CN103619966B - 具有高光催化性和清洁性作用的表面处理剂 - Google Patents
具有高光催化性和清洁性作用的表面处理剂 Download PDFInfo
- Publication number
- CN103619966B CN103619966B CN201280031239.4A CN201280031239A CN103619966B CN 103619966 B CN103619966 B CN 103619966B CN 201280031239 A CN201280031239 A CN 201280031239A CN 103619966 B CN103619966 B CN 103619966B
- Authority
- CN
- China
- Prior art keywords
- tio
- treatment agent
- nano particle
- adhesive composition
- coating
- 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.)
- Active
Links
- 230000000694 effects Effects 0.000 title claims abstract description 22
- 239000012756 surface treatment agent Substances 0.000 title claims abstract description 12
- 230000001699 photocatalysis Effects 0.000 title description 27
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 69
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 43
- 230000001070 adhesive effect Effects 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 239000002105 nanoparticle Substances 0.000 claims abstract description 28
- 239000000853 adhesive Substances 0.000 claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000000576 coating method Methods 0.000 description 40
- 239000011248 coating agent Substances 0.000 description 37
- 238000007146 photocatalysis Methods 0.000 description 23
- 239000000463 material Substances 0.000 description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000011575 calcium Substances 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000013543 active substance Substances 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 239000003570 air Substances 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 101100433192 Mus musculus Zfp1 gene Proteins 0.000 description 2
- 101100433201 Mus musculus Zfp2 gene Proteins 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 235000019504 cigarettes Nutrition 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 240000008067 Cucumis sativus Species 0.000 description 1
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 206010041925 Staphylococcal infections Diseases 0.000 description 1
- 241000191940 Staphylococcus Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 230000008485 antagonism Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000015243 ice cream Nutrition 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 208000015688 methicillin-resistant staphylococcus aureus infectious disease Diseases 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 235000013618 yogurt Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J35/39—Photocatalytic properties
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- 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
- C09D1/10—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances lime
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/32—Radiation-absorbing paints
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Paints Or Removers (AREA)
- Orthopedics, Nursing, And Contraception (AREA)
- Materials For Medical Uses (AREA)
- Absorbent Articles And Supports Therefor (AREA)
- Dispersion Chemistry (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
基于TiO2纳米颗粒的具有高催化性和清洁性作用的表面处理剂,其特征在于包括每升水10-500g的TiO2纳米颗粒,和粘合成分A;粘合成分A是一种无机粘合剂,其含量是相对于TiO2重量的0.1-10%重量比,其选自由ZnO、MgO、CaO、Ca(OH)2、Mg(OH)2、CaCO3、MgCO3、K2CO3、Na2CO3组成的组中。表面处理剂,其适用于表面,其含有最少50%的选自由ZnO、MgO、CaO、Ca(OH)2、Mg(OH)2、CaCO3、MgCO3组成的组中或它们的混合物;所述处理剂含有每升水10-500g的TiO2纳米颗粒,且可选择地含有相对于TiO2的重量的0.1%重量比的H2CO3。
Description
技术领域
本申请涉及基于TiO2纳米颗粒并用于表面处理的具有高催化性和清洁性作用的表面处理剂,其制备方法和其应用。通过光催化作用,该处理剂能够对各种材料,尤其是建筑物墙提供自清洗、清洁性、抗菌性、杀菌性的表面处理。
背景技术
建筑物中广泛使用现代塑料材料和通风***(HVAC),将醛和其它约200种有害有机物质释放到环境中。这使得消除其副作用成为必要。同时,防止染毒物通过贯通建筑物的HVAC管道传播也是重要的。
表面处理剂,即涂料和颜料,的基本功能一直集中于其覆盖功能和色彩。逐渐地,市场尝试提供具有更多功能的涂料,这趋势在近来已经变得普遍。历史上第一种涂料是水合(熟化)石灰,其在新鲜状态时兼有白色涂料和清洁功能。过去十年,市场热衷于开发纳米颗粒的基础光催化作用。虽然市场已经就TiO2的光催化性能有广泛深入的研究,但是直到今天,将TiO2应用到光活性涂料的技术还未令人满意。
开发这种技术的目的在于获得一种能够形成具有最高光催化性能和TiO2含量的光催化性表面的涂料组合物。
当TiO2纳米颗粒与硅酸盐无机涂料混合时,通常的结果是纳米颗粒的表面被二氧化硅覆盖,阻碍了期望获得的光催化性能。另一种最普遍将TiO2纳米颗粒混入涂料组合物的方式是将其直接混入丙烯酸涂料中,但问题在于TiO2纳米颗粒的光催化性能太猛烈,会光化学地分解并烧熔四周的有机丙烯酸酯物质,结果是这种涂料的强烈灰化和变黄。将额外的TiO2和稳定的聚合物加入涂料中能够缓和上述现象,但并不能完全解决问题。
在硅树脂基涂料组合物中使用TiO2纳米颗粒也有限制,因为,硅树脂类似于硅酸盐,会有效覆盖TiO2表面,进而阻碍光催化性能。
在直至目前为止开发的基于TiO2纳米颗粒并且具有光催化效果的涂料中,TiO2纳米颗粒都被涂料的一些成分覆盖,这严重降低消除有机物质的光催化能力,尤其是消除塑料材料、新家具等释放出来的烟、蒸发物和溶剂,例如醛这些有机物质的光催化能力。
捷克专利号300735(WO2009/074120)记载的多功能涂料含有达90%的TiO2,并展现出显著较高的光催化性。捷克专利号300735记载了基于TiO2纳米颗粒的具有光催化性和清洁性的涂料。该涂料包括通过至少两种成分反应产生的高孔隙度材料,而TiO2纳米颗粒位于高孔隙度材料(粘合剂)的表面。第一种成分是不溶性钙化合物,第二种成分是水溶性硫酸盐。
为了比较,我们根据捷克专利No.300735在施加到屋顶瓦上的涂料进行己烷的光降解测试。
实验开始时,己烷的浓度约为700ppm(注射10微升)。实验分如下几个阶段进行:20分钟(min)的黑暗,接下来的50min曝光在UV-A中。通过气相色谱监测己烷降解,并与纯纳米TiO2-DegussaP25(5gTiO2/m2)的降解速率进行比较,该纯纳米的降解速率表示理论上的最大值。
根据气相色谱,己烷的降解速率为:
纳米TiO2-DegussaP25-4.1mmolh/m2;
涂覆-2.4mmol/h/m2。
当粘合剂相对于TiO2的重量比为22%时,屋顶瓦表面上的的催化效率为通过DegussaP25(100%)获得的光催化效率的59%。粘合剂对于光催化性能的影响是非线性的,相对于理论效果,22%的粘合剂降低了涂料41%的光催化效率。
使用有机粘合剂或硅酸盐的基于TiO2的普通光催化涂料相对于CZ专利号300735的涂料显示出的光催化效果降低了一度。在附图1作为参考样本的普通光催化性硅酸盐涂料相对于纯TiO2的NOX降解效率仅为1.5%。
除了阻碍作用,所有提及的涂料材料和表面均含有高比例粘合剂(相对于纳米TiO2含量为百分之几十),这进一步降低光催化效果。
发明内容
通过具有非常高的光催化和清洁作用的表面处理剂能够解决以上描述的弊端,根据本发明的表面处理剂包括每升水中10-500g的TiO2纳米颗粒,和相对于TiO2的重量为0.1-10%重量比(wt%)的粘合成分A,其为选自由包括ZnO、MgO、CaO、Ca(OH)2、Mg(OH)2、CaCO3、MgCO3、K2CO3或Na2CO3所组成的组中,所述处理剂在使用和干燥后得到含有最少90wt%TiO2的层。
该处理剂通过以下方法制得:将TiO2纳米颗粒加入水中,同时强烈搅拌使TiO2在水中悬浮。向该悬浮液加入粘合成分A的溶液或悬浮液。在5-50℃的温度强烈搅拌下,加入粘合成分A后,悬浮液瞬间剧烈变浓稠。
结果得到浓稠的、稳定的酸奶状或冰淇淋稠度的涂料悬浮液,其能够被涂覆或喷洒到各种材料上,尤其是建筑物墙,从而在这些材料上产生具有高光催化活性的多孔表层。因为有高含量的而且具有完全可及表面的TiO2纳米颗粒,该表层的光催化效果接近于纯TiO2的光催化性能。
如果待处理区域已经具有粘合成分A,尤其是ZnO、MgO、Na2CO3、Ca(OH)2、CaCO3或MgCO3,例如石灰墙壁或用高含量的粘合成分A的涂料处理过的表面,本发明还描述了具有高光催化性和清洁作用的表面处理剂,根据本发明,这种表面处理剂每升水仅含有10-500gTiO2纳米颗粒,且可选择性地含有相对于TiO2的重量至少0.1wt%的H2CO3。
本申请中,处理剂还可含有粘合成分A。
在5-50℃的温度下剧烈混合后,若不加入粘合成分A,纯TiO2和水的悬浮液稳定性低。因此,将处理剂施加到墙体上时,要持续混合处理剂。当处理剂与处理区域表面含有的粘合成分A接触时,处理剂形成粘结物并且与处理表面紧密粘合。
相对地,若加入粘合成分A,在5-50℃的温度下TiO2和水的悬浮液稳定性很高,正如表3所示。表3显示了5天后不同处理剂的沉降速率,某些物质几乎可完全抑制沉降,而其它物质对于沉降没有抑制作用。
用于上述处理剂中的粘合剂含量绝对是最小的,到目前为止,尚未听闻使用超低浓度的无机材料达至粘合效果。这种低浓度粘合剂,相对于纯TiO2活性物质,可以达到90%以上的光催化作用水平。
尽管粘合作用必然与TiO2参与产生的某种表面粘结物的生成有关,但是对这一现象的条件或本质还不是完全清楚。TiO2实际上是完全惰性的,于实施例中提及的很多物质也都一样,尽管如此,这些物质中的一些都显示出高粘合能力,至于其他预计能够形成例如氢键或OH基团的键的物质,则是绝对非活性的。
优选地,涂层应用于房间天花板,此处由于空气循环的缘故,所以效果最好。为了增强除臭作用并消除各种气味,尤其是烟和做饭产生的气味,可通过在天花板安装电风扇和通过UV灯照射天花板,从而增加天花板附近的空气湍流。
通过将其不时曝光于强UV辐射源,能够使涂层的功能实现清洗和复原。
TiO2纳米颗粒的光催化作用还取决于涂层的厚度。涂层的建议厚度为1-50微米。最佳地,涂层厚度为5-30微米。
TiO2纳米颗粒的光催化作用使得位于TiO2纳米颗粒表面上的有机物质分解,从而消除了气味,并提供了抗菌性能。
根据本发明的处理剂用来形成一涂层,其中TiO2颗粒表面能够自由接触环境空气,因为它们没有被粘合剂覆盖,该而粘合剂会损害光催化作用。
由于涂层干燥后(99%干燥)具有高含量的TiO2,所以其表现出与纯TiO2涂层几乎相同的光催化效果。
具体实施方式
以下实施例对本发明进行了说明,但绝不意味着对本发明的限制。
实施例1
将具有特定表面积50m2/g(DegussaP25)的TiO2纳米颗粒以不同浓度与水混合,即分别使每升水含有20、30、50和100g的TiO2,且通过剧烈混合转变为悬浮液。不同量的Ca(OH)2饱和溶液被缓慢加入这些悬浮液中(见表1)。Ca(OH)2浓溶液含有最大量为每升2g的Ca(OH)2,pH值非常高,是14。
表1
当加入Ca(OH)2溶液时,在所有情况下,处理剂都几乎立即变得非常粘稠。在几种情况下,TiO2的浓度相对非常低,即低至20g/L。此外,1.4g/L的Ca(OH)2的加入量也非常低,这表明Ca(OH)2对TiO2有非常强的粘合效果。在两种情况下,还加入了浓度1g/L的少量ZnO,加入该物质后粘合效果变得更强。
这些处理剂沉降性低,Ph值几乎为中性,是应用于各种表面的理想材料。
通过若丹明B染料在表面上的降解,可测定根据本发明的处理剂产生的涂层的光催化作用。若丹明B染料喷涂在表面上并干燥后几分钟内即被降解。
进一步地,使用ISO22197-1限定的方法测定转化NOx的光子效率,比较由纯活性物质(DegussaP25)形成的膜和根据本发明的处理剂形成的涂层的效率(图1),其中根据本发明的处理剂形成的涂层每升含有以下比例的纳米TiO2和粘合成分A。
a)FNP1:100gTiO2+1gCa(OH)2(A)
b)FNP2:100gTiO2+1gCa(OH)2+1g纳米(nano)-ZnO(A)
该处理剂显示出a)纯活性物质92.5%的效率,且甚至能达到b)纯活性物质99%的效率(理论最大值)。
还进一步检测了处理剂a)和b)杀灭光活性表面上对抗性很强的金黄色葡萄糖菌MRSA的性能,其中处理剂的组分与前述相同:
a)FNP1:100gTiO2+1gCa(OH)2(A)
b)FNP2:100gTiO2+1gCa(OH)2+1g纳米(nano)-ZnO(A)
细菌的起始浓度为100,000CFU。暴露于柔性UV-A辐射80分钟(min)后,暴露的活性表面上CFU浓度下降到0。在20min内,在处理剂a)上的初始微生物浓度下降到92CFU,而处理剂b)上则下降到46CFU。两种处理剂都具有高性能,但处理剂b)的性能略高。
涂层可以通过湍动空气循环和高强光来倍增其效率,例如通过在屋顶安装具有风扇的灯和“黑光”荧光灯。通过不时让涂料接受强UV辐射源照射,可使涂料功能清洁和复原。
实施例2
以不同浓度将TiO2纳米颗粒混合到水中,并通过剧烈混合转变为悬浮液。将少量的测试粘合成分加入这些悬浮液中,并对这些通常为完全惰性的物质的粘合作用进行监测。悬浮液的最终浓度为每升20-300gTiO2,粘合成分的加入量通常仅为每升1-2g。
进行了粘合作用测定的物质的列表见表2。有些物质类似于实施例1,马上起作用,在加入粘合物质后悬浮液马上变得粘稠。这些处理剂是稳定的,几乎零沉降、pH值中性,是粘合到各种表面的理想材料。类似于前面的实施例,处理剂中TiO2的浓度分别为每升20、30、50、100和300g的TiO2,且加入的测试粘合物质浓度是1g/L。
有些物质根本没有展示出粘合作用。La2O3处于边缘状态,它的确使得悬浮液在一定程度上增稠,但紧接着悬浮液快速沉降。ZrO2和β(beta)Al2O3产生部分作用,但作用较小。一般上,人们可能会说,在各种化合物之间没有可以解释粘合剂对于TiO2的粘合性能的关系。H2CO3使得处理剂非常粘稠,但在使用和干燥后,它仅展示出低粘合性。但是,本发明的处理剂对于含有选自由包括ZnO、MgO、CaO、Ca(OH)2、Mg(OH)2,、CaCO3、MgCO3、Na2CO3、K2CO3所组成的组中的表面则显示出优异的粘合性。
表2
活性物质 | 粘合物质(1g/L) | 粘合效果 | Ph值 |
TiO2 | Na2CO3 | 是 | 7 |
TiO2 | Na2CO3+0.5gZnO | 是 | 7 |
TiO2 | K2CO3 | 是 | 7 |
TiO2 | LiOH | 否 | 10 |
TiO2 | NaOH | 否 | 8.5 |
TiO2 | NH4OH | 否 | 11 |
TiO2 | Ca(OH)2 | 是 | 7 |
TiO2 | (NH4)2SO4 | 是 | 6 |
TiO2 | ZnSO4 | 否 | 5 |
TiO2 | ZnO | 是 | 5.5 |
TiO2 | MgO | 是 | 5.5 |
TiO2 | Mg(OH)2 | 是 | 6.5 |
TiO2 | CaCO3 | 是 | 6.5 |
TiO2 | La2O3 | 否 | 6.5 |
TiO2 | ZrO2 | 否 | 5 |
TiO2 | Al2O3β(beta) | 否 | 5 |
TiO2 | Al2O3α(alpha) | 否 | 5 |
TiO2 | Fe3O4 | 否 | 5.5 |
TiO2 | Fe2O3纳米-红 | 否 | 5.5 |
TiO2 | Fe2O3纳米-黄 | 否 | 5.5 |
TiO2 | H2CO3 | 是 | 5 |
TiO2 | 乙醇 | 否 | 5 |
表3显示了TiO2浓度分别为100g/L和50g/L的悬浮液的沉降比较数据。柱的最大高度为150mm(试管高度)。用溶液填充试管至边缘位置,颈部密封并且悬浮液静止5天。随后,实验通过测定固体物质沉积柱的高度来完成。
表3
然后将处理剂的稠悬浮液施加到已经涂有丙烯酸涂料的石膏板上,然后整个表面喷涂若丹明B红色颜料。在日照下,所有测试表面均在几分钟内因光催化分解而褪色。
将20微米厚度并且含有100g纳米-TiO2/L+1g纳米-ZnO的处理剂涂层涂抹到由丙烯酸涂料覆盖的房屋墙壁上。涂抹后,房间的异味立即消失。
实施例3
将仅含有每升100gTiO2悬染液的处理剂以两层的形式喷涂到多孔石灰岩的外表面,形成5-10微米厚几乎透明并带有略微发白底色的膜。纯沙岩和用石灰水处理过的沙岩作为参考表面。两者均用相同TiO2处理剂喷涂。然后所有表面均暴露在外部环境中。三周内纯沙岩上的TiO2层被雨水冲走,在其它表面上,用石灰水喷涂的石灰岩和沙岩几乎保持完整。这些表面保持了长时间的自清洁性能。
工业应用性
具有光催化和清洁功能的涂覆材料可作为清洁涂料应用于医院、生物实验室、办公室和居住房屋中,特别是过敏人士使用的房间,也可用于对房间和设施进行除臭处理,例如餐馆。这些涂料还适用于活性表面能够清洁空气中的汽车污染物的地方,例如建筑物外墙、沿道路设置的混凝土减噪屏障等,或者作为保护性涂料应用于文物上。有益的是,它们也能够应用于农场和畜牧业中,以降低饲养过程中出现传染病和流行病的风险。
Claims (4)
1.基于TiO2纳米颗粒的具有高催化性和清洁性作用的表面处理剂,其特征在于包括每升水10-500g的TiO2纳米颗粒,和粘合成分A;粘合成分A是一种无机粘合剂,其含量是相对于TiO2重量的0.1-10%重量比,其选自ZnO或MgO或CaO或Ca(OH)2或Mg(OH)2或CaCO3或MgCO3或K2CO3或Na2CO3或它们的混合物;在TiO2纳米颗粒加入水中再通过搅拌形成的水悬浮液中加入粘合成分A后,粘合成分A对TiO2纳米颗粒产生粘合效果。
2.根据权利要求1所述的基于TiO2纳米颗粒的具有高催化性和清洁性作用的表面处理剂的制备方法,其特征在于将TiO2纳米颗粒与水混合搅拌形成水悬浮液,且在5-50℃的温度下使水悬浮液与粘合成分A的溶液或悬浮液混合,加入粘合成分A后,悬浮液瞬间剧烈变浓稠。
3.表面处理的方法,其特征在于在5-50℃的温度下将根据权利要求1的处理剂应用于表面形成1-50微米厚度,干燥后得到含有至少90wt%TiO2的层。
4.根据权利要求3所述的表面处理的方法,其特征在于应用于表面的处理剂形成5-30微米厚度。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CZPV2011-397 | 2011-06-30 | ||
CZ20110397A CZ303366B6 (cs) | 2011-06-30 | 2011-06-30 | Prostredek pro úpravu povrchu s vysoce fotokatalytickým a sanitárním efektem |
PCT/CZ2012/000054 WO2013000441A1 (en) | 2011-06-30 | 2012-06-21 | Surface treatment agent with high photocatalytic and sanitary effects |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103619966A CN103619966A (zh) | 2014-03-05 |
CN103619966B true CN103619966B (zh) | 2015-12-23 |
Family
ID=46545578
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201280031239.4A Active CN103619966B (zh) | 2011-06-30 | 2012-06-21 | 具有高光催化性和清洁性作用的表面处理剂 |
Country Status (17)
Country | Link |
---|---|
US (1) | US9200163B2 (zh) |
EP (1) | EP2726557B1 (zh) |
CN (1) | CN103619966B (zh) |
CA (1) | CA2839230C (zh) |
CY (1) | CY1117994T1 (zh) |
CZ (1) | CZ303366B6 (zh) |
DK (1) | DK2726557T3 (zh) |
ES (1) | ES2588767T3 (zh) |
HK (1) | HK1195331A1 (zh) |
HR (1) | HRP20161181T1 (zh) |
HU (1) | HUE029878T2 (zh) |
LT (1) | LT2726557T (zh) |
PL (1) | PL2726557T3 (zh) |
PT (1) | PT2726557T (zh) |
RS (1) | RS55082B1 (zh) |
SI (1) | SI2726557T1 (zh) |
WO (1) | WO2013000441A1 (zh) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MX2017006343A (es) | 2014-11-17 | 2017-08-21 | Univ Portland State | Composiciones que comprenden frustulos de diatomea y aplicaciones de las mismas. |
EP4008432A3 (de) | 2020-11-13 | 2022-07-27 | Pigmentsolution GmbH | Linoleum-granulat für den aussenbereich |
DE102020130071B3 (de) | 2020-11-13 | 2021-12-30 | Pigmentsolution GmbH | Linoleum-Granulat für den Außenbereich und seine Verwendung, sowie Außenanlagen-Bodenbelag daraus oder damit |
DE202020106542U1 (de) | 2020-11-13 | 2020-12-07 | Pigmentsolution GmbH | Linoleum-Granulat für den Aussenbereich |
KR20230123541A (ko) | 2022-02-16 | 2023-08-24 | 한림대학교 산학협력단 | 가시광선 활성 광촉매를 포함하는 광촉매 페인트 및 이의 제조방법 |
CN115888676B (zh) * | 2022-09-28 | 2024-05-14 | 电子科技大学长三角研究院(湖州) | 一种抑制硝酸盐分解的组合物及制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101896559A (zh) * | 2007-12-11 | 2010-11-24 | 高级材料-Jtj公司 | 多功能光催化卫生涂料及其施用方法 |
CN102220039A (zh) * | 2011-04-26 | 2011-10-19 | 福州大学 | 一种室内用光催化涂料及其制备方法和应用 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1239635C (zh) * | 2002-11-06 | 2006-02-01 | 中山大学 | 纳米CaCO3/TiO2复合粒子及其制备方法 |
US20070275168A1 (en) * | 2003-03-13 | 2007-11-29 | Jan Prochazka | Manufacturing of Photocatalytic, Antibacterial, Selfcleaning and Optically Non-Interfering Sufaces on Tiles and Glazed Ceramic Products |
FI116297B (fi) * | 2004-01-07 | 2005-10-31 | Kemira Pigments Oy | Menetelmä pintojen käsittelemiseksi |
EP2079302B1 (en) * | 2006-10-12 | 2014-03-26 | NM Tech Nanomaterials Microdevice Technology, Ltd. | Use of a composition having anti-microbial properties |
CZ300309B6 (cs) * | 2006-12-27 | 2009-04-15 | CTC AP a. s. | Smesný práškový dekontaminant na bázi TiO2 |
US7919425B2 (en) * | 2008-03-26 | 2011-04-05 | Toto Ltd. | Photocatalyst-coated body and photocatalytic coating liquid for the same |
US20100081563A1 (en) * | 2008-09-26 | 2010-04-01 | Andrew Edgar-Beltran | Adhesion and coating integrity of washcoats and overcoats |
ES2473469T3 (es) * | 2009-06-19 | 2014-07-07 | Granitifiandre S.P.A. | Artículo de cerámica fotocatal�tica y método para su producción |
-
2011
- 2011-06-30 CZ CZ20110397A patent/CZ303366B6/cs unknown
-
2012
- 2012-06-21 EP EP12737468.4A patent/EP2726557B1/en active Active
- 2012-06-21 PL PL12737468T patent/PL2726557T3/pl unknown
- 2012-06-21 RS RS20160628A patent/RS55082B1/sr unknown
- 2012-06-21 CN CN201280031239.4A patent/CN103619966B/zh active Active
- 2012-06-21 US US14/125,677 patent/US9200163B2/en active Active
- 2012-06-21 DK DK12737468.4T patent/DK2726557T3/en active
- 2012-06-21 HU HUE12737468A patent/HUE029878T2/en unknown
- 2012-06-21 SI SI201230650A patent/SI2726557T1/sl unknown
- 2012-06-21 LT LTEP12737468.4T patent/LT2726557T/lt unknown
- 2012-06-21 PT PT127374684T patent/PT2726557T/pt unknown
- 2012-06-21 WO PCT/CZ2012/000054 patent/WO2013000441A1/en active Application Filing
- 2012-06-21 ES ES12737468.4T patent/ES2588767T3/es active Active
- 2012-06-21 CA CA2839230A patent/CA2839230C/en active Active
-
2014
- 2014-08-26 HK HK14108670.4A patent/HK1195331A1/zh unknown
-
2016
- 2016-07-29 CY CY20161100751T patent/CY1117994T1/el unknown
- 2016-09-15 HR HRP20161181TT patent/HRP20161181T1/hr unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101896559A (zh) * | 2007-12-11 | 2010-11-24 | 高级材料-Jtj公司 | 多功能光催化卫生涂料及其施用方法 |
CN102220039A (zh) * | 2011-04-26 | 2011-10-19 | 福州大学 | 一种室内用光催化涂料及其制备方法和应用 |
Also Published As
Publication number | Publication date |
---|---|
ES2588767T3 (es) | 2016-11-04 |
EP2726557B1 (en) | 2016-06-15 |
RS55082B1 (sr) | 2016-12-30 |
HUE029878T2 (en) | 2017-04-28 |
CN103619966A (zh) | 2014-03-05 |
CZ2011397A3 (cs) | 2012-08-15 |
HK1195331A1 (zh) | 2014-11-07 |
US20140127414A1 (en) | 2014-05-08 |
DK2726557T3 (en) | 2016-09-12 |
US9200163B2 (en) | 2015-12-01 |
CY1117994T1 (el) | 2017-05-17 |
EP2726557A1 (en) | 2014-05-07 |
SI2726557T1 (sl) | 2016-09-30 |
WO2013000441A1 (en) | 2013-01-03 |
CA2839230C (en) | 2016-05-10 |
PL2726557T3 (pl) | 2017-09-29 |
LT2726557T (lt) | 2016-09-26 |
PT2726557T (pt) | 2016-08-05 |
CZ303366B6 (cs) | 2012-08-15 |
HRP20161181T1 (hr) | 2016-11-04 |
CA2839230A1 (en) | 2013-01-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103619966B (zh) | 具有高光催化性和清洁性作用的表面处理剂 | |
JP4398869B2 (ja) | チタニア−金属複合体及びその製造方法、並びにその複合体分散液を用いた造膜方法 | |
CN105315727B (zh) | 可释放负氧离子的生态型多功能无机干粉涂料 | |
CN101896559B (zh) | 多功能光催化涂层及其制备方法 | |
JP2011506647A5 (zh) | ||
Maulidiyah et al. | Photo-inactivation Staphylococcus aureus by using formulation of Mn-N-TiO2 composite coated wall paint | |
JP3340937B2 (ja) | 浄化性コーティング用組成物 | |
JP4157943B2 (ja) | 光活性を有する化合物及びその用途 | |
CN108129100A (zh) | 环保纳米硅藻泥干粉及其制备方法 | |
CN107141917A (zh) | 一种车用净化组合物 | |
JP2006233072A (ja) | 光触媒塗料、該塗料を塗布した室内内装品および壁紙 | |
JPH11264224A (ja) | 消臭・防汚内外装仕上げ材 | |
JP2009263651A (ja) | 光触媒コーティング組成物 | |
JP3814653B2 (ja) | 光触媒層形成用水性コーティング液、光触媒層を有する金属板の製造方法及び光触媒層を有する金属板 | |
WO2020101515A2 (en) | Coating polymeric resin composition, process for producing thereof and method of activating the polymeric composition | |
CN110183893A (zh) | 一种灰钙基耐水腻子 | |
US20220041258A1 (en) | Coatings that reduce or prevent barnacle attachment to a marine structure | |
JP2001261510A (ja) | 墓の防カビ方法 | |
CN103073996A (zh) | 绿氧源内墙健康漆及其制造方法 | |
KR20030066485A (ko) | 광촉매를 이용한 건축 구조물의 코팅방법 | |
JP2005068817A (ja) | 二酸化チタン被覆された窓枠及びその製造方法 | |
JP2009262554A (ja) | 光触媒塗装体およびそのための光触媒コーティング液 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1195331 Country of ref document: HK |
|
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
REG | Reference to a national code |
Ref country code: HK Ref legal event code: GR Ref document number: 1195331 Country of ref document: HK |