多级深度还原法制备Ti6Al4V合金粉体的基础研究

目前Ti6Al4V合金粉体的生产方法主要有雾化法、机械合金法和氢化脱氢法,它们都以Kroll法生产海绵钛为基础。使用钛的氧化物作为原料的熔盐电解法和金属热还原法仍处于研究阶段。本文依据变价金属Ti和V的氧化物在还原过程中逐级还原的特性,提出使用金属氧化物(TiO₂, V₂O₅)作为原料的多级深度还原法制备Ti6Al4V合金粉体的新思路。首先计算了TiO₂-V₂O₅-Mg-Ca体系的吉布斯自由能变,结果表明先进行镁热自蔓延反应,后进行钙热深度还原反应制备Ti6Al4V合金粉体在热力学上具备可行性。然后通过实验进行了的验证。镁热自蔓延反应产物酸浸后除去MgO可得到氧含量为15.84%的多孔Ti-Al-V-O前驱体。配入金属Ca后进行深度脱氧可得到低氧Ti6Al4V合金粉体(Al: 6.2wt.%, V: 3.64wt.%, O: 0.24wt.%, Mg: 0.01wt.%, Ca: < 0.01wt.%)。     

通过多级深度还原制备Ti6Al4V合金粉体的新工艺（英文）

介绍了一种以TiO_2、V_2O_5和Al为原料,Mg和Ca作为还原剂的通过多级深度还原法制备Ti6Al4V合金粉体的新方法。与传统的冶金方法制备Ti6Al4V粉末相比,该方法具有更高的生产效率和更少的环境污染。自蔓延初级还原实验的结果表明,Mg比Ca更适合在此阶段作为还原剂,当使用Mg作为还原剂时可以得到氧含量为6.74%～16.4%(质量分数,下同)的多孔Ti-Al-V-O前驱体。通过进一步的钙热深度还原(1173 K下保持3.5 h)可以得到含氧量为0.24%的Ti6Al4V粉体。     

多级深度还原法制备Ti6Al4V合金粉体

依据变价金属Ti和V的氧化物在还原过程中逐级还原的特性,提出使用金属氧化物(TiO_2, V_2O_5)作为原料的多级深度还原法制备Ti6Al4V合金粉体的新思路。首先计算了TiO_2-V_2O_5-Mg-Ca体系的吉布斯自由能变,结果表明先进行镁热自蔓延反应,后进行钙热深度还原反应制备Ti6Al4V合金粉体在热力学上具备可行性。然后通过实验进行了验证。镁热自蔓延反应产物酸浸后除去MgO可得到氧含量为15.92%的多孔Ti-Al-V-O前驱体。配入金属Ca后进行深度脱氧可得到低氧的Ti6Al4V合金粉体(Al:6.2%, V:3.64%, O:0.24%, Mg:0.01%, Ca含量0.01%,质量分数)。     

气–液反应激光原位增材制造TiN增强钛基复合材料组织结构及力学性能研究

本文采用选区激光熔化(SLM)工艺制备了Ti6Al4V合金,并系统研究了激光能量密度(LED)对其致密度、显微硬度、压缩强度和塑性的影响。获得了SLM制备Ti6Al4V合金的最佳LED工艺窗口为84.8–163.6 J/mm_³。在最佳LED窗口内,在不同N₂浓度(3 vol.%、10 vol.%、30 vol.%)工作气氛中,以气–液反应方式SLM制备了TiN为增强相的Ti6Al4V基复合材料。该新工艺制备复合材料的原理为：钛合金高温熔池附近的N₂裂解为N原子/离子,N与熔融状态的Ti原位反应生成均匀分散的TiN增强相,并与熔化–凝固过程中的Ti合金基体复合,最终以SLM逐层成形的方式制备出TiN增强钛基复合材料。本文探究了N₂浓度对钛基复合材料组织结构和力学性能的影响规律。其中,3 vol.%的N₂工作气氛中SLM成形的复合材料的强度和塑性同时得到提升,阐述了其强韧化机理。     

杂质Ca对Al-5Mg填充合金凝固组织及力学性能的影响

结合拉伸试验和冲击试验,采用SEM、EDS和XRD等分析方法研究了杂质元素Ca对铝镁焊接填充合金铸态凝固组织和力学性能的影响。结果表明,Ca元素的存在改变了合金相组成。当Ca小于0.28%,合金中晶界富集由块状(Ti,Cr)₂Ca(Al,Mg)₂₀金属间化合物相。当Ca大于等于0.28%时,块状(Ti,Cr)₂Ca(Al,Mg)₂₀相和不连续条状Al₂Ca相共同在晶界富集。随Ca含量的增加,合金中块状相和条状相尺寸逐渐增大,数量逐渐增加。合金抗拉强度随Ca元素的增加先升高再降低,Ca含量0.28%时抗拉强度达到峰值。Ca小于0.28%时,合金塑性和冲击韧性缓慢下降,当Ca大于0.28%时,条状Al₂Ca相和块状(Ti,Cr)₂Ca(Al,Mg)₂₀相在晶界共存,低应力下两相破裂成为裂纹源,Al₂Ca硬脆相削弱了晶间结合强度,合金塑韧性大幅下降。合金拉伸或冲击断口由穿晶延性断裂(Ca<0.28%)转变为脆性断裂(Ca>0.28%)。Ca含量0.28%为合金韧脆转变点。     

多级深度还原法制备Ti6Al4V合金粉体机理的研究

本文对多级深度还原法制备Ti6Al4V合金粉体过程中的镁热自蔓延反应机理进行了探究。使用XRD，SEM，ICP以及激光粒度分析仪对产物进行了表征。结果表明:Al和V元素会固溶进入Ti基体中使其衍射峰向高角度偏移；“预烧结-还原-烧结”和“还原-烧结”两种反应模式是造成产物形貌差异的主要原因；自蔓延产物的体积平均经D[4.3]和体系的燃烧温度正相关；残留的Mg主要以MgTiO3和MgAl2O4等复合物的形式存在。使用金属Ca进行深度还原可以将最终产物中的Mg和O含量分别降低至0.01wt.%和0.24wt.%。     

过渡元素改善B4C/Al材料界面润湿性的机理研究

B₄C/Al复合材料是目前最理想的中子吸收材料,但工业上常用的液态搅拌法制备过程中存在着界面润湿性差的问题。本文结合实验及第一性原理的方法,通过研究Al(111)/AlB₂(0001)和Al(111)/TiB₂(0001)界面的结构来分析工业上添加过渡元素Ti对B₄C/Al界面润湿性的改善机制。通过计算发现,Al(111)/TiB₂(0001)界面相对Al(111)/AlB₂(0001)界面具有更高的粘附功值,说明其界面结合更强。进一步对比Ti掺杂二硼化物和AlB₂的偏态密度结构,发现Ti掺杂体具有较低的反键态,表明Ti-3d和B-2p轨道电子杂化后,在B、Ti原子间形成了较强的化学键,从而促进了Al(111)/TiB₂(0001)界面处的强结合作用,提高了Al(111)/TiB₂(0001)界面粘附功,故而改善了B₄C/Al界面的润湿性。根据同样的理论依据,V掺杂体也具有较低的反键态,V和B之间的强结合效果或许能够改善B₄C/Al界面的润湿性,成为又一理想的溶体改性掺杂元素。     

添加RE和Ti元素对Zn-2.5Al-3Mg合金微观结构和耐腐蚀性能的影响

采用XRD、SEM、TEM和XPS等研究了RE和Ti元素对Zn-2.5Al-3Mg合金微观结构和耐蚀性的影响。结果表明,Zn-2.5Al-3Mg合金的微观结构由富Zn相、二元共晶（Zn-MgZn₂/Mg₂Zn₁₁）和三元共晶（Zn/Al/Mg₂Zn₁₁）组成,而含有RE和Ti元素的合金中出现了新相(Ce_1-xLa_x)Zn₁₁和Al₂Ti。电化学阻抗谱表明,相对于Zn-2.5Al-3Mg合金,Zn-2.5Al-3Mg-0.1RE-0.2Ti合金的耐蚀性得到了显著的提高。XPS分析结果表明,RE元素的添加促进腐蚀产物Zn₅(CO₃)₂(OH)₆和MgAl₂O₄的形成,而RE和Ti元素的同时添加促进腐蚀产物 Zn₅(CO₃)₂(OH)₆、ZnAl₂O₄和MgAl₂O₄的形成,且都抑制了疏松多孔ZnO的生成。Zn₅(CO₃)₂(OH)₆、ZnAl₂O₄和MgAl₂O₄能够很好地粘附在试样表面,提供一层致密的保护层,从而提高Zn-2.5Al-3Mg合金的耐腐蚀性。     

SiCp颗粒含量对SiCp/ Mg–5Al–2Ca复合材料组织与性能的影响

本研究通过搅拌铸造法制备了三种不同体积分数(2%,5%, 10%)的SiCp/Mg–5Al–2Ca复合材料,并在673 K下进行了热挤压。铸态复合材料中,少量SiCp颗粒的加入就能破坏了Al₂Ca相沿基体合金晶界分布并有效细化Al₂Ca相析出尺寸。随着SiCp体积分数的增高,Al₂Ca相尺寸有所降低,但不明显。经过热挤压后,Al₂Ca相破碎并沿挤压方向排布,基体合金晶粒得到细化。晶粒尺寸以及Al₂Ca相尺寸随着SiCp体积分数的增高呈微小降低。与单组元基体合金相比较,挤压态SiCp/Mg–5Al–2Ca复合材料的屈服强度和加工硬化率随着SiCp体积分数的增高而逐渐增高,而延伸率则逐渐下降;抗拉强度最大值则出现在SiCp体积分数为5%时。复合材料中SiCp颗粒以及Al₂Ca相的脱粘以及开裂是导致复合材料断裂的主要原因。     

钛合金氧碳共渗层性能

将经磨平、抛光、超声波乙醇清洗、吹干的Ti6Al4V合金样品放入专用设备中进行氧碳共渗。分别采用X射线衍射仪（XRD）、扫描电子显微镜（SEM）、能谱仪（EDS）、HV硬度仪、万能材料试验机对渗层的物相、显微组织形貌、成分、硬度、摩擦磨损、力学性能进行分析。XRD结果表明,渗层中出现TiC和TiO_x相。氧碳共渗改变了原Ti6Al4V合金的组织,渗层的显微组织明显区别于Ti6Al4V的渗碳、渗氧以及在CO₂气氛下处理的组织。EDS结果表明,C、O元素含量呈现梯度变化。相比基体硬度,渗层表面硬度提高了3.8倍,渗层硬度呈梯度变化。氧碳共渗改变了原始样的粘着磨损和摩擦状态,渗层样表面只有轻微的摩擦痕迹、无磨损。氧碳共渗后磨损量是原始样的3.5%,摩擦系数约为原始样的30%。渗层样在拉断过程中,外表面有一定的剥落,表面布满裂纹,样品的强度略有下降,断面延伸率和断面收缩率与原始样相当。Ti6Al4V合金经过氧碳共渗后,提高了表面硬度,降低了磨损率和摩擦系数,基本保持了基体的力学性能。     

The examination of corrosion behaviors of hap coated Ti implant materials and 316L SS by sol-gel method

In this research, hydroxyapatite (HAP) coatings have been produced on Ti, Ti6Al4V alloy and 316L stainless steel substrates by sol-gel method. (NH₄) · H₂PO₄ is taken as P precursor and Ca(NO₃)₂ · 4H₂O is taken as Ca precursor to obtain HAP coating. Additionally, three different pretreatment processes (HNO₃, anodic polarization, base-acide (BA)) have been applied to Ti, Ti6Al4V alloy and 316L stainless steel substrates. The corrosion behaviors of bare and HAP coated samples are examined in Ringer and 0.9% NaCl. HAP coated Ti have showed over 87.85% inhibition. HAP coated Ti6Al4V alloys have showed over 87.33% inhibition. In Ringer solution, 99.24% inhibition has been showed in HAP coated anodic pretreatment for 316L stainless steel. All pretreatment processes are effective on clinging of HAP coating to the surface. It is seen that impedance values have increased in HAP coatings (Ti and Ti6Al4V). HAP coatings have raised the corrosion resistance of Ti and Ti6Al4V. The values of polarization resistance in HAP coated samples have increased for 316L stainless steel in 0.9% NaCl and Ringer solutions. It is seen in SEM images that open pores and attachments among pores have been observed in the coating, which increases osteointegration. It is noted in EDX analyses of the surfaces of the HAP coated samples that there is only Ca, O, and P on the surface. Ca/P ratio varies in 1.84–2.00 ranges. As Ca/P ratio increases, the inhibition increases too. It is seen in XRD images of HAP powder that there are HA ate structures. Additionally, it is seen in FTIR analysis, characteristic HA absorption bands have occurred in sintered powders.     

Transient liquid phase (TLP) brazing of Mg–AZ31 and Ti–6Al–4V using Ni and Cu sandwich foils

Transient liquid phase (TLP) brazing of Mg–AZ31 alloy and Ti–6Al–4V alloy was performed using double Ni and Cu sandwich foils. Two configurations were tested; first, Mg–AZ31/Cu–Ni/Ti–6Al–4V and second, Mg–AZ31/Ni–Cu/Ti–6Al–4V. The effect of set-up configuration of the foils on microstructural developments, mechanical properties and mechanism of joint formation was examined. The results showed that different reaction layers formed inside the joint region depending on the configuration chosen. The formation of ? phase (Mg), ρ (CuMg₂), δ (Mg₂Ni) and Mg₃AlNi₂ was observed in both configurations. Maximum shear strength obtained was 57 MPa for Mg–AZ31/Ni–Cu/Ti–6Al–4V configuration and in both configurations, the increase in bonding time resulted in a decrease in joint strength to 13 MPa. The mechanism of joint formation includes three stages; solid state diffusion, dissolution and widening of the joint, and isothermal solidification.     

Thermodynamic evaluation of oxygen behavior in Ti powder deoxidized by Ca reductant

To produce low oxygen Ti powder of less than 1000 mass ppm, commercial Ti powder was deoxidized by two types of Ca reductants: a solid Ca and a Ca vapor. Compared with the iso-oxygen partial pressure in the Ti-O binary phase diagram, the P_O2 in the raw Ti powder increased with temperature compared to the reduction reaction of Ca. Therefore, the O₂ content in the Ti powder decreased as the deoxidation temperature increased from 873 K, showing a local minima at 1273 K. The oxygen concentration at 1373 K was greater than that at 1273 K because the oxygen solubility of the Ti powder was increased by the equilibrium relation between Ca and CaO. On the basis of the thermodynamic assessment, the deoxidation of Ti powder can be improved by increasing the temperature and lowering the oxygen solubility with the saturation of CaO.     

Direct laser cladding of Co on Ti–6Al–4V with a compositionally graded interface

In the present study, attempts have been made to fabricate Co layers on the surface of Ti–6Al–4V substrate with a compositionally graded interface by direct laser cladding. Laser processing is carried out by pre-placing the powder (or powder blends) on the substrate, and melting it using a high power continuous wave CO₂ laser with Ar as shrouding gas. A compositionally graded interface is developed by applying powder blends of Ti to Co at a ratio of 90:10 near to Ti–6Al–4V substrate to 10:90 prior to development of Co layer. A defect-free microstructure is developed with the presence of Ti₂Co and TiCo and Co₂Ti at the interface. The volume fraction of individual phase was found to vary with the depth from the Co-clad zone. A significant improvement in microhardness is achieved at the interfacial region. Uniform corrosion resistance increases along the graded interface, but the pitting corrosion resistance is marginally deteriorated. Direct laser clad layer possesses a better biocompatibility than that of as-received Ti–6Al–4V sample.     

Enhancement of the corrosion properties of cold sprayed Ti–6Al–4V coatings on mild steel via silica sealer

The pore formation associated with the cold spray process requires the development of an economical sealer to enhance the corrosion resistance of Ti–6Al–4V coatings on a mild steel substrate. Herein, a sound method is developed to seal pores in the cold sprayed Ti–6Al–4V coatings with silica sealer. Potentiodynamic polarization tests in 3.5 wt% sodium chloride electrolyte were employed to investigate the corrosion resistance of cold sprayed Ti–6Al–4V coatings fabricated at two standoff distances (30 and 70 mm) before and after the sealing process. The polarization resistance of cold sprayed Ti–6Al–4V coatings significantly increased by >80% after the sealing process. The electrochemical responses of cold sprayed Ti–6Al–4V were dependant on sealing the pores with agglomerated silica nanoparticles as observed by scanning electron microscopy and energy-dispersive X-ray analysis. The increase in polarization resistance makes the sealer an effective treatment for cold sprayed Ti–6Al–4V coatings used in marine environments and other engineering applications. This sophisticated sealing process can reduce the deposition cost by reducing the thickness of Ti–6Al–4V coatings and increasing their lifetime on metal components.     

Cleaner Production of Ti Powder by a Two-Stage Aluminothermic Reduction Process

A two-stage aluminothermic reduction process for preparing Ti powder under vacuum conditions using Na₂TiF₆ was investigated. An Al-Ti master alloy and a clean cryolite were simultaneously obtained as co-products. The first-stage reduction was an exothermic process that occurred at approximately 660°C. The Al and O contents of the Ti powder product were 0.18 wt.% and 0.35 wt.%, respectively, with an average particle size <74 μm. Ti(IV), Ti(III), and metallic Ti were present in the Ti-containing cryolite produced by the first-stage reduction, at a total content of approximately 3.13 wt.%. After second-stage reduction, the Ti elemental contents of the clean cryolite were reduced to 0.002 wt.%. The Al-Ti master alloy obtained by second-stage reduction was composed of Al and TiAl₃. The mechanisms involved in these reduction processes were also examined.     

Laser Powder Deposition Parametric Optimization and Property Development for Ti-6Al-4V Alloy

In this study, Ti6Al4V alloy was produced via laser powder deposition (LPD). To obtain Ti6Al4V alloy with maximum density, LPD parameters for preparing Ti6Al4V samples were optimized using the Taguchi method. Results were analyzed on the basis of the signal-to-noise (S/N) ratios and analyses of variance. A high energy density should be used to achieve higher levels of densification. The optimal combination of parameters for density was a scanning speed of 550 mm/min, laser power of 160 W, powder feeding rate of 0.99 g/min, and shield gas flow of 8 L/min. An almost fully dense Ti6Al4V sample was prepared using the optimized LPD process, and the relative density was greater than 99%. In addition, the microstructure and properties of Ti6Al4V samples prepared by optimized LPD process were investigated. The microstructure investigation revealed that the LPD-prepared Ti6Al4V sample was predominantly composed of fine acicular α phase and lath-type α phase. Tensile and microhardness tests indicated that the LPD sample had higher mechanical properties than the traditional cast Ti6Al4V alloy because of the acicular martensitic phase and smaller grain size.     

金属热还原法制备钛铝中间合金

以TiO_2为原料,KClO_3为发热剂,Al为还原剂和合金化剂,Ca为深度还原剂,通过金属热还原法制备钛铝中间合金,考察了单位质量热效应、造渣剂配比和还原剂加入量及组成对反应过程稳定性、合金成分及收率的关系。研究表明:用Ca和Al作为还原剂时,体系绝热温度分别是2426和1806 K,反应制得的钛铝中间合金由Ti Al、Ti_3Al和少量的Al_2O_3夹杂相组成,化学分析合金中Ti、Al、O质量分数分别为58.36%、40.19%和1.41%。