Corrosion behaviors of a new titanium alloy TZNT for surgical implant application in Ringer’s solution

A new near α-titanium alloy Ti12.5Zr2.5Nb2.5Ta (TZNT) for surgical implants was designed. The potentiodynamic technique was performed to investigate the corrosion behaviors of TZNT in Ringer's solution, and Ti6Al4V, Ti6Al7Nb, and TA2 were taken as comparison. The structure of the passive film was analyzed using an X-ray photoelectron spectrometer (XPS). The results indicate that TZNT possesses better corrosion resistance, when compared with Ti6Al4V, Ti6Al7Nb, and TA2. The passive film formed on the TZNT surface is composed of oxides, such as TiO2, ZrO2, Nb2O5, and Ta2O5. The elements Zr and Ta are rich, whereas Ti and Nb are poor in the passive film. The addi-tion of Zr, Nb, and Ta with relatively low electrochemical reaction potentials can reduce the anode activity and improve passive properties. Other than that, oxides such as ZrO2, Nb2O5, and Ta2O5 with the nobler equilibrium constants make the passive film more stable.     

Corrosion behavior of thermal-sprayed WC cermet coatings in SO4 2− environment

A series of the electrochemical and long-term corrosion tests was carried out in a 3.5 wt% Na2SO4 solution on thermal-sprayed WC-17Co and WC-10Co-4Cr cermet coatings in order to examine the effect of composition of binder materials on the corrosion behavior. The results reveal that the overall corrosion resistance of the WC-17Co coating is inferior to that of the WC–Co–Cr coatings due to the corrosion of binder materials which induce WC particles to fall off. CoO and WO3 oxide films form on the surface of WC-17Co coating in Na2SO4 solution electrochemical corrosion process, which will protect the coating in the process of corrosion. Cr2O3 oxide film formed on the WC-10Co-4Cr coating surface has a strong hindered role to corrosion. The corrosion mechanism of WC-17Co coating in Na2SO4 solution is entire corrosion of Co matrix, while it is film-hole corrosion mechanism for WC-10Co-4Cr coating.     

Electrochemical Performance of Passive Film Formed on Ti-Al-Nb-Zr Alloy in Simulated Deep Sea Environments

Titanium alloy Ti-Al-Nb-Zr has high specific strength and becomes a promising structural material used in the deep sea.The excellent corrosion resistance of the alloy is derived from the protective passive film formed on its surface.By now,full agreement on interpretation of the anti-corrosion performance of the film in marine environment,especially in the deep sea,has not been reached.In this work,the electrochemical performance of two-surface-state Ti-Al-Nb-Zr alloys which are treated by mechanical polishing and anodizing pre-passivation in the simulated shallow sea,1000 m and 3000 m deep sea environments,is investigated.By interpreting the electrochemical kinetic parameters,it is found that the dominant cathodic process becomes hydrogen evolution in simulated deep sea environments,but the reduction rate is restrained by high hydrostatic pressure,which arrests the passivation of the alloy.Assisted by X-ray photoelectron spectroscopy analysis,it is found that the passive film mainly consists of titanium oxides.There are intermediate oxides with non-stoichiometric ratio involved in the film formation due to the low dissolved oxygen concentration and low temperature.The results of Mott-Schottky and electrochemical impedance show that the film has n-type semiconducting property with oxygen vacancies as the main point defects.The anti-corrosion performance in simulated deep sea environments is one order of magnitude lower than that in the simulated shallow sea environment.However,from 1000 to 3000 m,the corrosion resistance is reduced very slightly.In the inner layers of the passive film and the passive film formed in simulated deep sea environments,the proportion of lowvalence titanium oxides is relatively high.The doping of low-valence titanium(Ti(Ⅱ) or Ti(Ⅲ)) results in a porous structure and ion permeability of the passive film,as well as relatively low corro sion resistance.     

Effects of W Addition on the Electrochemical Behaviour and Passive Film Properties of Fe-Based Amorphous Alloys in Acetic Acid Solution

The electrochemical behaviour and passive film properties of Fe–Cr–Mo–W–C–B–Y amorphous alloys in acetic acid solution were investigated. The potentiodynamic polarisation and Nyquist curves demonstrated that W addition significantly enhanced the corrosion resistance. Mott–Schottky plots and angle-resolved X-ray photoelectron spectra indicated that passive films with different W contents exhibited dipolar(p–n) semiconducting characteristics separated by flat-band potentials. The outer and inner oxide layers of the passive films were modified by reducing the acceptor and donor densities. Moreover, W addition favoured the formation of a thicker and more stable passive film to inhibit the dissolution of alloy elements.     

Threshold Chloride Concentration for Passivity Breakdown of Mg-Zn-Gd-Nd-Zr Alloy (EV31A) in Basic Solution

Mg-Zn-Gd-Nd-Zr alloy(EV31A) is a heat-treatable magnesium(Mg) cast alloy that can be used up to 200 ℃for automobile and aerospace applications.This alloy has excellent mechanical properties(ultimate tensile strength:280 MPa at room temperature,and ~ 230 MPa at 200 ℃) and improved corrosion resistance.Electrochemical corrosion studies were conducted on this alloy under different heat treatment conditions in 0.1 M NaOH solution with the addition of0-1000 ppm of chloride.The alloy showed excellent passivity in the 0.1 M NaOH solution.The passive potential range typically extended to more than 1.2 V_(Ag/AgC1).The transpassive potential was observed to be dependent on heat treatment condition of the alloy.More than 80 ppm of chloride was required to induce passivity breakdown in any heat treatment condition.Peak aging at 200 ℃ for 16 h imparted better resistance for localized corrosion than other heat-treated conditions.The alloy in the as-received condition showed the highest passivation kinetics due to its smaller grain size that possibly increased the diffusion of reactive elements to form protective oxide.The passive film of the EV31 A alloy showed n-type semiconductivity with a charge carrier density of ~2×10~(21) cm~(-3) with no chloride addition.The charge carrier density increased with chloride addition in the electrolyte which could be correlated with the susceptibility to localized corrosion.     

Stress and Defect Characteristics in Oxide Films and Corrosion Resistance of Zr-1Nb Alloy

Two approaches to testing corrosion in autoclave with different time intervals for heating and cooling were carried out to investigate the corrosion resistance of Zr-1Nb alloy in the 0.01 mol/L LiOH aqueous solution at 360 °C/18.6 MPa, the stress, and defect density in the oxide film. The stress and defect density in oxide film were measured by a curl method and the Ion Migration Method (IMM), respectively. Results showed that the stress level and defect density in the oxide film in the shorter interval corrosion tests were lower than that in the longer interval corrosion tests at the initial stage of corrosion with the weight gain less than 34.37 mg/dm2. The corrosion resistance in the subsequent stages of corrosion was better in the shorter interval corrosion tests. It indicates that at the initial stage of corrosion the weight gain shows no obvious difference between the two approaches of corrosion tests in autoclave under different time intervals for heating and cooling. However, the stress level and defect density in the oxide film exhibit noticeable differences, which leads to two distinct microstructural evolution rates of the oxide film. The distinct microstructural evolution rates cause different corrosion resistance in the subsequent corrosion stages.     

Corrosion behavior of a CuCrNiAl alloy in the presence of NaCl deposit

The corrosion behavior of a CuCrNiAl alloy with NaCl deposit at 700 and 900℃ was studied by means of metalloscope, XRD, SEM/EDX, and thermogravimetric analysis. The results indicated that the corrosion of the CuCrNiAl alloy beneath the NaCl deposit is severe; the corrosion production is loose and easy to scale off; the Cr phase is easier to erode than the Cu phase, and the contents of Cu and Cr decrease when the content of Ni increases in the matrix of the alloy beneath the corrosion region. The effects of distortion on the corrosion of the CuCrNiAl alloy were discussed, and the acceleration mechanisms of NaCl on the corrosion were also discussed.     

Influence of additive element on surface oxide film ofA356 alloy

The influences of RE-modification and Sr-modification on the hydrogen content and surface oxide film ofA356 aluminum alloy melt were investigated. The hydrogen content of the melt was measured by reduce pressure test. The phases in the surface oxide film were analyzed by X-ray diffractometry （XRD）, and the morphology of the surface oxide film was observed by scanning electronic microscopy （SEM）. The results show that RE-modification reduces the hydrogen content ofA356 aluminum alloy greatly. Contrarily, Sr-modification increases the hydrogen content remarkably. After being treated with RE, a large number of LaAl11O18 consisting of Al2O3 and La2O3, are generated in the surface oxide film of A356 alloy. The surface oxide film of Sr-modification is almost composed of Al2SrO4. According to the results of SEM, the surface oxide film of Sr-modification is very easy to crack, destroy the continuity and compactness of surface oxide film, accelerate the vapor diffusing into the melt, consequently, increase the hydrogen content of A356 alloy melt significantly. But RE-modification makes the surface oxide film compact, and restrains the aluminum exposed to water, so reduces the hydrogen content ofA356 alloy melt.     

Corrosion behavior of Cu-Ni-Ag-Al alloy anodes in aluminium electrolysis

The behavior of Cu-Ni-Ag-Al alloy used as anode for aluminum electrolysis was directly visualized in a two-compartment see-through cell during electrolysis, and its performances were tested at 850℃ in acidic electrolyte molten salts consisting of 39.3%NaF-43.7%AlF3-8%NaCl-5?F2-4%Al2O3 for 40 h in a laboratory cell. The results show that nascent oxygen oxidizes the anodic surface to form oxide film at the beginning of electrolysis. X-ray diffraction analysis of alloy surface show that the oxide film on the anodic surface consists of CuO, NiO, Al2O3,CuAl2O4 and NiAl2O4. However, SEM image shows the oxide film is porous, loose and easy to fall into electrolyte and to contaminate aluminum. The corrosion mechanism of metal anodes was analyzed.     

Improving tribological and corrosion resistance of Ti6Al4V alloy by hybrid microarc oxidation/enameling treatments

A promising duplex coating was prepared by microarc oxidation(MAO) and enameling processes onto polished Ti6A14V alloy. The TiO_2 ceramic coating deposited by MAO was characterized and then combined with an enameling treatment in order to improve the tribological and corrosion resistance of Ti6A14V alloy. The morphology, phase composition, and hardness of MAO and MAO/enameling-coated Ti6A14V alloy were evaluated by scanning electron microscopy(SEM), X-ray diffraction(XRD), and Vickers microhardness tester, respectively.The tribological performance was investigated using a ballon-disk tribometer. The corrosion resistance was studied using immersion tests and potentiodynamic polarization.Wear tests show that the enamel coating on the MAOcoated surface causes a reduction in the friction coefficient.Immersion tests demonstrate that the duplex coating is more effective in improving the corrosion resistance of Ti6A14V than the MAO coating especially at high temperature(80 ℃). Potentiodynamic polarization curves reveal that the corrosion potential of the duplex coating increases by about 250 mV and the corrosion current density is slightly lower than that of the MAO coating. The duplex coating is superior to the stand-alone MAO coating in improving the tribological and corrosion behavior of Ti6A14V.     

高熵合金CrNbTiVZr的微观组织及其在模拟PEMFC环境中腐蚀行为研究

采用真空电弧熔炼和热处理制备了CrNbTiVZr高熵合金,利用XRD、SEM/EDS、动电位与恒电位极化曲线测试及XPS表面分析等方法,研究了高熵合金铸态及退火后的微观组织特征以及合金在模拟PEMFC环境中的电化学腐蚀行为及其钝化膜组成。结果表明,CrNbTiVZr高熵合金的铸态和退火组织均由富集Ti、Nb元素的无序BCC相和富集Cr、V、Zr元素的Laves相组成。铸态和退火合金在模拟PEMFC阴极环境中腐蚀电流密度Icorr均比304SS不锈钢下降一个数量级,具有较好的耐蚀性和稳定性,但在阳极环境中其耐蚀性与304SS相当,其中铸态合金的稳定性较差。合金在阴极环境良好的耐蚀性主要与其表面形成由Cr2O3、Nb2O5、V2O3、Ti2O3及ZrO2组成的致密钝化膜关系密切。     

TiNi及Co合金生物医用材料的腐蚀行为及血液相容性

采用线性极化技术测量了生物医用材料TiNi形状记忆合金, CoCrNiMo和CoCrNiW的腐蚀速率, 并用动态电位扫描法考察了其阳极极化行为. 结果表明, 3种合金钝化电位区宽, 维钝电流密度小, 显示出优异的耐全面腐蚀性能. 电位扫描曲线滞后环面积及腐蚀后扫描电镜观察显示, 两种钴合金具有良好的耐孔蚀性能, 而TiNi的孔蚀倾向较大, 这是因为在TiNi合金表面夹杂的Ti2Ni易受活性阴离子的浸蚀, 而钴合金中的Co, Cr, Mo和W均易在表面形成钝性氧化膜, 抑制孔蚀的发生. 接触角、动态凝血时间和溶血率的测定表明TiNi具有更优的血液相容性, 这可能与其表面的TiO2膜具有较小的表面张力有关.     

PBS人工模拟体液中纤维蛋白原对CoCrNi合金的腐蚀行为的影响

采用电化学测试技术研究了在PBS人工模拟体液中纤维蛋白原对CoCrNiMo和CoCrNiW合金腐蚀行为的影响.结果表明,CoCrNi合金具有良好的耐孔蚀性能,其钝化电位区较宽,且电位扫描曲线滞后环面积小.用EDX能谱对试样进行分析发现,在CoCrNi合金表面形成了Co,Cr,Ni,Mo,W等的钝性金属氧化物膜.纤维蛋白原在CoCrNi合金表面发生了吸附,且吸附的蛋白质分布不连续.用紫外吸收法测量CoCrNiMo和CoCrNiW对纤维蛋白原的吸附量分别为10.628 μg/cm2和9.561μg/cm2.含有纤维蛋白原的PBS人工模拟体液中CoCrNi合金的腐蚀行为可用吸附理论解释.其反应步骤为:(1)氧原子吸附在合金能量较高的活性点上,形成较为稳定的吸附氧化膜;(2)纤维蛋白原扩散到合金表面以形成络合物的形式与氧原子构成竞争吸附;(3)形成的金属络合物向溶液产生电化学迁移,破坏了合金表面的钝性氧化膜,使icorr值显著增大,加剧了合金的腐蚀.     

人工模拟体液中pH值对离子注N人体医用合金腐蚀行为的影响

采用电化学测试技术研究了在人工模拟体液中pH值变化对离子注N人体用SUS316L不锈钢,Co-Cr合金,工业纯Ti和Ti-6Al-4V合金腐蚀行为的影响。结果表明,随着pH值的降低,试样的腐蚀电位负移,SUS316L不锈钢和Co-Cr合金的点蚀电位与缝隙腐蚀电位降低,使材料发生局部腐蚀的敏感性提高,工业纯Ti和Ti-6Al-4V合金的腐蚀电流密度增大,提高离子释放速度,加大对人体的潜在生理危害。     

藤壶附着对海水中金属腐蚀的影响

以室内试验为基础，观察了藤壶从附着到死亡全过程对四种海洋工程用金属材料腐蚀影响，并以海上试验结果作为对照，讨论了藤壶附着影响金属腐蚀的规律及机理。     

STUDIES OF LOW CONCENTRATION CHROMATE PASSIVE FILM FOR ZINC BASED ALLOY COATED STEEL WIRES

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模拟体液中纯钛及Ti6A14V合金的腐蚀行为

采用电化学测试技术研究了人体医用金属材料工业纯钛和Ti6A14V合金在人工模拟体液中的腐蚀行为,结果表明,阳极极化后两种合金均未发现点蚀,工业纯钛的维钝电流密度小于于Ti6A14V合金,前者的阳极极化性能优于后者,Ti6A14V合金缝隙试样在阳极电位超过＋2000mV(vsSCE)后,电流开始急剧增大,发生了缝隙腐蚀;通过电子探针分析发现,在缝隙内Al和V两种元素发生活性溶解。工业纯钛在电位达到＋4000mV/(vsSCE）时仍没有发生缝隙腐蚀。     

变形量对 690 合金在核电一回路水环境中电化学腐蚀行为的影响

目的研究变形量对690合金电化学行为的影响。方法采用动电位极化、电化学阻抗和高温高压浸泡实验,结合扫描电子显微镜(SEM)、X射线光谱仪(EDX)和X射线光电子能谱(XPS),研究不同变形量的690合金传热管在核电模拟液中的腐蚀行为。结果在常温常压下,50%变形量试样的自腐蚀电位比25%变形量试样正140 m V,维钝电流密度显著降低,阻抗模值高出约10倍。高温高压下浸泡后,XPS分析显示,50%变形量试样表面腐蚀产物膜中的Cr2O3含量远高于25%变形量试样,其富Cr内层致密,氧化层更厚。结论 50%变形量的690合金表面形成的钝化膜及腐蚀产物膜对基体的保护作用更强。     

合金元素对新型Co-Al-W合金热腐蚀行为的影响

研究了由γ'-Co₃(Al,W)相沉淀强化的新型钴基Co-Al-W 高温合金在800℃、75% Na₂SO₄+25% NaCl熔盐中的热腐蚀动力学及合金元素Mo、Nb、Ta和Ti对合金热腐蚀行为的影响。研究发现,2Mo、2Nb、 2Ta和2Ti合金比9.8W合金具有更好的抗热腐蚀能力,Mo和Ti对提高合金耐热腐蚀能力的效果比Ta和Nb显著。加入合金元素的合金热腐蚀膜由三层组成,即主要由Co氧化物CoO和Co₃O₄组成的腐蚀膜外层,由合金元素、Al、 Co及W复杂氧化物组成的中间过渡层和由Al、Co氧化物组成的腐蚀膜内层。随着腐蚀时间的增加,中间过渡层厚度逐渐增加,热腐蚀膜内、外层厚度变化不大,但内层致密性逐渐增加。     

不锈钢缝隙腐蚀的微区电化学行为及缝内钝化膜厚度的变化

利用微电极和椭圆偏振仪研究了2Cr13不锈钢在3.5%NaCl 溶液中的缝隙腐蚀历程。实验结果表明,不锈钢的缝隙腐蚀经历了三个阶段一孕育期,发展期和稳定期。缝内 pH 值下降和 Cl~-浓度增加均促进了钝化膜的溶解和加速了缝隙腐蚀。从孕育期向发展期的过渡中,存在着使合金钝化膜破裂的临界缝隙溶液(CCS)。在本试验条件下,其组成大约为 pH=3.5,[Cl~-]:1.2N。在孕育期,缝内钝化膜厚度随时间逐渐减薄,直到钝化膜肢裂,此时,缝隙腐蚀即进入发展期。微电极测试技术和椭圆偏振法可应用于不锈钢缝隙腐蚀过程的原位测试。