WO2018057156A1 - Process for making an article from polyolefin and composition thereof - Google Patents
Process for making an article from polyolefin and composition thereof Download PDFInfo
- Publication number
- WO2018057156A1 WO2018057156A1 PCT/US2017/047121 US2017047121W WO2018057156A1 WO 2018057156 A1 WO2018057156 A1 WO 2018057156A1 US 2017047121 W US2017047121 W US 2017047121W WO 2018057156 A1 WO2018057156 A1 WO 2018057156A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- tow
- crosslinked
- oven
- fiber
- heated
- Prior art date
Links
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000000203 mixture Substances 0.000 title description 10
- 230000008569 process Effects 0.000 title description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 37
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 105
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 21
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 230000000802 nitrating effect Effects 0.000 claims description 4
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000835 fiber Substances 0.000 description 107
- 239000002253 acid Substances 0.000 description 63
- 229920000049 Carbon (fiber) Polymers 0.000 description 44
- 239000004917 carbon fiber Substances 0.000 description 44
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 35
- 239000010453 quartz Substances 0.000 description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 125000000524 functional group Chemical group 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 23
- 229910021641 deionized water Inorganic materials 0.000 description 23
- 238000004132 cross linking Methods 0.000 description 21
- -1 CIO alkenes Chemical class 0.000 description 20
- 238000010894 electron beam technology Methods 0.000 description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 238000000944 Soxhlet extraction Methods 0.000 description 18
- 238000011282 treatment Methods 0.000 description 18
- 239000004698 Polyethylene Substances 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 229920005672 polyolefin resin Polymers 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 238000007669 thermal treatment Methods 0.000 description 14
- 239000002243 precursor Substances 0.000 description 13
- 229920000573 polyethylene Polymers 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000013043 chemical agent Substances 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- 238000003763 carbonization Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000006641 stabilisation Effects 0.000 description 6
- 238000011105 stabilization Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 101001073417 Homo sapiens Peflin Proteins 0.000 description 4
- 102100035845 Peflin Human genes 0.000 description 4
- 238000010382 chemical cross-linking Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 239000012756 surface treatment agent Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 230000000269 nucleophilic effect Effects 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 150000003738 xylenes Chemical class 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 2
- 238000004483 ATR-FTIR spectroscopy Methods 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000003466 anti-cipated effect Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000011020 pilot scale process Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- 230000007723 transport mechanism Effects 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- HQNSWBRZIOYGAW-UHFFFAOYSA-N 2-chloro-n,n-dimethylpyridin-4-amine Chemical compound CN(C)C1=CC=NC(Cl)=C1 HQNSWBRZIOYGAW-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical compound NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 150000004662 dithiols Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- ALPIESLRVWNLAX-UHFFFAOYSA-N hexane-1,1-dithiol Chemical compound CCCCCC(S)S ALPIESLRVWNLAX-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229960004011 methenamine Drugs 0.000 description 1
- PZRHRDRVRGEVNW-UHFFFAOYSA-N milrinone Chemical compound N1C(=O)C(C#N)=CC(C=2C=CN=CC=2)=C1C PZRHRDRVRGEVNW-UHFFFAOYSA-N 0.000 description 1
- 229960003574 milrinone Drugs 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- D06M11/51—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 sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/55—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 sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid 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
- D06M11/51—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 sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/52—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 sulfur, selenium, tellurium, polonium or compounds thereof with selenium, tellurium, polonium or their compounds; with sulfur, dithionites or compounds containing sulfur and halogens, with or without oxygen; by sulfohalogenation with chlorosulfonic acid; by sulfohalogenation with a mixture of sulfur dioxide and free halogens
-
- 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
- D06M11/58—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 nitrogen or compounds thereof, e.g. with nitrides
- D06M11/64—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 nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- 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
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
Definitions
- carbonaceous articles such as carbon fibers
- PAN polyacrylonitrile
- cellulose precursors a fabricated article, such as a fiber or a film
- Precursors may be formed into fabricated articles using standard techniques for forming or molding polymers.
- the fabricated article is subsequently stabilized to allow the fabricated article to substantially retain shape and mass during the subsequent heat-processing steps; without being limited by theory, such stabilization typically involves a combination of oxidation and heat and generally results in
- the stabilized fabricated article is then converted into a carbonaceous article by heating the stabilized fabricated article in an inert atmosphere. While the general steps for producing a carbonaceous article are the same for the variety of precursors, the details of those steps vary widely depending on the chemical makeup of the selected precursor.
- Polyolefins have been investigated as an alternative precursor for carbonaceous articles, but a suitable and economically viable preparation process has proven elusive.
- a suitable and economically viable preparation process has proven elusive.
- an economical process for preparing stabilized articles from polyolefin precursors such as stabilized articles which are suitable for subsequent processing to form carbonaceous articles. For example, maximizing mass retention, preventing filament fusion and improving tensile properties during the stabilization and carbonization steps are of interest.
- a method for preparing a polyolefin material comprising providing a crosslinked polyolefin material; surface treating the crosslinked polyolefin material with an acidic medium; heating the crosslinked polyolefin material at or below 140 degrees C.
- a stabilized polyolefin article comprising an empirical formula, CH X S Y O Z , where: 1.85 ⁇ X ⁇ 2.10; 0.000 ⁇ Y ⁇ 0.035; and 0.03 ⁇ Z ⁇ 0.20.
- numeric ranges for instance "from 2 to 10,” are inclusive of the numbers defining the range (e.g., 2 and 10).
- the crosslinkable functional group content for a polyolefin resin is characterized by the mol% crosslinkable functional groups, which is calculated as the number of moles of crosslinkable functional groups divided by the total number of moles of monomer units contained in the polyolefin.
- monomer refers to a molecule which can undergo polymerization, thereby contributing constitutional units to the essential structure of a macromolecule, for example, a polyolefin.
- alkene refers to CI to CIO alkenes.
- alkyne refers to CI to CIO alkynes.
- the present disclosure describes a method for preparing a polyolefin material.
- the polyolefin material is prepared by providing a crosslinked polyolefin material; surface treating the crosslinked polyolefin material with an acidic medium; heating the crosslinked polyolefin material at or below 140 degrees C, thereby providing a stabilized polyolefin material.
- the polyolefin material is further prepared by heating polyolefin material in an oxidizing environment at a temperature no greater than 500 degrees C, thereby providing an oxidized polyolefin material.
- the polyolefin material is further prepared by heating the polyolefin material in an inert environment, thereby providing a carbonaceous polyolefin material.
- Polyolefins are a class of polymers produced from one or more olefin monomer.
- the polymers described herein may be formed from one or more types of monomers.
- Polyethylene is the preferred polyolefin resin, but other polyolefin resins may be substituted.
- the polyolefins described herein are typically provided in resin form, subdivided into pellets or granules of a convenient size for further melt or solution processing.
- the treated olefin resin is processed to form a fabricated article.
- a fabricated article is an article which has been fabricated from the polyolefin resin.
- the fabricated article is formed using known polyolefin fabrication techniques, for example, melt or solution spinning to form fibers, film extrusion or film casting or a blown film process to form films, die extrusion or injection molding or compression molding to form more complex shapes, or solution casting.
- the fabrication technique is selected according to the desired geometry of the target article, and the desired physical properties of the same. For example, where the desired article is a fiber, fiber spinning is a suitable fabrication technique. As another example, where the desired article is a film, compression molding is a suitable fabrication technique.
- the fabricated articles described herein are subjected to a crosslinking step.
- the fabricated article has been melt blended with a treating agent prior to the crosslinking step.
- the fabricated article has been melt blended without the use of a treating agent prior to the crosslinking step.
- a variety of methods for crosslinking polyolefins are known.
- the fabricated articles are crosslinked by irradiation, such as by electron beam processing. Other crosslinking methods are suitable, for example, ultraviolet irradiation and gamma irradiation.
- an initiator such as benzophenone, may be used in conjunction with the irradiation to initiate crosslinking.
- the polyolefin resins have been modified to include crosslinkable functional groups which are suitable for reacting to crosslink the polyolefin resin.
- crosslinking may be initiated by known methods, including use of a chemical crosslinking agent, by heat, by steam, or other suitable method.
- copolymers are suitable to provide a polyolefin resin having crosslinkable functional groups where one or more alpha-olefins have been copolymerized with another monomer containing a group suitable for serving as a crosslinkable functional group, for example, dienes, carbon monoxide, glycidyl methacrylate, acrylic acid, vinyl acetate, maleic anhydride, or vinyl trimethoxy silane
- VTMS are among the monomers suitable for being copolymerized with the alpha-olefin.
- polyolefin resin having crosslinkable functional groups may also be produced from a poly(alpha-olefin) which has been modified by grafting a functional group moiety onto the base polyolefin, wherein the functional group is selected based on its ability to subsequently enable crosslinking of the given polyolefin.
- grafting of this type may be carried out by use of free radical initiators (such as peroxides) and vinyl monomers (such as VTMS, dienes, vinyl acetate, acrylic acid, methacrylic acid, acrylic and methacrylic esters such as glycidyl methacrylate and methacryloxypropyl trimethoxysilane, allyl amine, p-aminostyrene, dimethylaminoethyl methacrylate) or via azido-functionalized molecules (such as 4-[2-(trimethoxysilyl)ethyl)]benzenesulfonyl azide).
- free radical initiators such as peroxides
- vinyl monomers such as VTMS, dienes, vinyl acetate, acrylic acid, methacrylic acid, acrylic and methacrylic esters such as glycidyl methacrylate and methacryloxypropyl trimethoxysilane, allyl amine, p-aminostyrene, di
- Polyolefin resins having crosslinkable functional groups may be produced from a polyolefin resin, or may be purchased commercially.
- Examples of commercially available polyolefin resins having crosslinkable functional groups include SI-LINK sold by The Dow Chemical Company, PRIMACOR sold by The Dow Chemical Company, EVAL resins sold by Kuraray, and LOTADER AX8840 sold by Arkema.
- the polyolefin is crosslinked to yield a crosslinked fabricated article.
- crosslinking is carried out via chemical crosslinking.
- the crosslinked fabricated article is a fabricated article which has been treated with one or more chemical agents to crosslink the crosslinkable functional groups of the polyolefin resin having crosslinkable functional groups.
- Such chemical agent functions to initiate the formation of intramolecular chemical bonds between the crosslinkable functional groups or reacts with the crosslinkable functional groups to form intramolecular chemical bonds, as is known in the art.
- Chemical crosslinking causes the crosslinkable functional groups to react to form new bonds, forming linkages between the various polymer chains which define the polyolefin resin having crosslinkable functional groups.
- the chemical agent which effectuates the crosslinking is selected based on the type of crosslinkable functional group(s) included in the polyolefin resin; a diverse array of reactions are known which crosslink crosslinkable functional groups via intermolecular and intramolecular chemical bonds.
- a suitable chemical agent is selected which is known to crosslink the crosslinkable functional groups present in the fabricated article to produce the crosslinked fabricated article.
- suitable chemical agents include free radical initiators such as peroxides or azo-bis nitriles, for example, dicumyl peroxide, dibenzoyl peroxide, t-butyl peroctoate, azobisisobutyronitrile, and the like.
- a suitable chemical agent can be a compound containing at least two nucleophilic groups, including dinucleophiles such as diamines, diols, dithiols, for example ethylenediamine, hexamethylenediamine, butane diol, or hexanedithiol.
- dinucleophiles such as diamines, diols, dithiols, for example ethylenediamine, hexamethylenediamine, butane diol, or hexanedithiol.
- Compounds containing more than two nucleophilic groups for example glycerol, sorbitol, or hexamethylene tetramine can also be used.
- Lewis or Bronsted acid or base catalysts include aryl sulfonic acids, sulfuric acid, hydroxides, zirconium alkoxides or tin reagents.
- Crosslinking the fabricated article is preferred to ensure that the fabricated article retains its shape at the elevated temperatures required for the subsequent processing steps. Without crosslinking, polyolefin resins typically soften, melt or otherwise deform or breakdown at elevated temperatures. Crosslinking adds thermal stability to the fabricated article. Where the fabricated article is a fiber, crosslinking can contribute to an
- the fabricated article is crosslinked such that it has at least 50 percent gel fraction. In one instance, the fabricated article is crosslinked such that it has at least 55 percent gel fraction. In one instance, the fabricated article is crosslinked such that it has at least 60 percent gel fraction. In one instance, the fabricated article is crosslinked such that it has at least 65 percent gel fraction. In one instance, the fabricated article is crosslinked such that it has at least 70 percent gel fraction.
- the surface of the crosslinked fabricated article is modified with a surface-treating agent and a subsequent heat treatment to yield a surface-treated fabricated article.
- the surface of the fabricated article is defined as the outermost portion of the fabricated article.
- the surface-treating agent is a chemical agent which is suitable for pacifying the surface of the fabricated article.
- the surface of the fabricated article is pacified when adjacent fabricated articles do not fuse together when heated, such as during the air-oxidation process described herein.
- the surface of the fabricated article is pacified when adjacent fabricated articles are substantially not fused together when heated.
- the surface-treating agent is an acidic medium.
- the acidic medium is a sulfonating agent or a nitrating agent.
- the sulfonating agent is an SO3 containing moiety.
- the surface-treating agent is selected from the list consisting of sulfuric acid, fuming sulfuric acid, sulfur trioxide, and chlorosulfonic acid.
- the sulfur trioxide is a gaseous sulfur trioxide or a halogenated compound containing sulfur trioxide.
- the nitrating agent is nitric acid.
- the surface- treating agent serves to prevent the fabricated article from fusing together when heated by pacifying the surface of the fabricated article.
- the concentration of the sulfuric acid in the surface-treating agent is 90 percent or less. In one instance, the concentration of the sulfuric acid in the surface-treating agent is 98 percent or less. In one instance, the concentration of the sulfuric acid in the surface-treating agent is 10 percent or greater. In one instance, the concentration of the sulfuric acid in the surface-treating agent is 20 percent or greater. In one instance, the concentration of the sulfuric acid in the surface-treating agent is 30 percent or greater.
- the polyolefin material is heated.
- the initial temperature of this heating step is at or below the melting point of the polymer resin.
- the temperature of this heating step is at or above 120 °C.
- the temperature selected for this heating step is a function of the time of treatment. In one instance, this heating step is performed in an inert environment. In one instance, this heating step is performed in air.
- the fabricated article after treating the fabricated article with the surface treating agent, the fabricated article is subjected to a heating step and then is subsequently treated again with surface treating agent and subsequently subjected to an additional heating step and followed by one or more additional treatment with a surface treatment agent and heating step.
- a heating step for example, following the first treatment with a surface treatment agent the fabricated article is heated at 120 °C for 20 minutes, followed by treatment with a surface treatment agent, followed by heating at 130 °C for 20 minutes, followed by treatment with a surface treatment agent, followed by heating at 140 °C for 20 minutes.
- tension is applied during either or both of the surface-treatment or heating steps to maintain fiber tow length or reduce fiber tow shrinkage.
- the surface-treated fabricated article is then washed with water.
- the crosslinking step and the surface-treatment step are performed simultaneously by selecting a compound which performs the functions of both the chemical agent and the surface-treating agent.
- SO3 containing moieties are suitable for both crosslinking and surface treating a polyolefin fabricated article.
- chemical crosslinking and surface treating of the fabricated article are performed in a single step by treating the fabricated article with an SO3 containing moiety.
- the conditions for this single-step treatment include treating the fabricated article with the surface-treating agent and heating the fabricated article step- wise, for example, heating at 120 °C for 20 minutes, followed by heating at 130 °C for 20 minutes, followed by heating at 140 °C for 20 minutes.
- the fabricated article is then washed with water.
- the fabricated article is first crosslinked, and is second surface-treated.
- the surface-treated fabricated article is washed in a solvent.
- suitable solvents may include toluene, xylene, or a high-temperature halocarbon.
- An example of a suitable high-temperature halocarbon is tetrachloroethane.
- the temperature of the solvent is above room temperature. In one instance, the temperature of the solvent is at or is greater than 80 °C. In another instance, the temperature of the solvent is at or is less than 100 °C.
- washing the surface-treated fabricated article with the solvent removes at least some of the portions of the fabricated article which were not crosslinked. It was observed that washing with the solvent reduces the instances of filament fusion.
- the crosslinking step is more efficient, meaning a greater percentage of the fabricated article is crosslinked, the need to wash with the solvent will be reduced. It is anticipated that washing with the solvent will be unnecessary where there is extensive crosslinking in the fabricated article. For example, where the fabricated article is 70-100% crosslinked, the solvent wash step may be unnecessary.
- the surface treating and heating steps are repeated one or more times.
- the surface treating and heating steps are performed such that the fabricated article reaches a gel fraction of at least 70 percent.
- the desired gel fraction can be achieved by either or both of repeating the surface treating and heating steps or adjusting the conditions of the surface treating and heating steps (for example, increasing the duration of the steps or increasing the temperature of the heating steps or increasing the concentration of the surface treating agent).
- the polyolefin material is treated with a stabilizing agent to provide a stabilized fabricated article.
- the stabilizing agent is an oxidizing agent.
- the oxidizing agent is oxygen.
- the crosslinked fabricated article is treated with the stabilizing agent by exposing the crosslinked fabricated article to a heated oxidizing environment to yield a stabilized fabricated article.
- the temperature for the oxidizing environment is at least 120 °C, preferably at least 190 °C. In some embodiments, the temperature for the oxidizing environment is no more than 500 °C, preferably no more than 400 °C.
- the crosslinked fabricated article is introduced to a heating chamber which is already at the desired temperature.
- the fabricated article is introduced to a heating chamber at or near ambient temperature, which chamber is subsequently heated to the desired temperature.
- the heating rate is at least 1 °C/minute. In other embodiments the heating rate is no more than 15 °C/minute.
- the chamber is heated step wise, for instance, the chamber is heated to a first temperature for a time, such as, 120 °C for one hour, then is raised to a second temperature for a time, such as 180 °C for one hour, and third is raised to a holding temperature, such as 250 °C for 10 hours.
- the stabilization process involves holding the crosslinked fabricated article at the given temperature for periods up to 100 hours depending on the dimensions of the fabricated article.
- the stabilization process yields a treated stabilized fabricated article which is a precursor for a carbonaceous article.
- the stabilization process oxidizes at least a portion of the crosslinked fabricated article and causes changes to the hydrocarbon structure that increases at least a portion of the crosslink density while decreasing the hydrogen/carbon ratio of the crosslinked fabricated article.
- the stabilized article has a modified surface as compared to a control article.
- the present disclosure describes a stabilized polyolefin article comprising an empirical formula, CH x S Y Oz, where: 1.85 ⁇ X ⁇ 2.10; 0.00 ⁇ Y ⁇ 0.035; and 0.03 ⁇ Z ⁇ 0.20.
- the present disclosure describes an oxidized polyolefin article comprising an empirical formula, CHxOz, where: 0.35 ⁇ X ⁇ 0.50; and 0.5 ⁇ Z ⁇ 0.6. In one instance, 0.390 ⁇ X ⁇ 0.418. In one instance, 0.37 ⁇ X ⁇ 0.46. In one instance, 0.525 ⁇ Z ⁇ 0.562. In one instance, 0.51 ⁇ Z ⁇ 0.58.
- a carbonaceous article and a process for making the same are provided.
- Carbonaceous articles are articles which are rich in carbon; carbon fibers, carbon sheets and carbon films are examples of carbonaceous articles.
- Carbonaceous articles have many applications, for example, carbon fibers are commonly used to reinforce composite materials, such as in carbon fiber reinforced epoxy composites, while carbon discs or pads are used for high performance braking systems.
- the carbonaceous articles described herein are prepared by carbonizing the stabilized fabricated article by heat-treating the treated stabilized fabricated articles in an inert environment.
- the inert environment is an environment surrounding the treated stabilized fabricated article that shows little reactivity with carbon at elevated temperatures, preferably a high vacuum or an oxygen-depleted atmosphere, more preferably a nitrogen atmosphere or an argon atmosphere. It is understood that trace amounts of oxygen may be present in the inert atmosphere.
- the temperature of the inert environment is at or above 600 °C.
- the temperature of the inert environment is at or above 800 °C.
- the temperature of the inert environment is no more than 3000 °C. In one instance, the temperature is from 1400-2400 °C. Temperatures at or near the upper end of that range will produce a graphite article, while temperatures at or near the lower end of the range will produce a carbon article.
- the treated stabilized fabricated article is introduced to a heating chamber containing an inert environment at or near ambient temperature, which chamber is subsequently heated over a period of time to achieve the desired final temperature.
- the heating schedule can also include one or more hold steps for a prescribed period at the final temperature or an intermediate temperature or a programmed cooling rate before the article is removed from the chamber.
- the chamber containing the inert environment is subdivided into multiple zones, each maintained at a desired temperature by an appropriate control device, and the treated stabilized fabricated article is heated in a stepwise fashion by passage from one zone to the next via an appropriate transport mechanism, such as a motorized belt.
- this transport mechanism can be the application of a traction force to the fiber at the exit of the carbonization process while the tension in the stabilized fiber is controlled at the inlet.
- mm is the initial mass of polyethylene
- mox is the mass remaining after oxidation
- mc F is the mass remaining after carbonization
- M%PE is the mass % of polyethylene in the origin formed article.
- Soxhlet extraction is a method for determining the gel fraction and swell ratio of crosslinked ethylene plastics, also referred to herein as hot xylenes extraction.
- Soxhlet extraction is conducted according to ASTM Standard D2765- 11 "Standard Test Methods for Determination of Gel Content and Swell Ratio of Crosslinked Ethylene Plastics.”
- ASTM Standard D2765- 11 Standard Test Methods for Determination of Gel Content and Swell Ratio of Crosslinked Ethylene Plastics.
- a crosslinked fabricated article between 0.050 - 0.500 g is weighed and placed into a cellulose-based thimble which is then placed into a Soxhlet extraction apparatus with sufficient quantity of xylenes. Soxhlet extraction is then performed with refluxing xylenes for at least 12 hours.
- the TGA Method for determining percent stabilization by sulfonation is as follows: a TA Instruments Thermal Gravimetric Analyzer (TGA) Q5000 or Discovery Series TGA is used. Using ⁇ 10-20 mg for the analysis, the sample is heated at 10 °C/min to 800 °C under nitrogen. The final weight of the sample at 800 °C is referred to as the char yield.
- the VTMS content of the VTMS grafted resins was determined by 13C NMR.
- the treated articles are submitted for elemental analysis to determine the carbon, hydrogen, nitrogen, sulfur, and oxygen content.
- a Thermo Model Flash EA1112 Combustion CHNS/O Analyzer is used for determining carbon, hydrogen, nitrogen, sulfur, and oxygen components.
- Carbon fiber tensile properties (modulus, strength, strain) for single filaments/fibers are determined using a single column Instron model 5543 following procedures based on ASTM method C1557 (Standard Test Method for Tensile Strength and Young's Modulus of Fibers). A 5 N load cell with appropriate grips are used. Fiber diameter is determined by optical microscopy.
- Polyethylene fiber tows are crosslinked by electron beam exposure using the AEB Lab System (Advanced Electron Beams, Inc., Wilmington, MA).
- the batch-mode apparatus comprises of a sealed, high vacuum, electron emitter lamp with a maximum accelerating voltage of 150 kV and a maximum e-beam dose of 80 kGy per pass.
- a continuous fiber tow is wound around stainless steel pegs attached around the exterior of a similar 8" x 10" aluminum plate with the center section removed.
- the sample is purged with high purity nitrogen gas from a gas cylinder until the oxygen concentration within the apparatus dropped below a pre-set value, typically 200 ppm.
- the tows are irradiated by programming the control computer to execute the required number of passes, transporting the mounted samples under the beam on each pass, to achieve the desired total dosage.
- Polyethylene fiber tows are crosslinked by electron beam exposure using a pilot- scale PCT Engineered Systems apparatus (Davenport, IA).
- the polyethylene fiber tow is fed continuously at 25 ft/min to the electron beam apparatus using Izumi winders.
- the pilot-scale system comprises a controlled atmosphere housing and a rotating 24 in diameter cooled roller.
- the polyethylene fiber tow is irradiated continuously by accelerated electron beams from an emitter mounted in the top of the housing.
- the accelerating voltage is 200 kV and the current is 295-300 mA.
- Electron beam irradiation dosage is determined by residence time.
- the fiber tow identified as PEF2 in Table l is crosslinked with electron beam irradiation (1200 kGy; 80 kGy/dose) to yield a crosslinked tow with mean gel fraction of 89.7%, as determined by Soxhlet extraction.
- the crosslinked fiber tow is washed in deionized water for 1 hour at 60°C to remove the fiber spin finish; confirmed by ATR-FTIR spectroscopy.
- Three (3) washed crosslinked fiber tows (identified as 1A, IB and 1C) are tied between two sections of commercial carbon fiber and undergo the following acid thermal treatment:
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 60 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 60 min.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 130°C for 20 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
- Filaments are separable. 4.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 140°C for 20 min. After all treatments and carbon fiber leads are removed, the tow is removed from the oven, and is observed to be black in color, and flexible. Filaments are separable.
- the mean elemental composition of 1A is 72.5 wt% carbon, 11.7 wt% hydrogen, 3.9 wt% sulfur, and 12.0 wt% oxygen (by difference). See Tables 2-6.
- IB One fiber tow prepared according to Example 1, identified as IB, is stabilized unconstrained in a quartz boat in a batch tube furnace. Air is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 400°C and subsequently cooled to room temperature.
- the mean elemental composition of IB is 57.7 wt% carbon, 2.0 wt% hydrogen, ND ( ⁇ 0.5) wt% sulfur, and 40.3 wt% oxygen (by difference). See Tables 7-11.
- the fiber tow identified as PEF3 in Table 1 is crosslinked with electron beam irradiation (1200 kGy; 80 kGy/dose) to yield a crosslinked tow with mean gel fraction of 89.4%, as determined by Soxhlet extraction.
- the crosslinked fiber tow is washed in deionized water for 1 hour at 60°C to remove the fiber spin finish.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 60 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 60 min.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 130°C for 20 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 140°C for 20 min. After all treatments and carbon fiber leads are removed, the tow is removed from the oven, and is observed to be black in color, and flexible. Filaments are separable.
- the mean elemental composition of 2 A is 73.1 wt% carbon, 11.9 wt% hydrogen, 3.4 wt% sulfur, and
- the mean elemental composition of 2B is 56.7 wt% carbon, 2.0 wt% hydrogen, ND ( ⁇ 0.5) wt% sulfur, and 41.4 wt% oxygen (by difference). See Tables 7-11.
- the fiber tow identified as PEF4 in Table 1 is crosslinked with electron beam irradiation (1200 kGy; 80 kGy/dose) to yield a crosslinked tow with mean gel fraction of 91.0%, as determined by Soxhlet extraction.
- the crosslinked fiber tow is washed in deionized water for 1 hour at 60°C to remove the fiber spin finish; confirmed by ATR-FTIR spectroscopy.
- Three (3) washed crosslinked fiber tows (identified as 3 A, 3B, and 3C) are tied between two sections of commercial carbon fiber and undergo the following acid thermal treatment:
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 60 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
- Filaments are separable. 2.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 60 min.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 130°C for 20 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 140°C for 20 min. After all treatments and carbon fiber leads are removed, the tow is removed from the oven, and is observed to be black in color, and flexible. Filaments are separable.
- One fiber tow prepared according to Example 3, identified as 3A, is rinsed with 50 vol% sulfuric acid and deionized water and dried. A portion of 3A is heated in a nitrogen atmosphere using a TGA (10°C/min to 800°C). The final char yield is 6.0% of the initial mass at 800°C; 3A loses 73.7% of the initial mass between 400-500°C.
- the mean elemental composition of 3A is 70.4 wt% carbon, 11.8 wt% hydrogen, 3.9 wt% sulfur, and 13.9 wt% oxygen (by difference). See Tables 2-6.
- One fiber tow prepared according to Example 3, identified as 3B, is stabilized unconstrained in a quartz boat in a batch tube furnace. Air is continuously fed at
- the tube furnace is heated at 4°C/min from room temperature to 400°C and subsequently cooled to room temperature.
- the mean elemental composition of 3B is 56.1 wt% carbon, 1.8 wt% hydrogen, ND ( ⁇ 0.5) wt% sulfur, and 42.0 wt% oxygen (by difference). See Tables 7-11.
- One fiber tow prepared according to Example 3, identified as 3C, is stabilized unconstrained in a quartz boat in a batch tube furnace. Air is continuously fed at
- the tube furnace is heated at 4°C/min from room temperature to 400°C and subsequently cooled to room temperature.
- the tow is carbonized unconstrained in a quartz boat in a batch tube furnace. Nitrogen is continuously fed at 2000 seem.
- the tube furnace is heated at 4°C/min from room temperature to 1150°C and subsequently cooled to room temperature.
- the resulting carbon fiber tow is flexible and separable, indicating individual filaments. Individual filaments are mounted using a 0.28 inch gauge length and tensile tested. Two (2) filaments of 3C are tested to produce the following mean properties:
- the fiber tow identified as PEF3 in Table 1 is crosslinked with electron beam irradiation (1200 kGy; 80 kGy/dose) to yield a crosslinked tow with mean gel fraction of 89.4%, as determined by Soxhlet extraction.
- the crosslinked fiber tow is washed in deionized water for 1 hour at 60°C to remove the fiber spin finish.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 20 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 20 min.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 130°C for 20 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 140°C for 20 min. After all treatments and carbon fiber leads are removed, the tow is removed from the oven, and is observed to be black in color, and flexible. Filaments are separable.
- the tow is rinsed with deionized water and dried.
- the tow is stabilized
- the fiber tow identified as PEF3 in Table 1 is crosslinked with electron beam irradiation (1200 kGy; 80 kGy/dose) to yield a crosslinked tow with mean gel fraction of 89.4%, as determined by Soxhlet extraction.
- the crosslinked fiber tow is washed in deionized water for 1 hour at 60°C to remove the fiber spin finish.
- the tow is dipped in chlorosulfonic acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 20 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
- the tow is dipped in chlorosulfonic acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 20 min.
- the tow is dipped in chlorosulfonic acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 130°C for 20 min.
- the tow is removed from the oven, and is observed to be black in color, and flexible. Filaments are separable.
- the tow is dipped in chlorosulfonic acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 140°C for 20 min. After all treatments and carbon fiber leads are removed, the tow is removed from the oven, and is observed to be black in color, and flexible. Filaments are separable.
- the tow is rinsed with deionized water and dried. The tow is stabilized
- the fiber tow identified as PEF3 in Table 1 is crosslinked with electron beam irradiation (1200 kGy; 80 kGy/dose) to yield a crosslinked tow with mean gel fraction of 89.4%, as determined by Soxhlet extraction.
- the crosslinked fiber tow is washed in deionized water for 1 hour at 60°C to remove the fiber spin finish.
- the tow is dipped in 70 wt% nitric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 100°C for 20 min.
- the tow is dipped in 70 wt% nitric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 100°C for 20 min.
- the tow is dipped in 70 wt% nitric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 110°C for 20 min.
- the tow is dipped in 70 wt% nitric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 20 min. After all treatments and carbon fiber leads are removed, the sample is removed, brown in color, and flexible. Filaments are separable. [0059]
- the tow is rinsed with deionized water and dried. The tow is stabilized
- the fiber tow identified as PEF1 in Table 1 is crosslinked with electron beam irradiation (1200 kGy; 80 kGy/dose) to yield a crosslinked tow with mean gel fraction of 91.8%, as determined by Soxhlet extraction.
- the crosslinked fiber tow is washed in deionized water for 1 hour at 60°C to remove the fiber spin finish.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension.
- Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 20 min.
- the tow is removed from the oven, and is observed to be black in color, and flexible.
- the fiber tow identified as PEF2 in Table 1 is crosslinked with electron beam irradiation (1200 kGy; 80 kGy/dose) to yield a crosslinked tow with mean gel fraction of 89.7%, as determined by Soxhlet extraction.
- the crosslinked fiber tow is washed in deionized water for 1 hour at 60°C to remove the fiber spin finish.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension.
- Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 20 min.
- the tow is removed from the oven, and is observed to be black in color, and flexible.
- the tow is rinsed with 50 vol% sulfuric acid and deionized water and dried. A portion of the tow is heated in a nitrogen atmosphere using a TGA (10°C/min to 800°C). The final char yield is 2.0% of the initial mass at 800°C; the sample loses 85.6% of the initial mass between 400-500°C.
- the mean elemental composition of the surface treated sample is 81.7 wt% carbon, 13.6 wt% hydrogen, ND ( ⁇ 0.5) wt% sulfur, and 4.6 wt% oxygen (by difference). See Tables 2-6.
- the fiber tow identified as PEF1 in Table 1 is crosslinked with electron beam irradiation (400 kGy; 80 kGy/dose) to yield a crosslinked tow with mean gel fraction of 74.4%, as determined by Soxhlet extraction.
- the crosslinked fiber tow is washed in deionized water for 1 hour at 60°C to remove the fiber spin finish.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 20 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 20 min.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with 20g tension.
- Air flow is 1.5 L/min.
- the tow is heated in the oven at 130°C for 20 min.
- the tow is removed from the oven, and is observed to be black in color, and flexible.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 140°C for 20 min. After all treatments and carbon fiber leads are removed, the tow is removed from the oven, and is observed to be black in color, and flexible. Filaments are separable.
- the tow is rinsed with deionized water and dried.
- the tow is stabilized
- the fiber tow identified as PEF2 in Table 1 is crosslinked with electron beam irradiation (400 kGy; 80 kGy/dose) to yield a crosslinked tow.
- the crosslinked fiber tow is washed in deionized water for 1 hour at 60°C to remove the fiber spin finish.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 20 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 20 min.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 130°C for 20 min.
- the tow is removed from the oven, and is observed to be black in color, and flexible.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 140°C for 20 min. After all treatments and carbon fiber leads are removed, the tow is removed from the oven, and is observed to be black in color, and flexible. Filaments are separable.
- the tow is rinsed with 50 vol% sulfuric acid and deionized water and dried. A portion of the tow is heated in a nitrogen atmosphere using a TGA (10°C/min to 800°C). The final char yield is 2.0% of the initial mass at 800°C; the sample loses 85.6% of the initial mass between 400-500°C.
- the mean elemental composition of the surface treated sample is 75.1 wt% carbon, 13.0 wt% hydrogen, 2.0 wt% sulfur, and 9.9 wt% oxygen (by difference). See Tables 2-6.
- the fiber tow identified as PEF4 in Table 1 is crosslinked with electron beam irradiation (1200 kGy; 80 kGy/dose) to yield a crosslinked tow with mean gel fraction of 91.0%, as determined by Soxhlet extraction.
- the crosslinked fiber tow is washed in deionized water for 1 hour at 60°C to remove the fiber spin finish.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 60 min.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 18.5 hours. After all treatments and carbon fiber leads are removed, the tow is removed from the oven, and is observed to be black in color, and flexible. Filaments are separable.
- the surface treated fiber is carbonized unconstrained in a quartz boat in a batch tube furnace. Nitrogen is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 1150°C and subsequently cooled to room temperature. The resulting carbon fiber tow is flexible and separable, indicating individual filaments.
- the fiber tow identified as PEF1 in Table 1 is crosslinked with electron beam irradiation (1200 kGy; 80 kGy/dose) to yield a crosslinked tow with mean gel fraction of 88.7%, as determined by Soxhlet extraction.
- the crosslinked fiber tow is washed in deionized water for 1 hour at 60°C to remove the fiber spin finish.
- Each fiber tow is dipped in 30 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 20 min.
- the tow is removed from the oven, and is observed to be black in color, and flexible. Filaments are separable.
- Each fiber tow is dipped in 30 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 20 min.
- Each fiber tow is dipped in 30 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 130°C for 20 min.
- the tow is removed from the oven, and is observed to be black in color, and flexible. Filaments are separable.
- Each fiber tow is dipped in 30 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 140°C for 20 min. After all treatments and carbon fiber leads are removed, the tow is removed from the oven, and is observed to be black in color, and flexible. Filaments are separable.
- the fiber tow prepared according to Example 12 and identified as 12A is oxidized in air at 10°C/min to 350°C in a TGA.
- the tow is further carbonized in nitrogen at 10°C/min to 800°C in a TGA. Separable, individual, and hollow carbon fibers are observed by SEM.
- Example 12B
- the fiber tow prepared according to Example 12 and identified as 12B is oxidized in air at 10°C/min to 400°C in a TGA.
- the tow is further carbonized in nitrogen at 10°C/min to 800°C in a TGA. Separable, individual, and solid carbon fibers are observed by SEM.
- Example 12C
- the fiber tow prepared according to Example 12 and identified as 12C is stabilized unconstrained in a quartz boat in a batch tube furnace. Air is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 400°C and subsequently cooled to room temperature. The tow is carbonized unconstrained in a quartz boat in a batch tube furnace. Nitrogen is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 1150°C and subsequently cooled to room temperature. The resulting carbon fiber tows are flexible and separable, indicating individual filaments. Individual filaments are mounted using a 0.5 inch gauge length and tensile tested. 20 (20) filaments are tested to produce the following mean properties:
- VTMS vinyl trimethoxysilane
- MI 19 g/10 min, 190°C/2.16 kg
- 1.4 wt% grafted silane content determined by Fourier transform infrared spectroscopy FT-IR
- the VTMS-grafted precursor resin is melt spun to form fiber tows with the following properties: 1573 filaments, 1976.1 total denier, 2.22 gf/den, 12.32% elongation-to-break.
- the prepared fiber tows are continuously treated in a vessel containing an isopropanol solution with 5 wt% of an aryl sulfonic acid, Nacure B201, supplied by King Industries, for 30 min.
- the treated fiber tows are allowed to dry cure for 3 days.
- the fiber tows are subsequently moisture cured at 80 °C (100% relative humidity) for 5 days.
- the gel fraction is determined to be 58.2% by Soxhlet extraction.
- the crosslinked fiber tow is washed in isopropanol followed by deionized water for 1 hour at 60°C to remove the fiber spin finish.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 60 min.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 60 min.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 130°C for 20 min.
- the tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 140°C for 20 min. After all treatments and carbon fiber leads are removed, the tow is removed from the oven, and is observed to be black in color.
- the tow is stabilized unconstrained in a quartz boat in a batch tube furnace. Air is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 400°C and subsequently cooled to room temperature. The tow is carbonized unconstrained in a quartz boat in a batch tube furnace. Nitrogen is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 1150°C and subsequently cooled to room temperature. The resulting carbon fiber sample is brittle and fused. No individual filaments are separable.
- VTMS vinyl trimethoxysilane
- MI 19 g/10 min, 190°C/2.16 kg
- 1.4 wt% grafted silane content determined by Fourier transform infrared spectroscopy FT-IR
- the VTMS-grafted precursor resin is melt spun to form fiber tows with the following properties: 1573 filaments, 1976.1 total denier, 2.22 gf/den, 12.32% elongation-to-break.
- the prepared fiber tows are continuously treated in a vessel containing an isopropanol solution with 5 wt% of an aryl sulfonic acid, Nacure B201, supplied by King Industries, for 30 min.
- the treated fiber tows are allowed to dry cure for 3 days.
- the fiber tows are subsequently moisture cured at 80 °C (100% relative humidity) for 5 days.
- the gel fraction is determined to be 60.8% by Soxhlet extraction.
- the crosslinked fiber tow is washed in isopropanol followed by deionized water for 1 hour at 60°C to remove the fiber spin finish.
- the tow is dipped in 50 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 60 min.
- the tow is dipped in 50 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 120°C for 60 min.
- the tow is dipped in 50 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 130°C for 20 min.
- the tow is dipped in 50 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid.
- the tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min.
- the tow is heated in the oven at 140°C for 20 min. After all treatments and carbon fiber leads are removed, the tow is removed from the oven, and is observed to be black in color.
- the gel fraction of C2A after surface treatment is 68.9%, as determined by Soxhlet extraction.
- the fiber tow C2B is stabilized unconstrained in a quartz boat in a batch tube furnace. Air is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 400°C and subsequently cooled to room temperature. The tow is carbonized unconstrained in a quartz boat in a batch tube furnace. Nitrogen is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 1150°C and subsequently cooled to room temperature. The resulting carbon fiber sample is brittle and fused. No individual filaments are separable.
- Tables 2 through 11 report the elemental analysis for a portion of the preceding examples.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
A method for preparing a polyolefin material comprising providing a crosslinked polyolefin material; surface treating the crosslinked polyolefin material with an acidic medium; heating the crosslinked polyolefin material at or below 140 degrees C. A stabilized polyolefin article comprising an empirical formula, CHXSYOZ, where: 1.85 ≤ X ≤ 2.10; 0.000 ≤ Y ≤ 0.035; and 0.03 ≤ Z ≤ 0.20. An oxidized polyolefin article comprising an empirical formula, CHXOZ, where: 0.35 ≤ X ≤ 0.50; and 0.5 ≤ Z ≤ 0.6.
Description
PROCESS FOR MAKING AN ARTICLE FROM POLYOLEFIN AND
COMPOSITION THEREOF
BACKGROUND
[0001] Previously, carbonaceous articles, such as carbon fibers, have been produced primarily from polyacrylonitrile (PAN), pitch, or cellulose precursors. The process for making carbonaceous articles begins by forming a fabricated article, such as a fiber or a film, from the precursor. Precursors may be formed into fabricated articles using standard techniques for forming or molding polymers. The fabricated article is subsequently stabilized to allow the fabricated article to substantially retain shape and mass during the subsequent heat-processing steps; without being limited by theory, such stabilization typically involves a combination of oxidation and heat and generally results in
dehydrogenation, ring formation, oxidation and crosslinking of the precursor which defines the fabricated article. The stabilized fabricated article is then converted into a carbonaceous article by heating the stabilized fabricated article in an inert atmosphere. While the general steps for producing a carbonaceous article are the same for the variety of precursors, the details of those steps vary widely depending on the chemical makeup of the selected precursor.
[0002] Polyolefins have been investigated as an alternative precursor for carbonaceous articles, but a suitable and economically viable preparation process has proven elusive. Of particular interest is identifying an economical process for preparing stabilized articles from polyolefin precursors, such as stabilized articles which are suitable for subsequent processing to form carbonaceous articles. For example, maximizing mass retention, preventing filament fusion and improving tensile properties during the stabilization and carbonization steps are of interest.
SUMMARY
[0003] A method for preparing a polyolefin material comprising providing a crosslinked polyolefin material; surface treating the crosslinked polyolefin material with an acidic medium; heating the crosslinked polyolefin material at or below 140 degrees C.
[0004] A stabilized polyolefin article comprising an empirical formula, CHXSYOZ, where: 1.85≤ X≤ 2.10; 0.000 < Y < 0.035; and 0.03≤ Z≤ 0.20.
[0005] An oxidized polyolefin article comprising an empirical formula, CHxOz, where: 0.35≤ X≤ 0.50; and 0.5≤ Z≤ 0.6.
DETAILED DESCRIPTION
[0006] Unless otherwise indicated, numeric ranges, for instance "from 2 to 10," are inclusive of the numbers defining the range (e.g., 2 and 10).
[0007] Unless otherwise indicated, ratios, percentages, parts, and the like are by weight.
[0008] Unless otherwise indicated, the crosslinkable functional group content for a polyolefin resin is characterized by the mol% crosslinkable functional groups, which is calculated as the number of moles of crosslinkable functional groups divided by the total number of moles of monomer units contained in the polyolefin.
[0009] Unless otherwise indicated, "monomer" refers to a molecule which can undergo polymerization, thereby contributing constitutional units to the essential structure of a macromolecule, for example, a polyolefin.
[0010] Unless otherwise indicated, "alkene" refers to CI to CIO alkenes.
[0011] Unless otherwise indicated, "alkyne" refers to CI to CIO alkynes.
[0012] Unless stated otherwise, any method or process steps described herein may be performed in any order.
[0013] The present disclosure describes a method for preparing a polyolefin material. The polyolefin material is prepared by providing a crosslinked polyolefin material; surface treating the crosslinked polyolefin material with an acidic medium; heating the crosslinked polyolefin material at or below 140 degrees C, thereby providing a stabilized polyolefin material. The polyolefin material is further prepared by heating polyolefin material in an oxidizing environment at a temperature no greater than 500 degrees C, thereby providing an oxidized polyolefin material. The polyolefin material is further prepared by heating the polyolefin material in an inert environment, thereby providing a carbonaceous polyolefin material.
[0014] Polyolefins are a class of polymers produced from one or more olefin monomer. The polymers described herein may be formed from one or more types of monomers. Polyethylene is the preferred polyolefin resin, but other polyolefin resins may be substituted. For example, a polyolefin produced from ethylene, propylene, or other alpha- olefin (for instance, 1-butene, 1-hexene, 1-octene), or a combination thereof, is also suitable. The polyolefins described herein are typically provided in resin form, subdivided into pellets or granules of a convenient size for further melt or solution processing.
[0015] The treated olefin resin is processed to form a fabricated article. A fabricated article is an article which has been fabricated from the polyolefin resin. The fabricated article is formed using known polyolefin fabrication techniques, for example, melt or solution spinning to form fibers, film extrusion or film casting or a blown film process to form films, die extrusion or injection molding or compression molding to form more complex shapes, or solution casting. The fabrication technique is selected according to the desired geometry of the target article, and the desired physical properties of the same. For example, where the desired article is a fiber, fiber spinning is a suitable fabrication technique. As another example, where the desired article is a film, compression molding is a suitable fabrication technique.
[0016] The fabricated articles described herein are subjected to a crosslinking step. In one instance, the fabricated article has been melt blended with a treating agent prior to the crosslinking step. In one instance, the fabricated article has been melt blended without the use of a treating agent prior to the crosslinking step. A variety of methods for crosslinking polyolefins are known. In one instance, the fabricated articles are crosslinked by irradiation, such as by electron beam processing. Other crosslinking methods are suitable, for example, ultraviolet irradiation and gamma irradiation. In some instances, an initiator, such as benzophenone, may be used in conjunction with the irradiation to initiate crosslinking. In one instance, the polyolefin resins have been modified to include crosslinkable functional groups which are suitable for reacting to crosslink the polyolefin resin. Where the polyolefin resin includes crosslinkable functional groups, crosslinking may be initiated by known methods, including use of a chemical crosslinking agent, by heat, by steam, or other suitable method. In one instance, copolymers are suitable to provide a polyolefin resin having crosslinkable functional groups where one or more alpha-olefins have been copolymerized with another monomer containing a group suitable for serving as a crosslinkable functional group, for example, dienes, carbon monoxide, glycidyl methacrylate, acrylic acid, vinyl acetate, maleic anhydride, or vinyl trimethoxy silane
(VTMS) are among the monomers suitable for being copolymerized with the alpha-olefin.
Further, the polyolefin resin having crosslinkable functional groups may also be produced from a poly(alpha-olefin) which has been modified by grafting a functional group moiety onto the base polyolefin, wherein the functional group is selected based on its ability to subsequently enable crosslinking of the given polyolefin. For example, grafting of this type may be carried out by use of free radical initiators (such as peroxides) and vinyl monomers
(such as VTMS, dienes, vinyl acetate, acrylic acid, methacrylic acid, acrylic and methacrylic esters such as glycidyl methacrylate and methacryloxypropyl trimethoxysilane, allyl amine, p-aminostyrene, dimethylaminoethyl methacrylate) or via azido-functionalized molecules (such as 4-[2-(trimethoxysilyl)ethyl)]benzenesulfonyl azide). Polyolefin resins having crosslinkable functional groups may be produced from a polyolefin resin, or may be purchased commercially. Examples of commercially available polyolefin resins having crosslinkable functional groups include SI-LINK sold by The Dow Chemical Company, PRIMACOR sold by The Dow Chemical Company, EVAL resins sold by Kuraray, and LOTADER AX8840 sold by Arkema.
[0017] As noted above, at least a portion of the polyolefin is crosslinked to yield a crosslinked fabricated article. In some embodiments, crosslinking is carried out via chemical crosslinking. Thus, in some embodiments, the crosslinked fabricated article is a fabricated article which has been treated with one or more chemical agents to crosslink the crosslinkable functional groups of the polyolefin resin having crosslinkable functional groups. Such chemical agent functions to initiate the formation of intramolecular chemical bonds between the crosslinkable functional groups or reacts with the crosslinkable functional groups to form intramolecular chemical bonds, as is known in the art. Chemical crosslinking causes the crosslinkable functional groups to react to form new bonds, forming linkages between the various polymer chains which define the polyolefin resin having crosslinkable functional groups. The chemical agent which effectuates the crosslinking is selected based on the type of crosslinkable functional group(s) included in the polyolefin resin; a diverse array of reactions are known which crosslink crosslinkable functional groups via intermolecular and intramolecular chemical bonds. A suitable chemical agent is selected which is known to crosslink the crosslinkable functional groups present in the fabricated article to produce the crosslinked fabricated article. For example, without limiting the present disclosure, if the crosslinkable functional group attached to the polyolefin is a vinyl group, suitable chemical agents include free radical initiators such as peroxides or azo-bis nitriles, for example, dicumyl peroxide, dibenzoyl peroxide, t-butyl peroctoate, azobisisobutyronitrile, and the like. If the crosslinkable functional group attached to the polyolefin is an acid, such as a carboxylic acid, or an anhydride, or an ester, or a glycidoxy group, a suitable chemical agent can be a compound containing at least two nucleophilic groups, including dinucleophiles such as diamines, diols, dithiols, for example ethylenediamine, hexamethylenediamine, butane diol, or hexanedithiol. Compounds
containing more than two nucleophilic groups, for example glycerol, sorbitol, or hexamethylene tetramine can also be used. Mixed di- or higher- nucleophiles, which contain at least two different nucleophilic groups, for example ethanolamine can also be suitable chemical agents. If the crosslinkable functional group attached to the polyolefin is a mono-, di- or tri- alkoxy silyl group, water, and Lewis or Bronsted acid or base catalysts can be used as suitable chemical agents. For example, without limiting the present disclosure, Lewis or Bronsted acid or base catalysts include aryl sulfonic acids, sulfuric acid, hydroxides, zirconium alkoxides or tin reagents.
[0018] Crosslinking the fabricated article is preferred to ensure that the fabricated article retains its shape at the elevated temperatures required for the subsequent processing steps. Without crosslinking, polyolefin resins typically soften, melt or otherwise deform or breakdown at elevated temperatures. Crosslinking adds thermal stability to the fabricated article. Where the fabricated article is a fiber, crosslinking can contribute to an
improvement in fiber properties, for example, increase shape retention. In one instance, the fabricated article is crosslinked such that it has at least 50 percent gel fraction. In one instance, the fabricated article is crosslinked such that it has at least 55 percent gel fraction. In one instance, the fabricated article is crosslinked such that it has at least 60 percent gel fraction. In one instance, the fabricated article is crosslinked such that it has at least 65 percent gel fraction. In one instance, the fabricated article is crosslinked such that it has at least 70 percent gel fraction.
[0019] As noted above, the surface of the crosslinked fabricated article is modified with a surface-treating agent and a subsequent heat treatment to yield a surface-treated fabricated article. The surface of the fabricated article is defined as the outermost portion of the fabricated article. The surface-treating agent is a chemical agent which is suitable for pacifying the surface of the fabricated article. The surface of the fabricated article is pacified when adjacent fabricated articles do not fuse together when heated, such as during the air-oxidation process described herein. In some embodiments, the surface of the fabricated article is pacified when adjacent fabricated articles are substantially not fused together when heated. In one instance, the surface-treating agent is an acidic medium. In one instance, the acidic medium is a sulfonating agent or a nitrating agent. In some embodiments, the sulfonating agent is an SO3 containing moiety. In some embodiments, the surface-treating agent is selected from the list consisting of sulfuric acid, fuming sulfuric acid, sulfur trioxide, and chlorosulfonic acid. In one instance, the sulfur trioxide is a
gaseous sulfur trioxide or a halogenated compound containing sulfur trioxide. In one instance, the nitrating agent is nitric acid. Without being limited by theory, the surface- treating agent serves to prevent the fabricated article from fusing together when heated by pacifying the surface of the fabricated article. For example, where the fabricated article is a fiber, if the fabricated article is not treated with the surface-treating agent, the filaments which comprise the fiber will fuse together when heated. Treating the fiber with the surface-treating agent helps to prevent filament fusion. In one instance, the concentration of the sulfuric acid in the surface-treating agent is 90 percent or less. In one instance, the concentration of the sulfuric acid in the surface-treating agent is 98 percent or less. In one instance, the concentration of the sulfuric acid in the surface-treating agent is 10 percent or greater. In one instance, the concentration of the sulfuric acid in the surface-treating agent is 20 percent or greater. In one instance, the concentration of the sulfuric acid in the surface-treating agent is 30 percent or greater.
[0020] Following the surface-treating step the polyolefin material is heated. In one instance, the initial temperature of this heating step is at or below the melting point of the polymer resin. In one instance, the temperature of this heating step is at or above 120 °C. The temperature selected for this heating step is a function of the time of treatment. In one instance, this heating step is performed in an inert environment. In one instance, this heating step is performed in air.
[0021] In some embodiments, after treating the fabricated article with the surface treating agent, the fabricated article is subjected to a heating step and then is subsequently treated again with surface treating agent and subsequently subjected to an additional heating step and followed by one or more additional treatment with a surface treatment agent and heating step. For example, following the first treatment with a surface treatment agent the fabricated article is heated at 120 °C for 20 minutes, followed by treatment with a surface treatment agent, followed by heating at 130 °C for 20 minutes, followed by treatment with a surface treatment agent, followed by heating at 140 °C for 20 minutes. In some
embodiments, tension is applied during either or both of the surface-treatment or heating steps to maintain fiber tow length or reduce fiber tow shrinkage. In some embodiments, the surface-treated fabricated article is then washed with water.
[0022] In one instance, the crosslinking step and the surface-treatment step are performed simultaneously by selecting a compound which performs the functions of both the chemical agent and the surface-treating agent. For example, SO3 containing moieties are suitable for
both crosslinking and surface treating a polyolefin fabricated article. In some embodiments, chemical crosslinking and surface treating of the fabricated article are performed in a single step by treating the fabricated article with an SO3 containing moiety. In some
embodiments, the conditions for this single-step treatment include treating the fabricated article with the surface-treating agent and heating the fabricated article step- wise, for example, heating at 120 °C for 20 minutes, followed by heating at 130 °C for 20 minutes, followed by heating at 140 °C for 20 minutes. In some embodiments, the fabricated article is then washed with water. In some embodiments, the fabricated article is first crosslinked, and is second surface-treated.
[0023] In one instance, following surface treatment, the surface-treated fabricated article is washed in a solvent. Suitable solvents may include toluene, xylene, or a high-temperature halocarbon. An example of a suitable high-temperature halocarbon is tetrachloroethane. In some embodiments, the temperature of the solvent is above room temperature. In one instance, the temperature of the solvent is at or is greater than 80 °C. In another instance, the temperature of the solvent is at or is less than 100 °C. Without being limited by theory, washing the surface-treated fabricated article with the solvent removes at least some of the portions of the fabricated article which were not crosslinked. It was observed that washing with the solvent reduces the instances of filament fusion. It is anticipated that where the crosslinking step is more efficient, meaning a greater percentage of the fabricated article is crosslinked, the need to wash with the solvent will be reduced. It is anticipated that washing with the solvent will be unnecessary where there is extensive crosslinking in the fabricated article. For example, where the fabricated article is 70-100% crosslinked, the solvent wash step may be unnecessary.
[0024] In one instance, following the surface treating and heating steps are repeated one or more times. In one instance, the surface treating and heating steps are performed such that the fabricated article reaches a gel fraction of at least 70 percent. The desired gel fraction can be achieved by either or both of repeating the surface treating and heating steps or adjusting the conditions of the surface treating and heating steps (for example, increasing the duration of the steps or increasing the temperature of the heating steps or increasing the concentration of the surface treating agent).
[0025] Following the surface-treating step, including both treating with the surface treating agent and the heating step, the polyolefin material is treated with a stabilizing agent to provide a stabilized fabricated article. In one instance, the stabilizing agent is an oxidizing
agent. In one instance, the oxidizing agent is oxygen. In one instance, the crosslinked fabricated article is treated with the stabilizing agent by exposing the crosslinked fabricated article to a heated oxidizing environment to yield a stabilized fabricated article. In some embodiments, the temperature for the oxidizing environment is at least 120 °C, preferably at least 190 °C. In some embodiments, the temperature for the oxidizing environment is no more than 500 °C, preferably no more than 400 °C. In one instance, the crosslinked fabricated article is introduced to a heating chamber which is already at the desired temperature. In another instance, the fabricated article is introduced to a heating chamber at or near ambient temperature, which chamber is subsequently heated to the desired temperature. In some embodiments the heating rate is at least 1 °C/minute. In other embodiments the heating rate is no more than 15 °C/minute. In yet another instance, the chamber is heated step wise, for instance, the chamber is heated to a first temperature for a time, such as, 120 °C for one hour, then is raised to a second temperature for a time, such as 180 °C for one hour, and third is raised to a holding temperature, such as 250 °C for 10 hours. The stabilization process involves holding the crosslinked fabricated article at the given temperature for periods up to 100 hours depending on the dimensions of the fabricated article. The stabilization process yields a treated stabilized fabricated article which is a precursor for a carbonaceous article. Without being limited by theory, the stabilization process oxidizes at least a portion of the crosslinked fabricated article and causes changes to the hydrocarbon structure that increases at least a portion of the crosslink density while decreasing the hydrogen/carbon ratio of the crosslinked fabricated article. Without being limited by theory, the stabilized article has a modified surface as compared to a control article.
[0026] The present disclosure describes a stabilized polyolefin article comprising an empirical formula, CHxSYOz, where: 1.85≤ X≤ 2.10; 0.00 < Y < 0.035; and 0.03≤ Z≤ 0.20. In one instance, 1.9≤ X≤ 2.08. In one instance, 1.918≤ X≤ 2.062. In one instance, 0.00 < Y < 0.0209. In one instance, 0.001 < Y < 0.03. In one instance, 0.0424≤ Z≤ 0.148. In one instance, 0.035 < Z < 0.18.
[0027] The present disclosure describes an oxidized polyolefin article comprising an empirical formula, CHxOz, where: 0.35 < X < 0.50; and 0.5 < Z < 0.6. In one instance, 0.390≤ X≤ 0.418. In one instance, 0.37≤ X≤ 0.46. In one instance, 0.525≤ Z≤ 0.562. In one instance, 0.51 < Z < 0.58.
[0028] In yet another aspect, a carbonaceous article and a process for making the same are provided. Carbonaceous articles are articles which are rich in carbon; carbon fibers, carbon sheets and carbon films are examples of carbonaceous articles. Carbonaceous articles have many applications, for example, carbon fibers are commonly used to reinforce composite materials, such as in carbon fiber reinforced epoxy composites, while carbon discs or pads are used for high performance braking systems.
[0029] The carbonaceous articles described herein are prepared by carbonizing the stabilized fabricated article by heat-treating the treated stabilized fabricated articles in an inert environment. The inert environment is an environment surrounding the treated stabilized fabricated article that shows little reactivity with carbon at elevated temperatures, preferably a high vacuum or an oxygen-depleted atmosphere, more preferably a nitrogen atmosphere or an argon atmosphere. It is understood that trace amounts of oxygen may be present in the inert atmosphere. In one instance, the temperature of the inert environment is at or above 600 °C. Preferably, the temperature of the inert environment is at or above 800 °C. In one instance, the temperature of the inert environment is no more than 3000 °C. In one instance, the temperature is from 1400-2400 °C. Temperatures at or near the upper end of that range will produce a graphite article, while temperatures at or near the lower end of the range will produce a carbon article.
[0030] In order to prevent bubbling or damage to the fabricated article during carbonization, it is preferred to heat the inert environment in a gradual or stepwise fashion. In one embodiment, the treated stabilized fabricated article is introduced to a heating chamber containing an inert environment at or near ambient temperature, which chamber is subsequently heated over a period of time to achieve the desired final temperature. The heating schedule can also include one or more hold steps for a prescribed period at the final temperature or an intermediate temperature or a programmed cooling rate before the article is removed from the chamber.
[0031] In yet another embodiment, the chamber containing the inert environment is subdivided into multiple zones, each maintained at a desired temperature by an appropriate control device, and the treated stabilized fabricated article is heated in a stepwise fashion by passage from one zone to the next via an appropriate transport mechanism, such as a motorized belt. In the instance where a treated stabilized fabricated article is a fiber, this transport mechanism can be the application of a traction force to the fiber at the exit of the carbonization process while the tension in the stabilized fiber is controlled at the inlet.
Some embodiments of the invention will now be described in detail in the following Examples.
[0032] In the Examples, overall mass yield is calculated as the product of oxidation mass yield and carbonization mass yield (calculated as provided below). PHR refers to parts per hundred resin (mass basis). MI refers to melt index which is a measure of melt flow rate. Wt% refers to parts per 100 total parts, mass basis. PE refers to polyethylene. Definitions of measured yields:
Oxidation mass yield: YN =
mpE
Carbonization mass yield: YC =
mox
Overall mass yield: YM = YQ YQ
Overall mass yield (carbonaceous mass per initial mass of PE): YM PE = Y°YC
M%PE
Where mm is the initial mass of polyethylene; mox is the mass remaining after oxidation; mcF is the mass remaining after carbonization; M%PE is the mass % of polyethylene in the origin formed article.
[0033] Soxhlet extraction is a method for determining the gel fraction and swell ratio of crosslinked ethylene plastics, also referred to herein as hot xylenes extraction. As used herein, Soxhlet extraction is conducted according to ASTM Standard D2765- 11 "Standard Test Methods for Determination of Gel Content and Swell Ratio of Crosslinked Ethylene Plastics." In the method employed, a crosslinked fabricated article between 0.050 - 0.500 g is weighed and placed into a cellulose-based thimble which is then placed into a Soxhlet extraction apparatus with sufficient quantity of xylenes. Soxhlet extraction is then performed with refluxing xylenes for at least 12 hours. Following extraction, the thimbles are removed and the crosslinked fabricated article is dried in a vacuum oven at 80 °C for at least 12 hours and then weighed, thereby providing a Soxhlet-treated article. The gel fraction (%) is then calculated from the weight ratio (Soxhlet-treated article)/(crosslinked fabricated article). The TGA Method for determining percent stabilization by sulfonation is as follows: a TA Instruments Thermal Gravimetric Analyzer (TGA) Q5000 or Discovery Series TGA is used. Using ~ 10-20 mg for the analysis, the sample is heated at 10 °C/min to 800 °C under nitrogen. The final weight of the sample at 800 °C is referred to as the char yield. The VTMS content of the VTMS grafted resins was determined by 13C NMR. The treated articles are submitted for elemental analysis to determine the carbon, hydrogen,
nitrogen, sulfur, and oxygen content. A Thermo Model Flash EA1112 Combustion CHNS/O Analyzer is used for determining carbon, hydrogen, nitrogen, sulfur, and oxygen components.
[0034] Carbon fiber tensile properties (modulus, strength, strain) for single filaments/fibers are determined using a single column Instron model 5543 following procedures based on ASTM method C1557 (Standard Test Method for Tensile Strength and Young's Modulus of Fibers). A 5 N load cell with appropriate grips are used. Fiber diameter is determined by optical microscopy.
Polyethylene fiber preparation
[0035] An ethylene/octene copolymer (density = 0.955 g/cm3; MI = 30 g/10 min,
190°C/2.16 kg) is melt spun and hot-drawn to form five fiber tows (identified as PEF1, PEF2, PEF3, PEF4 and PEF5) with the following properties reported in Table 1.
Table 1
Polyethylene fiber crosslinking by batch electron beam exposure
[0036] Polyethylene fiber tows are crosslinked by electron beam exposure using the AEB Lab System (Advanced Electron Beams, Inc., Wilmington, MA). The batch-mode apparatus comprises of a sealed, high vacuum, electron emitter lamp with a maximum accelerating voltage of 150 kV and a maximum e-beam dose of 80 kGy per pass. A continuous fiber tow is wound around stainless steel pegs attached around the exterior of a similar 8" x 10" aluminum plate with the center section removed. Upon placement of the polyethylene tow in the AEB Lab System chamber, the sample is purged with high purity nitrogen gas from a gas cylinder until the oxygen concentration within the apparatus dropped below a pre-set value, typically 200 ppm. The tows are irradiated by programming
the control computer to execute the required number of passes, transporting the mounted samples under the beam on each pass, to achieve the desired total dosage.
Polyethylene fiber crosslinking by continuous electron beam exposure
[0037] Polyethylene fiber tows are crosslinked by electron beam exposure using a pilot- scale PCT Engineered Systems apparatus (Davenport, IA). The polyethylene fiber tow is fed continuously at 25 ft/min to the electron beam apparatus using Izumi winders. The pilot-scale system comprises a controlled atmosphere housing and a rotating 24 in diameter cooled roller. The polyethylene fiber tow is irradiated continuously by accelerated electron beams from an emitter mounted in the top of the housing. The accelerating voltage is 200 kV and the current is 295-300 mA. Electron beam irradiation dosage is determined by residence time.
Example 1
[0038] The fiber tow identified as PEF2 in Table lis crosslinked with electron beam irradiation (1200 kGy; 80 kGy/dose) to yield a crosslinked tow with mean gel fraction of 89.7%, as determined by Soxhlet extraction. The crosslinked fiber tow is washed in deionized water for 1 hour at 60°C to remove the fiber spin finish; confirmed by ATR-FTIR spectroscopy. Three (3) washed crosslinked fiber tows (identified as 1A, IB and 1C) are tied between two sections of commercial carbon fiber and undergo the following acid thermal treatment:
1. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 60 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
Filaments are separable.
2. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 60 min.
3. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min. The tow is heated in the oven at 130°C for 20 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
Filaments are separable.
4. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min. The tow is heated in the oven at 140°C for 20 min. After all treatments and carbon fiber leads are removed, the tow is removed from the oven, and is observed to be black in color, and flexible. Filaments are separable.
Example 1A
[0039] One fiber tow prepared according to Example 1, identified as 1A, is rinsed with 50 vol% sulfuric acid and deionized water and dried. A portion of 1A is heated in a nitrogen atmosphere using a TGA (10°C/min to 800°C). The final char yield is 10.4% of the initial mass at 800°C; 1 A loses 70.3% of the initial mass between 400-500°C. The mean elemental composition of 1A is 72.5 wt% carbon, 11.7 wt% hydrogen, 3.9 wt% sulfur, and 12.0 wt% oxygen (by difference). See Tables 2-6.
Example IB
[0040] One fiber tow prepared according to Example 1, identified as IB, is stabilized unconstrained in a quartz boat in a batch tube furnace. Air is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 400°C and subsequently cooled to room temperature. The mean elemental composition of IB is 57.7 wt% carbon, 2.0 wt% hydrogen, ND (<0.5) wt% sulfur, and 40.3 wt% oxygen (by difference). See Tables 7-11.
Example 1C
[0041] One fiber tow prepared according to Example 1, identified as 1C, is stabilized unconstrained in a quartz boat in a batch tube furnace. Air is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 400°C and subsequently cooled to room temperature. The fiber tow is carbonized unconstrained in a quartz boat in a batch tube furnace. Nitrogen is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 1150°C and subsequently cooled to room temperature. The resulting carbon fiber tow is flexible and separable, indicating individual filaments. Individual filaments are mounted using a 0.28 inch gauge length and tensile tested.. Nine (9) filaments of 1C are tested to produce the following mean properties: diameter = 9.7 μιη, modulus = 9.16 GPa, tensile strength = 0.12 GPa, tensile strain = 1.96%.
Example 2
[0042] The fiber tow identified as PEF3 in Table 1 is crosslinked with electron beam irradiation (1200 kGy; 80 kGy/dose) to yield a crosslinked tow with mean gel fraction of 89.4%, as determined by Soxhlet extraction. The crosslinked fiber tow is washed in deionized water for 1 hour at 60°C to remove the fiber spin finish.
[0043] Three (3) washed crosslinked fiber tows prepared according to Example 2 (identified as 2A, 2B and 2C) are tied between two sections of commercial carbon fiber and each undergo the following acid thermal treatment:
1. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 60 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
Filaments are separable.
2. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 60 min.
3. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min. The tow is heated in the oven at 130°C for 20 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
Filaments are separable.
4. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min. The tow is heated in the oven at 140°C for 20 min. After all treatments and carbon fiber leads are removed, the tow is removed from the oven, and is observed to be black in color, and flexible. Filaments are separable.
Example 2A
[0044] One fiber tow prepared according to Example 2, identified as 2A, is rinsed with 50 vol% sulfuric acid and deionized water and dried. A portion of 2A is heated in a nitrogen atmosphere using a TGA (10°C/min to 800°C). The final char yield is 8.9% of the initial mass at 800°C; 2A loses 73.1% of the initial mass between 400-500°C. The mean elemental composition of 2 A is 73.1 wt% carbon, 11.9 wt% hydrogen, 3.4 wt% sulfur, and
11.5 wt% oxygen (by difference). See Tables 2-6.
Example 2B
[0045] One fiber tow prepared according to Example 2, identified as 2B, is stabilized unconstrained in a quartz boat in a batch tube furnace. Air is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 400°C and subsequently cooled to room temperature. The mean elemental composition of 2B is 56.7 wt% carbon, 2.0 wt% hydrogen, ND (<0.5) wt% sulfur, and 41.4 wt% oxygen (by difference). See Tables 7-11.
Example 2C
[0046] One fiber tow prepared according to Example 2, identified as 2C, is stabilized unconstrained in a quartz boat in a batch tube furnace. Air is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 400°C and subsequently cooled to room temperature. Sample 2C is carbonized unconstrained in a quartz boat in a batch tube furnace. Nitrogen is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 1150°C and subsequently cooled to room temperature. The resulting carbon fiber tows are flexible and separable, indicating individual filaments. Individual filaments are mounted using a 0.5 inch gauge length and tensile tested. Eight (8) filaments of 2C are tested to produce the following mean properties: diameter = 8.0 μιη, modulus = 25.4 GPa, tensile strength = 0.18 GPa, tensile strain = 0.73%.
Example 3
[0047] The fiber tow identified as PEF4 in Table 1 is crosslinked with electron beam irradiation (1200 kGy; 80 kGy/dose) to yield a crosslinked tow with mean gel fraction of 91.0%, as determined by Soxhlet extraction. The crosslinked fiber tow is washed in deionized water for 1 hour at 60°C to remove the fiber spin finish; confirmed by ATR-FTIR spectroscopy. Three (3) washed crosslinked fiber tows (identified as 3 A, 3B, and 3C) are tied between two sections of commercial carbon fiber and undergo the following acid thermal treatment:
1. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 60 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
Filaments are separable.
2. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 60 min.
3. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min. The tow is heated in the oven at 130°C for 20 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
Filaments are separable.
4. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min. The tow is heated in the oven at 140°C for 20 min. After all treatments and carbon fiber leads are removed, the tow is removed from the oven, and is observed to be black in color, and flexible. Filaments are separable.
Example 3A
[0048] One fiber tow prepared according to Example 3, identified as 3A, is rinsed with 50 vol% sulfuric acid and deionized water and dried. A portion of 3A is heated in a nitrogen atmosphere using a TGA (10°C/min to 800°C). The final char yield is 6.0% of the initial mass at 800°C; 3A loses 73.7% of the initial mass between 400-500°C. The mean elemental composition of 3A is 70.4 wt% carbon, 11.8 wt% hydrogen, 3.9 wt% sulfur, and 13.9 wt% oxygen (by difference). See Tables 2-6.
Example 3B
[0049] One fiber tow prepared according to Example 3, identified as 3B, is stabilized unconstrained in a quartz boat in a batch tube furnace. Air is continuously fed at
2000 seem. The tube furnace is heated at 4°C/min from room temperature to 400°C and subsequently cooled to room temperature. The mean elemental composition of 3B is 56.1 wt% carbon, 1.8 wt% hydrogen, ND (<0.5) wt% sulfur, and 42.0 wt% oxygen (by difference). See Tables 7-11.
Example 3C
[0050] One fiber tow prepared according to Example 3, identified as 3C, is stabilized unconstrained in a quartz boat in a batch tube furnace. Air is continuously fed at
2000 seem. The tube furnace is heated at 4°C/min from room temperature to 400°C and subsequently cooled to room temperature. The tow is carbonized unconstrained in a quartz boat in a batch tube furnace. Nitrogen is continuously fed at 2000 seem. The tube furnace
is heated at 4°C/min from room temperature to 1150°C and subsequently cooled to room temperature. The resulting carbon fiber tow is flexible and separable, indicating individual filaments. Individual filaments are mounted using a 0.28 inch gauge length and tensile tested. Two (2) filaments of 3C are tested to produce the following mean properties:
diameter = 6.9 μιη, modulus = 24.5 GPa, tensile strength = 0.14 GPa, tensile strain = 0.56%. Example 4
[0051] The fiber tow identified as PEF3 in Table 1 is crosslinked with electron beam irradiation (1200 kGy; 80 kGy/dose) to yield a crosslinked tow with mean gel fraction of 89.4%, as determined by Soxhlet extraction. The crosslinked fiber tow is washed in deionized water for 1 hour at 60°C to remove the fiber spin finish.
[0052] One (1) washed crosslinked fiber tow is tied between two sections of commercial carbon fiber and each undergo the following acid thermal treatment:
1. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 20 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
Filaments are separable.
2. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 20 min.
3. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min. The tow is heated in the oven at 130°C for 20 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
Filaments are separable.
4. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min. The tow is heated in the oven at 140°C for 20 min. After all treatments and carbon fiber leads are removed, the tow is removed from the oven, and is observed to be black in color, and flexible. Filaments are separable.
[0053] The tow is rinsed with deionized water and dried. The tow is stabilized
unconstrained in a quartz boat in a batch tube furnace. Air is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 400°C and
subsequently cooled to room temperature. The tow is carbonized unconstrained in a quartz boat in a batch tube furnace. Nitrogen is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 1150°C and subsequently cooled to room temperature. The resulting carbon fiber tows are flexible and separable, indicating individual filaments. Individual filaments are mounted using a 0.28 inch gauge length and tensile tested. Seven (7) filaments are tested to produce the following mean properties: diameter = 8.8 μιη, modulus = 33.2 GPa, tensile strength = 0.34 GPa, tensile strain = 1.00%. Example 5
[0054] The fiber tow identified as PEF3 in Table 1 is crosslinked with electron beam irradiation (1200 kGy; 80 kGy/dose) to yield a crosslinked tow with mean gel fraction of 89.4%, as determined by Soxhlet extraction. The crosslinked fiber tow is washed in deionized water for 1 hour at 60°C to remove the fiber spin finish.
[0055] One (1) washed crosslinked fiber tows is tied between two sections of commercial carbon fiber and each undergo the following acid thermal treatment:
1. The tow is dipped in chlorosulfonic acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 20 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
Filaments are separable.
2. The tow is dipped in chlorosulfonic acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 20 min.
3. The tow is dipped in chlorosulfonic acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min. The tow is heated in the oven at 130°C for 20 min. The tow is removed from the oven, and is observed to be black in color, and flexible. Filaments are separable.
4. The tow is dipped in chlorosulfonic acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min. The tow is heated in the oven at 140°C for 20 min. After all treatments and carbon fiber leads are removed, the tow is removed from the oven, and is observed to be black in color, and flexible. Filaments are separable.
[0056] The tow is rinsed with deionized water and dried. The tow is stabilized
unconstrained in a quartz boat in a batch tube furnace. Air is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 400°C and subsequently cooled to room temperature. The tow is carbonized unconstrained in a quartz boat in a batch tube furnace. Nitrogen is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 1150°C and subsequently cooled to room temperature. The resulting carbon fiber tows are flexible and separable, indicating individual filaments. Individual filaments are mounted using a 0.5 inch gauge length and tensile tested. Seven (7) filaments are tested to produce the following mean properties: diameter = 10.2 μιη, modulus = 25.3 GPa, tensile strength = 0.20 GPa, tensile strain = 0.79%.
Example 6
[0057] The fiber tow identified as PEF3 in Table 1 is crosslinked with electron beam irradiation (1200 kGy; 80 kGy/dose) to yield a crosslinked tow with mean gel fraction of 89.4%, as determined by Soxhlet extraction. The crosslinked fiber tow is washed in deionized water for 1 hour at 60°C to remove the fiber spin finish.
[0058] One (1) washed crosslinked fiber tows is tied between two sections of commercial carbon fiber and each undergo the following acid thermal treatment:
1. The tow is dipped in 70 wt% nitric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min. The tow is heated in the oven at 100°C for 20 min.
2. The tow is dipped in 70 wt% nitric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min. The tow is heated in the oven at 100°C for 20 min.
3. The tow is dipped in 70 wt% nitric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min. The tow is heated in the oven at 110°C for 20 min.
4. The tow is dipped in 70 wt% nitric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 20 min. After all treatments and carbon fiber leads are removed, the sample is removed, brown in color, and flexible. Filaments are separable.
[0059] The tow is rinsed with deionized water and dried. The tow is stabilized
unconstrained in a quartz boat in a batch tube furnace. Air is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 400°C and subsequently cooled to room temperature. The tow is carbonized unconstrained in a quartz boat in a batch tube furnace. Nitrogen is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 1150°C and subsequently cooled to room temperature. The resulting tow is analyzed using SEM. The tow is flexible and separable, indicating individual filaments.
Example 7
[0060] The fiber tow identified as PEF1 in Table 1 is crosslinked with electron beam irradiation (1200 kGy; 80 kGy/dose) to yield a crosslinked tow with mean gel fraction of 91.8%, as determined by Soxhlet extraction. The crosslinked fiber tow is washed in deionized water for 1 hour at 60°C to remove the fiber spin finish.
[0061] One (1) washed crosslinked fiber tows is tied between two sections of commercial carbon fiber and each undergo the following acid thermal treatment:
1. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension.
Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 20 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
Filaments are separable.
[0062] The tow is stabilized unconstrained in a quartz boat in a batch tube furnace. Air is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 400°C and subsequently cooled to room temperature. The tow is carbonized unconstrained in a quartz boat in a batch tube furnace. Nitrogen is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 1150°C and subsequently cooled to room temperature. The resulting carbon fiber tows are flexible and separable, indicating individual filaments. Individual filaments are mounted using a 0.28 inch gauge length and tensile tested. Nine (9) filaments are tested to produce the following mean properties: diameter = 9.1 μιη, modulus = 20.5 GPa, tensile strength = 0.13 GPa, tensile strain = 0.63%.
Example 8
[0063] The fiber tow identified as PEF2 in Table 1 is crosslinked with electron beam irradiation (1200 kGy; 80 kGy/dose) to yield a crosslinked tow with mean gel fraction of
89.7%, as determined by Soxhlet extraction. The crosslinked fiber tow is washed in deionized water for 1 hour at 60°C to remove the fiber spin finish.
[0064] One (1) washed crosslinked fiber tows is tied between two sections of commercial carbon fiber and each undergo the following acid thermal treatment:
1. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension.
Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 20 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
Filaments are separable.
[0065] The tow is rinsed with 50 vol% sulfuric acid and deionized water and dried. A portion of the tow is heated in a nitrogen atmosphere using a TGA (10°C/min to 800°C). The final char yield is 2.0% of the initial mass at 800°C; the sample loses 85.6% of the initial mass between 400-500°C. The mean elemental composition of the surface treated sample is 81.7 wt% carbon, 13.6 wt% hydrogen, ND (<0.5) wt% sulfur, and 4.6 wt% oxygen (by difference). See Tables 2-6.
Example 9
[0066] The fiber tow identified as PEF1 in Table 1 is crosslinked with electron beam irradiation (400 kGy; 80 kGy/dose) to yield a crosslinked tow with mean gel fraction of 74.4%, as determined by Soxhlet extraction. The crosslinked fiber tow is washed in deionized water for 1 hour at 60°C to remove the fiber spin finish.
[0067] One (1) washed crosslinked fiber tow is tied between two sections of commercial carbon fiber and undergoes the following acid thermal treatment:
1. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 20 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
Filaments are separable.
2. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 20 min.
3. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with 20g tension.
Air flow is 1.5 L/min. The tow is heated in the oven at 130°C for 20 min. The tow
is removed from the oven, and is observed to be black in color, and flexible.
Filaments are separable.
4. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min. The tow is heated in the oven at 140°C for 20 min. After all treatments and carbon fiber leads are removed, the tow is removed from the oven, and is observed to be black in color, and flexible. Filaments are separable.
[0068] The tow is rinsed with deionized water and dried. The tow is stabilized
unconstrained in a quartz boat in a batch tube furnace. Air is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 400°C and subsequently cooled to room temperature. The tow is carbonized unconstrained in a quartz boat in a batch tube furnace. Nitrogen is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 1150°C and subsequently cooled to room temperature. The resulting carbon fiber tows are flexible and separable, indicating individual filaments. Individual filaments are mounted using a 0.5 inch gauge length and tensile tested. Ten (10) filaments are tested to produce the following mean properties: diameter = 10.8 μιη, modulus = 18.8 GPa, tensile strength = 0.19 GPa, tensile strain = 1.46%.
Example 10
[0069] The fiber tow identified as PEF2 in Table 1 is crosslinked with electron beam irradiation (400 kGy; 80 kGy/dose) to yield a crosslinked tow. The crosslinked fiber tow is washed in deionized water for 1 hour at 60°C to remove the fiber spin finish.
[0070] One (1) washed crosslinked fiber tows is tied between two sections of commercial carbon fiber and undergoes the following acid thermal treatment:
1. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 20 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
Filaments are separable.
2. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 20 min.
3. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min. The tow is heated in the oven at 130°C for 20 min. The tow is removed from the oven, and is observed to be black in color, and flexible.
Filaments are separable.
4. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min. The tow is heated in the oven at 140°C for 20 min. After all treatments and carbon fiber leads are removed, the tow is removed from the oven, and is observed to be black in color, and flexible. Filaments are separable.
[0071] The tow is rinsed with 50 vol% sulfuric acid and deionized water and dried. A portion of the tow is heated in a nitrogen atmosphere using a TGA (10°C/min to 800°C). The final char yield is 2.0% of the initial mass at 800°C; the sample loses 85.6% of the initial mass between 400-500°C. The mean elemental composition of the surface treated sample is 75.1 wt% carbon, 13.0 wt% hydrogen, 2.0 wt% sulfur, and 9.9 wt% oxygen (by difference). See Tables 2-6.
Example 11
[0072] The fiber tow identified as PEF4 in Table 1 is crosslinked with electron beam irradiation (1200 kGy; 80 kGy/dose) to yield a crosslinked tow with mean gel fraction of 91.0%, as determined by Soxhlet extraction. The crosslinked fiber tow is washed in deionized water for 1 hour at 60°C to remove the fiber spin finish.
[0073] One (1) washed crosslinked fiber tows is tied between two sections of commercial carbon fiber and undergoes the following acid thermal treatment:
1. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 60 min.
2. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 18.5 hours. After all treatments and carbon fiber leads are removed, the tow is removed from the oven, and is observed to be black in color, and flexible. Filaments are separable.
[0074] The surface treated fiber is carbonized unconstrained in a quartz boat in a batch tube furnace. Nitrogen is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min
from room temperature to 1150°C and subsequently cooled to room temperature. The resulting carbon fiber tow is flexible and separable, indicating individual filaments.
Individual filaments are mounted using a 0.5 inch gauge length and tensile tested. Fifteen (15) filaments are tested to produce the following mean properties: diameter = 8.8 μιη, modulus = 52.3 GPa, tensile strength = 0.61 GPa, tensile strain = 1.14%.
Example 12
[0075] The fiber tow identified as PEF1 in Table 1 is crosslinked with electron beam irradiation (1200 kGy; 80 kGy/dose) to yield a crosslinked tow with mean gel fraction of 88.7%, as determined by Soxhlet extraction. The crosslinked fiber tow is washed in deionized water for 1 hour at 60°C to remove the fiber spin finish.
[0076] Three (3) washed crosslinked fiber tows, identified as 12A, 12B, and 12C, are tied between two sections of commercial carbon fiber and each undergo the following acid thermal treatment:
1. Each fiber tow is dipped in 30 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 20 min. The tow is removed from the oven, and is observed to be black in color, and flexible. Filaments are separable.
2. Each fiber tow is dipped in 30 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 20 min.
3. Each fiber tow is dipped in 30 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min. The tow is heated in the oven at 130°C for 20 min. The tow is removed from the oven, and is observed to be black in color, and flexible. Filaments are separable.
4. Each fiber tow is dipped in 30 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min. The tow is heated in the oven at 140°C for 20 min. After all treatments and carbon fiber leads are removed, the tow is removed from the oven, and is observed to be black in color, and flexible. Filaments are separable.
Example 12 A
[0077] The fiber tow prepared according to Example 12 and identified as 12A is oxidized in air at 10°C/min to 350°C in a TGA. The tow is further carbonized in nitrogen at 10°C/min to 800°C in a TGA. Separable, individual, and hollow carbon fibers are observed by SEM. Example 12B
[0078] The fiber tow prepared according to Example 12 and identified as 12B is oxidized in air at 10°C/min to 400°C in a TGA. The tow is further carbonized in nitrogen at 10°C/min to 800°C in a TGA. Separable, individual, and solid carbon fibers are observed by SEM. Example 12C
[0079] The fiber tow prepared according to Example 12 and identified as 12C is stabilized unconstrained in a quartz boat in a batch tube furnace. Air is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 400°C and subsequently cooled to room temperature. The tow is carbonized unconstrained in a quartz boat in a batch tube furnace. Nitrogen is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 1150°C and subsequently cooled to room temperature. The resulting carbon fiber tows are flexible and separable, indicating individual filaments. Individual filaments are mounted using a 0.5 inch gauge length and tensile tested. 20 (20) filaments are tested to produce the following mean properties:
diameter = 10.8 μιη, modulus = 30.0 GPa, tensile strength = 0.20 GPa, tensile strain = 0.65%.
Comparative Example 1
[0080] An ethylene/octene copolymer (density = 0.941 g/cm3; MI = 34 g/10 min,
190°C/2.16 kg) is reactive extruded with vinyl trimethoxysilane (VTMS) to form a VTMS- grafted ethylene/octene copolymer (MI = 19 g/10 min, 190°C/2.16 kg; 1.4 wt% grafted silane content determined by Fourier transform infrared spectroscopy FT-IR) precursor resin. The VTMS-grafted precursor resin is melt spun to form fiber tows with the following properties: 1573 filaments, 1976.1 total denier, 2.22 gf/den, 12.32% elongation-to-break. The prepared fiber tows are continuously treated in a vessel containing an isopropanol solution with 5 wt% of an aryl sulfonic acid, Nacure B201, supplied by King Industries, for 30 min. The treated fiber tows are allowed to dry cure for 3 days. The fiber tows are subsequently moisture cured at 80 °C (100% relative humidity) for 5 days. The gel fraction is determined to be 58.2% by Soxhlet extraction.
[0081] The crosslinked fiber tow is washed in isopropanol followed by deionized water for 1 hour at 60°C to remove the fiber spin finish.
[0082] One (1) washed crosslinked fiber tow is tied between two sections of commercial carbon fiber and each undergo the following acid thermal treatment:
1. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 60 min.
2. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 60 min.
3. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min. The tow is heated in the oven at 130°C for 20 min.
4. The tow is dipped in 96 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min. The tow is heated in the oven at 140°C for 20 min. After all treatments and carbon fiber leads are removed, the tow is removed from the oven, and is observed to be black in color.
[0083] The tow is stabilized unconstrained in a quartz boat in a batch tube furnace. Air is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 400°C and subsequently cooled to room temperature. The tow is carbonized unconstrained in a quartz boat in a batch tube furnace. Nitrogen is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 1150°C and subsequently cooled to room temperature. The resulting carbon fiber sample is brittle and fused. No individual filaments are separable.
Comparative Example 2
[0084] An ethylene/octene copolymer (density = 0.941 g/cm3; MI = 34 g/10 min,
190°C/2.16 kg) is reactive extruded with vinyl trimethoxysilane (VTMS) to form a VTMS- grafted ethylene/octene copolymer (MI = 19 g/10 min, 190°C/2.16 kg; 1.4 wt% grafted silane content determined by Fourier transform infrared spectroscopy FT-IR) precursor resin. The VTMS-grafted precursor resin is melt spun to form fiber tows with the following properties: 1573 filaments, 1976.1 total denier, 2.22 gf/den, 12.32% elongation-to-break.
The prepared fiber tows are continuously treated in a vessel containing an isopropanol
solution with 5 wt% of an aryl sulfonic acid, Nacure B201, supplied by King Industries, for 30 min. The treated fiber tows are allowed to dry cure for 3 days. The fiber tows are subsequently moisture cured at 80 °C (100% relative humidity) for 5 days. The gel fraction is determined to be 60.8% by Soxhlet extraction.
[0085] The crosslinked fiber tow is washed in isopropanol followed by deionized water for 1 hour at 60°C to remove the fiber spin finish.
[0086] Two (2) washed crosslinked fiber tows, identified as C2A and C2B, are tied between two sections of commercial carbon fiber and each undergo the following acid thermal treatment:
1. The tow is dipped in 50 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 60 min.
2. The tow is dipped in 50 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with lOOg tension. Air flow is 1.5 L/min. The tow is heated in the oven at 120°C for 60 min.
3. The tow is dipped in 50 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min. The tow is heated in the oven at 130°C for 20 min.
4. The tow is dipped in 50 wt% sulfuric acid for 5-10 seconds and placed on Pigmat® to remove excess acid. The tow is placed in air convection oven with 20g tension. Air flow is 1.5 L/min. The tow is heated in the oven at 140°C for 20 min. After all treatments and carbon fiber leads are removed, the tow is removed from the oven, and is observed to be black in color.
Comparative Example 2A
[0087] The gel fraction of C2A after surface treatment is 68.9%, as determined by Soxhlet extraction.
Comparative Example 2B
[0088] The fiber tow C2B is stabilized unconstrained in a quartz boat in a batch tube furnace. Air is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 400°C and subsequently cooled to room temperature. The tow is carbonized unconstrained in a quartz boat in a batch tube furnace. Nitrogen is continuously fed at 2000 seem. The tube furnace is heated at 4°C/min from room temperature to 1150°C
and subsequently cooled to room temperature. The resulting carbon fiber sample is brittle and fused. No individual filaments are separable.
[0089] Tables 2 through 11 report the elemental analysis for a portion of the preceding examples.
Table 2
Surface C (wt%) H (wt%) N (wt%) S (wt%) O (wt%) Treated
Example
1A 72.5 11.7 ND (<0.5) 3.9 12.0
2A 73.1 11.9 ND (<0.5) 3.4 11.5
3A 70.4 11.8 ND (<0.5) 3.9 13.9
8 81.7 13.6 ND (<0.5) ND (<0.5) 4.6
10 75.1 13.0 ND (<0.5) 2.0 9.9
Table 3
Surface H/C (wt/wt) N/C (wt/wt) S/C (wt/wt) N/H (wt/wt) O/C (wt/wt) Treated
Example
1A 0.161 0.000 0.053 0.000 0.165
2A 0.163 0.000 0.047 0.000 0.157
3A 0.168 0.000 0.056 0.000 0.198
8 0.167 0.000 0.000 0.000 0.056
10 0.173 0.000 0.027 0.000 0.131
Table 4
Surface C (mol%) H (mol%) N (mol%) S (mol%) O (mol%) Treated
Example
1A 32.7 62.6 0.0 0.7 4.0
2A 32.4 63.2 0.0 0.6 3.8
3A 31.5 63.1 0.0 0.7 4.7
8 33.0 65.6 0.0 0.0 1.4
10 31.5 65.0 0.0 0.3 3.1
Table 5
Surface H/C N/C S/C N/H O/C
Treated (mol/mol) (mol/mol) (mol/mol) (mol/mol) (mol/mol)
Example
1A 1.918 0.0 0.0200 0.0 0.124
2A 1.950 0.0 0.0177 0.0 0.118
3A 2.001 0.0 0.0209 0.0 0.148
8 1.991 0.0 0.0 0.0 0.0424
10 2.062 0.0 0.0101 0.0 0.0987
Table 6
Table 7
Oxidized C (wt%) H (wt%) N (wt%) S (wt%) 0 (wt%) Example
IB 57.7 2.0 ND (<0.5) ND (<0.5) 40.3
2B 56.7 2.0 ND (<0.5) ND (<0.5) 41.4
3B 56.1 1.8 ND (<0.5) ND (<0.5) 42.0
Table 8
Oxidized H/C (wt/wt) N/C (wt/wt) S/C (wt/wt) N/H (wt/wt) O/C (wt/wt)
Example
IB 0.0350 0.0 0.0 0.0 0.700
2B 0.0350 0.0 0.0 0.0 0.730
3B 0.0327 0.0 0.0 0.0 0.749
Table 9
Oxidized C (mol%) H (mol%) N (mol%) S (mol%) 0 (mol%)
Example
IB 51.5 21.5 0.0 0.0 27.0
2B 50.9 21.3 0.0 0.0 27.9
3B 51.2 20.0 0.0 0.0 28.8
Table 10
Oxidized H/C N/C s/c N/H O/C
Example (mol/mol) (mol/mol) (mol/mol) (mol/mol) (mol/mol)
IB 0.418 0.0 0.0 0.0 0.525
2B 0.418 0.0 0.0 0.0 0.548
3B 0.390 0.0 0.0 0.0 0.562
Table 11
Claims
1. A method for preparing a polyolefin material comprising:
(a) providing a crosslinked polyolefin material;
(b) surface treating the crosslinked polyolefin material with an acidic medium;
(c) heating the crosslinked polyolefin material at or below 140 degrees C.
2. The method for preparing a polyolefin material of claim 1, wherein the crosslinked polyolefin material has at least 70% gel content
3. The method for preparing a polyolefin material of any one of claims 1 to 2, wherein the acidic medium is a sulfonating agent or nitrating agent.
4. The method for preparing a polyolefin material of claim 3, wherein the sulfonating agent is sulfuric acid, chlorosulfonic acid, fuming sulfuric acid, or sulfur trioxide.
5. The method for preparing a polyolefin material of claim 4, wherein the sulfur trioxide is a gaseous sulfur trioxide or a halogenated compound containing sulfur trioxide.
6. The method for preparing a polyolefin material of claim 3, wherein the nitrating agent is nitric acid.
7. The method for preparing a polyolefin material of any one of claims 1 to 6, wherein steps (b) and (c) are repeated one or more time.
8. The method for preparing a polyolefin material of any one of claims 1 to 7, further comprising:
(d) heating the polyolefin material in an oxidizing environment at a temperature no greater than 500 degrees C.
9. The method for preparing a polyolefin material further comprising:
(e) heating the polyolefin material in an inert environment at a temperature no greater than 3000 degrees C.
10. A stabilized polyolefin article comprising an empirical formula, CHXSYOZ, where:
1.85≤X≤2.10;
0.000 <Υ<0.035; and
0.03≤ Z≤ 0.20.
11. The stabilized polyolefin article of claim 10, where:
1.918≤X< 2.062;
0.000 < Y < 0.0209; and
0.0424 <Z<0.148.
12. An oxidized polyolefin article comprising an empirical formula, CHxOz, where:
0.35≤X<0.50; and
0.5≤Z≤0.6.
13. The oxidized polyolefin article of claim 12, where:
0.390 <X<0.418; and
0.525 <Z<0.562.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201662397021P | 2016-09-20 | 2016-09-20 | |
US62/397,021 | 2016-09-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2018057156A1 true WO2018057156A1 (en) | 2018-03-29 |
Family
ID=59799452
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2017/047121 WO2018057156A1 (en) | 2016-09-20 | 2017-08-16 | Process for making an article from polyolefin and composition thereof |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2018057156A1 (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3928544A (en) * | 1972-03-06 | 1975-12-23 | Sumitomo Chemical Co | Process for producing carbon products |
WO2014011462A1 (en) * | 2012-07-12 | 2014-01-16 | Dow Global Technologies Llc | Processes for preparing carbon fibers using sulfur trioxide in a halogenated solvent |
WO2015164144A1 (en) * | 2014-04-21 | 2015-10-29 | Dow Global Technologies Llc | Surface-treated fabricated article produced from polyolefin |
WO2016133670A1 (en) * | 2015-02-20 | 2016-08-25 | Dow Global Technologies Llc | Carbon fibers obtained from silicon treated polyolefin precursor fibers |
-
2017
- 2017-08-16 WO PCT/US2017/047121 patent/WO2018057156A1/en active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3928544A (en) * | 1972-03-06 | 1975-12-23 | Sumitomo Chemical Co | Process for producing carbon products |
WO2014011462A1 (en) * | 2012-07-12 | 2014-01-16 | Dow Global Technologies Llc | Processes for preparing carbon fibers using sulfur trioxide in a halogenated solvent |
WO2015164144A1 (en) * | 2014-04-21 | 2015-10-29 | Dow Global Technologies Llc | Surface-treated fabricated article produced from polyolefin |
WO2016133670A1 (en) * | 2015-02-20 | 2016-08-25 | Dow Global Technologies Llc | Carbon fibers obtained from silicon treated polyolefin precursor fibers |
Non-Patent Citations (3)
Title |
---|
ISMAIL KARACAN ET AL: "The effect of sulfonation treatment on the structure and properties of isotactic polypropylene fibers prior to the carbonization stage", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 123, no. 6, 15 September 2011 (2011-09-15), pages 3375 - 3389, XP055013887, ISSN: 0021-8995, DOI: 10.1002/app.34187 * |
MARCUS A. HUNT ET AL: "Patterned Functional Carbon Fibers from Polyethylene", ADVANCED MATERIALS, vol. 24, no. 18, 27 March 2012 (2012-03-27), pages 2386 - 2389, XP055026049, ISSN: 0935-9648, DOI: 10.1002/adma.201104551 * |
POSTEMA A R ET AL: "AMORPHOUS CARBON FIBRES FROM LINEAR LOW DENSITY POLYETHYLENE", JOURNAL OF MATERIALS SCIENCE, KLUWER ACADEMIC PUBLISHERS, DORDRECHT, vol. 25, no. 10, 1 October 1990 (1990-10-01), pages 4216 - 4222, XP000168890, ISSN: 0022-2461, DOI: 10.1007/BF00581075 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU2017435381B2 (en) | Precursor stabilisation process | |
EP3134467A1 (en) | Surface-treated fabricated article produced from polyolefin | |
WO2018057156A1 (en) | Process for making an article from polyolefin and composition thereof | |
EP3134565B1 (en) | A process for making a stabilized fabricated article from polyolefin | |
WO2016176021A1 (en) | Process for making a fabricated article from polyolefin | |
WO2017112388A1 (en) | Process for making an article from polyolefin and composition thereof | |
US20180037714A1 (en) | Boron-containing fabricated article prepared from polyolefin precursor | |
WO2018057157A1 (en) | Process for making a stabilized polyolefin article and composition thereof | |
WO2017112390A1 (en) | Process for making an article from polyolefin and composition thereof | |
WO2017112389A1 (en) | Method for making an article from polyolefin | |
EP3289122A1 (en) | Process for making a fabricated article from polyolefin | |
WO2018057155A1 (en) | Process for making an article from polyolefin and composition thereof | |
WO2016176024A1 (en) | Process for making a fabricated article from polyolefin | |
WO2018057154A1 (en) | Process for making an article from polyolefin and composition thereof | |
WO2016176023A1 (en) | Process for making a fabricated article from polyolefin | |
WO2021187160A1 (en) | Carbon fiber, manufacturing method therefor, and carbon fiber composite material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17762257 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 17762257 Country of ref document: EP Kind code of ref document: A1 |