WO2011090279A2 - Porous films comprising carbon nanostructure-metal composite and method of manufacturing the same - Google Patents
Porous films comprising carbon nanostructure-metal composite and method of manufacturing the same Download PDFInfo
- Publication number
- WO2011090279A2 WO2011090279A2 PCT/KR2011/000021 KR2011000021W WO2011090279A2 WO 2011090279 A2 WO2011090279 A2 WO 2011090279A2 KR 2011000021 W KR2011000021 W KR 2011000021W WO 2011090279 A2 WO2011090279 A2 WO 2011090279A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbon nanostructure
- metal composite
- porous films
- metal
- carbon
- Prior art date
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 131
- 239000002905 metal composite material Substances 0.000 title claims abstract description 113
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 239000012528 membrane Substances 0.000 claims abstract description 71
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- 239000002717 carbon nanostructure Substances 0.000 claims abstract description 27
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 229910052709 silver Inorganic materials 0.000 claims description 35
- 239000004332 silver Substances 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- -1 glycol ethers Chemical class 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 238000009832 plasma treatment Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 10
- 230000002829 reductive effect Effects 0.000 claims description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000002334 glycols Chemical class 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000002079 double walled nanotube Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002048 multi walled nanotube Substances 0.000 claims description 3
- 239000002116 nanohorn Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000002109 single walled nanotube Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 2
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- UNXHWFMMPAWVPI-QWWZWVQMSA-N D-threitol Chemical compound OC[C@@H](O)[C@H](O)CO UNXHWFMMPAWVPI-QWWZWVQMSA-N 0.000 claims description 2
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229930195725 Mannitol Natural products 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 230000004888 barrier function Effects 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- FBPFZTCFMRRESA-GUCUJZIJSA-N galactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-GUCUJZIJSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 230000005660 hydrophilic surface Effects 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 6
- 244000005700 microbiome Species 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000001471 micro-filtration Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920000151 polyglycol Polymers 0.000 description 3
- 239000010695 polyglycol Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- HOVAGTYPODGVJG-UVSYOFPXSA-N (3s,5r)-2-(hydroxymethyl)-6-methoxyoxane-3,4,5-triol Chemical compound COC1OC(CO)[C@@H](O)C(O)[C@H]1O HOVAGTYPODGVJG-UVSYOFPXSA-N 0.000 description 1
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 description 1
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [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 description 1
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 description 1
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- MZQZXSHFWDHNOW-UHFFFAOYSA-N 1-phenylpropane-1,2-diol Chemical compound CC(O)C(O)C1=CC=CC=C1 MZQZXSHFWDHNOW-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- ZUAURMBNZUCEAF-UHFFFAOYSA-N 2-(2-phenoxyethoxy)ethanol Chemical compound OCCOCCOC1=CC=CC=C1 ZUAURMBNZUCEAF-UHFFFAOYSA-N 0.000 description 1
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- CTXGTHVAWRBISV-UHFFFAOYSA-N 2-hydroxyethyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCO CTXGTHVAWRBISV-UHFFFAOYSA-N 0.000 description 1
- BHIZVZJETFVJMJ-UHFFFAOYSA-N 2-hydroxypropyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCC(C)O BHIZVZJETFVJMJ-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 description 1
- AGNTUZCMJBTHOG-UHFFFAOYSA-N 3-[3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy]propane-1,2-diol Chemical compound OCC(O)COCC(O)COCC(O)CO AGNTUZCMJBTHOG-UHFFFAOYSA-N 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- CCTFMNIEFHGTDU-UHFFFAOYSA-N 3-methoxypropyl acetate Chemical compound COCCCOC(C)=O CCTFMNIEFHGTDU-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000005441 aurora Substances 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- VUVZASHBYYMLRC-UHFFFAOYSA-N heptane-2,3-diol Chemical compound CCCCC(O)C(C)O VUVZASHBYYMLRC-UHFFFAOYSA-N 0.000 description 1
- QCIYAEYRVFUFAP-UHFFFAOYSA-N hexane-2,3-diol Chemical compound CCCC(O)C(C)O QCIYAEYRVFUFAP-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- HOVAGTYPODGVJG-UHFFFAOYSA-N methyl beta-galactoside Natural products COC1OC(CO)C(O)C(O)C1O HOVAGTYPODGVJG-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- HEGSGKPQLMEBJL-RKQHYHRCSA-N octyl beta-D-glucopyranoside Chemical compound CCCCCCCCO[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O HEGSGKPQLMEBJL-RKQHYHRCSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 239000000249 polyoxyethylene sorbitan monopalmitate Substances 0.000 description 1
- 235000010483 polyoxyethylene sorbitan monopalmitate Nutrition 0.000 description 1
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 description 1
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229940026235 propylene glycol monolaurate Drugs 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- CHACQUSVOVNARW-LNKPDPKZSA-M silver;(z)-4-oxopent-2-en-2-olate Chemical compound [Ag+].C\C([O-])=C\C(C)=O CHACQUSVOVNARW-LNKPDPKZSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- AKMXMQQXGXKHAN-UHFFFAOYSA-N titanium;hydrate Chemical compound O.[Ti] AKMXMQQXGXKHAN-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 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 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
- B01D71/0212—Carbon nanotubes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
- B01D67/00411—Inorganic membrane manufacture by agglomeration of particles in the dry state by sintering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0083—Thermal after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1213—Laminated layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1216—Three or more layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/022—Metals
- B01D71/0221—Group 4 or 5 metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/022—Metals
- B01D71/0223—Group 8, 9 or 10 metals
- B01D71/02231—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/022—Metals
- B01D71/0223—Group 8, 9 or 10 metals
- B01D71/02232—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/02—Hydrophilization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/219—Specific solvent system
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/34—Use of radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/0283—Pore size
- B01D2325/02831—Pore size less than 1 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/0283—Pore size
- B01D2325/02832—1-10 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/0283—Pore size
- B01D2325/02833—Pore size more than 10 and up to 100 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/0283—Pore size
- B01D2325/02834—Pore size more than 0.1 and up to 1 µm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
Definitions
- the present invention relates to porous films comprising carbon nanostructure-metal composite and a method of manufacturing the same, and more particularly, to porous films comprising carbon nanostructure-metal composite usable to manufacture a water treating membrane, a field emission display, a hydrogen storage device assembly, an electrode for a solar cell and a secondary battery, a supercapacitor, an electromagnetic wave shielding body, a high strength lightweight application product, or the like.
- Background Art
- the water treating field uses as membranes a micro filtration (MF) membrane, an ultra filtration (UF) membrane, a nano filtration (NF) membrane, a reverse osmosis (RO) membrane, and an ion exchange membrane, which are used for industrial wastewater treatment, water treatment, sewage treatment, wastewater treatment, seawater desalination, or the like.
- the water treatment plant additionally uses the micro filtration membrane as well as the sewage treatment using a membrane bio reactor (MBR).
- MLR membrane bio reactor
- the ultra filtration membrane is used to treat water by removing bacteria while the reverse osmosis membrane is used for seawater desalination facilities.
- the ion exchange membrane is mainly used for a dechlorination process.
- biofouling is due to microorganisms that degrade the separation capacity, which have a negative effect on the lifespan of the membrane. Consequently, biofouling caused by the microorganisms may degrade the performance and lifespan of the membrane. Therefore, research of the membrane having various functions for solving the above- mentioned problems has continued.
- An object of the present invention is to provide a new type of porous films comprising carbon nanostructure-metal composite capable of increasing a flow rate.
- porous films comprising carbon nanostructure-metal composite includes: a membrane support having micro or nano pores and carbon nanostructure-metal composite films formed on one side or both sides of the membrane support, wherein the surface of the porous films comprising carbon nanostructure- metal composite is subjected to a hydrophilic surface modifying treatment.
- a method of manufacturing the porous films comprising carbon nanostructure-metal composite includes: a) coating the carbon nanostructure- metal composite dispersed in a solvent on one surface or both surfaces of a membrane support; b) heat-treating the coated membrane support to fuse the carbon nanostructure-metal composite to the membrane support; and c) surface-modifying the membrane fused with the carbon nanostructure-metal composite and making it in a hydrophilic state.
- the porous films comprising carbon nanostructure-metal composite according to the present invention can control the size of the pores of the composite porous films according to the size of the carbon nanostructure.
- the porous films comprising plasma treated carbon nanostructure-metal composite according to the present invention can be melted at a low temperature since the metal size of the carbon nanostructure-metal composite is several nm to several hundred nm. Therefore, the present invention can provide a new type of composite porous films manufactured by performing heat treatment at a low temperature in order to connect the metal with the carbon nanostructure in a network structure and fusing the metal to the membrane support, and the method of manufacturing the same.
- the present invention connects the carbon nanostructure-metal composite in a network structure by melting or sintering the metal even though the heat treatment is performed at a relatively low temperature, thereby making it possible to attach the carbon nano structure to the membrane support well.
- the manufactured composite porous films can effectively filtrate the microorganisms when they are used for the water treating membrane since the microorganisms are not filtered due to the size of pores of the composite porous films. Further, the present invention can maintain the flow rate even though the carbon nanostructure-metal composite is formed on the membrane support.
- FIG. 1 is a photograph of carbon nanotube-silver composite manufactured in Manufacturing Example 1 and observed by a scanning electron microscope (SEM);
- FIG. 2 is a photograph of a filter fused with the carbon nanotube-silver composite at step b) of Example 1 and observed by a scanning electron microscope (SEM); and
- FIG. 3 is a diagram of comparing a flow rate of Example 1 with that of reference Example 1.
- porous films comprising carbon nanostructure-metal composite
- porous films comprising
- carbon nanostructure-metal composite includes a membrane support having micro or nano pores and carbon nanostructure-metal composite films formed on one side or both sides of the membrane support, and having a hydrophilic modified surface.
- the hydrophilic modified surface is formed by surface modifying using plasma.
- plasma has becomes more frequently used in various industries.
- plasma implies a state in which a material is electrically neutral due to the coexistence of positive and negative charged particles that freely move.
- plasma is called a fourth state of a material.
- a state of a material may be largely classified into solid, liquid, gas, or plasma.
- impact energy is ionization energy
- electrons in a gas atom come out.
- an atom is a cation, which becomes a plasma state, i.e., an ionization state that electrically separates gas into ions and electrons.
- This state is similar to an electrolyte solution state but is a gas state.
- plasma viewable around us may include a fluorescent lamp, a neon sign, flare, lightning, aurora lights, etc. Since it is difficult to raise temperature to tens of thousands 3 ⁇ 4C when gas is heated, plasma is generated by accelerating electrons and impacting them with gas atoms. Generally, when ionization energy is converted into voltage, it becomes about 10 to 20V, such that it can be easily changed into electric energy.
- the carbon-nanostructure-metal composite is formed by combining or mixing the carbon nano-structure with a metal or a metal oxide.
- the carbon nanostructure may be classified into a carbon nano tube, a
- the carbon nano tube can be applied to various fields, such as energy, environment, electronics, etc., due to excellent mechanical strength, thermal conductivity, electric conductivity, and chemical stability.
- the carbon nanos- grapplture-metal composite is formed by inducing a functional group into the carbon nanotube and chemically combining the induced functional group with a metal (cobalt, copper, nickel, silver, etc.) by the reaction therebetween.
- the carbon nanostructure- metal composite has excellent characteristics for manufacturing structure mold such as, a field emission display, hydrogen storage device assembly, an electrode for a solar cell and a secondary battery, supercapacitor, electromagnetic wave shielding body, high strength lightweight application product, or the like, due to the metal components included therein.
- a method of manufacturing the material for the carbon nanostructure- metal composite is disclosed in US Patent 7,217,331, WO 2009/145393 Al, etc.
- the metal or the metal oxide of the carbon nanostructure-metal composite can be melted or sintered at a low temperature, the metal or the metal oxide is melted or sintered when the membrane coated with the carbon nanostructure-metal composite is heat-treated at a relatively low temperature, such that the carbon nanostructure-metal composites are connected in a network structure, thereby making it possible to manufacture nano porous films.
- the carbon nanostructure, metal, and metal oxide of the carbon nanostructure-metal composite has a size of several nm to several hundred nm. More specifically, the carbon nanostructure metal composite is composed of spherical metal particles or the metal oxide particles of 1 to 500 nm and the carbon nanostructure. Since the size of the metal is a nano unit, the metal has a lower melting point than that of a metal of a normal size. For this reason, the metal is melted and sintered even though it is heat- treated at a relatively low temperature, such that the carbon nanostructure-metal composite is connected in a network structure. As a result, the carbon nanostructure- metal composite can be combined with the membrane support well.
- the metal or the metal oxide may include at least one selected from a group consisting of Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Cs, Ba, La, Ce, Nd, Sm, Eu, Gd, Tb, Hf, Ir, Pt, Tl, Pb, or Bi.
- the present invention it is possible to control the size of the pores of the porous films comprising carbon nanostructure-metal composite by the diameter size of the carbon nanostructure.
- the diameter of the carbon nanostructure is varied according to the type of carbon nanostructure, such that the size of the pores of the composite porous films can be controlled according to the type of carbon nanostructure.
- the controlled pore size of the porous films comprising carbon nanostructure-metal composite may be 0.1 to 500nm.
- the porous films comprising carbon nanostructure-metal composite according to the present invention can effectively filtrate microorganisms by controlling the size thereof.
- the carbon nanostructure-metal composite may be manufactured by mixing a dispersion of the carbon nanostructure dispersed in a reductive solvent with a metal precursor and heat-treating it.
- the dispersion may be further added with a stabilizer.
- the reductive solvent may be selected from polyhydric alcohol, glycol ethers, or a mixture thereof, wherein the polyhydric alcohol may be selected from a group consisting of glycols, glycerin, threitol, arabitol, glucose, mannitol, galactitol, and sorbitol according to the following chemical formula 1.
- R 1 is selected from a linear or branched alkylene of C 2 ⁇ C] 0 , and n is an integer of 1 to 100.
- glycol ethers may be selected from compounds of the following Chemical
- R 2 is selected from a linear or branched alkylene of C 2 ⁇ Ci 0 ;
- R 3 is a hydrogen atom, allyl, alkyl of Q -Qo, aryl of C 5 ⁇ C 20 , or aralkyl group of C 6 ⁇ C 3 () ;
- R 4 is selected from allyl, alkyl of C] ⁇ Ci 0 , aryl of C 5 ⁇ Ci 0 , aralkyl group of C 6 ⁇ C 30 , or alkyl carbonyl group of C 2 ⁇ Ci 0 , wherein the alkyl of alkyl carbonyl group may include a double bond in a carbon chain;
- m is an integer of 1 to 100).
- glycol ethers may be selected from methyl glycol, methyl diglycol, methyl
- triglycol methyl polyglycol, ethyl glycol, ethyl diglycol, butyl glycol, butyl diglycol, butyl triglycol, butyl polyglycol, hexyl glycol, hexyl diglycol, ethyl hexyl glycol, ethyl hexyl diglycol, allyl glycol, phenyl glycol, phenyl diglycol, benzil glycol, benzil diglycol, methyl propylene glycol, methyl propylene diglycol, methyl propylene triglycol, propyl propylene glycol, propyl propylene diglycol, butyl propylene glycol, butyl propylene diglycol, phenyl propylene glycol, methyl propylene glycol acetate, and poly methyl glycol, but is not limited thereto.
- the glycols may be selected from ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, and hexylene glycol, more preferably, ethylene glycol, but is not limited thereto.
- the reductive solvent may preferably use a mixture of glycols and glycol ethers.
- the reductive solvent may more preferably use a mixture of glycols and methyl poly glycol.
- the metal precursor may be selected from silver nitrate, silver acetylacetonate, silver acetate, silver carbonate, silver chloride, aluminum hydroxide, aluminum chloride, aluminum acetylacetonate, aluminum acetate, aluminum nitrate, manganese carbonate, manganese chloride, manganese nitrate, manganese acetylacetonate, manganese acetate, zinc chloride, zinc nitrate, zinc acetate, zinc acetylacetonate, cobalt acetylacetonate, cobalt acetate, copper acetylacetonate, copper acetate, nickel acetylacetonate, nickel acetate, iron acetylacetonate, iron acetate, titanium acetate, titanium acetylacetonate, and hydrate thereof.
- the stabilizer may be selected from a surfactant, a water soluble polymer, amines, and a mixture thereof.
- a detailed example of the water soluble polymer may include polyvinyl pyrrolidone
- the amines may be selected from primary amine, secondary amine, tertiary amine, aromatic amine, and a mixture thereof, more specifically, oleylamine.
- the carbon nanostructure may be selected from a single wall carbon nanotube, a double wall carbon nanotube, a multi wall carbon nanotube, a carbon nano horn, a carbon nano fiber, and a mixture thereof, more preferably, the single wall carbon nanotube, the double wall carbon nanotube, and the multi wall carbon nanotube.
- the size of the pore of the composite porous films according to the present invention may be controlled according to the diameter of the carbon nanostructure.
- An example of the method of manufacturing the porous films comprising a carbon nanostructure-metal composite includes: a) coating the carbon nanostructure-metal composite dispersed in a solvent on one surface or both surfaces of the membrane support; b) heat-treating the coated membrane support to fuse the carbon nanostructure-metal composite to the membrane support; and c) surface-modifying the membrane fused with the carbon nanostructure-metal composite and making it in a hy- drophilic state.
- the surface modification is performed during the plasma treatment. More specifically, the plasma treatment may be performed by a method using an inert gas as a discharge gas and in atmospheric pressure.
- the plasma treatment according to the present invention uses plasma selected from radio frequency (RF) plasma, corona discharge plasma, high frequency plasma, dielectric barrier discharge plasma, AC glow discharge plasma, DC discharge plasma, intermediate frequency plasma, and arc plasma, and may be performed by a method of treating plasma at a normal temperature.
- RF radio frequency
- the plasma may be performed for 1 to 60 minutes under the conditions of normal temperature and atmospheric pressure.
- the functional group is induced into the carbon nanostructure of the surface of the coated membrane to manufacture the structure of the hy- drophilic composite porous films.
- the plasma treatment may include an oxygen addition plasma treatment under a general vacuum or a normal pressure plasma treatment method, or a general corona treatment method, etc., but is not necessarily limited thereto.
- the coated membrane when the coated membrane is subjected to the atmospheric pressure plasma treatment, inert gas and oxygen in the air becomes a free radical.
- the free radical attacks the surface of the membrane, such that hydroxyl group is induced into the surface of the membrane to form the hydrophilic surface.
- the hydrophilic surface has hydrophilic property with water to reduce permeation resistance on the surface of the membrane, thereby increasing the permeation flow rate.
- the membrane support may use at least one selected from a HEPA filter, an ULPA filter, a ceramic filter, a glass fiber filter, a glass powder sintering filter, a polymer nonwoven filter, a Teflon separator filter, a metal powder sintering filter, and a metal wire woven filter, but is not necessarily thereto.
- the size of the metal may be 1 to 500 nm and when the metal is silver, silver may be preferably included as 5 to 90 wt% for the carbon nanostructure-metal composite.
- the carbon nanostructure-metal composite may be manufactured by
- the carbon nanostructure-metal composite may be manufactured by further including the stabilizer in the dispersion, mixing it, mixing the metal precursor therewith, and heat-treating it.
- the coating may be performed by a method of filtering the carbon nanostructure-metal composite in the membrane support and compressing the carbon nanostructure-metal composite remaining in the membrane support.
- An example of the coating method may include a spin coating method, a dip coating method, a spray coating method, a bar coating method, and a screen printing method, a method of performing filtering and coating on the support, or the like, but is not necessarily limited thereto.
- the solvent may be selected from a group consisting of mixtures of water, alcohol, polyhydric alcohol, glycol ethers, and a mixture thereof.
- the alcohol may be selected from a group consisting of methyl alcohol, ethanol, propyl alcohol, butanol, pentanol, hexanol, and octyl alcohol, more preferably, propyl alcohol.
- the solvent may include a surfactant.
- the amount of surfactant may be
- the surfactant may be selected from non-ionic surfactant, cationic surfactant, anionic surfactant, and a mixture thereof.
- the surfactant can prevent the carbon nanostructure-metal composite from being tangled in the above- mentioned range and can effectively disperse it.
- an example of the surfactant may include cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, sodium dodecyl sulfate, stearic acid, methyl glucoside, octyl glucoside, polyoxyethylene sorbitan monolaurate, poly- oxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, sorbitan monolaurate, ethylene glycol monolaurate, propylene glycol monolaurate, triglycerol monolaurate, and a mixture thereof, more preferably, cetyl trimethyl ammonium bromide or cetyl trimethyl ammonium chloride, but is not necessarily limited thereto.
- dispersing the carbon nanostructure-metal composite in the solvent may use all of the known methods, but dispersing the carbon nanostructure-metal composite in the solvent by using ultrasonic treatment is more preferable since it simplifies the manufacturing process and has excellent dispersibility.
- the case in which the carbon nanostructure-metal composites are tangled with each other can be generally confirmed by a scanning electron microscope. The tangle of the carbon nanostructure-metal composites may hinder the carbon nanostructure-metal composite from being uniformly dispersed when being coated on the membrane support, such that it is preferable that the ultrasonic treatment is performed at the time of manufacturing the membrane comprising the carbon nanostructure-metal composite.
- the heat treatment may be performed in the range of temperature in which the membrane support is not melted, while considering the melting or sintering of metal, the temperature of the heat treatment is not limited thereto.
- the heat treatment may be in the range of 100 to 700 °C more preferably, 100 to 500 °C.
- the heat treatment can be performed between 100 to 300 °C.
- the heat treatment is performed for 1 to 24 hours to melt or sinter the metal, thereby making it possible to form the network structure.
- the heat treatment is performed in a general low- temperature oven, by a method of passing a coated membrane support through a thermal roller, or in a high-temperature electric furnace, or the like, but is not limited thereto.
- the carbon nanostructure-metal composites Due to the heat treatment in the temperature range, the carbon nanostructure-metal composites are connected to each other by melting or sintering a metal as well as the carbon nanostructure-metal composite may be fused to the membrane support without melting the membrane support.
- a principle of combining the carbon nanostructure-metal composite to the membrane support is as follows.
- the carbon nanostructures do not have adhesion bonding therebetween.
- the carbon nanostructure-metal composite it is combined with the metal and in the case where the metal particles are a nanosize, it may be fused at a low temperature.
- the carbon nanostructure-metal composites are connected to each other using the metal component by the heat treatment and it is fused to the membrane support, thereby making it possible to manufacture the porous films in which the carbon nanostructure-metal composite having a network structure is combined with the membrane support.
- the silver containing composite porous films may be used for the separator of antibacterial water treatment. 5 to 90 wt% of silver for the whole carbon nanostructure-metal composite may effectively show the antibiosis.
- the content of silver is smaller than 5 wt%, it may be difficult to form the carbon nanostructure-metal composite in the network structure and if the content of silver exceeds 90 wt%, the liquid cannot smoothly flow when the porous films comprising the manufactured carbon nanostructure-metal composite are used as the separator.
- the synthesized carbon nanotube-silver composite was filtered by filter paper and washed with ethyl acetate and hexane several times, thereby obtaining the carbon nanotube-silver composite.
- the results of analyzing the carbon nanotube-silver composite by the scanning electron microscope (SEM) were shown in FIG. 1. It could be appreciated from FIG. 1 that the silver particles were a spherical shape and were uniformly dispersed at a predetermined size. In detail, the size of the silver particles was 5 to 40 nm and 30 to 70 wt% of silver particles were included in the whole composite.
- Step a) includes coating the carbon nanostructure-metal composite dispersed in the solvent on one surface or both surfaces of the membrane support.
- Step b) includes heat-treating the coated membrane support to fuse the metal to the membrane support.
- the washed composite porous filter was subjected to heat treatment of 150 to 180 °C for 1 to 24 hours in the oven to fuse the silver of the carbon nanotube-silver composite to the filter.
- the filter surface fused with the carbon nanotube-silver composite photographed by the scanning electron microscope (SEM) was shown in FIG. 2. It could be appreciated from FIG. 2 that the silver particles were dispersed in the carbon nanotube.
- Step c) includes surface-modifying the membrane fused with the carbon nanos- grapplture-metal composite and making it in a hydrophilic state.
- the present example treated plasma to modify the surface of the membrane fused with the carbon nanotube-silver composite.
- the apparatus used for the plasma treatment was the atmospheric pressure plasma reactor, which is the low-temperature flat apparatus generating plasma using an RF power supply of 13.56 MHz having low power of 30 to 500W, which is ATMOS developed by the PLASMART Co.
- the filter fused with the carbon nanotube-silver composite was hung from the sample holder and the rotating speed is then set to be rotated at a predetermined speed. In this case, the rotating speed was fixed to 0.5 cm/s.
- argon was used as the discharge gas for generating plasma.
- the flow rate of argon was maintained at 5 literl i (LPM).
- the plasma treatment frequency was performed for 5 periods at normal pressure and normal temperature and the plasma power was fixed to RF power of 100W.
- a total of plasma treatment time was 10 minutes by 2 minutes per 1 period, thereby manufacturing the porous films comprising the carbon nanotube-silver composite.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Thermal Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Carbon And Carbon Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
Provided is porous films comprising carbon nanostructure-metal composite in which a coating film comprising carbon nanostructure-metal composite is formed on one surface or both surface of a membrane support having micro or nano pores and is subjected to hydrophilic surface modification. Since the metal size is several nm to several hundred nm, it is melted at a low temperature and is heat-treated at a low temperature to connect the metal with the carbon nano structure in a network structure. The metal is fused to the membrane support to manufacture a new type of composite porous films. When the new type of composite porous films are used as a water treatment membrane, it increases the flow rate of water to solve the problem of the membrane transmitting flow rate of the membrane.
Description
Description
Title of Invention: POROUS FILMS COMPRISING CARBON NANOSTRUCTURE-METAL COMPOSITE AND METHOD OF
MANUFACTURING THE SAME
Technical Field
[1 ] The present invention relates to porous films comprising carbon nanostructure-metal composite and a method of manufacturing the same, and more particularly, to porous films comprising carbon nanostructure-metal composite usable to manufacture a water treating membrane, a field emission display, a hydrogen storage device assembly, an electrode for a solar cell and a secondary battery, a supercapacitor, an electromagnetic wave shielding body, a high strength lightweight application product, or the like. Background Art
[2] Recently, a technology for manufacturing a membrane having high-purity separation capacity has been recognized as a very important field for various industries. The importance of the membrane has increased in a variety of fields such as the chemical, food, pharmaceutical, medical, biochemistry, and environmental industries. In particular, in the environmental industry, a demand for clean water including an interest in water shortage has increased. One of the methods for solving the above problem has largely focused on a technology for using the membrane.
[3] In particular, the water treating field uses as membranes a micro filtration (MF) membrane, an ultra filtration (UF) membrane, a nano filtration (NF) membrane, a reverse osmosis (RO) membrane, and an ion exchange membrane, which are used for industrial wastewater treatment, water treatment, sewage treatment, wastewater treatment, seawater desalination, or the like. The water treatment plant additionally uses the micro filtration membrane as well as the sewage treatment using a membrane bio reactor (MBR). The ultra filtration membrane is used to treat water by removing bacteria while the reverse osmosis membrane is used for seawater desalination facilities. The ion exchange membrane is mainly used for a dechlorination process.
[4] However, the most serious problem of the membrane is fouling. In particular,
biofouling is due to microorganisms that degrade the separation capacity, which have a negative effect on the lifespan of the membrane. Consequently, biofouling caused by the microorganisms may degrade the performance and lifespan of the membrane. Therefore, research of the membrane having various functions for solving the above- mentioned problems has continued.
[5]
Disclosure of Invention
An object of the present invention is to provide a new type of porous films comprising carbon nanostructure-metal composite capable of increasing a flow rate.
Another object of the present invention is to provide porous films comprising carbon nanostructure-metal composite having a catalyst effect and a microorganism removing effect. Another object of the present invention is to provide composite porous films having controlled size pores according to a diameter size of the carbon nanostructure. Another object of the present invention is to provide porous films comprising carbon nanostructure-metal composite usable to manufacture a water treating membrane, a field emission display, a hydrogen storage device assembly, an electrode for a solar cell and a secondary battery, a supercapacitor, an electromagnetic wave shielding body, a high strength lightweight application product, or the like. Another object of the present invention is to provide porous films comprising carbon nanostructure-metal composite in which several nm to several hundred nm of metal particles are uniformly dispersed.
In one general aspect, porous films comprising carbon nanostructure-metal composite includes: a membrane support having micro or nano pores and carbon nanostructure-metal composite films formed on one side or both sides of the membrane support, wherein the surface of the porous films comprising carbon nanostructure- metal composite is subjected to a hydrophilic surface modifying treatment.
In another general aspect, a method of manufacturing the porous films comprising carbon nanostructure-metal composite includes: a) coating the carbon nanostructure- metal composite dispersed in a solvent on one surface or both surfaces of a membrane support; b) heat-treating the coated membrane support to fuse the carbon nanostructure-metal composite to the membrane support; and c) surface-modifying the membrane fused with the carbon nanostructure-metal composite and making it in a hydrophilic state.
The porous films comprising carbon nanostructure-metal composite according to the present invention can control the size of the pores of the composite porous films according to the size of the carbon nanostructure. The porous films comprising plasma treated carbon nanostructure-metal composite according to the present invention can be melted at a low temperature since the metal size of the carbon nanostructure-metal composite is several nm to several hundred nm. Therefore, the present invention can provide a new type of composite porous films manufactured by performing heat treatment at a low temperature in order to connect the metal with the carbon nanostructure in a network structure and fusing the metal to the membrane support, and the method of manufacturing the same. The present invention connects the carbon nanostructure-metal composite in a network structure by melting or sintering the metal even though the heat treatment is performed at a relatively low temperature, thereby making
it possible to attach the carbon nano structure to the membrane support well. The manufactured composite porous films can effectively filtrate the microorganisms when they are used for the water treating membrane since the microorganisms are not filtered due to the size of pores of the composite porous films. Further, the present invention can maintain the flow rate even though the carbon nanostructure-metal composite is formed on the membrane support.
[11]
Brief Description of Drawings
[12] FIG. 1 is a photograph of carbon nanotube-silver composite manufactured in Manufacturing Example 1 and observed by a scanning electron microscope (SEM);
[13] FIG. 2 is a photograph of a filter fused with the carbon nanotube-silver composite at step b) of Example 1 and observed by a scanning electron microscope (SEM); and
[14] FIG. 3 is a diagram of comparing a flow rate of Example 1 with that of reference Example 1.
Best Mode for Carrying out the Invention
[15] Hereinafter, porous films comprising carbon nanostructure-metal composite
according to the present invention will be described in more detail.
[16] In an exemplary embodiment of the present invention, porous films comprising
carbon nanostructure-metal composite includes a membrane support having micro or nano pores and carbon nanostructure-metal composite films formed on one side or both sides of the membrane support, and having a hydrophilic modified surface.
[17] In this case, the hydrophilic modified surface is formed by surface modifying using plasma.
[18] Recently, plasma has becomes more frequently used in various industries. Generally, plasma implies a state in which a material is electrically neutral due to the coexistence of positive and negative charged particles that freely move. As a result, plasma is called a fourth state of a material. A state of a material may be largely classified into solid, liquid, gas, or plasma. When gas is in a high-temperature state, impact between gases is frequent. When impact energy is ionization energy, electrons in a gas atom come out. In this case, an atom is a cation, which becomes a plasma state, i.e., an ionization state that electrically separates gas into ions and electrons. This state is similar to an electrolyte solution state but is a gas state. An example of plasma viewable around us may include a fluorescent lamp, a neon sign, flare, lightning, aurora lights, etc. Since it is difficult to raise temperature to tens of thousands ¾C when gas is heated, plasma is generated by accelerating electrons and impacting them with gas atoms. Generally, when ionization energy is converted into voltage, it becomes about 10 to 20V, such that it can be easily changed into electric energy.
[19] In the present invention, the carbon-nanostructure-metal composite is formed by combining or mixing the carbon nano-structure with a metal or a metal oxide.
[20] Generally, the carbon nanostructure may be classified into a carbon nano tube, a
carbon nano horn, a carbon nano fiber, or the like, according to a shape thereof, etc. In particular, the carbon nano tube can be applied to various fields, such as energy, environment, electronics, etc., due to excellent mechanical strength, thermal conductivity, electric conductivity, and chemical stability. In addition, the carbon nanos- tructure-metal composite is formed by inducing a functional group into the carbon nanotube and chemically combining the induced functional group with a metal (cobalt, copper, nickel, silver, etc.) by the reaction therebetween. The carbon nanostructure- metal composite has excellent characteristics for manufacturing structure mold such as, a field emission display, hydrogen storage device assembly, an electrode for a solar cell and a secondary battery, supercapacitor, electromagnetic wave shielding body, high strength lightweight application product, or the like, due to the metal components included therein. A method of manufacturing the material for the carbon nanostructure- metal composite is disclosed in US Patent 7,217,331, WO 2009/145393 Al, etc.
[21] Since the metal or the metal oxide of the carbon nanostructure-metal composite can be melted or sintered at a low temperature, the metal or the metal oxide is melted or sintered when the membrane coated with the carbon nanostructure-metal composite is heat-treated at a relatively low temperature, such that the carbon nanostructure-metal composites are connected in a network structure, thereby making it possible to manufacture nano porous films.
[22] The carbon nanostructure, metal, and metal oxide of the carbon nanostructure-metal composite has a size of several nm to several hundred nm. More specifically, the carbon nanostructure metal composite is composed of spherical metal particles or the metal oxide particles of 1 to 500 nm and the carbon nanostructure. Since the size of the metal is a nano unit, the metal has a lower melting point than that of a metal of a normal size. For this reason, the metal is melted and sintered even though it is heat- treated at a relatively low temperature, such that the carbon nanostructure-metal composite is connected in a network structure. As a result, the carbon nanostructure- metal composite can be combined with the membrane support well.
[23] In this case, the metal or the metal oxide may include at least one selected from a group consisting of Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Cs, Ba, La, Ce, Nd, Sm, Eu, Gd, Tb, Hf, Ir, Pt, Tl, Pb, or Bi.
[24] According to the present invention, it is possible to control the size of the pores of the porous films comprising carbon nanostructure-metal composite by the diameter size of the carbon nanostructure. The diameter of the carbon nanostructure is varied
according to the type of carbon nanostructure, such that the size of the pores of the composite porous films can be controlled according to the type of carbon nanostructure. As a result, the controlled pore size of the porous films comprising carbon nanostructure-metal composite may be 0.1 to 500nm. The porous films comprising carbon nanostructure-metal composite according to the present invention can effectively filtrate microorganisms by controlling the size thereof.
[25] In the present invention, the carbon nanostructure-metal composite may be manufactured by mixing a dispersion of the carbon nanostructure dispersed in a reductive solvent with a metal precursor and heat-treating it. In this case, the dispersion may be further added with a stabilizer.
[26] In this case, the reductive solvent may be selected from polyhydric alcohol, glycol ethers, or a mixture thereof, wherein the polyhydric alcohol may be selected from a group consisting of glycols, glycerin, threitol, arabitol, glucose, mannitol, galactitol, and sorbitol according to the following chemical formula 1.
[27] [Chemical Formula 1]
[28] H-(OR')n-OH
[29] (In Chemical Formula 1, R1 is selected from a linear or branched alkylene of C2~C]0, and n is an integer of 1 to 100.)
[30] The glycol ethers may be selected from compounds of the following Chemical
Formula 2.
[31] [Chemical Formula 2]
[32] R4-(OR2)m-OR3
[33] (In Chemical Formula 2, R2 is selected from a linear or branched alkylene of C2~Ci0;
R3 is a hydrogen atom, allyl, alkyl of Q -Qo, aryl of C5~C20, or aralkyl group of C6~C3() ; R4 is selected from allyl, alkyl of C]~Ci0, aryl of C5~Ci0, aralkyl group of C6~C30, or alkyl carbonyl group of C2~Ci0, wherein the alkyl of alkyl carbonyl group may include a double bond in a carbon chain; m is an integer of 1 to 100).
[34] The glycol ethers may be selected from methyl glycol, methyl diglycol, methyl
triglycol, methyl polyglycol, ethyl glycol, ethyl diglycol, butyl glycol, butyl diglycol, butyl triglycol, butyl polyglycol, hexyl glycol, hexyl diglycol, ethyl hexyl glycol, ethyl hexyl diglycol, allyl glycol, phenyl glycol, phenyl diglycol, benzil glycol, benzil diglycol, methyl propylene glycol, methyl propylene diglycol, methyl propylene triglycol, propyl propylene glycol, propyl propylene diglycol, butyl propylene glycol, butyl propylene diglycol, phenyl propylene glycol, methyl propylene glycol acetate, and poly methyl glycol, but is not limited thereto.
[35] The glycols may be selected from ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, and hexylene glycol, more preferably, ethylene glycol, but is not
limited thereto.
[36] The reductive solvent may preferably use a mixture of glycols and glycol ethers. In detail, the reductive solvent may more preferably use a mixture of glycols and methyl poly glycol.
[37] The metal precursor may be selected from silver nitrate, silver acetylacetonate, silver acetate, silver carbonate, silver chloride, aluminum hydroxide, aluminum chloride, aluminum acetylacetonate, aluminum acetate, aluminum nitrate, manganese carbonate, manganese chloride, manganese nitrate, manganese acetylacetonate, manganese acetate, zinc chloride, zinc nitrate, zinc acetate, zinc acetylacetonate, cobalt acetylacetonate, cobalt acetate, copper acetylacetonate, copper acetate, nickel acetylacetonate, nickel acetate, iron acetylacetonate, iron acetate, titanium acetate, titanium acetylacetonate, and hydrate thereof.
[38] The stabilizer may be selected from a surfactant, a water soluble polymer, amines, and a mixture thereof. A detailed example of the water soluble polymer may include polyvinyl pyrrolidone, the amines may be selected from primary amine, secondary amine, tertiary amine, aromatic amine, and a mixture thereof, more specifically, oleylamine.
[39] The carbon nanostructure may be selected from a single wall carbon nanotube, a double wall carbon nanotube, a multi wall carbon nanotube, a carbon nano horn, a carbon nano fiber, and a mixture thereof, more preferably, the single wall carbon nanotube, the double wall carbon nanotube, and the multi wall carbon nanotube. The size of the pore of the composite porous films according to the present invention may be controlled according to the diameter of the carbon nanostructure.
[40] Hereinafter, a method of manufacturing the porous films comprising a carbon nanostructure-metal composite according to the present invention will be described in more detail.
[41] An example of the method of manufacturing the porous films comprising a carbon nanostructure-metal composite includes: a) coating the carbon nanostructure-metal composite dispersed in a solvent on one surface or both surfaces of the membrane support; b) heat-treating the coated membrane support to fuse the carbon nanostructure-metal composite to the membrane support; and c) surface-modifying the membrane fused with the carbon nanostructure-metal composite and making it in a hy- drophilic state.
[42] At step c), the surface modification is performed during the plasma treatment. More specifically, the plasma treatment may be performed by a method using an inert gas as a discharge gas and in atmospheric pressure.
[43] In addition, the plasma treatment according to the present invention uses plasma selected from radio frequency (RF) plasma, corona discharge plasma, high frequency
plasma, dielectric barrier discharge plasma, AC glow discharge plasma, DC discharge plasma, intermediate frequency plasma, and arc plasma, and may be performed by a method of treating plasma at a normal temperature.
[44] At step c), the plasma may be performed for 1 to 60 minutes under the conditions of normal temperature and atmospheric pressure.
[45] When the plasma is treated, the functional group is induced into the carbon nanostructure of the surface of the coated membrane to manufacture the structure of the hy- drophilic composite porous films. The plasma treatment may include an oxygen addition plasma treatment under a general vacuum or a normal pressure plasma treatment method, or a general corona treatment method, etc., but is not necessarily limited thereto.
[46] In more detail, when the coated membrane is subjected to the atmospheric pressure plasma treatment, inert gas and oxygen in the air becomes a free radical. The free radical attacks the surface of the membrane, such that hydroxyl group is induced into the surface of the membrane to form the hydrophilic surface. The hydrophilic surface has hydrophilic property with water to reduce permeation resistance on the surface of the membrane, thereby increasing the permeation flow rate.
[47] At step a), the membrane support may use at least one selected from a HEPA filter, an ULPA filter, a ceramic filter, a glass fiber filter, a glass powder sintering filter, a polymer nonwoven filter, a Teflon separator filter, a metal powder sintering filter, and a metal wire woven filter, but is not necessarily thereto.
[48] At step a), the size of the metal may be 1 to 500 nm and when the metal is silver, silver may be preferably included as 5 to 90 wt% for the carbon nanostructure-metal composite.
[49] At step a), the carbon nanostructure-metal composite may be manufactured by
mixing the carbon nanostructure dispersion dispersed in the reductive solvent with the metal precursor and heat-treating it. In addition, the carbon nanostructure-metal composite may be manufactured by further including the stabilizer in the dispersion, mixing it, mixing the metal precursor therewith, and heat-treating it.
[50] At step a), the coating may be performed by a method of filtering the carbon nanostructure-metal composite in the membrane support and compressing the carbon nanostructure-metal composite remaining in the membrane support. An example of the coating method may include a spin coating method, a dip coating method, a spray coating method, a bar coating method, and a screen printing method, a method of performing filtering and coating on the support, or the like, but is not necessarily limited thereto.
[51] At step a), the solvent may be selected from a group consisting of mixtures of water, alcohol, polyhydric alcohol, glycol ethers, and a mixture thereof. In detail, the alcohol
may be selected from a group consisting of methyl alcohol, ethanol, propyl alcohol, butanol, pentanol, hexanol, and octyl alcohol, more preferably, propyl alcohol.
[52] At step a), the solvent may include a surfactant. The amount of surfactant may be
100 to 300 parts by weight for every 100 parts by weight of the carbon nanostructure- metal composite. In this case, the surfactant may be selected from non-ionic surfactant, cationic surfactant, anionic surfactant, and a mixture thereof. The surfactant can prevent the carbon nanostructure-metal composite from being tangled in the above- mentioned range and can effectively disperse it.
[53] In more detail, an example of the surfactant may include cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, sodium dodecyl sulfate, stearic acid, methyl glucoside, octyl glucoside, polyoxyethylene sorbitan monolaurate, poly- oxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, sorbitan monolaurate, ethylene glycol monolaurate, propylene glycol monolaurate, triglycerol monolaurate, and a mixture thereof, more preferably, cetyl trimethyl ammonium bromide or cetyl trimethyl ammonium chloride, but is not necessarily limited thereto.
[54] In the manufacturing method according to the present invention, the method of
dispersing the carbon nanostructure-metal composite in the solvent may use all of the known methods, but dispersing the carbon nanostructure-metal composite in the solvent by using ultrasonic treatment is more preferable since it simplifies the manufacturing process and has excellent dispersibility. The case in which the carbon nanostructure-metal composites are tangled with each other can be generally confirmed by a scanning electron microscope. The tangle of the carbon nanostructure-metal composites may hinder the carbon nanostructure-metal composite from being uniformly dispersed when being coated on the membrane support, such that it is preferable that the ultrasonic treatment is performed at the time of manufacturing the membrane comprising the carbon nanostructure-metal composite.
[55] Meanwhile, at step b), if the heat treatment may be performed in the range of temperature in which the membrane support is not melted, while considering the melting or sintering of metal, the temperature of the heat treatment is not limited thereto.
Preferably, the heat treatment may be in the range of 100 to 700 °C more preferably, 100 to 500 °C. When the metal of the carbon nanostructure-metal composite is silver, the heat treatment can be performed between 100 to 300 °C. The heat treatment is performed for 1 to 24 hours to melt or sinter the metal, thereby making it possible to form the network structure. The heat treatment is performed in a general low- temperature oven, by a method of passing a coated membrane support through a thermal roller, or in a high-temperature electric furnace, or the like, but is not limited thereto.
[56] Due to the heat treatment in the temperature range, the carbon nanostructure-metal composites are connected to each other by melting or sintering a metal as well as the carbon nanostructure-metal composite may be fused to the membrane support without melting the membrane support.
[57] In more detail, a principle of combining the carbon nanostructure-metal composite to the membrane support is as follows. The carbon nanostructures do not have adhesion bonding therebetween. However, in the case of the carbon nanostructure-metal composite, it is combined with the metal and in the case where the metal particles are a nanosize, it may be fused at a low temperature. The carbon nanostructure-metal composites are connected to each other using the metal component by the heat treatment and it is fused to the membrane support, thereby making it possible to manufacture the porous films in which the carbon nanostructure-metal composite having a network structure is combined with the membrane support.
[58] When the metal is silver, the silver containing composite porous films may be used for the separator of antibacterial water treatment. 5 to 90 wt% of silver for the whole carbon nanostructure-metal composite may effectively show the antibiosis. In the carbon nanostructure-metal composite, if the content of silver is smaller than 5 wt%, it may be difficult to form the carbon nanostructure-metal composite in the network structure and if the content of silver exceeds 90 wt%, the liquid cannot smoothly flow when the porous films comprising the manufactured carbon nanostructure-metal composite are used as the separator.
Mode for the Invention
[59] Examples for explaining in detail the present invention will be described below, but the present invention is not limited to the following examples.
[60] The following examples show that the carbon nanotube-silver composite is manufactured, the porous films comprising the hydrophilic surface modified carbon nanotube-silver composite are manufactured therefrom, and an experiment showing the advantages of the hydrophilic surface modification is performed. However, this is not limited to the carbon nanotube-metal composite or the porous films comprising carbon nanotube-metal composite as well as does not decrease the inherent effects of the porous films comprising carbon nanotube-metal composite. This aspect recites contents described in Korean Patent Application No. 2009-0026356 already filed by the applicant.
[61] [Manufacturing Example 1] Manufacturing of Carbon Nanotube-Silver Composite [62] 0.3g of multi-wall CNT grade (diameter 10 nm) put in 500 ml of a round flask and 280 ml of ethylene glycol (EG) was put in the round flask reactor. It was agitated for 30 minutes by an agitator and the reactor was put in the ultrasonic washer to disperse
the carbon nanotube in ethylene glycol for 3 hours by using an ultrasonic wave. In this case, the temperature of the reactor did not exceed 50°C. When the ultrasonic treatment is completed, the agitator was mounted again and a thermometer and a cooling condenser were connected thereto. 1.68g of poly vinlypyrrolidone (PVP)
(manufacturer: Fluka, average molecular weight (Mw): 40,000) and 5.6ml of oleylamine were introduced thereinto while agitating the reactor and 1.102g of silver nitrate (AgN03) was then introduced thereinto. The vacuum pump was connected to the reactor to remove air in the reactor, which substituted it into nitrogen. Nitrogen was continuously introduced into the reactor and flows to the outside through the inside of the reactor to prevent oxygen from being introduced thereinto. A mantle was mounted at the lower portion of the flask, the temperature in the reactor was increased to 200 °C for 40 minutes, and the reaction was performed in the reactor for 1 hour. When the reduction reaction was completed, the temperature of the reactor was slowly decreased to normal temperature for 3 hours. The synthesized carbon nanotube-silver composite was filtered by filter paper and washed with ethyl acetate and hexane several times, thereby obtaining the carbon nanotube-silver composite. The results of analyzing the carbon nanotube-silver composite by the scanning electron microscope (SEM) were shown in FIG. 1. It could be appreciated from FIG. 1 that the silver particles were a spherical shape and were uniformly dispersed at a predetermined size. In detail, the size of the silver particles was 5 to 40 nm and 30 to 70 wt% of silver particles were included in the whole composite.
[63] [Example 1] Manufacturing of Porous Films Comprising Carbon Nanotube-Silver Composite
[64] Step a) includes coating the carbon nanostructure-metal composite dispersed in the solvent on one surface or both surfaces of the membrane support.
[65] 0.45g of the carbon nanotube-silver composite manufactured in Manufacturing 1 was added to 100ml of ultra-pure water in 1000 ml of the round flask and 0.45g of anionic surfactant, i.e., sodium dodecy] sulfate was added thereto, which was in turn subjected to the ultrasonic dispersion for 60 minutes.
[66] 250 ml of dispersion of the carbon nanotube-silver composite was introduced into the cartridge mounted with a ceramic porous filter having a cylinder shape and was repeatedly coated on the surface of the ceramic porous filter by using a water pump four times in total. After the coating was completed, 250 ml of ethanol was injected into the cartridge and the washing was performed four times in total.
[67]
[68] Step b) includes heat-treating the coated membrane support to fuse the metal to the membrane support.
[69] The washed composite porous filter was subjected to heat treatment of 150 to 180 °C
for 1 to 24 hours in the oven to fuse the silver of the carbon nanotube-silver composite to the filter. The filter surface fused with the carbon nanotube-silver composite photographed by the scanning electron microscope (SEM) was shown in FIG. 2. It could be appreciated from FIG. 2 that the silver particles were dispersed in the carbon nanotube.
[70]
[71 ] Step c) includes surface-modifying the membrane fused with the carbon nanos- tructure-metal composite and making it in a hydrophilic state.
[72] The present example treated plasma to modify the surface of the membrane fused with the carbon nanotube-silver composite. The apparatus used for the plasma treatment was the atmospheric pressure plasma reactor, which is the low-temperature flat apparatus generating plasma using an RF power supply of 13.56 MHz having low power of 30 to 500W, which is ATMOS developed by the PLASMART Co. The filter fused with the carbon nanotube-silver composite was hung from the sample holder and the rotating speed is then set to be rotated at a predetermined speed. In this case, the rotating speed was fixed to 0.5 cm/s. As the discharge gas for generating plasma, argon was used. The flow rate of argon was maintained at 5 literl i (LPM). The plasma treatment frequency was performed for 5 periods at normal pressure and normal temperature and the plasma power was fixed to RF power of 100W. A total of plasma treatment time was 10 minutes by 2 minutes per 1 period, thereby manufacturing the porous films comprising the carbon nanotube-silver composite.
[73] [Reference Example 1]
[74] Reference Example 1 was performed similar to Example 1 except for step c), i.e., the surface modification was not performed.
[75] [Experimental Example]
[76] After the porous films comprising carbon nanotube-silver composite manufactured by Example 1 was fixed to the cartridge, 250 ml of deionized water was introduced thereinto to measure the flow rate per pressure. In this case, the pressure was set to 1, 2, 3, 4, and 5 kgf/cm2 by using the pressure gauge connected to the compressor, such that the comparative experiment with the porous films comprising carbon nanotube- silver composite of Reference Example 1 , which is not surface-modified with plasma, was performed according to the pressure. The comparative experimental results were arranged in the following Table and shown in FIG. 3. In FIG. 3, no plasma treatment shown the results of Reference Example 1 and plasma treatment shown the results of Example 1. It can be appreciated that the flow rate is further increased by 50.4% in Example 1 than in Reference Example 1.
[77] [Table 1] Comparison of flow rate before and after plasma treatment
[78]
Reference Example 1 Examaple 1
Improvement
Pressure Flow rate Pressure Flow rate
Rate (%)
( kqf/ cm2) ( L/min) (kqf/ cm2) (L/min)
1 0.460 1 0.622 35.4
2 0.780 2 1.199 53.7
3 1.157 3 1.812 56.5
4 1.538 4 2.417 57.1
5 1.932 5 2.885 49.3
Averaqe 50.4
Claims
Claims
Porous films comprising carbon nanostructure-metal composite, comprising a membrane support having micro or nano pores and carbon nanostructure-metal composite films formed on one side or both sides of the membrane support, and having a hydrophilic modified surface.
The porous films comprising carbon nanostructure-metal composite of claim 1, wherein the hydrophilic modified surface is formed by surface modifying using plasma.
The porous films comprising carbon nanostructure-metal composite of claim 1, wherein the carbon nanostructure-metal composite is bonded material or mixture of the carbon nano-structure and a metal or a metal oxide.
The porous films comprising carbon nanostructure-metal composite of claim 3, wherein the pore size of the porous films of the carbon nanostructure-metal composite is controlled by the diameter size of the carbon nanostructure.
The porous films comprising carbon nanostructure-metal composite of claim 4, wherein the pore size of the porous films of the carbon nanostructure-metal composite is 0.1 to 500 nm.
The porous films comprising carbon nanostructure-metal composite of claim 3, wherein the carbon nanostructure-metal composite is manufactured by heat-treatment following mixing a metal precursor with the dispersion of the carbon nanostructure dispersed in a reductive solvent. The porous films comprising carbon nanostructure-metal composite of claim 6, wherein the carbon nanostructure-metal composite is manufactured by mixing a stabilizer with the dispersion of the carbon nanostructure dispersed in the reductive solvent, mixing the metal precursor therewith, and heat-treating it.
The porous films comprising carbon nanostructure-metal composite of claim 6 or 7, wherein the reductive solvent is selected from polyhydric alcohol, glycol ethers, or a mixture thereof.
The porous films comprising carbon nanostructure-metal composite of claim 8, wherein the polyhydric alcohol is selected from a group consisting of glycols, glycerin, threitol, arabitol, glucose, mannitol, galactitol, and sorbitol of the following Chemical Formula 1.
[Chemical Formula 1]
H-(OR „-OH
in Chemical Formula 1, R1 is selected from a linear or branched alkylene of C2~C|0, and n is an integer of 1 to 100.
[Claim 10] The porous films comprising carbon nanostructure-metal composite of claim 8, wherein the glycol ethers are selected from compounds of the following Chemical Formula 2.
[Chemical Formula 2]
R4-(OR2)m-OR3
in Chemical Formula 2, R2 is selected from a linear or branched alkylene of C2~C10; R3 is a hydrogen atom, ally], alkyl of Ci~Cl0, aryl of C5~C20, or aralkyl group of C6~C30; R4 is selected from allyl, alkyl of Ci~Cio, aryl of C5~Ci0, aralkyl group of C6~C30, or alkyl carbonyl group of C2~C io, wherein the alkyl of alkyl carbonyl group may include a double bond in a carbon chain; m is an integer of 1 to 100.
[Claim 11] The porous films comprising carbon nanostructure-metal composite of claim 3, wherein the carbon nanostructure is selected from a single wall carbon nanotube, a double wall carbon nanotube, a multi wall carbon nanotube, a carbon nanohorn, and a carbon nano fiber, or a mixture thereof.
[Claim 12] The porous films comprising carbon nanostructure-metal composite of claim 3, wherein the metal or the metal oxide includes at least one selected from a group consisting of Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Cs, Ba, La, Ce, Nd, Sm, Eu, Gd, Tb, Hf, Ir, Pt, Tl, Pb, and Bi.
[Claim 13] A method of manufacturing the porous films comprising carbon nanostructure-metal composite, comprising:
a) coating the carbon nanostructure-metal composite dispersed in a solvent on one surface or both surfaces of a membrane support;
b) heat-treating the coated membrane support to fuse the carbon nanostructure-metal composite to the membrane support; and
c) surface-modifying the membrane fused with the carbon nanostructure-metal composite and making it in a hydrophilic state.
[Claim 14] The method of manufacturing the porous films comprising a carbon nanostructure-metal composite of claim 13, wherein at step c), the surface modifying is perfomed by a plasma treatment.
[Claim 15] The method of manufacturing the porous films comprising a carbon nanostructure-metal composite of claim 14, wherein the plasma treatment uses inert gas as discharge gas and is performed by an at-
mospheric pressure treatment method.
The method of manufacturing the porous films comprising a carbon nanostructure-metal composite of claim 14, wherein the plasma treatment uses plasma selected from radio frequency (RF) plasma, corona discharge plasma, high frequency plasma, dielectric barrier discharge plasma, AC glow discharge plasma, DC discharge plasma, intermediate frequency plasma, and arc plasma, and is performed at normal temperature.
The method of manufacturing the porous films comprising a carbon nanostructure-metal composite of claim 13, wherein at step a), the carbon nanostructure-metal composite is manufactured by mixing the carbon nanostructure dispersion dispersed in the reductive solvent with the metal precursor and heat-treating it.
The method of manufacturing the porous films comprising a carbon nanostructure-metal composite of claim 17, wherein at step a), the carbon nanostructure-metal composite is manufactured by mixing a stabilizer with the dispersion of the carbon nanostructure dispersion dispersed in the reductive solvent, mixing the metal precursor therewith, and heat-treating it.
The method of manufacturing the porous films comprising a carbon nanostructure-metal composite of claim 18, wherein at step a), the size of metal is 1 to 500 nm.
The method of manufacturing the porous films comprising a carbon nanostructure-metal composite of claim 19, wherein at step a), the heat treating is performed in a temperature range of 100 to 700°C.
The method of manufacturing the porous films comprising a carbon nanostructure-metal composite of claim 13, wherein at step a), the metal is silver having a size of 1 to 500nm, which is included at 5 to 90 wt% for the whole carbon nanostructure-metal composite.
The method of manufacturing the porous films comprising carbon nanostructure-metal composite of claim 13, wherein at step a), the coating is performed by a method of filtering the carbon nanostructure- metal composite in the membrane support and compressing the carbon nanostructure-metal composite remaining in the membrane support. The method of manufacturing the porous films comprising carbon nanostructure-metal composite of claim 13, wherein at step a), the solvent includes surfactant in an amount of 100 to 300 parts by weight for every 100 parts by weight of the carbon nanostructure-metal
composite.
[Claim 24] The method of manufacturing the porous films comprising carbon nanostructure-metal composite of claim 23, wherein the surfactant is selected from non-ionic surfactant, cationic surfactant, anionic surfactant, and a mixture thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100005932A KR101118475B1 (en) | 2010-01-22 | 2010-01-22 | Hydrophilic modified nanoporous films and method of manufacturing composite porous films |
| KR10-2010-0005932 | 2010-01-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2011090279A2 true WO2011090279A2 (en) | 2011-07-28 |
| WO2011090279A3 WO2011090279A3 (en) | 2011-11-24 |
Family
ID=44307362
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2011/000021 WO2011090279A2 (en) | 2010-01-22 | 2011-01-04 | Porous films comprising carbon nanostructure-metal composite and method of manufacturing the same |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR101118475B1 (en) |
| WO (1) | WO2011090279A2 (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102330119A (en) * | 2011-10-12 | 2012-01-25 | 电子科技大学 | Method for preparing high-purity porous iron film by adopting electrochemical method |
| CN103739865A (en) * | 2014-01-26 | 2014-04-23 | 江苏科德宝建筑节能科技有限公司 | Antimicrobial film |
| CN103753928A (en) * | 2014-01-26 | 2014-04-30 | 江苏兴华胶带股份有限公司 | Method for preparing nanometer functional film |
| CN103756589A (en) * | 2014-01-26 | 2014-04-30 | 江苏兴华胶带股份有限公司 | Method for preparing nanometer functional film |
| CN103770427A (en) * | 2014-01-26 | 2014-05-07 | 江苏兴华胶带股份有限公司 | Preparation method of nano functional film |
| CN103773262A (en) * | 2014-01-26 | 2014-05-07 | 江苏兴华胶带股份有限公司 | Nano functional film |
| CN103772729A (en) * | 2014-01-26 | 2014-05-07 | 江苏科德宝建筑节能科技有限公司 | Preparation method of antibacterial film |
| CN103820047A (en) * | 2014-01-26 | 2014-05-28 | 江苏兴华胶带股份有限公司 | Functional nanometer thin film |
| CN103820048A (en) * | 2014-01-26 | 2014-05-28 | 江苏兴华胶带股份有限公司 | Functional nanometer thin film |
| CN103831221A (en) * | 2014-01-26 | 2014-06-04 | 江苏科德宝建筑节能科技有限公司 | Method for preparing antibacterial film |
| US20140332728A1 (en) * | 2011-10-19 | 2014-11-13 | Environment energy nano technical research institute | Porous material including carbon nanohorns and use thereof |
| EP2740523A4 (en) * | 2011-08-04 | 2015-08-19 | Ls Nova Co Ltd | Multiple separation filter and antioxidizing water produced using same |
| WO2016190815A1 (en) * | 2015-05-22 | 2016-12-01 | Agency For Science, Technology And Research | Nanostructured iron/carbon for scavenging oxygen |
| CN110976897A (en) * | 2019-12-16 | 2020-04-10 | 河南英能新材料科技有限公司 | Preparation method of carbon nanohorn metal composite material adopting alternating current |
| EP2411128B1 (en) * | 2009-03-27 | 2020-08-05 | Bioneer Corporation | Nanoporous films and method for manufacturing the same |
| EP4226994A4 (en) * | 2021-12-29 | 2024-05-08 | Jiangsu Jiulang High-Tech Co., Ltd. | Preparation method for antibacterial and anti-virus air purification material |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101323306B1 (en) * | 2012-02-15 | 2013-10-29 | 고려대학교 산학협력단 | Manufacturing method of electron emitting device by using carbon nano tube |
| KR101409421B1 (en) * | 2012-09-20 | 2014-06-18 | 한국과학기술연구원 | Fiber-based filter with nanonet layer and preparation method thereof |
| KR101437592B1 (en) * | 2012-12-28 | 2014-09-04 | 전자부품연구원 | Graphene composite membrane for water treatment |
| KR101437442B1 (en) * | 2013-01-23 | 2014-09-11 | 전자부품연구원 | Method of graphene-cnt complex structure for water treatment and membrane using the same |
| US10322447B2 (en) * | 2013-05-09 | 2019-06-18 | Dresser-Rand Company | Anisotropically aligned carbon nanotubes in a carbon nanotube metal matrix composite |
| KR102254644B1 (en) * | 2014-12-19 | 2021-05-21 | (주)바이오니아 | Binder Connected Carbon Nano Structure Nano-porous Mambrane and Manufacturing the Same |
| KR101794440B1 (en) * | 2016-03-08 | 2017-11-07 | 한국과학기술원 | Method of manufacturing coated porous material, coated porous material and electrode comprising the coated porous material |
| CN114311225B (en) * | 2022-01-18 | 2023-11-03 | 重庆兀盾纳米科技有限公司 | Disc type ceramic membrane and high-pressure grouting forming method thereof |
| CN114887486B (en) * | 2022-05-09 | 2023-04-18 | 中国海洋大学 | Mannitol-based polyester loose composite nanofiltration membrane and preparation method and application thereof |
| CN116535227B (en) * | 2023-07-05 | 2023-10-10 | 西南交通大学 | Preparation method of carbon fiber in-situ generation nano silver enhanced pantograph carbon slide plate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5266207A (en) * | 1991-04-30 | 1993-11-30 | Techsep | Composite nanofiltration membrane |
| US20030116503A1 (en) * | 2001-12-21 | 2003-06-26 | Yong Wang | Carbon nanotube-containing structures, methods of making, and processes using same |
| JP2006515706A (en) * | 2002-07-03 | 2006-06-01 | シンテック，インコーポレイテッド | Fabrication method and activation treatment of nanostructured composite field emission cathode |
| US20060194097A1 (en) * | 2003-07-16 | 2006-08-31 | Kyungwon Enterprise Co., Ltd. | Nano-structured metal-carbon composite for electrode catalyst of fuel cell and process for preparation thereof |
| KR20100107960A (en) * | 2009-03-27 | 2010-10-06 | (주)바이오니아 | Nanoporous films and method of manufacturing nanoporous films |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100752265B1 (en) * | 2005-12-27 | 2007-08-29 | 경원엔터프라이즈 주식회사 | Nano-structured metal-carbon composite for electrode catalyst of fuel cell and process for preparation thereof |
| TW200911355A (en) | 2007-07-25 | 2009-03-16 | Dsm Ip Assets Bv | Hydrophilic membrane |
| KR101202405B1 (en) * | 2008-05-28 | 2012-11-23 | (주)바이오니아 | Nanocomposites consisting of carbon nanotube and metal and a process for preparing the same |
-
2010
- 2010-01-22 KR KR1020100005932A patent/KR101118475B1/en active IP Right Grant
-
2011
- 2011-01-04 WO PCT/KR2011/000021 patent/WO2011090279A2/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5266207A (en) * | 1991-04-30 | 1993-11-30 | Techsep | Composite nanofiltration membrane |
| US20030116503A1 (en) * | 2001-12-21 | 2003-06-26 | Yong Wang | Carbon nanotube-containing structures, methods of making, and processes using same |
| JP2006515706A (en) * | 2002-07-03 | 2006-06-01 | シンテック，インコーポレイテッド | Fabrication method and activation treatment of nanostructured composite field emission cathode |
| US20060194097A1 (en) * | 2003-07-16 | 2006-08-31 | Kyungwon Enterprise Co., Ltd. | Nano-structured metal-carbon composite for electrode catalyst of fuel cell and process for preparation thereof |
| KR20100107960A (en) * | 2009-03-27 | 2010-10-06 | (주)바이오니아 | Nanoporous films and method of manufacturing nanoporous films |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2411128B1 (en) * | 2009-03-27 | 2020-08-05 | Bioneer Corporation | Nanoporous films and method for manufacturing the same |
| EP2740523A4 (en) * | 2011-08-04 | 2015-08-19 | Ls Nova Co Ltd | Multiple separation filter and antioxidizing water produced using same |
| CN102330119A (en) * | 2011-10-12 | 2012-01-25 | 电子科技大学 | Method for preparing high-purity porous iron film by adopting electrochemical method |
| JPWO2013058383A1 (en) * | 2011-10-19 | 2015-04-02 | 株式会社環境・エネルギーナノ技術研究所 | Porous material containing carbon nanohorn and use thereof |
| US20140332728A1 (en) * | 2011-10-19 | 2014-11-13 | Environment energy nano technical research institute | Porous material including carbon nanohorns and use thereof |
| CN103773262A (en) * | 2014-01-26 | 2014-05-07 | 江苏兴华胶带股份有限公司 | Nano functional film |
| CN103831221B (en) * | 2014-01-26 | 2015-06-24 | 江苏科德宝建筑节能科技有限公司 | Method for preparing antibacterial film |
| CN103820047A (en) * | 2014-01-26 | 2014-05-28 | 江苏兴华胶带股份有限公司 | Functional nanometer thin film |
| CN103820048A (en) * | 2014-01-26 | 2014-05-28 | 江苏兴华胶带股份有限公司 | Functional nanometer thin film |
| CN103831221A (en) * | 2014-01-26 | 2014-06-04 | 江苏科德宝建筑节能科技有限公司 | Method for preparing antibacterial film |
| CN103770427A (en) * | 2014-01-26 | 2014-05-07 | 江苏兴华胶带股份有限公司 | Preparation method of nano functional film |
| CN103756589A (en) * | 2014-01-26 | 2014-04-30 | 江苏兴华胶带股份有限公司 | Method for preparing nanometer functional film |
| CN103772729A (en) * | 2014-01-26 | 2014-05-07 | 江苏科德宝建筑节能科技有限公司 | Preparation method of antibacterial film |
| CN103753928A (en) * | 2014-01-26 | 2014-04-30 | 江苏兴华胶带股份有限公司 | Method for preparing nanometer functional film |
| CN103739865B (en) * | 2014-01-26 | 2016-01-20 | 江苏科德宝建筑节能科技有限公司 | A kind of Antibiotic Membrane |
| CN103772729B (en) * | 2014-01-26 | 2016-01-20 | 江苏科德宝建筑节能科技有限公司 | A kind of preparation method of Antibiotic Membrane |
| CN103739865A (en) * | 2014-01-26 | 2014-04-23 | 江苏科德宝建筑节能科技有限公司 | Antimicrobial film |
| WO2016190815A1 (en) * | 2015-05-22 | 2016-12-01 | Agency For Science, Technology And Research | Nanostructured iron/carbon for scavenging oxygen |
| US11134707B2 (en) | 2015-05-22 | 2021-10-05 | Agency For Science, Technology And Research | Nanostructured iron/carbon for scavenging oxygen |
| CN110976897A (en) * | 2019-12-16 | 2020-04-10 | 河南英能新材料科技有限公司 | Preparation method of carbon nanohorn metal composite material adopting alternating current |
| EP4226994A4 (en) * | 2021-12-29 | 2024-05-08 | Jiangsu Jiulang High-Tech Co., Ltd. | Preparation method for antibacterial and anti-virus air purification material |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101118475B1 (en) | 2012-03-12 |
| KR20110086285A (en) | 2011-07-28 |
| WO2011090279A3 (en) | 2011-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2011090279A2 (en) | Porous films comprising carbon nanostructure-metal composite and method of manufacturing the same | |
| JP5393809B2 (en) | Nanoporous membrane and method for producing the same | |
| Mantilaka et al. | Photocatalytic activity of electrospun MgO nanofibres: Synthesis, characterization and applications | |
| Cao et al. | Superior selective adsorption of MgO with abundant oxygen vacancies to removal and recycle reactive dyes | |
| US8460547B2 (en) | Hollow porous microspheres | |
| WO2009120151A1 (en) | Membrane made of a nanostructured material | |
| KR101556466B1 (en) | Composite nanofibrous membrane for water purification and method of fabricating the same | |
| CN105189839A (en) | Electrospinning solution composition for preparing silver nanofiber | |
| KR101583593B1 (en) | Nano Porous Films Composed Carbon Nano Structure-Metal Composite or Carbon Nano Structure-Metal Oxide Composite and a process for preparing the same | |
| KR20140125416A (en) | Ordered porious nanofibers, methods, and applications | |
| Jing et al. | Hierarchical SrTiO 3/NiFe 2 O 4 composite nanostructures with excellent light response and magnetic performance synthesized toward enhanced photocatalytic activity | |
| CN110699849A (en) | Attapulgite nanofiber membrane for water treatment and preparation method thereof | |
| EP3235559A1 (en) | Binder-coupled carbon nanostructure nano-porous membrane and manufacturing method therefor | |
| KR102690354B1 (en) | Method and apparatus for preparing nanofibers | |
| Serik et al. | Effective photocatalytic degradation of sulfamethoxazole using PAN/SrTiO3 nanofibers | |
| CN111531174B (en) | Microfiltration membrane and preparation method and application thereof | |
| WO2012157816A1 (en) | Oil filter with nanoporous film | |
| CN109731543B (en) | Composite nanofiber as well as preparation and application thereof | |
| KR101394273B1 (en) | Sponge-like porous thin film layer and solid oxide fuel cell comprising thereof as a cathode | |
| KR102567441B1 (en) | Mxene fiber non-woven fabric, method for preparing the same, flow-through capacitive deionization apparatus and method for adsorbing ions in feed solution using the apparatus | |
| CN116328556A (en) | Nano catalytic composite fiber membrane and application thereof in Fenton method wastewater treatment | |
| KR20200057413A (en) | Functional filter and manufacturing therof | |
| JP2007015202A (en) | Composite structure and filter using the same | |
| CN209974372U (en) | Composite material nanofiber water purification device | |
| KR20140074697A (en) | Manufacturing Method of Polysulfone Filter Media has efficient Microorganism resolving power and Polysulfone Filter Media produced thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11734828 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 11734828 Country of ref document: EP Kind code of ref document: A2 |