CN111303671A - Composite functional coating and film, and preparation method and application thereof - Google Patents
Composite functional coating and film, and preparation method and application thereof Download PDFInfo
- Publication number
- CN111303671A CN111303671A CN202010083097.2A CN202010083097A CN111303671A CN 111303671 A CN111303671 A CN 111303671A CN 202010083097 A CN202010083097 A CN 202010083097A CN 111303671 A CN111303671 A CN 111303671A
- Authority
- CN
- China
- Prior art keywords
- thiocyanate
- film
- ion
- coating
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 128
- 239000002131 composite material Substances 0.000 title claims abstract description 106
- 239000011248 coating agent Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 91
- 229910052751 metal Inorganic materials 0.000 claims abstract description 56
- 239000002184 metal Substances 0.000 claims abstract description 56
- 239000007788 liquid Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000007787 solid Substances 0.000 claims abstract description 31
- 238000011065 in-situ storage Methods 0.000 claims abstract description 21
- 238000004381 surface treatment Methods 0.000 claims abstract description 12
- 230000003373 anti-fouling effect Effects 0.000 claims abstract description 11
- 238000011049 filling Methods 0.000 claims abstract description 10
- 238000005260 corrosion Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 48
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 45
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 45
- 229940112669 cuprous oxide Drugs 0.000 claims description 45
- 239000002070 nanowire Substances 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000000758 substrate Substances 0.000 claims description 41
- 229910021645 metal ion Inorganic materials 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 18
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 18
- 239000002086 nanomaterial Substances 0.000 claims description 18
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 16
- 229910052725 zinc Inorganic materials 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 14
- 229910045601 alloy Inorganic materials 0.000 claims description 13
- 239000000956 alloy Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- 229910021426 porous silicon Inorganic materials 0.000 claims description 8
- 239000010959 steel Substances 0.000 claims description 8
- -1 titanium ions Chemical class 0.000 claims description 8
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 7
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 7
- 239000010962 carbon steel Substances 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- JPBGLQJDCUZXEF-UHFFFAOYSA-N chromenylium Chemical compound [O+]1=CC=CC2=CC=CC=C21 JPBGLQJDCUZXEF-UHFFFAOYSA-N 0.000 claims description 6
- 230000007797 corrosion Effects 0.000 claims description 6
- 239000002135 nanosheet Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000005424 photoluminescence Methods 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910000604 Ferrochrome Inorganic materials 0.000 claims description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 229960004643 cupric oxide Drugs 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 230000002265 prevention Effects 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- PHCDZUPEIPGYOG-UHFFFAOYSA-N [Fe].[Co].[Zn] Chemical compound [Fe].[Co].[Zn] PHCDZUPEIPGYOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 2
- 229910001422 barium ion Inorganic materials 0.000 claims description 2
- 238000009395 breeding Methods 0.000 claims description 2
- 230000001488 breeding effect Effects 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 238000001311 chemical methods and process Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910001430 chromium ion Inorganic materials 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 claims description 2
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910001449 indium ion Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- 239000008204 material by function Substances 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 2
- 229940116357 potassium thiocyanate Drugs 0.000 claims description 2
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 230000001954 sterilising effect Effects 0.000 claims description 2
- 238000004659 sterilization and disinfection Methods 0.000 claims description 2
- 229910001427 strontium ion Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 229910000863 Ferronickel Inorganic materials 0.000 claims 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims 1
- WHROWQPBDAJSKH-UHFFFAOYSA-N [Mn].[Ni].[Cr] Chemical compound [Mn].[Ni].[Cr] WHROWQPBDAJSKH-UHFFFAOYSA-N 0.000 claims 1
- KOMIMHZRQFFCOR-UHFFFAOYSA-N [Ni].[Cu].[Zn] Chemical compound [Ni].[Cu].[Zn] KOMIMHZRQFFCOR-UHFFFAOYSA-N 0.000 claims 1
- 230000000903 blocking effect Effects 0.000 claims 1
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical compound [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 0.000 claims 1
- 229910052733 gallium Inorganic materials 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 230000005284 excitation Effects 0.000 abstract description 6
- 239000003086 colorant Substances 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 114
- 239000000463 material Substances 0.000 description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 description 5
- 229960001763 zinc sulfate Drugs 0.000 description 5
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000005693 optoelectronics Effects 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229920002457 flexible plastic Polymers 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000861 blow drying Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000007709 nanocrystallization Methods 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 1
- QDLZHJXUBZCCAD-UHFFFAOYSA-N [Cr].[Mn] Chemical compound [Cr].[Mn] QDLZHJXUBZCCAD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229960000359 chromic chloride Drugs 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- CKHJYUSOUQDYEN-UHFFFAOYSA-N gallium(3+) Chemical compound [Ga+3] CKHJYUSOUQDYEN-UHFFFAOYSA-N 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- PNHVEGMHOXTHMW-UHFFFAOYSA-N magnesium;zinc;oxygen(2-) Chemical compound [O-2].[O-2].[Mg+2].[Zn+2] PNHVEGMHOXTHMW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C—CHEMISTRY; METALLURGY
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/22—Luminous paints
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/44—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the coatings, e.g. passivation layer or anti-reflective coating
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Abstract
The invention belongs to the technical field of functional coatings and photoelectric functional films, and particularly relates to a composite functional coating and film, and a preparation method and application thereof. The invention takes 'metal ion-thiocyanate' aqueous solution as filling liquid and doping liquid, constructs a composite solid-liquid interface system together with a solid film or a solid surface, and then in-situ fills or in-situ grows various composite functional coatings and functional films. The composite coating and the film have good stability and wide application, including surface treatment, anti-corrosion treatment, weather-proof treatment, marine antifouling coating, marine organism propagation preventing coating and the like. Some composite functional films prepared by the invention can emit high-brightness red light under the excitation of green light, and can be used as one of three primary colors for constructing white Light Emitting Devices (LEDs). The method disclosed by the invention is green and environment-friendly, and has better universality.
Description
Technical Field
The invention belongs to the technical field of functional coatings and photoelectric functional films, and particularly relates to a composite functional coating and film, and a preparation method and application thereof.
Background
A wide variety of metal oxides, such as cuprous oxide, zinc oxide, and the like, have proven to be very valuable semiconductor materials. The composite of different kinds of metal oxides can further expand the functional properties and application fields of the material. But it is critical how to perform efficient compounding. Therefore, the development of a universal composite route is of great significance.
The surfaces of metal and alloy components are easily oxidized and corroded in the natural environment. Surface treatment or protective coating formation of metals and alloys can improve surface brightness of materials and components, enhance corrosion resistance, improve weatherability, and durability in use. Specific compositions and micro-nano structures are introduced on the surface of the member, so that pollution and propagation of marine organisms can be avoided, and an antifouling coating can be constructed.
The inventor has previously prepared cuprous oxide nanowire films that are macroscopically flat but microscopically interstitial. The micro-nano-scale gap and the high specific surface of the nanowire provide a foundation for further construction of a multiphase composite system. [ (1) Xuwei, Xiaoxing, Xiaheng, a cuprous oxide nanowire porous film and a preparation method and application thereof, the patent application number of the invention is 2014100140030; (2) xuwei, Xiaoxing, Xiacang, Suqian, Tianguo, a preparation method of cuprous oxide nanowire material, the patent application number of the invention is 2014100314653; (3) xuwei, Xiayeng, a flexible and bendable cuprous oxide film, a preparation method and application thereof, the invention has the patent application number of 2018101707840; (4) xuwei, Xiaxing, Zhang Hui, Gaying and nanostructured cuprous oxide photoelectric conversion film and a preparation method and application thereof, the invention has the patent application number of 2018101708881.
The inventor also proves that the 'metal ion-thiocyanate' aqueous solution system has unusual properties and can be used for preparing a plurality of metal oxide nano materials. These metal oxide and hydrated metal oxide nanomaterials have a variety of uses, including use as filling plugging materials and coating additives. [ (5) Xuwei, Sunjian, Xiaoxinxing, Xianceng, Tianguo, a simple preparation method of a sheet zinc oxide nano material, the invention has the patent application number: 2014100412374, respectively; (6) xuwei, Xianco, Sunjian, Zhanhui, green preparation method of metal oxide nano material, invention patent application No: 201810170300.2, respectively; (7) xuwei, Wang, Mat Shixu, Xulin Qi, the shape of the controllable zinc oxide nano material green preparation method, the invention patent application number: 201910359373.0.
during the research process, we further found that the 'metal ion-thiocyanate' aqueous solution can form a heterogeneous composite system with various solid surfaces. The invention proves that the metal ion-thiocyanate aqueous solution and the solid surface can form a composite solid-liquid interface and can be used for preparing a composite functional coating or a functional film, thereby opening a feasible technical route for the surface treatment of materials and the preparation of novel functional films.
Disclosure of Invention
The invention aims to provide a composite functional coating and a composite functional film, and a preparation method and application thereof.
The composite functional coating and the film provided by the invention are prepared by taking a composite solid-liquid interface system as a basis, reacting with a precipitator solution and carrying out in-situ reaction filling or in-situ reaction growth; and then washing, drying or baking to obtain the composite functional coating and the film.
The composite solid-liquid interface system consists of a solid substrate and a metal ion-thiocyanate aqueous solution; wherein:
the solid substrate can be one of a cuprous oxide nanowire film, a microporous ceramic film, foamed nickel, an iron sheet, carbon steel, weather-resistant steel, metal and alloy components, iron-based amorphous alloy, porous silicon, polycrystalline silicon, amorphous silicon, conductive glass, carbon fiber cloth, chemical fiber cloth and a polyimide film. The solid substrate may or may not be pre-treated with a surface treatment prior to use.
The metal ion-thiocyanate aqueous solution is used as a filling liquid or a doping liquid and is used for forming a composite solid-liquid interface system together with a solid substrate; the filling liquid and the doping liquid enter micro-nano gaps and holes on the surface of the solid substrate or are adsorbed on the surface, so that a composite solid-liquid interface system is formed.
The 'metal ion-thiocyanate' aqueous solution system can adopt a mixed aqueous solution of water-soluble metal salt and water-soluble thiocyanate. Compared with metal salt, the dosage of the water-soluble thiocyanate is equivalent, small or trace; the ratio of the amount of species of thiocyanate to metal ion is: 4.0 to 0.001 (molar ratio); the water-soluble thiocyanate adopts one of sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate.
The metal ion-thiocyanate aqueous solution and a solid substrate form a composite solid-liquid interface system through physical and chemical processes such as contact, diffusion or permeation. There are various methods for realizing the compounding of the solid-liquid system, including: soaking the solid substrate into a metal ion-thiocyanate aqueous solution; coating the aqueous solution of metal ion-thiocyanate on a solid substrate; spin coating the aqueous solution of metal ion-thiocyanate on the surface of a solid substrate; or spraying an aqueous solution of metal ion-thiocyanate onto the surface of the solid substrate. Specifically, one or more of these methods may be employed.
The precipitant solution is alkali water solution or inorganic salt water solution. Wherein the alkaline water solution is one of sodium hydroxide water solution, potassium hydroxide water solution and ammonia water solution; the aqueous solution of inorganic salt contains acid radical negative ions which can react with a metal ion-thiocyanate radical system to form precipitates which are insoluble or difficultly soluble in water.
The precipitant solution and the composite solid-liquid interface system react in situ to form a coating and a film. There are various ways to achieve this in situ reaction, including: soaking the composite solid-liquid interface system into a precipitant solution; coating a precipitant solution on the composite solid-liquid interface system; spin-coating a precipitant solution on the composite solid-liquid interface system; or spraying the precipitant solution on the composite solid-liquid interface system. Specifically, one or more of these methods may be employed.
The drying temperature is not more than 120 ℃; the baking temperature is usually not more than 350 ℃, and higher baking temperature can be adopted for some systems according to specific needs; for some materials and components, hot air drying instead of drying and flame baking instead of baking can also be adopted.
In the present invention, there are many metal ions for constructing the "metal ion-thiocyanate" aqueous solution system, and one of divalent metal ions, trivalent metal ions, tetravalent metal ions, or mixed metal ions of several of them may be used. The metal ion can be selected from one or more of indium ion, titanium ion, zirconium ion, chromium ion, manganese ion, iron ion, ferrous ion, cobalt ion, nickel ion, copper ion, lead ion, magnesium ion, calcium ion, barium ion, strontium ion, aluminum ion, gallium ion, and zinc ion. The metal ions and thiocyanate anions can form a metal ion-thiocyanate aqueous solution system.
The invention also provides a preparation method of the composite coating and the film, which comprises the following specific steps.
Optionally, a metal ion aqueous solution (such as a zinc ion aqueous solution) is added with a thiocyanate aqueous solution according to a predetermined ratio to form a metal ion-thiocyanate aqueous solution for later use.
The method comprises the following steps: and (3) immersing a solid substrate (such as a cuprous oxide nanowire film) into the metal ion-thiocyanate aqueous solution, soaking for 5 seconds to 30 minutes, taking out, removing redundant solution, immersing the film into a precipitant solution, reacting for 5 to 30 minutes (or optionally adopting ultrasonic assistance), washing, drying or baking to obtain the composite coating or film.
The second method comprises the following steps: coating a metal ion-thiocyanate aqueous solution on the surface of a solid substrate (such as a cuprous oxide nanowire film), standing for half an hour, quickly washing the surface, soaking the film into a precipitant solution, reacting for 5-30 minutes (or optionally adopting ultrasonic assistance), washing, drying or baking to obtain the composite coating or film.
When the precipitant is alkali solution (such as sodium hydroxide aqueous solution), the in-situ composite coating or film of the metal oxide and the hydrate thereof and the solid substrate is obtained.
When the precipitating agent is an inorganic salt aqueous solution (such as a sodium tungstate aqueous solution), an in-situ composite coating or film of the inorganic precipitate and the solid substrate is obtained.
The composite functional coating and the film prepared by the method have various types and adjustable performance, and the films with different compositions can have different purposes. Different metal ions or combinations of metal ions can be selected according to the methods described above, such as: a "zinc ion-thiocyanate" system, a "chromium ion-thiocyanate" system, a "nickel ion-thiocyanate" system, a "manganese ion-thiocyanate" system, a "titanium ion-thiocyanate" system, a "copper ion-thiocyanate" system, an "iron ion-thiocyanate" system, a "cobalt ion-thiocyanate" system, etc. of a single metal ion; a "zinc magnesium ion-thiocyanate" system, "ferrochromium ion-thiocyanate" system, "chromenium ion-thiocyanate" system, "ferrochromium ion-thiocyanate" system, "chromenium ion-thiocyanate" system, "zincium cobalt ion-thiocyanate" system, "cuprum nickel ion-thiocyanate" system, "chromenium ion-thiocyanate" system, etc. of the double metal ions; and ternary metal ion 'nickel iron chromium ion-thiocyanate' system, 'nickel manganese chromium ion-thiocyanate' system, 'copper nickel zinc ion-thiocyanate' system, 'iron cobalt zinc ion-thiocyanate' system and the like. The metal ion-thiocyanate aqueous solution can be used as a filling liquid or a doping liquid, and a composite type solid-liquid interface system is formed to prepare a composite type functional coating and a composite type functional film. It is also possible to select different substrates separately and to use similar methods for preparing coatings and films. For some substrates, surface treatment is required in advance, for example, the surface treatment can be carried out on carbon fiber cloth in advance, and then a coating is prepared; or the surface of the carbon steel is pretreated firstly, and then the composite coating is prepared.
The coating and the film prepared by the method can be dried only at a lower temperature, and can also be dried by hot air instead of drying; baking treatment can be adopted, and flame baking can also be used instead of baking. The process method has large selectable scope and convenient use.
The composite functional coating and the film prepared by the invention have a nano structure and are nano chemical materials.
The composite functional coating and the film prepared by the invention have various performances, so that the composite functional coating and the film can be applied in various ways.
The method for generating the coating in situ can be used as a general surface treatment method and a surface treatment technology, and can also be regarded as a surface nanocrystallization technology or a surface nanocrystallization engineering.
For example, some in situ formed coatings have plugging and corrosion inhibiting properties, which make them an effective surface treatment and corrosion inhibiting technique. Therefore, it can be used as a surface protective coating, an anticorrosion coating, a weather-resistant coating, etc. After the coating is formed on the surface of some materials and components in situ, the corrosion resistance is improved, the surface tissue form and structure of the materials can be obviously improved, and the chroma and the luster are improved.
The coating and surface treatment technology has important application in a wide range of industries such as steel, alloy, building materials, vehicles, transportation and the like. The preparation method of the coating comprises the following steps: preparing a 'metal ion-thiocyanate' aqueous solution, soaking the metal and alloy components in the solution for a period of time, or coating the 'metal ion-thiocyanate' aqueous solution on the surfaces of the metal and alloy components, then soaking the components in an alkaline solution or an inorganic salt aqueous solution to form a coating, and then washing, drying or baking the components.
The surface pretreatment is carried out on the carbon steel, the 'metal ion-thiocyanate' aqueous solution is coated on the surface of the carbon steel to construct a composite interface coating, then the composite interface coating is treated by an alkali solution or an inorganic salt solution, and then the composite interface coating is dried or baked to form a stable coating. In the aspect of post-treatment, hot air blow-drying can be used for replacing drying; flame heat treatment may also be used instead of baking.
The preparation method can construct the coating containing the copper component, and the coating containing the copper component has a bactericidal effect. The introduced components such as the cuprous oxide nanowire and the cupric oxide nanosheet have the bactericidal effect, and the mechanical stability and the durability of the coating can be enhanced. The cuprous oxide nanowires in the coating are similar to reinforcing steel bars in concrete, and the adhesion, mechanical property and stability of the film can be greatly enhanced. The coating with high stability and high performance can be used as a marine antifouling coating and a coating for preventing marine organism propagation, and is applied to marine equipment, particularly to the coating of ship bodies of large, medium and small ships and ship bodies.
The method for preparing the antifouling coating comprises the following steps: the method comprises the steps of depositing a copper film or a copper-containing film on the surfaces of steel and alloy components by a chemical coating method, an electrochemical coating method or a spraying method, and then reacting with a thiocyanate aqueous solution and a sodium hydroxide aqueous solution in sequence to prepare the cuprous oxide nanowire film in situ. Then, the composite solid-liquid interface system of the cuprous oxide nanowire and the metal ion-thiocyanate aqueous solution is prepared by treating the cuprous oxide nanowire and the metal ion-thiocyanate aqueous solution, and then the cuprous oxide nanowire and the composite solid-liquid interface system react with an alkaline aqueous solution or an inorganic salt aqueous solution to form various composite nano-structure films in situ composite with the cuprous oxide nanowire. The composite film has strong adhesive force, mechanical property, stability and antifouling capacity.
The method of the invention can also prepare the film with a loose pore structure, for example, the grown zinc tungstate film shows a distorted honeycomb-like structure and is formed by connecting loose ultrathin nano sheets. Coatings of different aggregate morphologies can meet different requirements. The coating with the micro-nano scale loose structure or the film with the multi-level hierarchical micro-nano structure can improve the ion transmission and embedding effect, improve the performance of the battery and be suitable for being used as the electrode material of lithium batteries and lithium ion secondary batteries; the film with the multilevel hierarchical micro-nano structure can also improve the light absorption and carrier conversion effects and can be used as the light absorption layer of the solar cell. Therefore, the method has application value in the field of energy storage and the field of solar photoelectric conversion.
In addition, the zinc-containing composite film also has excellent photoluminescence performance, and can be excited by ultraviolet light and green light (532 nm). When excited by green light (532 nm), the film can emit red light with high brightness, so that the film can be used as photoelectric functional material and photoelectric functional film.
The coating and the film prepared by the invention can obtain high-brightness luminescent property only by drying treatment. The characteristic is different from the common fluorescent powder which is processed at high temperature, and is a novel synthetic route for preparing luminescent materials and luminescent films. The high-performance thin film prepared by the low-temperature treatment has unique advantages in the manufacturing process of flexible light-emitting devices and large-area display screens, and can avoid the adverse effects of high-temperature treatment on the performance of flexible substrates and devices.
Most of the current commercialized white Light Emitting Devices (LEDs) adopt blue InGaN chips to excite yellow fluorescent powder, but the difficulties that the color rendering index is low, the color temperature is high (lack of red light components) and the like are difficult to overcome exist, so that the LEDs cannot well meet the indoor lighting requirements.
The synthesis route, the formula and the process provided by the invention are adjustable and controllable, and the high-performance luminescent material with various types and different luminescent wavelengths can be synthesized. The zinc-containing composite functional film can emit high-brightness red light under the excitation of green light, and the red light emitting film can be used as one of three primary colors to construct a white Light Emitting Device (LED).
The luminescent film and the photoelectric functional film prepared by the invention can also be made on a silicon substrate (for example, porous silicon is used as the substrate) to prepare a novel composite film of inorganic nano material and porous silicon, so that the quantum size effect of the nano material can be enhanced, the sensitivity can be improved, the problems of integration and compatibility of the inorganic nano material and a silicon-based device can be solved, and the integration and integration of the inorganic functional film, the silicon-based photoelectric device and a silicon-based circuit can be promoted from the aspects of the preparation method and the process.
The composite functional coating and the film prepared by the invention have various nano structures. For example, the structure of the nanometer wire wrapped by the superfine nanometer particles has nanometer scale effect and quantum effect, can be used as quantum material, and has potential application value in the field of new materials in the future.
The composite functional coating and film prepared by the invention can be used for photoluminescence materials and devices, and can also be used for other photoelectric functional films and device fields, such as the solar cell field (including photoelectric conversion), electroluminescence, photochromism, electrochromism, dielectric films, sensors, photocatalytic films and other wide fields.
Drawings
Fig. 1 is an SEM image (A, B) and photoluminescence spectrum (C) under 532 nm green excitation of a material sample prepared in example 1.
Fig. 2 is an SEM image (A, B) of a sample of the material prepared in example 2 and a photoluminescence spectrum (C) under excitation of 532 nm green light.
Detailed Description
The preparation method and the application of the composite functional coating and the film proposed by the invention are further described by the following embodiments:
example 1
Preparing 0.1 mol/l zinc sulfate (ZnSO)4) Aqueous solution, 0.5 mol/l aqueous solution of sodium thiocyanate (NaSCN) for use.
The preparation method of the cuprous oxide nanowire film is disclosed in previous invention patents. [ (1) Xuwei, Xiaoxing, Xiayeng, a cuprous oxide nanowire porous film, a preparation method and an application thereof, the patent application number of the invention is 2014100140030 ].
And depositing a copper film on the flexible plastic substrate by using a vacuum thermal evaporation method. And immersing the copper film into a thiocyanate aqueous solution for reaction, taking out the copper film after the reaction is finished, washing the copper film, and reacting the copper film with a sodium hydroxide aqueous solution to prepare the cuprous oxide nanowire film growing on the flexible plastic substrate for later use.
Uniformly mixing 10 ml of 0.5 mol/L sodium thiocyanate solution with 20 ml of 0.1 mol/L zinc sulfate aqueous solution to form a zinc ion-thiocyanate radical aqueous solution system, immersing the cuprous oxide nanowire film on the flexible plastic substrate into the zinc ion-thiocyanate radical aqueous solution, immersing for 15 minutes, and taking out; then immerging the mixture into excessive 1.0 mol/L sodium hydroxide aqueous solution, reacting for 30 minutes, washing, and drying at 60 ℃ to obtain the composite film of the zinc oxide nano material and the cuprous oxide nano wire.
Scanning electron microscope images (SEM) showed the thin film to be a composite of nanowires and nanoparticles, as shown in fig. 1 (a) and 1 (B). Due to the existence of the cuprous oxide nanowire, the aggregation form of the zinc oxide is changed from nanosheets under the conventional conditions into fine nanoparticles, and the nanoparticles and the nanowire are in a very good composite state.
Further tests have demonstrated that such simple composite films have strong photoluminescent properties. Under excitation of green light (532 nm), red light with high brightness can be emitted, as shown in fig. 1 (C).
By changing the experimental formula including the dosage of thiocyanate, a plurality of composite functional coatings and functional films can be prepared by adopting a similar method. The film can be used as a luminescent material and an optoelectronic functional film. The high-intensity red light can be used as one of three primary colors to construct a white light LED.
The coating and the film also have important application value in the fields of electroluminescence and solar cells; can also be used as a photocatalytic film for photocatalytic degradation of organic pollutants and promotion of environmental protection.
Example 2
The preparation is similar to example 1, but the precipitant is an aqueous solution of sodium tungstate.
The composite product obtained by the method is a composite of the zinc tungstate nanometer material and the cuprous oxide nanometer wire, and other components or different aggregation forms can exist. SEM images show that the aggregation morphology of the film is very special, and the film is connected into a honeycomb-like structure by ultrathin nanosheets, as shown in FIGS. 2 (A) and 2 (B).
Further tests have demonstrated that this simple composite precipitate film has a much stronger photoluminescence performance. Under green light (532 nm) excitation, red light emission of higher luminance can be emitted, as shown in fig. 2 (C).
By changing the experimental formula including the dosage of thiocyanate, a plurality of composite functional coatings and functional films can be prepared by adopting a similar method. The film can be used as a luminescent material and an optoelectronic functional film. The high-intensity red light can be used as one of three primary colors to construct a white light LED.
The coating and the film also have important application value in the fields of electroluminescence and solar cells; can also be used as a photocatalytic film for photocatalytic degradation of organic pollutants and promotion of environmental protection.
Example 3
Referring to the method of example 1, the plastic substrate is replaced by another substrate, and the zinc oxide and cuprous oxide nanowire composite film is prepared by a similar method, so that the photoelectric functional films on different substrates can be obtained.
This method also makes it possible to prepare marine antifouling coatings:
depositing copper film on the surface of steel and alloy members by chemical coating method (or electrochemical coating method), and reacting with thiocyanate aqueous solution and sodium hydroxide aqueous solution in turn to prepare cuprous oxide nanowire film. Then, by adopting a method similar to that in example 1, various "metal ion-thiocyanate" aqueous solutions are used to replace the "zinc ion-thiocyanate" aqueous solution, so as to prepare a cuprous oxide nanowire film and various "metal ion-thiocyanate" aqueous solution composite solid-liquid interface systems respectively, and then the cuprous oxide nanowire film or the composite coating of various oxides and cuprous oxide nanowires can be prepared by treating the solid-liquid interface systems with an alkali solution. The cuprous oxide nanowires in the coating are similar to reinforcing steel bars in concrete, and the adhesion, mechanical property and stability of the film can be greatly enhanced. The coating with stable structure has the bactericidal effect, can be used as an antifouling coating, is used for preventing marine organism pollution or marine organism propagation, and is applied to marine equipment, particularly to the coating of the ship bodies of large, medium and small ships and the ship body.
Example 4
Referring to the method of example 2, the plastic substrate is replaced by another substrate, and the zinc tungstate nanomaterial and cuprous oxide nanowire composite film is prepared by a similar method, so that photoelectric functional films on different substrates can be obtained.
The method can also be used for preparing marine antifouling coatings:
depositing copper-containing film on the surface of steel and alloy member by spraying method, and reacting with thiocyanate aqueous solution and sodium hydroxide aqueous solution in turn to obtain cuprous oxide nanowire film. Then, by adopting a method similar to that of example 2, various "metal ion-thiocyanate" aqueous solutions are used to replace "zinc ion-thiocyanate" aqueous solutions, cuprous oxide nanowire films and various "metal ion-thiocyanate" aqueous solution composite solid-liquid interface systems are respectively prepared, and then inorganic salt precipitator solutions are used for treatment, so that composite coatings or films of various precipitate metal nanomaterials and cuprous oxide nanowires can be prepared. The cuprous oxide nanowires in the coating are similar to reinforcing steel bars in concrete, and the adhesion, mechanical property and stability of the film can be greatly enhanced. The coating with stable structure has the bactericidal effect, can be used as an antifouling coating, is used for preventing marine organism pollution or marine organism propagation, and is applied to marine equipment, particularly to the coating of the ship bodies of large, medium and small ships and the ship body.
Example 5
150 ml of 1.0 mol/l aqueous sodium thiocyanate (NaSCN) solution was mixed with 100 ml of 0.5 mol/l aqueous chromium trichloride solution. Immersing the iron sheet in the solution for 15 min, taking out, reacting with excessive sodium hydroxide solution, washing, drying (or baking at 350 deg.C), and forming a coating on the surface.
Other metal ion-thiocyanate systems are adopted to replace chromium ion-thiocyanate systems, and similar preparation methods are adopted to form various coatings.
Other metal and alloy components, carbon steel and the like are used for replacing the iron sheet, and a coating can be formed on the surfaces of the components, the carbon steel and the like by adopting a similar method. In the aspect of post-treatment, hot air blow-drying can be used for replacing drying; flame heat treatment may also be used instead of baking.
The formed various coatings can be used as surface protection coatings, anticorrosion coatings, weather-resistant coatings and the like, and have important application in a wide range of industries such as steel, alloy, building materials, vehicles, transportation and the like;
when copper and other components (such as cuprous oxide nanowires and copper oxide nanosheets) are introduced into the coating, the coating can also be used as a high-strength marine antifouling coating and a coating for preventing marine organisms from breeding, and is applied to marine equipment, particularly to the coating of the ship bodies of large, medium and small ships and the ship bodies.
Example 6
Zinc sulfate (ZnSO) at 5 ml 0.1 mol/l4) To the aqueous solution, 5 drops of 0.1 mol/L ammonium thiocyanate (NH) were added dropwise4SCN) aqueous solution (about 0.2-0.25 ml) and evenly mixed (wherein, the dosage ratio of the zinc sulfate to the ammonium thiocyanate is about 25:1 by mol number). And soaking the porous silicon film in the solution for 2 hours, removing the redundant solution, treating with an excessive sodium hydroxide aqueous solution, washing and drying to obtain the nano zinc oxide-porous silicon composite film.
The composite film can be used as a luminescent film and an optoelectronic functional film, and can be integrated into a silicon-based device and a silicon-based circuit.
Example 7
20 ml of 0.5 mol/l zinc sulphate (ZnSO)4) Mixing the aqueous solution with 20 ml of 0.5 mol/L magnesium nitrate aqueous solution, adding 5 ml of 1.0 mol/L sodium thiocyanate (NaSCN) aqueous solution, uniformly mixing, immersing the porous silicon film into the mixed solution, immersing for 0.5 hour, taking out, immersing into excessive sodium hydroxide aqueous solution, washing, drying, and baking at 350 ℃ for 1 hour. And preparing the composite film of the zinc-magnesium oxide and the porous silicon.
The composite film can be used as a luminescent film and an optoelectronic functional film, and can be integrated into a silicon-based device and a silicon-based circuit.
Example 8
5 ml of 0.05 mol/l cobalt dichloride aqueous solution, 5 ml of 0.05 mol/l ferric trichloride aqueous solution and 5 ml of 0.05 mol/l zinc sulfate aqueous solution are mixed, 17.5 ml of 0.1 mol/l sodium thiocyanate aqueous solution is added, and the mixture is uniformly mixed.
The mixed solution was coated on a nickel foam and then immersed in 50 ml of a 0.2 mol/l aqueous solution of sodium hydroxide. Standing for 0.5 hour, taking out, washing, drying, and baking at 300 ℃ for 1 hour to obtain the foamed nickel loaded cobalt-iron-zinc ternary metal oxide composite membrane.
Can be used as functional materials, such as electrode materials of batteries and photocatalytic films. Can be used for photocatalytic degradation of organic pollutants and promote environmental protection.
Example 9
To 50 ml of a 0.5 mol/L aqueous titanium sulfate solution, 2.5 ml of 0.1 mol/L ammonium thiocyanate (NH) was added4SCN) aqueous solution, and mixing uniformly. And taking 5 ml of the mixed solution as filling liquid, dropwise adding the filling liquid onto the surface of the cuprous oxide nanowire film, coating to form a film, standing for 30 minutes under a moisture-preserving condition, removing the redundant solution, then immersing the film into an excessive sodium hydroxide aqueous solution, washing, drying, and baking for 1 hour at 350 ℃ to obtain the composite functional film of titanium dioxide and cuprous oxide nanowires.
The composite functional film containing the cuprous oxide nanowires has good mechanical property and high adhesive force, and also has the functions of sterilization, marine organism pollution prevention and marine organism propagation prevention. Can be applied to marine equipment, in particular to the coating of the ship bodies of large, medium and small ships and the ship body.
Claims (11)
1. A kind of compound functional coating and film, characterized by that, prepare and get by compound solid-liquid interface system and precipitant solution through reaction filling or reaction growing in situ; then washing, drying or baking to obtain a composite functional coating and a film;
the composite solid-liquid interface system consists of a solid substrate and a metal ion-thiocyanate aqueous solution; wherein:
the solid substrate is one of a cuprous oxide nanowire film, a microporous ceramic film, foamed nickel, an iron sheet, carbon steel, weather-resistant steel, metal and alloy components, iron-based amorphous alloy, porous silicon, polycrystalline silicon, amorphous silicon, conductive glass, carbon fiber cloth, chemical fiber cloth and a polyimide film; the solid substrate is subjected to surface treatment in advance before use or is not subjected to surface treatment in advance;
the metal ion-thiocyanate radical aqueous solution is used as filling liquid or doping liquid and enters micro-nano gaps and holes on the surface of the solid substrate or is adsorbed on the surface, so that a composite solid-liquid interface system is formed.
2. A composite functional coating and film as claimed in claim 1, wherein the "metal ion-thiocyanate" aqueous solution system is a mixed aqueous solution of water-soluble metal salt and water-soluble thiocyanate; compared with metal salt, the dosage of the water-soluble thiocyanate is equivalent, small or trace; the molar ratio of thiocyanate to metal ion is: 4.0 to 0.001; the water-soluble thiocyanate adopts one of sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate;
the precipitant solution adopts alkaline water solution or inorganic salt water solution; wherein the alkaline water solution is one of sodium hydroxide water solution, potassium hydroxide water solution and ammonia water solution; the aqueous solution of inorganic salt contains acid radical negative ions which can react with a metal ion-thiocyanate radical system to form precipitates which are insoluble or difficultly soluble in water.
3. A composite functional coating and film as claimed in claim 2, wherein the "metal ion-thiocyanate" aqueous solution forms a composite solid-liquid interface system with a solid substrate through physical and chemical processes of contact, diffusion or permeation; the method for realizing the compounding of the solid-liquid system comprises the following steps: soaking the solid substrate into a metal ion-thiocyanate aqueous solution; coating the aqueous solution of metal ion-thiocyanate on a solid substrate; spin coating the aqueous solution of metal ion-thiocyanate on the surface of a solid substrate; or spraying an aqueous solution of metal ion-thiocyanate onto the surface of the solid substrate.
4. A composite functional coating and film according to claim 3, wherein the precipitant solution reacts with the composite solid-liquid interface system in situ to form a coating and film, and a method for realizing the in situ reaction comprises: soaking the composite solid-liquid interface system into a precipitant solution; coating a precipitant solution on the composite solid-liquid interface system; spin-coating a precipitant solution on the composite solid-liquid interface system; or spraying the precipitant solution on the composite solid-liquid interface system.
5. A composite functional coating and film according to claim 1, wherein the drying temperature is not more than 120 ℃; the baking temperature does not exceed 350 ℃.
6. A composite functional coating and film as defined in claim 1, wherein the metal ions in the "metal ion-thiocyanate" aqueous solution system are one of divalent metal ions, trivalent metal ions, tetravalent metal ions, or mixed metal ions of several of them.
7. The composite functional coating and film according to claim 6, wherein the metal ions are selected from one or more of indium ions, titanium ions, zirconium ions, chromium ions, manganese ions, iron ions, ferrous ions, cobalt ions, nickel ions, copper ions, lead ions, magnesium ions, calcium ions, barium ions, strontium ions, aluminum ions, gallium ions, and zinc ions.
8. A method for preparing a composite functional coating and film according to any of claims 1 to 7, characterized by comprising the following steps:
(1) adding a metal ion aqueous solution into a thiocyanate aqueous solution according to a determined proportion to form a metal ion-thiocyanate aqueous solution;
(2) preparing the composite functional film
The method comprises the following steps: immersing the solid substrate into the metal ion-thiocyanate aqueous solution, soaking for 5 seconds to 30 minutes, taking out, removing redundant solution, immersing the film into a precipitator solution, reacting for 5 to 30 minutes, washing, drying or baking to obtain a composite functional coating or film;
the second method comprises the following steps: coating a 'metal ion-thiocyanate' aqueous solution on the surface of a solid substrate, standing for half an hour, quickly washing the surface, soaking the film into a precipitator solution, reacting for 5-30 minutes, washing, drying or baking to obtain a composite functional coating or film;
when the precipitant is an alkali solution, an in-situ composite coating or film of the metal oxide and the hydrate thereof and the solid substrate is obtained;
when the precipitating agent is inorganic salt water solution, the in-situ composite coating or film of the inorganic precipitate and the solid substrate is obtained.
9. A method for preparing a composite functional coating and film according to claim 8, wherein the following different metal ions or combinations of metal ions are selected respectively:
a single metal ion: a "zinc ion-thiocyanate" system, a "chromium ion-thiocyanate" system, a "nickel ion-thiocyanate" system, a "manganese ion-thiocyanate" system, a "titanium ion-thiocyanate" system, a "copper ion-thiocyanate" system, a "iron ion-thiocyanate" system, and a "cobalt ion-thiocyanate" system;
bimetallic ion: a "zinc magnesium ion-thiocyanate" system, a "ferrochromium ion-thiocyanate" system, a "chromenium ion-thiocyanate" system, a "ferronickel ion-thiocyanate" system, a "chromenium ion-thiocyanate" system, a "zincium copper ion-thiocyanate" system, a "zincium cobalt ion-thiocyanate" system, a "cupronium nickel ion-thiocyanate" system, and a "chromenium ion-thiocyanate" system;
ternary metal ions: the system comprises a nickel-iron-chromium ion-thiocyanate radical system, a nickel-manganese-chromium ion-thiocyanate radical system, a copper-nickel-zinc ion-thiocyanate radical system and a iron-cobalt-zinc ion-thiocyanate radical system.
10. Use of a composite functional coating and film according to any of claims 1 to 7, comprising:
(1) some in-situ formed coatings have blocking and corrosion resistance and are used as surface protection coatings, corrosion-resistant coatings, weather-resistant coatings and the like;
(2) some composite functional films have excellent photoluminescence performance and are used as photoelectric functional materials and photoelectric functional films.
11. The application of the composite functional coating and the film as claimed in one of claims 1 to 7, wherein the prepared composite functional coating contains copper-containing components of cuprous oxide nanowires or cupric oxide nanosheets, has a sterilization function, good adhesive force, mechanical property and stability, is used as a marine antifouling coating and a marine organism breeding prevention coating, and is applied to marine equipment, particularly to the coating of the ship bodies of large, medium and small ships and ship bodies; the method comprises the following steps: depositing a copper film or a copper-containing film on the surfaces of steel and alloy components by adopting a chemical coating method, an electrochemical coating method or a spraying method, and then sequentially and respectively reacting with a thiocyanate aqueous solution and a sodium hydroxide aqueous solution to prepare a cuprous oxide nanowire film in situ; then, the composite solid-liquid interface system of the cuprous oxide nanowire and the metal ion-thiocyanate aqueous solution is prepared by treating the cuprous oxide nanowire with the metal ion-thiocyanate aqueous solution, then the cuprous oxide nanowire and the composite solid-liquid interface system react with an alkaline aqueous solution or an inorganic salt aqueous solution to form various composite nanostructure coatings or films in situ compounded with the cuprous oxide nanowire, and the coatings or films are washed, dried or baked.
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| CN114316955A (en) * | 2021-12-29 | 2022-04-12 | 安徽科技学院 | Preparation method of porous silicon and cuprous thiocyanate compounded optical material |
| CN114990384A (en) * | 2022-06-10 | 2022-09-02 | 安徽科技学院 | Corrosion induction coating and spraying method thereof |
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| CN108654966A (en) * | 2018-05-16 | 2018-10-16 | 中国科学院上海高等研究院 | Electrically conducting transparent laminated film and preparation method thereof |
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| CN114316955B (en) * | 2021-12-29 | 2023-08-25 | 安徽科技学院 | Preparation method of porous silicon and cuprous thiocyanate composite optical material |
| CN114990384A (en) * | 2022-06-10 | 2022-09-02 | 安徽科技学院 | Corrosion induction coating and spraying method thereof |
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