GETTER CARTRIDGE FOR TOXIC GASES INSIDE VALVES

Abstract

The present invention relates to cylinder packages utilized in the delivery of highly toxic and/or flammable compounds to semiconductor manufacturers. More specifically, the present invention provides a cartridge adapted to removably attach to the gas outlet of a gas discharge passageway in a cylinder valve provided on a toxic gas containing cylinder package, the cartridge comprising a cylindrically shaped housing having at least one end fitted with a barrier member permeable to the toxic gas contained within the cylinder package and the housing containing a toxic-gas getter material.

Claims

1. A getter cartridge for operatively coupling to a gas discharge passageway of a cylinder valve installed on a cylinder package containing a toxic and/or flammable gas, the getter cartridge comprising: a cartridge housing body having an open end and a closed top end, and a center core extending along a housing longitudinal axis through the open end; an absorbing means contained within said cartridge housing body between said open end and said closed top end; an end cap having a through-hole centrally formed therein covering said open end of said cartridge housing; a positioning ring extending from said end cap, said positioning ring fitting configured to be received by said open end; a barrier member positioned within said centrally formed hole which is permeable to said gas, and in fluid communication with said filter media; and a sealing member extending from the said cartridge housing body disposed along the outer edge which is configured to seal against an inside surface of the gas discharge passageway when said getter cartridge is installed in the cylinder valve.

2. The apparatus of claim 1, wherein said absorbing means consisting of a gas absorbent material which chemically reacts with the gas to consume said gas to thereby produce a solid product that is impermeable to said barrier member which is permeable to said gas and impermeable to the toxic-gas absorbent and the reactant produced.

3. The apparatus of claim 2, wherein said gas absorbent comprising a metal such as copper, aluminum, manganese, sodium, calcium, magnesium, potassium and their respective groups such as oxides, hydroxides, carbonates, sulfates, sulfides, amides permanganates and combinations thereof.

4. The apparatus of claim 3, wherein said gas absorbent further includes high surface area adsorbent such as alumina, silica, carbon, molecular sieve, zeolite or metal organic framework for retaining said metals.

5. The apparatus of claim 1, wherein a socket is formed within said closed top end for engaging a wrench.

6. The apparatus of claim 1, wherein said housing body comprises a proximal end and a distal end wherein said sealing member positioned on the outer surface of said proximal end comprises threads that mate with internal threads positioned within said gas discharge passageway.

7. The apparatus of claim 1, wherein said housing body comprises a proximal end and a distal end wherein said positioning member positioned on the outer surface of said proximal end comprises O-rings that meet with the peripheral walls of a non-threaded said gas discharge passageway.

8. The apparatus of claim 1, wherein said absorbing means consisting of a gas absorbent material which absorbs the gas.

9. The apparatus of claim 1, wherein said proximal end has a smaller diameter than the diameter of said distal end which results in the formation of an annular seating surface extending radially outward for accepting a washer that seats the getter cartridge within said gas discharge passageway.

10. A getter cartridge for operatively coupling to a gas discharge passageway of a cylinder valve installed on a cylinder package containing a toxic/flammable gas, the getter cartridge comprising: a cartridge housing having a first end and a second end forming a longitudinal axis and a bore extending along said longitudinal axis through said first end and said second end; a filter media contained within said bore between said first end and said second end; a first end cap covering said first end of the cartridge housing; said first end cap having a through-hole centrally formed therein covering said first end of said cartridge housing; a first positioning ring extending from said first end cap, said first positioning ring fitting configured to be received by said first end; a second end cap covering said second end of said cartridge housing; said second end cap having a through-hole centrally formed therein covering said second end of said cartridge housing; a second positioning ring extending from said second end cap, said second positioning ring fitting configured to be received by said second end; and a barrier member positioned within said centrally formed hole which is permeable to the gas, and in fluid communication with said filter media.

11. The apparatus of claim 10, wherein said absorbing means consisting of a gas absorbent material which chemically reacts with the gas to consume said gas to thereby produce a solid product that is impermeable to said barrier member which is permeable to said gas and impermeable to the toxic-gas absorbent and the reactant produced.

12. The apparatus of claim 11, wherein said gas absorbent has a main reacting component comprising a metal such as copper, aluminum, manganese, sodium, calcium, magnesium, potassium and their respective groups such as oxides, hydroxides, carbonates, sulfates, sulfides, amides, permanganates and combinations thereof.

13. The apparatus of claim 3, wherein said gas absorbent further includes high surface area adsorbent such as alumina, silica, carbon, molecular sieve, zeolite or metal organic framework for retaining said metals.

14. A getter cartridge comprising: a cartridge housing body having an open end and a closed top end, and a center core extending along a housing longitudinal axis through the open end; an absorbing means contained within said cartridge housing body between said open end and said closed top end; an end cap having a through-hole centrally formed therein covering said open end of said cartridge housing; a positioning ring extending from said end cap, said positioning ring fitting configured to be received by said open end; a barrier member positioned within said centrally formed hole which is permeable to said gas, and in fluid communication with said filter media; and a sealing member extending from the said cartridge housing body disposed along the outer edge which is configured to seal against an inside surface of the gas discharge passageway when said getter cartridge is installed in the cylinder valve.

15. The apparatus of claim 14, wherein said absorbing means consisting of a gas absorbent material which chemically reacts with the gas to consume said gas to thereby produce a solid product that is impermeable to said barrier member which is permeable to said gas and impermeable to the toxic-gas absorbent and the reactant produced.

16. The apparatus of claim 15, wherein said gas absorbent comprising a metal such as copper, aluminum, manganese, sodium, calcium, magnesium, potassium and their respective groups such as oxides, hydroxides, carbonates, sulfates, sulfides, amides permanganates and combinations thereof.

17. The apparatus of claim 16, wherein said gas absorbent further includes high surface area adsorbent such as alumina, silica, carbon, molecular sieve, zeolite or metal organic framework for retaining said metals.

18. The apparatus of claim 14, wherein a socket is formed within said closed top end for engaging a wrench.

19. The apparatus of claim 14, wherein said housing body comprises a proximal end and a distal end wherein said sealing member positioned on the outer surface of said proximal end comprises threads that mate with internal threads positioned within said gas discharge passageway.

20. The apparatus of claim 14, wherein said housing body comprises a proximal end and a distal end wherein said positioning member positioned on the outer surface of said proximal end comprises O-rings that meet with the peripheral walls of a non-threaded said gas discharge passageway.

21. The apparatus of claim 14, wherein said absorbing means consisting of a gas absorbent material which absorbs the gas.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0010] The accompanying drawings, which are incorporated in and form a part of the specification, illustrate the preferred embodiments of the present invention, and together with the descriptions serve to explain the principles of the invention.

[0011] FIG. 1 is a partially enlarged cross-sectional view of a cylinder package having a gas discharge passageway which accommodates a getter cartridge according to one embodiment of the present invention;

[0012] FIG. 2 is a partially enlarged cross-sectional view of a cylinder package to which a getter cartridge according to one embodiment of the present invention is installed within the gas discharge passageway of a cylinder valve;

[0013] FIG. 3 is an enlarged, detailed view of the getter cartridge positioned within the gas discharge passageway shown in FIG. 2 indicated by dashed lines according to the present invention;

[0014] FIG. 4 is a perspective view of the getter cartridge of the present invention;

[0015] FIG. 5 is a cross-sectional view of the getter cartridge present invention taken along the line 5-5 of FIG. 4;

[0016] FIG. 6 is an exploded side elevation view of the getter cartridge of the present invention;

[0017] FIG. 7 is a top plan view of the getter cartridge of the present invention; and

[0018] FIG. 8 is another cross-sectional view showing an additional embodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0019] The getter cartridge 100, according to this invention, is best shown in FIG. 4 and can be seen, in FIGS. 2 and 3, as mounted within the gas discharge passageway 18 of a cylinder valve neck 12. The cartridge 100 comprises a housing 110, which comprises a housing body 112, a housing open end 114, and a housing closed top 116. The housing body 112 is a generally cylindrical casing having an outside diameter and an inside diameter and a hollow center core 118 extending through the open end 114 along the longitudinal axis of housing body 112 that receives and secures a toxic/flammable-gas absorbent 124. Preferably housing body 112 is constructed from a metal such as stainless steel, aluminum, monel, hastelloy, and brass or a polymer material such as polypropylene, polyimide, poly (ether ether ketone), PTFE, PFA fluorocarbon or an ABS material or some other material that does not chemically react with the toxic and/or flammable gas that will come in contact with cartridge 100. Essentially, getter cartridge 100 is assembled, as best seen in FIGS. 5 and 6, by introducing toxic/flammable-gas absorbent 124 into the hollow center core 118 of housing body 112 and then inserting the positioning ring 120 of end cap 126 into the open end 114 of housing body 112.

[0020] Referring to FIG. 1, there is shown a portion of a cylinder package 1 for containing and delivering a toxic/flammable gas G comprising a gas cylinder or bottle 2 in fluid communication with cylinder valve 6. The gas cylinder 2 is adapted to contain various toxic and/or flammable gases such as arsine, phosphine, boron trifluoride, nitrogen trifluoride, diborane, germane, silane, disilane, trisilane, dichlorosilane, monochlorosilane, trichlorosilane, tetrachlorosilane, hexachlorodisilane, tetrafluorosilane, boron tribromide, ammonia, tungsten hexafluoride, titanium tetrachloride, sulfur hexafluoride, carbonyl sulfide, digermane, hydrazine, hydrogen selenide, hydrogen sulfide, hydrogen chloride, hydrogen bromide, hydrogen fluoride, chlorine, fluorine, boron trichloride, carbon monoxide, sulfur dioxide, ozone, phosgene, including mixtures of these gases with hydrogen, nitrogen or inert balance gases. The gas cylinder 2 is provided with an internally threaded opening 4 formed in the top wall thereof.

[0021] The cylinder valve 6 comprises a valve body 8, the lower portion of which is externally threaded. The valve body 8 can be mounted on the gas cylinder 2 by threadedly engaging the external thread of the valve body 8 with the internal threads of the opening 4.

[0022] The valve body 8 also includes an axial or vertical passageway 16 formed therethrough, which may extend from the top portion to the lower portion of the valve body 8. This vertical passageway 16 is in communication with the interior of the gas cylinder 2 when the valve body 8 is attached to the opening 4 of the gas cylinder 2.

[0023] The cylinder valve 6 further includes a handle 24. The handle 24 comprises a rotating member 26 that abuts against the sealing member 28 of the seat assembly 30 and moves the whole seat assembly 30 downward against the biasing force of the coil spring 32 until the shutoff member 34 seats on the shoulder 36 to close the top opening of the upper portion of passageway 16.

[0024] The valve body 8 has a cylinder valve neck 12 which extends outwardly therefrom to define a peripheral wall for the horizontal gas discharge passageway 18. The cylinder valve neck 12 includes an external thread formed thereon at the outer end 14 thereof so that the dust cap 20 can be attached to the cylinder valve 6. The inner end 18′ of the horizontal gas discharge passageway 18 is located to communicate with the vertical passageway 16 while the outer end of the horizontal gas discharge passageway 18 is opened at the outer end 14 of the valve body 8 to define a gas outlet 18″.

[0025] As shown in FIG. 1 when the cylinder valve 6 is in the off position, that is, the vertical passageway 16 is not in fluid communication with the horizontal gas discharge passageway 18 and dust cap 20 is secured to outer end 14 of cylinder valve neck 12, a void or chamber 22 is formed. Leakage and/or outgassing of toxic and/or flammable gases will collect in this void 22 which poses a hazard for the end user when removing dust cap 20. Also, if the gas is corrosive, and especially if there is moisture present, it can lead to corrosion and particle formation. Typically, cylinder valves for use with toxic and/or flammable gases have internal threads 40 located at the inner end of most horizontal gas discharge passageway 18 for mounting a restricted flow orifice (RFO). The present invention contemplates the temporary removal and replacement of the RFO with the getter cartridge 100 of the present invention thereby allowing for the absorption or reacting away of small amounts of toxic and/or flammable gas that result from residual outgassing from the inner peripheral wall of the horizontal gas discharge passageway 18 as well as across the polymer seat (not shown) formed by shutoff member 34.

[0026] In FIG. 2, the getter cartridge 100 of the present invention is shown installed in the cylinder valve 6 of a cylinder package 1. In this embodiment, toxic/flammable gas G outgassing from the vertical passageway 16 across the polymer seat (not shown) formed by shutoff member 34 into to the inner end 18′ of most horizontal gas discharge passageway 18 is channeled through the permeable end cap 126 of getter cartridge 100 into the open end 114 of housing body 112 where it either reacts with or is absorbed by the toxic/flammable-gas absorbent 124. There are a number of toxic/flammable-gas absorbent materials available that may be of use in the present invention such as, but not limited to metals, such as copper, aluminum, manganese, sodium, magnesium, potassium and their respective groups such as oxides, hydroxides, carbonates, sulfates, sulfides, amides, permanganates and combinations thereof. These materials may also be present on a high surface area adsorbent such as alumina, silica, carbon, molecular sieve, zeolite or metal organic framework.

[0027] Referring now to FIGS. 3, 4 and 5, the cartridge 100 is preferably, but not necessarily molded from a unitary piece of rigid plastic material such as but not limited to polypropylene, polyimide, poly (ether ether ketone), PTFE, PFA fluorocarbon or an ABS that does not chemically react with the toxic and/or flammable gas that it will necessarily come in contact with. Alternatively, cartridge 100 could also be made from a metal such as stainless steel, aluminum or brass, monel, hastelloy, depending on the gas contemplated for use. The getter cartridge 100 comprises a housing 110, which comprises a housing body 112, a housing open end 114 and a housing closed top end 116. The housing body 112 is a generally cylindrical casing having an outside diameter and an inside diameter and a hollow center core 118 that receives and secures a toxic/flammable-gas absorbent 124. Preferably housing body 112 will have distal and proximal ends, 112′ and 112″, respectively, wherein the outer diameter of the distal end 112′ is less than outer diameter of the proximal end 112″ which results in the formation of an annular seating surface or shoulder 138 extending radially outward from the sidewall of the distal end 112′ to the sidewall forming the proximal end 112″ for receiving washer 140. The purpose of washer 140 is to provide protection to the getter cartridge as well as the gas discharge pathway consequently washer 140 may or may not be present. Washer 140 may be made of such a material that does not chemically react with the toxic and/or flammable gas contained in the cylinder 2, and particularly of such a material that will not chemically react with the toxic and/or flammable gas to degrade washer 140. Depending on the toxic and/or flammable gas G contained in the cylinder 2, the material of the washer 140 may be selected from the group of polymer resins such as but not limited to vinyl chloride, tetrafluoride, trifluoride, Viton®, Kalrez®, and PTFE, and various metals.

[0028] Referring now to FIG. 6 the housing open end 114 preferably has an inner diameter that is slightly larger than the inner diameter of the hollow center core 118 which results in the formation of a seating surface 119 which supports the positioning ring 120 of end cap 126. End cap 126 includes a through-hole centrally formed therein forming an annular rim top surface 128 allowing for a barrier member 130 which is permeable to the toxic and/or flammable gas G and impermeable to the toxic/flammable-gas absorbent 124 and the solid product produced by the toxic/flammable-gas absorbent 124 to be positioned therein. It is preferred that the barrier member 130 has some degrees of strength. For example, the barrier member may be preferably formed by a sintered plate of porous stainless steel. Positioning ring 120 is preferably perfectly-matched with the interior surface of housing open end 114, so that these two surfaces become sealing surfaces which mate to form a reliable seal. Also, optional attachment means may be added, such as the outer flange 122 edge snapping into a recess 123 in the upper surface of housing open end 114 to further secure to end cap 126 or end cap 126 may be positioned with the use of a retaining ring (not shown). In the alternative, external threads (not shown) could be positioned around the edge of flange positioning ring 120. Then end cap 126 could be removably attached by screwing the external threaded portion of edge 120 into an internally threaded opening (not shown) in the housing end 114. In yet another embodiment it is contemplated that upon filling the cartridge with the absorbent material 124 a press may be used to simply push/deform the barrier member 130 into open end 114, if the cartridge is made out of a softer material, such as aluminum (or vice versa) and thus an end cap would not be necessary as barrier member 130 would serve that function.

[0029] To complete the assembly of getter cartridge 100, as best seen in FIGS. 5 and 6, toxic/flammable-gas absorbent 124 is first introduced into the hollow center core 118 of housing body 112. Followed by the insertion of the positioning ring 120 of end cap 126 into the open end 114 of housing body 112 until the leading edge 121 of positioning ring 120 is seated on seating surface 119 and the lower surface 125 of cap flange 122 comes in contact with the recess 123 of open end 114. An adhesive such as a hot melt may further be applied to the recess 123 so that when the lower surface 125 of cap flange 122 comes in contact, a seal is formed, thereby further securing the end cap 126 in place.

[0030] The preferred getter cartridge housing 110 will have a sealing member, such as external threads 132 positioned around the exterior surface of proximal end 112″ thereby allowing the cartridge 100 to be removably positioned by mating with the internal threads 40 of the horizontal gas discharge passageway 18. However, in instances where internal threads are not available in the horizontal gas discharge passageway 18, an optional attachment means may be added, such as positioning O-rings (not shown) around the exterior surface of proximal end 112″ instead of threads. In the alternative, thermoplastic ribs may be co-molded into the exterior surface of proximal end 112″ making the use of O-rings unnecessary. Alternatively, ribs may be cut or molded into a metallic proximal end 112″.

[0031] As discussed previously housing body 110 is molded or machined as a unitary piece and the housing closed top 116 is molded with either a 4-, 6-, or 12-point socket 117, as shown in FIG. 7 formed therein to accommodate a key, such as a hex key, for insertion and removal of the getter cartridge 100. Alternatively, the housing closed top 116 is molded to accommodate a phillips-head screwdriver, flat head screwdriver, or some other means for securing and removing the getter cartridge 100 in the throat of the gas discharge passageway 18. Once getter cartridge 100 is secured into the horizontal gas discharge pathway 18 a Diameter Index Safety Standard (DISS) gasket 44 may be placed over the top of the cartridge 100, coming in contact with toroid 42 and as the dust cap 20, which also comprises a toroid 41 is the secured into place and DISS gasket 44 is indented by toroids 41 and 42 forming face seals.

[0032] In an alternate embodiment, as shown in FIG. 8, getter cartridge 200 has a housing 210 which comprises a housing body or sleeve 213 having a generally cylindrical casing having an outside diameter and an inside diameter and an axial bore or sleeve bore 218 extending therethrough forming an open distal end 214 and an open proximal end 216 for receiving an end cap 226 and top cap 236, respectively thereby closing off sleeve bore 218. Preferably housing body 213 will have a central portion 212 flanked by distal and proximal ends, 212′ and 212″, respectively, wherein the outer diameter of the distal and proximal ends, 212′ and 212″, respectively are less than outer diameter of the central portion 212 which results in the formation of two annular seating surfaces or shoulders 220 and 222 extending radially outward from the sidewalls of the distal and proximal ends, 212′ and 212″, respectively, to the sidewall forming the central portion 212. Shoulder 220 receives washer 240, and shoulder 222 receives a DISS gasket 242, which is connected to the dust cap, as discussed previously toroids (not shown) form sealing faces as the dust cap is tightened into position. The housing open distal end 214 and open proximal end 216 preferably have an inner diameter that is slightly larger than the inner diameter of the axial bore 218 which results in the formation of a seating surface (not shown) in both ends which supports the positioning ring (not shown) of end cap 226 and top cap 236. End cap 226 and top cap 236 both comprise an axial bore forming an annular rim top surface allowing for a barrier member 230 and 234, respectively, which is permeable to the toxic and/or flammable gas and impermeable to the toxic/flammable-gas absorbent 224 and the solid product produced by the toxic/flammable-gas absorbent 224 to be positioned therein. There are a number of toxic/flammable-gas absorbent materials available that may be of use in the present invention such as, but not limited to metals, such as copper, aluminum, manganese, sodium, calcium, magnesium, potassium and their respective groups such as oxides, hydroxides, carbonates, sulfates, sulfides, amides, permanganates and combinations thereof. These materials may also be present on a high surface area adsorbent such as alumina, silica, carbon, molecular sieve, zeolite or metal organic framework. It is preferred that the barrier members 230 and 234 have some degrees of strength. For example, the barrier member may be preferably formed by a sintered plate of stainless steel. After filling the cartridge with the absorbent material 224 a press may be used to simply push/deform the barrier members 230 and 234 into the cartridge body, if the cartridge is made out of a softer material, such as aluminum (or vice versa). Positioning rings of end cap 226 and top cap 236 are preferably perfectly-matched with the interior surface of the housing open distal end 214 and open proximal end 216, respectively so that these two surfaces become sealing surfaces which mate to form a reliable seal. Also, optional attachment means may be added, such as the outer flange (not shown) edge snapping into a recess in the flange upper surface (not shown) of housing body 213 to further secure to end cap 226 and top cap 236. In the alternative, external threads (not shown) could be positioned around the edge of flange positioning ring. Then end cap 226 and top cap 236 could be removably attached by screwing the external threaded portion of the positioning ring into an internally threaded opening (not shown) in the housing open distal end 214 and open proximal end 216.

[0033] The distal end 212″ can be cylindrical in shape; however, it may be advantageous to square off the sides so that a socket or wrench can be used to screw getter cartridge 200 securely into place.

[0034] Operation of the getter cartridge 100 will be described below. With the cylinder valve 6 being in its shutoff position, the getter cartridge 100 of the present invention is secured into the horizontal gas discharge passageway 18 and the dust cap 20 is securely positioned on the cylinder valve neck 12 forming void 22. Toxic and/or flammable gas temporarily having been adsorbed by the inner peripheral wall of the horizontal gas discharge passageway 18, will form in void 22 through the gradual outgassing from the inner peripheral wall of the horizontal gas discharge passageway 18 as well as across the polymer seat from vertical passageway 16. The toxic and/or flammable gas permeates through the barrier member 130 of the outlet cap 126 to the toxic/flammable-gas absorbent 124. The toxic/flammable-gas absorbent 124 then absorbs the toxic and/or flammable gas, thereby resulting in the formation of a solid product. The solid product cannot move through the barrier member 130. Consequently, the toxic gas will not diffuse externally from the cylinder valve 6 even when the dust cap 20 is removed from the cylinder valve 6.

[0035] Further, the toxic/flammable-gas absorbent 124 in the aforementioned embodiment may include a material that can absorb at least moisture and preferably the toxic gas and/or flammable gas in addition to the moisture, such as molecular sieve, zeolite, alumina or activated charcoal. This example is advantageous in that the toxic/flammable-gas absorbent 124 can hold water produced by its reaction with the toxic gas. Further, the toxic/flammable-gas absorbent 124 for absorbing the toxic and/or flammable gas by the chemical reaction as in the aforementioned embodiment may be replaced, for example, by a toxic/flammable-gas adsorbent formed of a material which can absorb at least the toxic and/or flammable gas and preferably moisture in addition to the toxic gas, such as molecular sieve, zeolite, alumina or active carbon. The toxic-gas adsorbent made of any one of the listed materials is particularly preferred since it can absorb not only the toxic and/or flammable gas, but also any moisture contained in the air within the gas discharge passageway. The moisture contained in the air within the horizontal gas discharge passageway 18 may corrode the metallic surface of the horizontal gas discharge passageway 18 to produce a corrosion reactant which may in turn degrade the purity of toxic and/or flammable gas when the toxic and/or flammable gas is used.

[0036] The foregoing description is considered as illustrative only of the principles of the invention. The words “comprise,” “comprising,” “include,” “including,” and “includes” when used in this specification and in the following claims are intended to specify the presence of one or more stated features, integers, components, or steps, but they do not preclude the presence or addition of one or more other features, integers, components, steps, or groups thereof. Furthermore, since a number of 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 process shown described above. Accordingly, all suitable modifications and equivalents may be resorted to falling within the scope of the invention as defined by the claims which follow.

[0037] Reference throughout this specification to “one embodiment,” “certain embodiments,” “one or more embodiments” or “an embodiment” means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. Thus, the appearances of the phrases such as “in one or more embodiments,” “in certain embodiments,” “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily referring to the same embodiment of the invention. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in one or more embodiments.

[0038] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention pertains. Although a number of methods and materials similar or equivalent to those described herein can be used in the practice of the present invention, materials and methods according to some embodiments are described herein. While the invention has been described in detail herein in accord with certain preferred embodiments thereof, many modifications and changes therein may be effected by those skilled in the art. Without further elaboration it is believed that one skilled in the art can, using the description set forth above, utilize the invention to its fullest extent.

[0039] Having disclosed several embodiments, it will be recognized by those of skill in the art that various modifications, alternative constructions, and equivalents may be used without departing from the spirit of the disclosed embodiments. Additionally, a number of well-known processes and elements have not been described in order to avoid unnecessarily obscuring the present invention. Accordingly, the above description should not be taken as limiting the scope of the invention.

[0040] As used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise.