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.     

Diffusion Barrier Selection from Refractory Metals (Zr,Mo and Nb) Via Interdiffusion Investigation for U-Mo RERTR Fuel Alloy

U-Mo alloys are being developed as low enrichment monolithic fuel under the Reduced Enrichment for Research and Test Reactor (RERTR) program. Diffusional interactions between the U-Mo fuel alloy and Al-alloy cladding within the monolithic fuel plate construct necessitate incorporation of a barrier layer. Fundamentally, a diffusion barrier candidate must have good thermal conductivity, high melting point, minimal metallurgical interaction, and good irradiation performance. Refractory metals, Zr, Mo, and Nb are considered based on their physical properties, and the diffusion behavior must be carefully examined first with U-Mo fuel alloy. Solid-to-solid U-10 wt.%Mo versus Mo, Zr, or Nb diffusion couples were assembled and annealed at 600, 700, 800, 900 and 1000 °C for various times. The interdiffusion microstructures and chemical composition were examined via scanning electron microscopy and electron probe microanalysis, respectively. For all three systems, the growth rate of interdiffusion zone were calculated at 1000, 900 and 800 °C under the assumption of parabolic growth, and calculated for lower temperature of 700, 600 and 500 °C according to Arrhenius relationship. The growth rate was determined to be about 10³ times slower for Zr, 10⁵ times slower for Mo and 10⁶ times slower for Nb, than the growth rates reported for the interaction between the U-Mo fuel alloy and pure Al or Al-Si cladding alloys. Zr, however was selected as the barrier metal due to a concern for thermo-mechanical behavior of UMo/Nb interface observed from diffusion couples, and for ductile-to-brittle transition of Mo near room temperature.     

Einflüsse von Mo,V, Nb,Ti, Zr und deren Karbiden auf die Korrosion und Wasserstoffaufnahme des Eisens in Schwefelsäure

Effects of Mo, V, Nb, Ti, Zr and their carbides on the corrosion and hydrogen uptake of iron in sulphuric acid The effects of Mo, V, Nb, Ti, Zr and their carbides on the corrosion and hydrogen uptake of iron in 1 M H₂SO₄/N₂/25°C were investigated by electrochemical and surface analytical methods using binary and ternary Fe-Me alloys with about 0.2 at.-%Me. Due to the experimental conditions, no protective surface layers formed. The transition metals were enriched at the iron surface only as a carbide or oxicarbide. Mo or Zr were not markedly enriched. The corrosion current density and the hydrogen activity were decreased only by Mo or Zr. Hydrogen permeation measurements were analysed in terms of the trapping theory. The average binding energy of shallow traps for hydrogen increases with increasing atomic radius of the substituted alloying elements in the order V, Mo, Ti, Nb and Zr. Correspondingly, the hydrogen diffusion coefficient (after saturation of the deep traps) decreases and the hydrogen solubility increases. The steadystate hydrogen permeation rate remains almost unaffected. The total hydrogen content is determined by the density of deep traps and thus mostly independent of the external hydrogen activity. The trapping effect of iron is strongly increased by dissolved Zr or Nb or in the presence of fine dispersed carbides as VC_x. The effect of coarse carbide particles at a lower density is small.     

Effect of Yttrium on Microstructure and Properties of High Temperature Alloys

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金属材料中微量氢和氧的分析

叙述了惰性气氛熔化法测定金属材料中微量氢和氧的条件和方法。着重研究影响分析限的空白因素及降低空白的方法和分析限，制定出了Ｔｉ，Ｚｒ，Ｈｆ，Ｔａ，Ｎｂ，Ｗ，Ｍｏ，Ａｌ，Ｃｕ等及其合金中微量氢和氧的分析方法。     

Investigation of mechanical and diffusion properties in bcc Ti−Nb−Zr−Sn alloys via a high-throughput method

The mechanical and diffusion properties of bcc Ti−Nb−Zr−Sn alloys in the Ti-rich corner were analyzed through a high-throughput method with the combination of nanoindentation and diffusion couple techniques. Nine groups of quaternary Ti−Nb−Zr−Sn diffusion couples were prepared after annealing at 1273 K for 25 h. The composition-dependent mechanical properties were determined by nanoindentation and electron probe microanalysis (EPMA) techniques. Moreover, the corresponding interdiffusion coefficients were confirmed from the composition gradients of the quaternary diffusion couples using a pragmatic numerical inverse method. A composition-dependent database on the mechanical and diffusion properties was utilized to discuss the processability during the hot working. The results reveal that the solute elements Nb and Sn are strictly controlled to increase the hardness and wear resistance of Ti−Nb−Zr−Sn alloys, and the additional element Zr is mainly useful to improve the processability during the hot working.     

钛合金中原子迁移性质的第一原理研究

钛合金作为一种重要的航空材料,具有比强度高,耐蚀性好等优异性能,并具有一定的高温蠕变抗力。但是在更高温度下,有限的蠕变抗力限制了钛合金的进一步应用。实验研究表明,钛合金稳态蠕变过程蠕变激活能与合金的表观扩散激活能非常接近,说明原子的扩散与蠕变过程密切相关。本文采用第一性原理的方法,计算了钛合金中常见的杂质及合金原子的迁移能垒。结果表明,对以空位机制扩散的合金原子,其在基面内迁移的能垒从高到低为Al、V、Ti、Sn、Ta、Mo、Nb、Zr,面间原子迁移由难到易为Al、Sn、V、Ti、Ta、Mo、Nb、Zr。以间隙机制迁移的Co、Fe、Ni迁移能垒较低,与实验观测到的这些原子为快扩散原子相符。     

Comparison of corrosion behaviour of thermal sprayed and diffusion‐coated materials

In this paper, the corrosion behaviour of thermal sprayed and diffusion‐coated materials are compared. The result of the high temperature corrosion test shows that the layers with NiCr applied by atmospheric plasma spraying (APS) and high velocity oxy fuel flame spraying (HVOF) are more resistant than the layers with NiCrBSi and Cr₃C₂/ NiCr. Furthermore, the layer with NiCr on 15 Mo 3 is more resistant than that on 13 CrMo 44 as base material. The corrosion behaviour of Al, Cr, and Cr/Si diffusion‐coated materials on 13 CrMo 44‐ are better than those same diffusion coatings on 15 Mo 3‐surfaces. In particular, the Cr diffusion‐coated materials show the highest corrosion resistances in this work. Also, the diffusion‐coated materials have higher resistances than thermal sprayed materials in HCl‐H₂O‐O₂‐N₂‐atmosphere.     

Influence of Zr content on microstructure and mechanical properties of implant Ti–35Nb–4Sn–6Mo–xZr alloys

The influence of Zr content on the microstructure and mechanical properties of implant Ti–35Nb–4Sn–6Mo–xZr (x=0, 3, 6, 9, 12, 15; mass fraction) alloys was investigated. It is shown that Ti–35Nb–4Sn–6Mo–xZr alloys appear to have equiaxed single β microstructure after solution treatment at 1023 K. It is found that the grains are refined first and then coarsened with the increase of Zr content. It is also found that Zr element added to titanium alloys has both the solution strengthening and fine-grain strengthening effect, and affects the lattice parameters. With increasing the Zr content of the alloys, the strength increases, the elongation decreases, whereas the elastic modulus firstly increases and then decreases. The mechanical properties of Ti–35Nb–4Sn–6Mo–9Zr alloy are as follows: σ_b=785 MPa, δ=11%, E=68 GPa, which is more suitable for acting as human implant materials compared to the traditional implant Ti–6Al–4V alloy.     

Beitrag zum physikalischen und korrosionschemischen Verhalten von IVa-Metallegierungen

The physical and corrosion-chemical behaviour of IVa metal alloys The stability of titanium in respect of non-oxidant acids can be considerably increased by alloying it with Zr, Hf, Nb, Mo or Re. In the case of Zr, Hf, Nb and Ta, a decisive improvement of the corrosion behaviour can only be attained if the At-percentage of these metals in the alloys exceeds 50 pC. In the case of molybdenum, a content from 20 pC upwards has already a markedly passivating effect. But the improvement in corrosion properties must be bought at the price of poorer machinability. A particularly effective alloying metal, even in small quantities, is Rhenium. An excellent corrosion resistance and, at the same time, good machinability can be attained with ternary Ti-Mo-Ta alloys (with Mo + Ta accounting for some 20 At-pC) and with a Ti-12Mo-1Re alloy. The alloying of titanium with Zr, Hf, V, Cr or Mo is apt to cause, in some cases, a considerable deterioration in the scaling resistance of titanium. Improvements can be obtained by using small quantities of Nb, W and particularly Ta. Ti-Ta alloys with Ta contents up to 10 At-pC still have a good scaling resistance at 900° C.     

Spraying of Metallic Powders by Hybrid Gas/Water Torch and the Effects of Inert Gas Shrouding

A hybrid DC arc plasma torch, combining water and gas stabilization, offers a high flexibility in plasma characteristics. These can be controlled in a wide range by the torch operational parameters, such as arc current and secondary gas flow rate. In this study, their influence on plasma spraying of tungsten and copper was investigated. To suppress the in-flight oxidation of the metals, inert gas shrouding was applied. In-flight particle diagnostics and analysis of free-flight particles and coatings was performed for spraying experiments in the open atmosphere and with argon shrouding. Both in-flight particle behavior and coating properties were found to be sensitive to the torch parameters. The application of shrouding was found to affect particle in-flight parameters, reduce the oxide content in the coatings and generally improve their properties, such as thermal conductivity. However, a different degree of these effects was observed for copper and tungsten.     

Schutz von hochschmelzenden Metallen und Graphit gegen Oxydation und Heißkorrosion bis 1500°C durch aufgesinterte MoSi2-Schichten

Protection of refractory metals and graphit against oxidation and hight temperature corrosion up to 1500 °C by sintered MoSi₂ coatings MoSi₂ coatings applied by plasma spraying or isostatic hot pressing protect Ta and Nb against oxidation by forming a glassy coating of SiO₂. Diffusion of Si to the bulk metal is slow because of the low mobility of Si in the intermediate layers of Me₅Si₃ which contain Nb and Ta; the oxidation rate depends from the slow oxygen permeation through the glass layer. A 200 μm silicide layer on Ta would, accordingly, provide some thousand hours' protection at 1500 °C. Silicide coatings on graphite, however, must be protected against carburization by applying a diffusion barrier; investigated for this purpose. The useful life data calculated on the basis of the diffusion data have been registered during oxidation tests too: silicide coated Ta and Nb withstood oxidation by air at 1500 °C for 1000 hrs, and at 1200 °C for 4000 hrs; carbon with an intermediate TiC layer resisted oxidation at 1500 °C for 400 hrs. Under temperature cycling conditions it is indispensable to adjust the coefficient of dilatation of the glassy coating to that of the base material by adding GeO₂.     

UO2与Zr包壳的扩散反应阻挡层

UO₂-Zr 燃料体系广泛应用于压水反应堆和各种研究试验堆中,但在反应堆运行工况下,UO₂燃料与 Zr 包壳会发生扩散反应。在 UO₂燃料与 Zr 包壳之间制备一层氧扩散阻挡层,阻止 UO₂中的氧原子向 Zr 包壳中扩散,是提高核燃料元件的安全性和使用寿命的方法之一。进行理论计算,结果表明 Nb 和 Cr 是最具潜力的氧扩散阻挡层材料。采用电弧离子镀技术制备 Nb、Cr、Nb / Cr 三种涂层,通过对这三种扩散阻挡层的研究,发现在 UO₂燃料上制备一层金属涂层能够有效阻止 UO₂与 Zr 包壳的扩散反应,Nb 涂层具有较好的氧阻挡能力,但是 Nb 与 Zr 在试验条件下能够无限固溶,形成 Nb 与 Zr 的双相结构。 Cr 与 UO₂ 燃料和 Zr 包壳均有较好的相容性,但是 Cr 与 O 原子的亲和性比 Nb 好,Cr 涂层中 O 原子浓度比 Nb 涂层中的 O 原子浓度高。Nb / Cr 复合涂层是一种比较理想的扩散阻挡层,且靠近 UO₂ 燃料一侧为 Nb 涂层,靠近 Zr 包壳一侧为 Cr 涂层。 研究结果表明 Nb / Cr 复合涂层作为氧阻挡层材料,在氧阻挡能力上优于 Nb 涂层和 Cr 涂层。扩散反应阻挡层的研究可为提高核燃料元件的安全性和使用寿命提供一定参考数据。     

Effect of Nb and Mo on the Microstructure,Mechanical Properties and Ductility-Dip Cracking of Ni–Cr–Fe Weld Metals

A series of Ni–Cr–Fe welding wires with different Nb and Mo contents were designed to investigate the effect of Nb and Mo on the microstructure, mechanical properties and the ductility-dip cracking susceptibility of the weld metals by optical microscopy(OM), scanning electron microscopy, X-ray diffraction as well as the tensile and impact tests. Results showed that large Laves phases formed and distributed along the interdendritic regions with high Nb or Mo addition. The Cr-carbide(M_(23)C_6) was suppressed to precipitate at the grain boundaries with high Nb addition. Tensile testing indicates that the ultimate strength of weld metals increases with Nb or Mo addition. However, the voids formed easily around the large Laves phases in the interdendritic area during tensile testing for the weld metal with high Mo content. It is found that the tensile fractographs of high Mo weld metals show a typical feature of interdendritic fracture. The high Nb or Mo addition, which leads to the formation of large Laves phases, exposes a great weakening effect on the impact toughness of weld metals. In addition, the ductility-dip cracking was not found by OM in the selected cross sections of weld metals with different Nb additions. High Nb addition can eliminate the ductility-dip cracking from the Ni–Cr–Fe weld metals effectively.     

热喷涂 Mo 及 Mo 基复合涂层研究进展

热喷涂Mo及Mo基复合涂层因熔点高、硬度高、耐磨损、耐腐蚀及高温性能稳定等诸多特点,而广泛应用于机械零件生产及表面修复。随着以资源有效利用和机械产品再制造为一体的可持续发展战略不断推进,此类涂层将拥有更为广阔的应用前景。首先介绍了国内外在热喷涂Mo及Mo基复合涂层方面的研究发展和应用现状;随后依据热喷涂技术的发展历程,分别总结论述了不同热喷涂技术,即火焰喷涂(普通火焰喷涂、高速火焰喷涂)、等离子喷涂(普通等离子喷涂、超音速等离子喷涂、微束等离子喷涂、低压等离子喷涂)及电热爆炸喷涂中,Mo及Mo基复合涂层的制备工艺、涂层性能特点及存在的问题;接着指出了热喷涂Mo及Mo基复合涂层在新概念武器、航空航天等高科技领域的应用前景。最后,就进一步拓展Mo及Mo基复合涂层在贫油减摩、高温高速耐磨、高温耐腐蚀及氧化等复杂环境下的应用范围,结合热喷涂技术的研究热点及发展方向,指出了未来热喷涂Mo及Mo基复合涂层在材料组分设计和工艺优化研究中应重点关注的方面。     

12吨级Ti80合金铸锭的成分均匀性及其偏析规律研究

随着海洋装备的大型化发展及其各项性能的提升,对高均匀超大规格钛合金铸锭的研发有了更加迫切的需求。本文利用MeltFlow模拟获得优化的熔炼工艺,制备出国内第一个12吨级Ti80合金铸锭,并完成2炉稳定性验证。成分检测结果表明,铸锭头、中、尾3点成分极差小于1000ppm,冒口17点成分极差小于3000ppm,成分均匀性与现行5吨级铸锭基本相当。分析冒口径向成分分布规律发现,Al、Nb和Mo元素呈现边部高、心部低,从边部到心部逐渐降低的趋势,而Zr元素的分布规律则与之相反。利用EDS对不同部位晶内和晶界的微区成分分析发现,Nb、Mo元素呈现晶内高、晶界低,而Al、Zr元素呈现晶内低、晶界高的分布规律。其中,Nb、Mo、Zr元素的宏、微观偏析规律基本一致,即随着凝固的进行,固相中Mo、Nb含量逐渐降低,Zr含量逐渐升高。然而,Al元素的宏、微观偏析规律正好相反,分析认为主要是由于Al元素的饱和蒸气压较高,与其他合金元素相比更容易挥发,在长时间、高真空熔炼和溶质再分配的共同作用下,铸锭中的宏、微观偏析规律出现不一致的现象。     

等离子喷涂Al-Mo涂层的高温硫化和氧化行为研究

烧嘴是水煤浆气化系统的重要部件。运行过程中的高温硫化经常导致烧嘴提前失效,进而影响设备的安全稳定运行。本文采用等离子喷涂方法制备了Mo为粘结层的Al-Mo涂层,测量其在973 K, 1073 K and 1173 K的硫化和氧化行为,并与Mo涂层和Inconel合金进行比较。结果表明Al-Mo涂层的高温硫化抗力和氧化抗力均优于Mo涂层,高温硫化抗力优于Inconel合金。该涂层的提出为喷嘴失效问题的解决提供了便捷、有效的技术方案。     

稀有难熔金属中氢的测定

叙述了脉冲加热、惰性气氛熔化法测氢的原理及有关试验条件的选择。结果表明，用Ｓｎ作熔池，选择合适的功率（Ｔｉ、Ｚｒ、Ｈｆ为２５００Ｗ，Ｔａ、Ｎｂ为２７００—２８００Ｗ）、试样量和加热时间（Ｔｉ、Ｚｒ、Ｈｆ及其合金３０ｓ，Ｔａ、Ｎｂ及其合金４０ｓ），可对Ｔｉ、Ｚｒ、Ｈｆ．Ｔａ、Ｎｂ及其合金中的氢进行分析，该法准确度高，优于真空热提取法。     

RF induction plasma spraying: State-of-the-art review

Radio frequency (RF) induction plasma technology has gained wide acceptance for the preparation of plasma spray coatings and structural free-standing parts of metals, ceramics, and metal-matrix composites. Its principal advantages are the relatively large volume and low velocity of the discharge, which coupled with the ease of axial injection of the powder into the plasma allows for the melting of relatively large particles at high throughput. The absence of electrodes offers the added advantage of ease of operation under a wide range of conditions at atmospheric and low pressure, with an inert, reducing, or oxidizing atmosphere. Highlights of recent advances in induction plasma melting and deposition of materials are presented in this article. The first section deals with advances in induction plasma spraying technology including system and torch design. This is followed by a brief overview of mathematical modeling and diagnostic studies of the induction plasma deposition process. Examples of applications of induction plasma spraying for the preparation of protective coatings and fiber-reinforced metal matrix composites are presented in the final section.     

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.