Source: http://www.google.com/patents/US7682697?dq=7,550,386
Timestamp: 2017-03-29 23:30:09
Document Index: 570440553

Matched Legal Cases: ['art 1', 'art 1', 'art 1', 'art 1', 'art 2', 'art 2']

Patent US7682697 - Fiber reinforced thermoplastic sheets with surface coverings - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsA composite sheet material in one embodiment includes a porous core layer. The porous core layer includes a thermoplastic polymer, about 20 weight percent to about 80 weight percent of reinforcing fibers based on a total weight of the porous core layer, and an effective amount of a flame retardant a...http://www.google.com/patents/US7682697?utm_source=gb-gplus-sharePatent US7682697 - Fiber reinforced thermoplastic sheets with surface coveringsAdvanced Patent SearchTry the new Google Patents, with machine-classified Google Scholar results, and Japanese and South Korean patents.Publication numberUS7682697 B2Publication typeGrantApplication numberUS 11/441,709Publication dateMar 23, 2010Filing dateMay 26, 2006Priority dateMar 26, 2004Fee statusPaidAlso published asCN101134380A, EP1859927A2, EP1859927A3, US20060240242Publication number11441709, 441709, US 7682697 B2, US 7682697B2, US-B2-7682697, US7682697 B2, US7682697B2InventorsVenkat Krishna Raghavendran, Thomas Arnold EbelingOriginal AssigneeAzdel, Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (40), Non-Patent Citations (10), Referenced by (8), Classifications (32), Legal Events (4) External Links: USPTO, USPTO Assignment, EspacenetFiber reinforced thermoplastic sheets with surface coverings
US 7682697 B2Abstract
A composite sheet material in one embodiment includes a porous core layer. The porous core layer includes a thermoplastic polymer, about 20 weight percent to about 80 weight percent of reinforcing fibers based on a total weight of the porous core layer, and an effective amount of a flame retardant agent.
1. A composite sheet material comprising a porous core layer, said core layer comprising:
a web of open celled structures defined by random crossing over of reinforcing fibers held together by a thermoplastic polymer;
said web comprising about 20 weight percent to about 80 weight percent of reinforcing fibers based on a total weight of said porous core layer, and
an effective amount of a flame retardant agent, said flame retardant agent comprising at least one of N, P, As, Sb, Bi, S, Se, Te, Po, F, Cl, Br, I, and At.
2. A composite sheet material in accordance with claim 1 wherein said flame retardant agent comprises a halogenated thermoplastic polymer.
3. A composite sheet material in accordance with claim 2 wherein said halogenated thermoplastic polymer comprises tetrabromo bisphenol-A polycarbonate.
4. A composite sheet material in accordance with claim 2 wherein said core layer comprises about 2.0 weight percent to about 13.0 weight percent bromine.
5. A composite sheet material in accordance with claim 2 wherein said core layer comprises about 2.0 weight percent to about 5.0 weight percent bromine.
6. A composite sheet material in accordance with claim 1 further comprising a smoke suppressant composition, said smoke suppressant composition comprising at least one of stannates, zinc borates, zinc molybdate, magnesium silicates, calcium zinc molybdate, calcium silicates and calcium hydroxides.
7. A composite sheet material in accordance with claim 1 further comprising at least one of sodium trichlorobenzene sulfonate potassium and diphenyl sulfone-3-sulfonate.
8. A composite sheet material in accordance with claim 1 further comprising at least one skin, each said skin covering at least a portion of a surface of said porous core layer, said skin comprising at least one of a thermoplastic film, an elastomeric film, a metal foil, a thermosetting coating, an inorganic coating, a fiber based scrim, a non-woven fabric, and a woven fabric, said skin having a limiting oxygen index greater than about 22, as measured at a predetermined thickness used to cover at least a portion of a surface of said porous core layer per ISO 4589-2, first edition, 1996.
9. A composite sheet material in accordance with claim 8 wherein said thermoplastic film comprises at least one of poly(ether imide), poly(ether ketone), poly(ether-ether ketone), poly(phenylene sulfide), poly(arylene sulfone), poly(ether sulfone), poly(antde-imide), poly(1,4-phenylene), polycarbonate, nylon, and silicone.
10. A composite sheet material in accordance with claim 8 wherein said fiber based scrim comprises at least one of glass fibers, aramid fibers, graphite fibers, carbon fibers, inorganic mineral fibers, metal fibers, metalized synthetic fibers, and metalized inorganic fibers.
11. A composite sheet material in accordance with claim 10 wherein said fiber based scrim comprises at least one of polyacrylonitrile, p-aramid, m-aramid, poly(p-phenylene2,6,benzobisoxazole), poly(ether-imide) and poly(phenylene sulfide).
12. A composite material in accordance with claim 8 wherein said thermal setting coating comprises at least one of unsaturated polyurethartes, vinyl esters, phenolics and epoxies.
13. A composite material in accordance with claim 8 wherein said inorganic coating comprises minerals containing cations selected from Ca, Mg, Ba, Si, Zn, Ti and Al.
14. A composite material in accordance with claim 13 wherein said inorganic coating comprises at least one of gypsum, calcium carbonate and mortar.
15. A composite sheet material in accordance with claim 8 comprising:
a first porous core layer having a first surface and a second surface; and
at least one skin covering at least a portion of at least one of said first and second surface.
16. A composite sheet material in accordance with claim 8 comprising:
a first and a second porous core layer, each said core layer comprising a first and a second surface, said second surface of said first core layer positioned adjacent said first surface of said second core layer; and
at least one skin covering at least a portion of at least one of said first and second surfaces of said first core layer and said first and second surface of said second core layer.
17. A composite sheet material in accordance with claim 16 wherein said first porous core layer comprises at least one of a different thermoplastic material and a different fiber than said second porous core layer.
18. A composite sheet material in accordance with claim 8 comprising:
a first, a second, and a third porous core layer, each said core layer comprising a first and a second surface, said second surface of said first core layer positioned adjacent said first surface of said second core layer, said second surface of said second core layer positioned adjacent said first surface of said third core layer; and
at least one skin covering at least one of said first and second surfaces of said first core layer, said first and second surface of said second core layer, and said first and second surface of said third core layer.
19. A composite sheet material in accordance with claim 18 wherein one of said porous core layers comprises at least one of a different thermoplastic material and a different fiber than at least one of said other layers.
20. A composite sheet material according to claim 1 wherein said thermoplastic polymer comprises at least one of polyethylene, polypropylene, polystyrene, acrylonitryistyrene, butadiene, polyethyleneterephthalate, polybutyleneterephthalate, polybutyleneterachlorate, polyvinyl chloride, polyphenylene ether, polycarbonates, polyestercarbonates, thermoplastic polyesters, polyetherimides, acrylonitrile-butylacrylate-styrene polymers, amorphous nylon, polyarylene ether ketone, polyphenylene sulfide, polyaryl sulfone, polyether sulfone, poly(1,4phenylene) compounds, and silicones.
21. A method of manufacturing a porous fiber-reinforced thermoplastic sheet, said method comprising:
providing a porous fiber-reinforced thermoplastic sheet comprising at least one porous core layer comprising a web of open celled structures defined by random crossing over of reinforcing fibers held together by a thermoplastic material, said web comprising from about 20 weight percent to about 80 weight percent fibers, and an effective amount of a flame retardant agent, said flame retardant agent comprising at least one of N, P, As, Sb, Bi, S, Se, Te, Po, F, Cl, Br, I, and At; and
laminating at least one skin to a surface of the porous fiber-reinforced thermoplastic sheet, each skin comprising at least one of a thermoplastic film, an elastomeric film, a metal foil, a thermosetting coating, an inorganic coating, a fiber based scrim, a non-woven fabric, and a woven fabric, the skin having a limiting oxygen index greater than about 22, as measured per ISO 4589-2, first edition, 1996, to enhance at least one of the flame, smoke, heat release and gaseous emissions characteristics of the porous fiber-reinforced thermoplastic sheet.
22. A method in accordance with claim 21 wherein the flame retardant agent comprises a halogenated thermoplastic polymer.
23. A method in accordance with claim 22 wherein the halogenated thermoplastic polymer comprises tetrabromo bisphenol-A polycarbonate.
24. A method in accordance with claim 21 wherein the core layer comprises about 2.0 weight percent to about 13.0 weight percent bromine.
25. A method in accordance with claim 21 wherein the core layer further comprises a smoke suppressant composition, said smoke suppressant composition comprising at least one of stannates, zinc borates, zinc molybdate, magnesium silicates, calcium zinc molybdate, calcium silicates and calcium hydroxides.
26. A method in accordance with claim 21 wherein the core layer further comprises at least one of sodium trichlorobenzene sulfonate potassium and diphenyl sulfone-3-sulfonate.
This application is a Continuation-In-Part application of U.S. patent application Ser. No. 10/810,739, filed Mar. 26, 2004 now U.S. Pat. No. 7,244,501, which is hereby incorporated by reference in its entirety.
This invention relates generally to porous fiber-reinforced thermoplastic polymer composite sheets, and more particularly to porous fiber-reinforced thermoplastic polymer composite sheets having flame retardants, smoke suppressants, and/or synergistic compounds along with surface coverings providing for at least one of reduced flame spread, reduced smoke density, reduced heat release, and reduced gas emissions.
Porous fiber-reinforced thermoplastic composite sheets have been described in U.S. Pat. Nos. 4,978,489 and 4,670,331 and are used in numerous and varied applications in the product manufacturing industry because of the ease molding the fiber reinforced thermoplastic sheets into articles. For example, known techniques such as thermo-stamping, compression molding, and thermoforming have been used to successfully form articles from fiber reinforced thermoplastic sheets.
Because of the varied applications, fiber-reinforced thermoplastic sheets are subjected to various performance tests. For example flame spread, smoke density, and gaseous emissions characteristics of the fiber-reinforced thermoplastic sheets are important when the formed articles are used in environments that might be subjected to a flame event, such as a fire. Because of safety concerns, there is a need to improve the flame, smoke and toxicity performance of fiber reinforced thermoplastic sheet products.
In one aspect, a composite sheet material is provided that includes a porous core layer. The porous core layer includes a thermoplastic polymer, about 20 weight percent to about 80 weight percent of reinforcing fibers based on a total weight of the porous core layer, and an effective amount of a flame retardant agent.
In another aspect, a method of manufacturing a porous fiber-reinforced thermoplastic sheet is provided. The method includes providing a porous fiber-reinforced thermoplastic sheet having at least one porous core layer including a thermoplastic material, from about 20 weight percent to about 80 weight percent of reinforcing fibers, and an effective amount of a flame retardant agent. The method also includes laminating at least one skin to a surface of the porous fiber-reinforced thermoplastic sheet. Each skin includes at least one of a thermoplastic film, an elastomeric film, a metal foil, a thermosetting coating, an inorganic coating, a fiber based scrim, a non-woven fabric, and a woven fabric, the skin having a limiting oxygen index greater than about 22, as measured per ISO 4589, to enhance at least one of the flame, smoke, heat release and gaseous emissions characteristics of the porous fiber-reinforced thermoplastic sheet.
FIG. 1 is cross sectional illustration of an exemplary fiber reinforced thermoplastic sheet in accordance with an embodiment of the present invention.
FIG. 2 is cross sectional illustration of an exemplary fiber reinforced thermoplastic sheet in accordance with another embodiment of the present invention.
FIG. 3 is cross sectional illustration of an exemplary fiber reinforced thermoplastic sheet in accordance with another embodiment of the present invention.
Multi-layered porous fiber-reinforced thermoplastic composite sheets having characteristics of reduced flame spread, reduced smoke density, reduced heat release, and reduced gas emissions are described below in detail. In an exemplary embodiment, the multi-layered porous fiber-reinforced thermoplastic sheets include one or more porous core layers that are formed from one or more thermoplastic materials, about 20 weight percent to about 80 weight percent of fibers dispersed in the thermoplastic material, and an effective amount of a halogen fire retardant agent. At least one surface of the core layer is covered by a skin laminated to the core layer under heat and/or pressure with or without the use of an adhesive or a tie layer. The skin materials are chosen, at least in part, to impart the desired reduction in flame spread, heat release, smoke density, and gaseous emissions of the composite sheet when exposed to a fire event. Also, handling, moldability and end use performance can be improved by laminating two or more porous core layers together having different thermoplastic materials and/or different fibers. Further, skins can be laminated between core layers to affect performance characteristics. Additionally, moldability and formability can be improved by laminating at least one skin to a surface of the core layer where the skin is at least one of a fiber-based scrim, a non-woven fabric and a woven fabric.
Referring to the drawings, FIG. 1 is a cross sectional illustration of an exemplary fiber reinforced thermoplastic composite sheet 10 that includes one porous core layer 12 and skins 14 and 16 laminated to outer surfaces 18 and 20 of core layer 12. In one embodiment, composite sheet 10 has a thickness of about 0.5 millimeters (mm) to about 50 mm and in another embodiment, a thickness of about 0.5 mm to about 25 mm. Also, skins 14 and 16 each have a thickness in one embodiment of about 25 micrometers to about 5 mm, and in another embodiment from about 25 micrometers to about 2.5 mm.
A high tensile modulus of elasticity means a tensile modulus of elasticity substantially higher than that of a consolidated sheet which could be formed from the web structure. Fibers falling into this category include metal, metalized inorganic, metalized synthetic, glass, graphite, carbon and ceramic fibers and fibers such as the aramid fibers sold under the trade names Kevlar and Nomex, and generally includes any fiber having a tensile modulus higher than about 10,000 Mega Pascals at room temperature and pressure.
Particulate plastic materials include short plastics fibers which can be included to enhance the cohesion of the web structure during manufacture. Bonding is effected by utilizing the thermal characteristics of the plastic materials within the web structure. The web structure is heated sufficiently to cause the thermoplastic component to fuse at its surfaces to adjacent particles and fibers.
In one embodiment, individual reinforcing fibers should not on he average be shorter than about 7 millimeters, because shorter fibers do not generally provide adequate reinforcement in the ultimate molded article. Also, fibers should not on average be longer than about 200 millimeters since such fibers are difficult to handle in the manufacturing process.
In one embodiment, the thermoplastics material is, at least in part, in a particulate form. Suitable thermoplastics include, but are not limited to, polyethylene, polypropylene, polystyrene, acrylonitrylstyrene, butadiene, polyethyleneterephthalate, polybutyleneterephthalate, polybutyleneterachlorate, and polyvinyl chloride, both plasticised and unplasticised, and blends of these materials with each other or other polymeric materials. Other suitable thermoplastics include, but are not limited to, polyarylene ethers, polycarbonates, polyestercarbonates, thermoplastic polyesters, polyetherimides, acrylonitrile-butylacrylate-styrene polymers, amorphous nylon, polyarylene ether ketone, polyphenylene sulfide, polyaryl sulfone, polyether sulfone, liquid crystalline polymers, poly(1,4 phenylene) compounds commercially known as PARMAX®, high heat polycarbonate such as Bayer's APEC® PC, high temperature nylon, and silicones, as well as alloys and blends of these materials with each other or other polymeric materials. Preferably, the thermoplastic material has a limited oxygen index (LOI) greater than about 22, as measured in accordance with ISO 4589-2, second edition, Mar. 15, 1996, test method. It is anticipated that any thermoplastics resin can be used which is not chemically attacked by water and which can be sufficiently softened by heat to permit fusing and/or molding without being chemically or thermally decomposed.
Core layer 12 further includes an effective amount of at least one flame retardant agent containing at least one of N, P, As, Sb, Bi, S, Se, Te, Po, F, Cl, Br, I, and At. In one exemplary embodiment, the flame retardant agent is a halogen flame retardant agent. In another embodiment, the flame retardant agent is a halogenated thermoplastic polymer, for example, tetra-bromo bisphenol-A. The amount of the flame retardant in core layer 12 can range in one embodiment from about 2 weight percent to about 13 weight percent, in another embodiment from about 2 weight percent to about 5 weight percent, and in another embodiment, from about 5 weight percent to about 13 weight percent.
Core layer 12 can also include one or more smoke suppressant compositions in the amount of about 0.2 weight percent to about 10 weight percent. Suitable smoke suppressant compositions include, but are not limited to, stannates, zinc borates, zinc molybdate, magnesium silicates, calcium zinc molybdate, calcium silicates, calcium hydroxides, and mixtures thereof.
Core layer 12 can also include a synergist material to increase the efficacy of the halogen flame retardants. Suitable synergist materials include, but are not limited to, sodium trichlorobenzene sulfonate potassium, diphenyl sulfone-3-sulfonate, and mixtures thereof.
Referring to FIG. 1, skins 14 and 16 are formed from materials that can withstand processing temperatures of between about 200° C. and about 425° C. Skins 14 and 16 can be thermoplastic films, elastomeric films, metal foils, thermosetting coating, inorganic coatings, fiber reinforced scrims, and woven or non-woven fabric materials. Any suitable thermoplastic material, including blends of thermoplastic materials, having a LOI greater than about 22, as measured in accordance with ISO 4589-2, second edition, Mar. 15, 1996, test method, can be used for forming the thermoplastic films, for example, poly(ether imide), poly(ether ketone), poly(ether-ether ketone), poly(phenylene sulfide), poly(ether sulfone), poly(amide-imide), poly(aryl sulfone) and combinations thereof. Suitable fibers for forming the scrims include, but are not limited to, glass fibers, aramid fibers, carbon fibers, inorganic fibers, metal fibers, metalized synthetic fibers, metalized inorganic fibers, and combinations thereof. Preferably, the fibers used in forming the scrims have a LOI greater than about 22, as measured in accordance with ISO 4589-2, second edition, Mar. 15, 1996, test method.
In one embodiment, the inorganic coating includes a layer of at least one of gypsum paste, a calcium carbonate paste, a mortar and a concrete. The fiber-based scrim includes a lightweight non-woven covering material manufactured via wet laid, air laid, spunbond, and spunlace processes. The fiber based scrim includes, for example, glass, carbon, polyacrylonitrile, aramid, poly(p-phenylene-benzobisoxazole), poly(ether-imide), poly(phenylene sulfide), etc. The non-woven fabric includes a thermoplastic material, a thermal setting binder, inorganic fibers, metal fibers, metallized inorganic fibers and metallized synthetic fibers.
Skins 14 and 16 are laminated to core layer 12 by any suitable lamination process using heat and/or pressure with or without the use of an adhesive or a tie layer, for example using nip rollers or a lamination machine. Skins 14 and 16 are laminated to core 12 after it has been formed, and in one embodiment, skins 14 and 16 are laminated to core layer 12 before it has been cut into sheets of predetermined size. In another embodiment, skins 14 and 16 are laminated to core layer 12 after it has been cut into sheets. In one embodiment, the temperature of the lamination process is greater than the glass transition temperature of the thermoplastic resins of the skins and core layer, for example, greater than about 100° C. In another embodiment, skins 14 and 16 are bonded to core layer 12 at room temperature using thermal setting adhesives and pressure.
FIG. 2 is a cross sectional illustration of another exemplary fiber reinforced thermoplastic sheet 30 that includes core layers 32 and 34, and skins 36, 38 and 40 laminated to core layers 32 and 34. Particularly, core layer 32 includes a first surface 42 and a second surface 44, and core layer 34 includes a first surface 46 and a second surface 48. Core layers 32 and 34 are arranged so that second surface 44 of core layer 32 is adjacent to first surface 46 of core layer 34. Skin 36 is positioned over first surface 42 of core layer 32, skin 38 is positioned over second surface 48 of core layer 34, and skin 40 is positioned between second surface 44 of core layer 32 and first surface 46 of core layer 34. Core layers 32 and 34, and skins 36, 38, and 40 are laminated together to form fiber reinforced thermoplastic sheet 30.
Core layers 32 and 34, similar to core layer 12 described above, includes about 20% to about 80% by weight fibers having a high tensile modulus of elasticity and about 20% to about 80% by weight of thermoplastics material. The thermoplastic material and/or the fibers of core layer 32 can be the same or different from the thermoplastic material and/or the fibers of core layer 34 depending on the desired properties of sheet 30.
Skins 36, 38, and 40, similar to skins 14 and 16 described above, are formed from materials that can withstand processing temperatures of between about 200° C. and about 425° C. Skins 36, 38, and 40 can be thermoplastic films, fiber reinforced scrims, and woven or non-woven fabric materials. Skins 36, 38, and 40 can be formed from the same materials or can be formed from different materials depending on the desired properties of sheet 30.
In an alternate embodiment, sheet 30 does not include skin 40 laminated between core layers 32 and 34. In further alternate embodiments, only one of the outer surfaces of sheet 30 includes a skin and/or a skin laminated between core layers 32 and 34. In a further alternate embodiment, sheet 30 includes a skin or a skin 40 laminated between core layers 32 and 34 that covers at least a part of second surface 44 of core layer 32 and first surface 46 of core layer 34.
FIG. 3 is a cross sectional illustration of another exemplary fiber reinforced thermoplastic sheet 60 that includes porous core layers 62, 64, and 66, and skins 68, 70, 72, and 74 laminated to core layers 62, 64, and 66. Particularly, core layer 62 includes a first surface 76 and a second surface 78, core layer 64 includes a first surface 80 and a second surface 82, and core layer 66 includes a first surface 84 and a second surface 86. Core layers 62, 64, and 66 are arranged so that second surface 78 of core layer 62 is adjacent to first surface 80 of core layer 64, and second surface 82 of core layer 64 is adjacent to first surface 84 of core layer 66. Skin 68 is positioned over first surface 76 of core layer 62, skin 70 is positioned over second surface 86 of core layer 66, skin 72 is positioned between second surface 78 of core layer 62 and first surface 80 of core layer 64, and skin 74 is positioned between second surface 82 of core layer 64 and first surface 84 of core layer 66. Core layers 62, 64, and 66, and skins 68, 70, 72, and 74 are laminated together to form fiber reinforced thermoplastic sheet 60.
Core layers 62, 64, and 66, similar to core layer 12 described above, includes about 20% to about 80% by weight fibers having a high modulus of elasticity and about 20% to about 80% by weight of one or more thermoplastic materials. The thermoplastic material and/or the fibers of each core layer 62, 64, and 66 can be the same or different from the thermoplastic material and/or the fibers of each other core layer depending on the desired properties of sheet 60.
Skins 68, 70, 72, and 74, similar to skins 14 and 16 described above, are formed from materials that can withstand processing temperatures of between about 200° C. and about 425° C. Skins 68, 70, 72, and 74 can be thermoplastic films, fiber reinforced scrims, and woven or non-woven fabric materials. Skins 68, 70, 72, and 74 can be formed from the same materials or can be formed from different materials depending on the desired properties of sheet 60. In an alternate embodiments, sheet 60 includes one or more of skins 68, 70, 72, and 74 but not all four skins. In another embodiment, sheet 60 includes one or more of skins 68, 70, 72, and 74 covering at least a part of the surfaces of core layers 62, 64, and 66.
The porous fiber-reinforced thermoplastic composite sheets described above can be used in, but not limited to, building infrastructure, aircraft, train and naval vessel side wall panels, ceiling panels, cargo liners, office partitions, elevator shaft lining, ceiling tiles, recessed housing for light fixtures and other such applications that are currently made with honeycomb sandwich structures, thermoplastic sheets, and FRP. The composite sheets can be molded into various articles using methods known in the art including, for example, pressure forming, thermal forming, thermal stamping, vacuum forming, compression forming, and autoclaving. The combination of high stiffness to weight ratio, ability to be thermoformed with deep draw sections, end of life recyclability, acoustics and desirable low flame spread index, heat release, smoke density and gas emission properties make the porous fiber-reinforced thermoplastic composite a more desirable product than the products currently being used.
The invention will be further described by reference to the following examples which are presented for the purpose of illustration only and are not intended to limit the scope of the invention. Unless otherwise indicated, all amounts are listed as parts by weight.
Comparative example tests comparing the flame, smoke and gaseous emissions of a control sample designated Sample A and exemplary samples of an embodiment of the invention designated Samples B and C. Sample A is a porous fiber-reinforced sheet formed from a blend of poly(ether-imide), commercially available from General Electric Company under the ULTEM trademark, and bisphenol A polycarbonate resin containing a bromine based fire retardant additive, commercially available from General Electric Company under the LEXAN trademark, the resins blended in weight ratios of 5 percent and 55 percent. The blended resins were dispersed in a porous fiber-reinforced sheet containing about 40 weight percent glass fibers having a nominal fiber diameter of 16 microns and an average length of 12.7 mm. Sample B is the porous fiber-reinforced sheet of Sample A laminated with 76 micron thick poly(ether-imide) films, commercially available from General Electric Company under the ULTEM trademark, in accordance with an embodiment of the present invention. Sample C is the porous fiber-reinforced sheet of Sample A laminated with 27 g/m2 aramid scrims, commercially available from E.I. du Pont de Nemours and Company under the KEVLAR trademark laminated onto the exterior surfaces in accordance with an embodiment of the present invention. Sample D is the porous fiber-reinforced sheet of Sample A laminated with 8 mil thick polypropylene films. Sample D is a comparative sample that contains laminated polypropylene films that have an LOI of 17. The results are presented below in Tables I to II.
Comparative example tests comparing the flame and smoke characteristics of Sample E, a porous fiber-reinforced sheet formed from a blend of poly(ether-imide) and polycarbonate resins in weight ratio of 25 percent each with 50 weight percent glass fibers of 16 micron in diameter and 12.7 mm in length, Sample F, a porous fiber-reinforced sheet formed from a blend of poly(ether-imide) and an eco-friendly flame retardant based polycarbonate resin in a weight ratios of 5 and 55 percent combined with 40 weight percent glass fibers of 16 microns diameter and 12.7 mm length, Sample G, a porous fiber-reinforced sheet formed from a polycarbonate resin with 50 weight percent glass fibers of 16 micron diameter and 12.7 mm length, Sample H, a porous fiber-reinforced sheet formed from polypropylene with 55 weight percent glass fibers of 16 micron diameter and 12.7 mm length, Sample I, a porous fiber-reinforced sheet formed from a polyarylene ether resin with 50 weight percent glass fibers, and Sample J, a porous fiber-reinforced sheet formed from blend of polycarbonate and polybutylene terephthalate combined in a weight ratio of 33 percent and 17 percent each with 50 weight percent glass fibers of 16 micron diameter and 12.7 mm length are presented below in Table IV.
The fiber-reinforced thermoplastic sheets for Samples A-J were made using the wet-laid paper making process described in United Kingdom Patent Nos. 1129757 and 1329409. The fiber-reinforced thermoplastic sheet was further subjected to heat and pressure in a double belt laminator at 325° C. and 2 bar to partially consolidate the sheet and have the resin wet the fibers. Sample B was prepared from the same fiber-reinforced thermoplastic sheet as Sample A, but with a 75 micrometer thick poly(ether-imide) film covering the surfaces using the double belt laminator under the conditions described above. Sample C was prepared from the same fiber-reinforced thermoplastic sheet as Sample A, but with a 27 g/m2 aramid scrim covering the surfaces using the double belt laminator under the conditions described above. Sample D was prepared from the same fiber-reinforced thermoplastic sheet as Sample A, but with a 8 mil thick polypropylene film covering the surfaces using the double belt laminator under the conditions described above.
The flame characteristics were measured using a radiant heat source and an inclined specimen of the sample material in accordance with ASTM method E-162-02A titled Standard Method for Surface Flammability of Materials Using a Radiant Heat Energy Source. A flame spread index was derived from the rate of progress of the flame front and the rate of heat liberation by the material under test. Key criteria are a flame spread index (FSI) and dripping/burning dripping observations. United States and Canadian requirements for passenger bus applications for interior materials are a FSI of 35 or less with no flaming drips. The Underwriters Laboratory (UL) requires that parts greater than 10 square feet should have an FSI of 200 or less to obtain a listing from UL.
The smoke characteristics were measured by exposing test specimens to flaming and non flaming conditions within a closed chamber according to ASTM method E-662-03 titled Standard Test Method for Specific Optical Density of Smoke Generated by Solid Materials. Light transmissions measurements were made and used to calculate specific optical density of the smoke generated during the test time period. Key criteria are an optical density (Ds) of smoke produced by a sample exposed to a radiant furnace or a radiant furnace plus multiple flames. The optical density is plotted versus time for generally 20 minutes. Maximum optical density and time to reach this maximum are important outputs. United States and Canadian Rail regulations and some United States and Canadian Bus guidelines set a maximum Ds of 100 or less at 1.5 minutes, and a maximum Ds of 200 or less at 4 minutes. Global Air regulations sets the Ds at 4 minutes for many large interior applications at 200 or less.
FAA requirements for toxicity and flame were also measured in accordance FAA tests BSS-7239, developed by Boeing Corporation, and FAR 25.853 (a) Appendix F, Part IV (OSU 65/65) Calorimeter.
A large part in an aircraft passenger cabin interior typically will need to meet the ASTM E162 and ASTM E662 described above as well a maximum Ds of 200 at 4 minutes. A difficult test for plastics has traditionally been the OSU 65/65 heat release test. In this test, the test material is exposed to defined radiant heat source, and calorimeter measurements are recorded. Key criteria are an average maximum heat release during the 5 minute test that should not exceed 65 kW/m2, and an average total heat released during the first 2 minutes of the test that should not exceed 65 kW-min/m2.
ASTM E-162:
Average Flame Spread Index
Fs Flaming Drips
Smoke Density Ds at 1.5
Smoke Density Ds at 4.0
DsMax FAR 25.853 (a) Appendix F,
2 minutes Total Heat Release
54 kW/m2 45 kW/m2 48 kW/m2 Maximum Heat Release
54 KW/m2 41 KW/m2 48 KW/m2 60 Second Vertical Burn:
Vertical Burn Time
(ppm at 4 minutes)
NO + NO3 2
SO2 <1
Fs 27.5
F.D.*
Ds at 1.5 minutes
Ds at 4.0 minutes
Max. DsMax 299
*F.D. = flaming drips.
The above test results show that the fiber reinforced thermoplastic sheet with poly(ether imide) skins of Sample B and with aramid scrims of Sample C exhibit a reduced flame spread index Fs, a reduced smoke density Ds, reduced heat release, and reduced gaseous emissions over Sample A. As shown in Table 1, Samples B and C exhibit test results that are superior to the test results of Sample A. For example, Samples B and C exhibited a lower flame spread index Fs, 5.5 and 6.0 respectively, than Sample A, which had a Fs of 10. Particularly, Samples B and C exhibited lower test results for the tests run according to ASTM E-162, ASTM E-662, FAR 25.853(a), and the 60 second vertical burn test. The only anomaly being the 4 minute smoke density D, result of Sample C. Comparative Example D, which included a thermoplastic film having an LOI of only 17, exhibited a flame spread index Fs of greater than 200 and exhibited flaming drips. Further, each of samples E-J exhibit at least one of a flame spread index Fs and a four minute smoke density Ds that are significantly higher than the flame spread index Fs and the four minute smoke density Ds of Samples B and C.
Further comparative example tests comparing the flame, smoke and gaseous emissions of a control sample designated Sample K and exemplary samples of an embodiment of the invention designated Samples L and M. Sample L is similar to Sample A described above. Sample K is similar to Sample G described above and is a porous fiber-reinforced sheet formed from a blend of poly(ether-imide), commercially available from General Electric Company under the ULTEM trademark, and bisphenol A polycarbonate resin free of fire retardant additives, commercially available from General Electric Company under the LEXAN trademark.
Further comparative example tests comparing the flame, smoke and gaseous emissions of a control sample designated Sample K and exemplary samples of an embodiment of the invention designated Samples L and M were made using nominal 16 micron, 12.7 mm long wet chopped glass fibers and a blended mixture of powdered polyetherimide resin, a relatively high flow Bisphenol-A Polycarbonate (BPA-PC) resin with a nominal MFI≧25 g/10 min @300° C./12.kgf, and a random copolymer polycarbonate resin containing Bisphenol-A and Tetra-bromo Bisphenol A (TBBPA) units in the polymer backbone with a nominal 26% Bromine content and MFI≧7 g/10 min @300° C./12.kgf. The powder blending of the polycarbonate resins at different blend ratios allowed for tuning the total bromine content of the resins used in the core web. The core web had an area weight of around 2000±100 grams/m2 and a w/w glass content of around 45%±5%. Sample K was made without the bromine containing resin. The fiber-reinforced thermoplastic sheets for Samples K-M were made using the wet-laid paper making process described in United Kingdom Patent Nos. 1129757 and 1329409. The fiber-reinforced thermoplastic sheets were further subjected to heat and pressure in a double belt laminator at 325° C. and 2 bar to partially consolidate the sheet and have the resin wet the fibers.
Bromine Content in weight %
Average Flame Spread Index Fs 45
Smoke Density Ds at 1.5 minutes
Smoke Density Ds at 4.0 minutes
Maximum Smoke Density DsMax 388
The test results of Samples K-M show that the addition of bromine in Samples L and M reduces the flame spread index F, in comparison to control Sample M. Also shown, is that the addition of bromine in Samples Land M reduces the maximum smoke density D, in comparison to control Sample M.
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