GB2467409A - Noble/inert gas treatment of a material to increase its resistance to flash fire exposure - Google Patents
Noble/inert gas treatment of a material to increase its resistance to flash fire exposure Download PDFInfo
- Publication number
- GB2467409A GB2467409A GB1000083A GB201000083A GB2467409A GB 2467409 A GB2467409 A GB 2467409A GB 1000083 A GB1000083 A GB 1000083A GB 201000083 A GB201000083 A GB 201000083A GB 2467409 A GB2467409 A GB 2467409A
- Authority
- GB
- United Kingdom
- Prior art keywords
- fabrics
- poly
- fabric
- inert gas
- nanoclay
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000463 material Substances 0.000 title claims abstract description 136
- 239000011261 inert gas Substances 0.000 title claims abstract description 30
- 238000011282 treatment Methods 0.000 title description 14
- 239000004744 fabric Substances 0.000 claims abstract description 166
- 229920000742 Cotton Polymers 0.000 claims abstract description 61
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 37
- 239000012802 nanoclay Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 24
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 229910052786 argon Inorganic materials 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 230000004907 flux Effects 0.000 claims description 24
- 239000003063 flame retardant Substances 0.000 claims description 22
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 21
- -1 polybenzarnidizoles Polymers 0.000 claims description 18
- 229920002577 polybenzoxazole Polymers 0.000 claims description 17
- 239000004753 textile Substances 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 229920001601 polyetherimide Polymers 0.000 claims description 13
- 229920006282 Phenolic fiber Polymers 0.000 claims description 11
- 239000004642 Polyimide Substances 0.000 claims description 11
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 11
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 11
- 229920001721 polyimide Polymers 0.000 claims description 11
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 4
- 239000004760 aramid Substances 0.000 abstract description 24
- 239000004927 clay Substances 0.000 abstract description 22
- 239000002048 multi walled nanotube Substances 0.000 abstract description 6
- 239000002109 single walled nanotube Substances 0.000 abstract description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical group O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 abstract description 4
- VRAYVWUMBAJVGH-UHFFFAOYSA-M ethenyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=C)C1=CC=CC=C1 VRAYVWUMBAJVGH-UHFFFAOYSA-M 0.000 abstract description 4
- 150000004714 phosphonium salts Chemical group 0.000 abstract description 4
- 150000004760 silicates Chemical class 0.000 abstract description 3
- 229910052756 noble gas Inorganic materials 0.000 abstract 1
- 241000219146 Gossypium Species 0.000 description 50
- BSBSDQUZDZXGFN-UHFFFAOYSA-N cythioate Chemical compound COP(=S)(OC)OC1=CC=C(S(N)(=O)=O)C=C1 BSBSDQUZDZXGFN-UHFFFAOYSA-N 0.000 description 25
- 229920000784 Nomex Polymers 0.000 description 13
- 239000004763 nomex Substances 0.000 description 13
- 239000002131 composite material Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 230000009970 fire resistant effect Effects 0.000 description 10
- 238000010410 dusting Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000004696 Poly ether ether ketone Substances 0.000 description 6
- 229920013632 Ryton Polymers 0.000 description 6
- 239000004736 Ryton® Substances 0.000 description 6
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 229920002530 polyetherether ketone Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000004951 kermel Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000009832 plasma treatment Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 210000002268 wool Anatomy 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002468 ceramisation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000005495 cold plasma Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005334 plasma enhanced chemical vapour deposition Methods 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 244000063103 Mangifera odorata Species 0.000 description 1
- 235000001375 Mangifera odorata Nutrition 0.000 description 1
- 229920002821 Modacrylic Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 229940094522 laponite Drugs 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical group [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Inorganic materials [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229940001496 tribasic sodium phosphate Drugs 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
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- D—TEXTILES; PAPER
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
- D06M10/025—Corona discharge or low temperature plasma
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/06—Inorganic compounds or elements
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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- D—TEXTILES; PAPER
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/313—Unsaturated compounds containing phosphorus atoms, e.g. vinylphosphonium compounds
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- D—TEXTILES; PAPER
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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- D—TEXTILES; PAPER
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
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- D—TEXTILES; PAPER
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- D—TEXTILES; PAPER
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
- D06M2101/36—Aromatic polyamides
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
In one aspect, a material which has been treated with a non-polymer forming noble/inert gas plasma, and a nanoclay material and/or a cross-linking agent. The preferred noble gas plasma is Argon. The nanoclay includes a range of layered silicates and also multiwalled/single-walled carbon nanotubes (MWCNTs/SWCNTs). The preferred nanoclay is sodium montmorillonite (Na-MMT) clay that has been functionalized with a quaternary phosphonium salt, preferably vinyltriphenylphosphonium bromide. Preferred fabrics to be treated include cotton and meta-aramid. The cross-linking agent may be the noble/inert gas plasma per se, although a silicon-containing monomer, especially hexamethyldisiloxane (HDMSO) is preferred In another aspect, a method of preparing a material having an increased resistance to flash fire exposure comprising contacting the material with a non-polymer forming noble or inert gas plasma. In yet another aspect, the use of a non-polymer forming noble or inert gas plasma in increasing resistance of a material to flash fire exposure.
Description
Flash Fire Resistant Material The present invention relates to a flash fire resistant material which substantially retains the properties and characteristics of the material in an untreated form.
Flash fires result from the rapid movement of a supersonic heat pulse emanating from an explosive or pyrotechnic device. Typically, such pulses are equivalent to a heat flux of the order of 75-100 kW/m2 incident on a target for up to 3 seconds. Under such conditions, many normal materials such as textiles, even those with moderate levels of flame retardancy, may ignite. The only cunent standard performance test for flash fire resistant garments is defined in the United States as NFPA 2112; Standard on Flame-Resistant Garments for Protection of Industrial Personnel Against Flash Fire (published in 2000), in which minimum performance criteria for flame resistant fabrics and guidelines for testing on instrumented thermal manikins are described. This performance standard requires that garment assemblies are subjected to manikin testing as defined in ASTM P1930-00; Standard Test Method for Evaluation of Flame Resistant Clothing for Protection Against Flash Fire Simulations Using an Instrumented Manikin (also published in 2000). NFPA 2112 calls for testing to be conducted under the flame source set at 84 kW/m2 for the duration of 3 seconds with a pass/fail rate of 50% under the testing protocols set in ASTM F1930. Only textile fabrics having the highest levels of flame resistance and comprising a suitably high area density (typically >300 g/m2) will conform to this performance standard. Certain flame retardant cottons, meta-and para-aramid (Nomex ITT�, DuPont) and PBI� (Celanese)/Kevlar� (DuPont) are typical examples.
A normal soldier's battledress, for example, comprises a clothing system having internal garments designed for comfort and external garments offering varying degrees of protection to external agencies. The outer materials such as cotton, polyester, polyamide and blends thereof, are rarely flame resistant unless the user is to be working in a high fire risk area (e.g. tank crew, special services). Furthermore, much so-called fire resistant clothing, tentage and rigid composite items will also be ignited following flash fire exposure. Similarly, the use of fibre-reinforced composite materials in military applications may also be ignited when subjected to high heat fluxes during flash fire and similar exposures.
Fire and heat resistance is normally conferred upon materials such as textile fabrics and composites and thin composites by conferring varying degrees of these properties upon the components present in a way that, at worst, has an overall additive effect. For instance, flame retardant fabrics based on conventional flammable fibres may be rendered flame retardant by the use of applied chemical treatments (on cotton and wool, for example), introduction of additives during manufacture (e.g. flame retardant viscose variants) or by the introduction of flame retardant co-monomers within the fibre/polymer structure (e.g. flame retardant acrylic (modacrylic) and polyester). The use of inherently fire resistant fibres such as the polyaramids, has enabled a class of materials possessing both heat and flame resistance to be developed in more recent years. Similarly, within the area of composites, heat and flame resistance is conferred upon them by the choice of resin and fibre components present.
The results of these possible solutions has given rise to a complex mix of materials such as textiles and composites in use and which may be the part of the same system chosen to create specified levels of heat and fire resistance at both individual component and full system levels. For instance, a modern firefighter wears a clothing system comprising an upper body clothing set, a lower body clothing set, gloves, shoes and head protection, each of which are constructed from a variety of materials to provide defined levels of protection and which, when worn together, must also provide complete body protection to a simulated fire condition. A similar situation exists on the battlefield where combat personnel use a variety of textile and composite materials within their clothing and equipment which may individually have varying levels of heat and fire performance.
However, while many of the above examples resist heat and flame to levels commensurate with the more common fire hazards, very few will resist the high temperature heat front associated with a neighbouring explosion or flash fire where for a short duration (typically <3s), flame front temperatures may exceed 1000 and even 2000°C. It is both impractical and not cost effective to manufacture such a level of fire resistance into all material textile and composite components because they are far in excess of normally-expected risk conditions. However, there would be considerable value in being able to add flash fire performance to culTent heat and fire resistant materials in a way which would be largely independent of material type and in a cost-effective manner.
Currently, there is only one example of such a method, namely the metallisation of the material surface by vapour deposition or fine coating with a metal such as aluminium, stainless steel or some other heat reflective metal. Such metal reflective treatments are applied to some metal workers clothing components including gloves as well as to other applications requiring radiant energy protection.
However, the use of such coatings significantly affects the appearance, handle and comfort and so limits their use on wide ranges of substrates and applications.
Also, in hot environments such as those encountered in processes in, for example, hot gas filtration, fires are often a problem initiated by oxidation of suspended particles in gas streams. There is also a need to provide film materials which are used in such processes which are also resistant to flash fire exposure.
Currently, there is no technology available that can apply a flash fire resistant surface coating to the outer surface of thin materials without adding undue weight and cost to the underlying material, coupled with the ability not to affect the underlying substrate properties, such as maintaining fabric camouflage effects and JR signatures; increasing weight and changing physical properties of thin composite shells and components.
The present invention addresses one or more of these shortcomings. It describes a material, such as a textile fabric or film, which has been provided with durable flash fire resistance without substantially impacting upon the properties and characteristics of the material in comparison with its untreated state.
Therefore, in accordance with the present invention, there is provided a material which has been treated with a non-polymer forming noble or inert gas plasma, and a nanoclay material and/or a cross-linking agent. The material is typically a textile fabric or film.
The present invention describes a means of providing durable flash fire resistance to any flexible and/or thin material, such as a clothing item, tent, camouflage netting or composite structure, in addition to any other inherent fire resistant character present in the material. The invention provides an immediate heat barrier that will protect the underlying material (e.g. textile, composite) when the wearer, occupant or other item is exposed to a flash fire typical of that emitted by an exploding and/or incendiary device. Thus the wearer or interior (if the material is a composite external container/component) is protected from the short term, high heat flux for a period in addition to that normally expected of the underlying material. The applied technology does not affect the functionality and performance of the base material, whether a textile or composite.
The non-polymer forming noble or inert gas plasma may comprise any noble or inert gas, other inert gas (for example nitrogen) but typically comprises argon. The addition of a reactive gas such as oxygen may also be included as a component in order to increase the subsequent reactivity of the material to the nanoparticle material, typically a functionalised nanoclay.
The non-polymer-forming noble or inert gas plasma, such as argon, acts to activate and cause surface erosive roughening at the nano-and micro-levels of the component fibre surfaces of the material.
According to another embodiment of the invention, the material may be further treated with a nanoclay material. The term "nanoclay" is a general term which encompasses a range of layered silicates, or clays. Most clays are 2:1 smectite layered silicates, meaning that there are 2 Si04 tetrahedral layers sandwiching one MO6 octahedral layer (where M is most commonly aluminium or magnesium). Non-limiting examples of nanoclay materials which may be used in the invention include sodium montmorillonite, POSS materials (polyhedral oligomer silsesquioxanes) - which are synthetic silica-cored organic species enabling the formation of inorganic-organic hybrid nanoparticle species, laponite [Na0.7 [(SigMg5.5Lio.3)020(OH)4]o.7], hectorite [M(Mg&Li)SigO2o(OH)4], saponite [MMg6(SigAl)O2o(OH)4] and magadiite [NaSi7On (OH)3.4(H20)], or multiwalled and single-walled carbon nanotubes (MWCNTs and SWCNTs).
Also included within the meaning of "nanoclay" according to the present invention are materials known as layered double hydroxides (LDH). The typical LDH has a Brucite (naturally occuning Mg(OH)2) structure in which some aluminium ion substitutes for magnesium ion to give an excess of positive charge on the clay layers which are balanced by anions in the gallery space. Such double layered hydroxides have an added advantage of being able to release significant amounts of water upon reaching burning temperatures, a favourable property for flame retardant polymer nanocomposite applications.
The nanoday materia' may be functionalised or non-functionalised. If the nanoclay material is functionalised, it is typically functionalised using a salt of a quaternised element from Group YB of the Periodic Table. Non-limiting examples of a functionalising agent include a quaternary phosphonium salt such as vinyl triphenyl phosphonium bromide, or an irnidazollum salt. If the nanoclay is not functionalised, an ionic character would typically be required in the material. Such an ionic character may be found, for example, in materials such as wool and polyamide.
According to a further embodiment of the invention, the material may be further treated with a cross-linking agent. This treatment with a cross-linking agent may be applied to a material which has only been treated with the non-polymer forming noble or inert gas plasma, or alternatively it may be applied to a material which has been treated with both the non-polymer forming noble or inert gas plasma and the functionalised or non-functionalised nanoclay material. The cross-linking agent may comprise, for example, a non-polymer forming noble or inert gas plasma alone, or it may comprise a non-polymer forming noble or inert gas plasma in combination with a silicon-containing monomer. A non-limiting example of a silicon-containing monomer which may be used comprises hexamethyldisiloxane (HDMSO).
However, other monomers comprising an element which would promote ceramisation could be used; such monomers would be apparent to a skilled person. Non-limiting examples of such monomers include silicon-containing monomers such as siloxanes (e.g. HMDSO, 1,1,3,3 tetramethyl disiloxane), and vinyl and allyl silanes (e.g. vinyltriethoxysilane).
The use of LDHs as the nanoclay in the invention also allows the possibility of introducing other metals into the particles. This allows for the improvement of the ceramisation process when subjected to high temperature.
Examples of a textile fabric material which may be used in accordance with the invention include a fabric selected from cotton, cotton which has been first treated with a flame-retardant substance, or an aromatic polymeric fabric. Non-limiting examples of aromatic polymeric fabrics which may be used include meta-or para-aramids (aromatic polyamides), polybenzamidizoles such as PBI�, polybenzoxazoles such as Zylon�, semicarbon and oxidised acrylic fabrics such as Panox� or Sigrafil O�, poly(aramid-arimid) fabrics such as Kermel�, poly(arimid) or polyimide fabrics such as P84�, novoloid fabrics such as Kynol�, polyfluoro-based fabrics such as PTFE�, PVF or FEP, poly(ether ketone) fabrics such as PEEK�, poly(phenylene) sulphide fabrics such as Ryton�, or poly(etherimide) fabrics which are often referred to as PET.
Examples of film materials which may be used in accordance with the invention include those selected from aromatic polymeric fabric including but not limited to meta-or para-aramids (aromatic polyamides), polybenzamidizoles such as PBI�, polybenzoxazoles such as Zylon�, poly(aramid-arimid) fabrics such as Kermel�, poly(arimid) or polyimide fabrics such as P84�, novoloid fabrics such as Kynol�, polyfluoro-based fabrics such as PTFE�, PVF or FEP, poly(ether ketone) fabrics such as PEEK�, poly(phenylene) suiphide fabrics such as Ryton�, or poly(etherimide) fabrics which are often referred to as PEI.
The invention combines new atmospheric plasma and nanoceramisation technologies to deposit one or more nanoceramic layers on the surface of any polymer-based substrate material in order to provide a thermal shield that will add a degree of flash fire resistance to any underlying substrate fire performance properties.
This is undertaken by the development and application of nanoparticulate species to the plasma-etched, material surface to provide a coherent ceramic nanolayer that has minimal effect to the aesthetics and other desirable material properties.
Further in accordance with the present invention there is provided a method of preparing a material having an increased resistance to flash fire exposure comprising contacting the material with a non-polymer forming noble or inert gas plasma.
The non-polymer forming noble or inert gas plasma may comprise any noble or inert gas, other inert gas (for example nitrogen) but typically comprises argon. The addition of a reactive gas such as oxygen may also be included as a component in order to increase the subsequent reactivity of the material to the nanoparticle material, typically a functionalised nanoclay.
The method may further include treating the material with a nanoclay. Non-limiting examples of nanoclay materials which may be used in the invention include sodium montmorillonite, POSS materials (polyhedral oligomer silsesquioxanes) which are synthetic silica-cored organic species enabling the formation of inorganic-organic hybrid nanoparticle species, or multi-walled and single-walled carbon nanotubes (MWCNTs and SWCNTs).
The nanoclay material may be functionalised or non-functionalised. If the nanoclay material is functionalised, it is typically functionalised using a salt of a quaternised Group VB element. Non-limiting examples of a functionalising agent include a quaternary phosphonium salt such as vinyl triphenyl phosphonium bromide, or an imidazolium salt. If the nanoclay is not functionalised, an ionic character would typically be required in the material. Such an ionic character may be found, for example, in a material such as wool and polyamide.
The method may also further include treating the material with a cross-linking agent. This treatment with a cross-linking agent may be applied to a material which has only been treated with the non-polymer forming noble or inert gas plasma, or alternatively it may be applied to a material which has been treated with both the non- polymer forming noble or inert gas plasma and the functionalised or non-functionalised nanoclay material. The cross-linking agent may comprise, for example, a non-polymer forming noble or inert gas plasma alone, or it may comprise a non-polymer forming noble or inert gas plasma in combination with a silicon-containing monomer. A non-limiting example of a silicon-containing monomer which may be used comprises hexamethyldisiloxane.
The textile fabric material which may be treated to increase the flash fire resistant properties may include a fabric selected from cotton, cotton which has been first treated with a flame-retardant substance, or an aromatic polymeric fabric. Non-limiting examples of aromatic polymeric fabrics which may be used include meta-or para-aramids (aromatic polyamides), polybenzamidizoles such as PBI�, polybenzoxazoles such as Zylon�, semicarbon and oxidised acrylic fabrics such as Panox� or Sigrafil O�, poly(aramid-arimid) fabrics such as Kermel�, poly(arimid) or polyimide fabrics such as P84�, novoloid fabrics such as Kynol�, polyfluoro-based fabrics such as PTFE�, PVF or FEP, poly(ether ketone) fabrics such as PEEK�, poly(phenylene) sulphide fabrics such as Ryton�, or poly(etherimide) fabrics which are often referred to as PET.
Examples of film materials which may be used in accordance with the invention include those selected from aromatic polymeric fabric including but not limited to meta-or para-aramids (aromatic polyarnides), polybenzamidizoles such as PBT�, polybenzoxazoles such as Zylon�, poly(aramid-arimid) fabrics such as Keirnel�, poly(arimid) or polyimide fabrics such as P84�, novoloid fabrics such as Kynol�, polyfluoro-based fabrics such as PTFE�, PVF or FEP, poly(ether ketone) fabrics such as PEEK�, poly(phenylene) sulphide fabrics such as Ryton�, or poly(etherimide) fabrics which are often referred to as PET.
Further according to the invention there is provided a material or a method of increasing the flash fire resistance of a material as detailed above, wherein the presence of particles of the nanoclay and/or a silicon-containing polymer deposited on a surface of the material, which material may be untreated or treated with a flame retardant material, increases the time-to-ignition (TTI) and/or time-to-peak heat (TTP) release and/or reduces the peak heat release rate (PHRR) values when measured by a cone calorimeter of the material when subjected to a heat flux which promotes normal material ignition in excess of 30 kW/m2. The materials which may be used for this include cotton which may or may not have been first treated with a flame-retardant substance.
Further according to the invention there is provided a material or method of increasing the flash fire resistance of a material as detailed above, wherein the presence of particles of the nanoclay and/or a silicon-containing polymer deposited on a surface of the material, which material may be untreated or treated with a flame retardant material, increases the time-to-ignition and/or time-to-peak heat release and/or reduces the peak heat release rate (PHRR) values when measured by a cone calorimeter of the material and/or increases the heat flux (or critical heat flux) required to promote ignition of the material when subjected to a heat flux which promotes normal material ignition in excess of 50 kW/m2. The materials which may be used for this include, but are not limited to, flame retardant forms of conventional fabrics such as flame retardant cotton or wool, an aromatic polymeric fabric such those selected from a meta-or para-aramid, polybenzarnidizoles such as PBI�, polybenzoxazoles such as Zylon�, semicarbon and oxidised acrylic fabrics such as Panox� or Sigrafil O�, poly(aramid-arimid) fabrics such as Kermel�, poly(arimid) or polyimide fabrics such as P84�, novoloid fabrics such as Kynol�, polyfluoro-based fabrics such as PTFE�, PVF or FEP, poly(ether ketone) fabrics such as PEEK�. poly(phenylene) sulphide fabrics such as Ryton�, or poly(etherimide) fabrics which are often referred to as PET.
Non-limiting examples of film materials which may be used in accordance with the invention include those selected from aromatic polymeric fabric including meta-or para-aramids (aromatic polyamides), polybenzamidizoles such as PBI�, polybenzoxazoles such as Zylon�, poly(aramid-arimid) fabrics such as Kermel�, poly(arimid) or polyimide fabrics such as P84�, novoloid fabrics such as Kynol�, polyfluoro-based fabrics such as PTFE�, PVF or FEP, poly(ether ketone) fabrics such as PEEK�, poly(phenylene) sulphide fabrics such as Ryton�, or poly(etherimide) fabrics which are often referred to as PEI.
The time-to-ignition is the time the material takes to ignite under exposure to flash fire conditions. Clearly, the greater the time, the more effective the material is at resisting ignition, thus providing a greater degree of protection. The peak heat release rate (PURR) is a measure of the rate of heat energy output that a material generates when it has ignited and determines the rate of energy transfer to an underlying surface such as an underlying garment and wearer's body. The lower the value, the lower is the potential burn risk to a wearer.
Also provided is the use of a non-polymer forming noble or inert gas plasma as described hereinabove in increasing resistance of a material to flash fire exposure.
The present invention will now be further described with reference to the following Examples and Figure, which are intended to be illustrative only and in no way limiting upon the scope of the invention.
Figure 1 depicts a graph showing the relationship between the time-to-ignition and time to peak heat release for (a) Cotton and (b) Proban-treated samples at 35 kW/m2 heat flux.
Examples
Plasma-enhanced chemical vapour deposition (PECVD) A two-step atmospheric, cold plasma process was carried out to produce a functionalised nano-particulate plasma coating on to the fabric surface. The first step comprised a non-polymer-forming argon (Ar) plasma for activation and surface erosive roughening at the nano-and micro-levels of the component fibre surfaces. This was followed by dusting the fabric sample with a functionalised nanoclay and a subsequent cross-linking of the latter to the pre-treated fibre surfaces using the Ar or Ar-HMDSO cold plasma where the active silicon-containing monomer hexamethyldisiloxane (HMDSO) had been introduced.
Changes in fabric mass arose from the ba'ance of initia' tosses during p'asma-activation and subsequent gains following depositions of nanoparticle and/or flame retardant monomer. Overall mass changes were monitored gravimetrically: Degree of grafting (%) = (Wg-Wo) x 100/ Wo where Wo and Wg are the weights of the fabric samples before and after plasma treatment.
Fabrics Cotton fabric and Proban�-treated, flame retardant cotton fabric of area densities 242 and 300 g/m2 respectively and meta-aramid (Nomex�) of area density g/m2 were selected as textile substrates for nanoparticulate treatments using atmospheric plasma. These fabrics were selected because of their wide usage in military clothing applications.
Nanoparticles Sodium montmorillonite (Na-MMT) clay was functionalised with a quaternary phosphonium salt (vinyl triphenyl phosphonium bromide). The salt was dissolved in distilled water and gently agitated to obtain a homogeneous solution of 0.1 M, to which 50g of Na-MMT was added and stirred for 6 hours at room temperature. The resulting mixture was filtered and washed repeatedly with hot water (60°C) until free of excess organic modifier (tested with AgNO3 solution). The exchange process was repeated for another 48 hrs and the resulting clay was collected by filtration, washed, finally dried in a vacuum oven (40°C, 24 hrs) and then ground into a fine powder.
To remove any unexchanged or excess organic modifier and anion exchanged product (sodium bromide/chloride), the clay was first extracted with ethanol and then with tetrahydrofuran using routine soxhlet extraction procedures for 4 hours. The organo-modified clay was dried under high vacuum for 18 hours at 120°C.
Durability to washing testing It is important that any flash fire treatment can withstand a laundering treatment with substantially no, or a minimal, loss of effectiveness in its flash fire resistivity, and so may be termed durable to washing. An accelerated laboratory-based washing procedure may be used to assess the durability of plasma treated fabrics. One such accelerated method which is considered to be equivalent to at least 10 domestic laundry cycles is that reported by W.F. McSherry, G.L. Drake, A.B. Cooper, A.R.
Markezich (Am. Dyest. Report., 1974: 63, 52) and used here. Samples were placed in a 1500 ml liquid solution, containing 0.5% w/v tribasic sodium phosphate and 0.1% v/v Triton X-100. Samples were kept in solution at 40°C for 1 h with continuous stirring. Samples were removed from solution after 1 h, rinsed with distilled water and allowed to dry overnight at room temperature.
Therefore, also provided in accordance with the present invention is a material or method as described herein wherein the material exhibits substantially no loss of effectiveness in its flash fire resistivity upon being washed.
Flash fire testing A cone calorimeter (Fire Testing Technology Ltd., UK) was used at an incident heat flux initially of 35 kW/m2. 75 x 75 mm samples were exposed to incident heat flux and auto-ignition times for all the samples that were recorded. In these experiments the spark ignition was not switched in accordance with the ISO 5660 standard. Significant burning parameters measured were time-to-ignition and peak heat release rate (PHRR), time at which PHRR occurs. The presence of a flash fire protective (nano-) coating and effect will manifest itself as an increase in TTI and/or and increase in TTP and a commensurate reduction in PHRR values.
For fabrics based on cellulose which starts to decompose at about 300°C and lower in the presence of flame retardants such as Proban�, a heat flux of 35 kW/m2 will promote ignition of the fabrics and so the above parameters may be determined.
For fabrics comprised of fibres with higher decomposition temperatures such as those based on all aromatic polymer chain structures, higher heat fluxes of often >50 kW/m2 are required for ignition to occur. In the case of the meta-aramid fibre Nornex� in Tables 1 and 2, a heat flux of 60 kW/m2 was required for the untreated fabric to ignite. Table 3 presents the cone calorimetric data from Proban�-treated cotton and the meta-aramid Nomex� when subjected to a heat flux of 70 kW/m2 before and after receiving an accelerated washing process.
Results Table 1 shows the fabric codes and conditions used to generate them.
Table 1. Fabric/sample codes and treatment conditions
Sample description Treatment
Cotton Untreated, bleached cotton fabric Ar-Cotton Cotton fabric exposed to Ar Plasma for 15 mm ArHMDSO-Cotton Cotton fabric exposed to ArHMDSO Plasma for 15 mm ArClayAr-Cotton Cotton fabric exposed to Ar plasma for 15 mm followed by dusting the fabric surface with functionalised clay and subsequent exposure to Ar plasma for 15 mm.
ArC1ayArHMDSO-Cotton fabric exposed to Ar plasma for 15 mm followed Cotton by dusting the fabric surface with functionalised clay and subsequent exposure to ArHMDSO plasma for 15 mm.
Proban-treated cotton Untreated Proban-treated cotton fabric Ar-Proban-treated cotton Proban-treated cotton fabric exposed to Ar Plasma for 15 mm ArHMDSO-Proban-Proban-treated cotton fabric exposed to ArHMDSO treated cotton Plasma for 15 mm ArClayAr-Proban-treated Proban-treated cotton fabric exposed to Ar plasma for 15 cotton mins followed by dusting the fabric surface with functionalised clay and subsequent exposure to Ar plasma for 15 mm.
ArC1ayArHMDSO-Proban-treated cotton fabric exposed to Ar plasma for 15 Proban-treated cotton mm followed by dusting the fabric surface with functionalised clay and subsequent exposure to ArHMDSO plasma for 15 mins Meta-aramid (Nomex�) Untreated Meta-aramid fabric Ar-Meta-aramid Meta-aramid fabric exposed to Ar Plasma for 15 mm ArHMDSO-Meta-aramid Meta-aramid fabric exposed to ArHMDSO Plasma for 15 mm ArClayAr-Meta-aramid Meta-aramid fabric exposed to Ar plasma for 15 mins followed by dusting the fabric surface with functionalised clay and subsequent exposure to Ar plasma for 15 mm.
ArC1ayArHMDSO-Meta-Meta-aramid fabric exposed to Ar plasma for 15 mm aramid followed by dusting the fabric surface with functionalised clay and subsequent exposure to ArHMDSO plasma for 15 mins Notes: Ar-= plasma treating in argon only; ArHMDSO-= plasma-treating in argon and HMDSO vapour; ArClayAr-= plasma treating in argon and in the presence of nanoclay; ArC1ayArHMDSO-= plasma treating in argon and in the presence of nanoclay and HMDSO Table 2 presents the cone calorimetric data from the samples in Table 1: Cotton samples It can be seen from Table 2 and Figure 1 that the TTI for Ar plasma-treated cotton sample is increased by about 30% when compared to untreated cotton. The time-to-ignition for ArHMDSO-treated cotton fabric does not show any significant change in TTI value despite its containing flame retardant monomer, albeit at a very low level where the degree of deposition of the HMDSO monomer is less than the mass loss following plasma ablation. A significant almost 50% increase in TTI is evident for cotton samples with a layer of functionalised nanoclay only on the fabric surface. Combined plasma HMDSO polymerisation in presence of the nanoclay also shows a significant increase (-40%) in ignition delay time. Times-to-peak heat release values show a marked increase for the Ar-nanoclay-only sample.
Proban�-cotton samples In Table 2 and Figure 1, Proban�-treated cotton samples show no change in ignition times but both the ArClay-and ArHMDSO-treated Proban� cotton show significant increases in TTP values, suggesting that while initial ignition is not suppressed, the overall time to achieve maximum burning rates is. The flash fire suppressing effect here is therefore shown as an increased TTP parameter.
Furthermore, the clay-containing Proban� samples show much reduced PHRR values are with respect to the non-plasma-treated fabric.
Meta-aramid (Nomex�) samples Table 2 shows clearly that even simple plasma treatment under argon increased the time-to-ignite of the fabric subjected to 60 kW/m2 incident heat flux as well as the time to achieve peak heat release. The PHRR value was also reduced from 83 to 73 kW/m2, a reduction of over 10%. More significant, however, was that subsequent treatment with HMDSO, clay alone or HMDSO and clay combined all prevented the ignition of the Nomex� fabric under the a heat flux of 60 kW/m2. It is evident that all three treatments have significantly increased the resistance of this already fire resistant fabric to high heat flux exposures that are typical of flash fire conditions.
Effect of accelerated washing: Proban� cotton and Nomex� Before washing, exposure of both fabrics to the high heat flux of 70 kW/m2, yields TTI and TTP values that are quite short but these are significantly increased only when each fabric has been subjected to the combined plasma treatment incorporating both clay and HMDSO. PHRR values are significantly reduced when fabrics are exposed to either the plasma treatment in the presence of clay only or clay and HMDSO are both present. Table 3 shows that the PHRR value for the clay-treated Proban� fabric is less than 50% of that of the untreated fabric and that plasma treatment when both clay and HMDSO are present renders it non-ignitable. For plasma-exposed Nomex� fabric this latter combined treatment reduces the value PHRR by about 20% with respect to the untreated fabric.
After accelerated washing, similar behaviour is observed with the plasma-treated clay Proban� fabric exhibiting non-ignitability and the PHRR of the clay and HMDSO, with the plasma-treated Nomex� sample showing a further lowering in value. For all plasma-treated Nomex� fabrics, PHRR values are reduced slightly after washing whereas if the treatments were not durable to washing, PHRR values would have been expected to increase. 2U
Table 2. Cone caloaimeic data from all plasmatreated samples Sample Code Mass change, % Incident Heal Ihneto.ignition, III, s Tinielopeak heal Peak heal release rate.
___________________ _______________ Flux, KvIni2 ____________________ release, TIP, s PHRR, Kv/rn2 Cotton 35 14 23 56 ArCoaon L4 19 25 58 ArHMDSOCotton 2 15 21 58 ArC1ayArCotton +2 27 32 45 AiClayArRMDSO + U.7 22 23 54 Cotton ________________ ______________ _______________________ __________________ _________________________ Proban-treated cotton 35 12 14 37 Ar-Proban-treated -27 to -32 12 17 39 cotton ArIIMDSO-Proban--2 to -3 12 14 41 treated cotton ArClayAr-Proban-2. 13 32. 33 treated cotton ArC1ayArRMDSO-+0.5 12 17 29 Proban-treated cotton _______________ _____________ ____________________ ________________ ______________________ Meta-aramid 60 13 16 83 Ar-Meta-aramid -2.8 16 20 73 ArFIMDSO-Meta--0.6 NP --aramid ArClayAr -Meta-1.6 NP --aramid ArC1ayArFIMDSO 3.5 NI* Meta-aramid _______________ _____________ 20) (20) (57) Notes: * NI: No Ignition; ( ) values are for one sample that ignited.
Table 3: Cone caloiimetry data for Proban� cotton and Nofflex� fabrics exposed to 70 kW/ril1 heat flux before and after washing.
Samples Cane Calorimetric data Before washing After washing TI!, s TIP, PIIRR, TI!, s TIP. s PHRR. kW/n __________________ ___ ___ kWIni ___ ____ ________ Proban� -treated cotton (7 kVIrn2) Untreated Proban�-treated cofton 3 4 113 3 4 100 Ar Proban�-treated cotton 4 4 110 4 4 131 Ar HMDSO Proban�-treated cotton 5 8 112 5 6 95 ArClayAr Proban�-treated cotton 4 4 52 N! * * ArClayArHMDSO Proban�-treated 7 8 * 7 11 107 cotton Nomex� (70 kWIm2) UntreatedNoiriex� 9 12 119 9 12 111 Ar Nomex� 8 10 119 10 10 114 Ar4IMDSO Nornex� 9 12 113 11 12. 107 ArClayArNomex� 9 12 109 11 12 107 ArClay-ArHMDSO Nomex� 12 16 99 12 14 80 Note: NI: no ignition, * no data recorded
Claims (30)
- Claims 1. A material which has been treated with a non-polymer forming noble or inert gas plasma, and a nanoclay material and/or a cross-linking agent.
- 2. A material according to claim 1 wherein the non-polymer forming noble or inert gas plasma comprises argon.
- 3. A material according to claim 1 or claim 2 wherein the nanoclay has been functionalised.
- 4. A material according to claim 3 wherein the nanoclay has been functionalised using a salt of a quaternised Group VB element.
- 5. A material according to any preceding claim wherein the cross-linking agent comprises a non-polymer forming noble or inert gas plasma alone or in combination with a silicon-containing monomer.
- 6. A material according to claim 5 wherein the silicon-containing monomer comprises hexamethyldisiloxane (HDMSO).
- 7. A material according to any preceding claim wherein the material is a textile fabric or film.
- 8. A material according to claim 7 wherein the textile fabric comprises a fabric selected from cotton, cotton which has been first treated with a flame-retardant substance, or an aromatic polymeric fabric.
- 9. A material according to claim 8 wherein the aromatic polymeric fabric is selected from a meta-or para-aramid, polybenzarnidizoles, polybenzoxazoles, semicarbon and oxidised acrylic fabrics, poly(aramid-arimid), poly(arimid) or polyimide fabrics, novoloid fabrics, polyfluoro-based fabrics, poly( ether ketone) fabrics, poly(phenylene) sulphide fabrics, or poly(etherimide) fabrics.
- 10. A material according to claim 7 wherein the film material is selected from meta-or para-aramids, polybenzamidizoles, polybenzoxazoles, poly(aramid-arimid) fabrics, poly(arimid) or polyimide fabrics, novoloid fabrics, polyfluoro-based fabrics, poly(ether ketone) fabrics, poly(phenylene) sulphide fabrics, or poly(etherimide) fabrics.
- 11. A method of preparing a material having an increased resistance to flash fire exposure comprising contacting the material with a non-polymer forming noble or inert gas plasma.
- 12. A method according to claim 11 wherein the non-polymer forming noble or inert gas plasma comprises argon.
- 13. A method according to claim 12 further comprising contacting the material with a nanoclay.
- 14. A method according to claim 13 wherein the nanoclay is functionalised.
- 15. A method according to claim 14 wherein the nanoclay has been functionalised using a salt of a quaternised Group VB element.
- 16. A method according to any of claims 10-15 wherein the material is further treated with a cross-linking agent.
- 17. A method according to claim 16 wherein the cross-linking agent is a non-polymer forming noble or inert gas plasma alone or in combination with a silicon-containing monomer.
- 18. A method according to claim 17 wherein the silicon-containing monomer comprises hexamethyldisiloxane.
- 19. A method according to any of claims 10-18 wherein the material is a textile fabric or film.
- 20. A method according to claim 19 wherein the textile fabric comprises a fabric selected from cotton, cotton which has been first treated with a flame-retardant substance, or an aromatic polymeric fabric.
- 21. A method according to claim 19 wherein the aromatic polymeric fabric is selected from a meta-or para-aramid, polybenzarnidizoles, polybenzoxazoles, semicarbon and oxidised acrylic fabrics, poly(ararnid-arimid), poly(arimid) or polyimide fabrics, novoloid fabrics, polyfluoro-based fabrics, poly(ether ketone) fabrics, poly(phenylene) suiphide fabrics, or poly(etherimide) fabrics.
- 22. A method according to claim 19 wherein the film material is selected from meta-or para-aramids, polybenzamidizoles, polybenzoxazoles, poly(aramid-arimid) fabrics, poly(arimid) or polyimide fabrics, novoloid fabrics, polyfluoro-based fabrics, poly(ether ketone) fabrics, poly(phenylene) sulphide fabrics, or poly(etherimide) fabrics.
- 23. A material or method according to any of claims 1-10 and 13-22 wherein the presence of particles of the nanoclay and/or a silicon-containing polymer deposited on a surface of the material, which material may be untreated or treated with a flame retardant material, increases the time-to-ignition and/or time-to-peak heat release values of the material when subjected to a heat flux which promotes normal material ignition in excess of 30 kW/m2.
- 24. A material or method according to claim 23 wherein the material comprises a fabric selected from cotton which may or may not have been first treated with a flame-retardant material.
- 25. A material or method according to any of claims 1-10 and 13-22 wherein the presence of particles of the nanoclay and/or a silicon-containing polymer deposited on a surface of the material, which material may be untreated or treated with a flame retardant material, increases the time-to-ignition and/or time-to-peak heat release values of the material and/or increases the heat flux (or critical heat flux) required to promote ignition of the material when subjected to a heat flux which promotes normal material ignition in excess of kW/m2.
- 26. A material or method according to claim 25 wherein the material comprises an aromatic polymeric fabric.
- 27. A material or method according to claim 26 wherein the aromatic polymeric fabric is selected from a meta-or para-aramid, polybenzamidizoles, polybenzoxazoles, semicarbon and oxidised acrylic fabrics, poly(aramid-arimid), poly(arimid) or polyimide fabrics, novoloid fabrics, polyfluoro-based fabrics, poly(ether ketone) fabrics, poly(phenylene) sulphide fabrics, or poly(etherimide) fabrics.
- 28. A material or method according to any preceding claim wherein the material exhibits substantially no loss of effectiveness in its flash fire resistivity upon being washed.
- 29. Use of a non-polymer forming noble or inert gas plasma in increasing resistance of a material to flash fire exposure.
- 30. A material or method substantially as herein described in the description and drawings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1000083A GB2467409A (en) | 2010-01-05 | 2010-01-05 | Noble/inert gas treatment of a material to increase its resistance to flash fire exposure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1000083A GB2467409A (en) | 2010-01-05 | 2010-01-05 | Noble/inert gas treatment of a material to increase its resistance to flash fire exposure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB201000083D0 GB201000083D0 (en) | 2010-02-17 |
| GB2467409A true GB2467409A (en) | 2010-08-04 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB1000083A Withdrawn GB2467409A (en) | 2010-01-05 | 2010-01-05 | Noble/inert gas treatment of a material to increase its resistance to flash fire exposure |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2467409A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012101036A1 (en) * | 2011-01-28 | 2012-08-02 | Siemens Aktiengesellschaft | Fibre composite polymer and production method therfor |
| EP3146106A4 (en) * | 2014-05-20 | 2017-05-31 | The Bombay Textile Research Association | Method and system for manufacturing multifunctional cotton fabric |
| US10233082B2 (en) | 2016-10-14 | 2019-03-19 | International Business Machines Corporation | Functionalized carbon nanotubes |
| CN112227072A (en) * | 2020-09-30 | 2021-01-15 | 周建萍 | Special acid and alkali resistant fabric for special clothes and processing technology thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3870610A (en) * | 1972-03-09 | 1975-03-11 | Grace W R & Co | Cold plasma treatment of materials |
| JPH0314677A (en) * | 1989-06-08 | 1991-01-23 | Toray Ind Inc | Processing of polyester-based fiber-structured material |
| JPH05140874A (en) * | 1991-11-19 | 1993-06-08 | Kanebo Ltd | Method for improving fastness to rubbing of textile product |
| JPH06136664A (en) * | 1992-10-26 | 1994-05-17 | Toray Ind Inc | Production of flame retardant fabric |
| US5376413A (en) * | 1990-08-22 | 1994-12-27 | Sommer Societe Anonyme | Treatment of textile fibers |
-
2010
- 2010-01-05 GB GB1000083A patent/GB2467409A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3870610A (en) * | 1972-03-09 | 1975-03-11 | Grace W R & Co | Cold plasma treatment of materials |
| JPH0314677A (en) * | 1989-06-08 | 1991-01-23 | Toray Ind Inc | Processing of polyester-based fiber-structured material |
| US5376413A (en) * | 1990-08-22 | 1994-12-27 | Sommer Societe Anonyme | Treatment of textile fibers |
| JPH05140874A (en) * | 1991-11-19 | 1993-06-08 | Kanebo Ltd | Method for improving fastness to rubbing of textile product |
| JPH06136664A (en) * | 1992-10-26 | 1994-05-17 | Toray Ind Inc | Production of flame retardant fabric |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012101036A1 (en) * | 2011-01-28 | 2012-08-02 | Siemens Aktiengesellschaft | Fibre composite polymer and production method therfor |
| EP3146106A4 (en) * | 2014-05-20 | 2017-05-31 | The Bombay Textile Research Association | Method and system for manufacturing multifunctional cotton fabric |
| US10233082B2 (en) | 2016-10-14 | 2019-03-19 | International Business Machines Corporation | Functionalized carbon nanotubes |
| US10633531B2 (en) | 2016-10-14 | 2020-04-28 | International Business Machines Corporation | Functionalized carbon nanotubes |
| CN112227072A (en) * | 2020-09-30 | 2021-01-15 | 周建萍 | Special acid and alkali resistant fabric for special clothes and processing technology thereof |
| CN112227072B (en) * | 2020-09-30 | 2021-11-02 | 福建七匹狼实业股份有限公司 | Special acid and alkali resistant fabric for special clothes and processing technology thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GB201000083D0 (en) | 2010-02-17 |
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| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |