CN113735456A - 以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法 - Google Patents
以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法 Download PDFInfo
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- 239000010936 titanium Substances 0.000 title claims abstract description 116
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 110
- 238000004140 cleaning Methods 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 63
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 title claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000000576 coating method Methods 0.000 claims abstract description 31
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 18
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 66
- 238000003756 stirring Methods 0.000 claims description 30
- 239000002244 precipitate Substances 0.000 claims description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 8
- 238000000975 co-precipitation Methods 0.000 claims description 8
- UFEKFJNLCSDWGL-UHFFFAOYSA-N dipotassium oxido-(oxido(dioxo)chromio)oxy-dioxochromium hydrochloride Chemical compound Cl.[Cr](=O)(=O)([O-])O[Cr](=O)(=O)[O-].[K+].[K+] UFEKFJNLCSDWGL-UHFFFAOYSA-N 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 7
- 231100001240 inorganic pollutant Toxicity 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000003518 caustics Substances 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000007888 film coating Substances 0.000 claims description 3
- 238000009501 film coating Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 238000002834 transmittance Methods 0.000 abstract description 7
- 238000005286 illumination Methods 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 238000005299 abrasion Methods 0.000 abstract description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract description 2
- 229910003074 TiCl4 Inorganic materials 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000002245 particle Substances 0.000 description 7
- 238000011056 performance test Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005485 electric heating Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229940057838 polyethylene glycol 4000 Drugs 0.000 description 2
- 229940093429 polyethylene glycol 6000 Drugs 0.000 description 2
- -1 radical free radical Chemical class 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000005348 self-cleaning glass Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B11/00—Cleaning flexible or delicate articles by methods or apparatus specially adapted thereto
- B08B11/04—Cleaning flexible or delicate articles by methods or apparatus specially adapted thereto specially adapted for plate glass, e.g. prior to manufacture of windshields
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- C—CHEMISTRY; METALLURGY
- 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
- C03C17/22—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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- 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
- 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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- 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
- 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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- 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
- 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
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Abstract
本发明公开了一种以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,属于纳米钛基薄膜制备技术领域。本发明为克服现有钛基薄膜的问题,提供了一种以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,包括:以TiCl4为钛源、加入聚乙二醇制备钛基水溶胶;基片处理;镀膜;热处理。本发明钛基纳米自清洁薄膜具有优异的亲水性能及光催化性能,薄膜透过率可达88%,光照下甲基蓝降解率提高65%,与水的接触角均较小,最小的接触角为6.5°,同时具有较宽的禁带宽度、较强的机械强度、良好的化学稳定性、抗磨损性、低成本、无毒性。
Description
技术领域
本发明属于钛基纳米薄膜制备技术领域,具体涉及一种以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法。
背景技术
目前玻璃在现代都市中大面积使用,楼的门窗、幕墙、车窗等等。但是,在经济日益繁荣和发展的今天,环境污染问题已成为一个直接威胁人类生存而急待解决的焦点问题,令人烦恼的玻璃清洁问题也随之而来。例如高空作业,危险性大;使用高强度洗涤剂,有一定的腐蚀性,同时产生的废水给环境带来二次污染;在清洁中需使用大量的水,浪费了水资源等问题。因此在玻璃表面制备一种自清洁薄膜,可以利用天然条件达到自清洁效果,就可以解决以上所有问题。
自清洁薄膜主要将玻璃、陶瓷等作为载体,镀上功能化后的薄膜,在紫外线光照下,使空气中水分和氧气转化为经基自由基和活性氧自由基然后这些游离的自由基使、等污染气体转化成各种无害的气体或酸类,现在自清洁薄膜都具有光催化的作用,向着可以吸收可见光、更高的量子效率、复合型发展。自清洁技术在消毒杀菌、防污除臭、净化空气以及分解水中有机污染物等方面都显示了良好的应用前景是近年来国内外研究的热点领域之一。
TiO2光催化产品的研究开发,目前已经到了基础理论完备、应用研究飞速发展的阶段,研究领域近年来也出现过制备二氧化钛薄膜等一系列的光催化领域的应用,但都出现了不同程度的弊端,例如光催化效率低、超亲水性只有在紫外光照条件下才能体现(光响应波长比较狭窄)、亲水性还有可提升空间、表面附着力不合格、表面直观感较差等问题。
发明内容
本发明为解决现有技术的上述问题,提供了一种以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,其包括以下步骤:
钛基水溶胶制备:
A、将四氯化钛溶液滴入水中,得溶液A;
B、将苛性碱与水混合,得溶液B;
C、搅拌下,向溶液A中滴加溶液B,当体系pH为6~7时,停止加入溶液B,经共沉淀反应,得沉淀,所得沉淀经洗涤后,分散于水,得悬浮液;
D、向悬浮液滴加双氧水,然后加入聚乙二醇,并搅拌至溶液呈透明状,再采用氨水调节体系pH至6~7,静置后,得钛基水溶胶;
基片处理:
E、先用浓盐酸-重铬酸钾混合液浸泡载体去除表面无机污染物,用水冲洗后,用无水乙醇超声振荡清洗,再用水超声振荡重复清洗三次,烘干,备用;
镀膜:
F、对经步骤E处理后的载体进行镀膜,镀膜3~5层,每镀一层膜先烘干再进行下一层镀膜;
热处理:
G、350~900℃煅烧镀膜后的载体,热处理后,钛基纳米防腐薄膜在载体表面生成。
其中,上述以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,步骤A中,所得溶液A的钛浓度为0.5~0.8mol/L。
其中,上述以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,步骤B中,所得溶液B的苛性碱浓度为4~6mol/L。
其中,上述以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,步骤C中,在200~500r/min转速向溶液A中滴加溶液B。
其中,上述以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,步骤C中,滴加完毕后,继续搅拌10~40min。
其中,上述以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,步骤C中,所述洗涤为:将沉淀依次用热水和无水乙醇交替清洗,直到AgNO3检测不出Cl-为止。
其中,上述以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,步骤C中,将沉淀分散于水中后,搅拌10min~30min。
其中,上述以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,步骤C中,所得悬浮液的钛浓度为0.2~0.4mol/L。
其中,上述以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,步骤D中,所述双氧水的浓度为不低于28%。
其中,上述以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,步骤D中,所述双氧水的加入量以体系内H2O2与Ti4+的摩尔比不小于4:1为准。
其中,上述以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,步骤D中,所述聚乙二醇的分子量为1000~6000。
其中,上述以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,步骤D中,所述聚乙二醇的加入量为占体系质量的1~3%。
其中,上述以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,步骤D中,所述搅拌的时间为30~60min。
其中,上述以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,步骤D中,所述静置的时间为10~18h。
其中,上述以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,步骤E中,所述浸泡的时间为15min~30min。
其中,上述以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,步骤E中,无水乙醇超声振荡清洗的时间为5min~15min。
其中,上述以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,步骤E中,所述烘干的温度为80~110℃。
其中,上述以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,步骤F中,采用浸渍提拉法或涂布法进行镀膜;浸渍提拉法中,控制浸渍时间为2min~5min,提拉机以1cm/min~3cm/min提拉;涂布法中,以1mm/s~3mm/s进行涂布。
其中,上述以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,步骤F中,所述烘干的温度为90~110℃,时间为5min~15min。
其中,上述以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,步骤G中,所述煅烧的时间为2h~4.5h。
需要说明的是,为了减少基片表面的离子存在,提高其自清洁作用,本发明各阶段(包括钛基水溶胶制备和基片处理)中需要使用不含Cl-等离子的水,如去离子水。
本发明的有益效果:
本发明以价格低廉的四氯化钛为钛源,较使用有机钛源(如钛酸正丁酯)更低廉和环保,以反应温和的溶胶凝胶法制备稳定性极佳的钛基水溶胶,其粒径大约20nm,通过涂布或提拉等手段将溶胶均匀涂抹在待保护载体表面,并通过热处理将钛基水溶胶转换为钛基薄膜。
本发明利用光催化作用及亲水性机理制备纳米钛基薄膜,形成具有光响应型的纳米级自清洁钛基薄膜,五次镀膜厚度<1μm,样品表面分布着许多气孔,钛基晶粒沿着纵向生长,增加的凸起使得薄膜的表面粗糙度增大,表面能提高,比表面积增加,表面的活性位点增加,进而提高了薄膜表面的亲水性能及光催化性能,薄膜透过率可达88%,光照下甲基蓝降解率提高65%,与水的接触角均减小,最小的接触角为6.5°。本发明钛基纳米自清洁薄膜性能优异,应用范围较广,市场较大,例如汽车后视镜、防雾镜面、自清洁玻璃、自清洁陶瓷、自清洁太阳能面板、室外广告牌等。
具体实施方式
具体的,以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,其包括以下步骤:
钛基水溶胶制备:
A、将四氯化钛溶液滴入水中,得溶液A;
B、将苛性碱与水混合,得溶液B;
C、搅拌下,向溶液A中滴加溶液B,当体系pH为6~7时,停止加入溶液B,经共沉淀反应,得沉淀,所得沉淀经洗涤后,分散于水,得悬浮液;
D、向悬浮液滴加双氧水,然后加入聚乙二醇,并搅拌至溶液呈透明状,再采用氨水调节体系pH至6~7,静置后,得钛基水溶胶;
基片处理:
E、先用浓盐酸-重铬酸钾混合液浸泡载体去除表面无机污染物,用水冲洗后,用无水乙醇超声振荡清洗,再用水超声振荡重复清洗三次,烘干,备用;
镀膜:
F、对经步骤E处理后的载体进行镀膜,镀膜3~5层,每镀一层膜先烘干再进行下一层镀膜;
热处理:
G、350~900℃煅烧镀膜后的载体,热处理后,钛基纳米防腐薄膜在载体表面生成。
本发明方法步骤A中,采用四氯化钛溶液,以实现对反应速度的可控性,并控制溶液A的钛浓度为0.5~0.8mol/L;步骤B中,控制溶液B的苛性碱(氢氧化钾或氢氧化钠)浓度为4~6mol/L;通过控制溶液A和B的浓度,使共沉淀反应速度适当,避免副产物生成;若浓度过高会造成反应过快,产生较多副产物,导致无法生成白色沉淀物质;浓度太低,实验所耗时间过长。其中,四氯化钛溶液、氢氧化钾或氢氧化钠均为市售品。
本发明方法步骤C中,在200~500r/min转速向溶液A中滴加溶液B,避免副反应发生,并使沉淀剂氢氧化钾或氢氧化钠与四氯化钛充分接触;由于每一个TiO2+需要和两个OH-反应,为了保证充足的OH-,经试验,当体系pH达到6~7时,停止滴加溶液B,能够保证沉淀反应充分完成,在此过程中不断出现白色沉淀,后续再搅拌10~40min使反应彻底。
本发明方法步骤C中,共沉淀反应完全后,将沉淀依次用热水(50~60℃)和无水乙醇交替清洗,直到AgNO3检测不出Cl-为止;然后将沉淀分散于水中后,搅拌10min~30min,使其充分分散,并控制悬浮液的钛浓度为0.2~0.4mol/L,以保证形成适宜浓度的水溶胶,提高其对载体的防护效果。
本发明方法步骤D中,采用浓度不低于28%的双氧水,一般采用市售品,其浓度一般为30%,双氧水的加入量以体系内H2O2与Ti4+的摩尔比不小于4:1为准,滴加双氧水时不断搅拌,然后加入聚乙二醇,再搅拌时间为30~60min,得到深黄色透明溶液,调pH后,静置10~18h,即得到浅黄色透明的钛基水溶胶。
试验发现,采用模板剂法,制备粗糙多孔的TiO2薄膜具有优异的超亲水性。因此本发明方法步骤D中选择聚乙二醇(长的曲折链状结构)作为孔状结构添加剂,当其溶解在水或乙醇中时会变为环状网络结构的聚合物。步骤D中,控制聚乙二醇的分子量为1000~6000,加入1~3%的聚乙二醇,控制聚乙二醇加入量,避免过多聚乙二醇分散于钛基水溶胶中,导致后续煅烧后形成孔状结构。
本发明步骤E中,载体可采用本领域内常规载体,如玻璃、陶瓷等。预处理时,先用浓盐酸-重铬酸钾混合液浸泡载体15min~30min去除表面无机污染物;待用水冲洗载玻片后,用无水乙醇超声振荡清洗5min~15min,再用水超声振荡重复清洗三次,然后80~110℃烘干候备用。
本发明方法步骤F中,采用浸渍提拉法或涂布法进行镀膜;浸渍提拉法中,控制浸渍时间为2min~5min,提拉机以1cm/min~3cm/min提拉;涂布法中,以1mm/s~3mm/s进行涂布。经试验镀膜3~5层时效果较佳,每镀一层膜先90~110℃烘干5min~15min,再进行下一层镀膜。
本发明方法步骤G中,将镀膜后的载体于350~900℃煅烧2h~4.5h,其中,350~600℃煅烧所得薄膜的晶型主要为锐钛矿型,600~900℃煅烧所得薄膜的晶型主要为金红石型;热处理后,钛基纳米自清洁薄膜在载体表面生成。
本发明钛基纳米自清洁薄膜具有较宽的禁带宽度、较强的机械强度、良好的化学稳定性、抗磨损性、低成本、无毒性,且具有良好的光催化性能使其在紫外光照射下产生电子空穴对,电子空穴对能有效的分解有机化合物为能被水带走的无害物,从而具备自清洁功能;同时表面具有较好的亲水性,当水接触到玻璃表面时,会迅速在其表明铺展形成均匀水膜,因而具备防雾及易干燥性能;其亲水性还能使水轻易地介入污染物和固体界面间,重力下落时即可带走尘埃,从而具有用雨水等条件自动清除污染物的效果。
下面通过实施例对本发明作进一步详细说明,但并不因此将本发明保护范围限制在所述的实施例范围之中。
实施例1
步骤一:将市售四氯化钛溶液逐滴滴入去离子水中配置成浓度为0.5mol/L溶液A。
步骤二:将NaOH颗粒分散于去离子水中,超声搅拌,配置浓度为4mol/L的NaOH溶液B。
步骤三:以300r/min转速搅拌溶液A,并将溶液B逐滴加入溶液A中,发生共沉淀反应,当体系pH达到6.5时,停止滴加溶液B,此过程中不断出现白色沉淀;后续接着搅拌15min待反应彻底,将白色沉淀过滤并分别用热去离子水和无水乙醇反复洗涤,直到用AgNO3检测不到Cl-为止;再将所得白色沉淀分散于去离子水中,并进行搅拌10min,得到浓度0.3mol/L的悬浮液。
步骤四:将市售30%H2O2溶液(H2O2:Ti4+摩尔比为4:1)用移液管缓慢滴加进悬浮液中,将体系分为三份,再分别加入占体系不同质量分数(0.1%,0.2%,0.3%)的聚乙二醇2000,并不断搅拌45min,至溶液深黄色透明,然后用氨水调节体系的pH值至7,静置12h,得到浅黄色透明的钛基水溶胶。
步骤五:本实施例以玻璃载玻片7101为基板,将准备好的基板先用浓盐酸-重铬酸钾混合液浸泡20min去除表面无机污染物;待用去离子水冲洗载玻片后,用无水乙醇超声振荡清洗10min;再用去离子水超声振荡重复清洗三次;放入电热恒温鼓风干燥箱80℃中烘干备用。
步骤六:使用钛基水溶胶以1mm/s速度对玻璃载玻片进行镀膜,每镀一次膜均需烘干5min再进行下一次镀膜,本实施例镀3次。
步骤七:将镀好的基片置于马弗炉内450℃高温煅烧4h。
步骤八:将镀膜好后的玻璃载玻片进行薄膜的结构与形貌、光学性能透光率测试、光催化性能测试、薄膜亲水性能测试。薄膜颗粒尺寸为25nm,有细微的孔隙,0.1%、0.2%和0.3%的聚乙二醇2000的结果依次为:表面粗糙度分别为5.12、6.78、7.33nm,薄膜透射率分别为63%、67%、72%,光照90min甲基蓝降解率分别为20.7%、25.3%、32.5%,表面接触角分别为21.3%、17.2%、9.6%。
实施例2
步骤一:将市售四氯化钛溶液逐滴滴入去离子水中配置成浓度为0.5mol/L溶液A。
步骤二:将NaOH颗粒分散于去离子水中,超声搅拌,配置浓度为5mol/L的NaOH溶液B。
步骤三:以400r/min转速搅拌溶液A,并将溶液B逐滴加入溶液A中,发生共沉淀反应,当体系pH达到7时,停止滴加溶液B,此过程中不断出现白色沉淀;后续接着搅拌15min待反应彻底,将白色沉淀过滤并分别用热去离子水和无水乙醇反复洗涤,直到用AgNO3检测不到Cl-为止;再将所得白色沉淀分散于一定量的去离子水中,并进行搅拌10min,得到浓度0.5mol/L的悬浮液。
步骤四:将市售30%H2O2溶液(H2O2:Ti4+摩尔比为4:1)用移液管缓慢滴加进悬浮液中,将体系分为三份,再分别加入占体系不同质量分数(0.1%,0.2%,0.3%)的聚乙二醇4000,并不断搅拌35min,至溶液深黄色透明,然后用氨水调节体系的pH值至7,静置12h,得到浅黄色透明的钛基水溶胶。
步骤五:本实施例以玻璃载玻片7105为基板,将准备好的基板先用浓盐酸-重铬酸钾混合液浸泡20min去除表面无机污染物;待用去离子水冲洗载玻片后,用无水乙醇超声振荡清洗10min;再用去离子水超声振荡重复清洗三次;放入电热恒温鼓风干燥箱80℃中烘干备用。
步骤六:使用钛基水溶胶以2mm/s速度对玻璃载玻片进行镀膜,每镀一次膜均需烘干5min再进行下一次镀膜,本实施例镀3次。
步骤七:将镀好的基片置于马弗炉内400℃高温煅烧4.5h。
步骤八:将镀膜好后的玻璃载玻片进行薄膜的结构与形貌、光学性能透光率测试、光催化性能测试、薄膜亲水性能测试。薄膜颗粒尺寸为23nm,有细微的孔隙,0.1%、0.2%和0.3%的聚乙二醇4000的结果依次为:表面粗糙度分别为5.74、6.99、8.01nm,薄膜透射率分别为64%、66%、73%,光照90min甲基蓝降解率分别为21.6%、26.5%、33.7%,表面接触角分别为22.5%、18.2%、9.1%。
实施例3
步骤一:将市售四氯化钛溶液逐滴滴入去离子水中配置成浓度为0.6mol/L溶液A。
步骤二:将NaOH颗粒分散于去离子水中,超声搅拌,配置浓度为5mol/L的NaOH溶液B。
步骤三:以400r/min转速搅拌溶液A,并将溶液B逐滴加入溶液A中,发生共沉淀反应,当体系pH达到6.5时,停止滴加溶液B,此过程中不断出现白色沉淀;后续接着搅拌15min待反应彻底,将白色沉淀过滤并分别用热去离子水和无水乙醇反复洗涤,直到用AgNO3检测不到Cl-为止;再将所得白色沉淀分散于去离子水中,并进行搅拌10min,得到浓度0.35mol/L的悬浮液。
步骤四:将市售30%H2O2溶液(H2O2:Ti4+摩尔比为4:1)用移液管缓慢滴加进悬浮液中,将体系分为三份,再分别加入占体系不同质量分数(0.1%,0.2%,0.3%)的聚乙二醇6000,并不断搅拌30min,至溶液深黄色透明,然后用氨水调节体系的pH值至7,静置12h,得到浅黄色透明的钛基水溶胶。
步骤五:本实施例以玻璃载玻片7110基板,将准备好的基板先用浓盐酸-重铬酸钾混合液浸泡20min去除表面无机污染物;待用去离子水冲洗载玻片后,用无水乙醇超声振荡清洗10min;再用去离子水超声振荡重复清洗三次;放入电热恒温鼓风干燥箱80℃中烘干备用。
步骤六:使用钛基水溶胶浸渍玻璃载玻片2min,提拉机以2cm/min速度提拉对玻璃载玻片进行镀膜,每镀一次膜均需烘干5min再进行下一次镀膜,本实施例镀3次。
步骤七:将镀好的基片置于马弗炉内500℃高温煅烧3h。
步骤八:将镀膜好后的玻璃载玻片进行薄膜的结构与形貌、光学性能透光率测试、光催化性能测试、薄膜亲水性能测试。薄膜颗粒尺寸为20nm,有细微的孔隙,0.1%、0.2%和0.3%的聚乙二醇6000的结果依次为:表面粗糙度分别为5.69、7.26、9.66nm,薄膜透射率分别为67%、75%、88%,光照90min甲基蓝降解率分别为21.6%、26.1%、33.4%,表面接触角分别为20.6.%、16.7%、6.5%。
Claims (10)
1.以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,其特征在于:包括以下步骤:
钛基水溶胶制备:
A、将四氯化钛溶液滴入水中,得溶液A;
B、将苛性碱与水混合,得溶液B;
C、搅拌下,向溶液A中滴加溶液B,当体系pH为6~7时,停止加入溶液B,经共沉淀反应,得沉淀,所得沉淀经洗涤后,分散于水,得悬浮液;
D、向悬浮液滴加双氧水,然后加入聚乙二醇,并搅拌至溶液呈透明状,再采用氨水调节体系pH至6~7,静置后,得钛基水溶胶;
E、基片处理:
先用浓盐酸-重铬酸钾混合液浸泡载体去除表面无机污染物,用水冲洗后,用无水乙醇超声振荡清洗,再用水超声振荡重复清洗三次,烘干,备用;
镀膜:
F、对经步骤E处理后的载体进行镀膜,镀膜3~5层,每镀一层膜先烘干再进行下一层镀膜;
热处理:
G、350~900℃煅烧镀膜后的载体,热处理后,钛基纳米防腐薄膜在载体表面生成。
2.根据权利要求1所述的以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,其特征在于:步骤A中,所得溶液A的钛浓度为0.5~0.8mol/L。
3.根据权利要求1所述的以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,其特征在于:步骤B中,所得溶液B的苛性碱浓度为4~6mol/L。
4.根据权利要求1所述的以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,其特征在于:步骤C中,至少满足下列的一项:
在200~500r/min转速向溶液A中滴加溶液B;
滴加完毕后,继续搅拌10~40min;
所述洗涤为:将沉淀依次用热水和无水乙醇交替清洗,直到AgNO3检测不出Cl-为止。
5.根据权利要求1所述的以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,其特征在于:步骤C中,至少满足下列的一项:
将沉淀分散于水中后,搅拌10min~30min;
所得悬浮液的钛浓度为0.2~0.4mol/L。
6.根据权利要求1所述的以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,其特征在于:步骤D中,至少满足下列的一项:
所述双氧水的浓度为不低于28%;
所述双氧水的加入量以体系内H2O2与Ti4+的摩尔比不小于4:1为准;
所述聚乙二醇的分子量为1000~6000;
所述聚乙二醇的加入量为占体系质量的1~3%。
7.根据权利要求1所述的以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,其特征在于:步骤D中,至少满足下列的一项:
所述搅拌的时间为30~60min;
所述静置的时间为10~18h。
8.根据权利要求1所述的以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,其特征在于:步骤E中,至少满足下列的一项:
所述浸泡的时间为15min~30min;
无水乙醇超声振荡清洗的时间为5min~15min;
所述烘干的温度为80~110℃。
9.根据权利要求1所述的以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,其特征在于:步骤F中,至少满足下列的一项:
采用浸渍提拉法或涂布法进行镀膜;浸渍提拉法中,控制浸渍时间为2min~5min,提拉机以1cm/min~3cm/min提拉;涂布法中,以1mm/s~3mm/s进行涂布;
所述烘干的温度为90~110℃,时间为5min~15min。
10.根据权利要求1~9任一项所述的以四氯化钛为钛源的制备钛基纳米自清洁薄膜的方法,其特征在于:步骤G中,所述煅烧的时间为2h~4.5h。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20040054263A (ko) * | 2002-12-18 | 2004-06-25 | 이성호 | 차량 시계 향상용 친수 유리 개발 방법 |
CN101559979A (zh) * | 2009-05-22 | 2009-10-21 | 东华大学 | 一种超细锐钛矿相二氧化钛纳米棒的制备方法 |
CN101913777A (zh) * | 2010-07-20 | 2010-12-15 | 河北师范大学 | 制备纳米TiO2薄膜的方法 |
CN102875034A (zh) * | 2012-09-14 | 2013-01-16 | 泉耀新材料科技(苏州)有限公司 | 多孔性结构低折射率二氧化钛薄膜制备方法 |
CN104195534A (zh) * | 2014-09-16 | 2014-12-10 | 中国建材国际工程集团有限公司 | 二氧化钛自洁薄膜的制备方法 |
-
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20040054263A (ko) * | 2002-12-18 | 2004-06-25 | 이성호 | 차량 시계 향상용 친수 유리 개발 방법 |
CN101559979A (zh) * | 2009-05-22 | 2009-10-21 | 东华大学 | 一种超细锐钛矿相二氧化钛纳米棒的制备方法 |
CN101913777A (zh) * | 2010-07-20 | 2010-12-15 | 河北师范大学 | 制备纳米TiO2薄膜的方法 |
CN102875034A (zh) * | 2012-09-14 | 2013-01-16 | 泉耀新材料科技(苏州)有限公司 | 多孔性结构低折射率二氧化钛薄膜制备方法 |
CN104195534A (zh) * | 2014-09-16 | 2014-12-10 | 中国建材国际工程集团有限公司 | 二氧化钛自洁薄膜的制备方法 |
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