CN104153124A - Flexible rare-earth oxide nanofiber membrane and preparation method thereof - Google Patents
Flexible rare-earth oxide nanofiber membrane and preparation method thereof Download PDFInfo
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- CN104153124A CN104153124A CN201410369285.6A CN201410369285A CN104153124A CN 104153124 A CN104153124 A CN 104153124A CN 201410369285 A CN201410369285 A CN 201410369285A CN 104153124 A CN104153124 A CN 104153124A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000002121 nanofiber Substances 0.000 title claims abstract description 15
- 239000012528 membrane Substances 0.000 title abstract description 67
- 229910001404 rare earth metal oxide Inorganic materials 0.000 title abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 88
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 69
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 55
- 239000000835 fiber Substances 0.000 claims abstract description 47
- 238000009987 spinning Methods 0.000 claims abstract description 45
- 239000007822 coupling agent Substances 0.000 claims abstract description 40
- 239000004094 surface-active agent Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 31
- -1 rare-earth metal salt Chemical class 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 104
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 100
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 90
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 88
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 76
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 60
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 58
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 56
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 54
- 230000036571 hydration Effects 0.000 claims description 53
- 238000006703 hydration reaction Methods 0.000 claims description 53
- 238000001354 calcination Methods 0.000 claims description 50
- 238000010041 electrostatic spinning Methods 0.000 claims description 47
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 46
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 44
- 235000011187 glycerol Nutrition 0.000 claims description 36
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 24
- 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 23
- 235000019253 formic acid Nutrition 0.000 claims description 23
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 21
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 20
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N acetaldehyde dimethyl acetal Natural products COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 claims description 19
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 14
- 238000001523 electrospinning Methods 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 13
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 13
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 claims description 12
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical class Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims description 9
- XWFVFZQEDMDSET-UHFFFAOYSA-N gadolinium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XWFVFZQEDMDSET-UHFFFAOYSA-N 0.000 claims description 9
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 229910052706 scandium Inorganic materials 0.000 claims description 9
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 9
- 229910052772 Samarium Inorganic materials 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 8
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 8
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 8
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 8
- NQFNBCXYXGZSPI-UHFFFAOYSA-L copper;diacetate;dihydrate Chemical compound O.O.[Cu+2].CC([O-])=O.CC([O-])=O NQFNBCXYXGZSPI-UHFFFAOYSA-L 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- BRDJPCFGLMKJRU-UHFFFAOYSA-N DDAO Chemical compound ClC1=C(O)C(Cl)=C2C(C)(C)C3=CC(=O)C=CC3=NC2=C1 BRDJPCFGLMKJRU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052689 Holmium Inorganic materials 0.000 claims description 4
- 229910052765 Lutetium Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- MIJKIIBNAPRONL-UHFFFAOYSA-N acetic acid;neodymium Chemical compound [Nd].CC(O)=O MIJKIIBNAPRONL-UHFFFAOYSA-N 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 4
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical group [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical group [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000014121 butter Nutrition 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 4
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 4
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 claims description 4
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 claims description 4
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 claims description 4
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 4
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 4
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 4
- 150000002596 lactones Chemical class 0.000 claims description 4
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 4
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 claims description 4
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 4
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- 150000004690 nonahydrates Chemical class 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 4
- HWZAHTVZMSRSJE-UHFFFAOYSA-H praseodymium(iii) sulfate Chemical class [Pr+3].[Pr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HWZAHTVZMSRSJE-UHFFFAOYSA-H 0.000 claims description 4
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 4
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical class Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 claims description 4
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 claims description 4
- NEEAOWXTIOQDFM-UHFFFAOYSA-H thulium(3+);trisulfate Chemical class [Tm+3].[Tm+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O NEEAOWXTIOQDFM-UHFFFAOYSA-H 0.000 claims description 4
- ILOTUXNTERMOJL-UHFFFAOYSA-K thulium(iii) chloride Chemical class Cl[Tm](Cl)Cl ILOTUXNTERMOJL-UHFFFAOYSA-K 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- PYOOBRULIYNHJR-UHFFFAOYSA-K trichloroholmium Chemical class Cl[Ho](Cl)Cl PYOOBRULIYNHJR-UHFFFAOYSA-K 0.000 claims description 4
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 4
- 159000000013 aluminium salts Chemical class 0.000 claims description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 150000002696 manganese Chemical class 0.000 claims description 3
- 150000003608 titanium Chemical class 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- KILURZWTCGSYRE-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]alumanyloxypent-3-en-2-one Chemical compound CC(=O)\C=C(\C)O[Al](O\C(C)=C/C(C)=O)O\C(C)=C/C(C)=O KILURZWTCGSYRE-LNTINUHCSA-K 0.000 claims description 2
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical group [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 claims description 2
- SWCIQHXIXUMHKA-UHFFFAOYSA-N aluminum;trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SWCIQHXIXUMHKA-UHFFFAOYSA-N 0.000 claims description 2
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical group Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims description 2
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 claims description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 2
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- ACXCKRZOISAYHH-UHFFFAOYSA-N molecular chlorine hydrate Chemical compound O.ClCl ACXCKRZOISAYHH-UHFFFAOYSA-N 0.000 claims description 2
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical class [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 2
- 235000013904 zinc acetate Nutrition 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- QAQSNXHKHKONNS-UHFFFAOYSA-N 1-ethyl-2-hydroxy-4-methyl-6-oxopyridine-3-carboxamide Chemical compound CCN1C(O)=C(C(N)=O)C(C)=CC1=O QAQSNXHKHKONNS-UHFFFAOYSA-N 0.000 claims 1
- 230000002045 lasting effect Effects 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 8
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 22
- 238000002156 mixing Methods 0.000 description 14
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 12
- 229910000420 cerium oxide Inorganic materials 0.000 description 9
- 239000002657 fibrous material Substances 0.000 description 9
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 9
- 229910001940 europium oxide Inorganic materials 0.000 description 6
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 6
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 6
- 229940075613 gadolinium oxide Drugs 0.000 description 6
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 6
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 6
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 6
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 6
- 229910001954 samarium oxide Inorganic materials 0.000 description 6
- 229940075630 samarium oxide Drugs 0.000 description 6
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 6
- 229910003451 terbium oxide Inorganic materials 0.000 description 6
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 description 6
- GEZAXHSNIQTPMM-UHFFFAOYSA-N dysprosium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Dy+3].[Dy+3] GEZAXHSNIQTPMM-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001330 spinodal decomposition reaction Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 3
- 150000000703 Cerium Chemical class 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 150000002603 lanthanum Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 102000040350 B family Human genes 0.000 description 1
- 108091072128 B family Proteins 0.000 description 1
- 229910016874 Fe(NO3) Inorganic materials 0.000 description 1
- 241000549556 Nanos Species 0.000 description 1
- 150000001206 Neodymium Chemical class 0.000 description 1
- 150000001213 Praseodymium Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000029918 bioluminescence Effects 0.000 description 1
- 238000005415 bioluminescence Methods 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- CQGVSILDZJUINE-UHFFFAOYSA-N cerium;hydrate Chemical compound O.[Ce] CQGVSILDZJUINE-UHFFFAOYSA-N 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 210000002950 fibroblast Anatomy 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- USJZIUVMYSUNGB-UHFFFAOYSA-N neodymium;hydrate Chemical compound O.[Nd] USJZIUVMYSUNGB-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- BOJUHNOLOKDHBE-UHFFFAOYSA-N praseodymium;hydrate Chemical compound O.[Pr] BOJUHNOLOKDHBE-UHFFFAOYSA-N 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- IPFZYNPDAIWERQ-UHFFFAOYSA-N samarium;hydrate Chemical compound O.[Sm] IPFZYNPDAIWERQ-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- RFASAXPGSBXKNJ-UHFFFAOYSA-N terbium;hydrate Chemical compound O.[Tb] RFASAXPGSBXKNJ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Nonwoven Fabrics (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a flexible rare-earth oxide nanofiber membrane and a preparation method thereof. The preparation method includes firstly dissolving rare-earth metal source and non-rare-earth metal salt into solvent, and sequentially adding coupling agent and surfactant to be uniformly mixed and obtain stable precursor solution with interpenetrating three-dimensional network structural molecular chains; later making the precursor solution into precursor fibers through a spinning and forming process; burning the precursor fibers in the air to obtain the flexible rare-earth oxide nanofiber membrane. The preparation method is simple and high in yield, and the obtained flexible rare-earth oxide nanofiber membrane is good in flexibility, and has promising application prospect in various application fields such as lighting, display and bioluminescene marking.
Description
Technical field
The invention belongs to new material technology field, relate to a kind of flexible rare-earth oxidate nano tunica fibrosa and preparation method thereof, particularly relate to a kind of precursor solution with IPN tridimensional network strand as flexible inorganic fibrous material of spinning solution and preparation method thereof, specifically a kind of flexible rare-earth oxidate nano tunica fibrosa and preparation method thereof.
Background technology
Rare earth element refers to lanthanide series in periodic table of elements ZhongⅢ B family and the totally 17 kind elements such as scandium (Sc) and yttrium (Y) close with its character.Due to features such as rare earth element has high electricity price, radius is large, polarization force is strong, chemical property is active, reducibility is strong, the Heat stability is goods of oxide, in ceramic material research, become the requisite property-modifying additive of a class, rare earth nano material has broad application prospects at multiple fields such as illumination, demonstration and bioluminescence marks.In the past during the decade, people synthesize a large amount of peacekeeping two dimension rare earth nanos or micron oxide fibre material by hydro-thermal or solvent-thermal method, these material patterns are varied, comprise rod, line, pipe, band and dish etc., how nanometer rare earth oxide fiber prepared by these methods is made up of microparticle, simultaneously fiber cannot use separately greatly because of fragility, and this has limited its practical application greatly.In recent years the electrostatic spinning technique of rise is simple with its manufacturing installation, spinning is with low cost, can spin the advantages such as substance classes is various, technique is controlled, become one of major technique of effectively preparing nano-fiber material, its fibrous material of preparing has the features such as tunica fibrosa aperture is little, fibre diameter is little, fibre diameter is even and is widely used, and utilizes electrostatic spinning technique now to prepare more than 50 kind of inorganic oxide nano fibrous membrane.But the large problem of inorganic oxide nano fibrous membrane ubiquity fragility of preparing at present, thereby limit its practical application.
Chinese patent CN201010187764.8 discloses a kind of La
2o
3the preparation method of nano-fiber catalyst, can spin macromolecule resin, lanthanum salt and polar solvent by even mixing and be mixed with electrostatic spinning liquid, then prepared lanthana nanofiber through calcining, because inorganic component content in precursor fibre is lower, the lanthana nanofiber output preparing is by this method on the low side.Bull.Korean Chem.Soc. (2011) 9 has reported a kind of method of preparing cerium oxide nano fiber, evenly be mixed with spinnable precursor solution by cerium salt, solvent and high polymer, and then prepare cerium oxide nano fiber by electrostatic spinning technique and calcining technology, but the cerium oxide nano fibre diameter that this method prepares is inhomogeneous, poor continuity, and in precursor fibre, inorganic component content is on the low side, a large amount of organic component spinodal decompositions in calcination process, inorganic component cannot support fiber reinforcement structure.
Summary of the invention
The object of the invention is to propose a kind of flexible rare-earth oxidate nano fibrous material and preparation method thereof, the flexible rare-earth oxidate nano fibrous material of preparing by this preparation method can solve the problems referred to above that prior art exists.
The preparation method of a kind of flexible rare-earth oxidate nano fibrous material of the present invention, concrete steps are:
The first step:
1) rare earth metal source and at least one non-rare earth metal salt are joined in corresponding solvent, make that hydrolysis condensation reaction occurs between rare earth metal source, non-rare earth metal salt and solvent in whipping process or chelation forms the strand with tridimensional network; The object that adds at least one non-rare earth metal salt is in calcination process, to suppress grain growth by ion doping, makes the crystal defect of generation less;
2) after stirring 10-60min, add coupling agent, on coupling agent, there are two kinds of groups, comprise the group of close inorganic molecule and the group of close organic molecule, now the close inorganic molecule group on coupling agent forms hydroxyl by there is part hydrolysis in solution, afterwards again with above-mentioned tridimensional network strand on part of hydroxyl generation condensation reaction, coupling agent is connected with covalent bond with the strand of tridimensional network;
3) continue to add surfactant after stirring 5-30min, now the close organic molecule group on coupling agent is connected by chemical reaction occurring or producing hydrogen bond action with the hydrophilic radical on surfactant again;
4) along with the increase of coupling agent hydrolysis degree, hydroxyl generation condensation reaction on hydroxyl continuation and above-mentioned tridimensional network strand on coupling agent, close organic molecule group on coupling agent and the hydrophilic radical on surfactant continue to occur chemical reaction or form hydrogen bond simultaneously, hydrophobic group on surfactant aligns by hydrogen bond, tridimensional network strand constantly interts and tangles, and between strand in tridimensional network-coupling agent-surfactant, produce " bridging ", thereby form the tridimensional network of IPN, the viscosity of precursor solution is increased, spinnability strengthens.
Wherein the ratio of rare earth metal source and solvent is 10g:10-30mL, the mol ratio of rare earth metal source and non-rare earth metal salt is 100:1-10, the mol ratio of rare earth metal source and coupling agent is 1:0.02-0.1, and the mol ratio of rare earth metal source and surfactant is 1:0.01-0.1;
Second step: under the condition of 20-28 DEG C and relative humidity 30-60%, above-mentioned precursor solution is carried out to electrostatic spinning, under electric field action, charged drop is broken through surface tension slenderizing fibroblast in air, fiber laydown is to receiving on substrate, obtain precursor fibre film, prepared precursor fibre has the characteristics such as fibre diameter is little, fiber continuity is good;
The 3rd step: above-mentioned precursor fibrous material is calcined under air atmosphere, can be prepared flexible rare-earth oxidate nano tunica fibrosa.The tridimensional network that in the precursor solution of preparing due to the present invention, strand is IPN, in precursor fibre, inorganic component content is higher simultaneously, therefore the skeleton structure that filament is complete in calcination process can not be damaged because of the spinodal decomposition of a large amount of organic components, makes the last nanometer rare earth oxide tunica fibrosa obtaining have good flexibility.
As preferred technical scheme:
The preparation method of a kind of flexible rare-earth oxidate nano tunica fibrosa as above, in the described first step,
The ratio of rare earth metal source and solvent is 10g:10-30mL, the mol ratio of rare earth metal source and non-rare earth metal salt is 100:1-10, the mol ratio of rare earth metal source and coupling agent is 1:0.02-0.1, and the mol ratio of rare earth metal source and surfactant is 1:0.01-0.1; The dynamic viscosity of described precursor solution is 0.1-1Pas, and electrical conductivity is 10-50mS/m.
The preparation method of a kind of flexible rare-earth oxidate nano tunica fibrosa as above, in described second step, described electrostatic spinning refers to that described precursor solution is input to the flow velocity of 1-4mL/h on the spinning head of electrospinning device, the high voltage source that simultaneously spinning head is connected to 10-30kV is carried out electrostatic spinning, and the distance between receiving system and spinning head is 10-30cm.
The preparation method of the flexible oxidate nano tunica fibrosa of a kind of flexibility as above, in the 3rd described step, described calcining refers to that calcining heat progressively rises to 400-700 DEG C from room temperature, and programming rate is 1-10 DEG C/min, and keeps 10-240min under the highest calcining heat.
The preparation method of a kind of flexible rare-earth oxidate nano tunica fibrosa described above, the one in Wei Lan source, described rare earth metal source, cerium source, praseodymium source, neodymium source, samarium source, europium source, gadolinium source, terbium source, dysprosium source, holmium source, erbium source, thulium source, ytterbium source, lutetium source, Huo Yi source, scandium source;
Lanthanum source: lanthanum nitrate, lanthanum hydroxide, lanthanum acetate, lanthanum chloride or acetylacetone,2,4-pentanedione lanthanum;
Cerium source: six nitric hydrate ceriums, cerous carbonate, cerium hydroxide or cerous acetate;
Praseodymium source: six nitric hydrate praseodymiums or eight hydration praseodymium sulfates;
Neodymium source: six nitric hydrate neodymiums, acetic acid neodymium or eight hydration Dineodymium trisulfates;
Samarium source: six nitric hydrate samariums or trifluoromethayl sulfonic acid samarium;
Europium source: six hydration Europium chlorides or six nitric hydrate europiums;
Gadolinium source: gadolinium nitrate hexahydrate or eight hydration Digadolinium trisulfates;
Terbium source: six water terbium chlorides or five nitric hydrate terbiums;
Dysprosium source: trifluoromethayl sulfonic acid dysprosium;
Holmium source: eight hydration sulfuric acid holmiums or six hydration holmium chlorides;
Erbium source: five nitric hydrate erbiums;
Thulium source: six hydrous thulium chlorides or eight hydration thulium sulfates;
Ytterbium source: ytterbium nitrate or trifluoromethayl sulfonic acid ytterbium;
Lutetium source: six hydration lutecium chlorides or eight hydration sulfuric acid lutetiums;
Scandium source: trifluoromethayl sulfonic acid scandium;
Yttrium source: six nitric hydrate yttriums.
The non-rare earth metal salt of described interpolation is the one in zirconates, aluminium salt, titanium salt, pink salt, antimonic salt, lanthanum salt, neodymium salt, manganese salt, molysite, cerium salt, praseodymium salt, cobalt salt, mantoquita, chromic salts or zinc salt.
Zirconates is zirconyl nitrate, chlorine hydrate zirconia, acetylacetone,2,4-pentanedione zirconium or zirconium acetate;
Aluminium salt is aluminium isopropoxide, ANN aluminium nitrate nonahydrate, Aluminium chloride hexahydrate or aluminium acetylacetonate;
Titanium salt is butyl titanate, isopropyl titanate or tetraethyl titanate;
Pink salt is two hydrated stannous chlorides, butter of tin or stannous sulfate;
Antimonic salt is Antimony pentachloride, trichloride antimony or antimony acetate;
Manganese salt is manganese acetylacetonate, manganese chloride, manganese acetate or four hydration manganese chlorides;
Molysite is ferric acetyl acetonade, Iron(III) chloride hexahydrate;
Cobalt salt is cobalt acetate, Cobalt monosulfate heptahydrate, acetylacetone cobalt or cabaltous nitrate hexahydrate;
Mantoquita is copper acetate dihydrate, Gerhardite or Salzburg vitriol;
Chromic salts is chromium acetate or Chromium nitrate (Cr(NO3)3),nonahydrate;
Zinc salt is zinc chloride, zinc acetylacetonate or two hydration zinc acetates.
The preparation method of a kind of flexible rare-earth oxidate nano tunica fibrosa as above, described solvent corresponds to respectively according to rare earth metal source:
Lanthanum nitrate: water, methyl alcohol, ethanol, isopropyl alcohol, glycerol or DMF;
Lanthanum hydroxide: DMF, formic acid, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid or nitric acid;
Lanthanum acetate: water, glycerol or DMF;
Lanthanum chloride: water, ethanol, pyridine or DMF;
Acetylacetone,2,4-pentanedione lanthanum: methyl alcohol, ethanol, ethylene glycol, isopropyl alcohol, DMF, DMA, acetic acid or oxolane;
Six nitric hydrate ceriums: water, methyl alcohol, ethanol, isopropyl alcohol, isobutanol, n-butanol, ethylene glycol or glycerol;
Cerous carbonate: phosphoric acid, sulfuric acid, hydrochloric acid or nitric acid;
Cerium hydroxide: formic acid, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid or nitric acid;
Cerous acetate: water, isobutanol or DMF;
Six nitric hydrate praseodymiums: water, methyl alcohol, ethanol, n-butanol, glycerol, DMF or DMA;
Eight hydration praseodymium sulfates: water, n-butanol, glycerol or DMF;
Six nitric hydrate neodymiums: water, methyl alcohol, ethanol, ethylene glycol, isopropyl alcohol, isobutanol, n-butanol, glycerol, DMF or DMA;
Acetic acid neodymium: water, methyl alcohol, acetone, isobutanol, n-butanol, glycerol, DMF or DMA;
Eight hydration Dineodymium trisulfates: water, formic acid, methyl alcohol, acetic acid, sulfuric acid, hydrochloric acid or nitric acid;
Six nitric hydrate samariums: water, ethylene glycol, isopropyl alcohol, isobutanol, DMF or DMA;
Trifluoromethayl sulfonic acid samarium: water, methyl alcohol;
Six hydration Europium chlorides: water, ethanol, methyl alcohol, ethanol, ethylene glycol or isopropyl alcohol;
Six nitric hydrate europiums: water, formic acid, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid or oxolane;
Gadolinium nitrate hexahydrate: water, ethanol, n-butanol, glycerol, DMF or DMA;
Eight hydration Digadolinium trisulfates: water, n-butanol, glycerol or DMF;
Six hydration terbium chlorides: water, methyl alcohol, ethanol, ethylene glycol, isopropyl alcohol, isobutanol, n-butanol, glycerol, DMF or DMA;
Five nitric hydrate terbiums: water, formic acid, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid or nitric acid;
Trifluoromethayl sulfonic acid dysprosium: water, formic acid, oxolane, ethylene glycol or isopropyl alcohol;
Eight hydration sulfuric acid holmiums: water, n-butanol, methyl alcohol, ethanol, ethylene glycol, isopropyl alcohol, glycerol or DMF;
Six hydration holmium chlorides: water, methyl alcohol, ethanol, ethylene glycol, isopropyl alcohol, isobutanol, n-butanol, glycerol, DMF or DMA;
Five nitric hydrate erbiums: water, formic acid, acetic acid, sulfuric acid, hydrochloric acid or oxolane;
Six hydrous thulium chlorides: water, methyl alcohol, ethanol, isopropyl alcohol, isobutanol, n-butanol, glycerol, DMF or DMA;
Eight hydration thulium sulfates: water, n-butanol, glycerol or DMF;
Ytterbium nitrate: water, methyl alcohol, ethanol, isopropyl alcohol, isobutanol, n-butanol, glycerol, DMF or DMA;
Trifluoromethayl sulfonic acid ytterbium: water;
Six hydration lutecium chlorides: water, formic acid, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid or nitric acid;
Eight hydration sulfuric acid lutetiums: water, methyl alcohol, ethanol, ethylene glycol or DMF;
Trifluoromethayl sulfonic acid scandium: water, n-butanol, glycerol or DMF;
Six nitric hydrate yttriums: water, formic acid, acetic acid or DMF.
The preparation method of a kind of flexible rare-earth oxidate nano tunica fibrosa as above, described coupling agent is the one in gamma-aminopropyl-triethoxy-silane, N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane, MTMS, vinyltrimethoxy silane or γ-(methacryloxypropyl) propyl group methyl dimethoxysilane.
The preparation method of a kind of flexible rare-earth oxidate nano tunica fibrosa as above, described surfactant is dodecyl benzyl dimethyl ammonium chloride, neopelex, DDAO, dodecyl-dimethyl amine second lactone, N, the one in N-bis-(2-ethoxy) laurylamide or glycerin polyoxyethylene ether.
The preparation method of a kind of flexible rare-earth oxidate nano tunica fibrosa as above, described electrostatic spinning refers to that described precursor solution is input to the flow velocity of 1-4mL/h on the spinning head of electrospinning device, the high voltage source that simultaneously spinning head is connected to 10-30kV is carried out electrostatic spinning, and the distance between receiving system and spinning head is 10-30cm.
The preparation method of flexible rare-earth oxidate nano tunica fibrosa as above, described calcining refers to that calcining heat progressively rises to 400-700 DEG C from room temperature under air atmosphere, programming rate is 1-10 DEG C/min, and keeps 10-240min under the highest calcining heat.The fibrous inside crystallite dimension obtaining is 1-100nm.
The present invention also proposes a kind of nanometer rare earth oxide fibrous material of preparing by above preparation method, described flexible rare-earth oxidate nano average fibre diameter is that 10nm-500nm and relative standard deviation are 1-5%, described flexible rare-earth oxidate nano tunica fibrosa compact structure and there is good flexibility (fibrous material prepared of electrostatic spinning is textile-like, can use for reference test paper pliability method and characterize its flexibility, flexible standard: pliability 0-80mN is flexible outstanding; Pliability 80-160mN is flexible good, referring to the mensuration of QB 3529-1999 the People's Republic of China light industry standard-tissue, GB/T 8942-2002 National Standard of the People's Republic of China-paper pliability), tunica fibrosa pliability is 10-100mN, and the fibrous inside crystallite dimension of acquisition is 1-100nm.
First the present invention is dissolved in rare earth metal source and a kind of non-rare earth metal salt in solvent, and add successively coupling agent and surfactant to mix, make the precursor solution of stable homogeneous by the chemical reaction between active group or hydrogen bond action, in described precursor solution, there is the tridimensional network strand of IPN; Through calcining organic component spinodal decomposition in precursor fibre, inorganic component is retained, due in fiber taking inorganic component as main body, therefore the skeleton structure that filament is complete in calcination process can not be damaged because of the spinodal decomposition of a large amount of organic components, makes the last nanometer rare earth oxide tunica fibrosa obtaining have good flexibility.
Beneficial effect:
The present invention is by being mixed with rare earth metal source, non-rare earth metal salt, solvent, coupling agent and surfactant the precursor solution of stable homogeneous, and molecules in solution chain has the tridimensional network of IPN.In precursor solution forming process of the present invention, without adding polymer or agingly can obtaining precursor fibre film by electrostatic spinning process, and obtain flexible rare-earth oxidate nano tunica fibrosa through calcining.And inorganic component content is high in precursor fibre film, inorganic fibers productive rate is high.
Brief description of the drawings:
Fig. 1 is the field emission scanning electron microscope photo of flexible lanthana nano fibrous membrane.
Detailed description of the invention
Below in conjunction with detailed description of the invention, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
A preparation method for flexible lanthana nano fibrous membrane, concrete steps are:
The first step: lanthanum nitrate and zirconium acetate are dissolved in water, after stirring 10min, add coupling agent gamma-aminopropyl-triethoxy-silane, after continuing again to stir 5min, add surfactant dodecyl benzyl dimethyl ammonium chloride, wherein the ratio of lanthanum nitrate and water is 10g:10mL, the mol ratio of lanthanum nitrate and zirconium acetate is 100:10, the mol ratio of lanthanum nitrate and coupling agent gamma-aminopropyl-triethoxy-silane is 1:0.02, and the mol ratio of lanthanum nitrate and surfactant dodecyl benzyl dimethyl ammonium chloride is 1:0.01; Mixing the dynamic viscosity of making stable homogeneous is the precursor solution that 1Pas and electrical conductivity are 50mS/m, has the tridimensional network strand of IPN in described precursor solution, and its structural formula is as follows:
Second step: under the condition of 20 DEG C of room temperatures and relative humidity 30%, described precursor solution is carried out to electrostatic spinning, obtain presoma nano fibrous membrane; Described electrostatic spinning refers to that described precursor solution is input to the flow velocity of 1mL/h on the spinning head of electrospinning device, and the high voltage source that simultaneously spinning head is connected to 10kV is carried out electrostatic spinning, and the distance between receiving system and spinning head is 10cm;
The 3rd step: above-mentioned precursor fibre film is calcined under air atmosphere, and described calcining refers to that calcining heat progressively rises to 500 DEG C from room temperature, and programming rate is 1 DEG C/min, and keeps 120min under the highest calcining heat, obtains flexible lanthana nano fibrous membrane.Average fibre diameter in described flexible lanthana nano fibrous membrane is 400nm, and relative standard deviation is 5%, described fibrous inside crystallite dimension is 50nm, described flexible lanthana nanofibrous structures is tight, described flexible lanthana nano fibrous membrane has good flexibility, use for reference test paper pliability method and characterize its flexibility, according to QB 3529-1999 the People's Republic of China light industry standard-tissue, the mensuration of GB/T 8942-2002 National Standard of the People's Republic of China-paper pliability, the pliability that records described flexible lanthana nano fibrous membrane is 100mN.Fig. 1 is the field emission scanning electron microscope photo of the flexible lanthana nanofiber of the present embodiment, and photo shows that lanthana nanofiber has the features such as continuity is good, Fiber Aspect Ratio is large, diameter is even, and filament is without obvious phenomenon of rupture.
Embodiment 2
A preparation method for flexible cerium oxide nano tunica fibrosa, concrete steps are:
The first step: six nitric hydrate ceriums and aluminium isopropoxide are dissolved in to N, in dinethylformamide/water, after stirring 30min, add coupling agent N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane, after continuing again to stir 30min, add surfactant neopelex, wherein six nitric hydrate cerium and N, the ratio of dinethylformamide/water is 10g:50mL, N, the volume ratio of dinethylformamide and water is 1:1, the mol ratio of six nitric hydrate ceriums and aluminium isopropoxide is 100:1, the mol ratio of six nitric hydrate ceriums and coupling agent N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane is 1:0.1, the mol ratio of six nitric hydrate ceriums and surfactant neopelex is 1:0.1, mixing the dynamic viscosity of making stable homogeneous is the precursor solution that 0.1Pas and electrical conductivity are 10mS/m, has the tridimensional network strand of the IPN similar with embodiment 1 in described precursor solution,
Second step: under the condition of 28 DEG C of room temperatures and relative humidity 30%, above-mentioned precursor solution is carried out to electrostatic spinning, obtain presoma nano fibrous membrane; Described electrostatic spinning refers to that described precursor solution is input to the flow velocity of 1mL/h on the spinning head of electrospinning device, and the high voltage source that simultaneously spinning head is connected to 10kV is carried out electrostatic spinning, and the distance between receiving system and spinning head is 30cm;
The 3rd step: above-mentioned precursor fibre film is calcined under air atmosphere, and described calcining refers to that calcining heat progressively rises to 800 DEG C from room temperature, and programming rate is 10 DEG C/min, and keeps 60min under the highest calcining heat, obtains flexible cerium oxide nano tunica fibrosa.Average fibre diameter in described flexible cerium oxide nano tunica fibrosa is 10nm, and relative standard deviation is 4%, described fibrous inside crystallite dimension is 1nm, described flexible cerium oxide nano fibre structure is tight, described flexible cerium oxide nano tunica fibrosa has good flexibility, use for reference test paper pliability method and characterize its flexibility, according to QB 3529-1999 the People's Republic of China light industry standard-tissue, the mensuration of GB/T 8942-2002 National Standard of the People's Republic of China-paper pliability, the pliability that records described flexible cerium oxide nano tunica fibrosa is 100mN.
Embodiment 3
A preparation method for flexible praseodymium oxide nano fibrous membrane, concrete steps are:
The first step: six nitric hydrate praseodymiums and copper acetate dihydrate are dissolved in to water/N, in dinethylformamide, after stirring 60min, add coupling agent MTMS, after continuing again to stir 15min, add surfactant DDAO, wherein six nitric hydrate praseodymium and water/N, the ratio of dinethylformamide is 10g:50mL, water and N, the volume ratio of dinethylformamide is 1:1, the mol ratio of six nitric hydrate praseodymiums and copper acetate dihydrate is 100:3, the mol ratio of six nitric hydrate praseodymiums and coupling agent MTMS is 1:0.05, the mol ratio of six nitric hydrate praseodymiums and surfactant DDAO is 1:0.05, mixing the dynamic viscosity of making stable homogeneous is the precursor solution that 0.5Pas and electrical conductivity are 20mS/m, has the tridimensional network strand of the IPN similar with embodiment 1 in described precursor solution,
Second step: under the condition of 27 DEG C of room temperatures and relative humidity 40%, above-mentioned precursor solution is carried out to electrostatic spinning, obtain presoma nano fibrous membrane; Described electrostatic spinning refers to that described precursor solution is input to the flow velocity of 2mL/h on the spinning head of electrospinning device, and the high voltage source that simultaneously spinning head is connected to 20kV is carried out electrostatic spinning, and the distance between receiving system and spinning head is 15cm;
The 3rd step: above-mentioned precursor fibre film is calcined under air atmosphere, and described calcining refers to that calcining heat progressively rises to 600 DEG C from room temperature, and programming rate is 5 DEG C/min, and keeps 10min under the highest calcining heat, obtains flexible praseodymium oxide nano fibrous membrane.Average fibre diameter in described flexible praseodymium oxide nano fibrous membrane is 200nm, and relative standard deviation is 3%, described fibrous inside crystallite dimension is 30nm, described flexible praseodymium oxide nanofibrous structures is tight, described flexible praseodymium oxide nano fibrous membrane has good flexibility, use for reference test paper pliability method and characterize its flexibility, according to QB 3529-1999 the People's Republic of China light industry standard-tissue, the mensuration of GB/T 8942-2002 National Standard of the People's Republic of China-paper pliability, the pliability that records described flexible praseodymium oxide nano fibrous membrane is 30mN.
Embodiment 4
A preparation method for flexible neodymia nano fibrous membrane, concrete steps are:
The first step: six nitric hydrate neodymiums and butyl titanate are dissolved in to N, in dinethylformamide, after stirring 30min, add coupling agent vinyltrimethoxy silane, after continuing again to stir 15min, add surfactant dodecyl-dimethyl amine second lactone, wherein six nitric hydrate neodymium and N, the ratio of dinethylformamide is 10g:20mL, the mol ratio of six nitric hydrate neodymiums and butyl titanate is 100:3, the mol ratio of six nitric hydrate neodymiums and coupling agent vinyltrimethoxy silane is 1:0.06, the mol ratio of six nitric hydrate neodymiums and surfactant dodecyl-dimethyl amine second lactone is 1:0.05, mixing the dynamic viscosity of making stable homogeneous is the precursor solution that 0.5Pas and electrical conductivity are 20mS/m, has the tridimensional network strand of the IPN similar with embodiment 1 in described precursor solution,
Second step: under the condition of 27 DEG C of room temperatures and relative humidity 50%, above-mentioned precursor solution is carried out to electrostatic spinning, obtain presoma nano fibrous membrane; Described electrostatic spinning refers to that described precursor solution is input to the flow velocity of 2mL/h on the spinning head of electrospinning device, and the high voltage source that simultaneously spinning head is connected to 25kV is carried out electrostatic spinning, and the distance between receiving system and spinning head is 18cm;
The 3rd step: above-mentioned precursor fibre film is calcined under air atmosphere, described calcining refers to that calcining heat progressively rises to 600 DEG C from room temperature, programming rate is 5 DEG C/min, and under the highest calcining heat, keeps 180min, obtains flexible neodymia nano fibrous membrane.Average fibre diameter in described flexible neodymia nano fibrous membrane is 400nm, and relative standard deviation is 5%, described fibrous inside crystallite dimension is 50nm, described flexible neodymia nanofibrous structures is tight, described flexible neodymia nano fibrous membrane has good flexibility, use for reference test paper pliability method and characterize its flexibility, according to QB 3529-1999 the People's Republic of China light industry standard-tissue, the mensuration of GB/T 8942-2002 National Standard of the People's Republic of China-paper pliability, the pliability that records described flexible neodymia nano fibrous membrane is 53mN.
Embodiment 5
A preparation method for flexible samarium oxide nano fibrous membrane, concrete steps are:
The first step: six nitric hydrate samariums and butter of tin are dissolved in to N, in N-dimethylacetylamide/ethanol, after stirring 30min, add coupling agent γ-(methacryloxypropyl) propyl group methyl dimethoxysilane, after continuing again to stir 15min, add surfactant N, N-bis-(2-ethoxy) laurylamide, wherein six nitric hydrate samarium and N, the ratio of N-dimethylacetylamide/ethanol is 10g:20mL, N, the volume ratio of N-dimethylacetylamide and ethanol is 2:1, the mol ratio of six nitric hydrate samariums and butter of tin is 100:5, the mol ratio of six nitric hydrate samariums and coupling agent γ-(methacryloxypropyl) propyl group methyl dimethoxysilane is 1:0.06, six nitric hydrate samariums and surfactant N, the mol ratio of N-bis-(2-ethoxy) laurylamide is 1:0.05, mixing the dynamic viscosity of making stable homogeneous is the precursor solution that 0.5Pas and electrical conductivity are 30mS/m, has the tridimensional network strand of the IPN similar with embodiment 1 in described precursor solution,
Second step: under the condition of 22 DEG C of room temperatures and relative humidity 43%, above-mentioned precursor solution is carried out to electrostatic spinning, obtain presoma nano fibrous membrane; Described electrostatic spinning refers to that described precursor solution is input to the flow velocity of 2mL/h on the spinning head of electrospinning device, and the high voltage source that simultaneously spinning head is connected to 25kV is carried out electrostatic spinning, and the distance between receiving system and spinning head is 20cm;
The 3rd step: above-mentioned precursor fibre film is calcined under air atmosphere, and described calcining refers to that calcining heat progressively rises to 600 DEG C from room temperature, and programming rate is 5 DEG C/min, and keeps 30min under the highest calcining heat, obtains flexible samarium oxide nano fibrous membrane.Average fibre diameter in described flexible samarium oxide nano fibrous membrane is 500nm, and relative standard deviation is 2%, described fibrous inside crystallite dimension is 60nm, described flexible samarium oxide nanofibrous structures is tight, described flexible samarium oxide nano fibrous membrane has good flexibility, use for reference test paper pliability method and characterize its flexibility, according to QB 3529-1999 the People's Republic of China light industry standard-tissue, the mensuration of GB/T 8942-2002 National Standard of the People's Republic of China-paper pliability, the pliability that records described flexible samarium oxide nano fibrous membrane is 65mN.
Embodiment 6
A preparation method for flexible europium oxide nano fibrous membrane, concrete steps are:
The first step: six hydration Europium chlorides and trichloride antimony are dissolved in to N, in dinethylformamide/ethanol, after stirring 30min, add coupling agent gamma-aminopropyl-triethoxy-silane, after continuing again to stir 15min, add surfactant N, N-bis-(2-ethoxy) laurylamide, wherein six hydration Europium chloride and N, the ratio of dinethylformamide/ethanol is 10g:20mL, N, the volume ratio of dinethylformamide and ethanol is 2:1, the mol ratio of six hydration Europium chlorides and trichloride antimony is 100:5, the mol ratio of six hydration Europium chlorides and coupling agent gamma-aminopropyl-triethoxy-silane is 1:0.06, six hydration Europium chlorides and surfactant N, the mol ratio of N-bis-(2-ethoxy) laurylamide is 1:0.05, mixing the dynamic viscosity of making stable homogeneous is the precursor solution that 0.5Pas and electrical conductivity are 30mS/m, has the tridimensional network strand of the IPN similar with embodiment 1 in described precursor solution,
Second step: under the condition of 24 DEG C of room temperatures and relative humidity 48%, above-mentioned precursor solution is carried out to electrostatic spinning, obtain presoma nano fibrous membrane; Described electrostatic spinning refers to that described precursor solution is input to the flow velocity of 2mL/h on the spinning head of electrospinning device, and the high voltage source that simultaneously spinning head is connected to 25kV is carried out electrostatic spinning, and the distance between receiving system and spinning head is 20cm;
The 3rd step: above-mentioned precursor fibre film is calcined under air atmosphere, described calcining refers to that calcining heat progressively rises to 600 DEG C from room temperature, programming rate is 8 DEG C/min, and under the highest calcining heat, keeps 120min, obtains flexible europium oxide nano fibrous membrane.Average fibre diameter in described flexible europium oxide nano fibrous membrane is 300nm, and relative standard deviation is 1%, described fibrous inside crystallite dimension is 30nm, described flexible europium oxide nanofibrous structures is tight, described flexible europium oxide nano fibrous membrane has good flexibility, use for reference test paper pliability method and characterize its flexibility, according to QB 3529-1999 the People's Republic of China light industry standard-tissue, the mensuration of GB/T 8942-2002 National Standard of the People's Republic of China-paper pliability, the pliability that records described flexible europium oxide nano fibrous membrane is 55mN.
Embodiment 7
A preparation method for flexible gadolinium oxide nano fibrous membrane, concrete steps are:
The first step: gadolinium nitrate hexahydrate and Cobalt monosulfate heptahydrate are dissolved in isopropanol/water, after stirring 30min, add coupling agent gamma-aminopropyl-triethoxy-silane, after continuing again to stir 15min, add surfactant N, N-bis-(2-ethoxy) laurylamide, wherein the ratio of gadolinium nitrate hexahydrate and isopropanol/water is 10g:20mL, the volume ratio of isopropyl alcohol and water is 2:1, the mol ratio of gadolinium nitrate hexahydrate and Cobalt monosulfate heptahydrate is 100:5, the mol ratio of gadolinium nitrate hexahydrate and coupling agent gamma-aminopropyl-triethoxy-silane is 1:0.06, gadolinium nitrate hexahydrate and surfactant N, the mol ratio of N-bis-(2-ethoxy) laurylamide is 1:0.05, mixing the dynamic viscosity of making stable homogeneous is the precursor solution that 0.5Pas and electrical conductivity are 30mS/m, has the tridimensional network strand of the IPN similar with embodiment 1 in described precursor solution,
Second step: under the condition of 20 DEG C of room temperatures and relative humidity 47%, above-mentioned precursor solution is carried out to electrostatic spinning, obtain presoma nano fibrous membrane; Described electrostatic spinning refers to that described precursor solution is input to the flow velocity of 2mL/h on the spinning head of electrospinning device, and the high voltage source that simultaneously spinning head is connected to 25kV is carried out electrostatic spinning, and the distance between receiving system and spinning head is 20cm;
The 3rd step: above-mentioned precursor fibre film is calcined under air atmosphere, described calcining refers to that calcining heat progressively rises to 600 DEG C from room temperature, programming rate is 10 DEG C/min, and under the highest calcining heat, keeps 50min, obtains flexible gadolinium oxide nano fibrous membrane.Average fibre diameter in described flexible gadolinium oxide nano fibrous membrane is 350n, and relative standard deviation is 5%, described fibrous inside crystallite dimension is 40nm, described flexible gadolinium oxide nanofibrous structures is tight, described flexible gadolinium oxide nano fibrous membrane has good flexibility, use for reference test paper pliability method and characterize its flexibility, according to QB 3529-1999 the People's Republic of China light industry standard-tissue, the mensuration of GB/T 8942-2002 National Standard of the People's Republic of China-paper pliability, the pliability that records described flexible gadolinium oxide nano fibrous membrane is 70mN.
Embodiment 8
A preparation method for flexible terbium oxide nano fibrous membrane, concrete steps are:
The first step: five nitric hydrate terbiums and Chromium nitrate (Cr(NO3)3),nonahydrate are dissolved in to N, in dinethylformamide/formic acid, after stirring 30min, add coupling agent gamma-aminopropyl-triethoxy-silane, after continuing again to stir 15min, add surfactant glycerin polyoxyethylene ether, wherein five nitric hydrate terbium and N, the ratio of dinethylformamide/formic acid is 10g:20mL, the mass ratio of five nitric hydrate terbiums and Fe(NO3)39H2O is 1:1, N, the volume ratio of dinethylformamide and formic acid is 3:1, the mol ratio of five nitric hydrate terbiums and Chromium nitrate (Cr(NO3)3),nonahydrate is 100:5, the mol ratio of five nitric hydrate terbiums and coupling agent gamma-aminopropyl-triethoxy-silane is 1:0.06, the mol ratio of five nitric hydrate terbiums and surfactant glycerin polyoxyethylene ether is 1:0.05, mixing the dynamic viscosity of making stable homogeneous is the precursor solution that 0.5Pas and electrical conductivity are 30mS/m, has the tridimensional network strand of the IPN similar with embodiment 1 in described precursor solution,
Second step: under the condition of 25 DEG C of room temperatures and relative humidity 45%, above-mentioned precursor solution is carried out to electrostatic spinning, obtain presoma nano fibrous membrane; Described electrostatic spinning refers to that described precursor solution is input to the flow velocity of 2mL/h on the spinning head of electrospinning device, and the high voltage source that simultaneously spinning head is connected to 25kV is carried out electrostatic spinning, and the distance between receiving system and spinning head is 20cm;
The 3rd step: above-mentioned precursor fibre film is calcined under air atmosphere, described calcining refers to that calcining heat progressively rises to 600 DEG C from room temperature, programming rate is 10 DEG C/min, and under the highest calcining heat, keeps 90min, obtains flexible terbium oxide nano fibrous membrane.Average fibre diameter in described flexible terbium oxide nano fibrous membrane is 200nm, and relative standard deviation is 4%, described fibrous inside crystallite dimension is 55nm, described flexible terbium oxide nanofibrous structures is tight, described flexible terbium oxide nano fibrous membrane has good flexibility, use for reference test paper pliability method and characterize its flexibility, according to QB 3529-1999 the People's Republic of China light industry standard-tissue, the mensuration of GB/T 8942-2002 National Standard of the People's Republic of China-paper pliability, the pliability that records described flexible terbium oxide nano fibrous membrane is 70mN.
Embodiment 9
A preparation method for flexible dysprosia nano fibrous membrane, concrete steps are:
The first step: trifluoromethayl sulfonic acid dysprosium and manganese acetate are dissolved in water, after stirring 30min, add coupling agent N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane, after continuing again to stir 20min, add surfactant N, N-bis-(2-ethoxy) laurylamide, wherein the ratio of trifluoromethayl sulfonic acid dysprosium and water is 10g:50mL, the mol ratio of trifluoromethayl sulfonic acid dysprosium and manganese acetate is 100:5, the mol ratio of trifluoromethayl sulfonic acid dysprosium and coupling agent N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane is 1:0.06, trifluoromethayl sulfonic acid dysprosium and surfactant N, the mol ratio of N-bis-(2-ethoxy) laurylamide is 1:0.05, mixing the dynamic viscosity of making stable homogeneous is the precursor solution that 0.3Pas and electrical conductivity are 23mS/m, has the tridimensional network strand of the IPN similar with embodiment 1 in described precursor solution,
Second step: under the condition of 25 DEG C of room temperatures and relative humidity 50%, above-mentioned precursor solution is carried out to electrostatic spinning, obtain presoma nano fibrous membrane; Described electrostatic spinning refers to that described precursor solution is input to the flow velocity of 3mL/h on the spinning head of electrospinning device, and the high voltage source that simultaneously spinning head is connected to 25kV is carried out electrostatic spinning, and the distance between receiving system and spinning head is 20cm;
The 3rd step: above-mentioned precursor fibre film is calcined under air atmosphere, and described calcining refers to that calcining heat progressively rises to 600 DEG C from room temperature, and programming rate is 8 DEG C/min, and keeps 60min under the highest calcining heat, obtains flexible dysprosia nano fibrous membrane.Average fibre diameter in described flexible dysprosia nano fibrous membrane is 450nm, and relative standard deviation is 2%, described fibrous inside crystallite dimension is 65nm, described flexible dysprosia nanofibrous structures is tight, described flexible dysprosia nano fibrous membrane has good flexibility, use for reference test paper pliability method and characterize its flexibility, according to QB 3529-1999 the People's Republic of China light industry standard-tissue, the mensuration of GB/T 8942-2002 National Standard of the People's Republic of China-paper pliability, the pliability that records described flexible ferric oxide nano tunica fibrosa is 60mN.
Embodiment 10
A preparation method for flexible holimium oxide nano fibrous membrane, concrete steps are:
The first step: eight hydration sulfuric acid holmiums and zinc acetylacetonate are dissolved in water, after stirring 30min, add coupling agent gamma-aminopropyl-triethoxy-silane, after continuing again to stir 20min, add surfactant N, N-bis-(2-ethoxy) laurylamide, wherein the ratio of eight hydration sulfuric acid holmiums and water is 10g:30mL, the mol ratio of eight hydration sulfuric acid holmiums and zinc acetylacetonate is 100:4, the mol ratio of eight hydration sulfuric acid holmiums and coupling agent gamma-aminopropyl-triethoxy-silane is 1:0.07, eight hydration sulfuric acid holmiums and surfactant N, the mol ratio of N-bis-(2-ethoxy) laurylamide is 1:0.03, mixing the dynamic viscosity of making stable homogeneous is the precursor solution that 0.5Pas and electrical conductivity are 23mS/m, has the tridimensional network strand of the IPN similar with embodiment 1 in described precursor solution,
Second step: under the condition of 26 DEG C of room temperatures and relative humidity 40%, above-mentioned precursor solution is carried out to electrostatic spinning, obtain presoma nano fibrous membrane; Described electrostatic spinning refers to that described precursor solution is input to the flow velocity of 2mL/h on the spinning head of electrospinning device, and the high voltage source that simultaneously spinning head is connected to 30kV is carried out electrostatic spinning, and the distance between receiving system and spinning head is 25cm;
The 3rd step: above-mentioned precursor fibre film is calcined under air atmosphere, described calcining refers to that calcining heat progressively rises to 600 DEG C from room temperature, programming rate is 5 DEG C/min, and under the highest calcining heat, keeps 240min, obtains flexible holimium oxide nano fibrous membrane.Average fibre diameter in described flexible holimium oxide nano fibrous membrane is 380nm, and relative standard deviation is 4%, described fibrous inside crystallite dimension is 40nm, described flexible holimium oxide nanofibrous structures is tight, described flexible holimium oxide nano fibrous membrane has good flexibility, use for reference test paper pliability method and characterize its flexibility, according to QB 3529-1999 the People's Republic of China light industry standard-tissue, the mensuration of GB/T 8942-2002 National Standard of the People's Republic of China-paper pliability, the pliability that records described flexible holimium oxide nano fibrous membrane is 50mN.
Embodiment 11
A preparation method for flexible erbium oxide nano fibrous membrane, concrete steps are:
The first step: five nitric hydrate erbiums and copper acetate dihydrate are dissolved in formic acid, after stirring 30min, add coupling agent N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane, after continuing again to stir 30min, add surfactant neopelex, wherein the ratio of five nitric hydrate erbiums and formic acid is 10g:50mL, the mol ratio of five nitric hydrate erbiums and copper acetate dihydrate is 100:1, the mol ratio of five nitric hydrate erbiums and coupling agent N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane is 1:0.1, the mol ratio of five nitric hydrate erbiums and surfactant neopelex is 1:0.1, mixing the dynamic viscosity of making stable homogeneous is 0.1Pas, and the electrical conductivity precursor solution that is 10mS/m, has the tridimensional network strand of the IPN similar with embodiment 1 in described precursor solution,
Second step: under the condition of 28 DEG C of room temperatures and relative humidity 30%, above-mentioned precursor solution is carried out to electrostatic spinning, obtain presoma nano fibrous membrane; Described electrostatic spinning refers to that described precursor solution is input to the flow velocity of 1mL/h on the spinning head of electrospinning device, and the high voltage source that simultaneously spinning head is connected to 10kV is carried out electrostatic spinning, and the distance between receiving system and spinning head is 30cm;
The 3rd step: above-mentioned precursor fibre film is calcined under air atmosphere, described calcining refers to that calcining heat progressively rises to 800 DEG C from room temperature, programming rate is 10 DEG C/min, and under the highest calcining heat, keeps 120min, obtains flexible erbium oxide nano fibrous membrane.Average fibre diameter in described flexible erbium oxide nano fibrous membrane is 100nm, and relative standard deviation is 5%, described fibrous inside crystallite dimension is 10nm, described flexible erbium oxide nanofibrous structures is tight, described flexible erbium oxide nano fibrous membrane has good flexibility, use for reference test paper pliability method and characterize its flexibility, according to QB 3529-1999 the People's Republic of China light industry standard-tissue, the mensuration of GB/T 8942-2002 National Standard of the People's Republic of China-paper pliability, the pliability that records described flexible erbium oxide nano fibrous membrane is 20mN.
Embodiment 12-41
Embodiment 12-41 preparation process is with embodiment 1, and wherein precursor solution parameter, technological parameter and flexible inorganic fibrous material performance parameter are as table (note: mixing time 1-source metal is dissolved in solvent, adds coupling agent after stirring 10-60min; Mixing time 2-continue to add surfactant after stirring 5-30min)
Claims (10)
1. a preparation method for flexible rare-earth oxidate nano tunica fibrosa, is characterized in that, concrete steps are:
The first step: rare earth metal source and a kind of non-rare earth metal salt are dissolved in solvent, after stirring 10-60min, add coupling agent, after continuing again to stir 5-30min, add surfactant, mix the precursor solution of making stable homogeneous, in described precursor solution, there is the strand of IPN tridimensional network;
Second step: under the condition of 20-28 DEG C and relative humidity 30-60%, above-mentioned precursor solution is carried out to electrostatic spinning, obtain
Obtain precursor fibre film;
The 3rd step: described precursor fibre film is calcined under air atmosphere, obtained flexible rare-earth oxidate nano tunica fibrosa.
2. the preparation method of a kind of flexible rare-earth oxidate nano tunica fibrosa according to claim 1, it is characterized in that, in the described first step, the ratio of rare earth metal source and solvent is 10g:10-30mL, the mol ratio of rare earth metal source and non-rare earth metal salt is 100:1-10, the mol ratio of rare earth metal source and coupling agent is 1:0.02-0.1, and the mol ratio of rare earth metal source and surfactant is 1:0.01-0.1; Described stirring refers at room temperature uses magnetic stirrer 10-60min; Described lasting stirring again refers at room temperature uses magnetic stirrer 5-30min; The dynamic viscosity of described precursor solution is 0.1-1Pas, and electrical conductivity is 10-50mS/m.
3. the preparation method of a kind of flexible rare-earth oxidate nano tunica fibrosa according to claim 1, it is characterized in that, in described second step, described electrostatic spinning refers to that described precursor solution is input to the flow velocity of 1-4mL/h on the spinning head of electrospinning device, the high voltage source that simultaneously spinning head is connected to 10-30kV is carried out electrostatic spinning, and the distance between receiving system and spinning head is 10-30cm.
4. the preparation method of a kind of flexible rare-earth oxidate nano tunica fibrosa according to claim 1, it is characterized in that, in the 3rd described step, described calcining refers to that calcining heat progressively rises to 400-700 DEG C from room temperature, programming rate is 1-10 DEG C/min, and keeps 10-240min under the highest calcining heat.
5. the preparation method of a kind of flexible rare-earth oxidate nano tunica fibrosa according to claim 1, it is characterized in that the one in Wei Lan source, described rare earth metal source, cerium source, praseodymium source, neodymium source, samarium source, europium source, gadolinium source, terbium source, dysprosium source, holmium source, erbium source, thulium source, ytterbium source, lutetium source, Huo Yi source, scandium source;
Lanthanum source: lanthanum nitrate, lanthanum hydroxide, lanthanum acetate, lanthanum chloride or acetylacetone,2,4-pentanedione lanthanum;
Cerium source: six nitric hydrate ceriums, cerous carbonate, cerium hydroxide or cerous acetate;
Praseodymium source: six nitric hydrate praseodymiums or eight hydration praseodymium sulfates;
Neodymium source: six nitric hydrate neodymiums, acetic acid neodymium or eight hydration Dineodymium trisulfates;
Samarium source: six nitric hydrate samariums or trifluoromethayl sulfonic acid samarium;
Europium source: six hydration Europium chlorides or six nitric hydrate europiums;
Gadolinium source: gadolinium nitrate hexahydrate or eight hydration Digadolinium trisulfates;
Terbium source: six hydration terbium chlorides or five nitric hydrate terbiums;
Dysprosium source: trifluoromethayl sulfonic acid dysprosium;
Holmium source: eight hydration sulfuric acid holmiums or six hydration holmium chlorides;
Erbium source: five nitric hydrate erbiums;
Thulium source: six hydrous thulium chlorides or eight hydration thulium sulfates;
Ytterbium source: ytterbium nitrate or trifluoromethayl sulfonic acid ytterbium;
Lutetium source: six hydration lutecium chlorides or eight hydration sulfuric acid lutetiums;
Scandium source: trifluoromethayl sulfonic acid scandium;
Yttrium source: six nitric hydrate yttriums.
6. the preparation method of a kind of flexible rare-earth oxidate nano tunica fibrosa according to claim 1, is characterized in that, described non-rare earth metal salt refers to:
Zirconates is zirconyl nitrate, chlorine hydrate zirconia, acetylacetone,2,4-pentanedione zirconium or zirconium acetate;
Aluminium salt is aluminium isopropoxide, ANN aluminium nitrate nonahydrate, Aluminium chloride hexahydrate or aluminium acetylacetonate;
Titanium salt is butyl titanate, isopropyl titanate or tetraethyl titanate;
Pink salt is two hydrated stannous chlorides, butter of tin or stannous sulfate;
Antimonic salt is Antimony pentachloride, trichloride antimony or antimony acetate;
Manganese salt is manganese acetylacetonate, manganese chloride, manganese acetate or four hydration manganese chlorides;
Molysite is ferric acetyl acetonade, Iron(III) chloride hexahydrate;
Cobalt salt is cobalt acetate, Cobalt monosulfate heptahydrate, acetylacetone cobalt or cabaltous nitrate hexahydrate;
Mantoquita is copper acetate dihydrate, Gerhardite or Salzburg vitriol;
Chromic salts is chromium acetate or Chromium nitrate (Cr(NO3)3),nonahydrate;
Zinc salt is zinc chloride, zinc acetylacetonate or two hydration zinc acetates.
7. the preparation method of a kind of flexible rare-earth oxidate nano fiber according to claim 1, is characterized in that, described solvent corresponds to respectively according to rare earth metal source:
Lanthanum nitrate: water, methyl alcohol, ethanol, isopropyl alcohol, glycerol or DMF;
Lanthanum hydroxide: DMF, formic acid, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid or nitric acid;
Lanthanum acetate: water, glycerol or DMF;
Lanthanum chloride: water, ethanol, pyridine or DMF;
Acetylacetone,2,4-pentanedione lanthanum: methyl alcohol, ethanol, ethylene glycol, isopropyl alcohol, DMF, DMA, acetic acid or oxolane;
Six nitric hydrate ceriums: water, methyl alcohol, ethanol, isopropyl alcohol, isobutanol, n-butanol, ethylene glycol or glycerol;
Cerous carbonate: phosphoric acid, sulfuric acid, hydrochloric acid or nitric acid;
Cerium hydroxide: formic acid, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid or nitric acid;
Cerous acetate: water, isobutanol or DMF;
Six nitric hydrate praseodymiums: water, methyl alcohol, ethanol, n-butanol, glycerol, DMF or DMA;
Eight hydration praseodymium sulfates: water, n-butanol, glycerol or DMF;
Six nitric hydrate neodymiums: water, methyl alcohol, ethanol, ethylene glycol, isopropyl alcohol, isobutanol, n-butanol, glycerol, DMF or DMA;
Acetic acid neodymium: water, methyl alcohol, acetone, isobutanol, n-butanol, glycerol, DMF or DMA;
Eight hydration Dineodymium trisulfates: water, formic acid, methyl alcohol, acetic acid, sulfuric acid, hydrochloric acid or nitric acid;
Six nitric hydrate samariums: water, ethylene glycol, isopropyl alcohol, isobutanol, DMF or DMA;
Trifluoromethayl sulfonic acid samarium: water, methyl alcohol;
Six hydration Europium chlorides: water, ethanol, methyl alcohol, ethanol, ethylene glycol or isopropyl alcohol;
Six nitric hydrate europiums: water, formic acid, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid or oxolane;
Gadolinium nitrate hexahydrate: water, ethanol, n-butanol, glycerol, DMF or DMA;
Eight hydration Digadolinium trisulfates: water, n-butanol, glycerol or DMF;
Six hydration terbium chlorides: water, methyl alcohol, ethanol, ethylene glycol, isopropyl alcohol, isobutanol, n-butanol, glycerol, DMF or DMA;
Five nitric hydrate terbiums: water, formic acid, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid or nitric acid;
Trifluoromethayl sulfonic acid dysprosium: water, formic acid, oxolane, ethylene glycol or isopropyl alcohol;
Eight hydration sulfuric acid holmiums: water, n-butanol, methyl alcohol, ethanol, ethylene glycol, isopropyl alcohol, glycerol or DMF;
Six hydration holmium chlorides: water, methyl alcohol, ethanol, ethylene glycol, isopropyl alcohol, isobutanol, n-butanol, glycerol, DMF or DMA;
Five nitric hydrate erbiums: water, formic acid, acetic acid, sulfuric acid, hydrochloric acid or oxolane;
Six hydrous thulium chlorides: water, methyl alcohol, ethanol, isopropyl alcohol, isobutanol, n-butanol, glycerol, DMF or DMA;
Eight hydration thulium sulfates: water, n-butanol, glycerol or DMF;
Ytterbium nitrate: water, methyl alcohol, ethanol, isopropyl alcohol, isobutanol, n-butanol, glycerol, DMF or DMA;
Trifluoromethayl sulfonic acid ytterbium: water;
Six hydration lutecium chlorides: water, formic acid, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid or nitric acid;
Eight hydration sulfuric acid lutetiums: water, methyl alcohol, ethanol, ethylene glycol or DMF;
Trifluoromethayl sulfonic acid scandium: water, n-butanol, glycerol or DMF;
Six nitric hydrate yttriums: water, formic acid, acetic acid or DMF.
8. the preparation method of a kind of flexible rare-earth oxidate nano tunica fibrosa according to claim 1, it is characterized in that, described coupling agent is the one in gamma-aminopropyl-triethoxy-silane, N-β-aminoethyl-γ-aminopropyl methyl dimethoxysilane, MTMS, vinyltrimethoxy silane or γ-(methacryloxypropyl) propyl group methyl dimethoxysilane.
9. the preparation method of a kind of flexible rare-earth oxidate nano tunica fibrosa according to claim 1, it is characterized in that, described surfactant is dodecyl benzyl dimethyl ammonium chloride, cetyl pyridinium bromide, neopelex, CSL, DDAO, dodecyl-dimethyl amine second lactone, N, the one in N-bis-(2-ethoxy) laurylamide or glycerin polyoxyethylene ether.
10. the flexible rare-earth oxidate nano tunica fibrosa of preparing according to method described in any one in claim 1-9, it is characterized in that, described flexible rare-earth oxidate nano average fibre diameter is 10nm-500nm, and relative standard deviation is 1-5%, described flexible rare-earth oxidate nano tunica fibrosa pliability is 10-100mN, and the fibrous inside crystallite dimension of acquisition is 1-100nm.
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