NiTi合金表面电化学氧化制备TiO2膜

采用恒电流阳极氧化法在NiTi形状记忆合金(SMA)表面制备完整致密且耐腐蚀的TiO2膜.通过对NiTi SMA和纯Ti在稀HCl中的动电位阳极极化曲线的分析,得到了选择性脱Ni阳极氧化电流密度工艺参数.试验采用稀HCl体系,以该工艺参数进行阳极氧化处理5min,在NiTi SMA表面制备出了完整致密的TiO2膜,并进行了其表面的SEM、XRD、XPS分析和NiTi SMA表面处理前后在模拟唾液fusayama中的对比腐蚀试验测试.结果表明:经阳极氧化处理的NiTi SMA表面形成了十几纳米厚的TiO2膜,且其耐蚀性有明显的提高.     

磁控溅射法制备PZT基SMA/PZT异质复合材料

采用直流磁控溅射法在PZT基体上溅射沉积NiTiSMA薄膜,而制备出PZT基NiTii SMA/PZT异质复合材料.研究了溅射工艺参数与晶化温度对NiTi SMA薄膜相组成及SMA/PZT异质复合材料膜/基间结合状态的影响规律.结果表明,为保障NiTi SMA薄膜的晶体颗粒均匀、结构致密,膜/基间成分交换范围小及结合紧密,制各NiTi SMA/PZT异质复合材料的适宜工艺为:于基体温度150℃、氩气压强0.7 Pa条件下溅射沉积NiTi SMA薄膜,再经600℃二次晶化处理.显微观察发现,NiTi SMA薄膜与PZT基体之间以化学方式,而非物理方式结合.     

多孔NiTi合金直流-脉冲阳极氧化表面改性研究

采用低温直流-脉冲阳极氧化技术对多孔NiTi合金表面进行改性,分析直流-脉冲阳极氧化过程,利用XPS、SEM、动电位极化对阳极氧化膜的组成、形貌以及耐腐蚀性进行研究,观察阳极氧化前后多孔NiTi合金在模拟人工体液中Ni离子释放行为。研究结果表明在直流3 A、脉冲6 A下阳极氧化的多孔NiTi合金表面形成了一层均匀的多孔氧化膜,其厚度在190 nm左右,主要成分为Ti的氧化物,阳极氧化后多孔NiTi合金的耐腐蚀性显著提高,其Ni离子释放速率大幅度降低。     

基于卤素效应的阳极氧化技术提高Ti48Al5Nb合金抗高温氧化性能

采用电化学阳极氧化技术在含NH_4F的乙二醇电解液中对Ti48Al5Nb合金进行阳极氧化处理,以获得富铝含氟阳极氧化膜。研究了阳极氧化处理对Ti48Al5Nb合金在1000℃空气中的氧化行为及氧化膜组成和结构的影响。结果表明:阳极氧化处理的Ti48Al5Nb合金经高温氧化后表面可形成连续、致密的Al_2O_3氧化膜,且氧化膜与基体具有良好结合力,有效阻止了氧向内扩散,进而显著提高了合金的抗高温氧化性能。经1000℃氧化100 h后,阳极氧化试样增重由未经阳极氧化处理试样的26.73 mg/cm~2降至1.18 mg/cm~2。同时,阳极氧化处理改变了合金的氧化机制,抑制了氧化膜/基体界面处富Nb层的出现。阳极氧化提高Ti48Al5Nb合金抗高温氧化性能是由于氧化膜中F在高温氧化过程中表现出的"卤素效应"所致。     

钛膜表面阳极氧化层制备及表征

为了研究钛膜表面阳极氧化层对吸附和解吸氢同位素特性的影响,需制备和表征钛膜表面阳极氧化层.设计了钛膜表面阳极氧化装置,确定了制备厚度不同的氧化层的阳极氧化工艺参数,其工艺简单、易操作;并对阳极氧化层进行了AES深度剖析和XPS化合价分析.其结果如下:在确定的工艺参数下,设计加工的阳极氧化装置能够制备出表面呈彩色的阳极氧化层,而且表面平整、光滑、均匀,与基体金属结合牢固;采用AES深度剖析确定了阳极氧化层的厚度,而且在其它条件相同时,获得阳极氧化层的厚度随着电压、H2SO4浓度和时间的增加而明显变厚的规律;采用XPS研究了阳极氧化层钛的主要价态为 4、 3和 2价,氧化层主要组成为TiO2、Ti2O3和TiO.     

在Na_2SiO_3溶液中NiTi合金的微弧氧化

在硅酸钠溶液中对NiTi合金进行了微弧氧化处理。结果表明,NiTi合金在Na2SiO3溶液中,微弧氧化过程分为2个阶段,即缓慢电压增长区和电压跃升区。微弧氧化获得氧化物层为Ti的氧化物。微弧氧化后表面硬度比NiTi要高出2倍以上。在NiTi合金微弧氧化过程中,首先是NiTi合金中的Ni氧化以离子形式溶解进入溶液,而Ti保留在合金表面。然后NiTi合金表面的Ti层在阳极电压下氧化形成绝缘层。当表面绝缘层达到一定厚度后就发生起弧现象。     

铈盐对铝合金硼酸?硫酸阳极氧化膜的封闭效应

将铝合金硼酸-硫酸阳极氧化膜浸入铈盐转化液中进行封闭。采用交流阻抗谱技术研究各封闭参数对氧化膜耐蚀性的影响,比较了不同方法封闭的氧化膜的耐蚀性差异。结果表明:将硼酸-硫酸阳极氧化试样浸入30℃的铈盐转化液(5 g/L Ce(NO3)3+0.5%H2O2)中处理30 min后,多孔层电阻Rp大幅增加,且腐蚀电流密度降低1个数量级,耐蚀性明显优于沸水封闭氧化膜的,也稍优于稀铬酸封闭氧化膜的耐蚀性。结合EDS分析表明:铈盐转化封闭后硼酸-硫酸阳极氧化膜的外表面形成了一层完整致密的铈盐转化膜,多孔层内也充满了铈的封闭产物,二者的协同作用几乎完全封住了硼酸-硫酸阳极氧化膜的孔隙,从而有效地提高了氧化膜的耐蚀性。     

Ti11V3Al3Sn合金的复合氧化研究

采用复合氧化(阳极极化 热氧化)法制备Ti11V3Al3Sn合金的表面转化膜.通过X射线衍射(XRD)、扫描电镜(ESEM)、显微硬度计和电化学分析仪分析了转化的膜物相、形貌、显微硬度和阳极极化曲线.结果表明:复合氧化转化膜由TiO2、TiO和Al2O3组成,以致密的金红石结构的TiO2为主.阳极氧化加复合的低温热氧化可以获得较致密、平坦的转化膜;阳极氧化加复合的较高温度的热氧化将得到粗糙、并分布着许多凹坑的转化膜层.复合氧化处理后,合金的表面硬度和耐电化学腐蚀性能大幅度提高.     

酒石酸钠体系阳极氧化对TB8钛合金薄板疲劳性能的影响

采用以酒石酸钠为成膜剂的电解体系对0.5 mm厚的TB8钛合金薄板进行阳极氧化处理,采用扫描电镜(SEM)观察疲劳断口及氧化膜的显微形貌,采用X射线衍射仪(XRD)、能谱分析仪(EDS)对覆在钛合金基体上的阳极氧化膜进行物相分析,研究以酒石酸钠为成膜剂的TB8钛合金薄板阳极氧化疲劳断裂机理。结果表明:阳极氧化处理后,表面形成了一层厚2μm左右的均匀致密的氧化膜,氧化膜主要由金红石型与锐钛型Ti O2混合晶体组成;阳极氧化处理可有效去除表面缺陷,降低了裂纹源的萌生及疲劳裂纹的扩展速率,使疲劳条纹更加均匀细致;以酒石酸钠为成膜剂制备的TB8钛合金薄板经阳极氧化处理,在疲劳寿命为1×104下,其疲劳强度相对于母材的提高了44%左右。     

镍钛合金光催化高级氧化表面改性与生物相容性

在UV/H2O2光催化体系中,通过高级氧化法在NiTi SMA表面生成贫Ni的Ti氧化膜.通过亲水性试验、血小板黏附试验以及MTT细胞毒性试验对改性后试样的生物相容性进行了系统的评价,研究发现改性后试样的亲水性得到明显改善.表面血小板黏附数量减少,变形和团聚现象得到抑制,形成血栓的可能性降低,血液相容性得到提高.改性后试样的细胞相对增殖率(RGR)高于化学抛光的试样,试样周围细胞分裂增生良好,与材料边缘结合自然,改性处理同样提高了试样的细胞相容性.结果表明光催化高级氧化是提高NiTi SMA生物相容性的一种有效方法.     

In situ synthesis of nanostructured titania film on NiTi shape memory alloy by Fenton＇s oxidation method

Fenton＇s oxidation method was successfully used to synthesize an ideal titania film in situ on NiTi shape memory alloy（SMA） for medical applications. Characterized with scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffractometry, inductively coupled plasma mass spectrometry and electrochemical tests, it is found that the titania film produced by Fenton＇s oxidation method on NiTi SMA is nanostructured and has a Ni-free zone near its top surface, which results in a notable improvement in corrosion resistance and a remarkable decrease in leaching of harmful Ni ions from NiTi SMA in simulated body fluids. The improvement of effectiveness to corrosion resistance and the reduction in Ni release of NiTi SMA by Fenton＇s oxidation method are comparable to those by oxygen plasma immersion ion implantation reported earlier.     

Corrosion resistance of PANi‐coated steel in simulated PEMFC anodic environment

By using electrochemical techniques, the corrosion resistance of polyaniline (PANi)‐coated 1Cr18Ni9Ti stainless steel was investigated in simulated proton exchange membrane fuel cell (PEMFC) anodic environment. The results indicated that the compact conductive PANi film could be obtained on 1Cr18Ni9Ti steel by pulse potentiostatic method (PPSM). When steel was coated with conductive PANi, its corrosion potential was improved from ?350 to 250 mV in simulated corrosion solution. During the potentiostatic polarization in PEMFC's anodic operation environment, the film is stable and there is no degradation of the PANi film. The film has no effect on the performance of the fuel cell. Further effort to improve the performance of conductive polymer coatings and to estimate the long‐term performance in actual PEMFC environment is desirable.     

Cu-Zn-Al形状记忆合金在模拟宫腔液中的腐蚀行为

采用化学失重法、电化学方法和原子吸收光谱法研究了紫铜、Cu-Zn-Al形状记忆合金和Cu-Zn-Al合金在模拟宫腔液中的腐蚀行为.结果表明, 模拟宫腔液中紫铜、Cu-Zn-Al形状记忆合金和Cu-Zn-Al合金的腐蚀历程受阴极氧去极化步骤控制.Cu-Zn-Al形状记忆合金和Cu-Zn-Al合金由于铝的表面离子化倾向比锌的大, 优先形成致密坚固的保护性氧化铝膜, 降低了腐蚀速率.在模拟宫腔液中发现Cu-Zn-Al形状记忆合金和Cu-Zn-Al合金发生脱铝腐蚀, Cl-参与腐蚀反应历程, 促进脱铝腐蚀的进行.白蛋白与氧的竞争吸附加速了阳极溶解, 使紫铜、Cu-Zn-Al形状记忆合金和Cu-Zn-Al合金的阳极活性电流密度随白蛋白浓度的上升而增加.     

Effect of surface preparation on corrosion properties and nickel release of a NiTi alloy

Surface preparation is potentially important to the corrosion and biomedical properties of NiTi shape memory alloys.The effect of surface preparation on corrosion properties and nickel release of a Ti-56 wt.%Ni alloy has been studied.Surface of the NiTi coupons were prepared by four methods, namely, chemical etching, electropolishing, mechanical polishing and oxidizing, and then examined by corrosion test system.Furthermore, the Ni ion releases from NiTi samples with different surface preparations dipped in 1% HCl solution were analysed.Compared with the surface after chemical treatment, mechanical polishing and thermal oxidation, electropolished surface has better corrosion resistance and less nickel release for not only its lower surface roughness, but also the composition and property of its surface film.     

Surface treatment of NiTi shape memory alloy by modified advanced oxidation process

A modified advanced oxidation process(AOP) utilizing a UV/electrochemically-generated peroxide system was used to fabricate titania films on chemically polished NiTi shape memory alloy(SMA). The microstructure and biomedical properties of the film were characterized by scanning electron microscopy(SEM), X-ray photoelectron spectroscopy(XPS), inductively-coupled plasma mass spectrometry(ICPMS), hemolysis analysis, and blood platelet adhesion test. It is found that the modified AOP has a high processing effectiveness and can result in the formation of a dense titania film with a Ni-free zone near its top surface. In comparison, Ni can still be detected on the outer NiTi surface by the conventional AOP using the UV/H2O2 system. The depth profiles of O, Ni, Ti show that the film possesses a smooth graded interface structure next to the NiTi substrate and this structure enhances the mechanical stability of titania film. The titania film can dramatically reduce toxic Ni ion release and also improve the hemolysis resistance and thromboresistance of biomedical NiTi SMA.     

激光表面重熔NiTi形状记忆合金组织及腐蚀性能

采用2kWNd：YAG激光器对NiTi合金进行表面重熔处理，利用扫描电镜、X射线衍射、X光电子能谱分析重熔层成分和组织结构，利用电化学测试研究重熔层耐腐蚀性能。结果表明：NiTi合金经过激光重熔处理后，可得到致密的重熔层；根据激光处理参数的不同，在重熔层中会出现TiNi、TiNi3等新相，重熔层表面Ti／Ni及Ti^4 /Ti比显著提高；电化学极化曲线表明激光重熔后NiTi合金的耐蚀性得到了显著改善。     

阳极氧化法制备TiO2膜在模拟深海热液区的耐腐蚀性能

以恒压阳极氧化方法在钛基体上制备TiO₂氧化膜,使用水热釜模拟深海热液区的条件研究其耐腐蚀性能。采用XRD、SEM、接触角测定仪对氧化膜以及腐蚀试样产物进行晶型、表面结构、化学成分和亲疏水性能测定,使用动电位扫描方法对其进行极化曲线测试。结果表明,钛试样和阳极氧化钛试样在模拟深海环境条件下,经过腐蚀反应在表面都生成了一层非致密的TiO₂ 膜,对基体并不能起到保护作用,而阳极氧化生成的致密TiO₂ 膜对基体能够起到很好的保护作用。经腐蚀后钛试样表面有TiH₂相的形成,腐蚀电位负移0.45 V。而阳极氧化钛试样表面没有TiH₂相的形成,且腐蚀电位负移较小,表现出良好的耐腐蚀性能。     

A comparative study on titania layers formed on Ti, Ti-6Al-4V and NiTi shape memory alloy through a low temperature oxidation process

For improving the bioactivity and biocompatibility of metals for medical applications, anatase titania layers were synthesized on Ti, Ti-6Al-4V and NiTi shape memory alloy (SMA) using the H₂O₂-oxidation and hot water aging treatment method at 80 °C. The thickness of the titania layers on Ti, Ti-6Al-4V and NiTi SMA was 7.43 ± 0.93 μm, 3.14 ± 0.38 μm and 4.04 ± 0.25 μm, respectively. X-ray diffraction (XRD) and transmission electron microscopic (TEM) analysis indicated that the titania layers formed were poorly crystalline anatase. Fourier transform infrared spectroscopy (FTIR) suggested that abundant Ti-OH functional groups were produced on titania, which could improve bioactivity of the metals. In addition, the titania layer formed on Ti substrate was shown to contain more molecularly chemisorbed water and Ti-OH functional groups than those on Ti-6Al-4V and NiTi SMA. Atomic force microscopic (AFM) results showed that the surface roughness values of metal samples depended on the scanning size and that surface roughness of samples significantly increased after the H₂O₂-oxidation and hot water aging treatment for all three metals. Compared to Ti-6Al-4V and NiTi SMA, the H₂O₂-treated and aged Ti samples exhibited the roughest surface. The wettability of samples was evaluated through water contact angle measurements. After the H₂O₂-oxidation treatment, the three metals exhibited high hydrophilicity. The bonding strength of titania layers on Ti, Ti-6Al-4V and NiTi was also investigated. Potentiodynamic polarization tests indicated that the corrosion resistance of H₂O₂-treated and aged Ti, Ti-6Al-4V and NiTi SMA was significantly improved due to the titania layer formation.     

In situ formation of titania film on NiTi alloy treated with hydrogen peroxide solution at low temperature

Chemically polished NiTi shape memory alloy（SMA） substrate was treated with a boiling aqueous solution containing hydrogen peroxide to form titania film in situ at low temperature. The surface characterizations of titania film on NiTi substrate were investigated by scanning electron microscopy, X-ray diffractometry and X-ray photoelectron spectroscopy. The results show that titania film is successfully fabricated in situ on NiTi SMA by this surface oxidation method. It is mainly composed of rutile and anatase, whose surface compositions and morphologies are sensitive to H2O2 content. In situ formation mechanism of titania film on NiTi substrate was discussed based on the experimental results.