CN1898172A - 带有被保护薄层覆盖的具有光催化性能层的基材,特别是玻璃基材 - Google Patents
带有被保护薄层覆盖的具有光催化性能层的基材,特别是玻璃基材 Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 32
- 239000011521 glass Substances 0.000 title claims description 28
- 239000000758 substrate Substances 0.000 title abstract description 5
- 230000001681 protective effect Effects 0.000 title 1
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 28
- 239000010703 silicon Substances 0.000 claims abstract description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 107
- 239000000463 material Substances 0.000 claims description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000000151 deposition Methods 0.000 claims description 22
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 21
- 239000005357 flat glass Substances 0.000 claims description 21
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 21
- 238000007146 photocatalysis Methods 0.000 claims description 20
- 239000006112 glass ceramic composition Substances 0.000 claims description 17
- 230000008021 deposition Effects 0.000 claims description 15
- 238000004544 sputter deposition Methods 0.000 claims description 15
- 239000002346 layers by function Substances 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 10
- 229910052728 basic metal Inorganic materials 0.000 claims description 10
- 150000003818 basic metals Chemical class 0.000 claims description 10
- 230000005012 migration Effects 0.000 claims description 9
- 238000013508 migration Methods 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 8
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- 238000000034 method Methods 0.000 claims description 8
- 230000003287 optical effect Effects 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 7
- 230000003373 anti-fouling effect Effects 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000004888 barrier function Effects 0.000 claims description 5
- 230000000903 blocking effect Effects 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229920000965 Duroplast Polymers 0.000 claims description 4
- 239000002241 glass-ceramic Substances 0.000 claims description 4
- 150000002927 oxygen compounds Chemical class 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
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- 238000005452 bending Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical group [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
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- 239000003365 glass fiber Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000005340 laminated glass Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims description 2
- 229910052712 strontium Chemical group 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical group [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910003087 TiOx Inorganic materials 0.000 claims 2
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 claims 2
- 239000000126 substance Substances 0.000 abstract description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 11
- 238000003475 lamination Methods 0.000 description 11
- 239000010408 film Substances 0.000 description 8
- 239000007921 spray Substances 0.000 description 4
- 239000004411 aluminium Substances 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
- 239000011941 photocatalyst Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 1
- -1 SiOC Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
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- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
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- 230000007246 mechanism Effects 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
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- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
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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
-
- 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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3423—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings comprising a suboxide
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- C03—GLASS; MINERAL OR SLAG WOOL
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- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3435—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
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- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3441—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising carbon, a carbide or oxycarbide
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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
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/71—Photocatalytic coatings
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- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
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- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
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- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
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Abstract
一种结构,该结构包括基材,在其至少一部分表面上有一层防污的具有光催化性能的二氧化钛(TiO2)基层,其特征在于所述的具有光催化性能的层被含有硅和氧的无孔薄层覆盖,该薄层具有覆盖能力,还能保证对下层光催化层进行机械和化学保护,同时保持TiO2的光催化活性。
Description
本发明涉及这些基材,例如用玻璃、玻璃陶瓷材料或塑料制成的基材,它们已配备有具有光催化的性能的涂层,从而使它们具有所谓的防污或自净功能。
这些基材的重要应用涉及玻璃板,它们可以有各种各样的应用,从实用玻璃板到家用电器用的玻璃板,从车辆用的玻璃板到建筑物用的玻璃板。
本发明还应用于镜子类的反射玻璃板(家用镜子或车辆的后视镜),还应用于轻型乳白玻璃板。
类似地,本发明还应用于不透明的基材,例如陶瓷基材或特别可以用作建筑材料的任何其它基材(金属、方砖等)。优选地,本发明还应用于基本平的或轻微弯曲的基材,不管该基材的性质怎样。
已经研究过这些光催化涂层,特别是以锐钛矿晶型结晶的二氧化钛基涂层。在紫外辐射作用下它们使有机源污物或微生物降解的能力是非常有意义的。它们往往还具有亲水的特性,这种特性能够通过喷洒水除去污物,对于外部玻璃板,能够通过雨水除去污物。
已经描述过这类具有防污、杀菌、灭藻性能的涂层,具体在专利WO 97/10186中描述过这类涂层,该专利描述了获得这种涂层的多种方式。
如果不对它加以保护,随着时间的推移,具有光催化性能的层受到磨损,这会显示出失去其活性,失去该结构的光学质量(出现模糊不清或着色),甚至该层会分层。
如果具有光催化性能的层的厚度降低,该层部分变坏时出现着色应不会很强,并且随着时间推移颜色的变化也不会很强。但是,这种厚度降低不利于该层的性能。
因此,需要从机械和化学方面保证保护这个层,该保护层的厚度应该很小,这样才能使具有光催化性能的层完全保持其功能。
由欧洲专利申请EP-A-0 820 967知道一种防雾元件,它包括透明基材、在这种透明基材上形成的光催化剂透明薄膜,以及在光催化剂薄膜上形成的透明的多孔无机氧化物薄膜,该薄膜的表面具有亲水性能。
由日本专利JP 2002 047 032还知道一种覆盖光催化膜的基材的生产方法,该方法包括这些步骤:使用喷枪喷洒具有锐钛矿晶体结构的5-10nm的TiO2毫微微粒,加热和采用阴极溅射沉积能覆盖TiO2微粒的SiO2膜。
这些结构中没有一种结构是令人满意的,第一因为保护涂层的多孔性质,这个涂层因为孔的存在而没有保证充分保护具有催化性质的层,第二因为没有足够的光催化材料比率,该材料没有形成连续的层。
本发明为这个问题提供了解决办法。
事实上,本发明首先一个目的是一种结构,该结构包括基材,在其至少一部分表面上有防污的具有光催化性能的二氧化钛(TiO2)基层,其特征在于所述的具有光催化性能的层被含有硅和氧的无孔薄层覆盖,该薄层具有覆盖能力,还能保证对下层光催化层进行机械和化学保护,同时保持TiO2的光催化活性。
为了获得防污的光催化的性能,应该以已知方式调整二氧化钛基层的制备条件,例如起始产品的性质和纯度、任选溶剂、热处理等。
优选地,所述的含有硅和氧的薄层呈连续薄膜形式。特别有利地,所述的薄层呈贴合具有光催化性能下层凸凹不平表面的薄膜形式。
这个含有硅和氧的薄层特别地是至少一种选自SiO2、SiOC、SiON、SiOx(其中x<2)和SiOCH的硅和氧化合物的层,SiO2是特别优选的。
根据本发明结构的有利具体实施方案,含有硅和氧的薄层是至少一种选自Al2O3和ZrO2的化合物与其结合的至少一种硅和氧化合物的层,这样一种化合物是化学惰性的,并增强耐水解性。可以强调Al2O3,一种熟知的惰性氧化物的作用,该化合物增加了整体的化学稳定性。
(Al和/或Zr)/Si原子比一般不大于1,Al/Si比有利地是0.03-0.5,特别地0.05-0.1,Zr/Si比是0.05-0.4。
这个含有硅和氧的薄层的厚度可以是至多15nm,特别地至多10nm,尤其至多8nm,优选地至多5nm或约5nm,尤其是2-3nm。
所述的薄层提供了润滑作用和有机械作用。它改善了抗划伤性和耐磨性。
但是,没有达到这种更高的机械阻力和这种较好的化学稳定性,还有损于降低光催化活性。事实上,尽管可能期望TiO2基层最后达到的光催化活性,因该层被SiO2上层掩蔽而降低,但保持了这种光催化活性,甚至还有改善;事实上,由于SiO2薄膜的亲水特性,稀释在该均匀薄膜中的污物更容易被TiO2破坏。
这个二氧化钛基层是由单一TiO2构成的,或由用至少一种特别选自N,五价阳离子,例如Nb、Ta和V,Fe和Zr的掺杂剂掺杂的TiO2构成的。可以采用溶胶-凝胶法、采用热解法,特别是气相热解法,或采用阴极溅射法沉积这个TiO2基层,阴极溅射法是在室温与真空条件下进行的,如果必要,可以用磁场和/或离子束增强,使用金属或TiOx靶(x<2)和氧化性气氛,或使用TiO2靶和惰性气氛,采用阴极溅射法得到的TiO2再可以进行热处理,以便它处于呈光催化活性形式的结晶态。
特别地,采用阴极溅射法沉积这个含有硅和氧的薄层,阴极溅射法在室温与真空条件下进行的,如果必要,可以用磁场和/或离子束增强,使用掺杂Al的Si靶(8%原子)与压力0.2Pa的Ar+O2气氛。
本发明的结构可以包括在紧挨TiO2基层下面的具有晶体结构的下层,这种结构有助于在TiO2基上层的锐钛矿晶型中,特别是在由ATiO3构成的上层中通过异质外延生长结晶,其中A代表钡或锶。这个下层厚度不是关键;该厚度可以例如是10nm-100nm。
这种基材例如由单片玻璃或层压玻璃、玻璃陶瓷材料或硬塑料(例如聚碳酸酯)的平板、弯曲或拱形面板构成,或由玻璃纤维或玻璃陶瓷纤维构成,所述的板或所述的纤维(如果必要)接受至少一个其它功能层,施用TiO2基层或有助于通过该层异质外延生长结晶的层。(在一层以上的情况下,还可以称之叠层或多层)。
前面列举了板的应用。关于纤维,可以列举它们在过滤空气或水的应用以及杀菌的应用。
这个或其它功能层选自具有光学功能的层、控热层、传导层,以及在这种基材是用玻璃或玻璃陶瓷材料制成的情况下,这些层构成了玻璃或玻璃陶瓷材料的碱金属迁移的阻挡层。
这些具有光学功能的层特别地是抗反射、过滤光辐射、着色、散射层等。可以列举SiO2、Si3N4、TiO2、SnO2、ZnO层。
这些控热层特别地是防晒层或所谓低发射层。
这些传导层特别地是加热层、天线(antenne)或抗静电层,在这些层中,可以考虑导线网络。
在基材是用玻璃或玻璃陶瓷材料制成的情况下,构成玻璃或玻璃陶瓷材料碱金属迁移阻挡层的至少一个功能层可以置于具有光催化性能的层下面,或有助于该层结晶的下层下面,如果有这样一个下层。其它功能层(具有光学功能、控热或传导层)存在时则它们处在这个或这些阻挡层上面。
碱金属迁移能导致施用温度超过600℃。在随后的热处理期间,构成碱金属阻档层的这样一些层是已知的,可以列举SiO2、SiOC、SiOxNy、Si3N4层,它们的厚度例如是至少5或10nm,在许多情况下是至少50nm,例如在国际申请PCT WO 02/24971中所描述的厚度。
作为实例,可以提到用玻璃或玻璃陶瓷材料制成的基材,特别地板类基材,它们有对玻璃或玻璃陶瓷材料的碱金属迁移构成阻挡层的层,然后有单-、双-或三个光学功能层。
本发明还有一个目的是一种如前面所定义的结构的生产方法,其特征在于在玻璃或玻璃陶瓷材料或聚碳酸酯类硬塑料的板类基材上,或在玻璃或玻璃陶瓷纤维上沉积任选掺杂的TiO2层,当沉积所采用的这些条件没有为这个层提供光催化性能时,该层应进行热处理,使它具有光催化性能,然后在所述的具有光催化性能的层上沉积例如前面定义的含有硅和氧的薄层。
特别地,在室温下,采用真空阴离子溅射相继地沉积TiO2层和含有硅和氧的薄层,如果必要,在同一室中,该阴离子溅射采用磁场和/或离子束增强,这些条件如下:
-对于沉积TiO2基层,以直流或交流方式供电,压力1-3mbar,氧+惰性气体(氩气)气氛,使用Ti靶或TiOx靶,其中x=1.5-2;
-对于含有硅和氧的层的沉积,以交流方式供电,压力0.1-1Pa,Ar+O2气氛,使用高硅含量的靶;
任选地,在TiO2层的锐钛矿晶型中,通过外延生长有助于结晶的下层沉积,进行TiO2层的沉积。
本技术领域的技术人员知道含有硅和氧的无孔层的沉积条件,特别是低压和高功率条件(Thornton图)。
在制备用玻璃或玻璃陶瓷材料制成的基材的涂层时,在涂布TiO2层或与其结合的下层之前,可以考虑在该基材上沉积至少一个对玻璃或玻璃陶瓷材料中存在的碱金属迁移构成阻档层的层,在沉积TiO2层和覆盖该层的硅基薄层后,这时可以在进行退火或淬火处理,退火温度为250-550℃,优选地350-500℃,淬火温度为至少600℃。
按照本发明还可以考虑,在任选涂布至少一个对碱金属迁移构成阻档层的层之后和涂布TiO2层或与其结合的下层之前,沉积至少一个功能层,该层选自具有光学功能的层、控热层和传导层,有利地,所述的功能层是采用真空阴极溅射法沉积的,如果必要,阴极溅射可采用磁场和/或离子束增强。
本发明还涉及特别是汽车或建筑物使用的单片或多片玻璃板,该玻璃板包括在至少一个面上的如前面定义的本发明结构,所述的面特别地是朝外取向的面,但还可以是朝内取向的面。
没有本发明结构的这些玻璃板的面可以包括至少一个其它功能层。
这样一些玻璃板可以用作“自净”玻璃板,特别是防雾,防冷凝和防污玻璃板,特别地双层玻璃板类的建筑物用玻璃板、风档、后窗类的车辆用窗玻璃、汽车的侧窗玻璃、后视镜、火车、飞机和轮船用的窗玻璃、实用玻璃板,例如玻璃鱼缸、玻璃橱窗、温室、室内家具、市政设施(公共汽车候车亭、广告牌等)的玻璃,镜子、计算机、电视机、电话类的显示***荧光屏、电控玻璃板,例如电致变色、液晶、电致发光玻璃板、光电玻璃板。
下面的实施例说明本发明,而不限制其保护范围。
实施例1a和1b(本发明):
玻璃叠层/SiO2:Al/TiO2/SiO2:Al
在厚度4mm玻璃板上,沉积下述的相继各层:
-厚度150nm的掺杂Al的SiO2下层;
-厚度100nm(实施例1a)或厚度20nm(实施例1b)的TiO2层;以及
-厚度2nm的掺杂Al的SiO2上层。
在下述条件下沉积SiO2:Al下层:使用Si:Al(8原子%铝)靶,功率2000W,气体流量:15sccm Ar和15sccm O2和压力2×10-3mbar。
在下述条件下沉积TiO2:使用TiOx靶,功率2000W,气体流量:200sccm Ar和2sccm O2和压力23×10-3mbar。
在下述条件下沉积SiO2:Al上层:使用Si:Al(8原子%铝)靶,功率1000W,气体流量:15sccm Ar和15sccm O2和压力2×10-3mbar。
实施例2a和2b(对比):
叠层/SiO2:Al/TiO2
生产与实施例1a和1b同样的叠层,只是没有上层SiO2:Al。
实施例3(对比):
玻璃叠层/SiO2:Al/TiO2/Si3N4:Al
生产与实施例1a同样的叠层,只是在下述条件下沉积厚度也为2nm的Si3N4:Al上层代替SiO2:Al上层:使用Si:Al(8原子%铝)靶,功率1000W,气体流量:18sccm Ar和12sccm O2和压力2×10-3mbar。
实施例4:耐Opel试验性
从实施例2a叠层到实施例1a的叠层,观察到耐Opel试验(使用毡垫干磨该叠层表面)性有很大的改善。
从实施例2a叠层到实施例3的叠层,没有观察到任何变化。
另外,在上述的Opel试验前后,根据在国际申请PCT WO 00/75087中描述的硬脂酸光降解试验,后接红外透射,评价了实施例1a,2a和3叠层的每个叠层的TiO2层光催化活性。
这些结果汇集于表I中。在这个表中还列出了由于Opel试验该层侧的反射色度变化(ΔE),因Opel试验而诱发的模糊不清,和Opel试验后该层的分层观察结果。
表I
实施例 | SAT(cm-1.min-1) | ΔE | 模糊不清(%) | 分层 | |
Opel试验前 | Opel试验后 | ||||
1a(本发明) | 59×10-3 | 41×10-3 | 2.0 | 0.5 | 否 |
2a(本发明) | 54×10-3 | 25×10-3 | 9.3 | 9.3 | 是 |
3(对比) | 40×10-3 | 15×10-3 | 10.0 | 12 | 是 |
实施例5:Taber试验
从实施例2b的叠层到实施例1b的叠层,现察到耐Taber试验(耐磨性=耐砂轮通过)性获得改善。
在Taber试验500转后,实施例2b的层分层了。对于实施例1b的叠层,在Taber试验200转后观察到0.8%模糊不清,而在Taber试验500转后2%模糊不清。
实施例6:BSN试验
从实施例2a的叠层到实施例1a的叠层,观察到耐BSN试验(中性盐雾)性获得改善。
Claims (20)
1、一种结构,该结构包括基材,在其至少一部分表面上有防污的具有光催化性能的二氧化钛(TiO2)基层,其特征在于所述的具有光催化性能的层被含有硅和氧的无孔薄层覆盖,该薄层具有覆盖能力,还能保证对下层光催化层进行机械和化学保护,同时保持TiO2的光催化活性。
2、根据权利要求1所述的结构,其特征在于所述的含有硅和氧的薄层呈连续薄膜形式。
3、根据权利要求1和2中任一项权利要求所述的结构,其特征在于所述的含有硅和氧的薄层呈贴合具有光催化性能下层的凸凹不平表面的薄膜形式。
4、根据权利要求1-3中任一项权利要求所述的结构,其特征在于这个含有硅和氧的薄层是至少一种选自SiO2、SiOC、SiON、SiOx和SiOCH的硅和氧化合物的层,其中x<2。
5、根据权利要求1-4中任一项权利要求所述的结构,其特征在于这个含有硅和氧的薄层是至少一种选自Al2O3和ZrO2的化合物与其结合的至少一种硅和氧化合物的层。
6、根据权利要求5所述的结构,其特征在于(Al和/或Zr)/Si原子比不大于1。
7、根据权利要求5和6中任一项权利要求所述的结构,其特征在于Al/Si比是0.03-0.5,特别地0.05-0.1。
8、根据权利要求5-7中任一项权利要求所述的结构,其特征在于Zr/Si比是0.05-0.4。
9、根据权利要求1-8中任一项权利要求所述的结构,其特征在于这个含有硅和氧的薄层的厚度是至多15nm,特别地至多10nm,尤其至多8nm,优选地至多5nm或约5nm,尤其是2-3nm。
10、根据权利要求1-9中任一项权利要求所述的结构,其特征在于该二氧化钛基层是由单一TiO2构成的或由用至少一种特别选自N,五价阳离子,例如Nb、Ta和V,Fe和Zr的掺杂剂掺杂的TiO2构成的。
11、根据权利要求1-10中任一项权利要求所述的结构,其特征在于采用溶胶-凝胶法、采用热解法,特别是气相热解法,或采用阴极溅射法沉积这个TiO2基层,阴极溅射法是在室温与真空条件下进行的,如果必要,可以用磁场和/或离子束增强,使用金属或TiOx靶和氧化性气氛,x<2,或使用TiO2靶和惰性气氛,采用阴极溅射法得到的TiO2再进行热处理,以便它处于呈光催化活性形式的结晶态。
12、根据权利要求1-11中任一项权利要求所述的结构,其特征在于采用阴极溅射法沉积这个含有硅和氧的薄层,阴极溅射法是在室温与真空条件下进行的,如果必要,可以用磁场和/或离子束增强,使用掺杂Al的Si靶(8%原子)与压力0.2Pa的Ar+O2气氛。
13、根据权利要求1-12中任一项权利要求所述的结构,其特征在于该结构包括在紧挨TiO2基层下面的具有晶体结构的下层,这种结构有助于在TiO2基上层的锐钛矿晶型中,特别是在由ATiO3构成的上层中通过异质外延生长结晶,其中A代表钡或锶。
14、根据权利要求1-13中任一项权利要求所述的结构,其特征在于这种基材由单片玻璃或层压玻璃、玻璃陶瓷材料或硬塑料,例如聚碳酸酯的平板、弯曲或拱形面板构成,或由玻璃纤维或玻璃陶瓷纤维构成,所述的板或所述的纤维,如果必要,接受至少一个其它功能层,施用TiO2基层或有助于通过该层异质外延生长结晶的层。
15、根据权利要求14所述的结构,其特征在于这个或其它功能层选自具有光学功能的层、控热层、传导层,在这种基材是用玻璃或玻璃陶瓷材料制成的情况下,这些层构成了玻璃或玻璃陶瓷材料碱金属迁移的阻挡层。
16、如根据权利要求1-15中任一项权利要求所限定的结构的生产方法,其特征在于在玻璃或玻璃陶瓷材料或聚碳酸酯类硬塑料的板类基材上,或在玻璃或玻璃陶瓷纤维上沉积任选掺杂的TiO2层,当沉积所采用的这些条件没有为这个层提供光催化性能时,该层应进行热处理,使它具有光催化性能,然后在所述的具有光催化性能的层上沉积例如根据权利要求1-9中任一项权利要求所限定的含有硅和氧的薄层。
17、根据权利要求16所述的方法,其特征在于在室温下,采用真空阴离子溅射相继地沉积TiO2层和含有硅和氧的薄层,如果必要,在同一室中,该阴离子溅射采用磁场和/或离子束增强,这些条件如下:
-对于沉积TiO2基层,以直流或交流方式供电,压力1-3mbar,氧+惰性气体(氩气)气氛,使用Ti靶或TiOx靶,其中x=1.5-2;
-对于含有硅和氧的层的沉积,以交流方式供电,压力0.1-1Pa,Ar+O2气氛,使用高硅含量的靶;
任选地,在TiO2层的锐钛矿晶型中,通过外延生长有助于结晶的下层沉积,进行TiO2层的沉积。
18、根据权利要求16和17中任一项权利要求所述的方法,其中制备用玻璃或玻璃陶瓷材料制成的基材的涂层,其特征在于在涂布TiO2层或与其结合的下层之前,在该基材上沉积至少一个对玻璃或玻璃陶瓷材料中存在的碱金属迁移构成阻档层的层,在沉积TiO2层和覆盖该层的硅基薄层后,这时可以在进行退火或淬火处理,退火温度为250-550℃,优选地350-500℃,淬火温度为至少600℃。
19、根据权利要求16-18中任一项权利要求所述的方法,其特征在于在任选涂布至少一个对碱金属迁移构成阻档层的层之后和涂布TiO2层或与其结合的下层之前,沉积至少一个功能层,该层选自具有光学功能的层、控热层和传导层,有利地,所述的功能层是采用真空阴极溅射法沉积的,如果必要,阴极溅射可采用磁场和/或离子束增强。
20、特别是汽车或建筑物使用的单片或多片玻璃板,该玻璃板分别包括在至少一个面上的如根据权利要求1-15中任一项权利要求所限定的结构,所述的面特别地是朝外取向的面,但还可以是朝内取向的面。
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EP (1) | EP1678093B1 (zh) |
JP (1) | JP2007512154A (zh) |
KR (1) | KR101131157B1 (zh) |
CN (1) | CN1898172B (zh) |
AT (1) | ATE471303T1 (zh) |
AU (1) | AU2004283938B2 (zh) |
BR (1) | BRPI0415700B1 (zh) |
CA (1) | CA2543156A1 (zh) |
DE (1) | DE602004027751D1 (zh) |
ES (1) | ES2347440T3 (zh) |
FR (1) | FR2861386B1 (zh) |
MX (1) | MXPA06004355A (zh) |
PL (1) | PL1678093T3 (zh) |
PT (1) | PT1678093E (zh) |
WO (1) | WO2005040056A2 (zh) |
ZA (1) | ZA200604042B (zh) |
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Also Published As
Publication number | Publication date |
---|---|
FR2861386B1 (fr) | 2006-02-17 |
EP1678093B1 (fr) | 2010-06-16 |
US20070148064A1 (en) | 2007-06-28 |
PT1678093E (pt) | 2010-09-22 |
ATE471303T1 (de) | 2010-07-15 |
BRPI0415700A (pt) | 2006-12-19 |
CN1898172B (zh) | 2012-03-21 |
AU2004283938A1 (en) | 2005-05-06 |
WO2005040056A3 (fr) | 2005-06-30 |
CA2543156A1 (fr) | 2005-05-06 |
PL1678093T3 (pl) | 2010-11-30 |
KR101131157B1 (ko) | 2012-03-28 |
EP1678093A2 (fr) | 2006-07-12 |
BRPI0415700B1 (pt) | 2016-01-19 |
FR2861386A1 (fr) | 2005-04-29 |
ZA200604042B (en) | 2007-03-28 |
AU2004283938B2 (en) | 2010-07-15 |
JP2007512154A (ja) | 2007-05-17 |
KR20060090829A (ko) | 2006-08-16 |
MXPA06004355A (es) | 2006-06-14 |
ES2347440T3 (es) | 2010-10-29 |
US7884047B2 (en) | 2011-02-08 |
WO2005040056A2 (fr) | 2005-05-06 |
DE602004027751D1 (de) | 2010-07-29 |
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