Flexible lightweight arc flash and flash fire resistant polyvinylchloride fabric and garments and methods therefor
11718064 · 2023-08-08
Assignee
Inventors
- Brian C. Nutt (Mendham, NJ, US)
- James P. Towey (Nutley, NJ, US)
- Dave Narasimhan (Flemington, NJ)
- Michael S. Zedalis (Mendham, NJ, US)
Cpc classification
B32B2307/3065
PERFORMING OPERATIONS; TRANSPORTING
B32B2307/546
PERFORMING OPERATIONS; TRANSPORTING
B32B27/12
PERFORMING OPERATIONS; TRANSPORTING
B32B27/304
PERFORMING OPERATIONS; TRANSPORTING
International classification
B32B5/02
PERFORMING OPERATIONS; TRANSPORTING
B32B27/12
PERFORMING OPERATIONS; TRANSPORTING
B32B27/30
PERFORMING OPERATIONS; TRANSPORTING
Abstract
A light weight flexible flame, arc flash and flash fire resistant fabric for protective garments is made from a flexible polyvinylchloride sheet having phthalate or phthalate free plasticizers coated with well defined parallel lines or grids of adhesive layer. The adhesive coated polyvinylchloride sheet contacts a non-woven meta-aramid fiber liner and is heated to produce a bond between the polyvinylchloride sheet and the liner. Both polyvinylchloride sheet and meta-aramid non-woven liner resist heat. When heat from arc flash or flash fire is applied, the heat is conducted away at local contacting regions of the adhesive with the polyvinylchloride sheet to the liner whereby the temperature of the polyvinylchloride is locally reduced preventing sagging, charring or burning of the space between adhesive contacting regions. This structure produces mechanically strong lightweight arc flash and flash fire resistant fabric suited for producing garments that meet all ASTM specifications for fireproof garments.
Claims
1. A heat resistant fabric comprising: a flexible polymeric sheet that is flame resistant and comprises a material of polyvinylchloride that has a thermal conductivity in the range of greater than or equal to 0.12 to less than or equal to 0.25 W.Math.m.sup.−1.Math.K.sup.−1 and a plasticizer, a non-woven liner that comprises fibers that are non-crystalline and has a thermal conductivity of less than or equal to 0.068 W.Math.m.sup.−1.Math.K.sup.−1; and an adhesive having a melting point of greater than 140° C. and less than or equal to 200° C. covering a part of the flexible polymeric sheet that forms a bond only between a part of the flexible polymeric sheet and a part of the non-woven liner thereby forming regions of unattached flexible polymeric sheet between discontinuous adhesive coated regions, wherein upon exposure to an arc flash and/or flash fire during use, the flexible polymeric sheet forms a side of the garment that is exposed to the arc flash and/or flash fire.
2. The heat resistant fabric of claim 1, wherein the adhesive contacts the part of the flexible polymeric sheet in parallel lines.
3. The heat resistant fabric of claim 1, wherein the adhesive contacts the part of the flexible polymeric sheet in closed cell grids.
4. The heat resistant fabric of claim 1, wherein the adhesive contacts the part of the flexible polymeric sheet in open cell grids.
5. The heat resistant fabric of claim 1, wherein the adhesive is insoluble in acetone.
6. The heat resistant fabric of claim 1, wherein the adhesive comprises a polyvinylchloride having greater than 50 wt. % chlorine.
7. The heat resistant fabric of claim 6, wherein the polyvinylchloride of the adhesive has a molecular weight of greater than 18,000.
8. The heat resistant fabric of claim 1, wherein the adhesive comprises polyvinylidenechloride, a copolymer of polyvinylchloride and vinyl acetate, a copolymer of polyvinylchloride and acrylonitrile, or combinations thereof.
9. The heat resistant fabric of claim 1, wherein upon exposure to an arc flash and/or flash fire during use, the regions of unattached flexible polymeric sheet do not sag, char, or ignite.
10. The heat resistant fabric of claim 1, wherein spaces between the discontinuous adhesive-coated regions contacting the flexible polymeric sheet are in the range of from 0.25 to 1.5 mm.
11. The heat resistant fabric of claim 10, wherein the spaces are in the range of from 0.5 to 1.0 mm.
12. The heat resistant fabric of claim 11, wherein the spaces are in the range of from 0.6 to 0.8 mm.
13. The heat resistant fabric of claim 1, wherein the non-woven liner comprises meta-aramid fibers.
14. The heat resistant fabric of claim 1 having no layers other than the flexible polymeric sheet and the non-woven liner bonded together with the adhesive.
15. The heat resistant fabric of claim 1 that meets the specifications of ASTM F2733 and ASTM F1891.
16. A method of providing protection from arc flash or flash fire comprising: obtaining a fabric that comprises: a flexible polymeric sheet that is flame resistant and comprises a material of polyvinylchloride that has a thermal conductivity in the range of greater than or equal to 0.12 to less than or equal to 0.25 W.Math.m.sup.−1.Math.K.sup.−1 and a plasticizer, a non-woven liner that comprises fibers that are non-crystalline and has a thermal conductivity of less than or equal to 0.068 W.Math.m.sup.−1.Math.K.sup.−1; and an adhesive having a melting point of greater than 140° C. and less than or equal to 200° C. covering a part of the flexible polymeric sheet that forms a bond only between a part of the flexible polymeric sheet and a part of the non-woven liner thereby forming regions of unattached flexible polymeric sheet between discontinuous adhesive coated regions; orienting the fabric such that the flexible polymeric sheet is exposed to any source of an arc flash and/or flash fire during use.
17. The method of claim 16, wherein: the adhesive comprises polyvinylchloride having greater than 50 wt. % chlorine and a molecular weight of greater than 18,000.
18. The method of claim 16, wherein the fabric meets the specifications of ASTM F2733 and ASTM F1891.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
(14) The present invention provides a method and a structure that produces a flexible arc flash and flash fire resistant fabric suited for forming garments meeting: ASTM D751: “Standard Test Methods for Coated Fabric”; ASTM D6413/D6413M: “Standard Test Method for Flame Resistance of Textiles (Vertical Test)”; ASTM F1891: “Standard Specification for Arc and Flame Resistant Rainwear”; ASTM F1930-00: “Standard Test Method for Evaluation of Flame Resistant Clothing for Protection Against Flash Fire Simulations Using an Instrumented Manikin”; and ASTM F2733-09: “Standard Specification for Flame Resistant Rainwear for Protection Against Flame Hazards”. These tests are extremely demanding and it difficult to pass all the requirements using a single layer of polyvinylchloride sheet adhesively bonded to a non-woven liner of meta-aramid (Nomex) fibers. Our experimental work has produced a combination of elements that produce this outcome as detailed below.
(15) Polyvinylchloride (PVC) sheets are commercially available from a number of commercial suppliers at different thickness levels. Flexible polyvinylchloride sheets usually contain plasticizers selected from DEHP (Di-2ethylhexylphthalate), Adipates, BTHC (Butyryltrihexylcitrate), Cyclohexane-1,2-dicarboxylic acid, DINCH (diisononylester), Di(2-ethylhexyl)terephthalate, polymerics and trimellitic acid, TOTM (2-ethylhexylester) or phthalate free plasticizers derived from partial tranesterification, acetylation and epoxidation of vegetable oils with ethanol or glycerin (U.S. Pat. Nos. 8,623,947 and 8,697,788). A polyvinylchloride sheet may be incorporated with high visibility organic dyes or inorganic pigments. Polyvinylchloride has inherently superior fire retarding properties due to its greater than 50 weight % chlorine content, even in the absence of fire retardants. For example, the ignition temperature of polyvinylchloride is as high as 455° C., and it is a material with low risk for fire incidents since it is not ignited easily. Furthermore, the heat released in burning is considerably lower with PVC, when compared with those for polyethylene and polypropylene. PVC therefore contributes much less to spreading fire to nearby materials even while burning. Polyvinylchloride has a typical melting point of 160° C. Unplasticized polyvinyl chloride has the following thermal properties.
(16) TABLE-US-00001 Coefficient Heat Heat- Lower Thermal Upper of Thermal deflection deflection working Specific Conductivity working Expansion × temperature temperature temperature heat W m.sup.−1K.sup.−1 temperature 10.sup.−6K 0.45 MPa ° C. 1.8 MPa ° C. ° C. J K.sup.−1kg.sup.−1 @25° C. ° C. 75-100 70 67 30 1000-1500 0.12-0.25 50-75
(17) While any non-woven meta-aramid fiber liner can be used in the fabric, a preferred non-woven meta-aramid fiber liner is readily available from Dupont, who sells such a fiber under the trade name NOMEX. This is a spunlaced fabric of meta-aramid fibers (Nomex). The non-woven fabric weighs about 1.1 oz per square yard. The machine direction grab strength is typically 26 pounds and in the cross direction grab strength is typically 16 pounds. Meta-aramid (Nomex) fibers in the fabric are non crystalline and do not conduct heat readily unlike para-aramid fibers (Kevlar) which is crystalline. Thus, meta-aramid fibers are more suited to provide insulation of heat from flame, arc flash or flash fire.
(18) The subject invention uses a polyvinylchloride sheet adhesively bonded to a non-woven liner of meta-aramid fibers. The adhesive bond is patterned so that spaces between adhesive lines or grids are maintained in the range of 0.25 to 1.50 mm using a patterning method. One of the key features of the subject invention is controlled progressive withdrawal of heat from the polyvinylchloride outer sheet into the non-woven fabric substrate so that the polyvinylchloride sheet does not reach high enough temperature to sag, soften and melt. The free space of the polyvinylchloride sheet not contacting the adhesive is therefore restricted in the range of 0.25 to 1.50 mm. The melt dripping of the polyvinylchloride sheet is not permitted according to ASTM specifications wherein melting and dripping is considered as a failure. The smaller gaps between adhesive lines or grids have only small portion of the polyvinylchloride sheet exposed to the high heat input of arc flash or a flash fire.
(19) The adhesive conducts the heat received to the non-woven meta-aramid fabric liner. The heat transfer through meta-aramid nonwovens is well known in the art (“Thermal Barrier Properties of Flame Resistant Nonwovens” thesis by Rahul Vallabh submitted to North Carolina State University in 2005). Since the non-woven meta-aramid (Nomex) fibers form enclosed spaces, convective heat flow is significantly reduced regardless of the packing density of the non-woven fabric as shown in
(20) The choice of adhesive is very important. It must have a high enough melting or softening point so that it does not separate the polyvinylchloride sheet and the non-woven meta-aramid liner. It must also have adequate strength when the flame, arc flash or flash fire is applied to the polyvinylchloride fabric or garment during handling or exposure to flame and flash fire. This requires the melting or softening point of the adhesive polymer to be greater than 140° C. In addition, the adhesive should not ignite or catch fire when the flame, arc flash or flash fire is applied to the polyvinylchloride fabric or garment. The adhesive applied needs to be flexible, not rigid so that the garment produced is not stiff. In accordance with an aspect of the present invention, the adhesive is a plurality of discontinuous lines and forms discrete locations that are spaced in the range of 0.25 to 1.5 mm. In an alternate embodiment, the adhesive lines are spaced in the range of 0.5 mm to 1.0 mm. In another embodiment, the adhesive lines are spaced in the range of 0.6 to 0.8 mm.
(21) A number of adhesives are suited for the bonding of polyvinylchloride sheet and a non-woven meta-aramid liner. Specifically, a polyvinylchloride adhesive is suited due to its high melting or softening point, the adhesive containing more than 50 percent of chlorine which is released at a temperature greater than the melting point of the adhesive and shields the adhesive area excluding any oxygen present preventing ignition of the adhesive. The molecular weight of the polyvinylchloride adhesive is very important since it directly controls the melting or softening point. A higher molecular weight of polyvinylchloride adhesive results in higher softening point and has a higher tensile modulus and strength properties resulting in a superior bond between the polyvinylchloride sheet and the non-woven meta-aramid liner even at elevated temperatures. The preferred adhesive has a molecular weight in the range of 18,000 to 40,000. A lower molecular weight of polyvinylchloride adhesive, typically in the molecular weight range of 4000 to 16,000 has low strength, melts or softens at a lower temperature and is unsuited for bonding the polyvinylchloride sheet and the non-woven meta-aramid liner and is unlikely to meet the ASTM standards for a flame, arc flash or a flash fire resistant fabric or garment. The higher molecular weight polyvinylchloride adhesive is insoluble in acetone as compared to the lower molecular weight polyvinylchloride adhesive which is dissolved by acetone solvent as detailed in U.S. Pat. Nos. 2,427,513; 2,517,356; and 2,646,414.
(22) Another adhesive suited for bonding polyvinylchloride sheet and non-woven meta-aramid liner is polyvinylidenechloride. This adhesive has a higher level of chlorine since the monomer molecule has two chlorine atoms. The melting or softening temperature is about 200° C., as compared to polyvinylchloride adhesive which is about 160° C. This adhesive also suppresses ignition of the adhesive in the presence of oxygen due to its higher level of chlorine released.
(23) Another adhesive suited for bonding polyvinylchloride sheet and non-woven meta-aramid liner is polyvinylchloride copolymers with vinyl acetate, commonly used electrical insulation and copolymer of vinyl chloride with acrylonitrile.
(24) The fabric, more fully described below, in one embodiment, is formed using one or more polyvinylchloride sheets, an adhesive and a non-woven liner of meta-aramid fibers. In another embodiment of the fabric of the present invention, the fabric only uses a single polyvinylchloride sheet in combination with the adhesive and the non-woven liner of meta-aramid fibers. Alternatively more than one non-woven liner may be interlocked together to form a heat resisting liner bonded to the polyvinylchloride sheet using an adhesive, Thus, one embodiment of the present invention is a three-layer fabric useful in clothing that meets the stringent specifications set forth above.
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(31) Two samples, Sample 1 and Sample 2, of a polyvinylchloride sheet adhesively bonded to a non-woven meta-aramid liner were prepared. Sample 1 had a high molecular weight polyvinyl chloride adhesive and was laid as a powder or a stiff gel in the form of lines. Sample 1 survived dissolution by acetone solvent indicating the high molecular weight of the polyvinylchloride adhesive. Sample 2, which is a comparative prior art sample, has been used to make coats for at least several years now, is believed to have had a low molecular weight polyvinylchloride adhesive, typically in the range of 4,000 to 16,000 units and was laid as a spray of solvent dissolved adhesive. Sample 2 had poor bonding between the polyvinylchloride sheet and the non-woven meta-aramid liner; and the polyvinylchloride sheet and non-woven meta-aramid liner and the bond could be completely separated by dissolution of the polyvinylchloride adhesive by using acetone solvent. This dissolution of the bond clearly verifies that the polyvinylchloride adhesive used for the bond creation of Sample 2 was a low molecular weight polyvinyl chloride polymer.
(32) Sample 1 and Sample 2 were subjected to ASTM specification tests and the results are reported in the table of
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(34) The distance between the locations where the polyvinylchloride sheet shows through the non-woven meta-aramid liner is analyzed by quantitative microcopy. The techniques of analyzing microscopic features are detailed in the book “Quantiative Microscopy” by DeHoff and Rhines, published by McGraw Hill Book Company, 1968. Three concentric circles having 6 mm, 5 mm and 4 mm diameter were drawn in the micrograph of
(35) TABLE-US-00002 Sample 1 Circle Diameter Circumference Crossings Crossings Crossings Mm mm # #/length # #/length # #/length 6 18.85 6 0.32 6 0.32 4 0.21 5 15.71 4 0.25 3 0.19 6 0.38 4 12.57 2 0.16 2 0.16 4 0.32 AVERAGE 0.24 0.22 0.30 0.26
(36) In accordance with other aspects of the invention, the average number of crossings of visible sections of the polyvinylchloride sheet, per length of concentric circle, when concentric circles of 6 mm, 5 mm and 4 mm are applied, as explained above, is no more than 0.26.
(37) A razor blade was used to carefully displace the liner at one end without scraping the adhesive bond.
(38) A higher magnification of the razor blade scraped Sample 1 at a different location is shown in
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(40) The distance between the locations where the polyvinylchloride sheet shows through the non-woven meta-aramid liner was again analyzed by quantitative microcopy. Three concentric circles having 6 mm, 5 mm and 4 mm diameter were drawn in the micrograph of
(41) TABLE-US-00003 Sample 2 Circle Diameter Circumference Crossings Crossings Crossings Mm mm # #/length # #/length # #/length 6 18.85 17 0.90 19 0.99 16 1.18 5 15.71 15 0.95 16 0.98 13 1.21 4 12.57 11 0.88 14 0.90 11 1.14 AVERAGE 0.91 0.96 1.18 1.01
(42) In accordance with other aspects of the invention, the average number of crossings of visible sections of the polyvinylchloride sheet, per length of concentric circle, when concentric circles of 6 mm, 5 mm and 4 mm are applied, as explained above, is no more than 1.
(43) A razor blade was used to carefully displace the liner at one end without scraping the adhesive bond.
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(46) As previously described, the fabric of the subject invention uses a polyvinylchloride sheet adhesively bonded to a non-woven liner of meta-aramid fibers. The adhesive bond is patterned so that spaces between adhesive lines or grids are maintained in the range of 0.25 to 1.50 mm using a patterning method. Other ranges may be used. For example, a range of 0.25 to 1.20 mm. can be maintained, or a range of 0.5 to 1.00 mm can be maintained or a range of 0.60 to 0.80 mm. can also be maintained. This spacing is critical to provide the arc flash or flash fire resistant and heat resistant qualities of the present invention.
(47) The key feature of the subject invention is controlled progressive withdrawal of heat from the polyvinylchloride outer sheet into the non-woven fabric substrate so that the polyvinylchloride sheet does not reach high enough temperature to sag, soften and melt, which is achieved by the structure and materials described herein.
(48) According to applicable tests for flame, arc flash and flash fire flame resistant clothing, including the aforementioned ASTM D751, ASTM D6413/D6413M, ASTM F1891, ASTM F2733, and ASTM F 1930-00, melt dripping of the polyvinylchloride sheet is not permitted as melting and dripping are considered as failures.
(49) The gaps between adhesive lines or grids in the present invention permit only a small portion of the polyvinylchloride sheet to be exposed to the high heat input of an arc flash or a flash fire. During a scenario where heat is applied to the fabric, the adhesive conducts the heat received to the non-woven meta-aramid fabric liner (see
(50) Therefore a garment made with the fabric of the present invention that is subjected to flame, arc flash or arc flash has to withstand several elements.
(51) First, heat from the arc flash or flash fire has to be removed from the polyvinylchloride sheet promptly to prevent sagging, melting and thermal decomposition of the sheet accomplished by thermal conduction through the bonding adhesive due to its intimate contact;
(52) Second, the adhesive cannot bond the entire surface of the polyvinylchloride sheet since this reduces or eliminates flexibility of the garment fabric created.
(53) Third, the heat transfer is adequate to sustain integrity of the sample within the limits stipulated in the ASTM specifications for the time period required passing these ASTM test requirements.
(54) Meeting the requirements 1 through 3 is made possible by adjusting the spacing between lines or grids of adhesive applied to a polyvinylchloride sheet prior to its bonding with the non-woven liner substrate made from meta-aramid (Nomex) fibers. This may be done by spraying a powdered adhesive and combing in one or two directions generating parallel lines or a closed cell or open celled grid. The bonding process is conventional and requires heating to a temperature that softens the adhesive and passing the bonding sample through pressure applying rollers, while other processes may be used equally well. Due to the precise positioning of the adhesive, heat collected by the polyvinylchloride outer layer of the fabric is conducted away through the adhesive and passed on to the non-woven meta-aramid liner.
(55) Briefly stated, the present invention manages the heat flow from an arc flash or flash fire resistant fabric with which the protective garment is made. This is accomplished by having controlled closely spaced contact regions between the bonding adhesive and the polyvinylchloride sheet, thereby the extent of regions of polyvinylchloride sheet not contacting the adhesive and receiving heat flux from the flame, arc flash or flash fire are controlled so that the polyvinyl chloride polymer does not sag, melt or catch fire or degrade. The adhesive serve to take away the heat flux received and transmits to the non-woven meta-aramid (Nomex) liner. The flash fire test imparts a higher level of heat flux load as compared to the flame exposure test and is more difficult to pass the ASTM specifications.
(56) In its preferred embodiment, the light weight flexible flame, arc flash and flash fire resistant polyvinylchloride garments of the present invention comprises:
(57) 1) a flexible polyvinylchloride sheet comprising plasticizers chosen from phthalates or modified organic phthalate free compositions;
(58) 2) said flexible polyvinylchloride provided with adhesive layer in the form of spaced lines or grids controlling free space distance between spaces in the range of 0.25 to 1.50 mm;
(59) 3) said flexible polyvinylchloride sheet with adhesive lines or grids contacting a non-woven liner of meta-aramid (Nomex) fiber liner and heated to soften or evaporate solvent of the adhesive and create a bond between the flexible polyvinylchloride sheet and the liner;
(60) whereby the spaces between the adhesive lines in combination with the contact of adhesive coated regions transmit incident heat flux from a flame, arc flash or flash fire on the polyvinylchloride outer sheet preventing sagging, melting or ignition of regions between adhesive coated regions in the polyvinyl sheet thereby passing ASTM specifications.
(61) In its preferred embodiment, the method for the manufacture of flexible, arc flash and flash fire resistant polyvinylchloride fabrics and garments of the present invention comprises:
(62) 1) selecting a flexible polyvinylchloride sheet comprising plasticizers chosen from phthalates or modified organic phthalate free compositions;
(63) 2) said flexible polyvinylchloride is provided with well defined spaces of adhesive layer in the form of parallel lines or grids controlling free space distance between spaces occupied by the adhesive by a spray and comb process or by screen printing of powder or liquid adhesive;
(64) 3) heating said flexible polyvinylchloride sheet with adhesive lines or grids contacting a non-woven liner of meta-aramid (Nomex) fiber liner to soften the adhesive or evaporate solvent used to create a bond between the flexible polyvinylchloride sheet and the liner;
(65) whereby the spaces between the adhesive lines in combination with the contact of adhesive coated regions transmit incident heat flux on the polyvinylchloride outer sheet preventing sagging, melting or ignition of regions between adhesive coated regions.
(66) This invention also relates to flexible arc flash and flash fire resistant garments made with the previously described fabric. The protective garments made from the fabric have to withstand severe heat flux condition such as exposure to arc flash as well as flash fire as detailed in the aforementioned ASTM test protocol, where the heat flux conditions are exposed to a fixed time period. The metrics of the test include temperature inside the garment and the status of the protective garment, for example the measured temperature in the interior of the garment, the degree of char generated, if the garment ignites or not and or melts and drips. Clearly melting of the outer protective layer of the garment, which is the polyvinylchloride sheet, results in loss of protective material and is not acceptable.
(67) The subject invention prevents excessive exposure to heat flux through controlled removal of heat accumulated from the polyvinylchloride sheet through the conductive properties of adhesive provided at predetermined spacing so that the unattached portion of the polyvinylchloride sheet does not sag, catch fire or drip during arc flash or flash fire exposure.
(68) Both the polyvinylchloride sheet and non-woven liner of meta-aramid are standard products commercially available. These components are bonded by an adhesive. The adhesive commonly used is polyvinylchloride adhesive, again due to its flame resistance properties. The molecular weight of polyvinylchloride adhesive used has a strong influence on its softening point and adhesion strength developed, and lower molecular weight adhesive has slightly lower softening point and generates lower adhesive strength. However, other adhesives can be used. By way of example only, polyvinylidinechloride, polyvinylchloride copolymers with vinyl acetate or copolymer of polyvinylchloride with acrylonitrile can also be used.
(69) Another aspect of the present invention is the fabric itself which is described herein. The fabric includes the polyvinylchloride sheet, the non-woven aramid liner and the adhesive that binds the polyvinylchloride sheet and the non-woven aramid liner together in the manner previously described. In accordance with an aspect of the invention, the fabric only has three layers—the polyvinylchloride sheet, the non-woven aramid liner and the adhesive.
(70) As previously described, another aspect is directed at using the fabric in garments. The garments include coats, overalls, pants, vests and the like. In accordance with an aspect of the invention, the entire garment is made with a fabric described herein. Alternatively one or more sections of the garment can be made with the fabric described herein.
(71) Having thus described the invention in rather full detail, it will be understood that such detail need not be strictly adhered to, but that additional changes and modifications may suggest themselves to one skilled in the art, all falling within the scope of the invention as defined by the claims.