CN114703528B - 一种纯钛表面改性纳米二氧化钛膜层的制备方法 - Google Patents
一种纯钛表面改性纳米二氧化钛膜层的制备方法 Download PDFInfo
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000010936 titanium Substances 0.000 title claims abstract description 87
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 87
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 47
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 claims abstract description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052709 silver Inorganic materials 0.000 claims abstract description 14
- 229960005489 paracetamol Drugs 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 239000004332 silver Substances 0.000 claims abstract description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 18
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- 238000002791 soaking Methods 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 101710134784 Agnoprotein Proteins 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 235000010333 potassium nitrate Nutrition 0.000 claims description 9
- 239000004323 potassium nitrate Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
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- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
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- 229910001069 Ti alloy Inorganic materials 0.000 abstract description 3
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- 238000001228 spectrum Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- DGLRDKLJZLEJCY-UHFFFAOYSA-L disodium hydrogenphosphate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].OP([O-])([O-])=O DGLRDKLJZLEJCY-UHFFFAOYSA-L 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
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Abstract
本发明属于医用钛合金技术领域,具体涉及一种纯钛表面改性纳米二氧化钛膜层的制备方法。本发明分别采用阳极氧化法、浸渍法和恒电位还原法三种方法,对纯钛表面依次进行处理,在钛表面获得掺杂有纳米银粒子、银离子和对乙酰氨基酚的锐钛矿纳米二氧化钛膜层,该膜层在钛基板表面直接原位生长出来,薄膜微观结构为纳米管状,掺杂的纳米银、银离子和对乙酰氨基酚在磷酸盐缓冲液中可以保持至少18天。本发明提供的纯钛表面改性纳米二氧化钛膜层的制备方法,采用化学、物理和电化学方法的结合,能够在钛基上直接原位生长得到具有杀菌消炎镇痛性能的改性纳米二氧化钛膜层。
Description
技术领域
本发明属于医用钛合金技术领域,具体涉及一种纯钛表面改性纳米二氧化钛膜层的制备方法。
背景技术
由于钛及其合金具有优异的机械性能、耐蚀性能和生物兼容性,因此大量用于人体内硬组织替换材料,如牙根、假体等植入物使用。但是骨整合,但其骨传导性欠佳,而产生过早失效,因此在作为植入体使用前有必要对其表面进行改性处理。钛基植入体的功效由其表面的化学组成、形貌和微观结构等特征决定,而表面改性可以提高钛基材料的表面特征及生物相容性,因此有必要对用于生物植入体的钛基材料进行表面改性,从而优化其综合性能。
目前钛合金表面改性方法主要采用氧化方法,但该方法制备的表面膜层性能单一,而且形成的薄膜与基体的结合强度较低,稳定性不够。
发明内容
本发明提供一种纯钛表面改性纳米二氧化钛膜层的制备方法,采用化学、物理和电化学方法的结合,能够在钛基上直接原位生长得到具有杀菌消炎镇痛性能的改性纳米二氧化钛膜层。
本发明的技术方案如下:
一种纯钛表面改性纳米二氧化钛膜层的制备方法,包括如下步骤:
(1)将钛基片在盐酸和硫酸混合溶液中浸泡,去除表面的氧化皮,然后用去离子水冲洗干净,接着在无水乙醇中超声波清洗,并用氮气将钛基片表面吹干;
(2)将表面清理后的钛基片作为阳极、石墨电极作为阴极分别连接在直流稳压电源的两极,调节电源电压和电流,在HNO3溶液中,对钛基片进行阳极氧化,取出后用去离子水冲洗干净;
(3)将阳极氧化后的钛基片放在炉子中,在70℃~80℃预加热2~3小时,接着升温到450℃~500℃煅烧2.5~3.5小时;随后将钛基片在对乙酰氨基酚的乙醇溶液中浸泡3~4小时,取出在100℃~120℃的炉子中煅烧25~35分钟;随后将钛基片在AgNO3溶液中浸泡25~35分钟,取出后在70℃~80°的炉子中煅烧25~35分钟;
(4)将浸渍后的钛基片连接到电化学工作站的工作电极上,饱和甘汞电极作为参比电极,铂网作为对电极,在硝酸银和硝酸钾混合溶液中恒电位还原20秒~35秒,经氮气干燥后在钛基片表面上获得改性纳米二氧化钛膜层。
进一步地,所述的纯钛表面改性纳米二氧化钛膜层的制备方法,所述步骤(4)中的硝酸银和硝酸钾混合溶液的浓度分别为0.01mol·L-1AgNO3、0.1mol·L-1KNO3。
进一步地,所述的纯钛表面改性纳米二氧化钛膜层的制备方法,所述步骤(4)中的硝酸银和硝酸钾混合溶液为经过高纯氮气除氧后的溶液。
进一步地,所述的纯钛表面改性纳米二氧化钛膜层的制备方法,所述步骤(4)中的恒电位还原过程中扫描速度范围为5mV/s~50mV/s,电压为相对于参比电极-0.5V。
进一步地,所述的纯钛表面改性纳米二氧化钛膜层的制备方法,所述步骤(4)中的硝酸银和硝酸钾混合溶液中硝酸钾能够用同样摩尔数的硝酸钠代替。
进一步地,所述的纯钛表面改性纳米二氧化钛膜层的制备方法,所述步骤(2)中阳极氧化时,采用磁力搅拌,防止阴极上反应产生的大量氢气聚集在溶液和两个电极表面。
进一步地,所述的纯钛表面改性纳米二氧化钛膜层的制备方法,所述改性纳米二氧化钛膜层为含有大量纳米微孔的锐钛矿结构。
进一步地,所述的纯钛表面改性纳米二氧化钛膜层的制备方法,所述改性纳米二氧化钛膜层是在纳米锐钛矿二氧化钛孔隙中掺杂了银粒子和对乙酰氨基酚,并且存在具有Ag-O-C化学键的有机金属化学物。
本发明的有益效果为:本发明制备的改性纳米二氧化钛膜层与钛基体结合力强,不易脱落,并具有很好的耐蚀性、生物相容性和机械性能。膜层微观结构为纳米管状,掺杂的纳米银、银离子和对乙酰氨基酚在磷酸盐缓冲液中可以保持至少18天。在磷酸盐缓冲液中浸泡18天后Ag-O-C化学键的有机金属化学物消失,但膜层中仍有微量银粒子和对乙酰氨基酚水解中间体。由于膜层中含有银粒子和对乙酰氨基酚,所以该材料具有一定的消炎杀菌镇痛作用。经表面改性处理的钛基材料可以用于牙根、假肢等植入体使用。
附图说明
图1为实施例1中经阳极氧化然后烧结获得的二氧化钛涂层表面的2万倍扫描电子显微镜图片;
图2为实施例1中经阳极氧化然后烧结获得的二氧化钛涂层表面的60万倍扫描电子显微镜图片;
图3为实施例1经阳极氧化然后烧结获得的二氧化钛涂层表面的X射线衍射图;
图4为实施例1制备的改性纳米二氧化钛膜层的16万倍扫描电子显微镜图片;
图5为实施例1制备的改性纳米二氧化钛膜层X射线衍射图;
图6为实施例1制备的改性纳米二氧化钛膜层的X射线光电子能谱图;
图7为实施例1改性纳米二氧化钛膜层浸泡9天后的2万倍扫描电子显微镜图片;
图8为实施例1改性纳米二氧化钛膜层浸泡9天后的16万倍扫描电子显微镜图片;
图9为实施例1改性纳米二氧化钛膜层浸泡18天后的X射线光电子能谱图。
具体实施方式
实施例1
(一)制备方法如下:
1.将钛基片在质量比为1:3的盐酸和硫酸混合溶液中浸泡30分钟,去除表面的氧化皮,然后用大量去离子水冲洗干净,接着在无水乙醇中超声波清洗15分钟,并用高纯氮气将其表面吹干。然后将钛基片作为阳极、石墨电极作为阴极分别连接在直流稳压电源的两极,调节电源电压为20V,电流为0.5A,在0.05mol·L-1HNO3溶液中,边磁力搅拌边对钛基片阳极氧化15分钟,取出后用大量去离子水冲洗干净;接着将阳极氧化的钛片放在炉子中,在70℃时预加热2小时,随后升温到490℃煅烧3小时,接着将煅烧后的钛片在0.05mol·L-1对乙酰氨基酚的乙醇溶液中浸泡4小时,随后取出在120℃的炉子中煅烧30分钟,随后在0.01mol·L-1AgNO3溶液中浸泡30分钟,取出后在70℃的炉子中煅烧30分钟后,接着连接到电化学工作站的工作电极上,饱和甘汞电极作为参比电极,铂网作为对电极,设置电压为相对于参比电极-0.5V、扫描速度范围为20mV/s,在经高纯氮气除氧后的0.01mol·L-1AgNO3和0.1mol·L-1KNO3混合溶液中恒电位还原30秒,经氮气干燥后在钛基体上获得改性纳米二氧化钛膜层。
(二)检测
1.采用扫描电子显微镜和X射线衍射仪对经阳极氧化然后烧结获得的二氧化钛膜层进行观察和表征:图1显示,膜层表面具有大量微裂纹;从图2可以看出,微裂纹放大有无数的纳米尺寸的微孔,这些特征有利于后期的改性处理;由图3可以看出,谱图中,当2θ=25.28°,37.8°,48.05°,53.89°和55.06°的衍射峰分别归属于锐钛矿二氧化钛的(101),(004),(200),(105)和(211)晶面。当2θ=38.42°,40.17°,53.04°,62.96°,70.66°和76.36°的衍射峰分别归属于基体钛的(002)、(101)、(102)、(110)、(103)和(112)晶面,表明在钛基体上制备了锐钛矿纳米二氧化钛膜层。
2.采用扫描电子显微镜和X射线衍射仪对改性纳米二氧化钛膜层进行观察和表征:图4所示,膜层表面及孔隙中随机分布着大量的纳米粒子;图5的X射线衍射图谱表明,当2θ=38.08°和44.24°的衍射峰归属于金属单质银;其他的衍射峰分别归属于锐钛矿二氧化钛和基体钛。
3.采用X射线光电子能谱对改性纳米二氧化钛膜层进行化学结构表征:如图6所示,(a)谱图鉴定出Ag、C、Ti和O元素;(b)表明,Ag3d5/2and Ag3d3/2主峰的结合能分别位于368eV和373.9eV,为金属银单质;(c)显示,O1s的峰可以分峰为结合能分别位于528.6eV,530.1eV,530.9eV,531.9eV和532.7eV的峰位,分别归属于Ag-O键、CONH键、O-Ag、苯基中的C-O键、以及C=O键;(d)中的氧元素高分辨谱图表明8个组分的峰位,键合能分别位于289.9eV,287.8eV,286.2eV,285.4eV,284.7eV,283.8eV,282.5eV和281.4eV,分别对应于C-O键、C=O键、C-N键、C-C键、C-C/C=C键、与氨基键合的C-C键、与苯基相连的C-O-Ag键以及与氨基键合的C-O-Ag,表明在改性纳米二氧化钛膜层中形成了稳定的含C-O-Ag键的复合物。
(三)降解性能评价
1.磷酸盐缓冲液(PBS)的配制:将17.9070g十二水磷酸氢二钠和7.8005g分别倒入500ml去离子水中,搅拌均匀,得到0.1mol·L-1磷酸盐缓冲液,用0.01mo L-1NaOH调节溶液的pH值为7.3。
2.将表面制备改性纳米二氧化钛膜层的钛片分别浸泡在37℃的PBS溶液中,每天更换新鲜的PBS溶液,浸泡9天和18天后,取出采用高纯氮气吹干。
3.采用扫描电子显微镜对浸泡后的改性纳米二氧化钛膜层表面进行观察:如图7、8所示,膜层表面的微裂纹及孔隙中仍残留有纳米颗粒,而且颗粒尺寸大于浸泡前的尺寸,说明在浸泡过程中,颗粒发生长大。
4.采用X射线光电子能谱对浸泡后的改性纳米二氧化钛膜层进行化学结构表征:如图9所示,(a)谱图鉴定出Ag、C、Ti和O元素;(b)表明,Ag3d5/2and Ag3d3/2主峰的结合能分别位于368eV和373.9eV,为金属银单质;(c)显示,C1s的峰可以分峰为结合能分别位于289.5eV,287.8eV,286.5eV,285.4eV,284.7eV和283.8eV的峰位,分别归属于C-O,C=O,C-N,C-C,C-C/C=C和C-C等键;(d)显示,O1s的峰可以分峰为结合能分别位于530.1eV,530.8eV,531.9eV和532.7eV峰位,分别归属于CONH键,O-H键,Ag-O键和C=O键,而528.6eV的峰位归属于Ag-O键,表明尽管在PBS溶液中浸泡了18天,该改性纳米二氧化钛膜层中仍然含有银离子和对乙酰氨基酚等有益成分。
实施例2:
将钛基片在质量比为1:3的盐酸和硫酸混合溶液中浸泡40分钟,去除表面的氧化皮,然后用大量去离子水冲洗干净,接着在无水乙醇中超声波清洗20分钟,并用高纯氮气将其表面吹干。然后将钛基片作为阳极、石墨电极作为阴极分别连接在直流稳压电源的两极,调节电源电压为15V,电流为0.5A,在0.05mol·L-1HNO3溶液中,边磁力搅拌边对钛基片阳极氧化20分钟,取出后用大量去离子水冲洗干净,接着将阳极氧化的钛片放在炉子中,在75℃时预加热2小时,随后升温到490℃煅烧3.5小时,接着将煅烧后的钛片在0.05mol·L-1对乙酰氨基酚的乙醇溶液中浸泡4小时,随后取出在120℃的炉子中煅烧30分钟,随后在0.01mol·L-1AgNO3溶液中浸泡30分钟,取出后在75℃的炉子中煅烧30分钟后,接着连接到电化学工作站的工作电极上,饱和甘汞电极作为参比电极,铂网作为对电极,设置电压为相对于参比电极-0.5V、扫描速度范围为15mV/s,在经高纯氮气除氧后的0.01mol·L-1AgNO3和0.1mol·L-1KNO3混合溶液中恒电位还原25秒,经氮气干燥后在钛基体上获得一种改性纳米二氧化钛涂层。
实施例3:
将钛基片在质量比为1:3的盐酸和硫酸混合溶液中浸泡30分钟,去除表面的氧化皮,然后用大量去离子水冲洗干净,接着在无水乙醇中超声波清洗20分钟,并用高纯氮气将其表面吹干。然后将钛基片作为阳极、石墨电极作为阴极分别连接在直流稳压电源的两极,调节电源电压为20V,电流为0.5A,在0.05mol·L-1HNO3溶液中,边磁力搅拌边对钛基片阳极氧化25分钟,取出后用大量去离子水冲洗干净,接着将阳极氧化的钛片放在炉子中,在75℃时预加热2小时,随后升温到480℃煅烧3.5小时,接着将煅烧后的钛片在0.05mol·L-1对乙酰氨基酚的乙醇溶液中浸泡3小时,随后取出在110℃的炉子中煅烧30分钟,随后在0.01mol·L-1AgNO3溶液中浸泡30分钟,取出后在75℃的炉子中煅烧30分钟后,接着连接到电化学工作站的工作电极上,饱和甘汞电极作为参比电极,铂网作为对电极,设置电压为相对于参比电极-0.5V、扫描速度范围为30mV/s,在经高纯氮气除氧后的0.01mol·L-1AgNO3和0.1mol·L-1KNO3混合溶液中恒电位还原25秒,经氮气干燥后在钛基体上获得一种改性纳米二氧化钛涂层。
Claims (8)
1.一种纯钛表面改性纳米二氧化钛膜层的制备方法,其特征在于,包括如下步骤:
(1)将钛基片在盐酸和硫酸混合溶液中浸泡,去除表面的氧化皮,然后用去离子水冲洗干净,接着在无水乙醇中超声波清洗,并用氮气将钛基片表面吹干;
(2)将表面清理后的钛基片作为阳极、石墨电极作为阴极分别连接在直流稳压电源的两极,调节电源电压和电流,在HNO3溶液中,对钛基片进行阳极氧化,取出后用去离子水冲洗干净;
(3)将阳极氧化后的钛基片放在炉子中,在70℃~80℃预加热2~3小时,接着升温到450℃~500℃煅烧2.5~3.5小时;随后将钛基片在对乙酰氨基酚的乙醇溶液中浸泡3~4小时,取出在100℃~120℃的炉子中煅烧25~35分钟;随后将钛基片在AgNO3溶液中浸泡25~35分钟,取出后在70℃~80°的炉子中煅烧25~35分钟;
(4)将浸渍后的钛基片连接到电化学工作站的工作电极上,饱和甘汞电极作为参比电极,铂网作为对电极,在硝酸银和硝酸钾混合溶液中恒电位还原20秒~35秒,经氮气干燥后在钛基片表面上获得改性纳米二氧化钛膜层。
2.根据权利要求1所述的纯钛表面改性纳米二氧化钛膜层的制备方法,其特征在于,所述步骤(4)中的硝酸银和硝酸钾混合溶液的浓度分别为0.01mol·L-1AgNO3、0.1mol·L- 1KNO3。
3.根据权利要求1所述的纯钛表面改性纳米二氧化钛膜层的制备方法,其特征在于,所述步骤(4)中的硝酸银和硝酸钾混合溶液为经过高纯氮气除氧后的溶液。
4.根据权利要求1所述的纯钛表面改性纳米二氧化钛膜层的制备方法,其特征在于,所述步骤(4)中的恒电位还原过程中扫描速度范围为5mV/s~50mV/s,电压为相对于参比电极-0.5V。
5.根据权利要求1所述的纯钛表面改性纳米二氧化钛膜层的制备方法,其特征在于,所述步骤(4)中的硝酸银和硝酸钾混合溶液中硝酸钾能够用同样摩尔数的硝酸钠代替。
6.根据权利要求1所述的纯钛表面改性纳米二氧化钛膜层的制备方法,其特征在于,所述步骤(2)中阳极氧化时,采用磁力搅拌,防止阴极上反应产生的大量氢气聚集在溶液和两个电极表面。
7.根据权利要求1所述的纯钛表面改性纳米二氧化钛膜层的制备方法,其特征在于,所述改性纳米二氧化钛膜层为含有大量纳米微孔的锐钛矿结构。
8.根据权利要求7所述的纯钛表面改性纳米二氧化钛膜层的制备方法,其特征在于,所述改性纳米二氧化钛膜层是在纳米锐钛矿二氧化钛孔隙中掺杂了银粒子和对乙酰氨基酚,并且存在具有Ag-O-C化学键的有机金属化学物。
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