CN106521494B - Ni、S共掺杂TiO2薄膜及其应用和制备方法 - Google Patents
Ni、S共掺杂TiO2薄膜及其应用和制备方法 Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 30
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910000975 Carbon steel Inorganic materials 0.000 claims abstract description 29
- 239000010962 carbon steel Substances 0.000 claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000004070 electrodeposition Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 27
- 238000005516 engineering process Methods 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 14
- 239000011159 matrix material Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 13
- 238000007747 plating Methods 0.000 claims description 11
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 5
- 229940078494 nickel acetate Drugs 0.000 claims description 5
- -1 Polyethylene Polymers 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 238000002203 pretreatment Methods 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 238000005282 brightening Methods 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 229940043237 diethanolamine Drugs 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 3
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims description 3
- 229940081974 saccharin Drugs 0.000 claims description 3
- 235000019204 saccharin Nutrition 0.000 claims description 3
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 239000003643 water by type Substances 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims 1
- 230000004913 activation Effects 0.000 claims 1
- 230000032683 aging Effects 0.000 claims 1
- 210000001367 artery Anatomy 0.000 claims 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical class [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 claims 1
- 239000004576 sand Substances 0.000 claims 1
- 210000003462 vein Anatomy 0.000 claims 1
- 238000004210 cathodic protection Methods 0.000 abstract description 18
- 238000005260 corrosion Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 5
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 4
- 230000004044 response Effects 0.000 abstract description 3
- 150000001455 metallic ions Chemical class 0.000 abstract description 2
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- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 40
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 14
- 230000007797 corrosion Effects 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000010409 thin film Substances 0.000 description 5
- 238000005286 illumination Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000080590 Niso Species 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000006424 Flood reaction Methods 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 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
- 238000007743 anodising Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000000280 vitalizing effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
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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
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- C23C18/04—Pretreatment of the material to be coated
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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
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- 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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- 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
- C23C18/1241—Metallic substrates
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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
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- C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
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- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
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Abstract
本发明公开了一种Ni、S共掺杂TiO2薄膜及其应用和制备方法。Ni、S共掺TiO2薄膜的制备过程是：首先在碳钢基底上进行脉冲复合电沉积，制备Ni‑P‑SnO2纳米复合中间镀层，再利用溶胶凝胶法在镀层上制备Ni、S共掺杂TiO2薄膜。Ni‑P镀层本身具有优异的抗腐蚀效果，加之表面纳米微粒SnO2的引入使得镀层微观表面粗糙，在提高结合力的同时，还可发挥SnO2粒子的储电子能力，使外层TiO2涂层在暗态下继续维持光致阴极保护效果。同时采用过渡金属离子和非金属离子共掺杂的协同效应，实现提高TiO2薄膜光电活性和光谱响应范围。
Description
技术领域
本发明涉及光致阴极保护领域，具体涉及是一种光致阴极保护半导体材料—Ni、S共掺杂TiO2薄膜的制备方法。
背景技术
金属材料的腐蚀给全世界带来巨大的经济损失，每年因腐蚀造成的损失约是地震、水灾、台风等自然灾害损失总和的6倍。因此金属腐蚀与防护技术一直是国内外学者研究的热点。环境友好、高性能和长效防腐技术也是当今科学家的主要目标。
金属的腐蚀与防护主要技术有表面处理与涂层技术、缓蚀剂技术、阴极保护技术。其中阴极保护技术就是将被保护的金属作为腐蚀电池的阴极或作为电解池的阴极而不受腐蚀，前一种是牺牲阳极保护法，后一种是外加电流法。牺牲阳极保护技术常用于保护海轮外壳、锅炉和海底设备。光致阴极保护是一种新型的阴极保护技术，20世纪90年代由日本Tsujikawa研究小组首次提出，随后，日本学者Fujishima等人对光致阴极保护作用机制进行了研究，至此，光致阴极保护技术成为金属腐蚀与防护领域的研究热点。
光致阴极保护技术是将半导体涂覆在被保护金属表面或作为阳极通过导线与被保护金属相连，半导体薄膜(如TiO2薄膜)在光照下，半导体薄膜价带(VB) 中的电子吸收光子能量被激发跃迁到导带(CB)，产生一对光生电子(e-)和光生空穴(h+)，在半导体薄膜与溶液界面处的空间电荷电场的作用下，空穴(h+) 被迁移到半导体粒子表面与溶液中的电子供体(如H2O、OH-等)发生氧化反应，而电子(e-)向被保护金属迁移，导致被保护金属表面电子密度增加，光生电位负移，自腐蚀电流密度下降，使金属进入热力学热稳定区域，达到阴极保护的目的。与牺牲阳极保护技术相比，半导体薄膜在保护过程中，并不牺牲，可以成为永久性保护涂层，具有节省资源的优势。
半导体是指电导率介于导体和绝缘体之间的物质。半导体材料具有带隙，所以具有独特的光学、电学性能。在众多半导体材料中，TiO2是一种稳定、无毒、价廉的半导体材料，属于N型半导体材料，在很多高科技领域有重要应用，如光催化、染料敏化太阳能电池、超亲水性研究、传感器、有机污染物降解、废水处理及光致阴极保护技术。在光致阴极保护过程中，将TiO2涂覆在被保护金属表面具有更明显的优势，这种阴极保护涂层，一方面，在光照下，可产生阴极保护作用，另一方面，涂层的存在可以大大减小保护电流的需求量，同时也避免外加电流阴极保护法需要外加电源的缺点。因此TiO2在光致阴极保护领域有着广泛的应用前景。
通过向TiO2涂层中掺杂金属或非金属元素可达到提高TiO2对可见光利用率的目的。掺杂的金属元素一般为过渡金属离子，通过其d电子与TiO2薄膜的导带或价带之间的电荷迁移或跃迁，即过渡金属离子成为光生电子和光生空穴的捕获势阱，减小电子与空穴的复合几率，提高了对可见光利用率；掺杂的非金属元素主要有N、C、S、卤素等，一般认为是TiO2薄膜中O原子的2P轨道和非金属中能级与其能量接近的p轨道杂化后，价带宽化上移，禁带宽度相应减小，从而可吸收可见光。由此可见，采用过渡金属离子和非金属离子共掺杂的协同效应，可实现提高TiO2薄膜光电活性和光谱响应范围。
本发明提供了一种Ni、S共掺杂TiO2薄膜的制备方法及其在碳钢等金属光致阴极保护领域中的应用。
发明内容
本发明的目的是提供一种Ni、S共掺杂TiO2薄膜的制备方法及其在碳钢等金属光致阴极保护领域中的应用。
尽管近年来国内外学者对二氧化钛光致阴极保护技术进行了不断的探索与研究，但目前光致阴极保护技术仍然存在以下几个问题，困扰着这一保护技术的进一步推广应用。首先，目前研究工作采用的基体多是导电玻璃，而在工业生产中大量用到的材料如碳钢基体上制备TiO2薄膜较少报道，同时，如何在碳钢等基底表面获得与基体结合较好TiO2涂覆层的技术与方法仍然没有很好解决；其次，在暗态下，光生电子(e-)和光生空穴(h+)的快速复合，使得TiO2薄膜难以维持阴极保护作用；第三，TiO2带隙较宽(约3.2eV)，只能吸收波长小于387nm的紫外光，对可见光的利用率较低(太阳能利用率约4％)。因此，研究在碳钢等通用基底上制备结合力好的、能利用可见光、暗态条件下保护效率高的TiO2薄膜是光致阴极保护技术走向实用化的关键，这对于在自然环境条件下实现碳钢等金属材料的防护具有重要的理论和实际意义。针对以上存在的技术问题，本专利首先先从基底与TiO2涂层结合力入手，在碳钢基底上进行了脉冲复合电沉积，制备Ni-P-SnO2纳米复合中间镀层，再利用溶胶凝胶法在镀层上制备TiO2薄膜及掺杂过渡金属或非金属的TiO2薄膜。Ni-P镀层本身具有优异的抗腐蚀效果，加之表面纳米微粒SnO2的引入使得镀层微观表面粗糙，在提高结合力的同时，还可发挥SnO2粒子的储电子能力，使外层TiO2涂层在暗态下继续维持光致阴极保护效果。与此同时，高温热处理过程镀层内Ni、P元素可作为掺杂元素扩散到TiO2涂层中，影响TiO2能带结构，提高其对可见光的利用率，为光致阴极保护顺利实施提供支撑。
一种Ni、S共掺杂TiO2薄膜的制备方法具体步骤如下：
1、Ni-P-SnO2复合镀层制备方法
a.Q235A碳钢片的前处理
选用规格50mm×10mm×2mm的Q235A碳钢片为基体，分别用 240-2000#水磨砂纸、金相砂纸逐级打磨碳钢片至表面光亮，在60℃下，在40g/L 碳酸钠，5g/L氢氧化钠溶液中，化学除油15分钟、5％盐酸酸洗活化3分钟，预处理后待镀。
b.电镀液的配制
按下列配方进行电镀液配置：称取120g/L的NiSO4·6H2O、40g/L的 NiCl2·6H2O、36g/L的H2BO3、20g/L的NaH2PO4·H2O、2g/L的糖精以及0.1g/L的十二烷基硫酸钠，经1升容量瓶定容后陈化10小时待用。
c.脉冲电沉积
施镀采用脉冲电沉积技术，用量筒量取250mL上述步骤b中陈化后的电镀液于烧杯中，加入0.5克SnO2和0.5克表面活性剂十二烷基硫酸钠，放入超声仪中超声震荡1小时使粒子均匀分散，磁力搅拌下将电镀液加热至镀液温度，将上述步骤a中预处理后的碳钢片、镍板接上脉冲电源进行施镀，最终在碳钢基体上获得Ni-P-SnO2复合镀层，其工艺条件为：镀液温度为60℃，脉冲时间为30分钟，平均电流密度为2A/dm2，溶液浓度为2g/L，占空比为30％，脉冲频率为150Hz。
2、Ni、S共掺杂TiO2薄膜的制备方法
a. Ni、S掺杂TiO2溶胶的制备方法
按照Ni、S与Ti摩尔比分别为0.001、0.005进行计算乙酸镍、硫脲加入量，分别用20mL的乙醇溶解0.0106克乙酸镍和0.0162克硫脲，待溶解完全后，转入100mL烧杯中，再加入40mL乙醇，以每2秒1滴的速度依次滴加1mL冰醋酸，3mL二乙醇胺，15mL钛酸丁酯，制成溶液A，将2mL无水乙醇和2mL 二次蒸馏水制成溶液B，将溶液A搅拌1小时后，将溶液B以每秒1滴速度加入至溶液A中，混合溶液A与溶液B，搅拌1小时后，加入0.5克聚乙二醇-2000，待聚乙二醇-2000充分溶解后，停止搅拌，最终制得浅黄色的透明溶胶。
b.浸渍提拉
镀膜采用浸渍提拉技术，将步骤(1)中c步获得镀有Ni-P-SnO2复合镀层的碳钢基体烘干，并固定在镀膜提拉机上，将步骤(2)中a步中配置好的TiO2掺杂溶胶置于基体下方，镀膜第一层TiO2掺杂溶胶，采用提拉速度为15mm/min，浸渍时间30秒，操作结束后，取下基体放于烘箱中烘10分钟，再拿出来进行第二次提拉，以获得第二层TiO2掺杂溶胶，采用的提拉速度是12mm/min，浸渍时间与第一次提拉相同，按第二次提拉方法进行操作，完成所需要的第三层 TiO2掺杂溶胶，将提拉三层Ni、S共掺杂TiO2薄膜的基体放于烘箱中30分钟；再将其放入马弗炉中，以10min/℃的速度升温到400℃，保温2小时，自然冷却到室温，即在镀有Ni-P-SnO2复合镀层的碳钢基体上面获得Ni、S共掺杂TiO2薄膜。
TiO2半导体薄膜的制备方法有多种，常见的有溶胶-凝胶法、阳极氧化法、水热法等，在近几年的研究中，将多种制备方法联用制备复合薄膜的方法也逐渐引起国内外学者的关注。溶胶-凝胶法是以钛的有机或无机溶液出发，加入适量的醇、醚类溶剂混合均匀，经一系列水解、缩聚反应，形成稳定TiO2溶胶。进一步凝胶化，并通过高温烧结过程将凝胶中的溶剂、水以及添加剂等物质分解，最终得到TiO2薄膜。溶胶-凝胶法制备的纳米TiO2涂层纯度高、均匀性强、反应条件不苛刻，并且制备工艺过程相对简单，是目前制膜方面应用最为广泛的方法之一，它不仅可在不同基体表面成膜，且较容易进行掺杂改性。
附图说明
图1为本发明实施例中Ni-P-SnO2/TiO2薄膜及掺杂薄膜的时间电位曲线。
具体实施方式
实施例：
1、Ni-P-SnO2复合镀层制备方法
a. Q235A碳钢片的前处理
选用规格50mm×10mm×2mm的Q235A碳钢片为基体，分别用 240-2000#水磨砂纸、金相砂纸逐级打磨碳钢片至表面光亮，在60℃下，在40g/L 碳酸钠，5g/L氢氧化钠溶液中，化学除油15分钟、5％盐酸酸洗活化3分钟，预处理后待镀。
b.电镀液的配制
按下列配方进行电镀液配置：称取120g/L的NiSO4·6H2O、40g/L的 NiCl2·6H2O、36g/L的H2BO3、20g/L的NaH2PO4·H2O、2g/L的糖精以及0.1g/L的十二烷基硫酸钠，经1升容量瓶定容后陈化10小时待用。
c.脉冲电沉积
施镀采用脉冲电沉积技术，用量筒量取250mL上述步骤b中陈化后的电镀液于烧杯中，加入0.5克SnO2和0.5克表面活性剂十二烷基硫酸钠，放入超声仪中超声震荡1小时使粒子均匀分散，磁力搅拌下将电镀液加热至镀液温度，将上述步骤a中预处理后的碳钢片、镍板接上脉冲电源进行施镀，最终在碳钢基体上获得Ni-P-SnO2复合镀层，其工艺条件为：镀液温度为60℃，脉冲时间为30分钟，平均电流密度为2A/dm2，溶液浓度为2g/L，占空比为30％，脉冲频率为150Hz。
2、Ni、S共掺杂TiO2薄膜的制备方法
a. Ni、S掺杂TiO2溶胶的制备方法
按照Ni、S与Ti摩尔比分别为0.001、0.005进行计算乙酸镍、硫脲加入量，分别用20mL的乙醇溶解0.0106克乙酸镍和0.0162克硫脲，待溶解完全后，转入100mL烧杯中，再加入40mL乙醇，以每2秒1滴的速度依次滴加1mL冰醋酸，3mL二乙醇胺，15mL钛酸丁酯，制成溶液A，将2mL无水乙醇和2mL 二次蒸馏水制成溶液B，将溶液A搅拌1小时后，将溶液B以每秒1滴速度加入至溶液A中，混合溶液A与溶液B，搅拌1小时后，加入0.5克聚乙二醇-2000，待聚乙二醇-2000充分溶解后，停止搅拌，最终制得浅黄色的透明溶胶。
b.浸渍提拉
镀膜采用浸渍提拉技术，将步骤(1)中c步获得镀有Ni-P-SnO2复合镀层的碳钢基体烘干，并固定在镀膜提拉机上，将步骤(2)中a步中配置好的TiO2掺杂溶胶置于基体下方，镀膜第一层TiO2掺杂溶胶，采用提拉速度为15mm/min，浸渍时间30秒，操作结束后，取下基体放于烘箱中烘10分钟，再拿出来进行第二次提拉，以获得第二层TiO2掺杂溶胶，采用的提拉速度是12mm/min，浸渍时间与第一次提拉相同，按第二次提拉方法进行操作，完成所需要的第三层 TiO2掺杂溶胶，将提拉三层Ni、S共掺杂TiO2薄膜的基体放于烘箱中30分钟；再将其放入马弗炉中，以10min/℃的速度升温到400℃，保温2小时，自然冷却到室温，即在镀有Ni-P-SnO2复合镀层的碳钢基体上面获得Ni、S共掺杂TiO2薄膜。
对本实施例中获得的Ni、S共掺杂TiO2薄膜进行了时间电位曲线测试，结果如图1所示。
从图1中可以看出光照下，与纯薄膜相比，掺杂薄膜的光生电位下降到 -6.89V左右，起到光生阴极保护作用；关闭光源后，碳钢电位无法回到初始电位，这与文献的结果一致，表明TiO2薄膜及其掺杂薄膜在可见光照射下产生的电子与空穴分离良好。整个光生电位之所以呈现阶梯式下降，一方面是因为SnO2的储存电子能力使得电位一直下降，没有恢复到初始电位；另一方面是因为由于入射电子激发半导体价带电子跃迁，产生光生电子-空穴对，Ni、S掺杂能够抑制TiO2晶型的长大。掺杂薄膜的碳钢基体比表面积大，反应面积就大，光生载流子容易迁移到粒子表面，电子与空穴复合几率小，因此，掺杂薄膜光生电位相对TiO2薄膜来说负移程度增加。以上结果表明，本发明制备的 Ni-P-SnO2/TiO2掺杂薄膜在可见光下比纯Ni-P-SnO2/TiO2薄膜对碳钢等金属具有更好的光生阴极保护效果。
Claims (1)
1.Ni、S共掺杂TiO2薄膜的制备方法，其特征在于具体步骤为：
(1)Ni-P-SnO2复合镀层制备方法
a.Q235A碳钢片的前处理
选用规格50mm×10mm×2mm的Q235A碳钢片为基体，分别用240-2000#水磨砂纸、金相砂纸逐级打磨碳钢片至表面光亮，在60℃下，在40g/L碳酸钠，5g/L氢氧化钠溶液中，化学除油15min、5％盐酸酸洗活化3min预处理后，待镀；
b.电镀液的配制
按下列配方进行镀液配置：NiSO4·6H2O 120g/L、NiCl2·6H2O 40g/L、H2BO3 36g/L、NaH2PO4·H2O 20g/L、糖精2g/L，十二烷基硫酸钠0.1g/L，经1升容量瓶定容后陈化8-10h待用；
c.脉冲电沉积
施镀采用脉冲电沉积技术，用量筒量取250mL上述步骤b中陈化后的镀液于烧杯中，加入一定量的纳米SnO2和表面活性剂十二烷基硫酸钠，放入超声仪中超声震荡1h使粒子均匀分散，磁力搅拌下将镀液加热至规定温度，将上述步骤a中预处理后的碳钢片、镍板接上脉冲电源进行施镀，最终在碳钢基体上获得Ni-P-SnO2复合镀层，其工艺条件为：镀液温度(T)为40～80℃，脉冲时间(t)为10～50min，平均电流密度(j)为1～3A/dm2，溶液浓度(c)为1～3g/L，占空比(γ)为10％～50％，脉冲频率(f)为50～250Hz；
(2)Ni、S共掺杂TiO2薄膜的制备方法
a.Ni、S掺杂TiO2溶胶的制备方法
按照Ni、S与Ti摩尔比分别为0.001、0.005进行计算乙酸镍、硫脲加入量，分别用20mL的乙醇溶解0.0106g乙酸镍和0.0162g硫脲，待溶解完全后，加入100mL烧杯中，再加入40mL乙醇，以每2s 1滴的速度依次滴加1mL冰醋酸，3mL二乙醇胺，15mL钛酸丁酯制成溶液A，将2mL无水乙醇和2mL二次蒸馏水制成溶液B，将溶液A搅拌1小时后，以每秒1滴缓慢加入溶液B至溶液A中，混合溶液A与溶液B，搅拌1小时后，加入0.5g/100mL聚乙二醇-2000，待聚乙二醇-2000充分溶解后，停止搅拌，最终可制得浅黄色的透明溶胶；
b.浸渍提拉
镀膜采用浸渍提拉技术，将步骤(1)中c步获得镀有Ni-P-SnO2复合镀层的碳钢基体烘干，并固定在镀膜提拉机上，将步骤(2)中a步中配置好的TiO2掺杂溶胶置于基体下方，镀膜第一层采用提拉速度为15mm/min，浸渍时间30s，操作结束后，取下基体放于烘箱中烘10分钟左右，再拿出来继续操作，第二层、采用的提拉速度是12mm/min，浸渍时间与第一层相同，继续进行操作，直到完成所需要的三层镀膜，将提拉三层Ni、S共掺杂TiO2薄膜的基体放于烘箱中30min；再将其放入马弗炉中，以10min/℃的速度分别升温到400℃，保温2h，自然冷却到室温，即可在镀有Ni-P-SnO2复合镀层的碳钢基体上面获得Ni、S共掺杂TiO2薄膜。
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