of Example 2, 45.0 parts by weight of stearic acid treated calcium carbonate, 0.7 parts by weight of polyalkyleneoxide organosilicone copolymer as a non-ionic surfactant, and 11.5 parts by weight of trimethylsilyl terminated polydimethyl siloxane in a continuous extrusion process, to provide Part 1 of the formulation.
Part 2 of Formulation 5 was prepared by combining 56.13 parts by weight of trimethylsilyl terminated diorganopolysiloxane, 11.5 parts by weight of octamethylcyclotetrasiloxane treated fumed silica, 0.37 parts of weight of carbon black, 15.9 parts by weight of aminoethyl aminopropyl trimethoxysilane, 4.0 parts by weight of tris-(trimethoxysilyl) propyl isocyanurate, 11.63 parts by weight of tetra-N-propylsilate and 0.47 parts by weight of dibutyltin dilaurate.
Parts 1 and 2 were combined in a static mixer at a Part 1/Part 2 weight ratio of 12.5:1. The composition of Formulation 5 is summarized below in Table 3.
Formulation 5 was then tested for lap shear adhesion in accordance with WPSTM test C-1221. The lap shear adhesion data was generated using 1 inch×3 inch coupons comprising polyvinylchloride (PVC) and glass substrates (i.e., PVC-to-PVC and glass-to-glass lap shear test specimens). The test specimens were prepared using a jig assembly to give a bond line thickness of 1/16 inch and a 0.5 inch overlap. The surfaces of all substrates were pre-cleaned with liquid detergent and water solution and then wiped dry with a clean cloth. The sealant was applied to the substrates and cured at 23° C. and 50% relative humidity for 24 hours.
Formulation 5 exhibited a cohesiveness failure of 100% with respect to both. PVC and glass substrate and an adhesive strength of 122 psi. These results are summarized below in Table 4.
Example 6
The formulation for this Example exemplifies the invention. Formulation 6 was prepared by combining 38.8 parts by weight of the silanol terminated diorganopolysiloxane of Example 2, 45.0 parts by weight of stearic acid treated calcium carbonate, 0.7 parts by weight of polyalkyleneoxide organosilicone co-polymer, 11.5 parts by weight of trimethylsily terminated polydimethylsiloxane, and 4.0 parts by weight of LLDPE to provide Part 1 of Formulation 6.
Part 2 of formulation 6 was prepared with the same components and percentage composition as Part 2 of Formulation 5. The composition of Formulation 6 is summarized in Table 3 below.
Parts 1 and 2 were then combined and tested in the same manner as in Example 5. Formulation 6 exhibited a cohesive failure of 100% with respect to both PVC and glass substrates and an adhesion strength of 119 psi. These results are summarized in Table 4 below.
Example 7
The formulation for this Example exemplifies the invention. Formulation 7 was prepared by combining 38.8 parts by weight of the silanol terminated diorganopolysiloxane of Example 2, 40.5 parts by weight of stearic acid treated calcium carbonate, 0.7 parts by weight of polyalkyleneoxide organosilicone co-polymer, 11.5 parts by weight of trimethylsily terminated polydimethylsiloxane, and 8.5 parts by weight of LLDPE to provide Part 1 of Formulation 7.
Part 2 of formulation 7 was prepared with the same components and percentage composition as Part 2 of Formulation 5. The composition of Formulation 7 is summarized in Table 3 below.
Parts 1 and 2 were then combined and tested in the same manner as in Example 5. Formulation 7 exhibited a cohesive failure of 100% with respect to both PVC and glass substrates and an adhesion strength of 104 psi. These results are summarized in Table 4 below.
Example 8
The formulation for this Example exemplifies the invention. Formulation 8 was prepared by combining 34.3 parts by weight of the silanol terminated diorganopolysiloxane of Example 2, 45.0 parts by weight of stearic acid treated calcium carbonate, 0.7 parts by weight of polyalkyleneoxide organosilicone co-polymer, 11.5 parts by weight of trimethylsily terminated polydimethylsiloxane, and 8.5 parts by weight of LLDPE to provide Part 1 of Formulation 8.
Part 2 of formulation 8 was prepared with the same components and percentage composition as Part 2 of Formulation 5. The composition of Formulation 8 is summarized in Table 3 below.
Parts 1 and 2 were then combined and tested in the same manner as in Example 5. Formulation 8 exhibited a cohesive failure of 100% with respect to both PVC and glass substrates and an adhesion strength of 119 psi. These results are summarized in Table 4 below.
Example 9
The formulation for this Example exemplifies the invention. Formulation 9 was prepared by combining 38.8 parts by weight of the silanol terminated diorganopolysiloxane of Example 2, 33.0 parts by weight of stearic acid treated calcium carbonate, 0.7 parts by weight of polyalkyleneoxide organosilicone co-polymer, 11.5 parts by weight of trimethylsily terminated polydimethylsiloxane, and 16.0 parts by weight of LLDPE to provide Part 1 of Formulation 9.
Part 2 of formulation 9 was prepared with the same components and percentage composition as Part 2 of Formulation 5. The composition of Formulation 9 is summarized in Table 3 below.
Parts 1 and 2 were then combined and tested in the same manner as in Example 5. Formulation 9 exhibited a cohesive failure of 100% with respect to both PVC and glass substrates and an adhesion strength of 75 psi. These results are summarized in Table 4 below.
TABLE 3
Formulation 5
Ingredients (weight %)
(Control)
Formulation 6
Formulation 7
Formulation 8
Formulation 9
Part 1
Silanol terminated diorganopolysiloxane
42.8
38.8
38.8
34.3
38.8
Stearic acid treated calcium carbonate
45.0
45.0
40.5
45.0
33
Polyalkyleneoxide organosilicone co-polymer
0.7
0.7
0.7
0.7
0.7
Trimethylsilyl terminated polydimethylsiloxane
11.5
11.5
11.5
11.5
11.5
Linear low density polyethylene (LLDPE)
—
4.0
8.5
8.5
16.0
Part 2
Trimethylsilyl terminated diorganopolysiloxane
56.13
56.13
56.13
56.13
56.13
Octamethylcyclotetrasiloxane treated fumed
11.5
11.5
11.5
11.5
11.5
silica
Carbon Black
0.37
0.37
0.37
0.37
0.37
Aminoethylaminopropyltrimethoxysilane
15.9
15.9
15.9
15.9
15.9
Tris-(trimethoxysilyl)propyl isocyanurate
4.0
4.0
4.0
4.0
4.0
Tetra-N-propylsilicate
11.63
11.63
11.63
11.63
11.63
Dibutylltin Oxide
0.47
0.47
0.47
0.47
0.47
TABLE 4
PVC
Glass
Cohesive
Cohesive
Adhesion
Failure %
Failure %
strength psi
Formulation 5
100
100
122
Formulation 6
100
100
119
Formulation 7
100
100
104
Formulation 8
100
100
119
Formulation 9
100
100
75
The adhesion of inventive formulations 6-9 incorporating LLDPE in a range of from 4.0% to 16% of Part 1 are substantially the same as the control Formulation 5 except that Formulation 9 does show some loss of adhesive strength (i.e., 75 psi vs. 122 psi for the control Formulation 5 without LLDPE). Nevertheless the failure mode remained 100% cohesive failure (i.e., the sealant advantageously failed prior to the bond line).
Example 10
Formulation 10 was prepared by combining 50 parts by weight of the silanol terminated diorganopolysiloxane of Example 2 with 45.5 parts by weight of stearic acid treated calcium carbonate and 5.0 parts nanoclay to provide part 1 of the formulation.
Part 2 of the formulation was prepared with the same components and in the same manner as Formulation 1. This formulation exhibited an Argon permeability of about 509 barrer units. The composition of Formulation 10 as well as for Formulations 1 and 2 are summarized in Table 5. The test data for Formulation 10 as well as for Examples 1 and 2 are presented in FIG. 3 .
Example 11
Formulation 11 was prepared by combining 45 parts by weight of the silanol terminated diorganopolysiloxane of Example 2 with 45 parts by weight of stearic acid treated calcium carbonate, 5 parts by weight of the same linear low density polyethylene (LLDPE) of Example 2 and 5.0 parts by weight of nanoclay to provide Part 1 of the formulation.
Part 2 of the formulation was prepared with the same components and in the same manner as Formulation 1. This formulation exhibited Argon permeability of about 268 barrer units. The composition of Formulation 11 is summarized in Table 5. The Argon permeability of Formulation 11, together with the test data for Formulations 1, 2 and 10, are presented in FIG. 3 .
TABLE 5
Formulation 1
Ingredients (weight %)
(Control)
Formulation 2
Formulation 10
Formulation 11
Part 1
Silanol terminated diorganopolysiloxane
50.0
45.3
50.0
45.0
Stearic acid treated calcium carbonate
50.0
50.0
45.0
45.0
Linear low density polyethylene (LLDPE)
—
4.7
—
5.0
Nano Clay
—
—
5.0
5.0
Part 2
Trimethylsilyl terminated
63.3
63.3
63.3
63.3
diorganopolysiloxane
Carbon Black
8
8
8
8
Aminopropyltriethoxysilane
15
15
15
15
Tetra-N-propylsilicate
13
13
13
13
Solubilized Dibutylltin Oxide
0.7
0.7
0.7
0.7
Examples 10 and 11 illustrate the unexpected results obtained by including a nanoclay in the formula together with linear low density polyethylene. The Argon permeability of Formulation 11 was less than half that of control formulation 1, and even less than 60% that of Formulation 2 of the invention without the nanoclay. These are surprisingly advantageous results.
While the preferred embodiment of the present invention has been illustrated and described in detail, various modifications of, for example, components, materials and parameters, will become apparent to those skilled in the art, and it is intended to cover in the appended claims all such modifications and changes which come within the scope of this invention. | The invention relates to an insulated glass unit having an increased service life. An outer glass pane and inner glass pane are sealed to a spacer to provide an improved gas impermeable space. The glass unit includes a curable two-part sealer composition which, upon curing, exhibits unexpectedly high adhesion to substrates. | 8 |
BACKGROUND
[0001] The present invention relates to a vehicle windshield wiper assembly.
[0002] Referring to FIGS. 6 and 7 , a conventional windshield wiper assembly 200 typically includes a wiper motor 210 , one or more wiper blades secured to wiper arms, and a pivotable linkage mechanism therebetween.
[0003] The wiper motor 210 has a housing 211 and a motor 220 which is connected to the housing 211 . The housing 211 has a top surface 212 and a side surface 213 . A projection 214 extends from the top surface 212 . The projection 214 pivotally supports an output shaft 230 of the wiper motor 210 . When the wiper motor 210 is driven, the output shaft 230 rotates in a predetermined direction r 1 .
[0004] The wiper motor 210 has a mounting bracket 215 integrally formed with the side surface 213 . The mounting bracket 215 is attached to a bar when mounted within a vehicle. The wiper assembly 200 is mounted to the vehicle at mounting parts 250 . A link mechanism 260 which is attached to the output shaft 230 moves back and forth in predetermined ranges r 2 , r 3 and r 4 due to rotation of the wiper motor 210 . As a result, the wiper arms reciprocate along a windshield.
[0005] When the wiper motor 210 rotates while under the influence of obstacles such as snow, sleet, and the like at or near the end-of-stroke reverse positions, the load on the link mechanism 260 becomes high. As a result, each part of the wiper assembly 200 undergoes considerable stress. In particular, the housing 211 of the wiper motor 210 becomes highly stressed at the top surface 211 , the side surface 212 and the mounting bracket 215 .
SUMMARY
[0006] One aspect of the invention overcomes many limitations and disadvantages of a conventional windshield wiper assembly for use in connection with the vehicle. For example, this windshield wiper assembly includes a wiper motor including a housing having a top surface and a side surface, a projection projecting from the top surface, a mounting bracket integrally extending from the side surface, and a rib integrally extending from the top surface and from the projection to a longitudinal end of the mounting bracket. Advantageously, by having the rib on the housing, the housing is more robust and stress resistant than the conventional windshield wiper assembly.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 is a perspective view of a cut away cowl cover plate which shows a windshield wiper assembly in the mounted state according to an embodiment of the present invention.
[0008] FIG. 2 is a front view of a wiper windshield assembly according to an embodiment of the present invention.
[0009] FIG. 3 is a perspective view of a wiper motor of the present invention.
[0010] FIG. 4 is a perspective view of a gear housing of the wiper motor to the present invention.
[0011] FIG. 5A is a side view of the gear housing as seen from the direction of an arrow 5 A in FIG. 4 .
[0012] FIG. 5B is a sectional view of the gear housing taken along line 5 B- 5 B in FIG. 4 .
[0013] FIG. 6 is a front view of a windshield wiper assembly according to the related art.
[0014] FIG. 7 is a perspective view of a wiper motor according to the related art.
DESCRIPTION OF EXEMPLARY EMBODIMENTS
[0015] Embodiments of the invention will be explained with reference to the drawings.
[0016] As shown in FIG. 1 , a vehicle 10 includes a windshield 11 and a body panel 12 . The body panel 12 includes a cowl box 13 and a cowl cover plate 14 which covers the cowl box 13 . A windshield wiper assembly 100 is mounted within the cowl box 13 .
[0017] As shown in FIGS. 1 to 3 , the wiper assembly 100 includes a first pivot assembly 110 , which includes a first pivot shaft 111 , a first pivot lever 112 , a first shaft supporting portion 113 , a first pivot cap 114 , a first bar coupling portion 115 , and first body mounting parts 116 , 116 .
[0018] Also, the wiper assembly 100 includes a second pivot assembly 120 , which includes a second pivot shaft 121 , a second pivot lever 122 , a second shaft supporting portion 123 , a second pivot cap 124 , a second bar coupling portion 125 , and second body mounting parts 126 , 126 . Further, the wiper assembly 100 includes a bar 130 and a link mechanism 140 .
[0019] Details of each of these structures are described below.
[0020] The first and second pivot shafts 111 and 121 are preferably formed of metal, and have an elongated cylindrical shape. The first and second pivot levers 112 and 122 are preferably formed of metal, and have a rectangular and thin plate shape.
[0021] A first end of the first pivot shaft 111 is coupled to a first end of the first pivot lever 112 . A first end of the second pivot shaft 121 is coupled to a first end of the second pivot lever 122 .
[0022] The first and second shaft supporting portions 113 and 123 are preferably formed of metal or plastic, and have a cylindrical bore shape. The first pivot shaft 111 is inserted into the first shaft supporting portion 113 so that the first pivot shaft 111 is pivotally supported by the first shaft supporting portion 113 . The second pivot shaft 121 is also inserted into the second shaft supporting portion 123 so that the second pivot shaft 121 is pivotally supported by the second shaft supporting portion 123 .
[0023] The first pivot cap 114 is attached to the first pivot shaft 111 or the first shaft supporting portion 113 so that grease is encased by the first pivot cap 114 . The second pivot cap 124 is attached to the second pivot shaft 121 or the second shaft supporting portion 123 so that grease is encased by the second pivot cap 124 . By providing the first and second pivot caps 114 and 124 , fluid (e.g., rain water, melting snow, washing fluid, and the like) is prevented from splashing on or encroaching between the first pivot shaft 111 and the first shaft supporting portion 113 , and between the second pivot shaft 121 and the second shaft supporting portion 123 .
[0024] The first and second bar coupling portions 115 and 125 are preferably formed of metal or plastic, and are integrally formed with the first and second shaft supporting portions 113 and 123 so that they project outwardly from the sides of the first and second shaft supporting portions 113 and 123 . The first and second bar coupling portions 115 and 125 are generally an elongated cylinder, for example, 23 mm in diameter, with a circular cross-section, and are coupled to both ends of the bar 130 by any suitable method of mounting such as press-fitting, swaging, or via threaded fasteners.
[0025] The first and second body mounting parts 116 and 126 are preferably formed of metal or plastic, and are integrally formed with the first and second shaft supporting portions 113 and 123 . The first and second body mounting parts 116 and 126 are mounted on the cowl box 13 by, for example, bolts. As such, the first and second bar coupling portions 115 and 125 are maintained stationary relative to the cowl box 13 while the first and second pivot levers 112 and 122 are pivotable about the first and second pivot shafts 111 and 121 .
[0026] The bar 130 is preferably formed of metal, and is generally an elongated straight cylinder, for example, 25 mm in diameter, with a circular cross-section that is cut to a predetermined length, for example, 300 mm.
[0027] The first bar coupling portion 115 is coupled to a first end 130 a of the bar 130 by, for example, press-fitting or swaging. Also, the second bar coupling portion 125 is coupled to a second end 130 b of the bar 130 by, for example, press-fitting or swaging.
[0028] As illustrated, the first and second bar coupling portions 115 and 125 may be inserted within both ends to enhance the interconnection therebetween.
[0029] As shown in FIG. 2 , the link mechanism 140 includes first and second link rods 141 and 142 . The first and second link rods 141 and 142 are preferably formed of metal although other materials may substitute therefor. The link mechanism 140 is pivotally connected to the first and second pivot levers 112 and 122 .
[0030] As shown in FIG. 2 , the second end 112 b of the first pivot lever 112 is pivotally connected to a first end 141 a of the first link rod 141 . The second end 122 b of the second pivot lever 122 is pivotally connected to a second end 141 b of the first link rod 141 . The second end 122 b of the second pivot lever 122 is pivotally connected to a first end 142 a of the second link rod 142 .
[0031] As shown in FIGS. 2 to 5B , the wiper motor 150 includes a motor 151 , and a housing 152 which is coupled to the motor 151 . The wiper motor 150 is directly mounted on one side of the bar 130 , and between the first and second bar coupling portions 115 and 125 by, for example, bolts and nuts. When the wiper motor 150 rotates in the predetermined range R 1 , the first and second levers 112 and 122 move in predetermined ranges R 2 , R 3 and R 4 . Further, the first and second link rods 141 and 142 move back and forth with the first and second levers 112 and 122 .
[0032] The housing 152 is preferably formed of metal or plastic, and is integrally formed with a top surface 153 , a side surface 154 , a projection 155 and a mounting bracket 156 . The top surface 153 has a shape which is a combination of a semicircle and a square.
[0033] The top surface 153 includes a projection 155 which has a longitudinal cylindrical bore extending therethrough. As shown in FIGS. 5A and 5B , a first direction A is defined as a top direction for providing relative orientation of the top surface 153 in FIG. 5A . In this case, the direction A is defined as a direction which the projection 155 extends from the top surface 153 . Also, a second direction B is defined as a bottom direction and is in an opposite direction relative to the first direction A. The side surface 154 extends from the edge of the top surface 153 in the second direction B.
[0034] The projection 155 is integrally formed with the housing 152 . The projection 155 has a longitudinal cylindrical shape and extends from the top surface 153 in the first direction A. The projection 155 pivotally supports an output shaft 160 . The projection 155 has, for example, a height of approximately 26 mm from the top surface 153 .
[0035] The mounting bracket 156 is integrally formed with the housing 152 and is mounted to the bar 130 . The mounting bracket 156 extends from the side surface 154 . The mounting bracket 156 includes a generally semicylindrical surface 156 a. The bar 130 is mounted onto the semicylindrical surface 156 a, secured the mounting bracket 156 to the bar 130 by bolts 156 b and nuts.
[0036] The mounting bracket 156 includes first and second top end surfaces 156 b 1 and 156 b 2 which lay in a plane perpendicular to the first direction A. The first top end surface 156 b 1 is located next to the side surface 154 . The second top end surface 156 b 2 is spaced apart from the first top end surface 156 b 1 . An inside edge of the second top end surface 156 b 2 is approximately 25.1 mm from an inside edge of the first top end surface 156 b 1 .
[0037] Further, the mounting bracket 156 includes first and second longitudinal end surfaces 156 e 1 and 156 e 2 . The first and second longitudinal end surfaces 156 e 1 and 156 e 2 lay in planes perpendicular to the longitudinal direction of the mounting bracket 156 .
[0038] The first longitudinal end surface 156 e 1 is located near the side surface 154 . The second longitudinal end surface 156 e 2 is located on the opposite side of the mounting bracket 156 relative to the first longitudinal end surface 156 e 1 . The first longitudinal end surface 156 e 1 is approximately 77 mm from the second longitudinal end surface 156 e 2 .
[0039] As shown in FIGS. 3 to 5B , the mounting bracket 156 also includes a boss 156 c on the semicylindrical surface 156 a. The boss 156 c is located at a center of a long side of the mounting bracket 156 . The boss 156 c extends from the semicylindrical surface 156 a in the first direction A. The boss 156 c has a height of approximately 3 mm from the semicylindrical surface 156 a . The boss 156 c is approximately 62 mm from the center axis of the projection 155 . When the bar 130 is mounted on the mounting bracket 156 , the boss 156 c inhibits longitudinal movement of the bar 130 .
[0040] The mounting bracket 156 includes four projections 156 d on the semicylindrical surface 156 a. Each projection 156 d is located at a corner among the first and second top end surfaces 156 b 1 and 156 b 2 and the first and second longitudinal end surfaces 156 e 1 and 156 e 2 . The projections 156 d contact with an outer periphery of the bar 130 . The projections 156 d prevent the bar 130 from rotating relative to the mounting bracket 156 .
[0041] A rib 157 extends from the projection 155 to the mounting bracket 156 and extends from the top surface 153 of the housing 152 in the first direction A. The rib 157 includes a top end 157 a and first and second side surfaces 157 b 1 and 157 b 2 .
[0042] The top end 157 a has a plane perpendicular to the first direction A. The top end 157 a of the rib 157 and the first top end surface 156 b 1 of the mounting bracket 156 are preferably co-planar. The top end 157 a has a height of approximately 13 mm from the top surface 153 . The top end 157 a has a constant width of approximately 5 mm. The first side surface 157 b 1 extends from the top end 157 a to an end surface 154 a of the side wall 154 in the direction B. The first side surface 157 b 1 has a height of approximately 28.5 mm from the top end 157 a to the end surface 154 a. The first side surface 157 b 1 has two heights of approximately 13 mm and 28.5 mm. The rib 157 is integrally formed with the mounting bracket 156 . The first side surface 157 b 1 is located on the side of a border between the top surface 153 and the side surface 154 . The second side surface 157 b 2 is located on an opposite side of the first side surface 157 b 1 . The first and second side surfaces 157 b 1 and 157 b 2 are parallel curves. The first side surface 157 b 1 has a radius of approximately 35 mm. The second side surface 157 b 2 has a radius of approximately 30 mm. The first side surface 157 b 1 is approximately 5 mm from the second side surface 157 b 2 .
[0043] The first side surface 157 b 1 is coextensive with the longitudinal end surface 156 e 1 . The rib 157 also extends from the top surface 153 to the end surface 154 a. The first side surface 157 b 1 has a common surface with the first longitudinal end surface 156 e 1 .
[0044] The opposite rib 158 is located at an opposite side of the rib 157 and is essentially aligned therewith. The opposite rib 158 includes a first opposite rib 158 a having a common plane with the top end 157 a, and a second opposite rib 158 b which inclines from the projection 155 to the first opposite rib 158 a . The first opposite rib 158 a has a constant width of approximately 5.5 mm. The first opposite rib 158 a has a height of approximately 7.5 mm from the top surface 153 . The second opposite rib 158 b has an angle of approximately 155 degrees relative to the first opposite rib 158 a. The opposite rib 158 extends from the projection 155 to the housing edge 153 a.
[0045] Reinforcement ribs 159 are located on the top surface 153 . The reinforcement ribs 159 extend radially outwardly from the projection 155 in a spoke-like manner. The reinforcement ribs 159 integrally extend from the top surface 153 in the first direction A, and radially extend around the projection 155 between the rib 157 and the opposite rib 158 . In this embodiment, the reinforcement ribs 159 include four ribs and extend from the projection 155 at angles about equal to adjacent ribs 159 . Each of the reinforcement ribs 159 has a generally triangular bar shape. Each reinforcement rib 159 has an angular range from about 20 degrees to about 45 degrees. Each reinforcement rib has a width of approximately 5 mm.
[0046] When the wiper motor 150 rotates in the presence of obstacles (e.g., snow and the like) at or near the end-of-stroke reverse positions, the housing 152 of the wiper motor 150 is resistant to high stresses among the top surface 153 , the side surface 154 and the mounting bracket 156 .
[0047] The windshield wiper assembly being thus described, it will be apparent that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be apparent to one of ordinary skill in the art are intended to be included within the scope of the following claims. | A windshield wiper assembly for a vehicle includes a wiper motor. The wiper motor has a housing having a top surface and a side surface, a projection projecting from the top surface, a mounting bracket integrally extending from the side surface, and a rib integrally extending from the top surface and between the projection and a longitudinal end of the mounting bracket. Advantageously, the rib enhances the robustness of the housing so that it is more tolerant of stresses experienced during use. | 1 |
This application is a continuation of application Ser. No. 07/984,884, filed on Dec. 2, 1992, now U.S. Pat. No. 5,614,499.
This invention relates to new competitive inhibitors of thrombin, their synthesis, pharmaceutical compositions containing the compounds as active ingredients, and the use of the compounds as anticoagulants for prophylaxis and treatment of thromboembolic diseases such as venous thrombosis, pulmonary embolism, arterial thrombosis, in particular myocardial infarction and cerebral thrombosis, general hypercoagulable states and local hypercoagulable states, e.g. following angioplasty and coronary bypass operations.
The invention also relates to novel use of a compound as a starting material in synthesis of a serine protease inhibitor. Furthermore the invention relates to a novel structural fragment in a serine protease inhibitor.
BACKGROUND
Blood coagulation is the key process involved in both haemostasis (i.e. prevention of blood loss from a damaged vessel) and thrombosis (i.e. the pathological occlusion of a blood vessel by a blood clot). Coagulation is the result of a complex series of enzymatic reactions, where one of the final steps is conversion of the proenzyme prothrombin to the active enzyme thrombin.
Thrombin plays a central role in coagulation. It activates platelets, it converts fibrinogen into fibrin monomers, which polymerise spontaneously into filaments, and it activates factor XIII, which in turn crosslinks the polymer to insoluble fibrin. Thrombin further activates factor V and factor VIII in a positive feedback reaction. Inhibitors of thrombin are therefore expected to be effective anticoagulants inhibition of platelets, fibrin formation and fibrin stabilization. By inhibiting the positive feedback mechanism they are expected to excert inhibition early in the chain of events leading to coagulation and thrombosis.
PRIOR ART
Inhibitors of thrombin based on the amino acid sequence around the cleavage site for the fibrinogen Aα chain were first reported by Blomback et al in J. Clin. Lab. Invest. 24, suppl 107, 59, (1969), who suggested the sequence Phe-Val-Arg (P9-P2-P1, herein referred to as the P3-P2-P1 sequence) to be the best inhibitor.
In U.S. Pat. No. 4,346,078 (Richter Gedeon Vegyeszeti Gyar R. T., priority date Oct. 7, 1980) and in Peptides 1983 by Walter de Gruyter & Co, Berlin, pp 643-647, S. Bajusz et al described the thrombin inhibitor H-DPhe-Pro-Agm, a dipeptidyl derivative with an aminoalkyl guanidine in the P1-position.
S. Bajusz et. al. also reported in J. Med. Chem. 1990, 33, 1729-1735 and in EP-A2-0,185,390 (Richter Gedeon Vegyeszeti Gyar R. T.) (priority date Dec. 21, 1984) that replacing the agmatine with an arginine aldehyde gave a thrombin inhibitor which had much higher potency.
The reason for the increased activity of this thrombin inhibitor is thought possibly to be due to interaction of the aldehyde function with the Ser-OH in the active site of the enzyme forming a hemiacetal. It is not concievable to have the same type of interaction in the dipetide derivative H-DPhe-Pro-Agm since it does not have an amino acid derivative with a carbonyl group in the P1-position.
In other work in the thrombin inhibitor field, inhibitors of serine proteases that are based on electrophilic ketones instead of aldehydes in the P1-position include the following:
E. N. Shaw et al. (Research Corporation) U.S. Pat. No. 4,318,904 (priority date Apr. 25, 1980) describing peptide chloro-methyl ketones e.g. H-DPhe-Pro-Arg-CH 2 Cl.
M. Szelke and D. M. Jones in EP-A1-0,118,280, (priority date Mar. 4, 1983) describing compounds derived from the P 3 -P 2 ' pentapeptide sequence of the fibrinogen Aα chain in which the scissile P 1 -P 1 ' peptide bond was replaced with the --CO--CH 2 -moiety, forming a keto isostere to the corresponding peptides.
M. Kolb et. al. (Merrell-Dow) EP-A2-0,195,212 (Priority date Feb. 4, 1985) describing peptidyl α-keto esters and amides.
B. Imperiali and R. H. Abeles, Biochemistry 1986. 25. 3760 describing peptidyl fluoroalkyl ketones.
D. Schirlin et al. (Merrell-Dow) EP-A1-0,362,002 (priority date Sep. 1, 1988) describing fluoroalkylamide ketones.
P. Bey et al., (Merrell-Dow) EP-A2-0,364,344 (priority date Sep. 1, 1988) describing α,β,δ- triketo compounds.
Ueda et al., Biochem. J. 1990, 265, 539 also describing peptidyl fluoroalkyl ketones.
Inhibitors of thrombin based on C-terminal boronic acid derivatives of arginine and isothiouronium analogues thereof have been reported by A. D Kettner et al. (Du Pont) EP-A2-0,293,881 (priority dates Jun. 5, 1987 and Apr. 6, 1988).
An object of the present invention is to provide novel and potent thrombin inhibitors with competitive inhibitory activity towards their enzyme i.e. causing reversible inhibition. A further object is to obtain inhibitors which are orally bioavailable and selective inhibiting thrombin over other serine proteases. Stability, duration of action, and low toxicity at therapeutic dosages are still further objects of the invention.
DISCLOSURE OF THE INVENTION
Compounds
Compounds of the invention relate to the peptide sequence of human fibrinogen Aa chain representing modified sub-sites P 9 . P 2 and P 1 : ##STR3## The above compound is identified as SEQ ID NO:1 in the Sequence Listing.
According to the invention it has been found that compounds of the general Formula I, either as such or in the form of physiologically acceptable salts, and including stereoisomers, are potent inhibitors of thrombin: ##STR4## wherein: A represents a methylene group, or
A represents an ethylene group and the resulting 5-membered ring may or may not carry one or two fluorine atoms, a hydroxy group or an oxo group in position 4, or may or may not be unsaturated, or
A represents --CH 2 --O--, --CH 2 --S--, --CH 2 --SO--, with the heteroatom functionality in position 4, or
A represents a n-propylene group and the resulting 6-membered ring may or may not carry in position 5 one fluorine atom, a hydroxy group or an oxo group, carry two fluorine atoms in one of positions 4 or 5 or be unsaturated in position 4 and 5, or carry in position 4 an alkyl group with 1 to 4 carbon atoms, or
A represents --CH 2 --O--CH 2 --, --CH 2 --S--CH 2 --, --CH 2 --SO--CH 2 --;
R 1 represents H, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 2-3 carbon atoms or R 11 OOC-alkyl-, where the alkyl group has 1 to 4 carbon atoms and R 11 is H or an alkyl group having 1 to 4 carbon atoms or an alkylene group having 2-3 carbon atoms intramolecularly bound alpha to the carbonyl group in R 1 , or
R 1 represents R 12 OOC-1,4-phenyl-CH 2 --, where R 12 is H or an alkyl group having 1 to 4 carbon atoms, or
R 1 represents R 13 --NH--CO-alkyl-, where the alkyl group has 1 to 4 carbon atoms and is possibly substituted alpha to the carbonyl with an alkyl group having 1 to 4 carbon atoms and where R 13 is H or an alkyl group having 1 to 4 carbon atoms or --CH 2 COOR 12 where R 12 is as defined above, or
R 1 represents R 12 OOC--CH 2 --OOC-alkyl-, where the alkyl group has 1 to 4 carbon atoms and is possibly substituted alpha to the carbonyl with an alkyl group having 1 to 4 carbon atoms and where R 12 is as defined above, or
R 1 represents CH 3 SO 2 --, or
R 1 represents R 12 OCOCO-- where R 12 is as defined above, or
R 1 represents --CH 2 PO(OR 14 ) 2 , --CH 2 SO 3 H or --CH 2 -(5-(1H)-tetrazolyl) where R 14 is, individually at each occurrence, H, methyl or ethyl;
R 2 represents H or an alkyl group having 1 to 4 carbon atoms or R 21 OOC-alkyl-, where the alkyl group has 1 to 4 carbon atoms and is possibly substituted in the position which is alpha to the carbonyl group, and the alpha substituent is a group R 22 --(CH 2 ) p --, wherein p=0-2 and R 22 is methyl, phenyl, OH, COOR 21 , and R 21 is H or an alkyl group having 1 to 4 carbon atoms.
m is 0, 1 or 2, R 3 represents a cyclohexyl group and R 4 represents H, or
m is 1 and R 3 represents a cyclohexyl or phenyl group and R 4 forms an ethylene bridge together with R 1 , or
m is 1 and R 3 and R 4 each represents a cyclohexyl or phenyl group;
R 5 represents H or an alkyl group having 1 to 4 carbon atoms;
n is an integer 2 to 6; and
B represents --N(R 6 )--C(NH)--NH 2 , wherein R 6 is H or a methyl group, or
B represents --S--C(NH)--NH 2 , or --C(NH)--NH 2 .
An alkyl group may be straight or branched unless specified otherwise. Alkyl groups having 1 to 4 carbon atoms are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl and t-butyl. When unsaturation is referred to, a carbon-carbon double bond is intended. Abbreviations are listed at the end of this specification.
According to a preferred embodiment the invention relates to compounds of Formula I, wherein R 1 represents R 11 OOC-alkyl-, where the alkyl group has 1 to 4 carbon atoms and R 11 is H. Of those compounds, the compounds where A is ethylene and R 5 is H or an alkyl group having 1 to 4 carbon atoms, particularly those where R 5 is H are preferred.
Of the compound of Formula I, those compounds where R 3 is cyclohexyl, m is 1 or 2, particularly m is 1 and R 4 is H constitute another preferred subclass.
Another preferred group of compounds are the compounds where A is n-propylene and the resulting 6-membered ring may or may not carry in position 4 an alkyl group with 1 to 4 carbon atoms, and R 5 is H or an alkyl group having 1 to 4 carbon atoms, particularly those where R 5 is H.
According to another preferred embodiment n is 3.
Compounds of Formula I having S-konfiguration on the α-amino acid in the P2-position are preferred ones, of those compounds also having R-konfiguration on the α-amino acid in the P3-position are particularly preferred ones.
Preferred compounds of the invention are:
______________________________________Example No. Compound______________________________________ 1 H--(R)Cha-Pro-Agm 2 Me-(R)Cha-Pro-Agm 3 HO--(CH.sub.2).sub.3 --(R)Cha-Pro-Agm 4 HOOC--CH.sub.2 --(R)Cha-Pro-Agm 5 .sup.i PrOOC--CH.sub.2 --(R)Cha-Pro-Agm 6 HOOC--CH.sub.2 -(Me)(R)Cha-Pro-Agm 7 HOOC--(R,S)CH(Me)-(R)Cha-Pro-Agm 8 HOOC--(RorS)CH(Me)-(R)Cha-Pro-Agm/a 9 HOOC--(RorS)CH(Me)-(R)Cha-Pro-Agm/b10 HOOC--(RorS)CH(.sup.n Pr)-(R)Cha-Pro-Agm/a11 HOOC--(RorS)CH(.sup.n Pr)-(R)Cha-Pro-Agm/b12 HOOC--(RorS)CH(Ph)-(R)Cha-Pro-Agm/b13 HOOC--(R,S)CH(CH.sub.2 CH.sub.2 Ph)-(R)Cha-Pro-Agm14 HOOC--(RorS)CH(CH.sub.2 CH.sub.2 Ph)-(R)Cha-Pro-Agm/a15 HOCC--CH.sub.2 -CH.sub.2 --(R)Cha-Pro-Agm16 EtCOC--CO--(R)Cha-Pro-Agm17 (R,S)Bla-(R)Cha-Pro-Agm18 HOOC--(RorS)CH(CH.sub.2 CH.sub.2 Ph)-(R)Cha-Pro-Agm/b19 H--(R)Cha-Pro-Nag20 .sup.n Bu-(R)Cha-Pro-Nag21 HO-(CH.sub.2).sub.3 --(R)Cha-Pro-Nag22 HOOC--CH.sub.2 --(R)Cha-Pro-Nag23 EtOOC--CH.sub.2 --(R)Cha-Pro-Nag24 .sup.n PrOOC--CH.sub.2 --(R)Cha-Pro-Nag25 .sup.t BuOOC--CH.sub.2 --(R)Cha-Pro-Nag26 HOOC--CH.sub.2 -OOC--CH.sub.2 --(R)Cha-Pro-Nag27 H.sub.2 N-CO-CH.sub.2 --(R)Cha-Pro-Nag28 HOOC--CH.sub.2 FNH-CO-CH.sub.2 --(R)Cha-Pro-Nag29 (HOOC--CH.sub.2).sub.2 --(R)Cha-Pro-Nag30 HOOC--CH.sub.2 -(Me)(R)Cha-Pro-Nag31 HOOC--CH.sub.2 -(nBu)(R)Cha-Pro-Nag32 HCOC--(R,S)CH(Me)-(R)Cha-Pro-Nag33 HOOC--(RorS)CH(Me)-(R)Cha-Pro-Nag/a34 HOCC--(RorS)CH(Me)-(R)Cha-Pro-Nag/b35 EtOOC--(R,S)CH(Me)-(R)Cha-Pro-Nag36 .sup.n HOOC--(RorS)CH(.sup.n Pr)--(R)Cha-Pro-Nag/a37 HOOC--(R)CH(CH.sub.2 -OH)--(R)Cha-pro-Nag38 HOOC--(R,S)CH(Ph)-(R)Cha-Pro-Nag39 HOOC-(S)CH(CH.sub.2 CH.sub.2 Ph)-(R)Cha-Pro-Nag40 HOOC--(R)CH(CH.sub.2 CH.sub.2 Ph)-(R)Cha-Pro-Nag41 HOOC--CH.sub.2 -CH.sub.2 --(R)Cha-Pro-Nag42 EtOOC--CH.sub.2 -CH.sub.2 --(R)Cha-Pro-Nag43 HOOC-(CH.sub.2).sub.3 --(R)Cha-Pro-Nag44 EtOOC-(CH.sub.2).sub.3 --(R)Cha-Pro-Nag45 HOOC--CO--(R)Cha-Pro-Nag46 MeOOC--CO--(R)Cha-Pro-Nag47 (R,S)Bla-(R)Cha-Pro-Nag48 HOOC--(R,S)CH(CH.sub.2 COOH)--(R)Cha-Pro-Nag49 MeOOC--(R,S)CH(CH.sub.2 COOMe)-(R)Cha-Pro-Nag50 HOOC-Ph-4-CH.sub.2 --(R)Cha-Pro-Nag51 (HO).sub.2 P(O)-CH.sub.2 --(R)Cha-Pro-Nag52 EtO(HO)P(O)-CH.sub.2 --(R)Cha-Pro-Nag53 (EtO).sub.2 P(O)-CH.sub.2 --(R)Cha-Pro-Nag54 HOOC--CH.sub.2 --(R)Cha-Pro-Mag55 H--(R,S)Pro(3-Ph)-Pro-Agm56 H--(R,S)Pro(3-(trans)Ch)-Pro-Agm57 HOOC--CH.sub.2 --(R,S)Pro(3-(trans)Ph)-Pro-Agm58 HOOC--CH.sub.2 --(R,S)Pro(3-(trans)Ph)-Pro-Nag59 HOOC--CH.sub.2 --(R)Cha-Pic-Agm60 HOOC--CH.sub.2 -(Me)(R)Cha-(R,S)Pic-Agm61 HOOC--(R,S)CH(Me)-(R)Cha-Pic-Agm62 HOOC--(RorS)CH(Me)-(R)Cha-Pic-Agm/a63 HOOC--(RorS)CH(Me)-(R)Cha-Pic-Agm/b64 HOOC--CH.sub.2 -CH.sub.2 --(R)Cha-Pic-Agm65 H--(R)Cha-Pic-Nag66 Me-(R)Cha-(R,S)Pic-Nag67 HOOC--CH.sub.2 --(R)Cha-Pic-Nag68 MeOOC--CH.sub.2 --(R)Cha-Pic-Nag69 .sup.i PrOOC--CH.sub.2 --(R)Cha-Pic-Nag70 HOOC--CH.sub.2 -(Me)(R)Cha-(RorS)Pic-Nag/b71 HOOC--(R,S)CH(Me)-(R)Cha-(R,S)Pic-Nag72 HOOC--(RorS)CH(Me)-(R)Cha-(RorS)Pic-Nag/c73 HOOC--(RorS)CH(Me)-(R)Cha-(RorS)Pic-Nag/d74 HOOC--CH.sub.2 -CH.sub.2 --(R)Cha-Pic-Nag75 HOOC--CH.sub.2 --(R)Cha-(R,S)Mor-Agm76 HOOC--CH.sub.2 --(R)Cha-(RorS)Mor-Nag77 H--(R)Cha-Aze-Nag78 HOOC--CH.sub.2 --(R)Cha-Aze-Nag79 H--(R)Cha-Pro(5-(S)Me)-Nag80 HOOC--CH.sub.2 --(R)Cha-Pro(5-(S)Me)-Nag81 HOOC--CH.sub.2 --(R)CHa-(RorS)Pic(4,5-dehydro)-Nag/b82 HOOC--CH.sub.2 --(R)Cha-Pic(4-(S)Me)-Nag83 HOOC--CH.sub.2 --(R)Cha(R)Pic(4(R)Me)-Nag84 HOOC--CH.sub.2 --(R)Cgl-Pic-Nag85 H--(R)Hoc-Pro-Nag86 HOOC--CH.sub.2 --(R)Hoc-Pro-Nag87 HOOC--CH.sub.2 --(R)Hoc-Pic-Nag88 HOOC--CH.sub.2 --(R)Dph-Pic-Nag89 HOOC--CH.sub.2 --(R)Dch-Pic-Nag90 HOOC--CH.sub.2 --(R)Cha-Pro(5-(R,S)Me)-Nag91 H--(R)Cha-Pic(4-(R)Me)-Nag92 HOOC--CH.sub.2 --(R)Cha-Pic(4-(R)Me)-Nag93 HOOC--CH.sub.2 --(R)Cha-Pic(6-(S)Me)-Nag______________________________________
Of those compounds, the compounds having Example Nos. 4, 6, 9, 22, 30, 34, 59, 63, 67, 73, 80 and 82 are particularly preferred, and of those the following compounds are most preferred:
______________________________________30 HOOC--CH.sub.2 -(Me)(R)Cha-Pro-Nag34 HOOC--(RorS)CH(Me)-(R)Cha-Pro-Nag/b67 HOOC--CH.sub.2 -(R)Cha-Pic-Nag______________________________________
The most preferred compound among compounds of Formula I is HOOC--CH 2 (R)Cha-Pic-Nag.
In the above tables of compounds, the letters /a, /b, /c and /d refer to a substantially pure stereoisomer at the carbon atom denoted "RorS". The stereoisomer can be identified for each compound with reference to the experimental part herein. "R,S" refers to a mixture of stereoisomers.
In a further embodiment the invention relates to novel use of a compound of the formula: ##STR5## as a starting material in synthesis of a serine protease inhibitor, and in particular in synthesis of a thrombin inhibitor. It can be used as such or having the guanidino group either mono protected at the δ-nitrogen or diprotected at the δ-nitrogens or the γ, δ-nitrogens, preferably with a protective group such as benzyloxy carbonyl. Protection of the noragmatine derivatives is carried out by methods known in the art for guanidino compounds. This compound is named "noragmatine" or "Nag" herein. The compound has been previously disclosed inter alia as a hair bleaching accelerator in GB 1,599,324 (Henkel, priority date Feb. 5, 1977). The structural fragment of the formula ##STR6## has however not been previously disclosed as a structural element in a pharmaceutically active compound. As such structural element the "noragmatine" fragment renders a serine protease inhibitor, and in particular a thrombin inhibitor valuable.
Medical and pharmaceutical use
In a further embodiment the invention relates to treatment, in a human or animal organism, of conditions where inhibition of thrombin is required. The compounds of the invention are expected to be useful in particular in animals including man in treatment or prophylaxis of thrombosis and hypercoagulability in blood and tissues. It is furthermore expected to be useful in situations where there is an undesirable excess of the thrombin without signes of hypercoagulability. Disease states in which the compounds have a potential utility, in treatment and/or prophylaxis, include venous thrombosis and pulmonary embolism, arterial thrombosis, such as in myocardial infarction, unstable angina, thrombosis-based stroke and peripheral arterial thrombosis. Further, the compounds have expected utility in prophylaxis of atherosclerotic diseases such as coronary arterial disease, cerebral arterial disease and peripheral arterial disease. Further, the compounds are expected to be useful together with thrombolytics in thrombotic diseases, in particular myocardial infarction. Further, the compounds have expected utility in prophylaxis for re-occlusion after thrombolysis, percutaneous trans-luminal angioplasty (PTCA) and coronary bypass operations. Further, the compounds have expected utility in prevention of re-thrombosis after microsurgery. Further, the compounds are expected to be useful in anticoagulant treatment in connection with artificial organs and cardiac valves. Further, the compounds have expected utility in anticoagulant treatment in haemodialysis and disseminated intravascular coagulation.
A further expected utility is in rinsing of catheters and mechanical devises used in patients in vivo, and as an anticoagulant for preservation of blood, plasma and other blood products in vitro.
Pharmaceutical preparations
The compounds of the Formula I will normally be administered by the oral, rectal, dermal, nasal or parenteral route in the form of pharmaceutical preparations comprising the active ingredient either as a free base or a pharmaceutical acceptable non-toxic acid addition salt, e.g. the hydrochloride, hydrobromide, lactate, acetate, citrate, p-toluenesulfonate, trifluoroacetate and the like in a pharmaceutically acceptable dosage form.
The dosage form may be a solid, semisolid or liquid preparation prepared by per se known techniques. Usually the active substance will constitute between 0.1 and 99% by weight of the preparation, more specifically between 0.1 and 50% by weight for preparations intended for parenteral administration and between 0.2 and 75% by weight for preparations suitable for oral administration.
Suitable daily doses of the compounds of the invention in therapeutical treatment of humans are about 0.001-100 mg/kg body weight at peroral administration and 0.001-50 mg/kg body weight at parenteral administration.
Preparation
A further objective of the invention is the mode of preparation of the compounds. The compounds of Formula I may be prepared by coupling of an N-terminally protected amino acid or dipeptide or a preformed, N-terminally alkylated protected dipeptide to a compound
H.sub.2 N--(CH.sub.2).sub.n --X
wherein n is as defined with Formula I and X is an unprotected or protected guanidino group or a protected amino group, or a group transferable into an amino group, where the amino group is subsequently transferred into a guanidino group.
The coupling is accordingly done by one of the following methods:
Method I
Coupling of an N-terminally protected dipeptide, prepared by standard peptide coupling, with either a protected- or unprotected amino guanidine or a straight chain alkylamine carrying a protected or masked amino group at the terminal end of the alkyl chain, using standard peptide coupling, shown in the formula ##STR7## wherein R 3 , R 4 , R 5 , n, m and A are as defined in Formula I, R 6 is H or alkyl, W 1 is an amino protecting group such as tertiarybutoxy carbonyl and benzyloxy carbonyl and X is --NH--C(NH)NH 2 , --NH--C(NH)NH--W 2 , --N(W 2 )--C(NH)NH--W 2 , --NH--C(NW 2 )NH--W 2 or --NH--W 2 , where W 2 is an amine protecting group such as tertiarybutoxy carbonyl or benzyloxy carbonyl, or X is a masked amino group such as azide, giving the protected peptide. The final compounds can be made in any of the following ways, depending on the nature of the X-group used: Removal of the protecting group(s) (when X=--NH--C(NH)NH 2 , --N(W 2 )--C(NH)NH--W 2 , --NH--C(NW 2 )NH--W 2 or --NH--C(NH)NH--W 2 ), or a selective deprotection of the W 1 -group (e.g when X=--NH--C(NH)NH--W 2 , --N(W 2 )--C(NH)NH--W 2 , --NH--C(NW 2 )NH--W 2 , W 2 in this case must be orthogonal to W 1 ) followed by alkylation of the N-terminal nitrogen and deprotection or a selective deprotection/unmasking of the terminal alkylamino function (X=NH--W 2 , W 2 in this case must be orthogonal to W 1 or X=a masked aminogroup, such as azide) followed by a guanidation reaction, using standard methods, of the free amine and deprotection of the W 1 -group.
Method II
Coupling of an N-terminally protected amino acid, prepared by standard methods, with either a protected- or unprotected amino guanidine or a straight chain alkylamine carrying a protected or masked amino group at the terminal end of the alkyl chain, using standard peptide coupling, shown in the formula ##STR8## wherein W 1 , A, R 5 and X are as defined above followed by deprotection of the W 1 -group and coupling with the N-terminal amino acid, in a protected form, leading to the protected peptide described in Method I or III, depending on the choice of the substitution pattern on the nitrogen of the N-terminal amino acid used in the coupling. The synthesis is then continued according to Method I or Method III to give the final peptides.
Method III
Coupling of a preformed N-terminally alkylated and protected dipeptide, prepared by standard peptide coupling, with either a protected or unprotected amino guanidine or a straight chain alkylamine carrying a protected or masked aminogroup at the terminal end of the alkyl chain, using standard peptide coupling, shown in the formula ##STR9## wherein R 2 , R 3 , R 4 , R 5 , n, m, A and X are defined as above provided that R 2 is other than H and W 3 is an acyl protecting group such as trifluoroacyl.
The final compounds can be made in any of the following ways depending on the nature of the X-group used: Removal of protecting groups (when X =NH--C(NH)NH 2 , NH--C(NH)NH-W 2 , N(W 2 )--C(NH)NH--W 2 , NH--C(NW 2 )NH--W 2 or NH--W 2 ) or a selective deprotection/unmasking of the terminal alkylamino function (X=NH--W 2 , W 2 in this case must be orthogonal to W 3 or X=a masked amino group such as azide) followed by a guanidation deprotection of the W 3 group
DETAILED DESCRIPTION OF THE INVENTION
The following description is illustrative of aspects of the invention.
EXPERIMENTAL PART
Synthesis of the compounds of the invention is illustrated in Schemes I to VI appended hereto.
General Experimental Procedures
The 1 H NMR and 13 C NMR measurements were performed on BRUKER AC-P 300 and BRUKER AM 500 spectrometers, the former operating at a 1 H frequency of 500.14 MHz and a 13 C frequency of 125.76 MHz and the latter at 1 H and 13 C frequency of 300.13 MHz and 75.46 MHz respectively.
The samples were 10-50 mg dissolved in 0.6 ml of either of the following solvents; CDCl 3 (isotopic purity>99.8%, Dr. Glaser A. G. Basel), CD 3 OD (isotopic purity>99.95%, Dr. Glaser A. G. Basel) or D 2 O (isotopic purity>99.98%, Dr. Glaser A. G. Basel).
The 1 H and 13 C chemical shift values in CDCl 3 and CD 3 OD are relative to tetramethylsilane as an external standard. The 1 H chemical shifts in D 2 O are relative to the sodium salt of 3-(trimethylsilyl)-d 4 -propanoic acid and the 13 C chemical shifts in D 2 O are referenced relative to 1,4-dioxane (67.3 ppm), both as external standard. Calibrating with an external standard may in some cases cause minor shift differences compared to an internal standard, however, the difference in 1 H chemical shift is less than 0.02 ppm and in 13 C less than 0.1 ppm.
The 1 H NMR spectrum of peptide sequences containing a proline residue frequently exhibits two sets of resonances. This corresponds to the existence of to contributing conformers with respect to the rotation around the amide bond, where proline is the N-part of the amide bond. The conformers are named cis and trans. In our compounds the sequences (R)Cha-Pro- and -(R)Cha-Pic- often give rise to a cis-trans equilibrium with one conformer as the preponderant conformer (>90%). In those cases only the 1 H chemical shifts of the major rotamer is reported.
Thin-Layer Chromatography was carried out on commercial Merck Silicagel 60F 254 coated glass or aluminium plates. Visualization was by a combination of UV-light, followed by spraying with a solution prepared by mixing 372 ml of EtOH(95%), 13.8 ml of concentrated H 2 SO 4 , 4.2 ml of concentrated acetic acid and 10.2 ml of p-methoxy benzaldehyde or phosphomolybdic acid reagent (5-10 w.t % in EtOH(95%)) and heating.
Flash chromatography was carried out on Merck Silicagel 60 (40-63 mm, 230-400 mesh) under pressure of N 2 .
Reversed phase high-performance liquid chromatography (in the Examples referred to as RPLC) was performed on a Waters M-590 instrument equipped with three reverse phase Kromasil 100, C8 columns (Eka-Nobel) having different dimensions for analytical (4.6 mm×250 mm), semipreparative (1"×250 mm) and preparative (2"×500 mm) chromatography detecting at 226 nm.
Freeze-drying was done on a Leybold-Heraeus, model Lyovac GT 2, apparatus.
Protection Procedures
Boc-(R)Cha-OH
To a solution of H-(R)Cha-OH, 21.55 g (125.8 mmol), in 130 ml 1M NaOH and 65 ml THF was added 30 g (137.5 mmol) of (Boc) 2 O and the mixture was stirred for 4.5 h at room temperature. The THF was evaporated and an additional 150 ml of water was added. The alkaline aqueous phase was washed twice with EtOAc, then acidified with 2M KHSO 4 and extracted with 3×150 ml of EtOAc. The combined organic phase was washed with water, brine and dried (Na 2 SO 4 ). Evaporation of the solvent afforded 30.9 g (90.5%) of the title compound as a white solid.
Z-(R)Cha-OH
The same procedure as described in Bodanszky M. and Bodanszky A. "The Practice of Peptide Synthesis", Springer-Verlag, 1984, p. 12, was used starting from H-(R)Cha-OH.
Boc-(Me)Phe-OH
Prepared in the same way as Boc-(R)Cha-OH from Me-(R)Phe-OH.
Boc-(R,S)Pro(3-(trans)Ph)-OH
To a well stirred solution of 2.0 g (8.8 mmol, 1 eq.) H-(R,S)Pro(3-(trans)Ph)-OH×HCl (Prepared as described in J. Org. Chem., 55, p. 270-75 , 1990 and J. Org. Chem., 39, 1710-1716, 1974), in 17.6 ml of 1N NaOH, 12 ml of H 2 O and 12 ml of THF at +5° C. was added 2.33 g (Boc) 2 O (10.7 mmol, 1.2 eq.). The reaction was allowed to reach room temperature and the stirring was continued for an additional 18 h. The organic solvent was evaporated and 50 ml of H 2 O was added to the residue. The basic water phase was washed with 2×50 ml of EtOAc and acidified with 2M KHSO4 (pH about 1). The acidic water phase was extracted with 4×75 ml of EtOAc and the combined organic phase was washed with 1×40 ml of H 2 O, 1×40 ml of brine and dried (MgSO 4 ). Evaporation of the solvent gave 2.0 g (78%) of pure product as a white solid.
1H-NMR (CDCl 3 , 500 MHz, mixture of two rotamers): δ1.4 and 1.5 (2 s, 9H), 2.0-2.1 (m, 1H), 2.3-2.4 (m, 1H), 3.45-3.88 (m, 3H), 4.3 and 4.45 (2d, 1H), 7.2-7.4 (m, 5H).
Boc-(R,S)Pro(3-Ph)-OH
Prepared as above starting from a cis/trans mixture of H-(R,S)Pro(3-Ph)-OH.
Boc-(R)Dph-OH
Prepared according to the method described by K. Hsich et.al. in J. Med. Chem., 32, p. 898 (1989) from H-(R)Dph-OH.
Boc-(R)Hop-OH
Prepared by the same procedure as described for Boc-(R)Cha-OH starting from H-(R)Hop-OH.
1 H-NMR (300 MHz, CDCl 3 ): δ1.45 (s, 9H), 2.00 (m, 1H), 2.22 (m, 1H), 2.75 (bt, 2H), 4.36 (bs, 1H), 5.05 (bs, 1H), 7.15-7.33 (m, 5H).
Deprotection Procedures
(a) The protected peptide was dissolved in EtOH (95%) and hydrogenated over 5% Pd/C at atmospheric pressure in the presence of an excess of TFA or HOAc (>2 eq.) for about 1-4 h. The catalyst was filtered off, the solvent evaporated and the final peptide (TFA or HOAc salt) was isolated as a white powder after freeze drying (H 2 O).
(b) The same as in (a) except that EtOH/H 2 O (ca:5/1) was used as solvent.
(c) The same procedure as in (a) but MeOH was used as solvent.
(d) The same procedure as in (a) but 2M HCl was used as acid to give the HCl-salt.
(e) Hydrolysis of esters, an illustrative example:
EtOOC-CH 2 -(R)Cha-Pro-Nag×2 HOAc (0.4 mmol) was dissolved in 1.5 ml of MeOH and 1.2 ml (1.2 mmol) of 1M NaOH was added at room temperature. After 3 h the methanol was evaporated and an excess HOAc was added to the residue and the mixture was freeze dried and purified by RPLC (CH 3 CN/0.1M NH 4 OAc (70/30)). The pure product was obtained as a powder in 73% yield after freeze drying from water.
(f) Cleavage of t-butyl esters, an illustrative example:
The t-butyl ester was dissolved in an excess of TFA. After stirring for 2 h at room temperature the TFA was evaporated. Purification by treatment with activated charcoal in water-ethanol was followed by freeze drying from water giving the desired compounds.
Preparation of Starting Materials
H-pic-OEt×HCl
L-Pipecolinic acid, 4.0 g (0.031 mol), was slurried in 100 ml of abs. ethanol and HCl (g) was briefly bubbled through until a clear solution was obtained. It was cooled in an ice bath and 17 ml of thionyl chloride was added dropwise over 15 min. The ice bath was removed and the mixture was refluxed for 2.5 h. The solvent was evaporated and the product was obtained as its hydrochloride salt in a quantitative yield.
1 H-NMR (300 MHz, D 2 O): δ1.33 (t, 3H), 1.8-2.1 (m, 5H), 2.3-2.5 (m, 1H), 3.1-3.3 (m, 1H), 3.5-3.7 (m, 1H), 4.14 (dd, 1H), 4.44 (q, 2H).
H-Pic-OMe×HCl
Prepared in the same way as described for H-Pic-OEt×HCl by replacing EtOH with MeOH.
H-Aze-OEt×HCl
Prepared in the same way as described for H-Pic-OEt×HCl from H-Aze-OH.
H-Pic(4-(S)Me)-OEt×HCl
Prepared in the same way as described for H-Pic-OEt×HCL from H-Pic(4-(S)Me)-OH (purchased from Synthelec, Lund, Sweden).
H-(R)Pic(4-(R)Me)-OEt×HCl
Prepared in the same way as described for H-Pic-OEt×HCl from H-(R)Pic(4-(R)Me)OH (purchased from Synthelec, Lund, Sweden).
H-(R)Dph-OH
Prepared by the general method given by A. Evans et. al. in JACS, 112, 4011 (1990).
H-(R,S)Pic(4,5-dehydro)-oEt
H-(R,S)Pic(4,5-dehydro)-OH, 3.05 g (18.1 mmol) (Prepared according to the procedure by Burgstahler et. al. J. Org. Chem, 25, 4, p. 489-92 (1960), was dissolved in 75 ml EtOH/HCl (saturated) and the mixture was refluxed for 5 hours. The solvent was evaporated and the remaining residue was dissolved in water, made alkaline with sodium hydroxide (aq) and extracted three times with ethylacetate. Drying (Na 2 SO 4 ) and care full evaporation gave 2,05 g (71%) of the title compound.
1 H-NMR (CDCl 3 ): δ1.28 (t, 3H), 1.88 (bs, NH) 2.2-2.4 (m, 2H), 3.45 (bs, 2H), 3.57 (dd, 1H), 4.21 (q, 2H), 5.68-5.82 (m, 2H).
Boc-(R)Cgl-OH
Boc-(R)Pgl-OH was hydrogenated over 5% Rh/Al 2 O 3 in MeOH at 5 Mpa. Filtration and evaporation of the solvent gave the title compound which was used without further purification.
1 H-NMR (300 MHz,CDCl 3 ): δ0.9-1.7 (m, 20H), 4.0-4.2 (m, 1H), 5.2 (d, 1H).
Boc-(R)Dch-OH
Boc-(R)Dph-OH, 0.75 g (2.2 mmol), was dissolved in 25 ml of MeOH and a catalytic amount of 5% Rh/Al 2 O 3 was added. The mixture was hydrogenated at 5 Mpa, 50° C. for 40 h, filtered and evaporated to give 0.72 g (93%) of the title compound.
1 H-NMR (CDCl 3 ): δ0.9-2.0 (m, 32H), thereof 1.45 (bs, 9H), 4.55 (bd) and 4.9 (bd); two rotamers integrating for a total of 1H, 5.7-6.1 (broad, NH).
H-(R)Pro(5-(S)Me)-OMe
Prepared according to the procedure given by B. Gopalan et.al. in J. Org. Chem., 51, 2405, (1986).
H-Mor-OH
Prepared according to the method of K. Nakajima. et al. Bull. Chem. Soc. Jpn., 51 (5), 1577-78, 1978 and ibid 60, 2963-2965, 1987.
H-Mor-OEt×HCl
Prepared in the same way as H-Pic-OEt×HCl from H-Mor-OH.
Boc-(R)Cha-OSu
Boc-(R)Cha-OH (1 eq.), HOSu (1.1 eq) and DCC or CME-CDI (1.1 eq) were dissolved in acetonitrile (about 2.5 ml/mmol acid) and stirred at room temperature over night. The precipitate formed during the reaction was filtered off, the solvent evaporated and the product dried in vacuo. (When CME-CDI was used in the reaction the residue, after evaporation of the CH 3 CN, was dissolved in EtOAc and the organic phase washed with water and dried. Evaporation of the solvent gave the title compound).
1 H-NMR (500 MHz, CDCl 3 , 2 rotamers ca: 1:1 ratio) δ0.85-1.1 (m, 2H), 1.1-1.48 (m, 4H), 1.5-1.98 (m, 16H; thereof 1.55 (bs, 9H)), 2.82 (bs, 4H), 4.72 (bs, 1H, major rotamer), 4.85 (bs, 1H, minor).
Boc-(Me)(R)Cha-OSu
(i) Boc-(Me)(R)Cha-OH
A solution of 11,9 g (42.6 mmol) Boc-(Me)(R)Phe-OH in 150 ml MeOH was hydrogenated over 5% Rh/Al 2 O 3 at 0,28 Mpa for 24 h. Filtration of the catalyst and evaporation of the solvent gave the product as a white solid (95% yield) which was used in the next step without further purification.
1 H-NMR (500 MHz, CDCl 3 , mixture of two rotamers ca: 1/1). δ0.8-1.1 (m, 2H), 1.1-1.9 (m, 20H, thereof 1.47 and 1.45 (s, 9H)), 2.82 and 2.79 (s, total 3H), 4.88 and 4.67 (m, total 1H).
(ii) Boc-(Me)(R)Cha-OSu
Prepared in the same way as described for Boc-(R)Cha-OSu- from Boc-(Me)(R)Cha-OH.
Boc-(R)Cha-Pro-OSu
(i) Boc-(R)Cha-Pro-OH
H-(S)Pro-OH (680 mmol) was dissolved in 0.87M sodium hydroxide (750 ml). Boc-(R)Cha-OSu (170 mmol) dissolved in DMF (375 ml) was added dropwise during 20 min. The reaction mixture was stirred at room temperature for 20 h. The mixture was acidified (2M KHSO 4 ) and extracted three times with ethyl acetate. The organic layers were combined and washed three times with water and once with brine. After drying over sodium sulphate and evaporation of the solvent, the syrupy oil was dissolved in diethyl ether, the solvent evaporated and finally the product dried in vacuo to yield Boc-(R)Cha-Pro-OH as a white powder in almost quantitative yield.
1 H-NMR (500 MHz, CDCl 3 , minor rotamer 10%) δ0.8-1.05 (m, 2H), 1.05-1-55 (m, 15H; thereof 1.5 (bs, 9H)), 1.55-1.8 (m, 5H), 1.8-2.15 (m, 3H), 2.47 (m, 1H), 3.48 (m, 1H), 3.89 (m, 1H), 4.55 (m, 2H), 5.06 (m, 1H); minor rotamer signals 2.27 (m, 1H), 3.58 (m, 1H), 4.33 (m, 1H), 5.0 (m, 1H)
(ii) Boc-(R)Cha-Pro-OSu
Prepared in the same way as described for Boc-(R)Cha-OSu- from Boc-(R)Cha-Pro-OH.
1 H-NMR (500 MHz, CDCl 3 , 2 rotamers, 5:1 ratio) δ0.78-1.05 (m, 2H), 1.05-1.83 (m, 20H; thereof 1.43 (bs, 9H)), 1.83-2.26 (m, 3H), 2.32 (m, 1H), 2.72-2.9 (m, 4H), 3.2 (m, 1H, minor rotamer), 3.52 (m, 1H, major), 3.68 (m, 1H, minor rotamer), 3.89 (m, 1H, major), 4.31 (bq, 1H, minor rotamer), 4.56 (bq, 1H, major), 4.71 (bt, 1H, major rotamer), 4.93 (bt, 1H, minor), 5.22 (bd, 1H, major rotamer), 5.44 (bd, 1H, minor).
Z-(R)Cha-Pro-OSu
Prepared in the same way as Boc-(R)Cha-Pro-OSu from Z-(R)Cha-OH.
Boc-(R)Cha-Pic-OSu
(i) Boc-(R)Cha-Pic-OEt
Boc-(R)Cha-OH, 6.3 g (0.023 mol), was dissolved in 150 ml of CH 2 Cl 2 . The solution was cooled in an ice bath and 6.3 g (0.047 mol) of N-hydroxybenzotriazole and 11.2 g (0.0265 mol) of CME-CDI were added. The ice bath was removed after 15 min and the reaction mixture was stirred for 4 h at room temperature. The solvent was evaporated and the residue dissolved in 150 ml of DMF and cooled in an ice bath. H-Pic-OEt×HCl, 4.1 g (0.021 mol) was added and the pH adjusted to approximately 9 by addition of N-methylmorpholine. The ice bath was removed after 15 min and the reaction mixture was stirred for 3 days. The solvent was evaporated and the residue was dissolved in ethyl acetate and washed with dilute KHSO 4 (aq), NaHCO 3 (aq) and water. The organic layer was dried (Na 2 SO 4 ) and evaporated to give 7.7 g (89%) of Boc-(R)Cha-Pic-OEt which was used without further purification.
1 H-NMR (500 MHz, CDCl 3 , 2 rotamers, 3:1 ratio ) δ0.7-1.0 (m, 2H), 1.1-1.9 (m, 29H; thereof 1.28 (t, 3H)), 1.45 (bs, 9H), 2.01 (bd, 1H, major rotamer), 2.31 (bd, 1H), 2.88 (bt, 1H, minor), 3.30 (bt, 1H, major), 3.80 (bd, 1H, major), 4.15-4.3 (m, 2H), 4.5-4.7 (m, 2H, minor), 4.77 (bq, 1H, major), 4.90 (bd, 1H, minor), 5.28 (bd, 1H, major), 5.33 (bd,1H, major).
(ii) Boc-(R)Cha-Pic-OH
Boc-(R)Cha-Pic-OEt, 5.6 g (0.014 mol), was mixed with 100 ml of THF, 100 ml of water and 7 g of LiOH. The mixture was stirred at room temperature overnight. The THF was evaporated and the aqueous solution was acidified with KHSO 4 (aq) and extracted three times with ethyl acetate. The combined organic phase was washed with water, dried (Na 2 SO 4 ) and evaporated to give 4.9 g (94%) of Boc-(R)Cha-Pic-OH which was used without further purification. The compound can be crystallized from diisopropyl ether/hexane.
1 H-NMR (500 MHz, CDCl 3 , 2 rotamers, 3.5:1 ratio) δ0.8-1.1 (m, 2H), 1.1-2.1 (m, 27H; thereof 1.43 (s, 9H, major rotamer), 1.46 (s, 9H, minor)), 2.33 (bd, 1H), 2.80 (bt, 1H, minor), 3.33 (bt, 1H, major), 3.85 (bd, 1H, major), 4.57 (bd, 1H, minor), 4.68 (m, 1H, minor), 4.77 (bq, 1H, major), 5.03 (bs, 1H, minor), 5.33 (bd, 1H, major), 5.56 (m, 1H, major).
(iii) Boc-(R)Cha-Pic-OSu
Boc-(R)Cha-Pic-OH (1 g, 2.6 mmol) was dissolved in DMF (15 ml) at room temperature and then cooled to -18° C., a temperature which was maintained during the additions of the reactants. Hydroxy succinimid (0.60 g, 5.2 mmol) was added and the reaction mixture was stirred for a few minutes until the crystals were dissolved. Dicyclohexyl carbodiimid (0.56 g, 2.7 mmol) dissolved in DMF (10 ml) and precooled was added dropwise to the reaction mixture. After a few minutes at -18° C. the reaction mixture was put into a water bath at 20° C. for 2 h under stirring. The solvent was evaporated, ethyl acetate (40 ml) was added and the precipitated urea was filtered off.
The organic phase was washed once with water, twice with 0.3M KHSO 4 , twice with diluted NaHCO 3 , once with water, once with brine and dried (Na 2 SO 4 ). The solvent was evaporated and the product dried in vacuo to yield 1.16 g (93%) of the product. According to 1 H-NMR the product contained two diastereoisomers (epimers in Pic, S/R) in a ratio of 95/5.
1 H-NMR (300 MHz, CDCl 3 , major diastereomer) δ0.7-2.0 (m, 27H; thereof 1.46 (bs, 9H)), 2.29 (bd, 1H), 2.85 (bs, 4H), 3.40 (m, 1H), 4.5-4.8 (m, 1H), 5.1-5.4 (m, 1H), 5.70 (bd, 1H, major).
Boc-(R)Cha-Mor-OSu
Prepared in the same way as Boc-(R)Cha-Pic-OSu from H-Mor-OEt×HCl except that CH 3 CN was used as solvent instead of DMF in the formation of the OSu-ester.
Boc-(Me)(R)Cha-Pro-OSu
Prepared in the same way as Boc-(R)Cha-Pro-OSu from Boc-(Me)-(R)Cha-OH.
Boc-(Me)(R)Cha-Pic-OSu
Prepared in the same way as Boc-(R)Cha-Pic-OSu from Boc-(Me)(R)Cha-OH.
Boc-(R,S)Pro(3-Ph)-Pro-OSu
Prepared in the same way as Boc-(R)Cha-Pro-OSu from Boc-(R,S)Pro(3-Ph)-OH.
Boc-(R,S)Pro(3-(trans)Ph)-Pro-OSu
(i) Boc-(R,S)Pro(3-(trans)Ph)-Pro-OBn
To a slurry of 1.0 g of Boc-(R,S)Pro(3-(trans)Ph)-OH (3.43 mmol, 1 eq.), 1.04 g of H-Pro-OBn×HCl (4.29 mmol, 1.25 eq.), 0.04 g of HOBt (0.24 mmol, 0.07 eq.) in 15 ml DMF was added 1.83 g of CME-CDI (4.29 mmol, 1.25 eq.) and 0.525 ml of NMM (4.73 mmol, 1.38 eq.) at room temperature. After stirring an additional 4 days the solvent was evaporated and the residue taken up in 200 ml EtOAc. The organic phase was washed with 2×40 ml of H 2 O, 2×25 ml of 1M KHSO 4 , 2×25 ml of 1M NaOH, 2×25 ml of H 2 O and dried (MgSO 4 ). Evaporation of the solvent and flash chromathography (CH 2 Cl 2 /MeOH, 97/3) gave the pure product (44% yield) as a ca: 1:1 mixture of diastereomers.
(ii) Boc-(R,S)Pro(3-(trans)Ph)-Pro-OH
The benzyl ester from the previous step was removed by hydrogenation over 5% Pd/C in EtOH at atmospheric pressure for 4 h. Filtration and evaporation gave the pure product as a ca: 1:1 mixture of diastereomers in quantitative yield.
1 H-NMR (CDCl 3 , 500 MHz, two diastereomers each consisting of two rotamers): δ1.3-2.4 (m+4 s from the Boc groups, total 14H), 2.5-2.9 (m, total 1H), 3.2-3.9 (m, total 5H), 4.3-4.65 (m, total 2H), 7.2-7.5 (m, 5H).
(iii) Boc-(R,S)Pro(3-(trans)Ph)-Pro-OSu
Prepared according to the procedure described for Boc-(R)Cha-OSu from Boc-(R,S)Pro(3-(trans)Ph)-Pro-OH.
Boc-(R,S)Pro(3-(trans)Ch)-Pro-OSu
(i) Boc-(R,S)Pro(3-(trans)Ch)-Pro-OH
Boc-(R,S)Pro(3-(trans)Ph)-Pro-OH was hydrogenated over 5% Rh/Al 2 O 3 in methanol together with a stall amount of HOAc for 7 days at 0,34 Mpa. Filtration of the catalyst, evaporation of the solvent and flash chromatograpy (CH 2 Cl 2 /MeOH, 94/6) gave the pure product as a white solid (mixture or two diastereomers).
(ii) Boc-(R,S)Pro(3-(trans)Ch)-Pro-OSu
Prepared according to the procedure described for Boc-(R)Cha-OSu from Boc-(R,S)Pro(3-(trans)Ch)-Pro-OH.
Boc-(R)Hoc-Pro-OH
(i) Boc-(R)Hoc-OH
Boc-(R)Hop-OH, 3.2 g (11.46 mmol) was dissolved in methanol (75 ml). Rhodium on activated aluminium oxide (Rh/Al 2 O 3 ), 0,5 g was added and the mixture stirred in hydrogen atmosphere at 0.41 MPa for 18 h. The catalyst was filtered off through celite and the solvent evaporated giving the product in almost quantitative yield.
1 H-NMR (500 MHz, CDCl 3 ): δ0.90 (m, 2H), 1.08-1.33 (m, 6H), 1.43 (s, 9H), 1.60-1.74 (m, 6H), 1.88 (bs, 1H), 4.27 (bs, 1H).
(ii) Boc-(R)Hoc-OSu
Prepared in the same way as described for Boc-(R)Cha-OSu from Boc-(R)Hoc-OH.
(iii) Boc-(R)Hoc-Pro-OH
Prepared in the same way as described for Boc-(R)Cha-Pro-OH from Boc-(R)Hoc-OSu.
1 H-NMR (500 MHz, CDCl 3 ): δ0.80-0.94 (m, 2H), 1.05-1.36 (m, 7H), 1.36-1.48 (bs, 9H), 1.48-1.78 (m, 7H), 1.98-2.14 (m, 2H), 2.34 (m, 1H), 3.48 (m, 1H), 3.85 (m, 1H), 4.43 (m, 1H), 4.52 (bd, 1H), 5.26 (bd, 1H), signals of a minor rotamer appears at: δ1.92, 2.25, 3.58, 4.20 and 4.93.
Boc-(R)Hoc-Pic-OH
(i) Boc-(R)Hoc-Pic-OMe
Prepared the same way as described for Boc-(R)Cha-Pic-OEt from Boc-(R)Hoc-OH and H-Pic-OMe×HCl.
(ii) Boc-(R)Hoc-Pic-OH
Prepared in the same way as described for Boc-(R)Cha-Pic-OH from Boc-(R)Hoc-Pic-OMe.
1 H-NMR (500 MHz, CDCl 3 ): δ0.82-0.97 (m, 2H), 1.10-1.36 (m, 7H), 1.36-1.50 (bs, 9H), 1.50-1.82 (m, 11H), 2.35 (bd, 1H) 3.28 (bt. 1H), 3.85 (bd, 1H) 4,63 (m, 1H), 5.33 (bs, 1H), 5.44 (bd, 1H), signals of a minor rotameter appears at: δ1.88, 2.80, 4.25, 4.55 and 4.97.
Boc-(R)Cha-Aze-OH
Prepared in the same way as described for Boc-(R)Cha-Pic-OH from H-Aze-OEt×HCL.
Boc-(R)Cha-Pic(4-(S)Me)-OH
Prepared in the same way as described for Boc-(R)Cha-Pic-OH from H-Pic(4-(S)Me)-OEt×HCl except that CH 2 Cl 2 was used as solvent.
Boc-(R)Cha-(R)Pic(4-(R)Me)-OSu
(i) Boc-(R)Cha-(R)Pic(4-(R)Me)-OEt
Prepared in the same way as described for Boc-(R)Cha-Pic-OEt from H-(R)Pic(4-(R)Me)-OEt×HCl.
(ii) Boc-(R)Cha-(R)Pic(4-(R)Me)-OH
Prepared by using the deprotection (e) on the product (i) above.
(iii) Boc-(R)Cha-(R)Pic(4-(R)Me)OSu
Prepared in the same way as described for Boc-(R)Cha-Pic-OSu from Boc-(R)Cha-(R)Pic(4-(R)Me)-OH.
Boc-(R)Cha-(R,S)Pic(4,5-dehydro)-OH
Prepared according to the procedure described for Boc-(R)Cha-Pic-OH from H-(R,S)Pic(4,5-dehydro)-OEt.
Boc-(R)Cgl-Pic-OH
(i) Boc-(R)Cgl-Pic-OMe
Pivaloyl chloride (1.000 mL, 8.1 mmol) was added to a solution of Boc-(R)Cgl-OH (2.086 g, 8.1 mmol) and triethyl amine (1.13 mL, 8.1 mmol) in toluene (25 mL) and DMF (5 mL). A mixture of H-Pic-OMe×HCl (1.46 g, 8.1 mmol) and triethyl amine (1.13 mL, 8.1 mmol) in DMF (20 mL) was subsequently added at ice bath temperature. The reaction mixture was slowly allowed to warm up to room temperature and after 24 h it was diluted with water and extracted with toulene. After washing with 0.3M KHSO 4 , 10% Na 2 CO 3 and brine the solvent was removed in vacuo to give 2.52 g (81%) of colorless oil which was used without further purification.
1 H-NMR (500 MHz, CDCl 3 , 2 rotamers, 5:1 ratio) δ0.8-1.8 (m, 25H), 2.25 (d, 1H), 2.75 (t, 1H, minor rotamer), 3.3 (t, 1H), 3.7 (s, 3H), 3.85 (d, 1H), 4.3 (t, 1H, mincr rotamer), 4.5-4.6 (m, 1H), 5.25 (d, 1H), 5.30 (d, 1H).
(ii) Boc-(R)Cgl-Pic-OH
Prepared according to the procedure for hydrolysis of Boc-(R)Cha-Pic-OEt using the product from (i) above. The product was crystallized from di-isopropyl ether and hexane.
1 H-NMR (500 MHz, CDCl 3 , 2 rotamers, 5:1 ratio) δ0.8-1.8 (m, 25H), 2.3 (d, 1H), 2.8 (t, 1H, minor rotamer), 3.3 (t, 1H), 3.9 (d, 1H), 4.4 (t, 1H, minor), 4.5-4.6 (m, 1H), 5.1 (s, 1H, minor rotamer), 5.3 (d, 1H), 5.40 (d, 1H).
Boc-(R)Dph-Pic-OH
Prepared in the same way as described for Boc-(R)Cha-Pic-OH from Boc-(R)Dph-OH.
Boc-(R)Dch-Pic-OH
Prepared in the same way as described for Boc-(R)Cha-Pic-OH from Boc-(R)Dch-OH.
Boc-(R)Cha-Pro(5-(S)Me)-OH
Prepared in the same way as described for Boc-(R)Cha-Pic-OH from H-Pro(5-(S)Me)-OMe.
Boc-Nag(Z)
(i) N-Bensyloxycarbonyl-O-methyl isourea
To a stirred solution of concentrated aqueous NaOH (2.8 L, 50% w/w, 19.1M, 53 mol) and water (32 L) at 18° C. was added in two portions O-methylisourea hemisulphate (1.7 kg, 94%, 13.0 mol) and 0-methylisourea hydrogensulphate (1.57 kg, 99%, 9.0 mol). The reaction mixture was cooled to 3°-50° C. Benzyl chloroformiate (3.88 kg, 92%, 20.9 mol) was added over a 20 minutes period under cooling and vigorous stirring. The reaction temperature went from 3° to 8° C. during the addition of Z-Cl. The addition funnel was rinsed with 5 liters of water which was added to the reactor. The reaction mixture was stirred at 0°-3° C. for 18 h, filtered and the crystals was washed with cooled (3° C.) water (10 L). Vacuum drying 25° C., 10-20 mbar) for 48 h gave 3.87 kg (89%) of the title compound as a white crystalline powder.
(ii) Boc-Nag(Z)
To a stirred solution Boc-NH-(CH 2 ) 3 -NH 2 ×HCl (prepared according to Mattingly P. G., Synthesis, 367 (1990)) (3.9 kg, 18.5 mol) in iso-propanol (24 kg) at 60°-70° C. was added in portions over a 30 minutes period KHCO 3 (4.2 kg, 42 mol). A slow evolution of CO 2 (g) occurs. The mixture was stirred for another 30 minutes followed by addition in portions over a 30 minutes period N-bensyloxycarbonyl-O-methyl isourea (3.74 kg, 18.0 mol). The reaction mixture was stirred at 65°-70° C. for 16 h, cooled to 20° C. and filtered. The precipitate was washed with iso-propanol (10+5 L). The combined filtrates was concentrated at reduced pressure keeping the heating mantle not warmer than 65°-70° C. When approximately 45 liters was distilled off EtOAc (90 L) was added. The reaction mixture was cooled to 20°-25° C., washed with water (10 and 5 L) and brine (5 L), and dried with Na 2 SO 4 (2 kg). After stirring the reaction mixture was filtered and the filter cake was washed with EtOAc (11 and 7 L). The combined filtrates were concentrated at reduced pressure keeping the heating mantle not warmer than 40°-50° C. When approximately 90 liters of EtOAc was distilled off, toluene (25 L) was added and the evaporation continued.
After collection of approximately another 18 liters of destillate, toulene (20 L) was added under vigorous stirring and the resulting mixture was cooled to -1° to 0° C. and gently stirred over night (17 h). The crystal slurry was filtered and the product was washed with cooled toluene (10 and 5 L). Vacuum drying (10-20 mbar, 40° C.) for 24 h gave 4.83 kg (13.8 mol, 76%) of Boc-Nag(Z).
1 H-NMR (300 MHz, CDCl 3 ): δ1.41 (s, 9H), 1.6-1.7 (m, 2H), 3.0-3.3 (m, 4H), 4.8-5.0 (bs, 1H), 5.10 (s, 2H), 7.2-7.4 (m, 5H).
Boc-Agm(Z)
(i) Boc-Agm
To a slurry of 14.95 g (65.5 mmol, 1 eq.) of agmatine sulphate (Aldrich), 13.7 ml of Et 3 N (98.25 mmol, 1.5 eq.), 165 ml of H 2 O and 165 ml of THF was added 21.5 g (98.25 mmol, 1.5 eq.) of (Boc) 2 O during 5 minutes at room temperature. The mixture was stirred vigorously over night, evaporated to dryness and the residue was washed with 2×100 ml of Et 2 O to give Boc-Agm as a white powder which was used without further purification in the next step.
(ii) Boc-Agm(Z)
To a cold (+5° C.) slurry of the crude Boc-Agm from the previous step (ca: 65.5 mmol) in 180 ml of 4N NaOH and 165 ml of THF was added 24 ml (169 mmol, 2.5 eq) of benzyl chloroformate during 10 minutes. After stirring at room temperature for 4 h methanol (150 ml) was added and the stirring was continued for an additional 20 h at room temperature. The organic solvent was evaporated and 200 ml of H 2 O was added to the residue. The basic water phase was extracted with 1×300 ml and 2×200 ml of EtOAc. The combined organic phases was washed with H 2 O (2×100 ml), brine (1×100 ml) and dried (MgSO 4 ). Evaporation of the solvent and flash chromathography (CH 2 Cl 2 /MeOH, a stepwise gradient of 97/3, 95/5 and 9/1 was used) gave 14.63 g (58%) of pure Boc-Agm(Z) as a white powder.
1 H-NMR (CDCl 3 , 500 MHz): δ1.35-1.40 (m, 2H), 1.45 (s, 9H), 1.5-1.6 (m, 2H), 3.0-3.2 (m, 4H), 4.65 (bs, 1H), 5.1 (s, 2H) 7.25-7.40 (m, 5H).
13 C-NMR (CDCl 3 , 75.5 MHz) δ25.44, 27.36, 28.21, 65.83, 79.15, 127.47, 127.66, 128.14, 137.29, 156.47, 161.48, 163.30.
Boc-NH-(CH 2 ) 3 -N 3
Prepared according to the method described by Mattingly P. G., in Synthesis 1990, 367.
Z--NH--(CH 2 ) 2 --NH 2
To a cold solution of 6 g ethylene diamine (0.1 mol) and 22 ml triethyl amine in 20 ml of chloroform was added 2.5 g of Z-OSu dissolved in 5 ml of chloroform. The mixture was allowed to reach room temperature and left over night under stirring. Filtration, evaporation of the solvent and flash chromatography (CH 2 Cl 2 /MeOH(NH 3 -saturated), 95/5) gave 0.9 g (46%) of the title compound.
1 H-NMR (300 MHz, CDCl 3 ): δ1.27 (s, 2H), 2.85 (t, 2H), 3.24 (q, 2H), 5.14 (s, 2H), 7.22-7.40 (m, 5H).
Agm×HCl
Prepared from Agm×H 2 SO 4 (Aldrich) by exchanging the hydrogen sulphate ion for chloride on an ion exchange column.
H-Nag(Z)×2 HCl
Prepared by bubbling HCl(e) into a solution of Boc-Nag(Z) in EtOAc followed by evaporation of the solvent.
BnOOC--CH 2 --NH--CO--CH 2 --Br
To a solution of p-TsOH×H-Gly-OBn (5 mmol) and triethyl amine (5 mmol) in 10 ml of CH 2 Cl 2 was added 2-bromoacetic acid (5 mmol) dissolved in 10 ml of CH 2 Cl 2 and dicyclohexyl carbodiimide (5 mmol). The mixture was stirred at room temperature over night and filtered. The organic phase was washed twice with 0.2M KHSO 4 , 0.2M NaOH, brine and dried. Evaporation and flash chromatography (CH 2 Cl 2 /MeOH, 95/5) gave a quantitative yield of the desired compound.
1 H-NMR (300 MHz, CDCl 3 ): δ=3.89 (s, 2H), 4.05-4.11 (d, 2H), 5.19 (s, 2H), 7.06 (bs, 1H), 7.3-7.4 (m, 5H)
BnOOC--CH 2 --OCO--CH 2 --Br
A mixture of 2.8 g (0.020 mmol) bromoacetic acid, 4.2 g (0.020 mmol) of benzyl bromoacetate and 2.0 g (0.020 mmol) of triethylamine in 25 ml of EtOAc was refluxed for 3 h. It was diluted with more EtOAc and cooled. The solution was washed with dilute HCl and thereafter with NaHCO 3 (aq) and finally with water. Drying (Na 2 SO 4 ) and evaporation followed by flash chromatography (heptane/etylacetate, 75/25) gave the title compound in 26% yield.
1 H-NMR (500 MHz, CDCl 3 ): δ3.95 (s, 2H), 4.75 (s, 2H), 5.23 (s, 2H), 7.35-7.45 (m, 5H).
BnO-(CH 2 ) 3 -OTf
Propanediol monobenzyl ether (0.83 g, 5 mmol) was dissolved in dry pyridine (0.6 g, 7 mmol) and dichloromethane (20 ml) and cooled to -15° C. Triflic anhydride, precooled to -15° C., was added and the reaction mixture stirred for 45 min under which the temperature was allowed to rize to 15° C. The solvent was evaporated and the product dissolved in hexane/ethyl-acetate 4:1 (10 ml) and filtered through silica.
Finally the solvent was evaporated and the product dried in vacuo to yield 0.95 g (64%) of 1-benzyloxy 3-trifluoromethanesulfonylpropane which was used directly (see Example 21).
1 H-NMR (500 MHz, CDCl 3 ): δ2.12 (m, 2H), 3.6 (t, 2H), 4.51 (s, 2H), 4.72 (t,2H), 7.22-7.42 (m, 5H).
BnO--(CH 2 ) 2 --CHO
Prepared by Swern oxidation (described by D. Swern et al., J. Org. Chem., 1978, 2480-82) of BnO--(CH 2 ) 3 --OH.
1 H-NMR (300 MHz, CDCl 3 ): δ2.63 (dt, 2H), 3.80 (t, 2H), 4.51 (s, 2H), 7.30 (m, 5H), 9.76 (bt, 1H).
Br--(S)CH(CH 2 OBn)--COOBn
(i) Br--(S)CH(CH 2 OBn)--COOH
O-Benzylserine (3.9 g, 19 mmol) in water (10 ml) was added to a solution of sodium bromide (11 g, 107 mmol) in water (20 ml) and sulphuric acid (2 g, 20 mmol). The reaction mixture was cooled to -10° C. and NaNO 2 (1.73 g, 25 mmol) was added under vigorous stirring. Another portion of water was added to the thick mixture followed, after a few minutes, by H 2 SO 4 (1 g, 10 mmol). The mixture was stirred at ambient temperature over night after which it was extracted twice with EtOAc (100 ml). The combined organic phase was washed twice with water and once with brine and dried (Na 2 SO 4 ). Evaporation of the solvent gave 3.7 g (75%) of the title compound as a yellow oil which was pure enough to use directly in the next step.
(ii)Br--(S)CH(CH 2 OBn)--COOBn
To a solution of the crude product from (i) above (2.6 g, 10 mol) in dry benzene (25 ml) was added oxalyl chloride (2.6 g, 20.5 nmol) and molecular sieves (4 Å, 1 g). The mixture as stirred at ambient temperature under an atmosphere of Argon for 18 h. The molecular sieves was removed by filtration and the solvent evaporated. The slightly yellow residue was dissolved in CH 3 CN (10 ml) and benzyl alcohol (1 g, 9.2 mmol) was added. The mixture was stirred at ambient temperature for 5 h. The solvent was evaporated and the residue dissolved in Et 2 O and washed once with 1M NaOH, water, brine and dried (Na 2 SO 4 ) Evaporation of the solvent followed by flash chromatography (CH 2 Cl 2 /MeOH, 95/5) gave 1.8 g (67%) of the desired compound.
1 H-NMR (500 MHz, CDCl 3 ): δ3.82 (dd, 1H), 3.99 (dd, 1H), 4.38 (dd, 1H), 4.56 (s, 2H), 5.23 (s, 2H), 7.23-7.46 (m, 5H).
WORKING EXAMPLES
Example 1
H-(R)Cha-Pro-Agm×2 HOAc
(i) Boc-(R)Cha-Pro-Agm×HOAc
Boc-(R)Cha-Pro-OSu (1.7 mmol) and agmatine dihydrochloride (2.0 mmol, 1.18 eq) was dissolved in DMF/H 2 O 95:5 (35 ml). Triethylamine was added to adjust the pH to about 10 and the solution was stirred at room temperature for 2 days. The solution was evaporated (5 mm Hg/ 60° C.) until dryness and the crude product was purified by RPLC (CH 3 CN/NH 4 OAc (0.1M), 38:62). The desired compound was obtained as a white powder after freeze-drying.
1 H NMR (500 MHz, CDCl 3 /DMSO-d 6 5:2, Two rotamers, 9:1 δ (major rotamer): 0.75-0.90 (m, 2H), 1.1-2.05 (m, 19H), 1.35 (s, 9H) 2.98-3.14 (m, 4H), 3.37 (q,1H), 3.76 (m, 1H), 4.20 (m,1H), 4.33 (dd, 1H), 6.30 (d, 1H), 7.05-7.80 (broad m, 5H), 8.67 (broad d, 1H).
Exchange broadened signals of the minor rotamer are unambiguously observed at δ3.44 (m, 1H), 3.62 (m, 1H), 4.10 (m, 1H), 4.64 (m, 1H), 5.56 (d, 1H), 9.08 (m, 1H)
(ii) H-(R)Cha-Pro-Agm×2 HOAc
A solution of Boc-(R)Cha-Pro-Agm (0.2 mmol) in TFA (2 ml) was stirred at room temperature for 4.5 h. The solvent was evaporated and the remaining oil was subjected to RPLC (CH 3 CN/NH 4 OAc (0.1M), 25:75). The diacetate salt was obtained as a white powder after repeated freeze-drying.
1 H NMR (500.13 MHz, D 2 O): δ0.80-0.95 (m, 2H), 1.00-1.21 (m, 3H), 1.32 (m, 1H), 1.40-1.78 (m,12H), 1.83-2.00 (m, 2H), 1.90 (s, acetate), 2.20(m, 1H), 3.06-3.14(m. 4H), 3.50(m, 1H), 3.67(m, 1H), 4.20-4.30(m, 2H).
13 C NMR (75.6 MHz, D 2 O): guanidine: δ157.4; carbonyl carbons: δ169.9, 174.5.
Example 2
Me-(R)Cha-Pro-Agm×2 HOAc
(i) Boc-(Me)(R)Cha-Pro-Agm
To a solution of 479.6 mg (1 mmol, 1 eq.) of Boc-(Me)(R)Cha-Pro-OSu and 500 ml of NMM in 16 ml DMF/H 2 O (15/1) was added 166.5 mg (1.2 mmol, 1.2 eq.) of Agm×HCl at room temperature. The reaction was stirred an additional 70 h and the solvent was evaporated to give a crude product as an oil. This was used without purification in the next step.
(ii) Me-(R)Cha-Pro-Agm×2 HOAc
The crude oil from the previous step was dissolved in 10 ml TFA/CH 2 Cl 2 (1:4) at room temperature. After stirring for 2 h 25 min the solvent was evaporated and the crude product was purified with RPLC (CH 3 CN/NH 4 OAc(0.1M), 35/65) to give the desired product as a white powder after freeze-drying.
1 H-NMR (500 MHz, D 2 O): δ0.93-1.05 (m, 2H), 1.10-1.29 (m, 3H), 1.33-1.43 (m, 1H), 1.50-1.80 (m, 12H), 1.88-2.10 (m, 2H, 1.92 (s, acetate), 2.27-2.36 (m, 1H), 2.68 (s, 3H), 3.15-3.23 (m, 3H), 3.24-3.31 (m, 1H), 3.57-3.66 (m, 1H), 3.76-3.83 (m, 1H), 4.28 (t, 1H), 4.39 (dd, 1H).
13 C-NMR (125.76 MHz, D 2 O): guanidine: δ157.24; carbonyl carbons: δ174.03, 168.24.
Example 3
HO-(CH 2 ) 3 -(R)Cha-Pro-Agm×2 HCl
(i) Boc-(R)-Cha-Pro-Agm(Z)
Boc-Agm(Z) (1 eq) was dissolved in TFA/CH 2 Cl 2 (1:4, ca: 6 ml/mmol) and stirred at room temperature for ca: 2 h. The solvent was evaporated and the product dissolved together with Boc-(R)Cha-Pro-OSu (1 eq) in DMF (ca: 1 ml/mmol), the pH was adjusted with NMM to ca: 9 and the mixture was stirred at room temperature for 20 h. The solvent was evaporated in vacuo, the crude product dissolved in CH 2 Cl 2 and washed three times with water and once with brine. After drying (sodium sulphate) the solvent was evaporated and the product flash chromatographed (CH 2 Cl 2 /MeOH) affording Boc-(R)Cha-Pro-Agm(Z) as a white powder.
(ii) H-(R)Cha-Pro-Agm(Z)
Boc-(R)Cha-Pro-Agm(Z) was dissolved in TFA/CH 2 Cl 2 (1:4, ca: 6 ml/mmol) and stirred at room temperature for 2 h. The solvent was evaporated, the product dissolved in 0.2M NaOH (20 ml/mmol) and extracted twice with dichloromethane. The organic layers were combined and washed with brine, dried (sodium sulphate) and the solvent evaporated to yield H-(R)Cha-Pro-Agm(Z) as a white powder.
(iii) BnO-(CH 2 ) 3 -(R)Cha-Pro-Agm(Z)
H-(R)Cha-Pro-Agm(Z) (1 mmol) was dissolved in methanol (10 ml). Triethylammonium hydrochloride (1 mmol), sodium cyanoborohydride (0.7 mmol) and thereafter BnO--(CH 2 ) 2 --CHO (1.05 mmol) were added and the reaction mixture stirred at room temperature over night. The solvent was evaporated and the crude product was dissolved in ethyl acetate, washed twice with water, once with brine and dried over sodium sulphate. The solvent was evaporated and the crude product was purified by flash chromatography (EtOAc/MeOH).
(iv) HO-(CH 2 ) 3 -(R)Cha-Pro-Agm×2 HCl
Prepared by using deprotection procedure (d) on the product (iii) above.
1 H-NMR (500 MHz, D 2 O): δ0.72 (m, minor rotamer), 0.84 (m, minor rotamer), 0.87-1.03 (m, 2H), 1.03-1-26 (m, 3H), 1.28-1.40 (bs, 1H), 1.44-1.80 (m, 11H), 1.80-1.95 (bs, 3H), 1.95-2.10 (bs, 2H), 2.28 (m, 1H), 3.04 (m, 1H), 3.08-3.27 (m, 5H), 3.58 (bs, 1H), 3.67 (bs, 2H), 3.78 (m, 1H), 4.12 (bd, minor rotamer), 4.30 (m,1H), 4.37 (m, 1H).
13 C-NMR (125 MHz, D 2 O): guanidine: δ157.26; carbonyl carbons: δ174.06, 168.36.
Example 4
HOOC-CH 2 -(R)Cha-Pro-Agm×HOAc
General Procedure for the alkylation of the N-terminal.
This procedure is described in more general terms and will be referred to in the Examples below together with the alkylating agent used in each specific Example.
The peptide to be alkylated (1 eq) and the alkylating agent (1.1-1.2 eq) were dissolved in acetonitrile (ca 10 ml/mmol). Potassium carbonate (2.0-2.2 eq) was added and the reaction mixture stirred at 50°-60° C. until the starting material was consumed (TLC, usually 1-5 h). Filtration, evaporation of the solvent and flash chromatography (CH 2 Cl 2 /MeOH, CH 2 Cl 2 /MeOH(NH 3 -saturated) or EtOAc/MeOH, ca 9/1) gave the alkylated product after evaporation of the solvent.
(i) BnOOC-CH 2 -(R)Cha-Pro-Agm(Z)
Prepared from H-(R)Cha-Pro-Agm(Z) (See Example 3) and Br--CH 2 COOBn according to the procedure described above.
(ii) HOOC-CH 2 -(R)Cha-Pro-Agm×HOAc
Prepared by using the deprotection procedure (b) on the product (i) above.
1 H-NMR (300 MHz, MeOD): δ0.9-1.1 (m, 2H), 1.1-2.3 (m, 19H) 1.95 (s, acetate), 3.1-3.2 (m, 4H), 3.2-3.65 (m, 3H), 3.85 (m, 1H), 4.0 (bt, 1H), 4.35 (dd, 1H).
13 C-NMR (75 MHz, D 2 O): guanidine: δ157.55; carbonyl carbons: δ168.71, 171.37 and 174.3.
Example 5
i Pr-OOC-CH 2 -(R)Cha-Pro-Agm×HOAc
Alkylation as in Example 4 using H-(R)Cha-Pro-Agm(Z) (See Example 3) and Br--CH 2 COO i Pr followed by deprotection procedure (b) gave the title compound.
1 H-NMR (500 MHz, MeOD): δ0.85-1.05 (m, 2H), 1.1-1.35 (m, 9H; thereof 1.23 (d, 3H), 1.25 (d, 3H)), 1.35-2.02 (m, 14H) 1.92 (s, acetate), 2.08 (m, 1H), 2.2 (m, 1H), 3.07-3.45 (m, 6H), 3.55 (m, 1H), 3.7-3.8 (m, 2H), 4.3 (dd, 1H), 5.05 (m, 1H)
13 C-NMR (125 MHz, D 2 O): guanidine: δ157.39; carbonyl carbons: δ171.10, 172.76 and 174.44.
Example 6
HOOC-CH 2 -(Me)(R)Cha-Pro-Agm×2 TFA
(i) Me-(R)Cha-Pro-Agm(Z)
Prepared from Boc-(Me)(R)Cha-Pro-OSu in the same way as described for H-(R)Cha-Pro-Agm(Z) in Example 3.
(ii) HOOC-CH 2 -(Me)(R)Cha-Pro-Agm×2 TFA
Alkylation as in Example 4 using Me-(R)Cha-Pro-Agm(Z) and Br--CH 2 COOBn followed by deprotection procedure (b) gave the title compound.
1 H-NMR (300 MHz, D 2 O): δ0.9-1.35 (m, 6H), 1.5-2.2 (m, 14H), 2.25-2.45 (m, 1H), 3.12 (s, 3H), 3.15-3.35 (m, 4H), 3.6-3.75 (m, 1H), 3.8-3.95 (m, 1H), 4.22 (apparent bs, 2H), 4.45 (m, 1H), 4.6 (bt, 1H).
13 C-NMR (75.47 MHz, D 2 O): guanidine: δ157.52; carbonyl carbons: δ173.86, 168.79, 167.38.
Example 7
HOOC-(R,S)CH(Me)-(R)Cha-Pro-Agm×HOAc
Alkylation as in Example 4 using H-(R)Cha-Pro-Agm(Z) (See Example 3) and Br--CH(Me)COOBn followed by deprotection procedure (a) gave the title compound as a mixture of two diastereomers.
Example 8
HOOC-(RorS)CH(Me)-(R)Cha-Pro-Agm/a×HOAc
Obtained by separating the diastereomers formed in Example 7 using RPLC (CH 3 CN/NH 4 OAc (0.1M), 1/4). This diastereomer came out first of the two from the column.
1 H-NMR (500 MHz, D 2 O; 2 rotamers ca: 5:1 ratio): δ0.74 (m, minor rotamer), 1.01 (m, 2H), 1.10-1.33 (m, 3H), 1.48-1.88 (m, 15H; thereof 1.51 (d, 3H)), 1.92-2.12 (m, 3H) 1.96 (s, acetate), 2.30 (m, 1H), 3.20 (m, 3H), 3.38 (m, 1H), 3.47 (q, minor rotamer), 3.53-3.68 (m, 2H), 3.73 (m, 1H), 4.20 (d, minor rotamer), 4.33 (m, 1H), 4.38 (m, 1H), 4.51 (d, minor rotamer).
13 C-NMR (125 MHz, D 2 O): guanidine: δ157.38; carbonyl carbons: δ174.11, 173.45, 168.64.
Example 9
HOOC-(RorS)CH(Me)-(R)Cha-Pro-Agm/b×HOAc
The diastereomer that came out after the first one from the column in the separation in Example 8 is the title compound above.
1 H-NMR (500 MHz, D 2 O, 2 rotamers ca 9:1 ratio): δ0.88 (m, minor rotamer), 1.05 (m, 2H), 1.12-1.33 (m, 3H), 1.42 (bs, 1H), 1.50-1.88 (m, 15H; thereof 1.55 (d, 3H)), 1.93-2.13 (m, 3H) 1.95 (s, acetate), 2.30 (m, 1H), 2.40 (m, minor rotamer), 3.22 (t, 2H), 3.28 (t, 2H), 3.64 (m, 1H), 3.70 (q, 1H), 3.98 (t, minor rotamer), 4.35 (t, 1H), 4.41 (dd, 1H).
Example 10
HOOC-(RorS)CH( n Pr)-(R)Cha-Pro-Agm/a×HOAc
Alkylation as in Example 4 using H-(R)Cha-Pro-Agm(Z) (See Example 3) and Br--CH( n Pr)COOEt and deprotection procedure (e) followed by deprotection procedure (b) gave HOOC-(R,S)CH( n Pr)-(R)Cha-Pro-Agm. The title compound was obtained by separating the diastereomers by RPLC (CH 3 CN/NH 4 OAc (0.1M), 1/4) and freeze drying (H 2 O) after evaporation of the solvent. This diastereomer came out first of the two from the column.
1 H-NMR (300 MHz, MeOD): δ0.8-1.1 (m, 5H; thereof 0.92 (t, 3H)), 1.1-2.1 (m, 22H) 1.95 (s, acetate), 2.2 (m, 1H), 3.1-3.35 (m, 5H), 3.48 (m, 1H), 3.88 (m, 1H), 4.0 (m, 1H), 4.4 (dd, 1H).
13 C-NMR (75 MHz, D 2 O): guanidine: δ157.50; carbonyl carbons: δ168.55 and 174.16.
Example 11
HOOC-(RorS)CH( n Pr)-(R)Cha-Pro-Agm/b×HOAc
The other diastereomer from the separation in Example 10 which came out after the first one from the column is the title compound above.
1 H-NMR (500 MHz, MeOD): δ0.85-1.05 (m, 5H; thereof 0.95 (t, 3H)) 1.1-2.08 (m, 22H) 1.9 (s, acetate), 2.14 (m, 1H), 3.1-3.4 (m, 5H), 3.45 (m, 1H), 3.62 (m, 1H), 3.80 (m, 1H), 4.34 (dd, 1H).
13 C-NMR (75 MHz, D 2 O): guanidine: δ157.53; carbonyl carbons: δ169.01 and 174.27.
Example 12
HOOC-(RorS)CH(Ph)-(R)Cha-Pro-Agm/b×HOAc
(i) t BuOOC-(RorS)CH(Ph)-(R)Cha-Pro-Agm(Z)
A mixture of H-(R)Cha-Pro-Agm(Z) (See Example 3) (0.55 mmol), tert.butyl-(R,S)phenyl bromoacetate (0.66 mmol), K 2 CO 3 (1.4 mmol) in CH 3 CN (10 ml) was stirred at room temperature for 28 h and an additional 5 h at 60° C. The diastereomeric mixture (ca: 3:1, according to NMR) was filtered and evaporated. The remaining oil was twice subjected to flash chromatography (CH 2 Cl 2 /MeOH, 92/8), which resulted in a complete separation of the two diastereomers (R f =0.36 (minor isomer) and 0.27 (major isomer), respectively).
1 H NMR of major isomer (500.13 MHz, CDCl 3 ): δ0.79 (quart,1H), 0.90 (quart,1H), 1.06-1.70 (m, H), 1.37 (s,9H), 1.85-2.03 (m,3H), 2.20 (m,1H), 3.10-3.24 (m,3H), 3.25-3.38 (m,2H), 3.42 (m,1H), 3.53 (m,1H), 4.30 (s,1H), 4.49 (dd,1H), 5.08 (s,2H), 7.19-7.40 (m,10H); broad NH signals are observed in the region 6.7-8.6.
(ii) HOOC-(RorS)CH(Ph)-(R)Cha-Pro-Agm/b×HOAc
The major isomer (50 mmol) and thioanisole (0.5 mmol) dissolved in TFA was kept at room temperature for 8 h. After evaporation (0.1 mm Hg) for 5 h, the remaining oil was purified on RPLC (CH 3 CN/NH 4 OAc (0.1M), 2:3) to give the title compound after evaporation of the solvent and freeze-drying.
1 H NMR (500.13 MHz, MeOD): δ0.85-1.01 (m, 2H), 1.13-1.38 (m, 4H), 1.53-2.05 (m, 14H), 1.92 (s, acetate) 2.18 (m, 1H), 3.08-3.26 (m, 3H), 3.32-3.45 (m, 2H), 3.64 (m, 1H), 3.93 (t, 1H), 4.37 (dd, 1H), 4.43 (s,1H), 7.28-7.50 (m, 5H).
13 C NMR (125.6 MHz, MeOD): guanidine: δ158.7; carbonyl carbons: δ173.8, 174.7, 177.0.
Example 13
HOOC-(R,S)CH(CH 2 CH 2 Ph)-(R)Cha-Pro-Agm×HOAc
Alkylation as in Example 4 using H-(R)Cha-Pro-Agm(Z) (See Example 3) and Br--CH(CH 2 --CH 2 --Ph)COOEt and deprotection procedure (a) followed by deprotection procedure (e) gave HOOC-(R,S)CH(CH 2 -CH 2 -Ph)-(R)Cha-Pro-Agm.
Example 14
HOOC-(RorS)CH(CH 2 CH 2 Ph)-(R)Cha-Pro-Agm/a×2 TFA
The title compound was obtained by separating the diastereomers obtained in Example 13 by RPLC (CH 3 CN/NH 4 OAc (0.1M), 2/3) and freeze drying (H 2 O TFA) after evaporation of the solvent. This diastereomer came out first of the two from the column is the title compound above.
1 H-NMR (500 MHz, MeOD): δ0.93-1.11 (m, 2H), 1.24 (m, 1H), 1.29-1.40 (m, 2H), 1.52-1.85 (m, 11H), 1.89-2.11 (m, 4H), 2.14-2.32 (m, 3H), 2.83 (t, 2H), 3.14 (t, 2H), 3.24 (t, 2H), 3.50 (q, 1H), 3.70 (m, 1H), 4.00 (t, 1H), 4.36-4.42 (m, 2H), 7.17-7.31 (m, 5H).
13 C-NMR (125 MHz, MeOD): guanidine: δ158.66; carbonyl carbons: δ168.08, 171.53, 174.16.
Example 15
HOOC-CH 2 -CH 2 -(R)Cha-Pro-Agm×HOAc
(i) BnOOC-CH 2 -CH 2 -(R)Cha-Pro-Agm(Z)
Benzyl acrylate (1.1 eq) and H-(R)Cha-Pro-Agm(Z) (See Example 3) (1 eq) were dissolved in ethanol (20 ml/mmol) and stirred at room temperature for 20 h. The solvent was evaporated and the crude product purified by flash chromatography (CH 2 Cl 2 /MeOH(NH 3 -saturated), 95/5). Finally the solvent was evaporated and the product dried in vacuo.
1 H-NMR (500 MHz, CDCl 3 ): δ0.7-0.95 (m, 2H), 1.0-1.5 (m, 10H), 1.5-1.75 (m, 5H), 1.75-1.92 (m, 2H), 2.0 (m, 1H), 2.17 (bs, 1H), 2.45 (m, 2H), 2.63 (m, 1H), 2.79 (m, 1H), 2.97-3.25 (m, 4H), 3.33 (m, 2H), 3.52 (bt, 1H), 4.45 (bd, 1H), 4.95-5.12 (m, 4H), 7.13-7.4 (m, 10H).
(ii) HOOC-CH 2 -CH 2 -(R)Cha-Pro-Agm×HOAc
Prepared by using the deprotection procedure (a) on the product (i) above.
1 H-NMR (500 MHz, D 2 O): δ0.88 (m, 2H), 1.00-1.23 (m, 3H), 1.33 (bs, 1H), 1.42-1.72 (m, 11H), 1.78-2.00 (m, 3H) 1.94 (s, acetate), 2.18 (m, 1H), 2.52 (m, 2H), 3.03-3.20 (m, 6H), 3.50 (m, 1H), 3.72 (m, 1H), 4.23 (m, 1H), 4.30 (m, 1H).
13 C-NMR (125 MHz, D 2 O): guanidine: δ157.25; carbonyl carbons: δ178.07, 173.96, 168.24.
Example 16
EtOOC-CO-(R)Cha-Pro-Agm×HOAc
(i) EtOOC-CO-(R)Cha-Pro-Agm(Z)
To a cold (-10° C.) solution of H-(R)Cha-Pro-Agm(Z) (See Example 3) (0.46 g, 0.89 mmol) and NMM (199 mg, 1.97 mmol) in 10 ml of THF was added Cl--COCOOEt (134 mg, 0.98 mmol) dissolved in 3 ml of THF. The mixture was kept at -10° C. for one hour after which it was stirred at room temperature for another hour. The solvent was evaporated and the residue was dissolved in ethyl acetate. The organic phase was washed twice with water and dried (Na 2 SO 4 ). Evaporation of the solvent and crystallization from EtOAc gave 0.275 g (50%) of the title compound as white crystals.
(ii) EtOOC-CO-(R)Cha-Pro-Agm×HOAc
Prepared by using the deprotection procedure (b) on the product (i) above.
1 H-NMR (300 MHz, MeOD): δ0.9-2.25 (m, 24H; thereof 1.17 (t, 3H)) 1.90 (s, acetate), 3.1-3.25 (m, 4H), 3.5-3.65 (m, 3H; thereof 3.59 (q,2H)), 3.88 (m, 1H), 4.35 (m, 1H), 4.69 (dd, 1H).
13 C-NMR (75.5 MHz, MeOD): guanidine: δ157.56 and carbonyl carbons: δ159.21, 160.74, 172.81, 174.56.
Example 17
(R,S)Bla-(R)Cha-Pro-Agm×2 TFA
Alkylation as in Example 4 using H-(R)Cha-Pro-Agm(Z) (See Example 3) and α-bromo butyrolacton followed by deprotection procedure (a) gave the title compound as a mixture of two diastereomers.
1 H-NMR (500 MHz, D 2 O, mixture of diastereomers ca: 1/1): δ0.93-1.06 (m, 2H), 1.09-1.30 (m, 3H), 1.37-1.49 (m, 1H), 1.50-1.87 (m, 11H), 1.89-2.10 (m, 3H), 2.24-2.36 (m, 1H), 2.44-2.56 (m, 1H), 2.72-2.85 (m, 1H), 3.10-3.30 (m, 4H), 3.56-3.65 (m, 1H), 3.75-3.84 (m, 1H), 4.2-5.0 (m, 5H, partially hidden by the H-O-D signal).
13 C-NMR (125.76 MHz, D 2 O) guanidine: δ157.34 (peaks overlapping); carbonyl carbons: δ174.34, 173.90, 173.62, 167.88, 167.58 (two peaks are overlapping).
Example 18
HOOC-(RorS)CH(CH 2 CH 2 Ph)-(R)Cha-Pro-Agm/b×2 TFA
The title compound was obtained by treating the diastereomer in Example 13 by the same way as described in Example 14. This diastereomer came out after the first one from the column.
1 H-NMR (500 MHz, MeOD): δ0.95-1.06 (m, 2H), 1.14-1.40 (m, 4H), 1.48-1.84 (m, 11H), 1.87-2.30 (m, 6H), 2.72-2.90 (m, 2H), 3.12-3.32 (m, 4H), 3.52 (m, 1H), 3.72 (m, 1H), 4.04 (dd, 1H), 4.27 (t, 1H), 4.37 (dd, 1H), 7.17-7.32 (m, 5H).
13 C-NMR (125 MHz, MeOD): guanidine: δ158.68; carbonyl carbons: δ168.14, 171.46, 174.03.
Example 19
H-(R)Cha-Pro-Nag×2 HOAc
(i) Z-(R)Cha-Pro-NH-(CH 2 ) 3 -NH(Boc)
To a solution of Z-(R)Cha-Pro-OSu (1 mmol) in 1 ml of DMF at 0° C. was added H 2 N--(CH 2 ) 3 --NH(Boc) (See Preparation of starting material) dissolved in 1 ml of DMF and the pH was adjusted to ca: 9 with NMM. The reaction was stirred at room temperature for 3 days after which it was poured out on water. The aqueous phase was extracted four times with EtOAc. The combined organic phase was washed twice with 0.3M KHSO 4 , 0.2M NaOH, brine and dried. Evaporation and flash chromathography (EtOAc/petroleum ether, 4/1) gave the title compound in 59% yield.
(ii) Z-(R)Cha-Pro-NH-(CH 2 ) 3 -NH 2
Z-(R)Cha-Pro-NH-(CH 2 ) 3 --NH(Boc) (0.6 mmol) was dissolved in CH 2 Cl 2 (8 ml). TFA (2 ml) was added and the reaction mixture was stirred for 1 h. The solvent was evaporated and the residue was dissolved in CH 2 Cl 2 , washed twice with 0.2M NaOH and dried (Na 2 SO 4 ). Evaporation of the solvent gave the amine in 93% yield.
1 H-NMR (500 MHz, CDCl 3 ) δ0.79-1.03 (m, 2H), 1.05-1.75 (m, 15H), 1.84-2.08 (m, 4H), 2.36 (m, 1H), 2.66 (m, 2H), 3.25 (m, 2H), 3.43 (q, 1H), 3.85 (m, 1H), 4.45 (m, 1H), 4.56 (d, 1H) 5.09 (m, 2H), 5.35 (d, 1H), 7.30-7.45 (m, 5H).
(iii) Z-(R)Cha-Pro-Nag×HOAc
Z-(R)Cha-Pro-NH-(CH 2 ) 3 -NH 2 (0.55 mmol, 1 eq) was dissolved in DMF (2 ml) and the pH adjusted with triethylamine to 8-9. 3,5-Dimethyl-1-pyrazolylformamidinium nitrate (0.55 mmol, 1 eq) dissolved in DMF (1 ml) was added and the reaction mixture stirred at room temperature for three days. The solvent was evaporated, the crude product freeze-dried (H 2 O) and purified with RPLC (CH 3 CN/NH 4 OAc (0.1M), 4/6) to give the title compound in 93% yield after evaporation of the solvent and freeze-drying (H 2 O).
(iv) H-(R)Cha-Pro-Nag×2 HOAc
Prepared by using the deprotection procedure (a) on the product (iii) above.
1 H-NMR (500 MHz, D 2 O): δ0.82-1.03 (m, 2H), 1.03-1.28 (m, 3H) 1.35 (m, 1H), 1.53-1.82 (m, 9H), 1.82-2.05 (m, 3H) 1.89 (s, acetate), 2.24 (m, 1H), 3.15 (t, 2H), 3.23 (q, 2H), 3.55 (m, 1H), 3.72 (m, 1H), 4.27-4.34 (m, 2H).
13 C-NMR (125 MHz, D 2 O): guanidine: δ157.37; carbonyl carbons: δ169.81, 174.52.
Example 20
n Bu-(R)Cha-Pro-Nag×2 HOAc
(i) H-(R)Cha-Pro-Nag(Z)
Prepared from Boc-(R)Cha-Pro-OSu and Boc-Nag(Z) in the same way as described for H-(R)Cha-Pro-Agm(Z) in Example 3.
1 H-NMR (500 MHz, CDCl 3 ): δ0.8-1.03 (m, 2H), 1.10-1.50 (m, 6H), 1.60-1.83 (m, 8H), 1.87-2.20 (m, 3H), 3.15 (m, 1H), 3.25 (m, 2H), 3.42 (m, 2H), 3.63 (dd, H), 3.70 (m, 1H), 4.36 (bs, 1H), 5.07 (s, 2H), 7.22-7.43 (m, 5H).
(ii) n Bu-(R)Cha-Pro-Nag(Z)
H-(R)Cha-Pro-Nag(Z) (0.5 g, 1 mmol) was dissolved in methanol (10 ml). Triethylammonium hydrochloride (0.1 g, 1 mmol), sodium cyanoborohydride (44 mg, 0.7 mmol) and thereafter butyric aldehyde (76 mg, 1.05 mmol) were added and the reaction mixture stirred at room temperature for 20 h. The solvent was evaporated and the crude product was dissolved in ethyl acetate, washed twice with water, once with brine and dried over sodium sulphate. The solvent was evaporated and the crude product was purified by flash chromatography (EtOAc/EtOH/Et 3 N, 88/10/2). Finally the solvent was evaporated and the product dried in vacuo to yield 0.22 g (40%) of n Bu-(R)Cha-Pro-Nag(Z).
1 H-NMR (500 MHz, CDCl 3 ): δ0.82-1.0 (m, 5H; thereof 0.88 (t, 3H)), 1.08-1.49(m, 1OH), 1.58-1.8 (m, 7H), 1.88-2.22 (m, 3H), 2.4 (m, 1H), 2.5 (m, 1H), 3.05 (bs, 1H), 3.3 (m, 1H), 3.4-3.53 (m, 3H), 3.73 (m, 1H), 4.42 (bs, 1H), 5.1 (s, 2H), 7.25-7.43 (m, 5H).
(iii) n Bu-(R)Cha-Pro-Nag×2 HOAc
Prepared by using the deprotection procedure (a) on the product (ii) above.
1 H-NMR (300 MHz, D 2 O): δ0.94 (t, 2H), 1.10-1.31 (m, 3H), 1.38 (m, 3H), 1.55-1.88 (m, 11H), 1.88-2.15 (m, 3H) 1.95 (s, acetate), 2.34 (m, 1H), 2.95 (m, 1H), 3.08 (m, 1H), 3.24 (t, 2H), 3.30 (m, 2H), 3.66 (m, 1H), 3.82 (m, 1H), 4.32 (t, 1H), 4.41 (dd, 1H).
13 C-NMR (125 MHz, D 2 O): guanidine: δ157.40; carbonyl carbons: δ180.39, 174.28, 168.55.
Example 21
HO-(CH 2 ) 3 -(R)Cha-Pro-Nag×2 TFA
(i) BnO-(CH 2 ) 3 -(R)Cha-Pro-Nag(Z)
1-Benzyloxy 3-trifluoromethanesulfonylpropane (See Prep. of Starting Materials) (0.5 g, 1 mmol) and H-(R)Cha-Pro-Nag(Z) (See Example 20) were dissolved in tetrahydrofurane (10 ml). Potassium carbonate (0.28 g, 2 mmol) was added and the reaction mixture was stirred at room temperature for two hours. The solvent was evaporated and the crude product extracted with ethyl acetate/water. The organic phase was washed once with aqueous sodium hydrogen carbonate, once with water and once with brine. After drying over sodium sulphate the solvent was evaporated and the crude product flash chromatographed (CH 2 CH 2 /MeOH(NH 3 -saturated), 95:5). Finally the solvent was evaporated and the product dried in vacuo to yield 0.29 g (45%) of the title compound.
1 H-NMR (500 MHz, CDCl 3 ): δ0.77-1.03 (m, 2H), 1.03-2.18 (m, 19H), 2.52 (m, 1H), 2.64 (m, 1H), 3.03 (bs, 1H), 3.1-3.6 (m, 7H), 3.66 (m, 1H), 4.41 (bs, 1H), 4.46 (s, 2H), 5.08 (s, 2H), 7.2-7.4 (m, 5H), 7.55 (m, 1H).
(ii) HO-(CH 2 ) 3 -(R)Cha-Pro-Nag×2 TFA
Prepared by using the deprotection procedure (a) on the product (i) above.
1 H-NMR (500 MHz, D 2 O): δ1.00 (bs, 2H), 1.10-1.32 (m, 3H), 1.40 (bs, 1H), 1.55-2.15 (m, 14H), 2.30 (m, 1H), 3.05-3.35 (m, 6H), 3.57-3.75 (m, 3H), 3.81 (bs, 1H), 4.35 (bs, 1H), 4.42 (bs, 1H).
Example 22
HOOC-CH 2 -(R)Cha-Pro-Nag×HOAc
(i) H-(R)Cha-Pro-NH-(CH 2 ) 3 -N 3
Prepared in the same way as H-(R)Cha-Pro-Agm(Z) (See Example 3) starting from Boc-(R)Cha-Pro-OSu and Boc-NH-(CH 2 ) 3 -N 3 (replacing Boc-Agm(Z)).
(ii) EtOOC-CH 2 -(R)Cha-Pro-NH-(CH 2 ) 3 -NH 2 ×HOAc
Alkylation as in Example 4 using H-(R)Cha-Pro-NH-(CH 2 ) 3 -N 3 and EtOOC--CH 2 --Br followed by deprotection procedure (a) to reduce the azide gave the title compound.
(iii) EtOOC-CH 2 -(R)Cha-Pro-Nag×HOAc
The same procedure as described in Example 19 (iii) for Z-(R)Cha-Pro-Nag was used to accomplish the guanidation of the amine from (ii) above. The title compound was obtained in a pure form after RPLC (CH 3 CN/NH 4 OAc (0.1M), 3/7) evaporation of the solvent and freeze drying (H 2 O).
(iv) HOOC-CH 2 -(R)Cha-Pro-Nag×HOAc
Prepared by using the deprotection procedure (e) on the product (iii) above.
1 H-NMR (500 MHz, D 2 O): δ0.99 (m, 2H), 1.09-1.30 (m, 3H), 1.44 (m, 1H), 1.59-2.09 (m, 12H) 1.92 (s, acetate), 2.29 (m, 1H), 3.20 (t, 2H), 3.28 (m, 2H), 3.52-3.63 (m, 3H), 3.76 (m, 1H), 4.38 (dd, 1H), 4.42 (t, 1H).
13 C-NMR (125 MHz, D 2 O): guanidine: δ157.43; carbonyl carbons: δ168.72, 171.36, 174.35.
Example 23
EtOOC-CH 2 -(R)Cha-Pro-Nag×HOAc
Prepared according to example 22 (iii).
1 H-NMR (300 MHz, D 2 O): δ1.07 (m, 2H), 1.17-1.59 (m, 7H; thereof 1.38 (t, 3H)), 1.60-2.24 (m, 12H) 2.04 (s, acetate), 2.39 (m, 1H), 3.31 (t, 2H), 3.39 (t, 2H), 3.63-3.90 (m, 4H), 4.12 (t, 1H), 4.36 (q, 2H), 4.46 (dd, 1H).
13 C-NMR (75 MHz, D 2 O,): guanidine: δ157.37; carbonyl carbons: δ173.73, 175.09, 175.70.
Example 24
i PrOOC-CH 2 -(R)Cha-Pro-Nag×HOAc
Alkylation as in Example 4 using H-(R)Cha-Pro-Nag(Z) (See Example 20) and Br--CH 2 COO i Pr followed by deprotection procedure (b) gave the title compound.
1 H-NMR (500 MHz, MeOD): δ0.85-1.05 (m, 2H), 1.1-2.15 (m, 22H; thereof 1.23 (d, 3H), 1.25 (d, 3H)), 1.92 (s, acetate), 2.2 (m, 1H), 3.10-3.35 (m, 5H), 3.4 (m, 1H), 3.55 (m, 1H), 3.65-3.8 (m, 2H), 4.28 (dd, 1H), 5.03 (m, 1H).
13 C-NMR (125 MHz, D 2 O): guanidine: δ157.39; carbonyl carbons: δ170.40, 172.00 and 174.50.
Example 25
t BuOOC-CH 2 -(R)Cha-Pro-Nag×2 TFA
Alkylation as in Example 4 using H-(R)Cha-Pro-Nag(Z) (See Example 20) and Br--CH 2 COO t Bu followed by deprotection procedure (b) gave the title compound.
1 H-NMR (300 MHz, MeOD): δ0.9-1.15 (m, 2H), 1.15-2.15 (m, 25H; thereof 1.55 (bs, 9H)), 2.3 (m, 1H), 3.15-3.45 (m, 4H), 3.55 (m, 1H), 3.7-3.95 (m, 3H), 4.3-4.4 (m, 2H).
13 C-NMR (75 MHz, D 2 O): guanidine: δ157.55; carbonyl carbons: δ166.55, 168.13 and 174.33.
Example 26
HOOC-CH 2 -OOC-CH 2 -(R)Cha-Pro-Nag×HOAc
(i) BnOOC-CH 2 -OOC-CH 2 -(R)Cha-Pro-Nag(Z)
H-(R)Cha-Pro-Nag(Z) (See Example 20), 0.20 g (0.40 mmol), was mixed with 0.115 g (0.40 mmol) of benzyloxycarbonylmethyl bromoacetate, 55 mg of K 2 CO 3 (0.40 mmol) and 5 ml of CH 3 CN. The mixture was stirred at room temperature for 6 h. The solvent was evaporated and the crude product chromatographed (CH 2 Cl 2 /MeOH, 9/1) to give 0.20 g (71%) of the desired compound after evaporation of the solvent.
(ii) HOOC-CH 2 -OOC-CH 2 -(R)Cha-Pro-Nag×HOAc
Prepared by using the deprotection procedure (a) on the product (i) above.
1 H-NMR (500 MHz, MeOD): δ0.85-1.1 (m, 2H), 1.1-1.6 (m, 8H), 1.6-2.15 (m, 10H) 1.99 (s, acetate), 2.23 (m, 1H), 3.1-3.4 (m, 4H), 3.45-3.65 (m, 4H), 3.7-3.9 (m, 3H), 4.34 (m, 1H), 4.48 (dd, 2H).
13 C-NMR (125 MHz, MeOD), guanidine: δ158.8; carbonyl carbons: δ176.1, 175.2, 174.9, 173.1.
Example 27
H 2 N-CO-CH 2 -(R)Cha-Pro-Nag×HOAc
Alkylation as in Example 4 using H-(R)Cha-Pro-Nag(Z) (See Example 20) and Cl--CH 2 CONH 2 , in the presence of a catalytic (10 mol %) amount of KI in the reaction, followed by deprotection procedure (a) gave the title compound.
1 H-NMR (500 MHz, D 2 O): δ1.02 (m, 2H), 1.12-1.34 (m, 3H), 1.46 (m, 1H), 1.61-2.13 (m, 9H) 1.99 (s, acetate), 2.34 (m, 1H), 3.25 (t, 2H), 3.33 (t, 2H), 3.60-3.82 (m, 4H), 4.22 (t, 1H), 4.41 (dd, 1H).
13 C-NMR (75 MHz, D 2 O): guanidine: δ157.5; carbonyl carbons: δ168.94, 169.40, 174.43.
Example 28
HOOC-CH 2 -NH-CO-CH 2 -(R)Cha-Pro-Nag×2 TFA
Alkylation as in Example 4 using H-(R)Cha-Pro-Nag(Z) (See Example 20) and Br--CH 2 CONHCH 2 COOBn (See Prep. of starting materials) followed by deprotection procedure (a) gave the title compound.
1 H-NMR (500 MHz, MeOD): δ1.01 (m, 2H), 1.15-1.38 (m, 3H), 1.47 (m, 1H), 1.64-2.13 (m, 12H), 2.27 (m, 1H), 3.17-3.26 (m, 3H), 3.37 (m, 1H), 3.51 (m, 1H), 3.83 (m, 1H), 3.88 (s, 2H), 3.93-4.06 (m, 2H), 4.35-4.45 (m, 2H).
13 C-NMR (75 MHz, MeOD): guanidine: δ158.71; carbonyl carbons: δ166.94, 168.35, 172.44, 174.17.
Example 29
(HOOC-CH 2 ) 2 -(R)Cha-Pro-Nag×HOAc
(i) (EtOOC-CH 2 ) 2 -(R)Cha-Pro-NH-(CH 2 ) 3 -NH 2 ×HOAc
Alkylation as in Example 4 using H-(R)Cha-Pro-NH-(CH 2 ) 3 -N 3 (See Example 22) and Br--CH 2 COOEt (10 eq. was used to accomplish the dialkylation) followed by deprotection procedure (a) gave the title compound.
(ii) (EtOOC-CH 2 ) 2 -(R)Cha-Pro-Nag×HOAc
The same procedure as described in Example 19 (iii) for Z-(R)Cha-Pro-Nag was used to accomplish the guanidation of the amine above. Purification of the compound was made with RPLC (CH 3 CN/NH 4 OAc (0.1M), 4:6)
(iii) (HOOC-CH 2 ) 2 -(R)Cha-Pro-Nag×HOAc
The hydrolysis of the ester groups was made according to deprotection procedure (e) using a double amount of NaOH. The final compound was obtained pure after RPLC (CH 3 CN/NH 4 OAc (0.1M), 2:8), evaporation of the solvent and freeze drying (H 2 O).
1 H-NMR (300 MHz, D 2 O): δ0.92-1.49 (m, 6H), 1.60-2.54 (m, 10H) 2.05 (s, acetate), 3.25-3.50 (m, 4H), 3.65-4.03 (m, 6H; thereof 3.95 (s, 4H)), 4.49 (m, 1H), 4.71 (m, 1H; partly hidden by the H-O-D peak).
13 C-NMR (75 MHz, D 2 O): guanidine: δ157.64; carbonyl carbons: δ168.62, 171.39, 174.30.
Example 30
HOOC-CH 2 -(Me)(R)Cha-Pro-Nag×2 TFA
(i) Me-(R)Cha-Pro-Nag(Z)
Prepared from Boc-(Me)(R)Cha-Pro-OSu and Boc-Nag(Z) in the same way as described for H-(R)Cha-Pro-Agm(Z) in Example 3.
(ii) HOOC-CH 2 -(Me)(R)Cha-Pro-Nag×2 TFA
Alkylation as in Example 4 using Me-(R)Cha-Pro-Nag(Z) and Br--CH 2 COOBn followed by deprotection procedure (b) gave the title compound.
1 H-NMR (500 MHz, D 2 O): δ0.8-1.06 (m, 2H), 1.08-1.27 (m, 4H), 1.55-2.10 (m, 12H), 2.30 (m, 1H), 3.04 (s, 3H), 3.14-3.33 (m, 4H), 3.63 (m, 1H), 3.81 (m, 1H), 4.13 (apparent bs, 2H), 4.38 (br.dd, 1H), 4.56 (bt, 1H).
13 C-NMR (125.76 MHz, D 2 O): guanidine: δ157.40; carbonyl carbons: δ174.05, 168.83, 167.44.
Example 31
HOOC-CH 2 -( n Bu)(R)Cha-Pro-Nag×2 TFA
Alkylation as in Example 4 using n Bu-(R)Cha-Pro-Nag(Z) (See Example 20) and Br--CH 2 COOBn followed by deprotection procedure (a) gave the title compound.
1 H-NMR (500 MHz, D 2 O): δ0.78-0.88 (m, 3H), 0.88-1.02 (m, 2H), 1.02-1.23 (m, 4H), 1.23-1.38 (m, 2H), 1.45-1.84 (m, 11H), 1.84-2.10 (m, 3H), 2.24 (m, 1H), 3.05-3.18 (m, 3H), 3.18-3.38 (m, 3H), 3.57 (m, 1H), 3.77 (m, 1H), 4.05-4.25 (m, 2H), 4.32 (m, 1H), 4.50 (m, 1H).
13 C-NMR (125 MHz, D 2 O): guanidine: δ159.17; carbonyl carbons: δ175.66, 171.13, 169.31.
Example 32
HOOC-(R,S)CH(Me)-(R)Cha-Pro-Nag×HOAc
Alkylation as in Example 4 using H-(R)Cha-Pro-Nag(Z) (See Example 20) and Br--CH(Me)COOBn followed by deprotection procedure (a) gave the title compound as a mixture of two diastereomers.
Example 33
HOOC-(RorS)CH(Me)-(R)Cha-Pro-Nag/a×HOAc
Obtained by separating the diastereomers formed in Example 32 using RPLC (CH 3 CN/NH 4 OAc (0.1M), 1/4) followed by evaporation of the solvent. This diastereomer came out first of the two from the column.
1 H-NMR (300 MHz, D 2 O, 2 rotamers ca: 9:1 ratio): δ0.78 (m, minor rotamer), 1.07 (m, 2H), 1.17-1.42 (m, 3H), 1.48-1.64 (m, 4H; thereof 1.56 (d, 3H)), 1.64-1.95 (m, 9H), 1.95-2.20 (m, 3H) 2.00 (s, acetate), 2.37 (m, 1H), 3.28 (t, 2H), 3.38 (t, 2H), 3.53 (m, minor rotamer), 3.63 (m, 2H), 3.77 (m, 1H), 4.24 (d, minor rotamer), 4.35-4.50 (m, 2H), 4.60 (d, minor rotamer).
Example 34
HOOC-(RorS)CH(Me)-(R)Cha-Pro-Nag/b×HOAc
The title compound was obtained by using the same procedure as described in Example 33 on the compound formed in Example 32. This diastereomer came out after the first one from the column.
1 H-NMR (300 MHz, D 2 O, 2 rotamers ca: 9:1 ratio): δ0.95 (m, minor rotamer), 1.12 (m, 2H), 1.22-1.40 (m, 3H), 1.40-1.67 (m, 4H; thereof 1.60 (d, 3H)), 1.67-2.00 (m, 9H), 2.00-2.25 (m, 3H) 2.03 (s, acetate), 2.40 (m, 1H), 3.25-3.48 (m, 4H), 3.66-3.84 (m, 2H), 3.93 (m, 1H), 4.38 (m, 1H), 4.50 (m, 1H), 4.93 (m, minor rotamer).
13 C-NMR (75.5 MHz, D 2 O): δ157.42; carbonyl carbons: δ168.05, 171.99, 174.04.
Example 35
EtOOC-(R,S)CH(Me)-(R)Cha-Pro-Nag×2 TFA
Prepared in the same way as described for Example 22 using EtOOC--CH(Me)--Br instead of Br--CH 2 --COOEt in the alkylation.
1 H-NMR (500 MHz, MeOD, 2 diastereomers ca: 2.5:1 ratio and 4 rotamers): δ0.88-2.43 (m, 25H), 3.1-4.55 (m, 11H).
13 C-NMR (75 MHz, MeOD): guanidine: δ158.65, carbonyl carbons: δ174.33, 170.66, 168.20.
Example 36
HOOC-(RorS)CH(nPr)-(R)Cha-Pro-Nag/a×HOAc
Alkylation as in Example 4 using H-(R)Cha-Pro-Nag(Z) (See Example 20) and Br--CH( n Pr)COOEt and deprotection procedure (e) followed by deprotection procedure (b) gave HOOC-(R,S)CH( n Pr)-(R)Cha-Pro-Agm. The title compound was obtained by separating the diastereomers (this diastereomer came out first of the two from the column) by RPLC (CH 3 CN/NH 4 OAc (0.1M), 1/4) and freeze drying (H 2 O) after evaporation of the solvent.
1 H-NMR (500 MHz, MeOD): δ0.85-1.05 (m, 5H; thereof 0.95 (t, 3H)), 1.1-2.05 (m, 20H) 1.95 (s, acetate), 2.18 (m, 1H), 3.15-3.3 (m, 4H), 3.35 (m, 1H), 3.46 (m, 1H), 3.85 (m, 1H), 4.04 (m, 1H), 4.38 (dd, 1H).
13 C-NMR (125 MHz, MeOD): guanidine: δ158.73; carbonyl carbons: δ171.63, 174.43 and 176.78.
Example 37
HOOC-(R)CH(CH 2 -OH)-(R)Cha-Pro-Nag×2 TFA
Alkylation as in Example 4 using H-(R)Cha-Pro-Nag(Z) (See Example 20) and Br--(S)CH(CH 2 --OBn)--COOBn followed by deprotection procedure (a) gave the title compound.
1 H-NMR (300 MHz, D 2 O): δ0.75-1.56 (m, 7H), 1.56-2.30 (m, 11H), 2.40 (m, 1H), 3.15-3.55 (m, 4H), 3.55-4.60 (m, 7H).
Example 38
HOOC-(R,S)CH(Ph)-(R)Cha-Pro-Nag×2 TFA
Alkylation as in Example 4 using H-(R)Cha-Pro-Nag(Z) (See Example 20) and Br--CH(Ph)COO t Bu and deprotection procedure (a) followed by (f) gave the title compound as a mixture of two diastereomers.
1 H-NMR (300 MHz, MeOD): δ0.8-1.1 (m, 2H), 1.1-2.18 (m, 16H), 2.26 (m, 1H), 3.04-3.35 (m, 5H), 3.45 (m, 1H), 3.7 (m, 1H), 4.35 (m, 1H), 4.85 (s, 1H, one isomer), 5.05 (s, 1H, the other isomer), 7.4-7.6 (m, 5H), 7.75 (bt, 1H).
13 C-NMR (75 MHz, D 2 O): guanidine: δ158.68; carbonyl carbons: δ174.39, 174.15 and 170.5, 170.06 and 168.32, 167.78.
Example 39
HOOC-(S)CH(CH 2 CH 2 Ph)-(R)Cha-Pro-Nag×HOAc
Alkylation as in Example 21 using H-(R)Cha-Pro-Nag(Z) (See Example 20) and TfO--(R)CH(CH 2 CH 2 Ph)--COOEt and deprotection procedure (e) followed by (a) gave the title compound.
1 H-NMR (300 MHz, MeOD): δ0.77-1.05 (m, 2H), 1.05-1.35 (m, 5H), 1.35-2.16 (m, 14H) 1.88 (s, acetate), 2.71 (t, 2H), 3.07-3.53 (m, 7H), 3.73 (m, 1H), 4.32 (m, 1H), 7.03-7.25 (m, 5H).
13 C-NMR (75 MHz, MeOD): guanidine: δ158.71; carbonyl carbons: δ174.15, 177.31, 182.61.
Example 40
HOOC-(R)CH(CH 2 CH 2 Ph)-(R)Cha-Pro-Nag×HOAc
Alkylation as in Example 4 using H-(R)Cha-Pro-Nag(Z) (See Example 20) and Br--CH(CH 2 CH 2 Ph)COOEt followed by deprotection procedure (a) and (e) gave HOOC-(R,S)CH(CH 2 -CH 2 -Ph)-(R)Cha-Pro-Nag. The title compound was obtained by separating the two diastereomers with RPLC (CH 3 CN/NH 4 OAc (0.1M), 2/3) and freeze drying (H 2 O) after evaporation of the solvent.
1 H-NMR (300 MHz, MeOD): δ0.97 (m, 2H), 1.10-1.41 (m, 3H), 1.43-2.30 (m, 16H) 1.96 (s, acetate), 2.70 (m, 2H), 3.06-3.26 (m, 3H), 3.28-3.66 (m, 3H), 3.84 (m, 1H), 4.14 (bt, 1H), 4.39 (dd, 1H), 7.11-7.28 (m, 5H).
13 C-NMR (75 MHz, MeOD): guanidine: δ158.66
Example 41
HOOC-CH 2 -CH 2 -(R)Cha-Pro-Nag×HOAc
(i) EtOOC-CH 2 -CH 2 -(R)Cha-Pro-NH-(CH 2 ) 3 -NH 2
Alkylation as described in Example 15 using H-(R)Cha-Pro-NH-(CH 2 ) 3 -N 3 instead of H-(R)Cha-Pro-Agm(Z) followed by deprotection procedure (a) gave the title compound.
(ii) Et-OOC-CH 2 -CH 2 -(R)Cha-Pro-Nag×HOAc
Guanidation of the amine above in the same way as described in Example 19 for Z-(R)Cha-Pro-Nag gave the title compound (ii).
(iii) HOOC-CH 2 -CH 2 -(R)Cha-Pro-Nag×HOAc
Prepared by using the deprotection procedure (e) on the product (ii) above.
1 H-NMR (500 MHz, D 2 O): δ1.12 (m, 2H), 1.22-1.48 (m,3H), 1.54 (bs, 1H), 1.70-2.37 (m, 12H) 2.14 (s, acetate), 2.53 (m, 1H), 2.70 (bs, 2H), 3.15 (tw1H), 3.25-3.55 (m, 5H), 3.75 (m, 1H), 3.93 (m, 1H), 4.43 (t, 1H), 4.52 (m, 1H).
Example 42
EtOOC-CH 2 -CH 2 -(R)Cha-Pro-Nag×HOAc
Prepared according to Example 41 (ii).
1 H-NMR (500 MHz, D 2 O): δ0.97 (m, 2H), 1.11-1.39 (m,7H; thereof 1.30 (t,3H)), 1.50 (t, 2H), 1.62-1.76 (m,5H), 1.76-2.14 (m, 5H) 1.93 (s, acetate), 2.29 (m, 1H), 2.62 (t, 2H), 2.77-2.94 (m, 2H), 3.23 (t, 2H), 3.32 (t, 2H), 3.60-3.87 (m, 3H), 4.20 (q, 2H), 4.36 (dd, 1H).
13 C-NMR, (125 MHz, D 2 O): guanidine: δ157.39; carbonyl carbons: δ182.05, 175.13, 175.02.
Example 43
HOOC-(CH 2 ) 3 -(R)Cha-Pro-Nag×2 HOAc
(i) Et-OOC-CH═CH-CH 2 -(R)Cha-Pro-Nag(Z)
H-(R)Cha-Pro-Nag(Z) (See Example 20) (1 eq) and ethyl 3-bromocrotonate (1.1 eq) were dissolved in acetonitrile (15 ml/mmol). Potassium carbonate was added and the reaction mixture stirred at room temperature for 2 h. After filtration and evaporation of the solvent, the crude product was purified by flash chromatography (CH 2 Cl 2 /MeOH). Finally the solvent was evaporated and product dried in vacuo.
1 H-NMR (500 MHz, CDCl 3 ): δ0.73-1.0 (m, 2H), 1.0-1.4 (m, 8H; thereof 1.33 (t, 3H)), 1.43-2.15 (m, 12H), 2.96 (bs, 1H), 3.12 (dd, 1H), 3.16-3.48 (m, 6H), 3.56 (m, 1H), 4.15 (q, 2H), 4.35 (bs, 1H), 5.03 (s, 1H), 6.0 (d, 1H), 6.85 (dt, 1H), 7.05 (bs, 1H), 7.17-7.37 (m, 5H), 7.5 (bs, 1H).
(ii) EtOOC-(CH 2 ) 3 -(R)Cha-Pro-Nag×2 TFA
Prepared by using the deprotection procedure (a) on the product (i) above.
(iii) HOOC-(CH 2 ) 3 -(R)Cha-Pro-Nag×2 HOAc
Prepared by using the deprotection procedure (e) on the product (ii) above.
1 H-NMR (500 MHz, D 2 O): δ1.02 (bs, 2H), 1.08-1.32 (m, 3H), 1.42 (bs, 1H), 1.55-2.15 (m, 14H) 1.92 (s, acetate), 2.33 (bs, 3H), 3.00 (bs, 1H), 3.07 (bs, 1H), 3.18-3.40 (m, 4H), 3.62 (bs, 1H), 3.82 (bs, 1H), 4.33 (bs, 1H), 4.40 (bs, 1H).
13 C-NMR (125 MHz, D 2 O): guanidine: δ157.42; carbonyl carbons: δ181.87, 174.34, 168.64.
Example 44
EtOOC-(CH 2 ) 3 -(R)Cha-Pro-Nag×2 TFA
Prepared according to Example 43 (ii).
1 H-NMR (300 MHz, MeOD/D 2 O): δ0.63-1.30 (m, 9H; thereof 1.02 (t, 3H)), 1.30-1.97 (m, 14H), 2.06 (bs, 1H), 2.28 (m, 2H), 2.72-3.20 (m, 6H), 3.36 (m, 1H), 3.60 (m, 1H), 3.94 (m, 2H), 4.06 (m, 1H), 4.17 (m, 1H).
13 C-NMR (75 MHz, MeOD/D 2 O): guanidine: δ158.10; carbonyl carbons: δ175.40, 174.23, 168.54.
Example 45
HOOC-CO-(R)Cha-Pro-Nag×HOAc
(i) EtOOC-CO-(R)Cha-Pro-Nag(z)
H-(R)Cha-Pro-Nag(Z), 0.50 g (0.97 mmol) was dissolved in 0.54 ml triethyl amine and 8 ml of CH 2 Cl 2 . Ethyl oxalylchloride, 0.146 g (1.07 mmol) dissolved in 2 ml of CH 2 Cl 2 was added while the temperature rose from 22°-28° C. and the reaction was stirred at room temperature for 2 h. The organic phase was washed twice with water, dried (Na 2 SO 4 ) and flash chromathographed (EtOAc/EtOH(99%), 9/1) to give 92 mg (15%) of the title compound.
(ii) HOOC-CO-(R)Cha-Pro-Nag×HOAc
Using the deprotection procedure (b) followed by (e) gave the title compound.
1 H-NMR (300 MHz, MeOD): δ0.88-1.14 (m, 2H), 1.15-1.5 (m, 4H), 1.5-2.3 (m, 13H) 1.9 (s, acetate), 3.1-3.43 (m, 4H), 3.6 (m 1H), 4.05 (m, 1H), 4.43 (dd, 1H), 4.5 (m, 1H).
13 C-NMR (75 MHz, D 2 O): guanidine: δ157.57; carbonyl carbons: δ165.94, 173.95, 174,85 and 181.22.
Example 46
MeOOC-CO-(R)Cha-Pro-Nag×HOAc
(i) MeOOC-CO-(R)Cha-Pro-Nag(Z)
The methyl ester was obtained by transesterification of EtOOC-CO-(R)Cha-Pro-Nag(Z) (See Example 45) on the column during flash chromatography when EtOAc/MeOH(9:1) was used as eluent. Yield 55%.
(ii) MeOOC-CO-(R)Cha-Pro-Nag×HOAc
Prepared by using the deprotection procedure (b) on the product (i) above.
1 H-NMR (300 MHz, MeOD): δ0.9-1.1 (m, 2H), 1.1-2.3 (m, 17H) 1.9 (s, acetate), 3.12-3.4 (m, 4H), 3.52-3.67 (m, 2H),3.9 (s, 3H), 4.35 (m, 1H), 4.65 (m, 1H).
13 C-NMR (75 MHz, D 2 O): guanidine: δ157.52; carbonyl carbons: δ159.11, 161.20 173.17 and 174.90.
Example 47
(R,S)Bla-(R)Cha-Pro-Nag×2 TFA
Alkylation as in Example 4 using H-(R)Cha-Pro-Nag(Z) (See Example 20) and α-bromo butyrolacton followed by deprotection procedure (a) gave the title compound as a mixture of two diastereomers.
1 H-NMR (300 MHz, D 2 O, mixture of diastreomers): δ1.0-1.43 (m, 5H), 1.45-1.60 (br.s, 1H), 1.64-2.28 (m, 12H), 2.31-2.50 (m, 1H), 2.80-2.98 (m, 1H), 3.23-3.46 (m, 4H), 3.66-3.79 (m, 1H), 3.82-3.96 (m, 1H), 4.33-5.08 (m, 5H, partially hidden by the H-O-D signal).
Example 48
HOOC-(R,S)CH(CH 2 COOH)-(R)Cha-Pro-Nag×HOAc
(i) BnOOC-(R,S)CH(CH 2 COOBn)-(R)Cha-Pro-Nag(Z)
H-(R)Cha-Pro-Nag(Z) (See Example 20), 0.21 g (0.42 mmol), and 0.12 g (0.42 mmol) of dibenzyl maleate were dissolved in 10 ml of CH 3 CN. The mixture was refluxed over night, evaporated and flash chromatographed (CH 2 Cl 2 /MeOH, 94/6). Evaporation of the solvent gave the desired compound in 22% yield.
(ii) HOOC-(R,S)CH(CH 2 COOH)-(R)Cha-Pro-Nag×HOAc
Prepared by using the deprotection procedure (a) on the product (i) above. 1 H-NMR (500 MHz, MeOD): δ0.9-2.4 (m, 19H), 2.00 (s, acetate) 2.7-3.0 (m, 2H), 3.1-3.6 (m, 5H), 3.75-3.9 (m, 2H), 4.2-4.5 (m, 2H).
Example 49
MeOOC-(R,S)CH(CH 2 COOMe)-(R)Cha-Pro-Nag×HOAc
(i) MeOOC-(R,S)CH(CH 2 COOMe)-(R)Cha-Pro-Nag(Z)
H-(R)Cha-Pro-Nag(Z) (See Example 20), 0.21 g (0.42 mmol), and 0.24 g (1.7 mmol) of dimethyl maleate were dissolved in 15 ml of MeOH. The mixture was refluxed over night, evaporated and flash chromatographed (CH 2 Cl 2 /MeOH, 9/1). Evaporation of the solvent gave the desired compound in 45% yield.
(ii) MeOOC-(R,S)CH(CH 2 COOMe)-(R)Cha-Pro-Nag×HOAc
Prepared by using the deprotection procedure (c) on the product (i) above.
1 H-NMR (500 MHz, MeOD): δ0.85-1.1 (m, 2H), 1.15-2.3 (m, 17H), 1.91 (s, acetate), 2.6-2.8 (m, 2H), 3.1-3.5 (m, 5H), 3.5-3.8 (m, 10H; thereof 4 singlets 3.66, 3.68, 3.71, 3.73), 4.29 (m, 1H).
Example 50
HOOC-Ph-4-CH 2 -(R)Cha-Pro-Nag×2 TFA
(i) t BuOOC-Ph-4-CH 2 -(R)Cha-Pro-NH-(CH 2 ) 3 -N 3
H-(R)Cha-Pro-NH-(CH 2 ) 3 -N 3 (See Example 22), 0.39 g (1.1 mmol) and 0.33 g (1.2 mmol) of tertiarybutyl p-bromomethylbenzoate were dissolved in 10 ml of CH 3 CN and 0.19 g (2.4 mmol) of K 2 CO 3 was added. The mixture was refluxed over night and evaporated. The crude product was flash chromatographed (CH 2 Cl 2 /MeOH, 92:8) to give 0.50 g (84%) of the title compound.
(ii) t BuOOC-Ph-4-CH 2 -(R)Cha-Pro-NH-(CH 2 ) 3 -NH 2
To a solution of 0.60 g (1.8 mmol) of bis-phenylthio stannane, 0.20 g (1.8 mmol) of thiophenol and 0.18 g (1.8 mmol) of triethyl amine in 50 ml of CH 2 Cl 2 at 0° C. was added 0.50 g (0.92 mmol) of t BuOOC-Ph-4-CH 2 -(R)Cha-Pro-NH-(CH 2 ) 3 -N 3 . The mixture was stirred at 0° C. for 30 min. and at room temperature for 4 h. It was then diluted with CH 2 Cl 2 and washed with aqueous sodium bicarbonate and subsequently 3 times with 2% H 2 O 2 . The organic layer was extracted with dilute HCl. The combined acidic water phase was washed with EtOAc and subsequently made alkaline with NaOH(aq). The aqueous layer was extracted twice with ethyl acetate. The combined organic layer was dried (Na 2 SO 4 ) and evaporated. Flash chromatography (CH 2 Cl 2 /MeOH(NH 3 -saturated), 8:2) gave 0.12 g (26%) of the title compound.
(iii) HOOC-Ph-4-CH 2 -(R)Cha-Pro-Nag×2 TFA
Guanidation of the amine above in the same way as described in Example 19 for Z-(R)Cha-Pro-Nag followed by deprotection procedure (f) gave the title compound. 1 H-NMR (500 MHz, MeOD): δ0.9-1.5 (m, 7H), 1.4-1.9 (m, 9H), 1.95-2.1 (m, 2H), 2.16 (m, 1H), 2.32 (m, 1H), 3.2-3.3 (m, 3H), 3.41 (pentet, 1H), 3.53 (m, 1H), 3.77 (m, 1H), 4.2-4.3 (m, 3H), 4.42 (dd, 1H), 7,15 (d, 2H), 8.10 (d, 2H).
13 C-NMR (125 MHz, MeOD), guanidine: δ160.8; carbonyl carbons: δ174.3, 168.9, 168.2.
Example 51
(HO) 2 P(O)-CH 2 -(R)Cha-Pro-Nag×HOAc
(EtO) 2 PO-CH 2 -(R)Cha-Pro-Nag(Z) (See Example 53), 60 mg (92 mmol), was dissolved in 3 ml of CH 3 CN. Trimethylsilyl bromide, 0.15 ml, was added and the mixture was left at room temperature for 21 h. After evaporation and NMR analysis it was found that some ester remained. The crude material was again dissolved in 3 ml of CH 3 CN and 0.15 ml of trimethylsilyl bromide was added. After 5 h the mixture was evaporated and purified with RPLC (CH 3 CN/NH 4 OAc (0.1M), 30:70) to give the final compound after filtration, evaporation and freeze drying in 8% yield.
1 H-NMR (500 MHz, MeOD): δ0.8-1.1 (m, 2H), 1.15-1.4 (m, 4H), 1.5-1.9 (m, 10H), 1.9-2.1 (m, 4H) 1.96 (s, acetate), 2.20 (m, 1H), 2.95 (m, 1H), 3.0-3.2 (m, 3H), 3.4-3.5 (m, 2H), 4.09 (m, 1H), 4.39 (bd, 1H), 4.59 (m, 1H).
13 C-NMR (125 MHz, MeOD): guanidine: δ158.6; carbonyl carbons: δ174.2, 170.6
Example 52
EtO(HO)P(O)-CH 2 -(R)Cha-Pro-Nag×2 HOAc
(i) (EtO)(HO)PO-CH 2 -(R)Cha-Pro-Nag(Z).
(EtO) 2 PO-CH 2 -(R)Cha-Pro-Nag(Z) (See Example 53), 50 mg (77 mmol) was dissolved in 2 ml of EtOH and 2 ml 2M NaOH. The mixture was stirred over night and evaporated. The crude material was purified with RPLC (CH 3 CN/NH 4 OAc (0.1M), 30:70) to give the title compound after filtration and evaporation of the solvent.
(ii) (EtO)(HO)PO-CH 2 -(R)Cha-Pro-Nag×2 HOAc
Prepared by using deprotection procedure (c) on the product (i) above.
1 H-NMR (500 MHz, MeOD): δ0.9-1.1 (m, 2H), 1.15-1.35 (m, 6H; thereof 1.28 (t, 3H)), 1.35-1.5 (m, 2H), 1.5-1.6 (m, 1H), 1.65-1.8 (m, 6H), 1.9-2.1 (m, 3H) 1.95 (s, acetate), 2.19 (m, 1H), 2.8-3.0 (m, 2H), 3.1-3.25 (m, 2H), 3.27 (m, 1H), 3.36 (m, 1H), 3.48 (m, 1H), 3.9-4.05 (m, 4H), 4.36 (bd, 1H)
13 C-NMR (125 MHz, MeOD): guanidine: δ158.6; carbonyl carbons: δ175.0, 174.7
Example 53
(EtO) 2 P(O)-CH 2 -(R)Cha-Pro-Nag×HOAc
(i) (EtO) 2 PO-CH 2 -(R)Cha-Pro-Nag(Z).
H-(R)Cha-Pro-Nag(Z) (See Example 20), 0.2 g (0.40 mmol), was dissolved in 5 ml of THF and 0.11 g (0.80 mmol) of potassium carbonate and 0.12 g (0.40 mmol) diethyl triflylmethyl-phosphonate were added. The mixture was stirred at room temperature for 2 h. The reaction was worked up with water and extraction of the aqueous layer three times with EtOAc. The combined organic layer was dried (Na 2 SO 4 ) and evaporated to yield 0.14 g (53%) of the title compound.
(ii) (EtO) 2 PO-CH 2 -(R)Cha-Pro-Nag×HOAc
Prepared by using the deprotection procedure (c) on the product (i) above.
1 H-NMR (500 MHz, MeOD): δ0.85-1.05 (m, 2H), 1.15-1.3 (m, 5H), 1.34 (t, 6H), 1.5-1.85 (m, 8H), 1.9-2.05 (m, 3H) 1.91 (s, acetate), 2.10 (m, 1H), 2.22 (m, 1H), 2.90 (dd, 1H), 3.05 (dd, 1H), 3.1-3.3 (m, 3H), 3.42 (m, 1H), 3.53 (m, 1H), 3.71 (dd, 1H), 3.82 (m, 1H), 4.1-4.2 (m, 4H), 4.28 (dd, 1H).
13 C-NMR (125 MHz, MeOD), guanidine: δ158.7; carbonyl carbons: δ176.1, 175.1.
Example 54
HOOC-CH 2 -(R)Cha-Pro-Mag×HOAc
(i) H-(R) Cha-Pro-H-(CH 2 ) 2 -NH(Z)
Prepared from Boc-(R)Cha-Pro-OSu and H 2 N--(CH 2 ) 2 --NH(Z) in the same way as described for H-(R)Cha-Pro-Agm(Z) in Example 3.
(ii) EtOOC-CH 2 -(R)Cha-Pro-NH-(CH 2 ) 2 -NH 2 ×HOAc
Alkylation as in Example 4 followed by deprotection procedure (a) gave the title compound.
(iii) HOOC-CH 2 -(R)Cha-Pro-Mag×HOAc
Guanidation of the amine above in the same way as described in Example 19 for Z-(R)Cha-Pro-Nag followed by deprotection procedure (e) gave the title compound after purification by RPLC (CH 3 CN/NH 4 OAc (0.1M), 1/4) and freeze drying(H 2 O).
1 H-NMR (300 MHz, D 2 O): δ0.90-1.18 (m, 2H), 1.19-1.43 (m, 3H), 1.52 (m, 1H), 1.63-2.20 (m, 10H) 2.06 (s, acetate), 2.31-2.47 (m, 1H), 3.44 (m, 2H), 3.50 (m, 2H), 3.60-3.75 (m, 3H), 3.85 (m, 1H), 4.46-4.54 (m, 2H).
13 C-NMR (75 MHz, D 2 O): guanidine: δ157.82; carbonyl carbons: δ168.80, 171.41, 174.81.
Example 55
H-(R,S)Pro(3-Ph)-Pro-Agm×2 TFA
Prepared from Boc-(R,S)Pro(3-Ph)-Pro-OSu (See Prep. of starting materials) in the same way as described for H-(R)Cha-Pro-Agm(Z) in Example 3 followed by deprotection procedure (b).
1 H-NMR (500 MHz, D 2 O, mixture of two diastereomers with unknown relative stereochemistry): δ1.0-1.8 (m, 7H), 2.0-2.5 (m, 3H), 2.8-4.3 (m, 10H), 4.56 (d, 1H, major), 4.90 (d, 1H, major), 7.2-7.5 (m, 5H).
13 C-NMR (125.76 MHz, D 2 O): guanidine: δ157.36 (minor and major); carbonyl carbons: δ174.1 (major), 174.0 (minor), 167.8 (major), 167.0 (minor).
Example 56
H-(R,S)Pro(3-(trans)Ch)-Pro-Agm×2 TFA
Prepared from Boc-(R,S)Pro(3-(trans)Ch)-Pro-OSu (See Prep. of starting materials) in the same way as described for H-(R)Cha-Pro-Agm(Z) in Example 3 followed by deprotection procedure (b).
1 H-NMR (500 MHz, D 2 O, mixture of two diastereomers, ratio 1.8/1): δ0.95-1.32 (m 5H), 1.35-1.46 (m, 1H), 1.50-1.92 (m, 10H), 1.93-2.15 (m, 4H), 2.23-2.43 (m, 2H), 3.15-3.30 (m, 4H), 3.35-3.50 (m, 2H), 3.57-3.68 (m, 1H), 3.74-3.82 (m, 1H), 4.34-4.41 (m, 1H), 4.51 (d, 1H, minor), 4.48 (d, 1H, major).
13 C-NMR (125.76 MHz, D 2 O): guanidine: δ157.36 (minor and major), carbonyl carbons: δ174.34 (major), 174.07 (minor), 168.94 (minor and major).
Example 57
HOOC-CH 2 -(R,S)Pro(3-(trans)Ph)-Pro-Agm×2 TFA
(i) H-(R,S)Pro(3-(trans)Ph)-Pro-Agm(Z)
Prepared from Boc-(R,S)Pro(3-(trans)Ph)-Pro-OSu (See Prep. of starting materials) in the same way as described for H-(R)Cha-Pro-Agm(Z) in Example 3.
(ii) HOOC-CH 2 -(R,S)Pro(3-(trans)Ph)-Pro-Agm×2 TFA
Alkylation as in Example 4 using Br--CH 2 COOBn followed by deprotection procedure (b) gave the title compound as a mixture of two diastereomers.
1 H-NMR (500 MHz, MeOD, mixture of two diastereomers, ratio ca: 1.1/1): δ1.40-1.80 (m, 6H), 1.85-2.05 (m, 1H), 2.10-2.30 (m, 1H), 2.50-2.65 (m, 2H), 3.10-3.40 (m, 6H), 3.50-3.70 (m, 2H), 3.9-4.40 (m, 4H), 4.63 (d, 1H, major), 4.67 (d, 1H, minor), 7.30-7.60 (m, 5H).
3 C-NMR (125.76 MHz, D 2 O): guanidine: δ157.52 (both isomers); carbonyl carbons: δ173.87, 173.73, 169.12, 168.94, 167.21, 167.00.
Example 58
HOOC-CH 2 -(R,S)Pro(3-(trans)Ph)-Pro-Nag×2 TFA
(i) H-(R,S)Pro(3-(trans)Ph)-Pro-Nag(Z)
Prepared from Boc-(R,S)Pro(3-(trans)Ph)-Pro-OSu (See Prep. of starting materials) and Boc-Nag(Z) in the same way as described for H-(R)Cha-Pro-Agm(Z) in Example 3.
(ii) HOOC-CH 2 -(R,S)Pro(3-(trans)Ph)-Pro-Nag×2 TFA
Alkylation as in Example 4 using Br--CH 2 COOBn followed by deprotection procedure (b) gave the title compound as a mixture of two diastereomers.
1 H-NMR (500MHz, MeOD, mixture of two diastereomers, ratio ca: 1.5/1): δ1.40-1.85 (m, 4H), 1.90-2.00 (m, 1H), 2.10-2.30 (m, 1H), 2.45-2.70 (m, 2H), 3.08-3.46 (m, 6H), 3.57-3.70 (m, 2H), 3.90-4.0 (m, 1H), 4.32-4.40 (m, 1H), 4.04 and 4.29 (AB-quartet, 2H, major), 4.16 and 4.37 (AB-quartet, 2H, minor), 4.60 (d, 1H, major), 4.64 (d, 1H, minor), 7.3-7.6 (m, 5H).
13 C-NMR (125.76 MHz, D 2 O): guanidine: δ157.48 (both isomers); carbonyl carbons: δ173.90, 173.71, 169.01, 168.94, 167.07 (both isomers).
Example 59
HOOC-CH 2 -(R)Cha-Pic-Agm×2 TFA
(i) H-(R)Cha-Pic-Agm(Z)
Prepared from Boc-(R)Cha-Pic-OSu (See Prep. of starting materials) in the same way as described for H-(R)Cha-Pro-Agm(Z) in Example 3.
(ii) HOOC-CH 2 -(R)Cha-Pic-Agm×2 TFA
Alkylation as in Example 4 using Br--CH 2 COOBn followed by deprotection procedure (a) gave the title compound.
1 H-NMR (300 MHz, MeOD): δ1.02 (m, 2H), 1.13-2.00 (m, 20H), 2.24 (bd, 1H), 3.12-3.45 (m, 5H), 3.71 (bd, 1H), 3.87 (s, 2H), 4.65 (bt, 1H), 5.06 (m, 1H).
13 C-NMR (75 MHz, D 2 O): guanidine: δ157.47; carbonyl carbons: δ169.42, 170.03, 172.71.
Example 60
HOOC-CH 2 -(Me)(R)Cha-(R,S)Pic-Agm×HOAc
(i) Me-(R)Cha-(R,S)Pic-Agm(Z)
Prepared from Boc-(Me)(R)Cha-Pic-OSu in the same way as described for H-(R)Cha-Pro-Agm(Z) in Example 3.
(ii) HOOC-CH2-(Me)(R)Cha-(R,S)Pic-Agm×HOAc
Alkylation as in Example 4 using Br--CH 2 COOBn followed by deprotection procedure (b) gave the title compound.
Comment: An epimerization of Pic occured somewhere during the synthesis.
The 1 H-NMR spectrum is complex consisting of two diastereomers ca: 1:1 ratio and rotamers thereof.
1 H-NMR (500 MHz, MeOD): δ0.75-2.15 (several m, 20H) 1.95 (bs, acetate), 2.2-2.7 (6H, two distinct sets of signals are observed in the ratio of ca: 1:1; thereof 2.35 and 2.55 (s, 3H)), 3.0-3.5 (m, 6H), 3.9-4.17 (m, 2H; thereof 4.14 (dd)), 4.4-4.5 (m, 1H), 4.97-5.15 (two bdd, 1H).
13 C-NMR (75 MHz, D 2 O): guanidine: δ157.50; carbonyl carbons: δ169.65, 170.01, 170.54, 172.67, 172.89.
Example 61
HOOC-(R,S)CH(Me)-(R)Cha-Pic-Agm×TFA
Alkylation as in Example 4 using H-(R)Cha-Pic-Agm(Z) (See Example 59) and Br--CH(Me)COOBn followed by deprotection procedure (a) gave the title compound as a mixture of two diastereomers.
Example 62
HOOC-(RorS)CH(Me)-(R)Cha-Pic-Agm/a×2 TFA
Obtained by separating the diastereomers formed in Example 61 using RPLC (CH 3 CN/NH 4 OAc (0.1M), 1/3) followed by evaporation of the solvent and freeze-drying from H 2 O/TFA. This diastereomer came out first of the two from the column.
1 H-NMR (300Mz, D 2 O, 2 rotamers ca: 5:1 ratio): δ0.70 (m, minor rotamer), 0.75-1.0 (m, 2H), 1.0-1.28 (m, 3H), 1.28-1.83 (m, 20H; thereof 1.57 (d, 3H)), 2.14 (bd, 1H), 2.92 (t, minor rotamer), 3.03-3.32 (m, 5H), 3.59 (bd, 1H), 3.85 (q, minor rotamer), 3.98 (q, 1H), 4.30-4.50 (m, minor rotamer), 4.54 (m, 1H), 4.95 (s. 1H).
13 C-NMR, (75 MHz, D 2 O): guanidine: δ157.39; carbonyl carbons: δ172.26 (2 carbons), 169.92.
Example 63
HOOC-(RorS)CH(Me)-(R)Cha-Pic-Agm/b×2 TFA
The title compound was obtained by using the same procedure as described in Example 62 on the compound formed in Example 61. This diastereomer came out after the first one from the column.
1 H-NMR (500 MHz, D 2 O, 2 rotamers ca: 5:1 ratio): δ0.72 (m, minor rotamer), 0.82 (m, minor rotamer), 0.97 (m, 2H), 1.0-1.23 (m, 3H), 1.23-1.40 (m, 2H), 1.40-1.83 (m, 18H; thereof 1.63 (d, 3H)), 2.11 (d, 1H), 2.17 (d, minor rotamer), 2.92 (t, minor rotamer), 3.05-3.25 (m, 4H), 3.29 (t, 1H), 3.74 (d, 1H), 4.02 (q, 1H), 4.34 (d, minor rotamer), 4.41 (dd, minor rotamer), 4.52 (t, 1H), 4.95 (s, 1H).
13 C-NMR (125 MHz, D 2 O): guanidine: δ154.68; carbonyl carbons: δ169.81, 169.60, 167.36.
Example 64
HOOC-CH2-CH2-(R)Cha-Pic-Agm×2 TFA
Prepared from H-(R)Cha-Pic-Agm(Z) (See Example 59) in the same way as described for HOOC-CH 2 -CH 2 -(R)Cha-Pro-Agm in Example 15 using 1.2 eq. of benzylacrylate instead of 1.1 eq.
1 H-NMR (500 MHz, D 2 O, 2 rotamers ca: 4:1 ratio): δ0.70-0.90 (m, minor rotamer), 0.90-1.0 (m, 2H), 1.05-1.25 (m, 3H), 1.30-1.45 (m, 2H), 1.45-1.85 (m, 15H), 2.1 (bd, 1H), 2.2 (bd, minor rotamer), 2.75 (t, 2H), 2.95 (t, minor rotamer),3.1-3.4 (m, 7H), 3.75 (bd, 1H), 4.55 (t, 1H), 4.95 (m, 1H).
13 C-NMR (75 MHz, D 2 O): guanidine: δ157.48; carbonyl carbons: δ170.10, 172.58, 174.75.
Example 65
H-(R)Cha-Pic-Nag×2 TFA
(i) Boc-(R)Cha-Pic-Nag(Z)
(ia) Prepared by starting from Boc-(R)Cha-Pic-OSu by using the same procedure as described for Boc-(R)Cha-Pro-Agm(Z) in Example 3.
(ib) Prepared by starting from Boc-(R)Cha-Pic-OH
Diphenylphosphoryl azide (0.432 ml, 2 mmol) was added to a stirred solution of Boc-(R)Cha-Pic-OH (765 mg, 2 mmol) in 5 ml DMF at -10° C. After 10 minutes H-Nag(Z)×2 HCl (600 mg, 2.1 mmol, see Preparation of Starting Materials) in 5 ml DMF and triethylamine (615 mg, 4.4 mmol) was added. The reaction mixture was kept in an ice bath for 3 h and then at room temperature for 12 h after which it was poured out in water. Extraction of the water phase with EtOAc followed by drying (MgSO 4 ) of the organic phase and evaporation of the solvent in vacuo gave 1.18 g (96%) of the product as a mixture of diastereomers (Epimers in Pic) in a ratio of 97:3 (RS/RR).
(ic) Starting from Boc-(R)Cha-Pic-OH
EDC hydrochloride (4.2 g, 21.9 mmol) was added at -15° C. to a stirred solution of Boc-(R)Cha-Pic-OH (8 g, 20.9 mmol), DMAP (10.6 g, 88 mmol) and H-Nag-(Z)×2 HCl (6.3 g, 19.5 mmol, see Preparation of Starting Materials) in acetonitrile. The reaction mixture was allowed to warm up to +15° C. during 16 h. The solvent was removed in vacuo an the residue was dissolved in ethyl acetate. Washing with water, 0.3M KHSO 4 , 0,3M NaHCO 3 , water and brine followed by drying (Na 2 SO 4 ) and evaporation of the solvent gave 11.9 g (92.5%) of the product as a mixture of diastereomers (Epimers in Pic) in a ratio of 98/2 (RS/RR).
1 H-NMR (500 MHz, CDCl 3 ): δ0.85-2.0 (m,29H; thereof 1.40 (bs, 9H)), 2.46 (bd, 1H), 3.1-3.4 (m, 5H), 3.92 (bd, 1H), 4.53 (bq, 1H), 5.10 (s, 2H), 5.22 (bs, 1H), 5.29 (bd, 1H), 6.7-7.2 (b, 3H), 7.25-7.45 (m, 5H).
13 C-NMR (125 MHz, CDCl 3 ): guanidine δ156.9; carbonyl carbons: δ173.6, 170.3, 163.7, 161.7.
(ii) H-(R)Cha-Pic-Nag(Z)
Prepared in the same way as described for H-(R)Cha-Pro-Agm(Z) in Example 3, starting from Boc-(R)Cha-Pic-Nag(Z).
1 H-NMR (500 MHz, CDCl 3 ): δ0.8-2.0 (m, 22H), 2.24 (bd, 1H), 3.1-3.4 (m, 5H), 3.72 (bd, 1H), 3.84 (bq, 1H), 5.05 (bd, 1H), 5.08 (s, 2H), 7.3-7.5 (m, 5H).
(iii) H-(R)Cha-Pic-Nag×2 TFA
Prepared by using the deprotection procedure (a) on the product (ii) above.
1 H-NMR (500 MHz, MeOD): δ0.9-1.1 (m, 2H), 1.2-2.0 (m, 18H), 2.32 (bd, 1H), 3.20 (t, 2H), 3.30 (t, 2H), 3.36 (m, 1H), 3.69 (bd, 1H), 4.49 (dd, 1H), 5.05 (bd, 1H).
13 C-NMR (125 MHz, MeOD): guanidine: δ158.7; carbonyl carbons: δ172.7, 171.4
Example 66
Me-(R)Cha-(R,S)Pic-Nag×2 TFA
(i) Me-(R)Cha-(R,S)Pic-Nag(Z)
Prepared in the same way as described for H-(R)Cha-Pro-Agm(Z) in Example 3 staring from Boc-(Me) (R)Cha-Pic-OSu and Boc-Nag(Z). An epimerization of Pic occured during the synthesis and the product was obtained as mixture of two diastereomers.
(ii) Me-(R)Cha-(R,S)Pic-Nag×2 TFA
Prepared by using deprotection procedure (b).
The 1 H-NMR spectrum is complex consisting of two diastereomers ca: 4:1 ratio and rotamers thereof.
1 H-NMR (500 MHz, MeOD): δ0.8-1.08 (m, 2H), 1.15-2.4 (several m, 19H), 2.6-2.75 and 2.9-2.95 (several s, 3H) 3.1-3.6 (several m, 5H), 3.75-4.1 (several m, 1H) 4.4-4.7 (several m, 1H), 5.05-5.15 (two dd, 1H).
13 C-NMR (125 MHz, D 2 O): guanidine: δ154.84; carbonyl carbons: δ167.60 and 169.99.
Example 67
HOOC-CH 2 -(R)Cha-Pic-Nag
(i) BnOOC-CH 2 -(R)Cha-Pic-Nag(Z)
Alkylation as in Example 4 using H-(R)Cha-Pic-Nag(Z) (See Example 65) and Br--CH 2 COOBn gave the title compound.
1 H-NMR (500 MHz, CDCl 3 ): δ0.8-1.0 (m, 2H), 1.1-1.7 (m, 19H), 1.79 (bd, 1H), 2.3-2.5 (m, 2H; thereof 2.38 (bd, 1H)), 3.00 (bt, 1H), 3.1-3.4 (m, 5H; thereof 3.38 (d, 1H)) 3.58 (d, 1H), 3.6-3.7 (m, 2H), 5.06 (dd, 2H), 5.07 (s, 2H), 5.16 (bs, 1H), 6.7-7.1 (b, 1H), 7.15 (bs, 1H), 7.2-7.4 (m, 10H).
13 C-NMR (125 MHz, CDCl 3 ) guanidine and carbonyl carbons: δ176.0, 173.6, 170.8, 163.8, 161.7.
(iia) HOOC-CH 2 -(R)Cha-Pic-Nag×2 HCl
Deprotection procedure (a) followed by purification with RPLC using CH 3 CN/0.1M NH 4 OAc, 1/3 as eluent, evaporation at 40°-50° C. and freeze drying gave the title compound as the acetate. Treatment with a 20-fold excess of hydrochloric acid, evaporation and renewed freeze drying gave the bis-hydrochloride of the desired compound.
1 H-NMR (500 MHz, D 2 O, mixture of two rotamers): δ0.7-2.0 (m, 20H), 2.17 (bd, 1H), 2.95 (t, minor rotamer), 3.17 (t, 2H), 3.25-3.35 (m, 3H), 3.72 (bd, 1H), 3.86 (dd, minor rotamer), 3.90 (s, 2H), 4.72 (t, 1H), 4.99 (bs, 1H).
13 C-NMR (75 MHz, D 2 O); guanidine δ157.4; carbonyl carbons δ169.9, 170.2, 173.0.
(iib) HOOC-CH 2 -(R)Cha-Pic-Nag×2 HBr
BnOOC-CH 2 -(R)Cha-Pic-Nag(Z) was dissolved in i Pr--OH/H 2 O (95/5) and hydrogenated over 5% Pd/C at atmospheric pressure in the presence of HBr (2.2 eq.). The catalyst was filtered off and the solvent evaporated to give a yellow oil (Alternatively, the acid can be added after hydrogenation and filtration). Crystallisation from i Pr--OH (or EtOH)/EtOAc (1/1) gave the title compound as a white crystalline powder.
1 H-NMR (500 MHz, D 2 O, mixture of two rotamers): δ1.15-2.0 (m, 20H), 2.30 (bd, 1H), 3.30 (m, 2H), 3.40-3.50 (m, 3H), 3.85-3.90 (m, 1H), 3,95 (apparent s, 2H), 4.75-4.85 (m, 1H, partially hidden by the H-O-D line), 5.10 (bs, 1H).
13 C-NMR (125 MHz, D 2 O): guanidine: δ157.6; carbonyl carbons: δ169.7, 170.2, 173.0.
Example 68
MeOOC-CH 2 -(R)Cha-Pic-Nag×2 TFA
The methyl ester MeOOC-CH 2 -(R)Cha-Pic-Nag(Z) was obtained by trans esterification of i PrOOC-CH 2 -(R)Cha-Pic-Nag(Z) (See Example 69) on the column during flash chromatography when CH 2 Cl 2 /MeOH was used as eluent. The title compound was obtained by the deprotection procedure (a).
1 H-NMR (500 MHz, MeOD): δ0.95-1.15 (m, 2H), 1.2-1.6 (m, 6H), 1.65-2.0 (m, 13H), 2.25 (bd, 1H), 3.21 (t, 2H), 3.30 (t, 2H), 3.37 (m, 1H), 3.71 (m, 1H), 3.83 (s, 3H), 3.97 (dd, 2H), 4.67 (bt, 1H), 5.05 (bs, 1H).
13 C-NMR (125 MHz, MeOD), guanidine: δ158.0; carbonyl carbons: δ173.0, 171.1, 168.3.
Example 69
i PrOOC-CH 2 -(R)Cha-Pic-Nag×2 TFA
Alkylation as described in Example 4 using H-(R)Cha-Pic-Nag(Z) (See Example 65) and Br--CH 2 --COO i Pr followed by deprotection procedure (a) gave the title compound.
1 H-NMR (500 MHz, MeOD): δ0.95-1.1 (m, 2H), 1.15-1.6 (m, 12H; thereof 1.25 (d, 3H), 1.28 (d, 3H)), 1.65-1.95 (m, 12H), 2.28 (bd, 1H), 3.21 (t, 2H), 3.30 (t,2H), 3.36 (m, 1H), 3.93 (dd, 2H), 4.67 (t, 1H), 5.04 (bs, 1H), 5.11 (pentet, 1H).
13 C-NMR (125 MHz, MeOD), guanidine: δ157.9; carbonyl carbons: δ173.1, 171.0, 168.3.
Example 70
HOOC-CH 2 -(Me)(R)Cha-(RorS)Pic-Nag/b×2 TFA
Alkylation as described in Example 4 using Me-(R)Cha-(R,S)Pic-Nag(Z) (See Example 66) and Br--CH 2 --COOBn followed by deprotection procedure (b) gave HOOC-CH 2 -(Me)(R)Cha-(R,S)Pic-Nag. The two diastereomers where separated by RPLC (CH 3 CN/NH 4 OAc, 1:3) followed by freeze-drying from H 2 O/TFA. This diastereomer came out last of the two from the column.
1 H-NMR (500 MHz, MeOD): δ0.9-1.1 (m, 2H), 1.15-1.35 (m, 4H), 1.4-1.55 (m, 2H), 1.6-1.85 (m, 12H), 2.3 (m, 1H), 2.85 (s, 3H), 3.15-3.45 (m, 5H), 3.65 (bs, 2H), 4.0 (m, 1H), 4.65 (m, 1H), 5.08 (dd, 1H).
13 C-NMR (75 MHz, D 2 O): guanidine: δ157.65; carbonyl carbons: δ169.86 and 172.48.
Example 71
HOOC-(R,S)CH(Me)-(R)Cha-(R,S)Pic-Nag×2 TFA
Alkylation as described in Example 4 using H-(R)Cha-Pic-Nag(Z) (See Example 65) and Br--CH(Me)--COOBn followed by deprotection procedure (a) gave the title compound as a mixture of four diastereomers.
Example 72
HOOC-(RorS)CH(Me)-(R)Cha-(RorS)Pic-Nag/c×2 TFA
Obtained by separating the diastereomers formed in Example 71 using RPLC (CH 3 CN/NH 4 OAc (0.1M), 1/4) followed by evaporation and freeze-drying from H 2 O/TFA. This diastereomer came out as the third one of the four from the column.
1 H-NMR (300 MHz, D 2 O, 2 rotamers ca: 5:1 ratio): δ0.88 (m, minor rotamer), 0.98-1.63 (m, 7H), 1.63-2.02 (m, 16H; thereof 1.68 (d,3H), 2.28 (m, 1H), 3.10 (t, minor rotamer), 3.25-3.50 (m, 5H; thereof 3.33 (t,2H) and 3.43 (t, 2H)), 3.82 (bd, 1H), 4.02 (q, 1H), 4.55 (d, minor rotamer), 4.65 (d, minor rotamer), 4.72 (m, 1H), 5.10 (m, 1H).
Example 73
HOOC-(RorS)CH(Me)-(R)Cha-(RorS)Pic-Nag/d×2 TFA
Obtained by separating the diastereomers formed in Example 71 using RPLC (CH 3 CN/NH 4 OAc (0.1M), 1:4) followed by evaporation and freeze-drying from H 2 O/TFA. This diastereomer came out last of the four diastereomers from the column.
1 H-NMR (500 MHz, D 2 O, 2 rotamers ca: 5:1 ratio): δ0.80 (m, minor rotamer), 0.90 (m, minor rotamer), 1.03 (m, 2H), 1.10-1.33 (m, 3H), 1.42 (m, 2H), 1.51-1.92 (m, 16H; thereof 1.57 (d, 3H)), 2.18 (d, 1H), 2.24 (d, minor rotamer), 2.98 (t, minor rotamer), 3.21 (t, 2H), 3.28-3.40 (m, 3H; thereof 3.44 (t, 2H)), 3.82 (d, 1H), 4.02 (q, 1H), 4.42 (d, minor rotamer), 4.50 (t, minor rotamer), 4.62 (t, 1H), 4.67 (s, minor rotamer), 5.03 (s, 1H).
Example 74
HOOC-CH2-CH2-(R)cha-Pic-Nag×2 TFA
Prepared from H-(R)Cha-Pic-Nag(Z) (See Example 65) in the same way as described for HOOC-CH 2 -CH 2 -(R)Cha-Pro-Agm in Example 15 using 1.2 eq. of benzylacrylate instead of 1.1 eq.
1H-NMR (500 MHz, D 2 O, 2 rotamers ca: 4:1 ratio): δ0.7-0.9 (m, minor rotamer), 0.9-1.0 (m, 2H), 1.05-1.3 (m, 3H), 1.3-1.45 (m, 2H), 1.5-1.8 (m, 13H), 2.10 (d, 1H), 2.20 (d, minor rotamer), 2.75 (t, 2H), 2.95 (t, minor rotamer), 3.15 (t, 2H), 3.2-3.35 (m, 5H), 3.75 (d, 1H), 4.55 (t, 1H), 4.95 (m, 1H).
13 C-NMR (75 MHz, D 2 O): guanidine: δ157.57; carbonyl carbons: δ170.16, 172.82, 174.75.
Example 75
HOOC-CH 2 -(R)Cha-(R,S)Mor-Agm×2 TFA
(i) H-(R)Cha-Mor-Agm(Z)
Prepared from Boc-(R)Cha-Mor-OSu (See Prep. of starting materials) in the same way as described for H-(R)Cha-Pro-Agm(Z) in Example 3.
(ii) HOOC-CH 2 -(R)Cha-(R,S)Mor-Agm×2 TFA
Alkylation as in Example 4 using Br--CH 2 COOBn followed by deprotection procedure (b) gave the title compound. An epimerization of Mor had occured somewhere during the synthesis and a mixture of about 9:1 of two diastereomers was observed in the final product.
1 H-NMR (300 MHz, MeOD): δ0.92-1.95 (m, 17H), 3.12-3.39 (m, 4H), 3.44-4.05 (m, 7H), 4.37 (d, 1H), 4.63 (m, 1H), 4.79 (bd, 1H).
13 C-NMR (75.47 MHz, MeOD): guanidine: δ158.63; carbonyl carbons: δ170.87, 170.82, 169.08 others: 5 69.06, 67.01 (C-O-C).
Example 76
HOOC-CH 2 -(R)Cha-(RorS)Mor-Nag×2 TFA
(i) H-(R)Cha-Mor-Nag(Z)
Prepared from Boc-(R)Cha-Mor-OSu (See Prep. of starting materials) and Boc-Nag(Z) in the same way as described for H-(R)Cha-Pro-Agm(Z) in Example 3.
(ii) HOOC-CH 2 -(R)Cha-(RorS)Mor-Nag×2 TFA
Alkylation as described in Example 4 using Br--CH 2 COOBn followed by deprotection procedure (b) gave the title compound.
1 H-NMR (300 MHz, MeOD): δ0.92-1.13 (m, 2H), 1.15-1.42 (m, 3H), 1.50 (br.s, 1H), 1.62-1.95 (m, 9H), 3.14-3.40 (m, 4H), 3.46-4.13 (m, 7H), 4.41 (d, 1H), 4.63 (m, 1H), 4.80 (br.d, 1H).
13 C-NMR (75.47 MHz, MeOD): guanidine: δ158.68; carbonyl carbons: δ171.19, 170.90, 169.46. others: δ68.81, 67.00 (C-O-C).
Example 77
H-(R)Cha-Aze-Nag×2 HOAc
(i) Boc-(R)Cha-Aze-Nag(Z)
Prepared from Boc-(R)Cha-Aze-OH in the same way as described for Boc-(R)Cha-Pic-Nag(Z) according to Example 65 (ic).
(ii) H-(R)Cha-Aze-Nag(Z)
Prepared in the same way as described for H-(R)Cha-Pro-Agm(Z) (See Example 3).
(iii) H-(R)Cha-Aze-Nag×2 HOAc
Prepared by using the deprotection procedure (a) on the product (ii) above.
1 H-NMR (300 MHz, D 2 O): δ0.85-1.10 (m, 2H), 1.10-2.04 (m, 13H) 1.95 (s, acetate), 2.20-2.37 (m, 1H), 2.60-2.82 (m, 1H), 3.15-3.40 (m, 4H), 3.96-4.15 (m, 2H), 4.18-4.30 (m, 1H), 4.30-4.42 (m, 1H), signals of a minor rotamer appears at: δ0.70, 3.90 and 5.10.
13 C-NMR (75 MHz, D 2 O): guanidine: δ157.39 and carbonyl carbons: δ170.22 and 172.38.
Example 78
HOOC-CH 2 -(R)Cha-Aze-Nag×HOAc
(i) BnOOC-CH 2 -(R)Cha-Aze-Nag(Z)
Prepared from H-(R)Cha-Aze-Nag(Z) (See Example 77) according to the procedure described in Example 4.
(ii) HOOC-CH 2 -(R)Cha-Aze-Nag×HOAc
Prepared by using the deprotection (a) on the product (i) above.
1 H-NMR (500 MHz, MeOD): δ0.90-1.10 (m, 2H), 1.15-2.00 (m, 13H) 1.95 (s, acetate), 2.20-2.30 (m, 1H), 2.58-2.70 (m, 1H), 3.17-3.30 (m, 4H), 3.35-3.50 (m, 2H), 3.55-3.68 (m, 1H), 4.10-4.20 (m, 1H), 4.30-4.38 (m, 1H), 4.65-4.77 (m, 1H), signals of minor rotamer appears at: 5 3.75, 3.98, 4.03 and 5.08.
13 C-NMR (75 MHz, D 2 O): guanidine: δ157.40 and carbonyl carbons: δ169.16, 171.92 and 172.13.
Example 79
H-(R)Cha-Pro(5-(S)Me)-Nag×2 HCl
(i) Boc-(R)Cha-Pro(5-(S)Me)-Nag(Z)
The same procedure as described for the coupling between Boc-(R)Cha-OH and H-Pic-OEt×HCl (See Preparation of Starting Materials) was used to accomplish the coupling between Boc-(R)Cha-Pro(5-(S)Me)-OH and H-Nag(Z)×2 HCl.
(ii) H-(R)Cha-Pro(5-(S)Me)-Nag(Z)
The same procedure as described for the synthesis of H-(R)-Cgl-Pic-Nag(Z) (See Example 84 (ii) was used.
(iii) H-(R)Cha-Pro(5-(S)Me)-Nag×2 HCl
Prepared by using the deprotection procedure (d) on the product (ii) above.
1 H-NMR (300 MHz, D 2 O): δ1.0-2.3 (m, 21H); thereof 1.47 (d, 3H), 2.4-2.55 (m, 1H), 3.3-3.6 (m, 4H), 4.30 (bt, 1H), 4.38 (dd, 1H), 4.47 (bt, 1H).
13 C-NMR (75 MHz, D 2 O): guanidine: δ157.6 carbonyl carbons: δ174.6, 169.6.
Example 80
HOOC-CH 2 -(R)Cha-Pro(5-(S)Me)-Nag×HOAc
Alkylation as in Example 4 using H-(R)Cha-Pro(5-(S)Me)-Nag(Z) (See Example 79) and Br--CH 2 --COOBn followed by deprotection procedure (a) gave the title compound.
1 H-NMR (300 MHz, D 2 O): δ0.9-1.9 (m, 19H); thereof 1.34 (bd, 3H), 1.93 (s, acetate), 2.0-2.2 (m, 3H), 2.34 (m, 1H), 3.1-3.5 (m, 7H), 3.97 (m, 1H), 4.20 (m, 1H), 4.31 (bt, 1H)
13 C-NMR (75 MHz, D 2 O): guanidine: δ157.4.
Example 81
HOOC-CH 2 -(R)Cha-(RorS)Pic(4,5-dehydro)-Nag/b×HOAc
(i) Boc-(R)Cha-(R,S)Pic(4,5-dehydro)-Nag(Z)
Prepared from Boc-(R)Cha-(R,S)Pic(4,5-dehydro)-OH in the same way as described for Boc-(R)Cha-Pic-Nag(Z) (See Example 65 (ic)).
(ii) H-(R)Cha-(R,S)Pic(4,5-dehydro)-Nag(Z)
Prepared in the same way as described for H-(R)Cha-Pro-Agm(Z) (See Example 3).
(iii) BnOOC-CH 2 -(R)Cha-(R,S)Pic(4,5-dehydro)-Nag(Z)
Prepared from H-(R)Cha-(R,S)Pic(4,5-dehydro)-Nag(Z) according to the procedure described in Example 4.
(iv) HOOC-CH 2 -(R)Cha-(RorS)Pic(4,5-dehydro)-Nag/b×HOAc
A mixture of 356 mg (0.539 nmol) of BnOOC-CH 2 -(R)Cha-(R,S) Pic(4,5-dehydro)-Nag(Z), 10.8 mL trifluoroaceticacid and 3.4 ml tioanisole was stirred at room temperature for 3.5 h. Water was added and the mixture was washed twice with CH 2 Cl 2 evaporation of the solvent gave HOOC-CH 2 -(R)Cha-(R,S)Pic(4,5-dehydro)-Nag. The title compound was obtained by separating the diastereomers by RPLC (CH 3 CN/NH 4 OAc (0.1M), 3/7) and freeze drying (H 2 O) after evaporation of the solvent. The diastereomer came out last of the two from the column.
1 H-NMR (300 MHz, D 2 O) δ0.85-1.95 (m, 15H), 2.50-2.80 (m, 2H), 3.25 (t, 2H), 3.35 (t, 2H), 3.55 (bs, 2H), 3.85-4.6 (m, 3H), 4.92 (minor rotamer), 5.30 (d, 1H), 5.85-6.1 (m, 2H),
13 C-NMR (75 MHz, D 2 O): guanidine: δ157.59; carbonyl carbons: δ171.46, 172.58, 173.03.
Example 82
HOOC-CH 2 -(R)Cha-Pic(4-(S)Me)-Nag×2 HCl
(i) Boc-(R)Cha-Pic(4-(S)Me)-Nag(Z)
Prepared from Boc-(R)Cha-Pic(4-(S)Me)-OH in the same way as described for Boc-(R)Cha-Pic-Nag(Z) according to method (ic) in Example 65.
(ii) H-(R)Cha-Pic(4-(S)Me)-Nag(Z)
Prepared in the same way as described for H-(R)Cha-Pro-Agm(Z) (See Example 3).
(iii) BnOOC-CH 2 -(R)Cha-Pic(4-(S)Me)-Nag(Z)
Prepared from H-(R)Cha-Pic(4-(S)Me)-Nag(Z) according to the procedure described in Example 4.
(iv) HOOC-CH 2 -(R)Cha-Pic(4-(S)Me)-Nag×2 HCl
Prepared by using the deprotection procedure (d) on the product (iii) above.
1 H-NMR (500 MHz, D 2 O): δ0.95-2.05 (m, 22H; thereof 1.05 (d, 3H)), 2.30-2.38 (bd, 1H), 3.28-3.36 (m, 2H) 3.36-3.50 (m, 3H), 3.85-3.95 (m, 1H), 3.98 (s, 2H), 4.70-4.90 (m, 1H; partly hidden behind the HOD signal), 5.22-5.27 (d, 1H), signal of a minor rotamer appears at δ0.93, 3.13 and 4.57.
13 C-NMR (125 MHz, D 2 O): guanidine: δ157.58; carbonyl carbons: δ170.12, 170.32 and 172.82.
Example 83
HOOC-CH 2 -(R)Cha-(R)Pic(4-(R)Me)-Nag×2 HCl
(i) Boc-(R)Cha-(R)Pic(4-(R)Me)-Nag(Z)
Prepared from Boc-(R)Cha-(R)Pic(4-(R)Me)-OSu and Boc-Nag(Z) in the same way as described for Boc-(R)Cha-Pro-Agm(Z) (See Example 3).
(ii) H-(R)Cha-(R)Pic(4-(R)Me)-Nag(Z)
Prepared in the same way as described for H-(R)Cha-Pro-Agm(Z) (See Example 3).
(iii) BnOOC-CH 2 -(R)Cha-(R)Pic(4-(R)Me)-Nag(Z)
Prepared from H-(R)Cha-(R)Pic(4-(R)Me)-Nag(Z) according to the procedure described in Example 4.
(iv) HOOC-CH 2 -(R)Cha-(R)Pic(4-(R)Me)-Nag×2 HCl
Prepared by using the deprotection procedure (d) on the product (iii) above.
1 H-NMR (500 MHz, D 2 O): δ1.00-2.05 (m, 22H), 2.18-2.26 (bd, 1H), 3.28-3.36 (m, 2H), 3.36-3.55 (m, 3H), 3.85-4.05 (m, 3H), 4.70-4.90 (m, 1H; partly hidden behind the HOD signal), 5.25-5.30 (d, 1H), signals of minor rotamer appears at: δ2.40, 2.90, 4.10, 4.42, 4.55 and 5.23.
13 C-NMR (125 MHz, D 2 O): guanidine: δ157.56: carbonyl carbons: δ169.69, 169.84 and 173.20.
Example 84
HOOC-CH 2 -(R)Cgl-Pic-Nag×2 HCl
(i) Boc-(R)Cgl-Pic-Nag(Z)
Prepared from Boc-(R)Cgl-Pic-OH in the same way as described for Boc-(R)Cha-Pic-Nag(Z) according to method (ic) in Example 65.
1H-NMR (300 MHz, CDCl 3 ): δ0.9-1.8 (m, 27H), 2.4 (d, 1H), 3.1-3.3 (m, 5H), 3.9 (d, 1H), 4.2 (t, 1H), 5.1 (s, 2H), 5.2 (bd, 2H), 6.7-7.4 (m, 9H).
(ii) H-(R)Cgl-Pic-Nag(Z)
Gaseous hydrogen chloride was bubbled through a solution of Boc-(R)Cgl-Pic-Nag(Z) (1.38 g, 2.22 mmol) in ethyl acetate (25 ml). After 10 minutes the solvent was evaporated and the residue was dissolved in ethyl acetate and 10% Na 2 CO 3 . The organic phase was separated, washed with brine and dried (MgSO 4 ). Evaporation of the solvent gave 1.02 g (92%) of the title compound.
1 H-NMR (300 MHz, MeOD): δ1.0-1.9 (m, 18H), 2.2-2.3 (m, 1H), 3.2-3.3 (m, 5H), 3.6 (d, 1H), 3.8-3.9 (bd, 1H), 4.2 (t, 1H), 4.7-4.8 (bs, 5H), 5.1 (s, 2H), 5.2 (s, 1H), 7.2-7.3 (m, 5H).
(iii) BnOOC-CH 2 -(R)Cgl-Pic-Nag(Z)
A solution of the triflate ester of benzyl glycolate (291 mg, 0.98 mmol) in CH 2 Cl 2 (2 ml) was added at -25° C. to a stirred mixture of H-(R)Cgl-Pic-Nag(Z) (0.52 g, 1.04 mmol) and K 2 CO 3 (494 mg, 3.58 mmol) in acetonitrile (5 ml) and CH 2 Cl 2 (1 ml). The temperature was allowed to reach room temperature during a couple of hours and after 5 days the reaction mixture was diluted with water and extracted with EtOAc and toluene. Drying of the organic phase (MgSO 4 ) and concentration of the solution gave 319 mg (47%) of colorless crystals.
1 H-NMR (500 MHz, CDCl 3 ): δ1.0-1.1 (m, 1H), 1.1-1.3 (m, 4H), 1.35-1.6 (m, 5H), 1.6-1.85 (m, 8H), 1.8-2.2 (bs, 1H), 2.23-2.5 (m, 2H), 2.9 (t, 1H), 3.1-3.5 (m, 6H), 3.6-3.7 (m, 2H), 5.0-5.1 (m, 4H), 5.2 (s, 1H), 6.5-7.4 (m, 13H).
(iv) HOOC-CH2-(R)Cgl-Pic-Nag×2 HCl
BnOOC-CH2-(R)Cgl-Pic-Nag(Z) (319 mg, 0.49 mmol) was dissolved by heating in isopropanol (50 ml) and water (5 ml) and hydrogenated for 24 h over 10% Pd/C (228 mg). After filtration and evaporation of the solvent and susequent dissolution in dilute hydrochloric acid followed by freeze drying, the peptide (223 mg, 91%) was isolated as a white powder.
1 H-NMR (500 MHz, D 2 O): δ1.1-2.1 (m, 18H) 2.3 (d, 1H), 3.3 (t, 2H), 3.4 (t, 3H), 3.85-4.05 (m, 3H), 4.6 (d, 1H), 5.15 (s, 1H).
13 C-NMR (75 MHz, D 2 O): guanidine: δ157.43 carbonyl carbons: δ169.2, 172.94.
Example 85
H-(R)Hoc-Pro-Nag×2 TFA
(i) Boc-(R)Hoc-Pro-Nag(Z)
Prepared from Boc-(R)Hoc-Pro-OH in the same way as described for Boc-(R)Cha-Pic-Nag(Z) according to Example 65 (ic).
(ii) H-(R)Hoc-Pro-Nag(Z)
Prepared in the same way as described for H-(R)Cha-Pro-Agm(Z) (See Example 3).
(iii) H-(R)Hoc-Pro-Nag×TFA
Prepared by using the deprotection procedure (a) on the product (ii) above.
1 H-NMR (300 MHz, D 2 O): δ0.90-1.05 (m, 2H), 1.16-1.48 (m, 6H), 1.48-1.84 (m, 6H), 1.84-2.24 (m, 6H), 2.40 (m, 1H), 3.25-3.45 (m, 4H), 3,74 (m, 1H), 3.85 (m, 1H), 4.42 (m, 1H), 4.51 (m, 1H).
Example 86
HOOC-CH 2 -(R)Hoc-Pro-Nag×HOAc
(i) BnOOC-CH 2 -(R)Hoc-Pro-Nag(Z)
Prepared from H-(R)Hoc-Pro-Nag(Z) (See Example 85) according to the procedure described in Example 4.
(ii) HOOC-CH 2 -(R)Hoc-Pro-Nag×HOAc
Prepared by using the deprotection procedure (a) on the product (i) above.
1 H-NMR (300 MHz, D 2 O): δ0.76-0.97 (m, 2H), 1.00-1.37 (m, 6H), 1.50-2.12 (m, 12H) 1.89 (s, acetate), 2.27 (m, 1H), 3.10-3.33 (m, 4H), 3.41 (bs, 2H), 3.61 (m, 1H), 3.77 (m, 1H), 4.12 (m, 1H), 4.37 (m, 1H).
13 C-NMR (75 MHz, D 2 O): guanidine: δ157.4; carbonyl carbons: δ170.8, 173.9, 174.5.
Example 87
HOOC-CH 2 -(R)Hoc-Pic-Nag×HOAc
(i) Boc-(R)Hoc-Pic-Nag(Z)
Prepared from Boc-(R)Hoc-Pic-OH in the same way as described for Boc-(R)Cha-Pic-Nag(Z) according to method (ic) in Example 65.
(ii) H-(R)Hoc-Pic-Nag(Z)
Prepared in the same way as described for H-(R)Cha-Pro-Agm(Z) (See Example 3).
(iii) BnOOC-CH 2 -(R)Hoc-Pic-Nag(Z)
Prepared according to the procedure described in Example 4.
(iv) HOOC-CH 2 -(R)Hoc-Pic-Nag×HOAc
Prepared by using the deprotection procedure (a) on the product (iii) above.
1 H-NMR (300 MHz, D 2 O): δ0.75-0.95 (m, 2H), 1.00-1.30 (m, 6H), 1.30-1.50 (m, 2H), 1.50-1.82 (m, 12H), 1.82-1.95 (bs, acetate), 2.23 (bd, 1H), 3.08-3.32 (m, 6H), 3.52 (bs, 2H), 3.77 (bd, 1H), 4.50 (bs, 1H), 5.00 (bs, 1H).
Example 88
HOOC-CH 2 -(R)Dph-Pic-Nag×2 HCl
(i) Boc-(R)Dph-Pic-Nag(Z)
Prepared from Boc-(R)Dph-Pic-OH in the same way as described for Boc-(R)Cha-Pic-Nag(Z) (See Example 65 (ic)).
(ii) H-(R)Dph-Pic-Nag(Z)
Prepared in the same way as described for H-(R)Cgl-Pic-Nag(Z) (See Example 84 (ii)).
(iii) BnOOC-CH 2 -(R)Dph-Pic-Nag(Z)
Prepared from H-(R)Dph-Pic-Nag(Z) according to the procedure described in Example 4.
(iv) HOOC-CH 2 -(R)Dph-Pic-Nag×2 HCl
Prepared by using the deprotection procedure (d) on the product (iii) above.
1 H-NMR (500 MHz, D 2 O): δ0.46 (m, 1H), 1.2-1.35 (m, 2H), 1.45 (m, 1H), 1.53 (m, 1H), 1.89 (pentet, 2H), 2.03 (bd, 1H), 3.24 (bt, 1H), 3.29 (t, 2H), 3.38 (t, 2H), 3.72 (d, 1H), 3.78 (d, 1H), 3.79 (m, 1H), 4.68 (d, 1H), 4.89 (m, 1H), 5.73 (d, 1H), 7.4-7.6 (m, 6H), 7.65 (t, 2H), 7.81 (d, 2H).
Example 89
HOOC-CH 2 -(R)Dch-Pic-Nag×HOAc
(i) Boc-(R)Dch-Pic-Nag(Z)
Prepared from Boc-(R)Dch-Pic-OH in the same way as described for Boc-(R)Cha-Pic-Nag(Z) (in Example 65 (ic).
(ii) H-(R)Dch-Pic-Nag(Z)
Prepared in the same way as described for H-(R)Cgl-Pic-Nag(Z) (in Example 84 (ii).
(iii) BnOOC-CH 2 -(R)Dch-Pic-Nag(Z)
Prepared from H-(R)Dch-Pic-Nag(Z) according to the procedure described in Example 4.
(iv) HOOC-CH 2 -(R)Dch-Pic-Nag×HOAc
Prepared by using the deprotection procedure (a) on the product (iii) above.
1 H-NMR (500 MHz, D 2 O): δ1.2-2.0 (m, 30H), 2.09 (s, acetate), 2.30 (bd, 1H), 3.32 (t, 2H), 3.4-3.5 (m, 3H), 3.65 (d, 1H), 3.70 (d, 1H), 3.86 (bd, 1H), 4.86 (m, 1H), 5.09 (m, 1H).
13 C-NMR (125 MHz, D 2 O): guanidine: δ159.4, carbonyl carbons: δ172.5, 173.3, 174.9.
Example P1
Solution for parenteral administration
A solution is prepared from the following ingredients:
______________________________________HOOC--CH.sub.2 --(R)Cha-Pic-Nag × 2HBr 5 gSodium chloride for injection 9 gAcetic acid 3 gWater for inj. up to 1000 ml______________________________________
The active constituent, the sodium chloride and the acetic acid are dissolved in the water. The pH is adjusted with 2M NaOH to pH 3-7. The solution is filtered through a sterile 0.2 μm filter and is aseptically filled into sterile ampoules.
Example P2
Tablets for oral administration
1000 tablets are prepared from the following ingredients:
______________________________________Thrombin inhibitor 100 gLactose 200 gPolyvinyl pyrrolidone 30 gMicrocrystalline cellulose 30 gMagnesium stearate 6 g______________________________________
The active constituent and lactose are mixed with an aqueous solution of polyvinyl pyrrolidone. The mixture is dried and milled to form granules. The microcrystalline cellulose and then the magnesium stearate are then admixed. The mixture is then compressed in a tablet machine giving 1000 tablets, each containing 100 mg of active constituent.
Biology
Determination of thrombin clotting time and IC 50 TT
Human thrombin (T 6769, Sigma Chem Co) in buffer solution, pH 7.4, 100 μl, and inhibitor solution, 100 μl, were incubated for one min. Pooled normal citrated human plasma, 100 μl, was then added and the clotting time measured in an automatic device (KC 10, Amelung).
The clotting time in seconds was plotted against the inhibitor concentration, and the IC 50 TT was determined by interpolation.
IC 50 TT is the concentration of inhibitor that doubles the thrombin clotting time for human plasma. pIC 50 TT is the -log 10 of IC 50 TT in mol/l. The preferred compounds of the invention have an pIC 50 TT in the range 6.6-8.2.
Determination of Activated Partial Thromboplastin Time (APTT)
APTT was determined in pooled normal human citrated plasma with the reagent PTT Automated 5 manufactured by Stago. The inhibitors were added to the plasma (10 μl inhibitor solution to 90 μl plasma) and APTT was determined in the mixture by use of the coagulation analyser KC10 (Amelung) according to the instructions of the reagent producer. The clotting time in seconds was plotted against the inhibitor concentration in plasma and the IC 50 APTT was determined by interpolation.
IC 50 APTT is defined as the concentration of inhibitor in plasma that doubled the Activated Partial Thromboplastin Time. pIC 50 APTT is the -log 10 of IC 50 APTT in mol/l. Those of the preferred compounds of the invention that were tested showed a pIC 50 APTT of 5.1-6.4.
______________________________________ABBREVIATIONS______________________________________Agm = AgmatineAgm(Z) = ω-N-benzyloxycarbonyl agmatineAA.sub.1 = Amino acid 1AA.sub.2 = Amino acid 2Aze = (S)-Azetidin-2-carboxylic acidBla = α-substituted butyrolactoneBoc = tertiary butoxy carbonylBrine = saturated water/NaCl solutionBu = butylBn = benzylCgl = (S)-Cyclohexyl glycineCh = cyclohexylCha = (S)-β-cyclohexyl alanineCME-CDI = 1-Cyclohexyl-3-(2-morpholinoethyl) carbodiimide netho-p-toluenesulfonateDCC = dicyclohexyl carbodiimideDch = (S)-Dicyclohexyl alanineDMAP = N,N-diimethyl amino pyridineDMF = dimethyl formamideDMSO = dimethyl sulphoxideDph = (S)-Diphenyl alanineEDC = 1-(3-Dimetylaminopropyl)-3-ethylcarbodiimide hydrochlorideEt = ethylEtOAc = ethyl acetateHOAc = acetic acidHOBt = N-hydroxy benzotriazoleHoc = (S)-Homocyclohexyl alanineHop = (S)-Homophenyl alanineHOSu = N-hydroxysuccinimideMag = miniagmatineMe = methylMor = (S)-morpholine-2-carboxylic acidMpa = mega pascalNag = noragmatineNag (Z) = δ-N-benzyloxycarbonyl-noragmatineNMM = N-methyl morpholinePgl = (S)-phenyl glycinePh = phenylPhe = (S)-phenyl alaninePic = (S)-pipecolinic acidPr = propylPro = (S)-prolineRPLC = reverse phase high-performance liquid chromatographyTf = trifluoromethyl sulphonylTFA = trifluoracetic acidTHF = tetrahydrofuranp-TsOH = para-toluenesulfonic acidVal = (S)-valineZ = benzyloxy carbonyl______________________________________
Prefixes n, s, i and t have their usual meanings: normal, iso, sec and tertiary. ##STR10##
__________________________________________________________________________SEQUENCE LISTING(1) GENERAL INFORMATION:(iii) NUMBER OF SEQUENCES: 1(2) INFORMATION FOR SEQ ID NO:1:(i) SEQUENCE CHARACTERISTICS:(A) LENGTH: 20 amino acids(B) TYPE: amino acid(D) TOPOLOGY: linear(ii) MOLECULE TYPE: peptide(iv) ANTI-SENSE: NO(v) FRAGMENT TYPE: N-terminal(xi) SEQUENCE DESCRIPTION: SEQ ID NO:1:AlaAspSerGlyGluGlyAspPheLeuAlaGluGlyGlyGlyValArg151015GlyProArgVal20__________________________________________________________________________ | The invention relates to new competitive inhibitors of thrombin, their synthesis, pharmaceutical compositions containing the compounds as active ingredients, and the use of the compounds as anticoagulants for prophylaxis and treatment of thromboembolic diseases, according to the formula ##STR1## wherein A represents a methylene group, an ethylene group or a propylene group, which may be substituted or
A represents --CH 2 --O--CH 2 --, --CH 2 --S--CH 2 --, --CH 2 --SO--CH 2 --, or
A represents --CH 2 --O--, --CH 2 --S--, --CH 2 --SO--, with the heteroatom functionality in position 4, or
n is an integer 2 to 6; and
B represents --N(R 6 )--C(NH)--NH 2 , wherein R 6 is H or a methyl group, or
B represents --S--C(NH)--NH 2 , or --C(NH)--NH 2 .
Further described is new use in synthesis of pharmaceutical compounds of a compound of the formula: ##STR2## | 2 |
This is a divisional of co-pending application Ser No. 148,743, filed on Jan. 27, 1988, now U.S. Pat. No. 4,861,887, issued Aug. 29, 1989.
BACKGROUND OF THE INVENTION
This invention pertains to imidazolinone compounds and particularly to methods and intermediates useful for the preparation of o-carboxyarylimidazolinone compounds which are useful as herbicides.
Novel herbicidal imidazolinyl benzoic acids, nicotinic acids and quinoline-3-carboxylic acids, esters, and salts, and their preparation and use are disclosed in U.S. Pat. Nos. 4,188,487, 4,297,128, and 4,638,068.
SUMMARY OF THE INVENTION
The present invention provides a method for the preparation of o-carboxyarylimidazolinone compounds by oxidizing the appropriate 2-{[(1-carbamoyl-1,2-dimethylpropyl)amino]methyl}benzoic acid, nicotinic acid or quinoline-3-carboxylic acid with a brominating agent.
The invention also provides a method for preparing the intermediate 2-{[(1-carbamoyl-1,2-dimethylpropyl)amino]methyl} compounds by alkylating 2-methylvalineamides with the appropriate o-halomethylarylcarboxylate. In the case of pyridine halomethyl compounds, a 2-chloro-4-halo acetoacetate ester is reacted with an α,β-unsaturated aldehyde or ketone to form a 2-(halomethyl)nicotinic ester.
The invention further provides certain 2-{[(1-carbamoyl-1,2-dimethylpropyl)amino]methyl}benzoic acid, nicotinic acid, or quinoline-3-carboxylic acid compounds and certain 2-(halomethyl)benzoic esters, nicotinic esters, a quinoline-3-carboxylic ester compound useful as intermediates in the above methods.
The invention also provides a method for the preparation of o-carboxypyridyl imidazoline compounds by a sequence proceeding from the 2-chloro-4-haloacetoacetates, through reactions as described above, to oxidation of 2-{[(1-carbamoyl-1,2-dimethylpropyl)amino]methyl} nicotinic acid ester with a brominating agent.
The oxidation method of this invention based on use of a bromine source provides unexpected results. Other oxidizing agents such as sulfur, chlorine, iodine and manganese oxide were ineffective for the result desired.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
o-Carboxyaryl imidazolinone compounds represented by formula I ##STR1## wherein
A is CH or N;
R 1 is H or C 1 -C 12 alkyl;
R 2 is H or C 1 -C 6 alkyl;
R 3 is H, C 1 -C 6 alkyl, or when R 2 and R 3 are taken together they may form a ring represented by
--CH═C--CH═CH--;
are prepared by reacting a 2-{[(1-carbamoyl-1,2-dimethylpropyl)amino]methyl]}benzoic acid, nicotinic acid, or quinoline-3-carboxylic acid of formula II ##STR2## wherein A, R 1 , R 2 , and R 3 are as described for formula I above with a minimum of two molar equivalents of a brominating agent such as bromine, N-bromosuccinimide, N-bromoacetamide or the like in an inert organic solvent such as acetic acid, in the presence of an acid acceptor such as sodium acetate, in a temperature range of about 20° C. to 100° C. for a sufficient period of time to essentially complete the reaction as illustrated in Flow Diagram I below. ##STR3## Formula II 2-{[(1-carbamoyl-1,2-dimethylpropyl)amino]methyl}compounds suitable for use in the method of this invention may be prepared by reacting a 2-(halomethyl)-benzoic ester, nicotinic ester, or quinoline-3-carboxylic ester of formula III ##STR4## wherein R 1 is C 1 -C 12 alkyl and A, R 2 , and R 3 are as a minimum of one molar equivalent of racemic 2-amino-3-dimethylbutyramide or an individual optical isomer thereof, in an inert organic solvent such as dimethylsulfoxide, acetone or the like; in the presence of a base such as sodium bicarbonate; optionally in the presence of a catalytic amount of NaI; in a temperature range of about 25° C. to 100° C. as illustrated in flow diagram II below. ##STR5## Formula II compounds wherein R 1 is hydrogen which are suitable for use in the method of this invention may readily be prepared from compounds of formula II wherein R 1 is C 1 -C 12 alkyl by hydrolysis.
The present invention includes novel compounds represented by formula II below ##STR6## wherein
A is CH or N;
R 1 is H or C 1 -C 12 alkyl;
R 2 is H or C 1 -C 6 alkyl;
R 3 is H, C 1 -C 6 alkyl, or when R 2 and R 3 are taken together they may form a ring represented by --CH═CH--CH═CH--; and novel compounds represented by formula III below ##STR7## wherein R 1 =C 1 -C 12 alkyl and R 2 and R 3 are described for formula II above, and X is Cl or Br, which are useful intermediates for the preparation of herbicidal imidazolinone compounds utilizing the methods of this invention. A preferred group of novel formula II and formula III compounds above are those wherein
R 1 is C 1 -C 3 alkyl;
R 2 is H, or C 1 -C 3 alkyl; and
R 3 is H.
Formula III pyridine halomethyl compounds for use in the method of this invention may be prepared by a method analogous to that described in pending application for United States Letters Patent of R. Doehner, Ser. No. 791,671 filed Oct. 28, 1985 by reacting a 2-chloro-4-haloacetoacetate ester of formula IV ##STR8## wherein R 1 is C 1 -C 12 alkyl; and X is Cl or Br with an α,β-unsaturated aldehyde or ketone of formula V ##STR9## wherein R 2 is H or C 1 -C 6 alkyl and R 3 is H in the presence of a minimum of two molar equivalents of ammonium salt in an organic solvent, in a temperature range of ambient temperature to the boiling point of the solvent until the reaction is essentially complete, as illustrated in Flow Diagram III below. ##STR10## wherein R 1 , R 2 , R 3 and X are as described for formula IV and Formula V above.
The present invention also includes a method for the preparation of o-carboxypyridyl imidazolinone compounds represented by formula I ##STR11## wherein
R 1 is H, or C 1 -C 12 alkyl;
R 2 is H, or C 1 -C 6 alkyl; and
R 3 is H;
by reacting, in sequence, a 2-chloro-4-haloacetoacetate ester of formula IV ##STR12## with an α,β-unsaturated aldehyde or ketone of formula V ##STR13## in the presence of a minimum of two molar equivalents of ammonium salt in an organic solvent, in a temperature range of ambient temperature to the boiling point of the solvent until the reaction is essentially complete, and reacting the thus formed 2-(halomethyl)nicotinic ester, of formula III ##STR14## wherein R 1 , R 2 , R 3 and X are as previously described for formula IV and V, with a minimum of one molar equivalent of racemic 2-amino-2,3-dimethylbutyramide or an individual optical isomer thereof in an inert organic solvent in the presence of a base, optionally in the presence of a catalytic amount of NaI, in a temperature range of about 25° C. to 100° C., and further reacting the thus-formed 2-{[(1-carbamoyl-1,2-dimethylpropyl)amino]methyl}nicotinic ester, or acid derived therefrom, of formula II ##STR15## wherein R 1 , R 2 and R 3 , are as described for formula I above with a minimum of two molar equivalents of a brominating agent in an inert organic solvent in the presence of an acid acceptor in a temperature range of about 25° C. to 100° C. for a sufficient period of time to essentially complete the reaction.
The preparation of other intermediates of formula III closely follows literature procedures such as oxidation of a 2-methyl-3-pyridinecarboxylate or a 2-methyl-3-quinolinecarboxylate, followed by rearrangement of the resulting N-oxide with POCl 3 , to give compounds of formula III as illustrated below.
The invention is further illustrated by the following non-limiting examples.
EXAMPLE 1
Preparation of ethyl 2-chloromethyl-5-ethylnicotinate
A solution of 61 g of ethyl-2,4-dichloroacetoacetate (0.306 mol) and 30 g of 2-ethylacrolein (0.357 mol) in 500 mL of absolute ethanol is mixed with 85.5 g of ammonium sulfamate (0.75 mol), and the stirred mixture is heated at reflux for 90 minutes. The reaction is concentrated in vacuo and the residue is partitioned between ethyl acetate and water. The organic phase is concentrated in vacuo, and the residue is chromatographed on silica gel using hexane-ethyl acetate mixtures to give 50 g of crude product. This material is purified by extraction into aqueous hydrochloric acid, washing with hexanes, making the aqueous phase basic with cold ammonium hydroxide, and extracting with hexanes to afford 30 g of the title product as an oil (43%), having elemental analysis calculated for C 11 H 14 ClNO 2 % C 58.03, H 6.20, N 6.15, Cl 15.57 found % C 58.29, H 6.30, N 6.02, Cl 15.49.
Utilizing the above procedure yields the formula III compounds listed in Table I below.
TABLE I______________________________________ ##STR17##mp R.sub.1 R.sub.2 R.sub.3 X analysis (calc)______________________________________low-melting C.sub.2 H.sub.5 CH.sub.3 H Cl C, 56.13 (56.22)solid H, 5.65 (5.66) N, 6.57 (6.56) Cl, 16.40 (16.59)oil CH.sub.3 C.sub.2 H.sub.5 H Cl C, 55.68 (56.22) H, 5.63 (5.66) N, 6.25 (6.56) Cl, 16.70 (16.59)low-melting CH.sub.3 CH.sub.3 H Cl C, 54.12 (54.15) H, 5.07 (5.05) N, 6.98 (7.02) Cl, 17.79 (17.76)low-melting C.sub.2 H.sub.5 CH.sub.3 H Br C, 47.86 (46.53) H, 4.75 (4.69) N, 5.51 (5.43) Br, 31.28 (30.96)______________________________________
EXAMPLE 2
Preparation of ethyl 2-chloromethylnicotinate
A solution of 9 g of ethyl 2-methylnicotinate in 250 mL methylene chloride is stirred at room temperature and 32 g of 80% metachloroperoxybenzoic acid is added in one portion. The resulting solution is stirred for three days. The precipitated solid is filtered off, and the filtrate is washed with cold, dilute aqueous sodium hydroxide, dried, and concentrated in vacuo to afford the crude N-oxide. This material is digested in 75 mL of 1,2-dichloroethane; 15 mL of phosphorous oxychloride is added, and the solution is heated at reflux overnight. The solution is concentrated in vacuo, and the residue is taken up in methylene chloride and neutralized with aqueous sodium acetate. The organic phase is dried, concentrated in vacuo, and the residue is chromatographed on silica gel using hexane-ethyl acetate mixtures to afford 1.2 g of the title product as an oil having NMRδmCDCl 3 ): 1.4 (+, 3H), 4.5 (q, 2H), 5.1 (2H), 7.4 (, 1H), 8.4 (dd, 1H), 8.8 (dd, 1H).
Also prepared by this method is ethyl 2-chloromethylquinoline-3-carboxylate; NMR(δ CDCl 3 ): 1.4 (+, 3H), 4.5 (q, 2H), 5.3 (5,2H), 7.5-8.3 (m, 4H), 9.0 (5, 1H).
EXAMPLE 3
Preparation of ethyl 2-{[(1-carbamoyl-1,2-dimethylpropyl)amino]methyl}-5-ethylnicotinate
A mixture of 77 g of ethyl 2-chloromethyl-5-ethylnicotinate (0.338 mol), 44 g of α-methylvalinamide (0.338 mol) and 33.5 g of sodium bicarbonate (0.4 mol) in 60 mL dimethylsulfoxide is stirred and heated at 80° for 16 hours. The reaction is partitioned between 1:1 ethylacetate-hexane and water. The organic layer is washed thoroughly with water, dried, and concentrated in vacuo to a gum. Chromatography of this gum on silica gel using hexane-ethyl acetate mixtures as eluant affords the title product, mp 68°-72°.
The above reaction is conducted with acetone as solvent (with cat. NaI) and also yields the title product.
Utilizing the above procedure with analogous formula III halomethyl compounds yields the formula II compounds listed in Table II below.
TABLE II______________________________________ ##STR18##mp °C. R.sub.1 R.sub.2 R.sub.3 A______________________________________106-107 CH.sub.3 CH.sub.3 H Nsolid C.sub.2 H.sub.5 H H N138-139 C.sub.2 H.sub.5 CHCHCHCH N81-83 C.sub.2 H.sub.5 H H CH______________________________________
EXAMPLE 4
Preparation of ethyl 5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinate
A mixture of 1 g of ethyl 2-{[(1-carbamoyl-1,2-dimethylpropyl)amino]methyl}-5-ethylnicotinate (3.1 mmol) and 0.58 g anhydrous sodium acetate (7 mmol) in 10 mL acetic acid is warmed to 50° C., at which point the reaction is a homogeneous solution. A solution 1 g of bromine (6.2 mmol) in 2 mL acetic acid is added in two portions over two minutes, and the reaction is stirred at 50° C. for 16 hours. The reaction mixture is concentrated in vacuo, and the residue is partitioned between ethyl acetate and water. The organic layer is washed with aqueous sodium bisulfite, dried over MgSO 4 , diluted with an equal volume of hexanes, and filter-chromatographed through a pad of silica gel. The silica gel is further eluted with additional 1:1 hexane-ethyl acetate, and the combined eluates are concentrated in vacuo to afford 0.6 g product having mp 84.5°-86.5° C.
The title product is also obtained using N-bromoacetamide or N-bromosuccinimide in place of bromine.
Utilizing the above procedure with various formula II compounds yields the formula I compounds listed in Table III below.
TABLE III______________________________________ ##STR19##R.sub.1 R.sub.2 R.sub.3 A mp °C.______________________________________CH.sub.3 CH.sub.3 H N 129.0-130.5C.sub.2 H.sub.5 H H N 72.0- 75.0C.sub.2 H.sub.5 CHCHCHCH N 146.0-147.5H H H CH 163.0-165.0______________________________________
EXAMPLE 5
Preparation of 2-{[(1-carbamoyl-1,2-dimethylpropyl)amino]methyl}-5-ethylnicotinic acid
A solution of 5.6 g of ethyl 2-{[(1-carbamoyl-1,2-dimethylpropyl)amino]methyl}-5-ethylnicotinate (0.0174 mol) in 30 mL of methanol containing 2 g of NaOH (0.05 mol) and 10 mL water is stirred at room temperature for two hours and 30 minutes. The reaction is concentrated in vacuo and redissolved in 30 mL water; adjustment of the pH to 4 with concentrated hydrochloric acid and concentration in vacuo gives a gum. This residue is dissolved in a mixture of ethyl acetate, tetrahydrofuran, and methanol, dried over MgSO 4 , and concentrated in vacuo to 6 g foam. Crystallization from methanol-ether affords 3.1 g product, mp 180°-181° C.
EXAMPLE 6
Preparation of 5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid
A mixture of 0.8 g of 2-{[(1-carbamoyl-1,2-dimethylpropyl)amino]methyl}-5-ethylnicotinic acid (2.7 mmol) and 0.56 g sodium acetate (6.8 mmol) in 10 mL acetic acid is warmed until homogeneous and cooled to room temperature. The solution is treated with 0.88 g bromine (5.45 mmol), and the reaction is stirred at 25° C. for 16 hours, then at 75° C. for three days. The reaction mixture is partitioned between CH 2 Cl 2 and water, and the organic phase is dried and concentrated in vacuo. The residue is recrystallized from ethyl acetate-hexanes to afford 0.4 g of the title product having mp 172°-175° C. | A method for the preparation of o-carboxyl imidazolinone compounds including oxidizing the appropriate 2-{[(1-carbamoyl-1,2-dimethylpropyl)amino]methyl}-benzoic acid intermediate with a brominating agent. Compounds useful as intermediates in the oxidation method and methods for preparing them are disclosed. | 2 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation of U.S. Application Ser. No. 09/303,428, filed May 3, 1999, by Donald O'Connor and entitled “Sonet Add/Drop Multiplexer With Packet Over Sonet Capability”.
TECHNICAL FIELD OF THE INVENTION
[0002] The present invention relates generally to a SONET add/drop multiplexer enhanced so as to support Packet over SONET (POS) and Multiprotocol Label Switching (MPLS). Such a device will allow packet traffic, such as Internet Protocol traffic, which is added to and/or dropped from various points in a SONET network to be carried over the same SONET path on the network.
BACKGROUND ART
[0003] Traditionally telephony networks have been synchronous in nature. They were initially constructed for the purpose of carrying narrowband voice signals, as wideband and broadband traffic, such as data and video, did not exist. Today, both network operators and equipment vendors face the challenge of handling wideband and broadband traffic with an infrastructure that is essentially inadequate because it was not designed for this purpose.
[0004] With the proliferation of the Internet and the integration of Internet traffic onto telephony networks, the networks are now dealing with large volumes of data traffic. As the Internet grows and more Internet service providers arise, telephony service providers and Internet service providers are investing more money in capital equipment in order to provide more bandwidth and paths for the Internet service traffic to flow.
[0005] One way Internet Protocol data could be routed in through a telephony network is over an ATM network. However, such a method of transmission of Internet Protocol data is inefficient due to cell header, packet-to-cell adaptation and encapsulation overhead.
[0006] Another method of routing Internet Protocol data is over a SONET network. Traditionally, if an Internet service provider point of presence would be connected into a SONET network, it would be through a device such as an add/drop multiplexer.
[0007] If that Internet service provider point of presence was to be connected to another Internet service provider point of presence, a dedicated STS link within the SONET network would need to be established between the two points of presence. As more and more Internet service providers are added to such a network, the number of dedicated STS links dramatically increases, causing allocation of network bandwidth to become very inefficient.
[0008] Recently, the Internet Engineering Task Force approved a draft of a new standard known as Multiprotocol Label Switching (MPLS). MPLS attempts to merge layer 2 and layer 3 data switching. Under MPLS, an edge node converts regular packets into an MPLS format. The edge node also handles priority. Core nodes, however, do not need to look deeper then the assigned label to perform a switching function. This speeds up the switching process because the core nodes no longer need to look at a packet's source and destination address and priority. The draft MPLS standards are available to the public for download from the Internet at www.ietf.cnri.reston.va.us/lD.html. Currently available drafts include 1) draft-ietf-mpls-arch-04.txt; 2) draft-ietf-mpls-framework-02.txt, 3) draft-ietfmpls-label-emcaps-03.txt; 4) draft-ietf-mpls-fr-03.txt; 5) draft-ietf-mpls-ldp-03.txt; 6) draft-ietf-mpls-ldp-03.txt; 7) draft-ietf-mpls-rsvp-ldp-tunnel-01.txt; and 8) draft-ietf-mpls-bgp4-mpls-02.txt. Each of these draft MPLS standards is hereby incorporated by reference.
[0009] MPLS offers the Internet service provider community the ability to offer different grades of service. It also provides the ability to create virtual private networks through the stacking of labels. For instance, one label can designate a particular company, while a sub-label can indicate a specific group of users within that company. MPLS also makes it easier for Internet service providers to perform traffic engineering by permitting Internet service providers to explicitly route certain labels to alleviate congestion.
[0010] However, the MPLS standards do not address integration of MPLS switching into a SONET network.
SUMMARY OF THE INVENTION
[0011] The present invention provides an apparatus and method for efficiently utilizing bandwidth within a SONET network carrying data packets such as Internet Protocol packets. The invention does so by providing packet switching capability within SONET add/drop multiplexers.
[0012] An embodiment of the present invention provides for the inclusion of MPLS switching capability within a SONET add/drop multiplexer.
[0013] Another embodiment of the present invention provides for the inclusion of packet switching capability within a SONET add/drop multiplexer along with ATM switching capability.
[0014] Another embodiment of the present invention provides for the inclusion of edge node service adaptation functionality within a SONET add/drop multiplexer.
[0015] Thus, it is an object of the present invention to optimize allocation of SONET transport bandwidth carrying packet traffic.
[0016] It is a further object of the present invention to provide the ability to offer different grades of packet traffic service in a SONET network.
[0017] It is another object of an embodiment of the present invention to provide the ability to create virtual private networks over a SONET network.
[0018] It is a further object of embodiment of the present invention to provide the ability to perform traffic engineering in a SONET network carrying packet traffic.
[0019] It is another object of the present invention to reduce capital costs for Internet service providers connecting to SONET networks.
[0020] It is a further object of the present invention to reduce the amount of state information that must be maintained in a SONET network.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] These and other objects and advantages of this invention will become more apparent and more readily appreciated by reference to the description of the preferred embodiments, taken in conjunction with the accompanying drawings, of which:
[0022] [0022]FIG. 1 (Prior Art) is a block diagram of a SONET network carrying packet traffic of the prior art;
[0023] [0023]FIG. 2 is a block diagram according to an embodiment of the present invention of a SONET network;
[0024] [0024]FIG. 3 is a block diagram of a SONET network according to an embodiment of the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0025] The present invention will be better understood by reference to the accompanying drawings.
[0026] [0026]FIG. 1 (prior art) depicts a SONET network consisting of SONET add/drop multiplexers 71 through 78 , regional Internet service provider points of presence 81 through 83 , and national Internet service provider points of presence 84 and 85 of the prior art. Under the prior art, if each local Internet service provider point of presence was to be connected to both of the national Internet service provider points of presence, and the two national Internet service provider points of presence were to be 5 interconnected, then 7 separate STS links within the SONET network would have to be dedicated to carrying the packet traffic between the various Internet service providers.
[0027] For example, to connect regional Internet service provider point of presence 81 to national Internet service provider point of presence 85 , add/drop multiplexer 71 would have to connect input 51 from regional Internet service provider 81 to add/drop multiplexer 78 through dedicated STS link 91 . Add/drop multiplexer 78 would then have to connect dedicated STS link 91 to line 61 to connect it to the national Internet service provider 85 . To connect regional Internet service provider 81 to national Internet service provider 84 , add/drop multiplexer 71 would have to connect input 52 to add/drop multiplexer 77 through dedicated STS link 92 . Add/drop multiplexer 77 would then have to connect STS link 92 to national Internet service provider 84 through line 60 .
[0028] To connect regional Internet service provider 82 to national Internet service provider 85 , add/drop multiplexer 74 would have to connect input line 53 to add/drop multiplexer 78 through dedicated STS link 97 . Add/drop multiplexer 78 would then have to connect dedicated STS link 97 to line 62 . To connect regional Internet service provider 82 to national Internet service provider 84 , add/drop multiplexer 74 would have to connect input line 54 to add/drop multiplexer 77 through dedicated STS link 96 . Add/drop multiplexer 77 would then have to connect dedicated STS link 96 to input line 59 .
[0029] To connect regional Internet service provider 83 to national Internet service provider 85 , add/drop multiplexer 76 would have to connect input line 55 to add/drop multiplexer 78 through dedicated STS link 95 . Add/drop multiplexer 78 would then have to connect dedicated STS link 95 to input line 63 . To connect regional Internet service provider 83 to national Internet service provider 84 , add/drop multiplexer 76 would have to connect input line 56 to add/drop multiplexer 77 via dedicated STS link 94 . Add/drop multiplexer 77 would then have to connect dedicated STS link 94 to line 58 .
[0030] To connect the two national Internet service providers 84 and 85 to each other, add/drop multiplexer 78 would have to connect input line 64 to add/drop multiplexer 77 via dedicated STS link 93 . Add/drop multiplexer 77 would then have to connect dedicated STS link 93 to input line 57 .
[0031] It doesn't take too many Internet service providers to make this SONET network of the prior art very inefficient. Moreover, an expensive IP switch port would be necessary for each of the connections. Thus, two IP switch ports would be necessary at each of the regional Internet service provider points of presence 81 through 83 and four IP switch ports would be necessary at each of the national Internet service provider points of presence 84 and 85 .
[0032] In FIG. 2, a SONET network according to an embodiment of present invention is shown. In this figure, at least SONET add/drop multiplexers 101 , 104 , 106 , 107 and 108 are equipped with POS/MPLS capability. This enables the add/drop multiplexers to process labels and concentrate label switch paths into a single STS path between the add/drop multiplexer nodes. Add/drop multiplexers 102 , 103 , and 105 may be of the traditional type or may include the MPLS capability. Preferably, each of the add/drop multiplexers would include this capability to enable Internet service providers to connect directly to add/drop multiplexers 102 , 103 and 105 in the future. By including POS/MPLS capability in SONET add/drop multiplexers 101 , 104 , 106 , 107 and 108 , a single STS link between each of the nodes can be devoted to carrying packet data. This STS link would flow along the path of 111 , 112 , 113 and 114 . The MPLS labels with PPP or frame relay encapsulation would define virtual circuits over the SONET network. SONET add/drop multiplexers 101 , 104 , 106 , 107 and 108 can then concentrate/groom the MPLS label delineated virtual circuits onto a common SONET transport path. Additionally, communications between the Internet service provider points of presence and their respective add/drop multiplexers can now be combined into one respective pipe. This reduces the number of IP switch ports required at each Internet service provider point presence down to one.
[0033] Traditional engineering methods can be utilized by one skilled in the art to design POS/MPLS capability into a SONET add/drop multiplexer.
[0034] Although it is preferable to provide POS/MPLS capability within the SONET add/drop multiplexer, similar savings can be realized in bandwidth and switch port costs without utilizing MPLS. For instance, if layer 2 encapsulation is frame relay, then the SONET add/drop multiplexer can utilize the frame relay address (DLCI) field to delineate virtual circuits for concentration into the common STS path 111 , 112 , 113 and 114 .
[0035] An additional benefit of providing POS/MPLS capability within the SONET add/drop multiplexer is that MPLS label switched paths can be merged to form multipoint-to-point trees. This reduces the amount of state information that must be maintained by the network.
[0036] Preferably, the SONET add/drop multiplexers of the present invention would each contain a route processor that would run standard IP routing protocols such as OSPF, BGP, and multicast (e.g. PIM) as well as label distribution protocols, such as LDP. Additionally, the SONET add/drop multiplexers would contain interfaces for Ethernet, IDS 3, OC-3, OC-12, and others. The SONET add/drop multiplexers of the present invention may also contain an ATM switching fabric in order to switch ATM traffic that may be present on the SONET network. Again, traditional engineering methods can be used by those skilled in the art to build such devices.
[0037] [0037]FIG. 3 depicts a SONET network according to an embodiment of present invention. In this figure, edge node service adaptation function has been incorporated into the POS/MPLS add/drop multiplexer. As can be seen in FIG. 3, SONET add/drop multiplexers 121 , 123 , and 124 have MPLS router functions built into them, 131 , 133 and 134 respectively. SONET add/drop multiplexers 122 , 125 and 126 have MPLS functionality as discussed previously. This functionality enables them to label switch. By providing MPLS edge router functionality in SONET add/drop multiplexers 121 , 123 and 124 , computer network 141 and computer network 142 can be connected in a virtual private network. Additionally, computer networks 141 and 142 can access the Internet through line 150 to an Internet service provider (not shown). Such devices can be built by those skilled in the art using traditional engineering methods.
[0038] Although each of the preferred embodiments discussed above was discussed with reference to a SONET network, the same may be applicable to an SDH network or any other synchronous optical network.
[0039] Although the preferred embodiments of the present invention have been described and illustrated in detail, it will be evident to those skilled in the art that various modifications and changes may be made thereto without departing from the spirit and scope of the invention as set forth in the appended claims and equivalents thereof. | An advanced SONET add/drop multiplexer capable of supporting packet over SONET and multiprotocol label switching. The add/drop multiplexer is capable of adding and/or dropping both STM and packet traffic, such as Internet Protocol traffic. This SONET add/drop multiplexer allows Internet Protocol streams which are added or dropped at different nodes to be carried over the same SONET path in a network, thereby greatly saving bandwidth. | 7 |
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