The invention relates to dental cleaning articles and in one embodiment to a band of expanded fluoropolymer that is highly distensible at room temperature such that it can be stretched from a first state to a second state. The band of expanded fluoropolymer may be more easily held and manipulated than a strand of material for flossing between teeth.
Expanded fluoropolymer provides many advantages over conventional material for dental cleaning. One advantage is the low friction characteristics of expanded fluoropolymer, which allows it to more easily glide through tight teeth. This low friction however, makes it difficult to grip and hold during flossing. The expanded fluoropolymer strands currently available come in various sizes and density. Unfortunately, many people have a wide range of gaps between their teeth and one size, density, or type of floss may not adequately clean between all their teeth.
There exists a need for an expanded fluoropolymer dental cleaning article that is easy to hold and can effectively clean a wide range of gaps between teeth.
The invention is directed to a dental cleaning article comprising a band of expanded fluoropolymer that is distensible from a first state to a second stretched state. In one embodiment, the circumference of the band of expanded fluoropolymer is increased by a factor of at least two, from the first state to the second stretched state. Likewise, in one embodiment the cross sectional area of the band in the second stretched state is one quarter or less of the cross-sectional area of the band in the first state.
In one embodiment, the microstructure of the expanded fluoropolymer comprises nodes and interconnecting fibrils wherein the nodes have an aspect ratio that changes from the first state to the second stretched state. The aspect ratio in the second stretched state is in one embodiment, at least two times greater than the aspect ratio of the nodes in the first state.
The band of expanded fluoropolymer in one embodiment consists essentially of a seamless tube section, and in another embodiment the band comprises at least one strip of material attached to form a band having one or more seams. In yet another embodiment, the band comprises a section of material having a slit or shaped opening, such as a circle or oval and is a referred herein as a sheet band. The sheet band may have a regular or irregular shape and in one embodiment has a generally rectangular outer shape. In another embodiment, the sheet band has a circular or oval outer shape, and a slit or shaped opening, such as a circle or oval.
The band of expanded polymer may have a generally consistent cross section around the circumference, or it may have a variable cross section. In one embodiment, at least one region of the band of expanded fluoropolymer has a higher density than an adjacent region. The band may be compressed or imbibed with another material to produce these higher density regions. In another embodiment, the band may be compressed in at least one region to provide a larger surface region that may be used to facilitate stretching the band to a second state. In yet another embodiment, additional material is attached or detachably attached to the band for stretching and or handling, such as but not limited to another polymer film.
The dental cleaning article may also comprise wax or other additional material on one or more surfaces. Wax may increase the friction of the band and increase dental cleaning performance. In addition, the wax or other material may be continuous on discontinuous. In one embodiment, the wax or other material is continuous in the first state, but becomes discontinuous after the band is stretched to a second state. In yet another embodiment additional material is incorporated at least partially into the expanded fluoropolymer such as an imbibed material or filler material.
The dental cleaning article may be supported on a support device and in some embodiments the support device provides the user with a means to stretch the band. The support device in one embodiment may comprise a pair of support members connected at a pivot point, and a distensible band securing portion. The securing portion may comprise a recess in the support member. The user may squeeze the support members such that they move about the pivot and stretch the band.
Numbers used to indicate a feature or element in a figure are used consistently throughout all figures.
The dental cleaning article 10 of the present invention comprises a band of expanded fluoropolymer 12 having a first state 14 and a second stretched state 16 as shown in
The band of expanded fluoropolymer can be stretched manually, by inserting fingers 48 and 48′ into the band 12 and pulling to increase the circumference of the band, as depicted in
In one embodiment, the band of expanded fluoropolymer is made from porous expanded polytetrafluoroethylene (PTFE), for instance as generally described in U.S. Pat. No. 3,953,566 to Gore. The expandable fluoropolymer may comprise in one embodiment, PTFE homopolymer. In alternative embodiments, blends of PTFE, expandable modified PTFE and/or expanded copolymers of PTFE may be used. Non-limiting examples of suitable fluoropolymer materials are described in, for example, U.S. Pat. No. 5,708,044, to Branca, U.S. Pat. No. 6,541,589, to Baillie, U.S. Pat. No. 7,531,611, to Sabol et al., U.S. patent application Ser. No. 11/906,877, to Ford, and U.S. patent application Ser. No. 12/410,050, to Xu et al. The expanded fluoropolymer of the present invention may comprise any suitable microstructure for achieving the desired combination of properties required, such as but not limited to, strength, matrix tensile strength, percent elongation, extension, density, and abrasion resistance as described herein. In one embodiment, the expanded fluoropolymer may comprise a microstructure of nodes interconnected by fibrils such as described in U.S. Pat. No. 3,953,566 to Gore. In a preferred embodiment, the expanded fluoropolymer comprises expanded PTFE and in another embodiment, the expanded fluoropolymer consists essentially of PTFE.
The expanded fluoropolymer shown in the surface SEM 18 of
The dental cleaning article as described herein comprises a band of expanded fluoropolymer that may be formed from a single piece of material, as depicted in
The dental cleaning article in one embodiment comprises a generally tubular section configuration, having a width 13, thickness 17, inner diameter 11 and circumference 15 as depicted in
The inner diameter of the distensible band 9 may be determined by measuring the length of the inner circumference or inner surface and dividing by the constant pi as depicted in
The distensible band may have any suitable dimensions, and in some embodiments, the inner diameter is large enough to allow for the insertion of a finger or fingers into the band and subsequently stretch it. In these embodiments, the inner diameter of the band may be greater than about 10 mm, or between 10 and 25 mm, 10 and 50 mm, or between 10 and 75 mm. In other embodiments, the inner diameter may be too small to allow for the insertion of a finger or fingers into the band, such as less than 10 mm, or between 3 mm and 10 mm, or between 5 mm and 10 mm. The width of the dental cleaning article may be selected to be greater than 0.50 mm and less than 1.5 mm, 3.0 mm, 10 mm, 15 mm, or 25 mm, or between 3 mm and 25 mm, or between 3 mm and 15 mm.
In some embodiments, the distensible band in the first state may be effectively unsuitable for use as a dental cleaning article. For example, the inner diameter or circumference may be too small for the distensible band to be effectively manually manipulated as a dental cleaning article. For example, distensible bands with an inner diameter of less than 10 mm or in some cases less than 20 mm are considered too small to be effectively manually manipulated as a dental cleaning article. Likewise, in some embodiments, the width or thickness of the band may be too large in the first state for the distensible band to be effectively used as a dental cleaning article. For example, when the width or thickness of the distensible band is greater than about 5 mm, the band may not be useful as a dental cleaning article, as it may be too large to fit between the gaps in-between teeth. In these embodiments, the distensible band only becomes effectively useful as a dental cleaning article after being stretched to a second stretched state.
The band of expanded fluoropolymer may have any irregular shape, such as that shown in
The band of expanded fluoropolymer may be cut or otherwise formed from a tube 50 of expanded fluoropolymer as depicted in
The dental cleaning article may comprise one more high density regions 30′, 30″, 30′″, that in one embodiment may stretch and deform less than adjacent lower density regions, resulting in a irregularly shaped band in the second stretched state, as depicted in
The dental cleaning article may comprise a combination of features herein described, such as those shown in
In some embodiments, additional material may be incorporated into or on the dental cleaning article, including but not limited to, wax, flavor containing materials, such as mint, coloring materials, such as dyes or pigments, or abrasive materials, such filler particles, or combinations thereof and the like. The additional materials may be attached to one or more surfaces of the dental cleaning article or may be at least partially imbibed into or incorporated into the structure of the band, or expanded polymer or fluoropolymer. In one embodiment, an additional material 52, comprising a wax is attached to the outside surface 54 of a band of expanded fluoropolymer 12 as depicted in
In another embodiment, both the inside and outside surfaces of the band of expanded fluoropolymer comprise an additional material as depicted in
The band of expanded fluoropolymer may be distended manually in one embodiment to a desired extent. It was surprisingly discovered that the bands of the present invention could be extended to such a high degree as depicted in
It is preferable that the force required to distend the band is sufficiently low, such that the band does not cause the user discomfort during the distention process. In some embodiments, as shown in
The axial strength of the distensible band in some embodiments is much greater than the strength in the radial direction as shown in
The distensible band of the present invention in some embodiments changes dimensions dramatically as it is stretched from a first state to a second stretched state. In one embodiment the distensible band is stretched from a first state in which the band is unsuitable for use as a dental cleaning article to a second state, where it can be easily manipulated as a dental cleaning article. The diameter of the distensible band increases as the band is stretched and in some cases the width and/or thickness decrease. The width in a second state may be less than one quarter the width of the band in the first state. The cross sectional area of the band may be reduced to one quarter the cross sectional area of the band in the first state. The dimensional changes of some bands stretched to various strain levels is reported in Table 8A through 8C.
Expanded polymer and expanded fluoropolymer in many cases exhibits no or limited elastic properties. Therefore, in some embodiments, the distensible band of the present invention may not be elastic nor substantially dimensionally recoverable, as it does not exhibit any substantial dimensional recovery after stretching from a first state to a second stretched state. In particular, when the distensible band is comprised essentially of expanded fluoropolymer, the band is substantially dimensionally non-recoverable. In other embodiments however, an elastomeric material may be incorporated into or on the dental cleaning article and provide elastic, or dimensional recovery properties.
An important attribute of dental cleaning articles such as dental floss, is abrasion resistance or abrasion durability. Dental cleaning articles are traversed across and between teeth which can be rough or have sharp edges that can abrade and cause the article to break prematurely. Some embodiments of the present invention have been found to be surprisingly abrasion resistant. Table 9 provides abrasion results of distended bands made according to the examples herein and tested according to the abrasion test described herein. The abrasion test is shown in
The dental cleaning article of the present invention can be used in any conventional way including manually, or as a floss pick, wherein the band is attached to a support. In another embodiment, the band is configured onto a support device that in one embodiment comprises a means to facilitate the distension of the band. In one embodiment, the support device comprises a first support member 142, a second support member 144, and a pivoting point 146, whereby the user can squeeze the support and distend the band, as is depicted in
Test Methods
Matrix Tensile Stress and Strength
Matrix tensile strength (MTS) is calculated using the following equation:
where the cross-sectional area and density ρ0 of the sample are measured prior to the tensile test. The cross-sectional area of the sample is measured using a standard snap gauge to measure the thickness of the sample, and the width of the sample is measured using a standard dial caliper. The cross-sectional area is the product of the width and thickness. The mass of the sample is measured using a mass balance having one-thousandth gram resolution and the length of the sample is measured using a standard dial caliper. Density ρ0 is calculated by dividing the mass by the product of the length and cross-sectional area.
The matrix tensile stress was calculated using the same method as the matrix tensile strength, except that the tensile load was used in place of the maximum load.
Band Radial Mechanical Test Method
For the purposes of this invention, test fixtures 120, 122 were constructed to support the band during mechanical testing. The test fixtures depicted in
Axial Mechanical Test Method
A 15.24 cm long sample of tubing was clamped into the grips of an Instron, Model 5567 with the length of the tubing substantially parallel with the direction of testing. The gauge length between the grips was 5.08 cm and the rate of pull was 50.8 cm/min. The load and displacement was recorded. The engineering stress, matrix tensile stress, and matrix tensile strength were calculated using the initial dimensions of the material, including width, thickness, length, mass, and a density of PTFE of 2.2 g/cc. Matrix tensile stress and strength values were calculated by multiplying the engineering stress by the ratio of the density of PTFE to the density of the sample.
Interval Stain Test Method
A tensile tester, Instron Machine, Model 5567 outfitted with a pair of standard pneumatic actuator grips dimensioned 2.54 cm by 2.54 cm flat grips was use to strain samples to discrete intervals. Three specimens per sample were tested to each of the displacements. A 6.35 mm wide tube section was cut across the width and placed in the Instron with the long axis, or radial direction in alignment with the pulling direction. To minimize moment generation about the specimen during testing, specimens were oriented in the Instron grips such that they were directly in line and centered under the load cell. The gauge length was 25.4 mm, and the cross head speed was 50.8 cm per minute. The test was completed when the specimen was extended to the desired percent strain, (100%=25.4 mm cross-head displacement, 400%=76.2 mm cross-head displacement and 800%=177.8 mm cross-head displacement). The load and displacement were recorded. The matrix tensile stress at each interval of strain was calculated and reported.
Sheet Band Mechanical Test Method
A 2.54 cm outer diameter by 1.95 cm inner diameter doughnut shaped article was stamped out of sheets of expanded fluoropolymer. The machine direction was marked on the sample for orientation on the test fixture. Five samples of the sheet band were tested in the machine direction and five samples were tested in the cross-machine direction. When testing the machine direction, the mark 76 indicating the machine direction was aligned in the direction of the pull as shown in
Sheet Material Mechanical Test Method
The machine and cross machine matrix tensile stress of sheet material was determined using an Instron Machine, Model 5567. The gauge length was set to 25.4 mm, and the samples were pulled at a rate of 50.8 cm/minute. Three 6.35 mm wide cm by at least 5 cm long samples were cut from the sheet material with the longer dimension in the machine direction, and three were cut with the longer dimension in the cross machine direction. A sample of sheet material was placed in the 2.54×2.54 cm square knurled surface grips of the Instron with the longer dimension aligned with the direction of pull. The matrix tensile strength was calculated as described herein.
Abrasion Test Method
The distended bands of expanded fluoropolymer produced according to this invention were tested for abrasion resistance. The bands were distended and then cut to form a strand of floss for mounting in the abrasion resistance device 70 as shown in
As shown in
Dental cleaning article as used herein is defined as a band of material for cleaning between teeth.
Distensible band as used herein refers to the dental cleaning article of the present invention in the first state.
Tube section as used herein is defined as a section formed from a tube, as for example, through cutting across the length of the tube, to form a band.
Sheet band as used herein is defined as a material having a central opening and in one embodiment is formed from a sheet or sheets of material.
High density region as used herein is defined as a region along the band that has a density greater than an adjacent region. In one embodiment the density of the high density region is at least twice the density of an adjacent region.
Low density region as used herein is defined as a region along the band that has a density lower than an adjacent region. In one embodiment the density of the low density region is at least one half the density of an adjacent region.
Force to break of the distensible band as used herein is defined as the maximum load measured when tested according to the Band Radial Mechanical Test Method described herein.
Matrix tensile strength ratio as used herein is the ratio of the matrix tensile strength of the distensible band in two orthogonal directions, such as axial and radial, or longitudinal and cross machine directions.
Radial matrix tensile strength as used herein is defined as the matrix tensile strength measured according to the Radial Test Method described herein.
Stretched as used herein, in reference to stretching the distensible band from a first state to a second stretched state, is performed at room temperature conditions.
Room temperature as used herein means the temperature at which people are accustom while indoors, and is usually approximately 20° C.
Bands of dental floss of the present invention were made by extruding and expanding a tube of PTFE and cutting the tube into bands. Mineral spirit ISOPAR® K from the EXXON Company was blended with a fine powder PTFE from the DuPont De Nemours Company (Wilmington, Del.) at a ratio of 0.217 g/g of resin. The mixture was permitted to rest for a period of 24 hours at a temperature of 30° C. Following the resting period, the mixture was placed into and compressed inside an extruder having an inner diameter of approximately 116.8 mm. The compressed mixture was extruded through a die and tip arrangement, heated to approximately 30° C., at a reduction ratio of approximately 350:1, to produce an extruded tube having an approximately 23.9 mm outer diameter and an approximately 0.406 mm wall thickness.
The extruded tubing was then heated, expanded and sintered to produce an expanded fluoropolymer tube having nodes interconnected by fibrils. The extruded tubing was preheated in a forced air oven, set to a temperature of 415° C., and expanded at a ratio of 4.3:1 in an oven set to a temperature of approximately 355° C. The tubing was then sintered while held in tension at a temperature of approximately 445° C. for approximately 12 seconds. The take up speed of the tubing from this process was approximately 3.0 m/min. This process produced an expanded fluoropolymer tube having the properties listed in Table 2.
The expanded tubing was cut into 15.24 cm lengths and tested according to the Axial Mechanical Testing Protocol described herein, and the results are reported in Table 5 and
As can be seen in
An expanded fluoropolymer tube was created according to the process described in Example 1 except that the expansion ratio was 6.2:1, as described in Table 1. This process produced an expanded fluoropolymer tube having the properties listed in Table 2.
The expanded tubing was cut into 15.24 cm lengths and tested according to the Axial Mechanical Testing Protocol described herein, and the results are reported in Table 5 and
An expanded fluoropolymer tube was created according to process described in Example 1 except that the expansion ratio was 4.2:1, the duration of sintering was approximately 20 seconds, and the take up speed was 1.8 m/min as described in Table 1. This process produced an expanded fluoropolymer tube having the properties listed in Table 2.
The expanded tubing was cut into 15.24 cm lengths and tested according to the Axial Mechanical Testing Protocol described herein, and the results are reported in Table 5 and
An expanded fluoropolymer tube was created according to the process described in Example 1 except that the expansion ration was 6.1:1, the duration of sintering was approximately 20 seconds, and the take up speed was approximately 1.8 m/min as described in Table 1. This process produced an expanded fluoropolymer tube having the properties listed in Table 2.
The expanded tubing was cut into 15.24 cm lengths and tested according to the Axial Mechanical Testing Protocol described herein, and the results are reported in Table 5 and
A band of dental floss of the present invention was made by extruding and expanding a tube of PTFE and cutting the tube into bands. Mineral spirit ISOPAR® K from the EXXON Company was blended with a fine powder PTFE from the DuPont De Numerous Company (Wilmington, Del.) at a ratio of 0.217 g/g of resin. The mixture was permitted to rest for a period of 24 hours at a temperature of 30° C. Following the resting period, the mixture was placed into and compressed inside an extruder having an inner diameter of approximately 116.8 mm. The compressed mixture was extruded through a die and tip arrangement, heated to approximately 40° C., at a reduction ratio of approximately 752:1, to produce an extruded tube having an approximately 15.8 mm outer diameter and approximately 0.23 mm wall thickness.
The extruded tubing was then heated, expanded and sintered according to the process of Example 1, with the following exceptions, the expansion ratio was 4.3:1; the duration of sintering was approximately 5 seconds; and the take up speed was approximately 7.3 m/min (24 ft/min). This process produced an expanded fluoropolymer tube having the properties listed in Table 2.
The expanded tubing was cut into approximately 6.35 mm wide bands and tested according to the Radial Mechanical Testing Protocol described herein, and the results are reported in Table 3 and 4. An SEM of this expanded tubing before and after radial mechanical testing is shown in
Three approximately 0.95 cm wide sections of the floss band made according to Example 5 were stretched with a Shimpo Model FGE-100X digital force gauge, available from Electromatic Equipment Co., Inc. (Cedarhurst, N.Y.), in one hand and the index finger on the other hand. Force to stretch to a comfortable size without breaking was 24N, 25N, and 26N. The floss bands were each removed from the force gauge after stretching and used as dental floss.
A sheet band was cut from a sheet of expanded PTFE membrane having a thickness of approximately 0.173 mm, and a density of approximately 0.95 g/cc. Fine powder of PTFE polymer as described and taught in U.S. Pat. No. 6,541,589 was blended with Isopar K (Exxon Mobil Corp., Fairfax, Va.) in the proportion of 0.201 g/g of fine powder. The lubricated powder was compressed in a cylinder to form a pellet and placed into an oven set at 70° C. for approximately 12 hours. Compressed and heated pellets were ram extruded to produce tapes approximately 15.2 cm wide by 0.508 mm thick. Two separate rolls of extruded tape were produced and layered together between compression rolls, and calendared down to thickness of 0.508 mm. The tape was then transversely stretched to approximately 55 cm (i.e., at a ratio of 2.8:1), and then dried in an oven set to approximately 250° C. while being restrained in the machine or longitudinal direction. The width after drying was approximately 33.7 cm. The dry tape was then longitudinally expanded between banks of rolls over a heated plate set to a temperature of 300° C. The speed ratio between the second bank of rolls and the first bank of rolls, and hence the expansion ratio, was 10:1. The approximately 8.9 cm wide longitudinally expanded tape was then restrained longitudinally and sintered at a temperature of approximately 365° C. for approximately 5 minutes. The process produced a thin strong porous expanded fluoropolymer sheet.
The sheet of expanded fluoropolymer was tested for longitudinal and transverse matrix tensile strength, by cutting 0.635 cm wide sample strips from the sheet in both the machine and cross-machine directions. The cut sections of material were oriented in the Instron with the long axis parallel to the direction of pull, and the sample was pulled at a rate of 50.8 cm/min. The gauge length was 2.54 cm. Three tests were performed in both the longitudinal and cross machine directions. The average machine and cross machine direction matrix tensile strengths were 180 MPa, and 7.5 MPa respectively. The ratio of the machine to cross machine strength was approximately 24. This is a very high ratio of strength in two orthogonal directions, much like the axial to radial matrix tensile strength ratios reported for the tubing made according to examples 1 through 4.
Ring shaped sheet bands were die cut from the sheet of expanded PTFE, having a 2.54 cm outer diameter by 1.95 cm inner diameter. The results of the Sheet Band Mechanical Testing Procedure are reported in
Table 1 provides a summary of some of the processing conditions used to make expanded fluoropolymer tubes.
Table 2 provides a summary of some of the recorded physical properties of the expanded fluoropolymer tubes.
Table 3 provides a summary of some of the radial mechanical testing results.
Table 4 provides the dimensions of the distensible band after being tested according to the radial mechanical test method described herein. The dimensional properties reported in Table 6 were measured approximately in the middle of the length of the broken band.
Table 5 provides summary of some of the axial mechanical testing results.
Table 6 provides summary of some of the axial mechanical testing results along with the calculated matrix tensile strength (MTS) ratio.
Table 7 provides the matrix tensile stress as measured at various strain intervals according to the interval strain method described herein.
Table 8A provides the initial dimensions and the dimensions of the distensible band after 100% strain as tested according to the interval strain method described herein.
Table 8B provides the dimensions of the distensible band after 400% strain as tested according to the interval strain method described herein.
Table 80 provides the dimensions of the distensible band after 800% strain as tested according to the interval strain method described herein.
Table 9 provides a summary of the data recorded from the abrasion test described herein.
In addition to being directed to the teachings described above and claimed below, devices and/or methods having different combinations of the features described above and claimed below are contemplated. As such, the description is also directed to other devices and/or methods having any other possible combination of the dependent features claimed below.
Numerous characteristics and advantages have been set forth in the preceding description, including various alternatives together with details of the structure and function of the devices and/or methods. The disclosure is intended as illustrative only and as such is not intended to be exhaustive. It will be evident to those skilled in the art that various modifications may be made, especially in matters of structure, materials, elements, components, shape, size and arrangement of parts including combinations within the principles of the invention, to the full extent indicated by the broad, general meaning of the terms in which the appended claims are expressed. To the extent that these various modifications do not depart from the spirit and scope of the appended claims, they are intended to be encompassed therein.
Number | Name | Date | Kind |
---|---|---|---|
3247857 | Kanbar | Apr 1966 | A |
3953566 | Gore | Apr 1976 | A |
4550741 | Krag | Nov 1985 | A |
4836226 | Wolak | Jun 1989 | A |
5518012 | Dolan et al. | May 1996 | A |
5566691 | Dolan et al. | Oct 1996 | A |
5708044 | Branca | Jan 1998 | A |
5819769 | Gutierrez | Oct 1998 | A |
5947132 | Swanson | Sep 1999 | A |
6055993 | Meyer et al. | May 2000 | A |
6161555 | Chen | Dec 2000 | A |
6340027 | Hagne et al. | Jan 2002 | B1 |
6371133 | Gant | Apr 2002 | B1 |
6539951 | Baillie et al. | Apr 2003 | B2 |
6541589 | Baillie | Apr 2003 | B1 |
7521010 | Kennedy et al. | Apr 2009 | B2 |
7531611 | Sabol et al. | May 2009 | B2 |
20030172951 | Baillie et al. | Sep 2003 | A1 |
20030196676 | Baillie et al. | Oct 2003 | A1 |
20050016563 | Prins | Jan 2005 | A1 |
20050257801 | Kayser | Nov 2005 | A1 |
20060105179 | Hofman | May 2006 | A1 |
20060147869 | Hekimian | Jul 2006 | A1 |
20070087310 | Giusti | Apr 2007 | A1 |
20070131242 | Fleck | Jun 2007 | A1 |
20070204877 | Dolan et al. | Sep 2007 | A1 |
20080017218 | Lutz et al. | Jan 2008 | A1 |
20080053892 | Bacino et al. | Mar 2008 | A1 |
20090020134 | Tomsic et al. | Jan 2009 | A1 |
20090032470 | Bacino et al. | Feb 2009 | A1 |
20090093602 | Ford | Apr 2009 | A1 |
20100248324 | Xu et al. | Sep 2010 | A1 |
20110155168 | Chung | Jun 2011 | A1 |
Number | Date | Country |
---|---|---|
WO 9206648 | Apr 1992 | WO |
Entry |
---|
International Search Report—PCT/US2012/057557 dated Mar. 28, 2013. |
Number | Date | Country | |
---|---|---|---|
20130081648 A1 | Apr 2013 | US |