CN114250454A - 一种金属氧化物电极用钛基体防护涂层及其制备方法 - Google Patents
一种金属氧化物电极用钛基体防护涂层及其制备方法 Download PDFInfo
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- CN114250454A CN114250454A CN202111388698.5A CN202111388698A CN114250454A CN 114250454 A CN114250454 A CN 114250454A CN 202111388698 A CN202111388698 A CN 202111388698A CN 114250454 A CN114250454 A CN 114250454A
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- 239000010936 titanium Substances 0.000 title claims abstract description 123
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 120
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 60
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 58
- 239000011159 matrix material Substances 0.000 title claims abstract description 45
- 239000011253 protective coating Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title description 7
- 238000000576 coating method Methods 0.000 claims abstract description 106
- 239000011248 coating agent Substances 0.000 claims abstract description 105
- RQVJYRSUFJTNEP-UHFFFAOYSA-N [Ti].[Ru]=O Chemical compound [Ti].[Ru]=O RQVJYRSUFJTNEP-UHFFFAOYSA-N 0.000 claims abstract description 36
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims abstract description 6
- 229910009848 Ti4O7 Inorganic materials 0.000 claims abstract description 4
- 229910009870 Ti5O9 Inorganic materials 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 19
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 239000004408 titanium dioxide Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 11
- DPGAAOUOSQHIJH-UHFFFAOYSA-N ruthenium titanium Chemical compound [Ti].[Ru] DPGAAOUOSQHIJH-UHFFFAOYSA-N 0.000 claims description 11
- 230000001680 brushing effect Effects 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000012300 argon atmosphere Substances 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000003618 dip coating Methods 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000002608 ionic liquid Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- OIWSIWZBQPTDKI-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole;hydrobromide Chemical compound [Br-].CCCC[NH+]1CN(C)C=C1 OIWSIWZBQPTDKI-UHFFFAOYSA-N 0.000 claims description 3
- FXARDXGINRROHY-UHFFFAOYSA-N ClC([O-])(CCC)Cl.[Ti+4].ClC([O-])(CCC)Cl.ClC([O-])(CCC)Cl.ClC([O-])(CCC)Cl Chemical compound ClC([O-])(CCC)Cl.[Ti+4].ClC([O-])(CCC)Cl.ClC([O-])(CCC)Cl.ClC([O-])(CCC)Cl FXARDXGINRROHY-UHFFFAOYSA-N 0.000 claims description 3
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 3
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 claims description 2
- XUHHZNLAPUWRHH-UHFFFAOYSA-N 3-butyl-1-methyl-1,2-dihydroimidazol-1-ium;methanesulfonate Chemical compound CS(O)(=O)=O.CCCCN1CN(C)C=C1 XUHHZNLAPUWRHH-UHFFFAOYSA-N 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- -1 titanium ions Chemical class 0.000 claims 3
- 238000007598 dipping method Methods 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 8
- 239000012535 impurity Substances 0.000 abstract description 4
- 230000002028 premature Effects 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- MPCQNSCUKOECNW-UHFFFAOYSA-N butan-1-ol;ethanol Chemical compound CCO.CCCCO MPCQNSCUKOECNW-UHFFFAOYSA-N 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- WGKMWBIFNQLOKM-UHFFFAOYSA-N [O].[Cl] Chemical compound [O].[Cl] WGKMWBIFNQLOKM-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012932 thermodynamic analysis Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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Abstract
本发明公开了一种金属氧化物电极用钛基体防护涂层，该防护涂层位于钛基体与金属氧化物活性涂层的中间，由内到外，依次由钛钌氧化物涂层和亚氧化钛膜层组成；按总质量百分比为100％计，所述的钛钌氧化物涂层组分含量为氧化钛：47％～71％；氧化钌为29％～53％；所述的亚氧化钛膜层成分为Ti4O7或Ti5O9或两者的混合物。本发明防护涂层对F‑、SCN‑等有害杂质起阻挡层的作用，解决了现有金属氧化物电极因耐F‑、SCN‑腐蚀性能不足造成金属氧化物电极的过早失效的问题。
Description
技术领域：
本发明涉及一种金属氧化物电极用钛基体防护涂层及其制备方法。
背景技术：
金属氧化物电极是一种在钛基表面涂覆或者电沉积金属氧化物活性成分而制成的复合电极。金属氧化物电极一般分为贵金属氧化物电极和贱金属氧化物电极。贵金属氧化物电极，如氧化铱电极、氧化钌电极，具有析氧(氯)电催化活性高、化学稳定性等优点，在金属电镀、金属电解、铝箔化成和氯碱工业等领域具有较大应用价值；贱金属氧化物电极，如氧化锡电极、氧化铅电极，则对有机污染物具有较好的催化降解性能，在有机废水处理领域有良好的应用前景。因矿石的带入或添加剂的引入，所以电解液常存在F-、SCN-等有害杂质。在电解过程中，F-等杂质通过电极金属氧化物涂层的裂纹或孔隙渗入到钛基体表面，与钛材发生配合反应，生成水溶性的化合物，削弱了氧化物涂层与钛基的结合力，从而加速了氧化物涂层的脱落，造成金属氧化物电极的过早失效。因此，金属氧化物电极用低成本防护涂层制备研究具有十分重要的意义。
发明内容：
本发明的目的是提供一种金属氧化物电极用钛基体防护涂层及其制备方法，该防护涂层位于钛基体与金属氧化物活性涂层的中间，对F-、SCN-等有害杂质起阻挡层的作用，解决了现有金属氧化物电极因耐F-、SCN-腐蚀性能不足造成金属氧化物电极的过早失效的问题。
本发明是通过以下技术方案予以实现的：
一种金属氧化物电极用钛基体防护涂层，该防护涂层位于钛基体与金属氧化物活性涂层的中间，由内到外，依次由钛钌氧化物涂层和亚氧化钛膜层组成；按总质量百分比为100％计，所述的钛钌氧化物涂层组分含量为氧化钛：47％～71％；氧化钌为29％～53％；所述的亚氧化钛膜层成分为Ti4O7或Ti5O9或两者的混合物。
所述的金属氧化物为氧化钌、氧化铱、氧化锡中的一种。
所述的钛钌氧化物涂层是过渡层，起连接钛基体和亚氧化钛膜层的作用。因为钛钌氧化物涂层与钛基体的结合较亚氧化钛膜层牢固，所以可起到锚定亚氧化钛膜层的作用。
所述的亚氧化钛膜层是耐蚀膜层，为电解液中F-、SCN-等有害杂质的主要阻挡层，也是钛基体的主要防护层。因为亚氧化钛对F有较强的抵御能力，所以可起到有效保护钛基体的作用。
所述的钛钌氧化物涂层厚度为2～4μm。
所述的亚氧化钛膜层厚度为0.5～3μm。
本发明所述的金属氧化物电极用钛基体防护涂层制备方法，包括以下步骤：
①用质量分数为5％～10％的草酸溶液在85～95℃下蚀刻钛材2～3h，水洗后在110～130℃下烘干5～20min得到清洁的钛基体；
②将钛钌涂液均匀涂覆在清洁的钛基体上，在100～120℃下固化10～15min，然后420～460℃下热氧化分解10～15min，空冷；所述的钛钌涂液为钛钌前驱体的有机溶液，其含钛离子量为0.18～0.24mol/L(摩尔浓度)，钌离子浓度为0.06～0.12mol/L(摩尔浓度)，盐酸质量分数为0.1～0.5％，所用溶剂为正丁醇；
③重复步骤②1～5次，制得钛钌氧化物涂层；
④将钛涂液均匀涂覆在制得的钛钌氧化物涂层上，在100～120℃下固化10～15min，然后420～460℃下热氧化分解10～15min，空冷；重复1～7次，制得二氧化钛涂层；所述的钛涂液为钛前驱体的有机溶液，其含钛离子量为0.1～0.3mol/L，盐酸质量分数为0.1～0.5％，离子液体质量分数为0.05％～0.2％；所用溶剂为乙醇和正丁醇；
⑤在420～480℃下，空气气氛中，热处理0.5h，制得钛钌氧化物/二氧化钛复合涂层；
⑥在输出功率300～600W下，50％H2+50％Ar等离子体气氛中，还原5～30min，将二氧化钛涂层原位转化为亚氧化钛膜层；
⑦在450～500℃下，氩气气氛中，热处理0.5～1h，最终制得金属氧化物电极用钛基体防护涂层。
所述的钛前驱体是钛金属源物质，为钛酸丁酯、三氯化钛、二氯二丁醇钛中的一种。
所述的钌前驱体是钌金属源物质，为β型三氯化钌。
所述的盐酸为钛水解抑制剂，用以保持涂液均匀、澄清。
所述的离子液体为1-丁基-3-甲基咪唑氯盐、1-丁基-3-甲基咪唑溴盐、1-丁基-3-甲基咪唑甲基磺酸盐中的一种，其作用是改善涂层的湿润性能。
涂覆时，涂液浓度大，涂覆次数少；浓度小，涂覆次数多，操作中灵活使用。涂覆可以采用刷涂、浸涂方式。选用刷涂时，用力适度，横向和纵向刷涂交替进行，以保证涂层的均匀性。采用浸涂时，提拉速度为1～30μm/s。考虑到操作简单和制备效率，涂覆优选浸涂方式。
所述的固化是在热力的作用下去除有机溶剂，将前驱物附着在钛基体或涂层上。当温度高于120℃时，溶剂挥发过快，会影响涂层的结合力，一般选择100～120℃进行干燥固化。
热氧化分解是将金属前驱体转变为金属氧化物。当温度低于420℃时，金属前驱体氧化分解不彻底。当高于460℃时，钛材会发生明显氧化，因此理想的热分解温度为420～460℃。热处理是消除涂层中的内应力，提高涂层的稳定性。温度高于520℃时，钛材会发生严重氧化，因此理想的热处理温度为420～480℃。
氢等离子体还原是将二氧化钛涂层的表层转变为亚氧化钛膜层。所用还原剂为活性氢粒子，如原子态(H)、离子态(H+、H2 +、H3 +)和激发态(H*、H2*)等物种。为方便实施，优选射流型氢等离子体还原。还原时间一般取决于亚氧化钛膜的物相，要制得Ti4O7则还原时间长些。
所述的热处理是在氩气气氛中进行，其目的是防止亚氧化钛膜层发生氧化，提高复合涂层间的结合力，改善防护涂层的性能。
本发明的有益效果如下：本发明防护涂层位于钛基体与金属氧化物活性涂层的中间，对F-、SCN-等有害杂质起阻挡层的作用，解决了现有金属氧化物电极因耐F-、SCN-腐蚀性能不足造成金属氧化物电极的过早失效的问题。
附图说明：
图1是金属氧化物电极用钛基体防护涂层的结构示意图。
具体实施方式：
以下是对本发明的进一步说明，而不是对本发明的限制。
实施例1：
选用纯钛片TA2为基体，用10％(质量分数)的草酸90℃下蚀刻3h，水洗后120℃下干燥，得到清洁的钛基体。
按钛摩尔浓度0.21mol/L、钌摩尔浓度0.09mol/L、盐酸质量浓度0.1％，将钛酸丁酯、β-三氯化钌、盐酸溶于正丁醇溶剂中，得到钛钌有机涂液。
用软毛刷均匀涂刷在清洁的钛基体上，接着在110℃下干燥固化10min，然后在430℃下热氧化12min，空冷，反复进行4次，制得钛钌氧化物涂层。
按钛摩尔浓度0.2mol/L、盐酸浓度0.1wt％、离子液体浓度0.1wt％，将钛酸丁酯、盐酸和1-丁基-3-甲基咪唑氯盐溶于体积比为2：1的乙醇-正丁醇混合溶剂中，得到钛有机涂液。
用软毛刷均匀涂刷在制得的钛钌氧化物涂层上，接着在120℃下干燥固化10min，然后在440℃下热氧化10min，空冷，反复进行4次，制得二氧化钛涂层。
在460℃下，空气气氛中，热处理0.5h，制得钛钌氧化物/二氧化钛复合涂层。
将复合氧化物涂层置于氢等离子体射流中，反应气氛为50％H2+50％Ar，输出功率控制300W，还原时间为15min。在450℃下，氩气气氛中，对上述氧化物涂层进行热处理0.5h，最终制得金属氧化物电极用钛基体防护涂层。
借助X射线衍射仪分析，可知该防护涂层为Ti/TiO2-RuO2/Ti4O7。
从热力学角度分析，材料的开路电位越正，材料的耐腐蚀性越强。为了便于对照，制备了清洁的纯钛试片，并在常温下分别测试了本发明金属氧化物电极用钛基体防护涂层、纯钛试片等样品在含氟20mg/L的0.5mol/L硫酸溶液中的开路电位。测试结果为：本发明钛表面金属氧化物电极用钛基体防护涂层开路电位为0.72V(Vs SCE)，纯钛试片开路电位为-0.21V(Vs SCE)。由此可见，本发明金属氧化物电极用钛基体防护涂层显著提高了钛基体的耐氟腐蚀性能。
实施例2
选用纯钛片TA2为基体，用8％(质量分数)的草酸95℃下蚀刻3h，水洗后125℃下干燥，得到清洁的钛基体。
按钛摩尔浓度0.18mol/L、钌摩尔浓度0.12mol/L、盐酸质量浓度0.1％，将钛酸丁酯、β-三氯化钌溶于正丁醇溶剂中，得到钛钌有机涂液。
用软毛刷均匀涂刷在清洁的钛基体上，接着在120℃下干燥固化15min，然后在440℃下热氧化10min，空冷，反复进行3次，制得钛钌氧化物涂层。
按钛摩尔浓度0.1mol/L、盐酸浓度0.1wt％、离子液体浓度0.1wt％，将三氯化钛、盐酸和1-丁基-3-甲基咪唑溴盐溶于体积比为1：1的乙醇-正丁醇混合溶剂中，得到钛有机涂液。
用软毛刷均匀涂刷在制得的钛钌氧化物涂层上，接着在120℃下干燥固化8min，然后在450℃下热氧化10min，空冷，反复进行5次，制得二氧化钛涂层。
在470℃下，空气气氛中，热处理0.5h，制得钛钌氧化物/二氧化钛复合涂层。
将复合氧化物涂层置于氢等离子体射流中，反应气氛为50％H2+50％Ar，输出功率控制350W，还原时间为10min。在480℃下，氩气气氛中，对上述氧化物涂层进行热处理0.5h，最终制得金属氧化物电极用钛基体防护涂层。
为了便于对照，制备了清洁的纯钛片，并在常温下分别测试了本发明金属氧化物电极用钛基体防护涂层、纯钛试片等样品在含氟20mg/L的0.5mol/L硫酸溶液中的开路电位。测试结果为：本发明金属氧化物电极用钛基体防护涂层开路电位为0.75V(Vs SCE)，纯钛试片开路电位为-0.2V(Vs SCE)。由此可见，本发明金属氧化物电极用钛基体防护涂层显著改善了钛基体的耐氟腐蚀性能。
实施例3
选用纯钛片TA2为基体，用10％(质量分数)的草酸90℃下蚀刻3h，水洗后120℃下干燥，得到清洁的钛基体。
按钛摩尔浓度0.24mol/L、钌摩尔浓度0.06mol/L、盐酸质量浓度0.4％，将钛酸丁酯、β-三氯化钌溶于正丁醇溶剂中，得到钛钌有机涂液。
用软毛刷均匀涂刷在清洁的钛基体上，接着在110℃下干燥固化10min，然后在430℃下热氧化10min，空冷，反复进行4次，制得钛钌氧化物涂层。
按钛摩尔浓度0.3mol/L、盐酸浓度0.2wt％、离子液体浓度0.15wt％，将钛酸丁酯、盐酸和1-丁基-3-甲基咪唑氯盐溶于体积比为2：1的乙醇-正丁醇混合溶剂中，得到钛有机涂液。
浸涂时，以10μm/s的提拉速度涂覆，接着在110℃下干燥固化15min，然后在430℃下热氧化10min，空冷，反复进行6次，制得二氧化钛涂层。
在480℃下，空气气氛中，热处理0.5h，制得钛钌氧化物/二氧化钛复合涂层。
将复合氧化物涂层置于氢等离子体射流中，反应气氛为50％H2+50％Ar，输出功率控制300W，还原时间为15min。在470℃下，氩气气氛中，对上述氧化物涂层进行热处理0.5h，最终制得金属氧化物电极用钛基体防护涂层。
为了便于对照，制备了清洁的纯钛片，并在常温下分别测试了本发明金属氧化物电极用钛基体防护涂层、纯钛试片等样品在含硫氰酸根20mg/L的0.5mol/L硫酸溶液中的开路电位。测试结果为：本发明金属氧化物电极用钛基体防护涂层开路电位为0.64V(VsSCE)，纯钛试片开路电位为0.15V(Vs SCE)。由此可见，本发明金属氧化物电极用钛基体防护涂层显著提高了钛基体的耐腐蚀性能。
实施例4
选用纯钛片TA2为基体，用10％(质量分数)的草酸90℃下蚀刻2.5h，水洗后130℃下干燥，得到清洁的钛基体。
按钛摩尔浓度0.21mol/L、钌摩尔浓度0.09mol/L、盐酸质量浓度0.1％，将钛酸丁酯、β-三氯化钌溶于正丁醇溶剂中，得到钛钌有机涂液。
浸涂时，以10μm/s的提拉速度涂覆，接着在110℃下干燥固化15min，然后在430℃下热氧化10min，空冷，反复进行4次，制得钛钌氧化物涂层。
按钛摩尔浓度0.25mol/L、盐酸浓度0.15wt％、离子液体浓度0.1wt％，将二氯二丁醇钛、盐酸和1-丁基-3-甲基咪唑氯盐溶于体积比为1：2的乙醇-正丁醇混合溶剂中，得到钛有机涂液。
用软毛刷均匀涂刷在制得的钛钌氧化物涂层上，接着在115℃下干燥固化10min，然后在450℃下热氧化10min，空冷，反复进行4次，最后480℃下、空气气氛中，热处理1h，制得二氧化钛涂层。
在460℃下，空气气氛中，热处理0.5h，制得钛钌氧化物/二氧化钛复合涂层。
将复合氧化物涂层置于氢等离子体射流中，反应气氛为50％H2+50％Ar，输出功率控制400W，还原时间为5min。在450℃下，氩气气氛中，对上述氧化物涂层进行热处理0.5h，最终制得金属氧化物电极用钛基体防护涂层。借助X射线衍射仪分析，可知该防护涂层为Ti/TiO2-RuO2//Ti5O9。
为了便于对照，制备了清洁的纯钛片，并在常温下分别测试了本发明金属氧化物电极用钛基体防护涂层、纯钛试片等样品在含氟20mg/L的0.5mol/L硫酸溶液中的开路电位。测试结果为：本发明金属氧化物电极用钛基体防护涂层开路电位为0.65V(Vs SCE)，纯钛试片开路电位为-0.21V(Vs SCE)。显而易见，本发明金属氧化物电极用钛基体防护涂层显著提高了钛基体的耐氟腐蚀性能。
Claims (10)
1.一种金属氧化物电极用钛基体防护涂层，其特征在于，该防护涂层位于钛基体与金属氧化物活性涂层的中间，由内到外，依次由钛钌氧化物涂层和亚氧化钛膜层组成；按总质量百分比为100％计，所述的钛钌氧化物涂层组分含量为氧化钛：47％～71％；氧化钌为29％～53％；所述的亚氧化钛膜层成分为Ti4O7或Ti5O9或两者的混合物。
2.根据权利要求1所述的金属氧化物电极用钛基体防护涂层，其特征在于，所述的金属氧化物为氧化钌、氧化铱、氧化锡中的一种。
3.根据权利要求1所述的金属氧化物电极用钛基体防护涂层，其特征在于，所述的钛钌氧化物涂层厚度为2～4μm。
4.根据权利要求1所述的金属氧化物电极用钛基体防护涂层，其特征在于，所述的亚氧化钛膜层厚度为0.5～3μm。
5.权利要求1所述的金属氧化物电极用钛基体防护涂层制备方法，其特征在于，包括以下步骤：
①用质量分数为5％～10％的草酸溶液在85～95℃下蚀刻钛材2～3h，水洗后在110～130℃下烘干5～20min得到清洁的钛基体；
②将钛钌涂液均匀涂覆在清洁的钛基体上，在100～120℃下固化10～15min，然后420～460℃下热氧化分解10～15min，空冷；所述的钛钌涂液为钛钌前驱体的有机溶液，其含钛离子0.18～0.24mol/L，钌离子0.06～0.12mol/L，盐酸质量分数为0.1～0.5％，所用溶剂为正丁醇；
③重复步骤②1～5次，制得钛钌氧化物涂层；
④将钛涂液均匀涂覆在制得的钛钌氧化物涂层上，在100～120℃下固化10～15min，然后420～460℃下热氧化分解10～15min，空冷；重复1～7次，制得二氧化钛涂层；所述的钛涂液为钛前驱体的有机溶液，其含钛离子0.1～0.3mol/L，盐酸质量分数为0.1～0.5％，离子液体质量分数为0.05％～0.2％；所用溶剂为乙醇和正丁醇；
⑤在420～480℃下，空气气氛中，热处理0.5h，制得钛钌氧化物/二氧化钛复合涂层；
⑥在输出功率300～600W下，50％H2和50％Ar等离子体气氛中，还原5～30min，将二氧化钛涂层原位转化为亚氧化钛膜层；
⑦在450～500℃下，氩气气氛中，热处理0.5～1h，最终制得金属氧化物电极用钛基体防护涂层。
6.根据权利要求5所述的金属氧化物电极用钛基体防护涂层制备方法，其特征在于，所述的钛前驱体是钛金属源物质，为钛酸丁酯、三氯化钛、二氯二丁醇钛中的一种。
7.根据权利要求5所述的金属氧化物电极用钛基体防护涂层制备方法，其特征在于，所述的钌前驱体为β型三氯化钌。
8.根据权利要求5所述的金属氧化物电极用钛基体防护涂层制备方法，其特征在于，所述的离子液体为1-丁基-3-甲基咪唑氯盐、1-丁基-3-甲基咪唑溴盐、1-丁基-3-甲基咪唑甲基磺酸盐中的一种。
9.根据权利要求5所述的金属氧化物电极用钛基体防护涂层制备方法，其特征在于，涂覆采用刷涂、浸涂方式。
10.根据权利要求9所述的金属氧化物电极用钛基体防护涂层制备方法，其特征在于，选用刷涂时，横向和纵向刷涂交替进行；采用浸涂时，提拉速度为1～30μm/s。
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