Ni—Ti—Nb基形状记忆合金的耐蚀性能

利用磁悬浮水冷铜坩埚冶炼四元Ｎｉ－Ｔｉ－Ｎｂ基形状记忆合金,对板材试样模拟其典型的介质－人体组织液和人工海水,运用ＭＪｏｎｔａｋｌｏ ｍｏｄｅ测定阳极极化曲线,并对该体系合金纯化膜进行了耐蚀行为评价。结果表明：Ｎｉ－Ｔｉ－Ｎｂ基形状记忆合金具有良好遥耐蚀性。合金化元素Ｚｒ提高其耐蚀性,Ｃｒ降低其耐蚀性,而Ｖ对该行为影响不大。     

Untersuchungen über das Korrosionsverhalten von Zirkoniumlegierungen. III. Untersuchungen an Zirkonium-Titan-Legierungen

Investigations into the corrosion behaviour of zirconium alloys III. Investigations on zirconium titanium alloys Investigations on zirconium alloys containing up to 4OO% titanium and, eventually, up to 10% Nb or Mo and small amounts of Fe, Ni and Cr (together 1.5% maximum) have revealed that titanium increases the dissolution power of zirconium for other alloying elements without tending to form two-phase structures. As to corrosion behaviour the better alloys are somewhat superior to other alloys. While titanium impairs the corrosion resistance of pure zirconium with respect to boiling mineral acids (20% HCl, sulphuric or nitric acids) titanium additions up to 10% of improve the corrosion behaviour of ZrNb and ZrMo alloys; alloys of the type Zr10Nb10Ti or Zr10Ti10Ta are comparable, with respect to the corrosion resistance, to pure zirconium. The scaling resistance of zirconium passes through a minimum at a five to ten percent Ti and arrives at its maximum value with 40% Ti. Further improvements may be obtained by addition of 10% Nb.     

Corrosion behavior of Zr–Nb–Cr cladding alloys

Zr-Nb-Cr alloys were used to evaluate the effects of alloying elements Nb and Cr on corrosion behavior of zirconium alloys. The microstructures of both Zr substrates and oxide films formed on zirconium alloys were characterized. Corrosion tests reveal that the corro- sion resistance of ZrxNb0.1Cr （x = 0.2, 0.5, 0.8, 1.1; wt%） alloys is first improved and then decreased with the increase of the Nb content. The best corrosion resistance can be obtained when the Nb concentration in the Zr matrix is nearly at the equilibrium solution, which is closely responsible for the formation of columnar oxide grains with protective characteristics. The Cr addition degrades the corrosion resistance of the Zrl.lNb alloy, which is ascribed to Zr（Cr,Fe,Nb）2 precipitates with a much larger size than β-Nb.     

金属材料在液态Al-Mg合金中的腐蚀行为

本文对 Fe、Ni、Mo、Zr、Nb、Cr、V、Ta 等金属或以它们为基的合金进行了抗液态 Al-Mg 合金腐蚀试验.材料的耐蚀性系借助金相观察测定溶解扩散层厚度和测定蚀损这两项指标来予以评定的。结果表明绝大多数金属及其合金均不耐液态 Al-Mg 合金的腐蚀,仅 Nb 和合金化程度低的Nb 基合金(如 Nb-2Al,Nb-1Cr)以及 Ta 显示山具有良好的耐蚀性.     

The site occupancies of alloying elements in TiAl and Ti3Al alloys

The site occupancies of V, Cr, Mn, Fe, Ni, Zr, Nb, Mo, Ta, Ga and Sn (1–5 at.%) in TiAl alloys with different compositions, and in Ti₃Al with the compositions of Ti–26 at.%Al–(1–2 at.%)X, were measured by the atom location channelling enhanced microanalysis (ALCHEMI) method. For TiAl alloys, the results show that Zr, Nb and Ta atoms invariably occupy Ti sites, while Fe, Ni, Ga and Sn atoms occupy Al sites, the alloy composition having no significant influence on their site preference. By contrast, the site preference of V, Cr, and Mn changes considerably with alloy composition (the Ti/Al ratio in particular), the probability of these elements substituting for Ti decreasing in the above order. For quaternary Ti–Al–V–Cr alloys, the site occupancies of V and Cr do not show much mutual influence. In general, with increasing atomic number, elements in the same period show increasing tendency to substitute for Al, as is the tendency to substitute for Ti for elements in the same group of the periodic table. For Ti₃Al alloys, Ga and Sn atoms occupy Al sites, while V, Cr, Mn, Zr, Nb, Mo and Ta atoms occupy Ti sites, the site preference of V, Cr, Mn and Mo in TiAl alloys being different from that in Ti₃Al. The experimental results are interpreted in terms of a Bragg–Williams-type model and bond-order data obtained from electronic structure calculation. Qualitative agreement between the model and measurements is reached.     

Corrosion behavior of Ti‐xNb‐13Zr alloys in Ringer's solution

Ti‐6Al‐4V alloy has been widely used in restorative surgery due to its high corrosion resistance and biocompatibility. Nevertheless, some studies showed that V and Al release in the organism might induce cytotoxic effects and neurological disorders, which led to the development of V‐free alloys and both V‐ and Al‐free alloys containing Nb, Zr, Ta, or Mo. Among these alloys, Ti‐13Nb‐13Zr alloy is promising due to its better biomechanical compatibility than Ti‐6Al‐4V. In this work, the corrosion behavior of Ti, Ti‐6Al‐4V, and Ti‐xNb‐13Zr alloys (x = 5, 13, and 20) was evaluated in Ringer's solution (pH 7.5) at 37 °C through open‐circuit potential measurements, potentiodynamic polarization, and electrochemical impedance spectroscopy. Spontaneous passivity was observed for all materials in this medium. Low corrosion current densities (in the order of 10^?7 A/cm²) and high impedance values (in the order of 10⁵ Ωcm² at low frequencies) indicated their high corrosion resistance. EIS results showed that the passivating films were constituted of an outer porous layer (very low resistance) and an inner compact layer (high resistance), the latter providing the corrosion resistance of the materials. There was evidence that the Ti‐xNb‐13Zr alloys were more corrosion resistant than both Ti and Ti‐6Al‐4V in Ringer's solution.     

Zr含量对磁控溅射NiCrZr薄膜结构及耐蚀性的影响

目的在316L不锈钢基体表面磁控溅射Ni CrZr薄膜,提高其在3.5%NaCl溶液中的耐蚀性。方法采用非平衡磁控溅射技术,在316L不锈钢基体上,用Ni Cr(原子比80:20)复合靶和纯Zr靶制备了不同Zr含量的Ni CrZr薄膜。采用XRD、原子力显微镜、扫描电镜和Gamry电化学工作站,分别分析了Ni Cr Zr薄膜的物相组成、表面形貌、表面粗糙度、截面形貌、元素组成、厚度以及在3.5%NaCl溶液中的电化学腐蚀性能。结果随着Zr靶功率的增加,薄膜中Zr含量不断增加,薄膜的组织结构不断细化,表面粗糙度由4.91 nm减小到了2.79 nm。薄膜主要由Cr3Ni2、Cr1.2Ni0.8Zr、Cr2Zr、CrO3、Ni Cr O4和ZrO2相组成,表明薄膜容易在空气中氧化。此外,随着Zr含量的增加,与316L基体相比,Ni Cr Zr薄膜在3.5%NaCl溶液中的腐蚀电流减小,腐蚀电位增大。当Zr原子分数为24.73%时,NiCrZr薄膜可以在溶液中形成稳定的钝化膜,从而表现出最佳的耐蚀性,腐蚀电流密度达到最小值13.10nA/cm2,与316L基体相比减小了95%。结论 Zr含量的增加可以使薄膜变得更加细密,有效阻隔电解质与基体的接触,从而提高涂层的耐蚀性。     

In vitro corrosion resistance and cytotoxicity of novel TiNbTaZr alloy

A novel β type Ti35Nb2Ta3Zr alloy with low modulus (48 GPa) was fabricated using vacuum consumable arc melting. The corrosion resistance and cytotoxicity of Ti35Nb2Ta3Zr were evaluated. The open circuit potential, electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization methods were used to determine the corrosion resistance. In Ringer's solution, Ti35Nb2Ta3Zr alloy exhibits better corrosion resistance, as compared to that of Ti6Al4V and Ti. The cytotoxicity tests indicate that the biocompatibility of Ti35Nb2Ta3Zr is as good as Ti and Ti6Al4V which are widely used in biomedical fields. Based on corrosion resistance and cytotoxicity, the novel β type Ti35Nb2Ta3Zr alloy can be considered as a potential biomaterial.     

Composition and processing effects on the electrochemical characteristics of biomedical titanium alloys

The electrochemical behaviour of the Ti–13Nb–13Zr and Ti–6Al–4V ELI alloys with martensitic microstructures was investigated by polarization and electrochemical impedance spectroscopy (EIS) in Ringer’s solution. The impedance spectra were interpreted by a two time-constants equivalent circuit. Both investigated alloys showed high corrosion resistance, but the thin and uniform passive film on the Ti–6Al–4V ELI alloy surface was more protective. The inner barrier and outer porous layer were highly resistant and capacitive. However, thicker and more porous passive film on the Ti–13Nb–13Zr alloy surface may be beneficial for osteointegration. The suitable thermomechanical processing improved the corrosion resistance of Ti–13Nb–13Zr alloy.     

新型TiNbTaZr合金的生物腐蚀性和细胞毒性(英文)

通过真空自耗电弧炉开发一种新型β钛合金Ti35Nb2Ta3Zr,其弹性模量仅为48GPa,探讨该合金的耐腐蚀性能和细胞毒性。在Ringer模拟体液中,通过测量开路电位、极化阻抗谱和极化曲线发现Ti35Nb2Ta3Zr的腐蚀性优于Ti6Al4V和Ti。细胞毒性试验证明Ti35Nb2Ta3Zr的生物相容性与目前临床常用的Ti6Al4V和Ti相当。因此,该新型β钛合金Ti35Nb2Ta3Zr具有良好的耐腐蚀性和生物相容性,未来作为生物材料具有广阔前景。     

Microstructure and properties of novel quinary multi-principal element alloys with refractory elements

Five equiatomic alloys(Ti Zr Hf VNb, Ti Zr Hf VTa, Ti Zr Nb Mo V, Ti Zr Hf Mo V and Zr Nb Mo Hf V) composed of five elements with high melting temperature, respectively were prepared by arc-melting to develop a novel high temperature alloy. The five alloys exhibit different dendritic and interdendritic morphologies. The Ti Zr Hf VNb, Ti Zr Hf VTa and Ti Zr Nb Mo V alloys formed disordered solid solution phases with body-centered cubic structure, and exhibited high compressive strength and good plasticity. The Ti Zr Hf Mo V and Zr Nb Mo Hf V alloys are composed with Laves phase(Hf Mo2) and disordered solid solution phases with body-centered cubic structure. The Ti Zr Hf Mo V and Zr Nb Mo Hf V alloys are harder and more brittle than the other three alloys due to the existence of hard and brittle Laves phases. At high temperatures, the strength decreases to below 300 MPa for the Ti Zr Hf VNb and Ti Zr Hf Mo V alloys. Solution strengthening is the primary strengthening mechanism of the Ti Zr Hf VNb, Ti Zr Hf VTa and Ti Zr Nb Mo V alloys, and brittle Laves phase is the main cause for the low ductility of the Ti Zr Hf Mo V and Zr Nb Mo Hf V alloys.     

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。     

Untersuchungen über das Korrosionsverhalten von Zirkoniumlegierungen I. Verhalten gegenüber wäßrigen Medien

Investigations into the corrosion behaviour of zirconium alloys I. Behaviour in the presence of aqueous media Extensive corrosion research covering 5O Zr alloys have shown that the good corrosion resistance of pure Zr cannot be improved to any greater extent by alloying. Pur Zr as well as most of its alloys have a high corrosion resistance; even in boiling mineral acids (20% H₂SO₄, HNO₃, and HCl) the corrosion rate is below 0.5 g/m²·d and no attack can be recognized in neutral salt solutions. The metal also resists attack by boiling 2O% KOH. Strong attack, however, it caused bv Fe-III-chloride. The metals do not resist attack by HF, while neutral KF attacks but little, however produces pitting. The effect of alloying additions is due to the structure produces by them: pure grain boundaries or very fine heterogeneous structures show good corrosion resistance. Ti, Hf, Sn and small amounts of Nb have little influence, Mo, W, larger amounts Nb and small pt and Re additions give rise to Local cells, while Fe, Cr and Ni have practically no influence.     

合金元素对铸造Fe-Cr铁素体不锈钢耐浓硫酸腐蚀性能的影响

采用电化学技术、浸泡腐蚀及能谱分析等研究了合金元素对铸造Fe-Cr铁素体不锈钢耐浓硫酸腐蚀行为的影响。结果表明:随铬含量的增加,Fe-Cr合金的耐浓硫酸腐蚀性能增强,单一的铬合金化不能使Fe-Cr合金在60℃,98%H2SO4中自钝化;钼能促进Fe-Cr25-Mo合金的钝化和自钝化,随钼含量的增加,Fe-Cr25-Mo合金的耐浓硫酸腐蚀性能增强;辅助合金元素镍、铜可促进Fe-Cr25Mo2合金的钝化和自钝化,而钛、铌的影响不大。     

合金化元素Ti对Laves相Cr_2Nb力学性能及耐蚀性的影响

采用真空非自耗电弧熔炼工艺制备了Cr2Nb-XTi(X=5,10,15,at%)合金,利用光学显微镜(OM),X射线衍射(XRD)仪,扫描电镜(SEM)对电弧熔炼态铸锭的组织进行了研究,探讨了合金化元素Ti的含量对Laves相Cr2Nb力学性能及耐蚀性的影响。结果表明:3种成分的电弧熔炼态合金凝固组织主要由C15-Cr2(Nb,Ti)相和六方的β-(Ti,Nb)以及体心立方结构的β-(Nb,Ti)相组成。在5Ti和10Ti合金冷速较小的铸锭上部凝固组织中出现了亚稳相C14-Cr2(Nb,Ti)。通过对合金力学性能研究表明,随合金化元素Ti含量的增加,Laves相Cr2Nb合金的显微硬度逐渐降低,断裂韧性增大,当Ti含量达到15at%时,合金的断裂韧性达到了3.1 MPa·m1/2,比单相Laves相Cr2Nb提高1倍。另外,对腐蚀性能的测试表明,Ti含量增加材料腐蚀性能下降,但15Ti合金仍表现出良好的耐蚀性。     

Untersuchungen über das Korrosionsverhalten von Zirkoniumlegierungen II. Verhalten bei Wasserdampfkorrosion

Investigation into the corrosion behaviour of zirconium alloys. 11. Behaviour under steam corrosion conditions An investigation into the corrosion behaviour of about 50 Zr alloys in high pressure high temperature steam (240 atm, 400°C) and hot air (4OO°C) has revealed a clear correlation between the behaviour in the two media. Alloys characterized by lower scaling susceptibility are also less susceptible to corrosion in steam, while, on the other hand, thicker scale layers tend to reduce hydrogen embrittlement. From the alloying additions studied Sn, Fe, Cr and Ni have a clearly favourable influence and W may have a similar effect. Ti has an outspoken negative influence on the behaviour in steam (spalling off of the scale) and Si, too, is deleterious because the SiO₂ being formed is soluble in steam, so that the scale layers retain their penetrability. Mo cannot be recommended either, while Nb is favourable in particular because of its grain refining effect. The favourable effect of Cu additions has been confirmed. Alloys with Fe, Cr and Ni and single types with Mo, Nb and Cu are superior to pure Zr with respect to steam resistance and are in part superior to Zircaloy 2 with respect to their mechanical strength.     

The first-principles design of ductile refractory alloys

The purpose of this work is to predict elastic and thermodynamic properties of chromium-based alloys based on first-principles calculations and to demonstrate an appropriate computational approach to develop new materials for high-temperature applications in energy systems. In this study, Poisson ratio is used as a screening parameter to identify ductilizing additives to the refractory alloys. The results predict that elements such as Ti, V, Zr, Nb, Hf, and Ta show potential as ductilizers in Cr while Al, Ge, and Ga are predicted to decrease the ductility of Cr. Experimental evidence, where available, validates these predictions. The purpose of this work is to predict elastic and thermodynamic properties of chromium-based alloys based on first-principles calculations and to demonstrate an appropriate computational approach to develop new materials for high-temperature applications in energy systems. In this study, Poisson ratio is used as a screening parameter to identify ductilizing additives to the refractory alloys. The results predict that elements such as Ti, V, Zr, Nb, Hf, and Ta show potential as ductilizers in Cr while Al, Ge, and Ga are predicted to decrease the ductility of Cr. Experimental evidence, where available, validates these predictions.     

Untersuchung über das Korrosionsverhalten von Zirkoniumlegierungen. IV. Das Lochfraßverhalten Zirkoniumlegierungen

Investigation into corrosion behaviour of zirconium alloys. IV-Pitting behaviour of zirconium alloys Electrochemical investigations into the resistance of a number of Zr-alloys in different solutions against pitting corrosion have shown that additions of Va- and VIa-group metals and in particular Ti improve the resistance of pure Zr. Metals forming local elements decrease pitting corrosion resistance. Minor amounts of Fe, Ni and Cr have practically no influence. The pitting corrosion resistance of Zr and its alloys decreases with increasing concentration of chloride ions in the solutions. Additions of SO₄-ions retard the beginning of the pitting but do not shift the pitting corrosion potential. NO₃-ions on the other hand produce a real inhibition. Newly developed methods for the quick determination of the pitting corrosion potential were very useful for the described investigations.     

Einflüsse von Mo,V, Nb,Ti, Zr und deren Karbiden auf die Korrosion und Wasserstoffaufnahme von Eisen in H2S-haltigen Lösungen

Effects of Mo, V, Nb, Ti, Zr and their carbides on the corrosion and hydrogen uptake of iron in H₂S-solutions Effects of the transition metals Mo, V, Nb, Ti, Zr and their carbides as well as of phosphorous on the corrosion and hydrogen uptake of iron in acid to weakly acid NaCl solutions with and without H₂S are discussed. Investigations were carried out on binary, ternary and quaternary iron based alloys, using electrochemical and surface analytical methods. No specific effect of one of the alloying elements or the carbides on the corrosion or hydrogen uptake is observed. Due to the experimental conditions, sulphur and oxygen enriched surface scales form, by which the kinetics of the corrosion processes are determined. The alloying elements are enriched on the iron surface only as a carbide. Phosphorous is enriched as a phosphide at low pH and as a phosphate at higher pH. H₂S and phosphides increase the corrosion rate and hydrogen uptake. In pure iron or low strength iron alloys, at the very high H₂S affected hydrogen activities new lattice defects are induced permanently resulting in extremely high hydrogen concentrations.     

Ti—Mn基储氢合金电化学容量的一个简易模型

针对Ti-Mn基储氢合金循环稳定性差这一问题。提出了一关于Ti-Mn基储氢合金循环稳定性的简易模型,并引入两个表示储氢合金本征属性的因子;活化特征因子β和容量衰减因子A。采用该模型可以描合金活化与容量衰减的全过程。实验测量了Ti0.26Zr0.07V0.21Mn0.1Ni0.3Cr0.03和Ti0.07V0.19Mn0.1Ni0.3Cr0.05合金的活化与充放电循环过程,理论与实验有较好的吻合关系。