FR2738812A1 - New photo-catalytic coatings based on titanium di:oxide in a mineral or organic dispersion - Google Patents
New photo-catalytic coatings based on titanium di:oxide in a mineral or organic dispersion Download PDFInfo
- Publication number
- FR2738812A1 FR2738812A1 FR9510838A FR9510838A FR2738812A1 FR 2738812 A1 FR2738812 A1 FR 2738812A1 FR 9510838 A FR9510838 A FR 9510838A FR 9510838 A FR9510838 A FR 9510838A FR 2738812 A1 FR2738812 A1 FR 2738812A1
- Authority
- FR
- France
- Prior art keywords
- coating
- substrate
- particles
- oxide
- titanium
- 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 107
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 27
- 239000006185 dispersion Substances 0.000 title claims abstract description 8
- 239000010936 titanium Substances 0.000 title claims description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 18
- 229910052719 titanium Inorganic materials 0.000 title claims description 18
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims description 6
- 239000011707 mineral Substances 0.000 title claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 111
- 239000011248 coating agent Substances 0.000 claims abstract description 97
- 239000000758 substrate Substances 0.000 claims abstract description 89
- 239000002245 particle Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 26
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 34
- 238000000151 deposition Methods 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 21
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 20
- 239000011521 glass Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 11
- 230000008021 deposition Effects 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000003373 anti-fouling effect Effects 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 230000003287 optical effect Effects 0.000 claims description 8
- 125000002524 organometallic group Chemical group 0.000 claims description 8
- 238000000197 pyrolysis Methods 0.000 claims description 8
- 239000011135 tin Substances 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 230000004888 barrier function Effects 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- 238000003618 dip coating Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 229910001887 tin oxide Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000005012 migration Effects 0.000 claims description 3
- 238000013508 migration Methods 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 230000010287 polarization Effects 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002800 charge carrier Substances 0.000 claims description 2
- 239000013522 chelant Substances 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 238000013032 photocatalytic reaction Methods 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000011941 photocatalyst Substances 0.000 claims 3
- 230000000996 additive effect Effects 0.000 claims 2
- 230000003667 anti-reflective effect Effects 0.000 claims 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims 1
- 238000003780 insertion Methods 0.000 claims 1
- 230000037431 insertion Effects 0.000 claims 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- 239000010410 layer Substances 0.000 description 38
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000008034 disappearance Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
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- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 150000001343 alkyl silanes Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000037338 UVA radiation Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000005329 float glass Substances 0.000 description 2
- 239000002241 glass-ceramic Substances 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011158 quantitative evaluation Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-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
- GIMXAEZBXRIECN-UHFFFAOYSA-J 2-hydroxyacetate;titanium(4+) Chemical compound [Ti+4].OCC([O-])=O.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O GIMXAEZBXRIECN-UHFFFAOYSA-J 0.000 description 1
- DNECTNVFMNQSRV-UHFFFAOYSA-N C(CCC)OC(N(CCO)OCCCC)CO.[Ti] Chemical compound C(CCC)OC(N(CCO)OCCCC)CO.[Ti] DNECTNVFMNQSRV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101100295848 Drosophila melanogaster Optix gene Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- 208000035874 Excoriation Diseases 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 108700010572 Sine oculis homeobox homolog 3 Proteins 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- MUKBXHSHQQKVDX-UHFFFAOYSA-N [Ti].COC(=O)CC(C)=O Chemical compound [Ti].COC(=O)CC(C)=O MUKBXHSHQQKVDX-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
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- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- UTLYKVGGKZYRRQ-UHFFFAOYSA-L dibutyltin(2+);difluoride Chemical compound CCCC[Sn](F)(F)CCCC UTLYKVGGKZYRRQ-UHFFFAOYSA-L 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- MAIANFGYWPRQDZ-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO MAIANFGYWPRQDZ-UHFFFAOYSA-N 0.000 description 1
- NRHMQDVIKPCCRT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO NRHMQDVIKPCCRT-UHFFFAOYSA-N 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- WIEGKKSLPGLWRN-UHFFFAOYSA-N ethyl 3-oxobutanoate;titanium Chemical compound [Ti].CCOC(=O)CC(C)=O WIEGKKSLPGLWRN-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
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- 230000005499 meniscus Effects 0.000 description 1
- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229960002715 nicotine Drugs 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/245—Oxides by deposition from the vapour phase
- C03C17/2456—Coating containing TiO2
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
- C03C17/25—Oxides by deposition from the liquid phase
- C03C17/256—Coating containing TiO2
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5041—Titanium oxide or titanates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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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
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
- C09D17/007—Metal oxide
- C09D17/008—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1225—Deposition of multilayers of inorganic material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1245—Inorganic substrates other than metallic
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1258—Spray pyrolysis
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
- C23C18/127—Preformed particles
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
- C01P2004/86—Thin layer coatings, i.e. the coating thickness being less than 0.1 time the particle radius
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- C01P2006/82—Compositional purity water content
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/212—TiO2
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- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/29—Mixtures
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- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
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- C03C2217/00—Coatings on glass
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Abstract
Description
SUBSTRAT A REVETEMENT PHOTO-CATALYTIQUE
L'invention concerne des substrats à base verrière, céramique ou vitrocéramique, plus particulièrement en verre, notamment transparents, que l'on munit de revêtements à propriétés photo-catalytiques, en vue de fabriquer des vitrages d'applications diverses, comme les vitrages utilitaires, vitrages pour véhicules ou pour bâtiments.SUBSTRATE WITH PHOTO-CATALYTIC COATING
The invention relates to glass-based, ceramic or glass-ceramic substrates, more particularly glass, in particular transparent, which are provided with coatings with photo-catalytic properties, in order to manufacture glazing of various applications, such as utility glazing. , glazing for vehicles or for buildings.
De plus en plus, on cherche à fonctionnaliser les vitrages en déposant à leur surface des couches minces destinées à leur conférer une propriété particulière selon l'application visée. Ainsi, il existe des couches à fonction optique, comme les couches dites anti-reflet composées d'un empilement de couches alternativement à haut et bas indices de réfraction. Pour une fonction anti-statique, ou chauffante du type anti-givre, on peut aussi prévoir des couches minces conductrices électriquement, par exemple à base de métal ou d'oxyde métallique dopé. Pour une fonction thermique, de bas-émissivité ou anti-solaire par exemple, on peut se tourner vers des couches minces en métal du type argent ou à base de nitrure ou d'oxyde métallique. Pour obtenir un effet anti-pluie , peuvent être prévues des couches à caractère hydrophobe, par exemple à base d'organo-silane fluoré
Cependant, il existe encore un besoin pour un substrat, notamment un vitrage que l'on pourrait qualifier d'anti-salissures , c'est-à-dire visant la permanence dans le temps des propriétés d'aspect et de surface, et permettant notamment d'espacer les nettoyages et/ou d'améliorer la visibilité, en parvenant à éliminer au fur et à mesure les salissures se déposant progressivement à la surface du substrat, notamment les salissures d'origine organique comme les traces de doigts ou des produits organiques volatils présents dans l'atmosphère, ou même des salissures du type buée. Increasingly, it is sought to functionalize the glazing by depositing on its surface thin layers intended to give them a particular property according to the intended application. Thus, there are layers with an optical function, such as the so-called anti-reflection layers composed of a stack of layers alternately with high and low refractive indices. For an anti-static or heating function of the anti-frost type, it is also possible to provide thin electrically conductive layers, for example based on metal or doped metal oxide. For a thermal, low-emissivity or anti-solar function for example, one can turn to thin layers of metal of the silver type or based on nitride or metal oxide. To obtain an anti-rain effect, hydrophobic layers may be provided, for example based on fluorinated organosilane
However, there is still a need for a substrate, in particular a glazing which could be described as anti-fouling, that is to say targeting the permanence over time of the appearance and surface properties, and allowing in particular to space cleaning and / or to improve visibility, by succeeding in eliminating progressively the stains gradually depositing on the surface of the substrate, in particular stains of organic origin such as fingerprints or products volatile organic substances present in the atmosphere, or even soiling of the fogging type.
Or on sait qu'il existe certains matériaux semi-conducteurs, à base d'oxyde métallique, qui sont aptes, sous l'effet d'un rayonnement de longueur d'onde adéquate, à initier des réactions radicalaires provoquant l'oxydation de produits organiques : on parle en général de matériaux photo-catalytiques ou encore photo-réactifs . Now we know that there are certain semiconductor materials, based on metal oxide, which are capable, under the effect of radiation of adequate wavelength, to initiate radical reactions causing the oxidation of products. organic: we generally speak of photo-catalytic or photo-reactive materials.
L'invention a alors pour but la mise au point de revêtements photocatalytiques sur substrat, qui présentent un effet anti-salissures marqué vis-à-vis du substrat et que l'on puisse fabriquer de manière industrielle. The object of the invention is therefore to develop photocatalytic coatings on the substrate, which have a marked anti-fouling effect on the substrate and which can be manufactured industrially.
L'invention a pour objet un substrat à base verrière, céramique ou vitrocéramique, notamment en verre et transparent, muni sur au moins une partie d'au moins une de ses faces d'un revêtement à propriété photo-catalytique comportant de l'oxyde de titane au moins partiellement cristallisé, incorporé audit revêtement sous forme de particules, notamment de taille comprise entre 5 et 70 nm, pour l'essentiel cristallisées sous forme anatase ou anatase/rutile. The subject of the invention is a glass-based, ceramic or glass-ceramic substrate, in particular glass and transparent, provided on at least part of at least one of its faces with a coating with photo-catalytic property comprising oxide. of at least partially crystallized titanium, incorporated into said coating in the form of particles, in particular of size between 5 and 70 nm, essentially crystallized in anatase or anatase / rutile form.
L'incorporation se fait de préférence avec un liant.The incorporation is preferably done with a binder.
L'oxyde de titane fait en effet partie des semi-conducteurs qui, sous l'action de la lumière dans le domaine visible ou des ultraviolets, dégradent des produits organiques qui se déposent à leur surface. Choisir l'oxyde de titane pour fabriquer un vitrage à effet anti-salissures est donc particulièrement indiqué, et ce d'autant plus que cet oxyde présente une bonne résistance mécanique et chimique : pour être efficace longtemps, il est évidemment important que le revêtement conserve son intégrité, alors même qu'il se trouve directement exposé à de nombreuses agressions, notamment lors du montage du vitrage sur chantier (bâtiment) ou sur ligne de production (véhicule), ce qui implique des manipulations répétées par des moyens de préhension mécaniques ou pneumatiques, et également une fois le vitrage en place, avec des risques d'abrasion (essuie-glace, chiffon abrasif) et de contact avec des produits chimiques agressifs (polluants atmosphériques du type SO2, produit d'entretien, ...). Titanium oxide is in fact part of the semiconductors which, under the action of light in the visible range or ultraviolet, degrade organic products which deposit on their surface. Choosing titanium oxide to manufacture glazing with an anti-fouling effect is therefore particularly recommended, and all the more so since this oxide has good mechanical and chemical resistance: to be effective for a long time, it is obviously important that the coating retains its integrity, even when it is directly exposed to numerous attacks, in particular when mounting the glazing on site (building) or on production line (vehicle), which implies repeated handling by mechanical gripping means or tires, and also once the glazing is in place, with the risk of abrasion (windscreen wiper, abrasive cloth) and contact with aggressive chemicals (atmospheric pollutants such as SO2, cleaning product, etc.).
Le choix s'est porté, en outre, sur un oxyde de titane qui soit au moins partiellement cristallisé parce qu'il a été montré qu'il était beaucoup plus performant en termes de propriété photo-catalytique que l'oxyde de titane amorphe. De préférence, il est cristallisé sous forme anatase, sous forme rutile ou sous forme d'un mélange d'anatase et de rutile, avec un taux de cristallisation d'au moins 25%, notamment d'environ 30 à 80%. (On comprend par taux de cristallisation la quantité en poids de TiO2 cristallisé par rapport à la quantité en poids totale de TiO2 dans le revêtement). The choice was made, moreover, on a titanium oxide which is at least partially crystallized because it has been shown to be much more efficient in terms of photo-catalytic property than amorphous titanium oxide. Preferably, it is crystallized in anatase form, in rutile form or in the form of a mixture of anatase and rutile, with a crystallization rate of at least 25%, in particular around 30 to 80%. (The amount by weight of TiO2 crystallized relative to the total amount by weight of TiO2 in the coating is understood by degree of crystallization.
On a également pu observer, notamment dans le cas d'une cristallisation sous forme anatase, que l'orientation des cristaux de TiO2 croissant sur le substrat avait une influence sur les performances photo-catalytiques de l'oxyde : il existe une orientation privilégiée (1,1,0) qui favorise nettement la photocatalyse. It has also been observed, in particular in the case of crystallization in anatase form, that the orientation of the growing TiO2 crystals on the substrate had an influence on the photo-catalytic performances of the oxide: there is a preferred orientation ( 1,1,0) which clearly promotes photocatalysis.
Avantageusement, la fabrication du revêtement est opérée de manière à ce que l'oxyde de titane cristallisé qu'il contient se trouve sous forme de cristallites , c'est-à-dire de monocristaux, ayant une taille moyenne comprise entre 0,5 et 60 nm, de préférence 1 à 50 nm, notamment 10 à 40 nm. C'est en effet dans cette gamme de dimension que l'oxyde de titane paraît avoir un effet photo-catalytique optimal, vraisemblablement parce que les cristallites de cette taille développent une surface active importante. Advantageously, the coating is produced in such a way that the crystallized titanium oxide which it contains is in the form of crystallites, that is to say single crystals, having an average size of between 0.5 and 60 nm, preferably 1 to 50 nm, especially 10 to 40 nm. It is indeed in this dimension range that titanium oxide appears to have an optimal photo-catalytic effect, probably because the crystallites of this size develop a large active surface.
Comme on le verra plus en détails ultérieurement par la description des différents modes d'obtention du revêtement, on peut en fait incorporer les particules d'oxyde de titane au revêtement de multiples façons. Ces particules sont en fait en général des agglomérats de cristallites et ont notamment une taille moyenne de l'ordre de 5 à 70 nm. As will be seen in more detail later on by the description of the various methods of obtaining the coating, the titanium oxide particles can in fact be incorporated into the coating in multiple ways. These particles are in fact in general agglomerates of crystallites and in particular have an average size of the order of 5 to 70 nm.
Le liant utilisable pour incorporer les particules au revêtement peut être minéral, notamment sous forme d'un oxyde (ou mélange d'oxydes) amorphe ou partiellement cristallisé, par exemple en oxyde de silicium, de titane, d'étain, de zirconium ou d'aluminium. II peut être cantonné à son rôle de matrice vis-à-vis des particules actives en oxyde de titane, ce qui est le cas par exemple de l'oxyde de silicium. Mais il peut aussi participer à l'effet photocatalytique des particules, en présentant lui-même un certain effet photocatalytique, même faible par rapport à celui des particules, ce qui est le cas de l'oxyde de titane amorphe ou partiellement cristallisé. The binder which can be used to incorporate the particles into the coating may be mineral, in particular in the form of an amorphous or partially crystallized oxide (or mixture of oxides), for example made of silicon, titanium, tin, zirconium or d oxide. 'aluminum. It can be confined to its role as a matrix with respect to the active particles of titanium oxide, which is the case for example of silicon oxide. But it can also participate in the photocatalytic effect of the particles, by itself presenting a certain photocatalytic effect, even weak compared to that of the particles, which is the case of amorphous or partially crystallized titanium oxide.
Le liant peut aussi être choisi partiellement ou essentiellement organique, notamment sous forme d'une matrice polymérique. II peut s'agir d'un polymère qui peut présenter des propriétés complémentaires à celles des particules d'oxyde de titane, et notamment des propriétés hydrophobes et/ou oléophobes et que l'on peut déposer par une technique du type sol-gel. Comme exemple de telles matrices, on peut se reporter à la demande de brevet FR-94/03689 du 29 mars 1994, qui décrit une telle matrice parfois qualifiée d'hybride et obtenue à partir d'une solution comprenant un alkoxysilane époxydé, un silane non époxydé hydrolysable, de la silice colloidale, un catalyseur et au moins un alkylsilane fluoré hydrolysable. L'alkylsilane fluoré est de formule générale: CF,-(CF,),-(CH2),-SiX3, avec n de 0 à 12, m de 2 à 5, X une fonction hydrolysable. L'alkylsilane époxydé est de formule
dans laquelle p est O ou A, r est 0,1 ou 2, s est un nombre entier entre 1 et 6,
M = H ou un alkyle comprenant 1 à 4 atomes de carbone, M' et M " sont des alkyles comprenant 1 à 3 atomes de carbone. Le silane non époxydé est de formule générale
dans laquelle N et N' sont des groupements organiques liés à l'atome de silicium par une liaison Si-C et qui ne comportent pas de groupement susceptible de réagir avec les silanes hydrolysés présents dans la compositions, et où Q et Q' sont des fonctions hydrolysables.The binder can also be chosen partially or essentially organic, in particular in the form of a polymer matrix. It can be a polymer which can have properties complementary to those of titanium oxide particles, and in particular hydrophobic and / or oleophobic properties and which can be deposited by a technique of the sol-gel type. As an example of such matrices, reference may be made to patent application FR-94/03689 of March 29, 1994, which describes such a matrix sometimes qualified as hybrid and obtained from a solution comprising an epoxidized alkoxysilane, a silane hydrolysable non-epoxidized, colloidal silica, a catalyst and at least one hydrolyzable fluorinated alkylsilane. The fluorinated alkylsilane has the general formula: CF, - (CF,), - (CH2), - SiX3, with n from 0 to 12, m from 2 to 5, X a hydrolysable function. The epoxidized alkylsilane has the formula
where p is O or A, r is 0.1 or 2, s is an integer between 1 and 6,
M = H or an alkyl comprising 1 to 4 carbon atoms, M ′ and M "are alkyls comprising 1 to 3 carbon atoms. The non-epoxidized silane has the general formula
in which N and N 'are organic groups linked to the silicon atom by an Si-C bond and which do not comprise a group capable of reacting with the hydrolysed silanes present in the compositions, and where Q and Q' are hydrolyzable functions.
On peut aussi choisir de superposer au revêtement selon l'invention une couche oléophobe et/ou hydrophobe greffée, par exemple à base de l'organosilane fluoré décrit dans les brevets US-5 368 892 et US-5 389 427, ainsi qu'à base du perfluoroalkylsilane décrit dans la demande de brevet FR94/08734 du 13 juillet 1994, notamment de formule CF3~(CF2)n~(CH2)m~Six3 dans laquelle n est de 0 à 12, m est de 2 à 5 et X est un groupe hydrolysable. One can also choose to superimpose on the coating according to the invention an oleophobic and / or hydrophobic layer grafted, for example based on the fluorinated organosilane described in patents US-5,368,892 and US-5,389,427, as well as base of perfluoroalkylsilane described in patent application FR94 / 08734 of July 13, 1994, in particular of formula CF3 ~ (CF2) n ~ (CH2) m ~ Six3 in which n is from 0 to 12, m is from 2 to 5 and X is a hydrolyzable group.
Pour amplifier l'effet photo-catalytique des particules d'oxyde de titane du revêtement selon l'invention, on peut y incorporer des additifs adaptés. To amplify the photo-catalytic effect of the titanium oxide particles of the coating according to the invention, suitable additives can be incorporated therein.
On peut tout d'abord augmenter la bande d'absorption du revêtement, en incorporant au revêtement d'autres particules notamment métalliques et à base de cadmium, d'étain, de tungstène, de zinc, de cérium, ou de zirconium. We can first of all increase the absorption band of the coating, by incorporating into the coating other particles, in particular metallic and based on cadmium, tin, tungsten, zinc, cerium, or zirconium.
On peut aussi augmenter le nombre de porteurs de charge par dopage du réseau cristallin de l'oxyde de titane constitutif des particules, en y insérant au moins un des éléments métalliques suivants : niobium, tantale, fer, bismuth, cobalt, nickel, cuivre, ruthénium, cérium, molybdène. It is also possible to increase the number of charge carriers by doping the crystal lattice of the titanium oxide constituting the particles, by inserting therein at least one of the following metallic elements: niobium, tantalum, iron, bismuth, cobalt, nickel, copper, ruthenium, cerium, molybdenum.
Ce dopage peut aussi se faire par un dopage de surface seulement des particules d'oxyde de titane, dopage de surface réalisé en recouvrant au moins une partie desdites particules d'une couche d'oxydes ou de sels métalliques, le métal étant choisi parmi le fer, le cuivre, le ruthénium, le cérium, le molybdène, le vanadium et le bismuth. This doping can also be done by surface doping only of the titanium oxide particles, surface doping carried out by covering at least part of said particles with a layer of oxides or metal salts, the metal being chosen from among iron, copper, ruthenium, cerium, molybdenum, vanadium and bismuth.
Enfin, on peut amplifier le phénomène photocatalytique en augmentant rendement et/ou cinétique des réactions photocatalytiques, en recouvrant au moins une partie des particules par un métal noble sous forme de couche mince du type platine, rhodium, argent. Finally, the photocatalytic phenomenon can be amplified by increasing the yield and / or kinetics of the photocatalytic reactions, by covering at least part of the particles with a noble metal in the form of a thin layer of the platinum, rhodium, silver type.
De manière tout-à-fait surprenante, le revêtement présente en fait non pas une propriété mais deux, dès qu'il est exposé à un rayonnement adéquat comme la lumière visible et/ou les ultraviolets : par la présence d'oxyde de titane photo-catalytique, comme déjà vu, il favorise la disparition progressive, au fur et à mesure de leur accumulation, de salissures d'origine organique, en provoquant leur dégradation par un processus d'oxydation radicalaire. Surprisingly, the coating actually has not one property but two, as soon as it is exposed to adequate radiation such as visible light and / or ultraviolet light: by the presence of photo titanium oxide -catalytic, as already seen, it promotes the progressive disappearance, as and when they accumulate, of dirt of organic origin, by causing their degradation by a process of radical oxidation.
Mais le revêtement de l'invention présente également de préférence une surface extérieure à caractère hydrophile et/ou oléophile prononcé, notamment dans le cas où le liant est minéral, ce qui amène deux avantages non négligeables : un caractère hydrophile permet un mouillage parfait de l'eau qui peut se déposer sur le revêtement. Au lieu d'un dépôt de gouttelettes d'eau sous forme de buée gênant la visibilité, on a en fait un mince film continu d'eau qui se forme à la surface du revêtement et qui est tout-à-fait transparent. Cet effet anti-buée est notamment démontré par le mesure d'un angle de contact à l'eau inférieur à 50après exposition à la lumière. However, the coating of the invention also preferably has an outer surface with a pronounced hydrophilic and / or oleophilic character, in particular in the case where the binder is mineral, which brings two significant advantages: a hydrophilic character allows perfect wetting of the water that can settle on the coating. Instead of depositing water droplets in the form of a mist which impairs visibility, there is in fact a thin continuous film of water which forms on the surface of the coating and which is completely transparent. This anti-fog effect is demonstrated in particular by measuring a contact angle with water less than 50 after exposure to light.
Conjointement à un caractère hydrophile, il peut aussi présenter un caractère oléophile, permettant le mouillage des salissures organiques qui, comme pour l'eau, tendent alors à se déposer sur le revêtement sous forme d'un film continu moins visible que des taches bien localisées. On obtient ainsi un effet anti-salissures organiques qui s'opère en deux temps : dès qu'elle se dépose sur le revêtement, la salissure est déjà peu visible. Ensuite, progressivement, elle disparaît par dégradation radicalaire amorcée par photocatalyse. In conjunction with a hydrophilic character, it can also have an oleophilic character, allowing the wetting of organic dirt which, as for water, then tends to be deposited on the coating in the form of a continuous film less visible than well localized spots. . An organic anti-fouling effect is thus obtained which takes place in two stages: as soon as it is deposited on the coating, the soiling is already hardly visible. Then, gradually, it disappears by radical degradation initiated by photocatalysis.
L'épaisseur du revêtement selon l'invention est variable, elle est de préférence comprise entre 5 nm et 1 micron, notamment entre 5 et 100 nm, notamment entre 10 et 80 nm, ou entre 20 et 50 nm. En fait, le choix de l'épaisseur peut dépendre de différents paramètres, notamment de l'application envisagée du substrat du type vitrage, ou encore de la taille des cristallites de TiO2 dans le revêtement. Le revêtement peut également être choisi de surface plus ou moins lisse : une faible rugosité de surface peut en effet être avantageuse, si elle permet de développer une surface photocatalytique active plus grande. Cependant, trop prononcée, elle peut être pénalisante en favorisant l'incrustation, l'accumulation des salissures. Dans le cas où le revêtement est à base de particules de TiO2 enrobées dans un liant, on peut choisir le mode de dépôt et l'épaisseur du revêtement de telle sorte que les particules ou les cristallites dont elles sont constituées émergent en surface de ce liant. The thickness of the coating according to the invention is variable, it is preferably between 5 nm and 1 micron, in particular between 5 and 100 nm, in particular between 10 and 80 nm, or between 20 and 50 nm. In fact, the choice of thickness may depend on various parameters, in particular on the envisaged application of the glazing type substrate, or even on the size of the TiO2 crystallites in the coating. The coating can also be chosen to have a more or less smooth surface: a low surface roughness can indeed be advantageous, if it makes it possible to develop a larger active photocatalytic surface. However, too pronounced, it can be penalizing by favoring the incrustation, the accumulation of dirt. In the case where the coating is based on TiO2 particles coated in a binder, the mode of deposition and the thickness of the coating can be chosen so that the particles or the crystallites from which they are formed emerge on the surface of this binder .
Entre le substrat et le revêtement selon l'invention, on peut disposer une ou plusieurs autres couches minces à fonction différente ou complémentaire de celle du revêtement. Il peut s'agir, notamment, de couches à fonction antistatique, thermique, optique ou de couches faisant barrière à la migration de certains éléments provenant du substrat, notamment faisant barrière aux alcalins et tout particulièrement aux ions sodium quand le substrat est en verre. On peut aussi envisager un empilement de couches anti-reflets alternant des couches minces à haut et bas indices, le revêtement selon l'invention constituant la dernière couche de l'empilement. Dans ce cas, il est préférable que le revêtement soit d'indice de réfraction relativement peu élevé, ce qui est le cas quand il est constitué, notamment, d'une matrice minérale du type oxyde de silicium dans laquelle sont noyées des particules d'oxyde de titane, ou d'un oxyde mixte de titane et de silicium. Between the substrate and the coating according to the invention, one or more other thin layers can be arranged with a function different or complementary to that of the coating. They can be, in particular, layers with an antistatic, thermal, optical function or layers making a barrier to the migration of certain elements coming from the substrate, in particular making a barrier to alkalis and very particularly to sodium ions when the substrate is made of glass. One can also envisage a stack of anti-reflection layers alternating thin layers with high and low indices, the coating according to the invention constituting the last layer of the stack. In this case, it is preferable for the coating to have a relatively low refractive index, which is the case when it is made up, in particular, of a mineral matrix of the silicon oxide type in which particles of titanium oxide, or a mixed oxide of titanium and silicon.
La couche à fonction anti-statique et ou thermique (chauffante en la munissant d'amenées de courant, bas-émissive, anti-solaire, ...) peut notamment être choisie à base d'un matériau conducteur du type métal, comme l'argent, ou du type oxyde métallique dopé comme l'oxyde d'indium dopé à l'étain ITO, L'oxyde d'étain dopé avec un halogène du type fluor
SnO2:F, ou de l'oxyde de zinc dopé à l'indium ZnO:ln, au fluor ZnO:F, à l'aluminium ZnO:A ou à l'étain ZnO:Sn.The layer with an anti-static and or thermal function (heating by providing it with current leads, low-emissivity, anti-sun, etc.) can in particular be chosen based on a conductive material of the metal type, such as silver, or of the metal oxide type doped like indium oxide doped with tin ITO, Tin oxide doped with a halogen of fluorine type
SnO2: F, or zinc oxide doped with indium ZnO: ln, fluorine ZnO: F, aluminum ZnO: A or tin ZnO: Sn.
La couche à fontion anti-statique a de préférence un valeur de résistance carrée de 20 à 1000 ohms/carré. On peut prévoir de la munir d'amenées de courant afin de la polariser (tensions d'alimentation par exemple comprises entre 5 et 100V). Cette polarisation contrôlée permet notamment de lutter contre le dépôt de poussières de taille de l'ordre du millimètre susceptibles de se déposer sur le revêtement, notamment des poussières sèches adhérentes que par effet électro-statique : en inversant brutalement la polarisation de la couche, on éjecte ces poussières. The anti-static function layer preferably has a square resistance value of 20 to 1000 ohms / square. Provision can be made for supplying current in order to polarize it (supply voltages for example between 5 and 100V). This controlled polarization makes it possible in particular to combat the deposition of dust of size on the order of a millimeter capable of being deposited on the coating, in particular adherent dry dust only by electro-static effect: by brutally reversing the polarization of the layer, ejects this dust.
La couche mince à fonction optique peut être choisie afin de diminuer la réflexion lumineuse et/ou rendre plus neutre la couleur en réflexion du substrat. Elle présente dans ce cas, de préférence, un indice de réfraction intermédiaire entre celui du revêtement et celui du substrat et une épaisseur optique apprpriée, et peut être constituée d'un oxyde ou d'un mélange d'oxydes du type oxyde d'aluminium Al2O3, oxyde d'étain SnO2, oxyde d'indium Ion203, oxycarbure ou oxynitrure de silicium. Pour obtenir une atténuation maximale de la couleur en réflexion, il est préférable que cette couche mince présente un indice de réfraction proche de la racine carrée du produit des carrés des indices de réfraction des deux matériaux qui l'encadrent, c'est-à-dire le substrat et le revêtement selon l'invention. The thin layer with an optical function can be chosen in order to reduce the light reflection and / or make the color in reflection of the substrate more neutral. In this case, it preferably has a refractive index intermediate between that of the coating and that of the substrate and an appropriate optical thickness, and may consist of an oxide or a mixture of oxides of the aluminum oxide type. Al2O3, tin oxide SnO2, indium oxide Ion203, oxycarbide or silicon oxynitride. To obtain maximum attenuation of the color in reflection, it is preferable that this thin layer has an index of refraction close to the square root of the product of the squares of the indices of refraction of the two materials which surround it, that is to say say the substrate and the coating according to the invention.
Parallèlement, il est avantageux de choisir son épaisseur optique (c'est-à-dire le produit de son épaisseur géométrique et de son indice de réfraction) voisine de lambda/4, lambda étant approximativement la longueur d'onde moyenne dans le visible, notamment d'environ 500 à 550 nm.At the same time, it is advantageous to choose its optical thickness (that is to say the product of its geometric thickness and its refractive index) close to lambda / 4, lambda being approximately the average wavelength in the visible range, especially around 500 to 550 nm.
La couche mince à fonction de barrière aux alcalins peut être notamment choisie à base d'oxyde, de nitrure, d'oxynitrure ou d'oxycarbure de silicium, en oxyde d'aluminium contenant du fluor Al2O3:F, ou encore en nitrure d'aluminium. En fait, elle s'est avérée utile quand le substrat est en verre, car la migration d'ions sodium dans le revêtement selon l'invention peut, dans certaines conditions, en altérer les propriétés photo-catalytiques. The thin layer with an alkali barrier function may in particular be chosen based on silicon oxide, nitride, oxynitride or oxycarbide, in aluminum oxide containing fluorine Al2O3: F, or also in nitride of aluminum. In fact, it has been found to be useful when the substrate is made of glass, since the migration of sodium ions into the coating according to the invention can, under certain conditions, alter its photocatalytic properties.
Toutes ces couches minces optionnelles peuvent, de manière connue, être déposées par des techniques sous vide du type pulvérisation cathodique ou par d'autres techniques du type décomposition thermique telles que les pyrolyses en phase solide, liquide ou gazeuse. Chacune des couches prémentionnées peut cumuler plusieurs fonctions, mais on peut aussi les superposer. All these optional thin layers can, in known manner, be deposited by vacuum techniques of the sputtering type or by other techniques of the thermal decomposition type such as pyrolysis in solid, liquid or gas phase. Each of the aforementioned layers can combine several functions, but they can also be superimposed.
L'invention a également pour objet les vitrages anti-salissures et/ou anti-buée , qu'ils soient monolithiques, multiples isolants du type doublevitrage ou feuilletés, et qui incorporent les substrats revêtus précédemment décrits. The subject of the invention is also anti-fouling and / or anti-fog glazing, whether monolithic, multiple insulators of the double-glazing or laminated type, and which incorporate the coated substrates previously described.
L'invention vise donc la fabrication de produits verriers, céramiques ou vitro-céramiques, et tout particulièrement la fabrication de vitrages autonettoyants . Ceux-ci peuvent avantageusement être des vitrages de bâtiment, comme des double-vitrages (on peut alors disposer le revêtement côté extérieur et/ou côté intérieur , c'est-à-dire en face 1 et/ou en face 4). The invention therefore relates to the manufacture of glass, ceramic or vitro-ceramic products, and in particular the manufacture of self-cleaning glazing. These can advantageously be building glazing, such as double glazing (the coating can then be placed on the outside and / or on the inside, that is to say on face 1 and / or on face 4).
Cela s'avère tout particulièrement intéressant pour les vitrages peu accessibles au nettoyage et/ou qui ont besoin d'être nettoyés très fréquemment, comme des vitrages de toîture, des vitrages d'aéroports, ... II peut aussi s'agir de vitrages pour véhicules où le maintien de la visibilité est un critère essentiel de sécurité. Ce revêtement peut ainsi être disposé sur des pare-brise, latéraux ou lunettes arrière de voiture, notamment sur la face des vitrages tournée vers l'intérieur de l'habitacle. Ce revêtement peut alors éviter la formation de buée, et/ou supprimer les traces de salissures du type trace de doigts, nicotine ou matériau organique du type plastifiant volatil relargué par le plastique habillant l'intérieur de l'habitacle, notamment celui du tableau de bord (relargage connu parfois sous le terme anglais de fogging ). D'autres véhicules tels qu'avions ou trains peuvent aussi trouver intérêt à utiliser des vitrages munis du revêtement de l'invention.This is particularly advantageous for glazing that is difficult to access for cleaning and / or that needs to be cleaned very frequently, such as roof glazing, airport glazing, etc. It may also be glazing for vehicles where maintaining visibility is an essential safety criterion. This coating can thus be arranged on windshields, lateral or rear windows of the car, in particular on the face of the glazing turned towards the interior of the passenger compartment. This coating can then prevent the formation of fogging, and / or remove the traces of soiling of the fingerprint type, nicotine or organic material of the volatile plasticizer type released by the plastic covering the interior of the passenger compartment, in particular that of the switchboard. edge (salting known sometimes under the English term of fogging). Other vehicles such as planes or trains may also find it advantageous to use glazing provided with the coating of the invention.
Nombre d'autres applications sont possibles, notamment pour les verres d'aquarium, les vitrines de magasin, les serres, les vérandas, les verres utilisés dans l'ameublement intérieur ou le mobilier urbain, mais aussi les miroirs, les écrans de télévision,
Une autre application intéressante du revêtement selon l'invention consiste à l'associer à un vitrage à absorption variable commandée électriquement du type vitrage électrochrome, vitrage à cristaux liquides éventuellement avec colorant dichroïque, vitrage à système de particules suspendues, vitrage viologène... Tous ces vitrages étant constitués en général d'une pluralité de substrats transparents entre lesquels sont disposés les éléments actifs , on peut alors avantageusement disposer le revêtement sur la face extérieure d'au moins un de ces substrats.Many other applications are possible, in particular for aquarium glasses, shop windows, greenhouses, verandas, glasses used in interior or street furniture, but also mirrors, television screens,
Another interesting application of the coating according to the invention consists in associating it with an electrically controlled variable absorption glazing of the electrochromic glazing type, liquid crystal glazing optionally with dichroic dye, glazing with suspended particle system, viologen glazing ... All these glazings being generally made up of a plurality of transparent substrates between which the active elements are arranged, it is then advantageously possible to arrange the coating on the external face of at least one of these substrates.
Notamment dans le cas d'un vitrage électrochrome, lorsque ce dernier est à l'état coloré, son absorption conduit à un certain échauffement en surface, ce qui, de fait, est susceptible d'accélérer la décomposition photocatalytique des substances carbonées se déposant sur le revêtement selon l'invention. In particular in the case of an electrochromic glazing, when the latter is in the colored state, its absorption leads to a certain heating on the surface, which, in fact, is capable of accelerating the photocatalytic decomposition of the carbonaceous substances depositing on the coating according to the invention.
Pour plus de détails sur la structure d'un vitrage électrochrome, on se reportera avantageusement à la demande de brevet EP-A-O 575 207 décrivant un double vitrage feuilleté électrochrome, le revêtement selon l'invention pouvant, de préférence, être disposé en face 1.For more details on the structure of an electrochromic glazing, advantageously reference will be made to patent application EP-AO 575 207 describing an electrochromic laminated double glazing, the coating according to the invention preferably being able to be placed opposite 1 .
L'invention a également pour objet les différents procédés d'obtention du revêtement selon l'invention. On peut avoir recours à une technique de dépôt du type pyrolyse, intéressante car elle permet notamment le dépôt du revêtement en continu, directement sur le ruban de verre float, lorsqu'on utilise un substrat verrier. The invention also relates to the various methods of obtaining the coating according to the invention. It is possible to use a deposition technique of the pyrolysis type, which is advantageous because it allows the coating to be deposited continuously, directly on the ribbon of float glass, when a glass substrate is used.
La pyrolyse peut s'effectuer en phase liquide, à partir d'une solution comprenant les particules d'oxyde de titane et au moins un précurseur organométallique, notamment de titane du type chélate de titane et/ou alcoolate de titane. Pour plus de détails sur la nature du précurseur de titane ou sur les conditions de dépôt, on se rapportera par exemple aux brevets FR-2 310 977 et EP-O 465 309. The pyrolysis can be carried out in the liquid phase, from a solution comprising the particles of titanium oxide and at least one organometallic precursor, in particular of titanium of the titanium chelate type and / or titanium alcoholate. For more details on the nature of the titanium precursor or on the deposition conditions, reference will be made, for example, to patents FR-2 310 977 and EP-O 465 309.
On peut également déposer le revêtement par d'autres techniques, notamment par la technique dite sol-gel . Différents modes de dépôt sont possibles, comme le trempé aussi appelé dip-coating ou un dépôt à l'aide d'une cellule appelé cell-coating , cette dernière technique étant décrite en détails dans la demande de brevet FR-95/05978 déposée le 19 mai 1995. Il peut aussi s'agir d'un mode de dépôt par spray-coating ou par enduction laminaire, cette dernière technique étant détaillée dans la demande de brevet WO-94/01598. Tous ces modes de dépôt utilisent en général une solution comprenant au moins un précurseur organo-métallique, notamment de titane du type alcoolate que l'on décompose thermiquement après enduction du substrat par la solution sur l'une de ses faces, ou sur ses deux faces. The coating can also be deposited by other techniques, in particular by the so-called sol-gel technique. Different deposition modes are possible, such as quenching also called dip-coating or deposition using a cell called cell-coating, the latter technique being described in detail in patent application FR-95/05978 filed on May 19, 1995. It can also be a mode of deposition by spray-coating or by laminar coating, the latter technique being detailed in patent application WO-94/01598. All of these deposition methods generally use a solution comprising at least one organometallic precursor, in particular titanium of the alcoholate type which is thermally decomposed after coating of the substrate with the solution on one of its faces, or on both. faces.
Ces techniques de dépôt précédemment énoncées qui ont recours à une solution, incorporent donc à la solution de précurseurs métalliques une poudre ou une dispersion colloïdale de particules d'oxyde de titane déjà formé et cristallisé, notamment sous forme anatase ou anatase/rutile. Ces particules, évoquées plus haut, sont hautement actives sur le plan photocatalytique et peuvent en outre favoriser la cristallisation du TiO2 formé par décomposition thermique à partir des précurseurs, en jouant vraisemblablement le rôle de germes de cristallisation. Dans le revêtement final, on a ainsi de l'oxyde de titane fabriqué de deux façons différentes. Avantageusement, on peut choisir un taux d'introduction de particules d'oxyde de titane dans la solution de manière à utiliser de 0,1 à 0,6 gramme de ces particules par gramme d'oxyde de titane efffectivement déposé sur le substrat. De préférence, les particules d'oxyde de titane ont une répartition granulométrique telle qu'au moins 80% d'entre-elles présentent un même diamètre moyen, notamment d'environ 20 ou 40 nm. La dispersion de particules de TiO2 présente avantageusement des caractéristiques spécifiques, notamment elle comprend des particules de dioxyde de titane au moins partiellement cristallisées et monodisperses . These previously stated deposition techniques, which use a solution, therefore incorporate into the solution of metallic precursors a colloidal powder or dispersion of titanium oxide particles already formed and crystallized, in particular in the anatase or anatase / rutile form. These particles, mentioned above, are highly active on the photocatalytic level and can further promote the crystallization of the TiO2 formed by thermal decomposition from the precursors, probably playing the role of seeds of crystallization. In the final coating, titanium oxide is thus produced in two different ways. Advantageously, one can choose a rate of introduction of titanium oxide particles into the solution so as to use from 0.1 to 0.6 gram of these particles per gram of titanium oxide effectively deposited on the substrate. Preferably, the titanium oxide particles have a particle size distribution such that at least 80% of them have the same mean diameter, in particular around 20 or 40 nm. The dispersion of TiO2 particles advantageously has specific characteristics, in particular it comprises at least partially crystallized and monodisperse titanium dioxide particles.
On entend par monodisperses des particules présentant un indice de dispersion d'au plus 0,5, de préférence d'au plus 0,3, L'indice de dispersion étant donné par la formule suivante : I = (84-16) / 2. 50 dans laquelle 84 est le diamètre des particules pour lequel 84% des particules ont un diamètre inférieur à 84 16 est le diamètre des particules pour lequel 16% des particules ont un diamètre inférieur à 16
II peut être intéressant, par ailleurs, de déposer le revêtement, quelle que soit la technique de dépôt envisagée, non pas en une seule fois, mais par au moins deux étapes successives, ce qui paraît favoriser la cristallisation de l'oxyde de titane sur toute l'épaisseur du revêtement lorsqu'on le choisit relativement épais.The term “monodisperses” is understood to mean particles having a dispersion index of at most 0.5, preferably at most 0.3, the dispersion index being given by the following formula: I = (84-16) / 2 .50 in which 84 is the particle diameter for which 84% of the particles have a diameter less than 84 16 is the particle diameter for which 16% of the particles have a diameter less than 16
It may also be advantageous to deposit the coating, whatever the deposition technique envisaged, not at once, but by at least two successive stages, which appears to favor the crystallization of titanium oxide on the entire thickness of the coating when chosen relatively thick.
De même, il est avantageux de faire subir au revêtement à propriété photo-catalytique, après dépôt, un traitement thermique du type recuit. Un traitement thermique est indispensable pour une technique du type sol-gel ou enduction laminaire afin de décomposer le((s) précurseur(s) organométallique(s) en oxyde, une fois l'enduction du substrat effectuée, ce qui n'est pas le cas lorsqu'on utilise une technique de pyrolyse où le précurseur se décompose dès qu'il se trouve au contact du substrat. Dans le premier cas comme dans le second, cependant, un traitement thermique post-dépôt, une fois le TiO2 formé, améliore son taux de cristallisation. La température de traitement choisie peut en outre permettre de mieux contrôler le taux de cristallisation et la nature cristalline, anatase et/ou rutile, de l'oxyde. Likewise, it is advantageous to subject the coating with photo-catalytic property, after deposition, to a heat treatment of the annealed type. A heat treatment is essential for a technique of the sol-gel or laminar coating type in order to decompose the organometallic precursor (s) into oxide, once the substrate has been coated, which is not the case when a pyrolysis technique is used where the precursor decomposes as soon as it comes into contact with the substrate. In the first case as in the second, however, a post-deposition heat treatment, once the TiO2 is formed, improves its crystallization rate The chosen treatment temperature can also allow better control of the crystallization rate and the crystalline, anatase and / or rutile nature of the oxide.
D'autres détails et caractéristiques avantageuses de l'invention ressortent de la description ci-après d'exemples de réalisation non limitatifs, à l'aide des figures suivantes e figure 1: une coupe transversale d'un substrat verrier muni du revêtement
selon l'invention,
figure 2 : un schéma d'une technique de dépôt sol-gel, dite par trempé
ou par dip-coating du revêtement,
figure 3 : un schéma d'une technique de dépôt dite cell-coating ,
figure 4 : un schéma d'une technique de dépôt dite spray-coating ,
figure 5 : un schéma d'une technique de dépôt par enduction laminaire.Other details and advantageous characteristics of the invention emerge from the description below of nonlimiting exemplary embodiments, with the aid of the following figures e Figure 1: a cross section of a glass substrate provided with the coating
according to the invention,
Figure 2: a diagram of a sol-gel deposition technique, called soaking
or by dip-coating the coating,
FIG. 3: a diagram of a so-called cell-coating deposition technique,
FIG. 4: a diagram of a spray-coating deposition technique,
FIG. 5: a diagram of a deposition technique by laminar coating.
Comme représenté de manière extrêmement schématique en figure 1, tous les exemples suivants concernent le dépôt d'un revêtement 3 dit antisalissures essentiellement à base d'oxyde de titane sur un substrat transparent 1. As shown very diagrammatically in FIG. 1, all of the following examples relate to the deposition of a coating 3 known as antifouling essentially based on titanium oxide on a transparent substrate 1.
Le substrat 1 est en verre clair silico-sodo-calcique de 6 mm d'épaisseur et 50 cm de long et de large. Il va de soi que l'invention n'est pas limitée à ce type spécifique de verre. Le verre peut en outre ne pas être plan, mais bombé. The substrate 1 is made of clear soda-lime-silica glass 6 mm thick and 50 cm long and wide. It goes without saying that the invention is not limited to this specific type of glass. The glass may also not be flat, but curved.
Entre le revêtement 3 et substrat 1, se trouve une couche mince optionnelle 2 soit à base d'oxycarbure de silicium noté SiOC en vue de constituer une barrière à la diffusion aux alcalins et/ou une couche atténuant la réflexion lumineuse, soit à base d'oxyde d'étain dopé au fluor SnO2:F en vue de constituer une couche anti-statique et/ou bas-émissive, même à effet basémissif peu accentué, et/ou atténuant la couleur notamment en réflexion. Between the coating 3 and substrate 1, there is an optional thin layer 2 either based on silicon oxycarbide denoted SiOC in order to constitute a barrier to diffusion to alkalis and / or a layer attenuating light reflection, or based on tin oxide doped with fluorine SnO2: F in order to constitute an anti-static and / or low-emissive layer, even with a weakly accentuating effect, and / or attenuating the color in particular in reflection.
EXEMPLES 1 A 3
Les exemples 1 à 4 concernent un revêtement 3 déposé à l'aide d'une technique de pyrolyse en phase liquide. On peut procéder en continu, en utilisant une buse de distribution adaptée disposée transversalement et audessus du ruban de verre float, au sortir de l'enceinte du bain float proprement dit. Ici, on a procédé de façon discontinue, en utilisant une buse statique disposée face au substrat 1 déjà découpé aux dimensions indiquées, substrat qui est d'abord chauffé dans un four à une température de 400 à 6500C avant de défiler à vitesse constante devant la buse projetant une solution appropriée.EXAMPLES 1 TO 3
Examples 1 to 4 relate to a coating 3 deposited using a liquid phase pyrolysis technique. One can proceed continuously, using a suitable dispensing nozzle arranged transversely and above the float glass ribbon, out of the enclosure of the float bath itself. Here, we proceeded discontinuously, using a static nozzle arranged opposite the substrate 1 already cut to the dimensions indicated, substrate which is first heated in an oven at a temperature of 400 to 6500C before running at constant speed in front of the nozzle projecting an appropriate solution.
EXEMPLE 1
Dans cet exemple, il n'y a pas de couche optionnelle 2. Le revêtement 3 est déposé à l'aide d'une solution comprenant deux précurseurs organométalliques de titane, le di-iso-propoxy di-acétylacétonate de titane et le tétraoctylène glycolate de titane dissous dans un mélange de deux solvants, qui sont de l'acétate d'éthyle et de l'isopropanol et une suspension colloïdale de particules d'oxyde de titane, dans une proportion de 5 grammes de TiO2 par litre de solution. Les particules sont constituées de cristallites agglomérées d'anatase, cristallites de taille moyenne d'environ 5 nm. Les particules présentant une taille répartie dans une gamme allant de 5 à 45 nm, sont en suspension dans de l'éthylène glycol dans une concentration massique de 5 à 20%. Le TiO2 peut être dopé avec du bismuth ou du niobium.EXAMPLE 1
In this example, there is no optional layer 2. The coating 3 is deposited using a solution comprising two organometallic titanium precursors, titanium di-iso-propoxy di-acetylacetonate and tetraoctylene glycolate titanium dissolved in a mixture of two solvents, which are ethyl acetate and isopropanol and a colloidal suspension of titanium oxide particles, in a proportion of 5 grams of TiO2 per liter of solution. The particles consist of agglomerated crystallites of anatase, crystallites of average size of approximately 5 nm. The particles having a size distributed in a range from 5 to 45 nm, are suspended in ethylene glycol in a mass concentration of 5 to 20%. TiO2 can be doped with bismuth or niobium.
Pour connaître un mode de préparation préférée de ces particules, on se reportera avantageusement à la demande de brevet EP-A-O 335 773. To find out a preferred method of preparation of these particles, reference is advantageously made to patent application EP-A-0 335 773.
On peut noter que d'autres précurseurs de même type sont tout-à-fait utilisables également, notamment d'autres chélates de titane du type acétylacétonate de titane, méthylacétoacétate de titane, éthylacétoacétate de titane ou encore le titane tri-éthanol amine ou le titane di-éthanol amine. It may be noted that other precursors of the same type are also quite usable, in particular other titanium chelates of the titanium acetylacetonate, titanium methylacetoacetate, titanium ethylacetoacetate or else the titanium tri-ethanol amine or the titanium di-ethanol amine.
Dès que le substrat 1 a atteint la température voulue dans le four, soit notamment environ 5000C, celui-ci défile devant la buse projetant à température ambiante le mélange indiqué à l'aide d'air comprimé. As soon as the substrate 1 has reached the desired temperature in the oven, in particular about 5000C, the latter passes in front of the nozzle projecting the indicated mixture at ambient temperature using compressed air.
On obtient alors une couche de TiO2 d'environ 90 nm d'épaisseur,
I'épaisseur pouvant être contrôlée par la vitesse de défilement du substrat 1 devant la buse et/ou la température dudit substrat. La couche est partiellement cristallisée sous forme anatase.We then obtain a TiO2 layer about 90 nm thick,
The thickness being able to be controlled by the running speed of the substrate 1 in front of the nozzle and / or the temperature of said substrate. The layer is partially crystallized in anatase form.
On fait ensuite subir au substrat 1 muni de ce revêtement un recuit dans un four à une température d'environ 500 à 5500C pendant un laps de temps pouvant aller de 1 minute à 3 heures. The substrate 1 provided with this coating is then subjected to annealing in an oven at a temperature of approximately 500 to 5500C for a period of time which can range from 1 minute to 3 hours.
Après dépôt et recuit, on obtient un revêtement 3 d'oxyde de titane plus cristallisé que dans le cas de l'exemple 1, sous forme anatase. Ce revêtement contient ainsi à la fois du TiO2 provenant de la décomposition des organométalliques et du TiO2 provenant des particules de TiO2 en suspension colloïdale, le premier jouant en quelque sorte le rôle de liant minéral par rapport au second. After deposition and annealing, a coating 3 of more crystallized titanium oxide is obtained than in the case of Example 1, in anatase form. This coating thus contains both TiO2 from the breakdown of organometallics and TiO2 from TiO2 particles in colloidal suspension, the former in a way playing the role of mineral binder compared to the latter.
EXEMPLE 2
II renouvelle l'exemple 1, mais en intercalant entre le substrat 1 et revêtement 3 une couche 2 en SnO2:F de 73 nm d'épaisseur. Cette couche est obtenue par pyrolyse de poudre à partir de difluorure de dibutylétain DBTF.EXAMPLE 2
He repeats Example 1, but by inserting between the substrate 1 and coating 3 a layer 2 of SnO2: F 73 nm thick. This layer is obtained by powder pyrolysis from dibutyltin difluoride DBTF.
On peut aussi l'obtenir, de manière connue, par pyrolyse en phase liquide ou vapeur, comme cela est par exemple décrit dans la demande de brevet EP-A-O 648 196. En phase vapeur, on peut notamment utiliser un mélange de monobutyl trichlorure d'étain et d'un précurseur fluoré associé éventuellement à un oxydant doux du type H2O. It can also be obtained, in known manner, by pyrolysis in the liquid or vapor phase, as is for example described in patent application EP-AO 648 196. In the vapor phase, it is in particular possible to use a mixture of monobutyl trichloride d tin and a fluorinated precursor possibly associated with a mild oxidant of the H2O type.
L'indice de la couche obtenue est d'environ 1,9. Sa résistance carrée est d'environ 50 ohms/carré. The index of the layer obtained is approximately 1.9. Its square resistance is around 50 ohms / square.
Dans l'exemple 1 précédent, le substrat 1 revêtu, monté en doublevitrage de manière à ce que le revêtement soit en face 1 (avec un autre substrat 1' non revêtu mais de même nature et dimensions que le substrat 1 par l'intermédiaire d'une lame d'air de 12 mm) présente une valeur de pureté de couleur en réflexion de 26% et une valeur de pureté de couleur en transmission de 6,8%. In Example 1 above, the coated substrate 1, mounted in double glazing so that the coating is on face 1 (with another substrate 1 'not coated but of the same nature and dimensions as the substrate 1 via (12 mm air gap) has a color purity value in reflection of 26% and a color purity value in transmission of 6.8%.
Dans cet exemple 3, la pureté de couleur en réflexion (dans les dorés) n'est plus que de 3,6%, et elle est de 1,1 % en transmission. In this example 3, the color purity in reflection (in gold) is no more than 3.6%, and it is 1.1% in transmission.
Ainsi, la sous-couche en SnO2:F permet de conférer au substrat des propriétés anti-statiques dues à sa conductivité électrique, elle a également une influence favorable sur la colorimétrie du substrat, en rendant nettement plus neutre sa coloration, aussi bien en transmission qu'en réflexion, coloration provoquée par la présence du revêtement 3 d'oxyde de titane présentant un indice de réfraction relativement élevé. On peut la polariser en la munissant d'une alimentation électrique adaptée, pour limiter le dépôt de poussières de taille relativement importante de l'ordre du millimètre. Thus, the SnO2: F sublayer makes it possible to impart anti-static properties to the substrate due to its electrical conductivity, it also has a favorable influence on the colorimetry of the substrate, by making its coloration much more neutral, both in transmission that in reflection, coloring caused by the presence of the coating 3 of titanium oxide having a relatively high refractive index. It can be polarized by providing it with a suitable electrical supply, in order to limit the deposition of dust of relatively large size of the order of a millimeter.
EXEMPLE 3
II renouvelle l'exemple 2, mais en intercalant cette fois entre substrat 1 et revêtement 3 une couche 2 à base d'oxycarbure de silicium, d'indice d'environ 1,75 et d'épaisseur environ 50 nm, couche que l'on peut obtenir par CVD à partir d'un mélange de SiH4 et d'éthylène en dilution dans de l'azote, comme décrit dans la demande de brevet EP-A-O 518 755. Cette couche est particulièrement efficace pour empêcher la tendance à la diffusion d'alcalins (Na+, K+) et d'alcalino-terreux (Ca++) provenant du substrat 1 vers le revêtement 3. Ayant, comme SnO2:F, un indice de réfraction intermédiaire entre celui du substrat (1,52) et du revêtement 3 (environ 2,30 à 2,35 ), elle permet également d'atténuer l'intensité de la coloration du substrat aussi bien en réflexion qu'en transmission et de diminuer globalement la valeur de réflexion lumineuse RL dudit substrat.EXAMPLE 3
It repeats Example 2, but this time intercalating between substrate 1 and coating 3 a layer 2 based on silicon oxycarbide, with an index of about 1.75 and a thickness of about 50 nm, which layer is can be obtained by CVD from a mixture of SiH4 and ethylene diluted in nitrogen, as described in patent application EP-AO 518 755. This layer is particularly effective in preventing the tendency to diffusion alkalis (Na +, K +) and alkaline earths (Ca ++) from substrate 1 to coating 3. Having, as SnO2: F, a refractive index intermediate between that of the substrate (1.52) and the coating 3 (approximately 2.30 to 2.35), it also makes it possible to attenuate the intensity of the coloring of the substrate both in reflection and in transmission and to globally reduce the light reflection value RL of said substrate.
EXEMPLE 4
Cet exemple utilise la technique dite sol-gel utilisant un mode de dépôt par trempé encore appelé dip-coating dont le principe ressort de la figure 2: il s'agit d'immerger le substrat 1 dans la solution liquide 4 contenant le(s) précurseur(s) adéquat(s) du revêtement 3, puis d'en extraire le substrat 1 à vitesse contrôlée à l'aide d'un moyen moteur 5, le choix de la vitesse d'extraction permettant d'ajuster l'épaisseur de solution restant à la surface des deux faces du substrat et, de fait, I'épaisseur des revêtements déposés, après traitement thermique de ce dernier pour à la fois évaporer le solvant et décomposer le ou les précurseurs en oxyde.EXAMPLE 4
This example uses the so-called sol-gel technique using a dip coating method also called dip-coating, the principle of which emerges from FIG. 2: it involves immersing the substrate 1 in the liquid solution 4 containing the adequate precursor (s) of the coating 3, then extract the substrate 1 therefrom at a controlled speed using a motor means 5, the choice of the extraction speed making it possible to adjust the thickness of solution remaining on the surface of the two faces of the substrate and, in fact, the thickness of the coatings deposited, after heat treatment of the latter in order both to evaporate the solvent and to decompose the precursor (s) into oxide.
On utilise pour déposer le revêtement 3 une solution 4 comprenant soit du tétrabutoxyde de titane Ti(O-Bu)4 stabilisé avec de la diéthanol amine DEA en proportion molaire 1:1 dans un solvant type éthanol à 0,2 mole de tétrabutoxyde par litre d'éthanol, soit le mélange de précurseurs et de solvants décrits dans l'exemple 1. ( Peut aussi être utilisé un autre précurseur comme le dibutoxy-diéthanolamine de titane), solution additionnée de 5 grammes/litre de solution de TiO2 sous forme de particules anatase en solution colloïdale à 10% dans de l'éthylène glycol, de manière à utiliser environ 0,24 gramme de ces particules par gramme de TiO2 effectivement déposé. Is used to deposit the coating 3 a solution 4 comprising either titanium tetrabutoxide Ti (O-Bu) 4 stabilized with diethanol amine DEA in molar ratio 1: 1 in an ethanol solvent at 0.2 mole of tetrabutoxide per liter ethanol, i.e. the mixture of precursors and solvents described in Example 1. (Another precursor such as titanium dibutoxy-diethanolamine) can also be used, solution containing 5 grams / liter of TiO2 solution in the form of anatase particles in colloidal solution at 10% in ethylene glycol, so as to use approximately 0.24 gram of these particles per gram of TiO2 actually deposited.
Après extraction de chacune des solutions 4, les substrats 1 sont chauffés 1 heure à 1000C puis environ 3 heures à 5500C avec une montée en température progressive. After extraction of each of the solutions 4, the substrates 1 are heated for 1 hour at 1000C and then about 3 hours at 5500C with a gradual rise in temperature.
On obtient sur chacune des faces un revêtement 3, dans les deux cas en
TiO2 bien cristallisé sous forme anatase.A coating 3 is obtained on each of the faces, in both cases in
TiO2 well crystallized in anatase form.
EXEMPLE 5
Cet exemple utilise la technique appelée cell-coating dont le principe est rappelé dans la figure 3 et dont la description détaillée est donnée dans la demande de brevet FR-95/05978 du 19 mai 1995 précitée. Il s'agit de former une cavité étroite délimitée par deux faces sensiblement parallèles 6, 7 et deux joints 8, 9, au moins une de ces faces 6, 7 étant constituée par la face du substrat 1 à traiter. Puis on remplit la cavité de la solution 4 de précurseur(s) du revêtement, et on retire la solution 4 de manière contrôlée, de manière à forme un ménisque de mouillage à l'aide d'une pompe 10 péristaltique par exemple, en laissant un film de la solution 4 sur le face du substrat 1 au fur et à mesure du retrait de la solution.EXAMPLE 5
This example uses the technique called cell-coating, the principle of which is recalled in FIG. 3 and the detailed description of which is given in the above-mentioned patent application FR-95/05978 of May 19, 1995. This involves forming a narrow cavity delimited by two substantially parallel faces 6, 7 and two seals 8, 9, at least one of these faces 6, 7 being formed by the face of the substrate 1 to be treated. Then the cavity is filled with the solution 4 of precursor (s) of the coating, and the solution 4 is removed in a controlled manner, so as to form a wetting meniscus using a peristaltic pump 10 for example, leaving a film of the solution 4 on the face of the substrate 1 as the solution is withdrawn.
La cavité 5 est ensuite maintenue au moins le temps nécessaire à un séchage, durcissement par traitement thermique du film sur le substrat. The cavity 5 is then maintained for at least the time necessary for drying, curing by heat treatment of the film on the substrate.
L'avantage de cette technique par rapport au dip-coating est notamment que l'on peut traiter qu'une seule des deux faces du substrat 1, et non les deux systématiquement, à moins d'avoir recours à un système de masquage. The advantage of this technique compared to dip-coating is in particular that it is possible to treat only one of the two faces of the substrate 1, and not both systematically, unless recourse is had to a masking system.
Cet exemple utilise la solution 4 décrite dans l'exemple 5. Les mêmes traitements thermiques sont ensuite opérés pour obtenir le revêtement 3 de TiO2. This example uses the solution 4 described in example 5. The same heat treatments are then carried out to obtain the coating 3 of TiO2.
Dans les deux cas, les revêtements 3 présentent une bonne durabilité mécanique, les revêtements selon l'exemple 9 ayant eu recours à la suspension colloïdale de TiO2 sont bien cristallisés : les particules devraient faciliter la cristallisation anatase du liant TiO2 provenant du (des) précurseur(s) organo-métallique(s) qui est plutôt amorphe avant les traitements thermiques post-dépôt. In both cases, the coatings 3 have good mechanical durability, the coatings according to Example 9 having used the colloidal suspension of TiO2 are well crystallized: the particles should facilitate the anatase crystallization of the binder TiO2 coming from the precursor (s) (s) organo-metallic (s) which is rather amorphous before post-deposition heat treatments.
Ces mêmes types de solutions 4 peuvent être également utilisées pour déposer des revêtements par spray-coating , comme représenté en figure 4, où l'on pulvérise la solution 4 sous forme d'un nuage contre le substrat 1 en statique, ou par enduction laminaire comme représenté en figure 5. Dans ce dernier cas, on fait passer le substrat 1, maintenu par succion sous vide, contre un support 1 1 en inox et Téflon au-dessus d'un réservoir 12 contenant la solution, solution dans laquelle est partiellement immergé un cylindre 14 fendu, on déplace ensuite l'ensemble du réservoir 12 et du cylindre 14 sur toute la longueur du substrat 1, le masque 13 évitant une évaporation trop rapide du solvant de la solution 4. Pour plus de détails sur cette dernière technique, on se reportera avantageusement à la demande de brevet WO94/01598 pré-citée. These same types of solutions 4 can also be used to deposit coatings by spray-coating, as shown in FIG. 4, where the solution 4 is sprayed in the form of a cloud against the substrate 1 in static form, or by laminar coating. as shown in Figure 5. In the latter case, the substrate 1 is passed, maintained by suction under vacuum, against a support 1 1 made of stainless steel and Teflon over a tank 12 containing the solution, solution in which is partially submerged a split cylinder 14, the entire reservoir 12 and the cylinder 14 are then moved over the entire length of the substrate 1, the mask 13 avoiding too rapid evaporation of the solvent from the solution 4. For more details on this latter technique , advantageously refer to the patent application WO94 / 01598 cited above.
Des tests ont été effectués sur les substrats obtenus selon les exemples précédents afin de caractériser les revêtements déposés et évaluer leurs performances anti-buée et anti-salissures . Tests were carried out on the substrates obtained according to the preceding examples in order to characterize the coatings deposited and assess their anti-fog and anti-fouling performance.
O Test 1 : c'est le test des figures de buée. II consiste à observer les
conséquences de la photo-catalyse et de la structure du revêtement (taux
de groupes hydroxyl, porosité, rugosité) sur le mouillage. Si la surface est
photo-réactive, les micro-pollutions carbonées qui se déposent sur le
revêtement sont détruites en permanence, et la surface est hydrophile donc
anti-buée. On peut aussi faire une évaluation quantitative en réchauffant
brusquement le substrat revêtu initialement entreposé au froid ou
simplement en soufflant sur le substrat, en mesurant s'il apparaît de la buée
et dans l'affirmative, à quel moment, puis en mesurant le temps nécessaire
à la disparition de ladite buée.O Test 1: this is the fogging pattern test. It consists in observing the
consequences of photo-catalysis and the structure of the coating (rate
hydroxyl groups, porosity, roughness) on wetting. If the surface is
photo-reactive, carbonaceous micro-pollution that is deposited on the
coating are permanently destroyed, and the surface is hydrophilic therefore
antifog. We can also make a quantitative evaluation by warming up
suddenly the coated substrate initially stored cold or
simply by blowing on the substrate, measuring if it appears fogging
and if so, when and then measuring the time required
when said mist disappears.
O Test 2 : il s'agit d'évaluer l'hydrophilie et l'oléophilie à la surface du
revêtement 3, en comparaison de celles de la surface d'un verre nu, par la
mesure d'angles de contact d'une goutte d'eau et d'une goutte de DOP (di
octyl-phtalate) à leurs surfaces, après avoir laissé les substrats une semaine
à l'atmosphère ambiante sous éclairage naturel, dans le noir puis les avoir
soumis 20 minutes à un rayonnement UVA.O Test 2: this involves evaluating the hydrophilicity and oleophilicity on the surface of the
coating 3, in comparison with those of the surface of a bare glass, by the
measurement of contact angles of a drop of water and a drop of DOP (di
octyl-phthalate) on their surfaces, after leaving the substrates for a week
in the ambient atmosphere under natural light, in the dark then have them
subjected to UVA radiation for 20 minutes.
O Test 3 : il s'agit d'un test d'évaluation quantitative de la photocatalyse par
dépôt d'une salissure connue et bien calibrée . On greffe par trempé une
mono-couche carbonée à partir d'octadécyltrichlorosilane (OTS) sur les
revêtements de l'invention - conditions opératoires : OTS à 0,3% dans le décane, greffage à OOC sous atmosphère anhydre sur substrat propre - couche obtenue : 2 à 3 nm d'épaisseur.O Test 3: this is a quantitative evaluation test of photocatalysis by
deposit of known and well calibrated soiling. We graft by soaking a
carbon monolayer from octadecyltrichlorosilane (OTS) on
coatings of the invention - operating conditions: 0.3% OTS in decane, grafting with OOC under anhydrous atmosphere on clean substrate - layer obtained: 2 to 3 nm thick.
2
On irradie les substrats ainsi greffés sous UVA à environ 25 mW/cm2.
2
The substrates thus grafted are irradiated under UVA at approximately 25 mW / cm 2.
On caractérise la disparition de la couche organique par des mesures d'angle de contact à l'eau périodiquement. Initialement, on a environ 1000. The disappearance of the organic layer is characterized by measurements of the angle of contact with water periodically. Initially, we have around 1000.
Quand l'angle chute à 1 50 environ, on considère que la salissure organique déposée est entièrement détruite : on a alors de plus un effet anti-buée marqué.When the angle drops to approximately 150, it is considered that the organic dirt deposited is completely destroyed: there is then a marked anti-fogging effect.
On donne ci-après le temps de disparition de la mono-couche pour différents exemples du brevet. The disappearance time of the monolayer is given below for various examples of the patent.
Tous les exemples précédents réussissent le test 1, c'est-à-dire que lorsqu'on souffle sur les substrats revêtus du revêtement, ils restent parfaitement transparents, alors que se depose une couche de buée bien visible sur des substrats non revêtus. All the preceding examples pass test 1, that is to say that when blowing on the substrates coated with the coating, they remain perfectly transparent, while a layer of fogging is clearly visible on uncoated substrates.
Les exemples 2, 3 et 4 ont subi le test 2 : les substrats revêtus, après exposition aux rayonnements UVA, présentent un angle de contact à l'eau et au DOP d'au plus 5 . Au contraire, un verre nu dans les mêmes conditions présente un angle de contact à l'eau de 400 et un angle de contact au DOP de 200. Examples 2, 3 and 4 underwent test 2: the coated substrates, after exposure to UVA radiation, have a contact angle with water and with DOP of at most 5. On the contrary, a bare glass under the same conditions has a contact angle with water of 400 and a contact angle with DOP of 200.
Les exemples 4 et 5 ont subi le test 3 : dans les deux exemples, dans le cas où la solution utilise du tétrabutoxyde de titane, la durée de disparition de la mono-couche obtenue à partir d'OTS est d'environ 6 heures. Dans le cas où la solution utilise le mélange de précurseurs di-iso-propoxy-diacétylacétonate et tétra-octylène phtalate de titane, la durée de disparition se réduit à 20 minutes. Examples 4 and 5 underwent test 3: in the two examples, in the case where the solution uses titanium tetrabutoxide, the duration of disappearance of the monolayer obtained from OTS is approximately 6 hours. In the case where the solution uses the mixture of di-iso-propoxy-diacetylacetonate and titanium tetra-octylene phthalate precursors, the disappearance time is reduced to 20 minutes.
Claims (22)
Priority Applications (18)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9510838A FR2738812B1 (en) | 1995-09-15 | 1995-09-15 | SUBSTRATE WITH PHOTOCATALYTIC COATING |
AU69927/96A AU6992796A (en) | 1995-09-15 | 1996-09-13 | Titanium dioxide-based photocatalytic coating substrate, and titanium dioxide-based organic dispersions |
DE69611618T DE69611618T3 (en) | 1995-09-15 | 1996-09-13 | SUBSTRATE WITH A PHOTOCATALYTIC COATING BASED ON TITANDIOXYD |
US09/043,063 US6037289A (en) | 1995-09-15 | 1996-09-13 | Titanium dioxide-based photocatalytic coating substrate, and titanium dioxide-based organic dispersions |
EP96931129A EP0850203B2 (en) | 1995-09-15 | 1996-09-13 | Titanium dioxide-based photocatalytic coating substrate, and titanium dioxide-based organic dispersions |
PT96931129T PT850203E (en) | 1995-09-15 | 1996-09-13 | SUBSTRATE WITH TITANIUM DIOXIDE-BASED PHOTOCATALITIC COATING AND TITANIUM DIOXIDE-BASED ORGANIC DISPERSIONS |
TR1998/00474T TR199800474T1 (en) | 1995-09-15 | 1996-09-13 | Organic dispersions based on titanium dioxide and a ground-forming layer with a photocatalytic coating based on titanium dioxide. |
KR10-1998-0701924A KR100377606B1 (en) | 1995-09-15 | 1996-09-13 | Titanium dioxide-based photocatalyst coating substrate, and titanium dioxide-based organic dispersion |
AT96931129T ATE198733T1 (en) | 1995-09-15 | 1996-09-13 | SUBSTRATE WITH A PHOTOCATALYTIC COATING OF TITANIUM DIOXIDE AND ORGANIC DISPERSIONS WITH TITANIUM DIOXIDE |
PL96325526A PL325526A1 (en) | 1995-09-15 | 1996-09-13 | Substrate carrying a photocatalytic coating based on titanium dioxide and organic titanium dioxide suspensions for producing such coating |
DK96931129T DK0850203T3 (en) | 1995-09-15 | 1996-09-13 | Photocatalytic coating substrate based on titanium dioxide and organic dispersions based on titanium dioxide |
JP9511720A JPH11512336A (en) | 1995-09-15 | 1996-09-13 | Substrate with photocatalytic coating based on titanium dioxide and organic dispersion based on titanium dioxide |
CZ0075698A CZ297518B6 (en) | 1995-09-15 | 1996-09-13 | Substrate provided with coating exhibiting photocatalytic properties, glazing material containing such substrate, use of said substrate, process for producing thereof, dispersion for the production process as well as use of such dispersion in the pro |
BR9610289-6A BR9610289A (en) | 1995-09-15 | 1996-09-13 | Substrate, glazing, use of the substrate, process of obtaining the substrate, organic dispersion and use of the dispersion. |
ES96931129T ES2155941T5 (en) | 1995-09-15 | 1996-09-13 | Substrate with photocatalytic coating based on titanium dioxide and organic dispersions based on titanium dioxide |
PCT/FR1996/001419 WO1997010185A1 (en) | 1995-09-15 | 1996-09-13 | Titanium dioxide-based photocatalytic coating substrate, and titanium dioxide-based organic dispersions |
MX9802017A MX9802017A (en) | 1995-09-15 | 1998-03-13 | Titanium dioxide-based photocatalytic coating substrate, and titanium dioxide-based organic dispersions. |
US09/488,760 US6362121B1 (en) | 1995-09-15 | 2000-01-21 | Substrate with a photocatalytic coating based on titanium dioxide and organic dispersions based on titanium dioxide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9510838A FR2738812B1 (en) | 1995-09-15 | 1995-09-15 | SUBSTRATE WITH PHOTOCATALYTIC COATING |
Publications (2)
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FR2738812A1 true FR2738812A1 (en) | 1997-03-21 |
FR2738812B1 FR2738812B1 (en) | 1997-10-17 |
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FR9510838A Expired - Lifetime FR2738812B1 (en) | 1995-09-15 | 1995-09-15 | SUBSTRATE WITH PHOTOCATALYTIC COATING |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1081108A1 (en) * | 1999-09-02 | 2001-03-07 | Central Glass Company, Limited | Article with photocatalytic film |
DE102011101179A1 (en) * | 2011-05-11 | 2012-11-15 | Fachhochschule Kiel | Coatings for polymers |
WO2013007254A1 (en) * | 2011-07-08 | 2013-01-17 | Scheer Heizsysteme & Produktionstechnik Gmbh | Thick ceramic coating |
US9738967B2 (en) | 2006-07-12 | 2017-08-22 | Cardinal Cg Company | Sputtering apparatus including target mounting and control |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2570369C (en) | 2004-07-12 | 2008-02-19 | Cardinal Cg Company | Low-maintenance coatings |
US7923114B2 (en) | 2004-12-03 | 2011-04-12 | Cardinal Cg Company | Hydrophilic coatings, methods for depositing hydrophilic coatings, and improved deposition technology for thin films |
US8092660B2 (en) | 2004-12-03 | 2012-01-10 | Cardinal Cg Company | Methods and equipment for depositing hydrophilic coatings, and deposition technologies for thin films |
US7989094B2 (en) | 2006-04-19 | 2011-08-02 | Cardinal Cg Company | Opposed functional coatings having comparable single surface reflectances |
EP2261186B1 (en) | 2007-09-14 | 2017-11-22 | Cardinal CG Company | Low maintenance coating technology |
WO2018093985A1 (en) | 2016-11-17 | 2018-05-24 | Cardinal Cg Company | Static-dissipative coating technology |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4041194A (en) * | 1975-09-29 | 1977-08-09 | Hercules Incorporated | Decorative coating composition for coating glassware |
JPS63100042A (en) * | 1986-10-14 | 1988-05-02 | Nippon Sheet Glass Co Ltd | Glass article difficult-to be dirtied |
SU1663046A1 (en) * | 1988-01-19 | 1991-07-15 | Научно-исследовательский институт физико-химических проблем Белорусского государственного университета им.В.И.Ленина | Method for selective activation of smooth surfaces of glass and ceramics before formation of a coating by chemical conversion |
EP0544577A1 (en) * | 1991-11-26 | 1993-06-02 | Saint-Gobain Vitrage International | Glass substrate coated with a low emissivity coating |
-
1995
- 1995-09-15 FR FR9510838A patent/FR2738812B1/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4041194A (en) * | 1975-09-29 | 1977-08-09 | Hercules Incorporated | Decorative coating composition for coating glassware |
JPS63100042A (en) * | 1986-10-14 | 1988-05-02 | Nippon Sheet Glass Co Ltd | Glass article difficult-to be dirtied |
SU1663046A1 (en) * | 1988-01-19 | 1991-07-15 | Научно-исследовательский институт физико-химических проблем Белорусского государственного университета им.В.И.Ленина | Method for selective activation of smooth surfaces of glass and ceramics before formation of a coating by chemical conversion |
EP0544577A1 (en) * | 1991-11-26 | 1993-06-02 | Saint-Gobain Vitrage International | Glass substrate coated with a low emissivity coating |
Non-Patent Citations (3)
Title |
---|
CHEMICAL ABSTRACTS, vol. 116, no. 10, 9 March 1992, Columbus, Ohio, US; abstract no. 89812a, page 396; XP000405429 * |
DATABASE WPI Week 23, Derwent World Patents Index; AN 88-158890, XP002005574 * |
M.TAKAHASHI ET AL.: "pt-tio2 thin films on glass substrates as efficient photocatalysts", JOURNAL OF MATERIALS SCIENCE, vol. 24, no. 1, January 1989 (1989-01-01), LONDON GB, pages 243 - 246, XP000046035 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1081108A1 (en) * | 1999-09-02 | 2001-03-07 | Central Glass Company, Limited | Article with photocatalytic film |
US6582839B1 (en) | 1999-09-02 | 2003-06-24 | Central Glass Company, Limited | Article with photocatalytic film |
US9738967B2 (en) | 2006-07-12 | 2017-08-22 | Cardinal Cg Company | Sputtering apparatus including target mounting and control |
DE102011101179A1 (en) * | 2011-05-11 | 2012-11-15 | Fachhochschule Kiel | Coatings for polymers |
WO2013007254A1 (en) * | 2011-07-08 | 2013-01-17 | Scheer Heizsysteme & Produktionstechnik Gmbh | Thick ceramic coating |
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