CN108867028A - 一种柔性硅酸盐纳米纤维膜的制备方法 - Google Patents
一种柔性硅酸盐纳米纤维膜的制备方法 Download PDFInfo
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- CN108867028A CN108867028A CN201810788712.2A CN201810788712A CN108867028A CN 108867028 A CN108867028 A CN 108867028A CN 201810788712 A CN201810788712 A CN 201810788712A CN 108867028 A CN108867028 A CN 108867028A
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- flexible
- silicate
- tunica fibrosa
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000012528 membrane Substances 0.000 claims abstract description 74
- 239000000835 fiber Substances 0.000 claims abstract description 34
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 34
- 239000002121 nanofiber Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000001523 electrospinning Methods 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 11
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 8
- 239000000391 magnesium silicate Substances 0.000 claims abstract description 7
- 229910052919 magnesium silicate Inorganic materials 0.000 claims abstract description 7
- 235000019792 magnesium silicate Nutrition 0.000 claims abstract description 7
- VIAPNRBXEJNZKV-UHFFFAOYSA-N nickel silicic acid Chemical compound [Ni].[Si](O)(O)(O)O VIAPNRBXEJNZKV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZZBBCSFCMKWYQR-UHFFFAOYSA-N copper;dioxido(oxo)silane Chemical compound [Cu+2].[O-][Si]([O-])=O ZZBBCSFCMKWYQR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002071 nanotube Substances 0.000 claims abstract description 6
- 238000010521 absorption reaction Methods 0.000 claims abstract description 5
- 239000007772 electrode material Substances 0.000 claims abstract description 5
- 239000000945 filler Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 51
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 239000010703 silicon Substances 0.000 claims description 46
- 229910052710 silicon Inorganic materials 0.000 claims description 46
- 229920000642 polymer Polymers 0.000 claims description 40
- 238000010041 electrostatic spinning Methods 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 235000019441 ethanol Nutrition 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000002131 composite material Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000009987 spinning Methods 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052681 coesite Inorganic materials 0.000 claims description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 229910052682 stishovite Inorganic materials 0.000 claims description 11
- 229910052905 tridymite Inorganic materials 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000005030 aluminium foil Substances 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 241001502050 Acis Species 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005695 Ammonium acetate Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229940043376 ammonium acetate Drugs 0.000 claims description 4
- 235000019257 ammonium acetate Nutrition 0.000 claims description 4
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229940053662 nickel sulfate Drugs 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims 1
- 238000007654 immersion Methods 0.000 claims 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims 1
- 239000004926 polymethyl methacrylate Substances 0.000 claims 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 description 15
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 7
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004110 Zinc silicate Substances 0.000 description 1
- XMOKRCSXICGIDD-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O XMOKRCSXICGIDD-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- WXYNCCWBUXKSBG-UHFFFAOYSA-N copper;nitric acid Chemical compound [Cu].O[N+]([O-])=O WXYNCCWBUXKSBG-UHFFFAOYSA-N 0.000 description 1
- ASTZLJPZXLHCSM-UHFFFAOYSA-N dioxido(oxo)silane;manganese(2+) Chemical compound [Mn+2].[O-][Si]([O-])=O ASTZLJPZXLHCSM-UHFFFAOYSA-N 0.000 description 1
- ZOIVSVWBENBHNT-UHFFFAOYSA-N dizinc;silicate Chemical compound [Zn+2].[Zn+2].[O-][Si]([O-])([O-])[O-] ZOIVSVWBENBHNT-UHFFFAOYSA-N 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- BYOBIQOEWYNTMM-UHFFFAOYSA-N manganese;nitric acid Chemical compound [Mn].O[N+]([O-])=O BYOBIQOEWYNTMM-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- 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
- D06M11/56—Sulfates or thiosulfates other than of elements of Groups 3 or 13 of the Periodic Table
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- 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
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Abstract
本发明涉及的一种柔性硅酸盐纳米纤维膜及其制备方法,该柔性纤维膜是以柔性的电纺SiO2纳米纤维膜为前驱体模板,通过水热反应过程将柔性的SiO2纳米纤维膜转变为柔性的硅酸盐纳米纤维膜。本发明提供的一维柔性硅酸盐纳米纤维膜其纤维长而连续,得到的硅酸盐纳米纤维可以为实心纤维也可以为空心纳米管纤维。纤维膜可以随意弯曲折叠具有良好的机械强度,此制备方法具有普适性,简单的改变水热反应溶液中可溶性无机盐的种类,就可以制备出不同种类的柔性硅酸盐(硅酸镁、硅酸铜、硅酸镍、硅酸钴、硅酸锰等)纳米纤维膜。本发明得到的柔性硅酸盐纳米纤维膜可应用在填充剂、催化、无机荧光、电极材料、吸附、分离等诸多领域。
Description
技术领域
本发明属于新型材料制备领域,具体涉及一种柔性硅酸盐纳米纤维膜的制备方法。
背景技术
硅酸盐材料因其廉价、稳定、环境友好等特点,被广泛应用在填充剂、催化、无机荧光、电极材料、吸附、分离等领域。相比于块状材料,纳米级别的硅酸盐材料因表面效应、量子尺寸效应、小尺寸效应、宏观量子隧道效应等,在具体领域更具应用潜力。在众多制备纳米硅酸盐材料的方法中,由纳米尺度二氧化硅(SiO2)为前驱体通过水热反应过程制备的硅酸盐材料引起了大量的关注。通常得到的纳米硅酸盐结构有纳米球、短纤维、纳米线、纳米管等。例如宋卫国等人公开了一种层状多级硅酸锌纳米球(中国专利申请号201110328921.2)。罗绍华等人公开了一种棒状的硅酸锰锂短纳米线(中国专利申请号201210113571.7)。然而目前报道的纳米尺度硅酸盐材料虽然微观尺度是纳米级别,但是宏观形态都呈粉末状或颗粒状,在材料的使用过程中普遍存在纳米材料团聚的问题,使用过后不易分离回收,限制了操作性和实际应用性。
近些年来,通过静电纺丝技术制备的一维纳米纤维膜材料,由于高的孔隙率、高的比表面积、良好的柔韧性和机械强度,在诸多领域都有着良好的应用前景。静电纺丝技术是在高压静电的作用下将聚合溶液或者熔体纺制成一维连续的微/纳米纤维,通常纤维直径都在500nm以下。改变聚合物溶液/熔体或结合后处理方法,经由静电纺丝技术就可以得到有机纳米纤维、无机纳米纤维以及有机/无机复合纳米纤维。因为电纺纤维的形貌结构特性,静电纺丝方法常用来制备一维柔性的有机、无机纳米纤维膜。这些柔性纳米纤维膜材料可以解决上述的传统纳米材料存在的问题,可以推进纳米材料进一步应用。但是,柔性硅酸盐纳米纤维膜的制备还未见报道。
基于以上背景介绍,本发明提出一种柔性硅酸盐纳米纤维膜的制备方法。首先通过静电纺丝技术及后煅烧方法制备柔性的SiO2纳米纤维膜,以SiO2纳米纤维膜为前驱体模板,通过水热反应过程将柔性的SiO2纳米纤维膜转变为柔性的硅酸盐纳米纤维膜。此外,通过改变水热反应条件,得到的硅酸盐纤维可以为实心纤维、也可以为空心纳米管纤维,极大丰富了材料的结构类型,满足不同应用对纤维结构形貌的需求。由于硅酸盐本身的物理化学性质以及纳米纤维膜的结构特性,得到的柔性硅酸盐纳米纤维膜在环境、催化、电子、能源等领域都将具有非常好的应用前景。
发明内容
本发明的目的是提供一种柔性硅酸盐纳米纤维膜及其制备方法,以解决传统的纳米硅酸盐材料在使用过程中存在纳米材料团聚以及使用过后不易分离回收的问题,最大限度提高硅酸盐材料的操作性和实际应用性。
为实现上述目的,本发明的一种柔性硅酸盐纳米纤维膜的制备方法为:以柔性的SiO2纳米纤维膜为前驱体模板,通过水热反应过程将柔性的SiO2纳米纤维膜转变为柔性的硅酸盐纳米纤维膜。
具体制备步骤如下:
一种柔性硅酸盐纳米纤维膜的制备方法,以柔性的电纺SiO2纳米纤维膜为前驱体模板,通过水热反应过程将柔性的SiO2纳米纤维膜转变为柔性的硅酸盐纳米纤维膜,具体制备方法步骤如下:
(1)将选用的聚合物溶解在其适合的溶剂中搅拌至完全溶解,配置质量分数为4~30 wt%的聚合物溶液A;
(2)将硅酸酯、水、乙醇、无机酸按摩尔比1:(2~5):(0.4~1.6):(0.01~0.04)进行混合,搅拌4~36h后得到硅源溶液B;
(3)将聚合物溶液A与硅源溶液B按体积比1:(0.2~3)充分搅拌混合后得到静电纺丝液C;
(4)将静电纺丝液C放入纺丝设备的喷丝管中,玻璃喷丝管的管头内径是0.5~2mm,电纺丝设备的工作电压为15~30kV,以铝套为阳极,以铝箔为阴极接收,两极间的距离为 10~30cm;进行静电纺丝从而获得聚合物/硅源复合纤维膜;
(5)将步骤(4)得到的聚合物/硅源复合纤维膜放入管式炉中,升温速度为1~5℃/min,在600~1200℃下煅烧4~24h,得到柔性SiO2纳米纤维膜;
(6)步骤(5)得到的柔性SiO2纳米纤维膜置于含可溶性无机盐、无机铵盐、碱液的混合溶液中,其中可溶性无机盐、无机铵盐、碱液的摩尔比为1:(25~100):(0.2~1.5) 至纤维膜完全浸泡后,将混合溶液至于密闭水热反应釜中,在120~200℃下水热反应6~30h,将得到的产物用水和乙醇反复洗涤,最后得到柔性的硅酸盐纳米纤维膜。
所述步骤(1)中的聚合物为聚丙烯腈、聚乙烯醇、聚乙烯醇缩丁醛、聚甲基丙烯酸甲酯、聚乙烯基吡咯烷酮、聚环氧乙烷、聚苯乙烯、聚丙烯酸和羧甲基纤维素中的一种。
所述步骤(1)中的溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、丙酮、氯仿、二氯甲烷、乙醇、水中的一种或者几种混合。
所述步骤(2)中的硅酸酯为正硅酸甲酯、正硅酸乙酯、正硅酸丙酯和三甲基硅烷氧基硅酸酯中的一种。
所述步骤(2)中的无机酸为盐酸、硫酸、磷酸、草酸、甲酸、醋酸和硝酸中的一种。
所述步骤(6)中的可溶性无机盐为氯化镁、硝酸镁、醋酸镁、硫酸镁、氯化铜、硝酸铜、醋酸铜、硫酸铜、氯化镍、硝酸镍、醋酸镍、硫酸镍、氯化锰、硝酸锰、醋酸锰、硫酸锰、氯化钴、硝酸钴、醋酸钴和硫酸钴中的一种。
所述步骤(6)中的无机铵盐为氯化铵、硝酸铵、硫酸铵、溴化铵或醋酸铵中的一种。
所述步骤(6)中的碱液为30%氨水、10%氢氧化钠溶液和10%氢氧化钾溶液中的一种。
所述步骤(6)中得到的柔性硅酸盐纳米纤维膜为柔性硅酸镁纳米纤维膜、柔性硅酸铜纳米纤维膜、柔性硅酸镍纳米纤维膜、柔性硅酸钴纳米纤维膜、柔性硅酸锰纳米纤维膜。
所述步骤(6)中得到硅酸盐纳米纤维为实心纤维或空心纳米管纤维,纤维平均直径为300~600nm。
所述步骤(6)中得到柔性的硅酸盐纳米纤维膜具有良好的机械性能,纤维膜拉伸强度为4~15MPa,断裂伸长率为3~20%。
所述步骤(6)中得到的柔性硅酸盐纳米纤维膜可应用在填充剂、催化、无机荧光、电极材料、吸附、分离领域。
本发明的有益效果在于:
本发明提供的一种柔性硅酸盐纳米纤维膜的制备方法是以柔性的电纺SiO2纳米纤维膜为前驱体模板,通过水热反应过程将柔性的SiO2纳米纤维膜转变为柔性的硅酸盐纳米纤维膜。与以往报道的纳米尺度硅酸盐材料相比,本发明提供的一维柔性硅酸盐纳米纤维膜其纤维长而连续、纤维膜可以随意弯曲折叠具有良好的机械强度,可以避免在使用过程中纳米材料的团聚问题、并且使用过后可以较易分离回收,最大限度提高硅酸盐材料的操作性和实际应用性。此制备方法具有普适性,简单的改变水热反应溶液中可溶性无机盐的种类,就可以制备出不同种类的柔性硅酸盐(硅酸镁、硅酸铜、硅酸镍、硅酸钴、硅酸锰)纳米纤维膜。此外,改变反应温度或者反应时间,得到的硅酸盐纳米纤维可以为实心纤维也可以为空心纳米管纤维,极大提高了材料的应用范围和应用潜力,本发明提供的柔性硅酸盐纳米纤维膜可应用在填充剂、催化、无机荧光、电极材料、吸附、分离等诸多领域。最后,从制备过程可以看出,本发明提供的制备方法原料易得,操作简单、安全,易实现工业化生产。
附图说明
图1:实施例1得到的柔性硅酸铜纳米纤维膜被弯曲折叠图例;
图2:实施例2得到的柔性硅酸镁实心纳米纤维膜的扫描电镜照片;
图3:实施例3中得到的柔性硅酸镍空心管状纳米纤维膜的扫面电镜照片;
图4:实施例4中得到的柔性硅酸锰纳米纤维膜的应力-应变曲线。
具体实施方式
为了更好地理解本发明,下面结合实施例进一步阐明本发明的内容,但本发明的内容不仅仅局限于下面的实施例,不能理解为对发明保护范围的限制。
实施例1:
(1)将2.00g聚乙烯醇缩丁醛溶解在8.00g乙醇和水的混合溶液(乙醇和水的体积比为2:1)中,配置质量分数为20wt%的聚合物溶液;
(2)将4.16g正硅酸乙酯、1.60g水、1.48g乙醇、0.08g磷酸进行混合,搅拌36h 后得到硅源溶液;
(3)将上述聚合物溶液与硅源溶液充分搅拌混合后得到静电纺丝液;
(4)将静电纺丝液放入纺丝设备的喷丝管中,玻璃喷丝管的管头内径是2mm,电纺丝设备的工作电压为30kV,以铝套为阳极,以铝箔为阴极接收产物,两极间的距离30cm;进行静电纺丝从而获得聚合物/硅源复合纤维膜;
(5)将步骤(4)得到的聚合物/硅源复合纤维膜放入管式炉中,升温速度为5℃/min,在600℃下煅烧24h,得到柔性SiO2纳米纤维膜;
(6)将0.1g步骤(5)得到的柔性SiO2纳米纤维膜置于40mL水热反应溶液(含硫酸铜2mmol、溴化铵5mmol、10%氢氧化钠溶液2mL)中至纤维膜完全浸泡后,将混合溶液至于密闭水热反应釜中,在120℃下水热反应30h,将得到的产物用水和乙醇反复洗涤,最后得到柔性的硅酸铜纳米纤维膜。硅酸铜纳米纤维为实心纤维,纤维膜可以随意弯曲折叠具(图1),纤维平均直径为302nm,纤维膜拉伸强度为8.3MPa,断裂伸长率为 10.2%。
实施例2:
(1)将3.00g聚乙烯醇在70℃下溶解于7.00g水中,配置质量分数为30wt%的聚合物溶液;
(2)将7.55g正硅酸甲酯、1.80g水、0.95g乙醇、0.02g盐酸进行混合,搅拌4h 后得到硅源溶液;
(3)将上述聚合物溶液与硅源溶液充分搅拌混合后得到静电纺丝液;
(4)将静电纺丝液放入纺丝设备的喷丝管中,玻璃喷丝管的管头内径是0.5mm,电纺丝设备的工作电压为15kV,以铝套为阳极,以铝箔为阴极接收产物,两极间的距离10 cm;进行静电纺丝从而获得聚合物/硅源复合纤维膜;
(5)将步骤(4)得到的聚合物/硅源复合纤维膜放入管式炉中,升温速度为1℃/min,在1200℃下煅烧4h,得到柔性SiO2纳米纤维膜;
(6)将0.02g步骤(5)得到的柔性SiO2纳米纤维膜置于40mL水热反应溶液(含氯化镁0.2mmol、氯化铵20mmol、30%氨水0.5mL)中至纤维膜完全浸泡后,将混合溶液至于密闭水热反应釜中,在160℃下水热反应6h,将得到的产物用水和乙醇反复洗涤,最后得到柔性的硅酸镁纳米纤维膜。硅酸镁纳米纤维为实心纤维,纤维平均直径为450nm (图2),纤维膜拉伸强度为15.0MPa,断裂伸长率为7.1%。
实施例3:
(1)将0.40g聚环氧乙烷溶解于9.60g水中,配置质量分数为4wt%的聚合物溶液;
(2)将5.28g正硅酸丙酯、1.08g水、1.38g乙醇、0.03g草酸进行混合,搅拌10h 后得到硅源溶液;
(3)将上述聚合物溶液与硅源溶液按体积比1:1充分搅拌混合后得到静电纺丝液;
(4)将静电纺丝液放入纺丝设备的喷丝管中,玻璃喷丝管的管头内径是1mm,电纺丝设备的工作电压为20kV,以铝套为阳极,以铝箔为阴极接收产物,两极间的距离15cm;进行静电纺丝从而获得聚合物/硅源复合纤维膜;
(5)将步骤(4)得到的聚合物/硅源复合纤维膜放入管式炉中,升温速度为2℃/min,在800℃下煅烧10h,得到柔性SiO2纳米纤维膜;
(6)将0.05g步骤(5)得到的柔性SiO2纳米纤维膜置于40mL水热反应溶液(含醋酸镍1mmol、硫酸铵10mmol、10%氢氧化钾1mL)中至纤维膜完全浸泡后,将混合溶液至于密闭水热反应釜中,在200℃下水热反应15h,将得到的产物用水和乙醇反复洗涤,最后得到柔性的硅酸镍纳米纤维膜。硅酸镍纳米纤维为空心纳米管纤维(图3),纤维平均直径为537nm,纤维膜拉伸强度为4.0MPa,断裂伸长率为10.2%。
实施例4:
(1)将2.50g聚乙烯基吡咯烷酮溶解在7.50g乙醇和N,N-二甲基甲酰胺的混合溶液(乙醇和N,N-二甲基甲酰胺的体积比为7:1)中,配置质量分数为25wt%的聚合物溶液;
(2)将13.28g三甲基硅烷氧基硅酸酯、3.84g水、3.68g乙醇、0.11g甲酸进行混合,搅拌24h后得到硅源溶液;
(3)将上述聚合物溶液与硅源溶液充分搅拌混合后得到静电纺丝液;
(4)将静电纺丝液放入纺丝设备的喷丝管中,玻璃喷丝管的管头内径是1mm,电纺丝设备的工作电压为25kV,以铝套为阳极,以铝箔为阴极接收产物,两极间的距离20cm;进行静电纺丝从而获得聚合物/硅源复合纤维膜;
(5)将步骤(4)得到的聚合物/硅源复合纤维膜放入管式炉中,升温速度为4℃/min,在900℃下煅烧20h,得到柔性SiO2纳米纤维膜;
(6)将0.08g步骤(5)得到的柔性SiO2纳米纤维膜置于40mL水热反应溶液(含硝酸锰1.8mmol、醋酸铵4mmol、10%氢氧化钠溶液1mL)中至纤维膜完全浸泡后,将混合溶液至于密闭水热反应釜中,在150℃下水热反应20h,将得到的产物用水和乙醇反复洗涤,最后得到柔性的硅酸锰纳米纤维膜。硅酸锰纳米纤维为实心纤维,纤维平均直径为 470nm,纤维膜拉伸强度为5.2MPa,断裂伸长率为3.5%(图4)。
实施例5:
(1)将2.35g聚丙烯腈溶解在7.65g N,N-二甲基甲酰胺中,配置质量分数为23.5wt%的聚合物溶液;
(2)将15.84g正硅酸丙酯、3.84g水、4.14g乙醇、0.23g磷酸进行混合,搅拌30h 后得到硅源溶液;
(3)将上述聚合物溶液与硅源溶液充分搅拌混合后得到静电纺丝液;
(4)将静电纺丝液放入纺丝设备的喷丝管中,玻璃喷丝管的管头内径是1.4mm,电纺丝设备的工作电压为18kV,以铝套为阳极,以铝箔为阴极接收产物,两极间的距离20 cm;进行静电纺丝从而获得聚合物/硅源复合纤维膜;
(5)将步骤(4)得到的聚合物/硅源复合纤维膜放入管式炉中,升温速度为1℃/min,在800℃下煅烧24h,得到柔性SiO2纳米纤维膜;
(6)将0.1g步骤(5)得到的柔性SiO2纳米纤维膜置于40mL水热反应溶液(含氯化锰2mmol、溴化铵10mmol、30%氨水1.5mL)中至纤维膜完全浸泡后,将混合溶液至于密闭水热反应釜中,在180℃下水热反应10h,将得到的产物用水和乙醇反复洗涤,最后得到柔性的硅酸锰纳米纤维膜。硅酸锰纳米纤维为实心纤维,纤维平均直径为520nm,纤维膜拉伸强度为4.8MPa,断裂伸长率为5.2%。
实施例6:
(1)将3.00g聚苯乙烯溶解在7.00g N,N-二甲基甲酰胺中,配置质量分数为30wt%的聚合物溶液;
(2)将10.4g正硅酸乙酯、2.16g水、2.76g乙醇、0.02g草酸进行混合,搅拌14h 后得到硅源溶液;
(3)将上述聚合物溶液与硅源溶液充分搅拌混合后得到静电纺丝液;
(4)将静电纺丝液放入纺丝设备的喷丝管中,玻璃喷丝管的管头内径是1mm,电纺丝设备的工作电压为20kV,以铝套为阳极,以铝箔为阴极接收产物,两极间的距离25cm;进行静电纺丝从而获得聚合物/硅源复合纤维膜;
(5)将步骤(4)得到的聚合物/硅源复合纤维膜放入管式炉中,升温速度为3℃/min,在1000℃下煅烧18h,得到柔性SiO2纳米纤维膜;
(6)将0.06g步骤(5)得到的柔性SiO2纳米纤维膜置于40mL水热反应溶液(含硝酸镍1.6mmol、氯化铵13mmol、10%氢氧化钠溶液1mL)中至纤维膜完全浸泡后,将混合溶液至于密闭水热反应釜中,在200℃下水热反应12h,将得到的产物用水和乙醇反复洗涤,最后得到柔性的硅酸镍纳米纤维膜。硅酸镍纳米纤维为空心纤维,纤维膜可以随意弯曲折叠具,纤维平均直径为498nm,纤维膜拉伸强度为5.1MPa,断裂伸长率为11.7%。
实施例7:
(1)将2.20g聚丙烯酸溶解于7.80g N,N-二甲基乙酰胺中,配置质量分数为22wt%的聚合物溶液;
(2)将12.40g正硅酸甲酯、5.38g水、4.42g乙醇、0.08g硫酸进行混合,搅拌22h 后得到硅源溶液;
(3)将上述聚合物溶液与硅源溶液充分搅拌混合后得到静电纺丝液;
(4)将静电纺丝液放入纺丝设备的喷丝管中,玻璃喷丝管的管头内径是2mm,电纺丝设备的工作电压为15kV,以铝套为阳极,以铝箔为阴极接收产物,两极间的距离20cm;进行静电纺丝从而获得聚合物/硅源复合纤维膜;
(5)将步骤(4)得到的聚合物/硅源复合纤维膜放入管式炉中,升温速度为3℃/min,在1000℃下煅烧20h,得到柔性SiO2纳米纤维膜;
(6)将0.07g步骤(5)得到的柔性SiO2纳米纤维膜置于40mL水热反应溶液(含硫酸钴2mmol、醋酸铵18mmol、10%氢氧化钾1.6mL)中至纤维膜完全浸泡后,将混合溶液至于密闭水热反应釜中,在160℃下水热反应18h,将得到的产物用水和乙醇反复洗涤,最后得到柔性的硅酸钴纳米纤维膜。硅酸钴纳米纤维为实心纤维,纤维平均直径为600nm,纤维膜拉伸强度为9.7MPa,断裂伸长率为12.3%。
Claims (10)
1.一种柔性硅酸盐纳米纤维膜的制备方法,其特征在于:以柔性的电纺SiO2纳米纤维膜为前驱体模板,通过水热反应过程将柔性的SiO2纳米纤维膜转变为柔性的硅酸盐纳米纤维膜,具体制备方法步骤如下:
(1)将选用的聚合物溶解在其适合的溶剂中搅拌至完全溶解,配置质量分数为4~30wt%的聚合物溶液A;
(2)将硅酸酯、水、乙醇、无机酸按摩尔比1:(2~5):(0.4~1.6):(0.01~0.04)进行混合,搅拌4~36h后得到硅源溶液B;
(3)将聚合物溶液A与硅源溶液B按体积比1:(0.2~3)充分搅拌混合后得到静电纺丝液C;
(4)将静电纺丝液C放入纺丝设备的喷丝管中,玻璃喷丝管的管头内径是0.5~2mm,电纺丝设备的工作电压为15~30kV,以铝套为阳极,以铝箔为阴极接收,两极间的距离为10~30cm;进行静电纺丝从而获得聚合物/硅源复合纤维膜;
(5)将步骤(4)得到的聚合物/硅源复合纤维膜放入管式炉中,升温速度为1~5℃/min,在600~1200℃下煅烧4~24h,得到柔性SiO2纳米纤维膜;
(6)步骤(5)得到的柔性SiO2纳米纤维膜置于含可溶性无机盐、无机铵盐、碱液的混合溶液中,其中可溶性无机盐、无机铵盐、碱液的摩尔比为1:(25~100):(0.2~1.5)至纤维膜完全浸泡后,将混合溶液至于密闭水热反应釜中,在120~200℃下水热反应6~30h,将得到的产物用水和乙醇反复洗涤,最后得到柔性的硅酸盐纳米纤维膜。
2.根据权利要求1所述一种柔性硅酸盐纳米纤维膜的制备方法,其特征在于:所述步骤(1)中的聚合物为聚丙烯腈、聚乙烯醇、聚乙烯醇缩丁醛、聚甲基丙烯酸甲酯、聚乙烯基吡咯烷酮、聚环氧乙烷、聚苯乙烯、聚丙烯酸和羧甲基纤维素中的一种。
3.根据权利要求1所述一种柔性硅酸盐纳米纤维膜的制备方法,其特征在于:所述步骤(1)中的溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、丙酮、氯仿、二氯甲烷、乙醇、水中的一种或者几种混合。
4.根据权利要求1所述一种柔性硅酸盐纳米纤维膜的制备方法,其特征在于:所述步骤(2)中的硅酸酯为正硅酸甲酯、正硅酸乙酯、正硅酸丙酯和三甲基硅烷氧基硅酸酯中的一种。
5.根据权利要求1所述一种柔性硅酸盐纳米纤维膜的制备方法,其特征在于:所述步骤(2)中的无机酸为盐酸、硫酸、磷酸、草酸、甲酸、醋酸和硝酸中的一种。
6.根据权利要求1所述一种柔性硅酸盐纳米纤维膜的制备方法,其特征在于:所述步骤(6)中的可溶性无机盐为氯化镁、硝酸镁、醋酸镁、硫酸镁、氯化铜、硝酸铜、醋酸铜、硫酸铜、氯化镍、硝酸镍、醋酸镍、硫酸镍、氯化锰、硝酸锰、醋酸锰、硫酸锰、氯化钴、硝酸钴、醋酸钴和硫酸钴中的一种。
7.根据权利要求1所述一种柔性硅酸盐纳米纤维膜的制备方法,其特征在于:所述步骤(6)中的无机铵盐为氯化铵、硝酸铵、硫酸铵、溴化铵和醋酸铵中的一种。
8.根据权利要求1所述一种柔性硅酸盐纳米纤维膜的制备方法,其特征在于:所述步骤(6)中的碱液为30%氨水、10%氢氧化钠溶液和10%氢氧化钾溶液中的一种。
9.根据权利要求1所述一种柔性硅酸盐纳米纤维膜的制备方法,其特征在于:所述步骤(6)中得到的柔性硅酸盐纳米纤维膜为柔性硅酸镁纳米纤维膜、柔性硅酸铜纳米纤维膜、柔性硅酸镍纳米纤维膜、柔性硅酸钴纳米纤维膜、柔性硅酸锰纳米纤维膜,柔性硅酸盐纳米纤维为实心纤维或空心纳米管纤维,纤维平均直径为300~600nm,具有良好的机械性能,纤维膜拉伸强度为4~15MPa,断裂伸长率为3~20%。
10.根据权利要求1所述一种柔性硅酸盐纳米纤维膜的制备方法,其特征在于:所述步骤(6)中得到的柔性硅酸盐纳米纤维膜可应用在填充剂、催化、无机荧光、电极材料、吸附、分离领域。
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