Formation of intermetallic phases on 55 wt.%Al–Zn–Si hot dip strip

A study has been conducted to probe the formation of intermetallic phases on steel substrates immersed in 55 wt.%Al–Zn–Si hot dip baths as a function of dipping time and bath silicon content. Two bath compositions containing 1.3 and 1.5 wt.% Si, respectively, combined with two immersion times of 3 and 9 s were studied. It was found that the reaction rate and intermetallic phase formation varied in response to silicon content. Optical microscopy revealed a quantifiable difference in the development of the reaction layer between the two bath compositions. SEM-EDS revealed that the reaction layer that evolved on samples dipped in the 1.5 wt.% silicon bath were comprised of two intermetallic species, -AlFeSi/Fe₂Al₅, whilst in the 1.3 wt.% bath there were three clearly identifiable intermetallic species -AlFeSi/FeAl₃/Fe₂Al_5. A fourth phase appeared to be present in samples immersed in the 1.3 wt.% Si bath that, due to its fine structure, could not be conclusively identified. Experimental results from the literature and from this study have been assessed with reference to the phase stability predicted by MTDATA, a thermodynamic modelling package.     

45钢表面Ni/WC复合熔覆层的形成机制

采用真空熔覆技术在45钢表面制备Ni +WC复合熔覆层并进行阶段性取样,研究镍基复合涂层的形成机制。结果表明：在45钢表面生成与基体冶金熔合、WC硬质颗粒分布均匀的Ni基复合熔覆层。整个熔覆层由4 mm厚的复合层、1 mm厚的过渡层、20 μm厚的扩散熔合区以及250 μm厚的扩散影响区组成。复合层区由WC和分解形成的富W复相碳化物包围在Ni颗粒周围组成;复合熔覆层的主要组成相有γ-Ni固溶体、Cr₇C₃、Ni_2.9Cr_0.7Fe_0.36、Cr₂₃C₆、Ni₃Fe、Ni₃Si、Ni₃B、W₂C以及C等;真空熔覆过程包括：镍基合金颗粒达到熔点(900℃)前升温阶段颗粒间微烧结颈的形成、升温达到熔点(1020℃)开始的镍基合金颗粒熔融以及保温阶段(1060℃)的熔合扩散与WC颗粒微区位置的调整。     

Y2O3对钛基激光熔覆层组织及性能的影响

针对Ti811钛合金硬度低、耐磨性差的问题,以TC4粉、Ni45A粉和Y₂O₃粉为原料,采用同轴送粉激光熔覆技术在Ti811钛合金表面进行了激光熔覆制备耐磨复合涂层的实验,分析了熔覆层的组织和相组成,测试了熔覆层的显微硬度和摩擦磨损等力学性能。研究表明:复合涂层组织由枝晶TiC、依附生长于枝晶TiC表面的纳米颗粒TiC、生长于基体表面的等轴球形（近球形）TiC、金属间化合物Ti₂Ni、增强相TiB、TiB₂及基体α-Ti组成,所有生成相呈均匀弥散分布状态;涂层中等轴球形（近球形）TiC和Y₂O₃构成了复合相结构,经二维点阵错配度计算表明,Y₂O₃的（111）晶面与TiC的（110）晶面的二维点阵错配度δ=6.54%,因此Y₂O₃可作为TiC的有效异质形核核心细化晶粒;涂层的显微硬度处于HV_0.5 655~700之间,较Ti811基材提高了约1.6~1.8倍;涂层的磨损机制主要为磨粒磨损,摩擦磨损性能较基材显著提升。      

TiAl合金表面Si-Al-Y共渗层的组织及高温抗氧化性能

通过在1050℃下Si-Al-Y扩散共渗0~4 h在TiAl合金表面制备了Al、Y改性的硅化物抗氧化渗层, 分析了共渗层的结构及相组成, 并对其组织形成机理及高温抗氧化性能进行了研究。结果表明: 1050℃共渗4 h所制备的共渗层具有多层结构, 由外向内依次为TiSi₂外层、(Ti,X)₅Si₄及(Ti,X)₅Si₃(X表示Nb, Cr)中间层、TiAl₂和γ-TiAl内层及富Al的过渡层, 其中Y元素主要富集于共渗层的外层和中间层。不同时间共渗的结果表明, Si-Al-Y共渗层的形成是一个在基体表面先沉积Al, 后沉积Si的有序过程。经1000℃高温氧化20 h后共渗层表面形成了由TiO₂外层及SiO₂·Al₂O₃次外层组成的致密氧化膜; Y的氧化物主要存在于氧化膜与残余共渗层的界面处, 能够有效地增强膜层的附着力。     

Mechanical alloying and microstructure of a Nb–20% V–15% Al alloy

A niobium-based alloy with 20% V–15% Al (at.%) was synthesized by mechanical alloying of elemental powders. During milling, the splitting of Nb X-ray peaks into two components was observed. Each component was found to correspond to a niobium solid solution (Nb_I and Nb_II) with a different lattice parameter. The intensities of Nb_I peaks on X-ray diffraction patterns decreased with the milling time and disappeared completely after 180 h of milling while the intensities of Nb_II peaks gradually increased. The powders were hot pressed and microstructural and phase analyses of the consolidated material were carried out. The microstructure consisted of Nb solid solution, Nb₃Al-base intermetallic with the A15 crystal structure and dispersoid Al₂O₃. Also an unexpected, detrimental, Nb₂Al-base σ phase was found. The volume fraction of the σ phase depended on the temperature of consolidation.     

Microstructural study of titanium–palladium–nickel base thin film shape memory alloys

A new generation of thin film shape memory alloys has been developed with 1.65 μm thickness for micro-actuator applications. In this work, the microstructure of thin film Titanium–Palladium–Nickel (TiPdNi) shape memory alloys deposited using ion beam assisted deposition from a Ti₅₀Pd₃₀Ni₂₀ target is studied. The TiPdNi thin films were deposited with and without substrate heating during deposition. As-deposited films without substrate heating were found to be amorphous. Deposition on heated substrate produced a dense, columnar crystalline structure. Microstructures of bulk TiPdNi thin films as well as the interfacial region between the film and substrate were characterized by various techniques including transmission electron microscope, scanning transmission electron microscope, scanning electron microscope-energy dispersive X-ray spectroscopy and scanning transmission electron microscope-energy dispersive X-ray spectroscopy. A transition layer with 70 nm thickness is observed at the interface between the bulk film and silicon substrate. It is composed of three layers; two amorphous layers above the silicon substrate and a 50 nm thick twin absent layer, which was identified as B2 austenite phase by Fourier spectra analysis. In the bulk film, nano-scale grains in the range of 80–200 nm were observed. The width of twin band of the film was very narrower in the range of 5 nm.     

Aluminum Coatings for Steel

Aluminum coated steel possesses excellent oxidation and corrosion resistance in sulfur and marine: environments and can substitute for expensive alloy of steels. Hot dip aluminizing (HAD) and pack cementation calorizing (CAL) are dealt with in detail. IN HDA coats, some alloying action takes place, when the substrate is dipped in molten Al at 973 K for 1-2 minutes. The coat consists of an outer pure Al layer, followed by a hard intermetallic layer consisting of FeAl₃ and Fe₂Al₅, forming a serrated interface with the base. Isothermal holding of such samples at 773-933 K for 10 minutes leads to further diffusion and phase changes. This improves resistance to thermal shock and bending. In CAL coats, the process parameters (1173-1223 K/2-4 h and pack composition), were optimized, resulting in appreciable alloying. The surface layer consists of Fe3Al and FeAl, which is comparable to the inner alloy layer of HDA coats. The structures/ property correlation is carried out for both coatings and the results compared.     

High temperature oxidation of Ni–W coatings electroplated on steel

The high-temperature oxidation of Ni–16 at.% W coating electroplated on the steel substrate was studied at 700 and 800 °C in air. Before oxidation, the coating consisted of supersaturated, nanocrystalline Ni grains. During oxidation, oxygen diffused inward, Ni and the substrate elements such as Fe and Cr diffused outward. The outer NiO layer was not pure but had some dissolved ions of W⁶⁺ and Fe³⁺. Some Fe³⁺ ions were dissolved in the inner (NiO+NiWO₄) mixed layer, below which (W, Fe)-supersaturated, unoxidized Ni grains existed. Below these grains, tiny Ni–W–Fe precipitates, which were formed by the outward diffusion of Fe from the substrate, were surrounded by unoxidized (Fe-enriched, Cr-containing) Ni grains. Detailed oxidation mechanism of Ni–16 at.% W coating is proposed.     

Formation of intermetallic compounds in the Cr–Al–Si ternary system

The microstructure and composition of binary and ternary intermetallics have been studied in ternary diffusion couples of Cr and an Al–Si eutectic alloy. The ternary intermetallic always formed in the liquid part of the diffusion couple as a dendritic structure. Two intermetallics compounds, CrSi₂ and Cr₅Si₃, of the Cr–Si binary system have been observed. The CrSi₂ intermetallic has a high solubility of up to 20 at.% Al and forms as faceted plates. A number of intermetallics, namely, CrAl₇, Cr₂Al₁₁, CrAl₄, Cr₄Al₉, Cr₅Al₈ and Cr₂Al, of the Cr–Al system have been observed. The solubility of Si varies from as low as 0.8 at.% in Cr₂Al to as high as 9 at.% in Cr₄Al₉. A schematic of the reaction scheme of the Cr–Al–Si system is presented. This has been based on the observed microstructure and composition of phases.     

Ellipsometric and X-ray specular reflection studies on naturally grown overlayers on aluminium thin films

The results of detailed investigations on the natural surface layer formed at room temperature on aluminium films exposed to air are presented. Aluminium films of high perfection, deposited onto very smooth glass substrates, have been studied over a 2 year period using ellipsometry. Soft X-ray specular reflection analysis revealed a composite surface layer structure composed by a thin (d₂ = 0.8 nm) very compact alumina layer in contact with the aluminium substrate and by a thick (d₃ = 3 nm) hydrated oxide layer. A new computer procedure was applied for this composite layer system, which evaluated 72 ellipsometric experimental data and achieved a best fit of the measured and calculated Ψ and Δ values. The resultant optical constants of the aluminium substrate were n = 1.09, 0.95, 0.535 and 0.370 for λ = 579 nm, 546 nm, 436 nm and 365 nm respectively, whereas k = 6.72, 6.40, 4.96 and 4.23 respectively for the same mercury lines. Among widely scattered data from the literature, these are in good agreement with results of Hass on the assumption of a similar surface layer structure, using n₂ = 1.77 (alumina) and n₃ = 1.58 (hydrated oxide).

Our optical constants for aluminium were applied for evaluating ellipsometric experimental data obtained during the 2 year period. A slight systematic change in the d₂ and d₃ values of the samples was found, owing to hydration.     

加热温度与保温时间对铝-硅镀层组织演变的影响

采用扫描电镜观察了钢板表面铝-硅镀层的微观组织,利用热模拟机研究了铝-硅镀层在不同加热温度和保温时间下镀层中合金层厚度的变化规律,利用辉光光谱仪测定了铁元素向合金层中的扩散规律。结果表明:热处理前镀层合金层组织由Fe₂Al₅二元金属间化合物和Fe₂SiAl₇三元金属间化合物组成,热处理后镀层合金层组织由Fe₂SiAl₂,Fe₂Si₂Al₅等金属间化合物组成,镀层表面生成致密的Al₂O₃膜;硅元素在合金层与镀层的交界处富集,抑制了铁元素由钢基体向镀层表面的扩散,可以有效阻止合金层厚度的进一步增加;随着加热温度升高、保温时间延长,铁元素溶出量增多,镀层表面铁质量分数达到45%~55%,导致合金层的厚度逐渐增大。     

Synthesis of Al–Mn–Ce alloy by the spark plasma sintering

The bulk Al₉₀Mn₈Ce₂ alloy is sintered by spark plasma sintering (SPS) method. The microstructures and the hardness and wear resistance of the Al₉₀Mn₈Ce₂ samples are investigated. The results show that bulk Al₉₀Mn₈Ce₂ alloy with less than 2% porosity has been obtained at 673 K. At 723 K the Rockwell hardness of the alloy reaches 97 HRB and the wear resistance of the alloy is three times as high as that of the conventional A390 aluminum alloy. The high wear resistance of the Al₉₀Mn₈Ce₂ alloy is attributed to the existence of the large amount of the intermetallic compounds.     

WC-氧化石墨烯/Ni复合熔覆层的制备及形成机制

采用真空熔覆技术制备了WC-氧化石墨烯(GO)/Ni复合熔覆层,运用扫描电镜、能谱仪、X射线衍射仪观察并分析在不同温度下熔覆层内显微形貌的变化与物相组成。结果表明:在ZG45表面制备了组织致密、与基体形成良好冶金熔合的WC-GO/Ni复合熔覆层;熔覆层的微观结构组成从表面至基体依次是约1.5 mm厚的复合层、360 μm左右的过渡层、50 μm左右的扩散熔合层和100 μm左右的扩散影响层,其主要组成相有Cr₇C₃、FeNi₃、WC、Cr₂₃C₆、Ni₃Si、C、Fe₇W₆、γ-Ni固溶体等,FeNi₃、Fe₇W₆分散在冶金熔合带,扩散影响区主要组织为珠光体;复合区的物相尺寸小于界面区的物相尺寸,熔覆层形成过程中复合区的金属颗粒变化先于界面区,凝固时熔化不完全的颗粒表面长出团簇物(Cr₇C₃/Cr₂₃C₆),随着保温长大逐渐变成针状物镶嵌在Ni基固溶体中。      

AZ31镁合金表面激光熔覆Al-TiC复合涂层微观组织与腐蚀性能

为有效改善AZ31镁合金表面的腐蚀性能，本文采用激光熔覆技术在AZ31镁合金表面成功制备了无缺陷的Al-TiC复合涂层。研究了不同成分含量的Al-TiC复合涂层的相组成、微观组织和耐腐蚀性能的影响。结果表明：在Al-TiC复合涂层内形成了大量的Al₁₂Mg₁₇、Mg₂Al₃和TiC相。复合涂层内微观组织呈现出连续网络状分布特征。随着Al-TiC混合粉末中Al含量的减小，复合涂层中Al₁₂Mg₁₇、Mg₂Al₃和TiC相的含量呈递增趋势，网络状分布的微观组织结构变得更加均匀连续。复合涂层与AZ31基体之间形成了良好的冶金结合界面。激光熔覆制备的Al-TiC复合涂层耐腐蚀性能较AZ31基体显著提升。自腐蚀电位由基体的-1.563 V提升至-1.144 V，自腐蚀电流由基体的1.55×10^-4 A减小至2.63×10^-6 A。     

Effect of minor alloying with Al on oxidation behaviour of MoSi2 at 1200°C

Effect of Al alloying in small concentrations on oxidation behaviour of molybdenum di-silicide (MoSi₂) at 1200°C has been investigated. MoSi₂–2.8 and 5.5 at.% Al alloys possessed 0.5, and 2.5 at.% Al in solid solution, respectively, and dispersoids of -Al₂O₃. On the other hand, MoSi₂–9 at.% Al alloy possessed 3.1 at.% in solid solution in MoSi₂ and Mo(Si,Al)₂ phase, besides -Al₂O₃ dispersoids. The kinetics of oxidation of all the alloys followed a parabolic rate law. The oxidation rate was higher in the MoSi₂–Al alloys in comparison to MoSi₂, with weight gain values varying by an order of magnitude. The MoSi₂–5.5 and 9 at.% alloys demonstrated closely related oxidation characteristics and proved to be more resistant to oxidation than MoSi₂–2.8 at.% Al alloy. The oxide scale comprised of SiO₂ in MoSi₂, mixture of SiO₂ and -Al₂O₃ in MoSi₂–2.8 at.% Al alloy, and -Al₂O₃ in case of MoSi₂–5.5 and 9 at.% Al alloys. The mechanism of oxidation has been analysed using thermodynamic and kinetic considerations.     

The relationship of the volume fraction of martensite vs. plastic strain in an Fe–Mn–Si–Cr–N shape memory alloy

The volume fractions of stress-induced martensite formed by certain plastic strains were determined by X-ray diffraction and quantitative metallography in an Fe–Mn–Si–Cr–N alloy at room temperature. The results are fitted by least square method and are well consistent with an exponential function f_M=1−exp{−β[1−exp(−η)]ⁿ} deduced by Olson and Cohen, who used it to fit with experimental data for AISI304 stainless steel. The similarity of and β, as well as the difference in n for these two alloys are discussed in relation to their nucleation mechanisms.     

Microstructure and strength of diffusion-bonded joints of TiAl base alloy to steel

Diffusion bonding of TiAl-based alloy to steel was carried out at 850–1100 °C for 1–60 min under a pressure of 5–40 MPa in this paper. The relationship of the bond parameters and tensile strength of the joints was discussed, and the optimum bond parameters were obtained. When products are diffusion-bonded, the optimum bond parameters are as follows: bonding temperature is 930–960 °C, bonding pressure is 20–25 MPa, bonding time is 5–6 min. The maximum tensile strength of the joint is 170–185 MPa. The reaction products and the interface structures of the joints were investigated by scanning electron microscopy (SEM), electron probe X-ray microanalysis (EPMA) and X-ray diffraction (XRD). Three kinds of reaction products were observed to have formed during the diffusion bonding of TiAl-based alloy to steel, namely Ti₃Al+FeAl+FeAl₂ intermetallic compounds formed close to the TiAl-based alloy. A decarbonised layer formed close to the steel and a face-centered cubic TiC formed in the middle. The interface structure of diffusion-bonded TiAl/steel joints is TiAl/Ti₃Al+FeAl+FeAl₂/TiC/decarbonised layer/steel, and this structure will not change with bond time once it forms. The formation of the intermetallic compounds results in the embrittlement of the joint and poor joint properties. The thickness of each reaction layer increases with bonding time according to a parabolic law. The activation energy Q and the growth velocity K₀ of the reacting layer Ti₃Al+FeAl+FeAl₂+TiC in the diffusion-bonded joints of TiAl base alloy to steel are 203 kJ/mol and 6.07 mm²/s, respectively. Careful control of the growth of the reacting layer Ti₃Al+FeAl+FeAl₂+TiC can influence the final joint strength.     

Investigation of hydrogen induced cracking in 2205 duplex stainless steel in wet H2S environments after isothermal treatment at 675, 750 and 900 °C

The effect of isothermal treatment (at 675, 750 and 900 °C) on HIC (hydrogen induced cracking) in sour environments containing hydrogen sulphide of a 2205 duplex stainless steel has been investigated. The performance and microstructure of failed material were characterized by optical microscopy, scanning electron microscopy and also X-ray diffraction. Two kinds of Cr-, Mo-enriched intermetallic phases, σ and χ, were found to precipitate preferentially at /γ interfaces and within grains after different times of aging in the temperature range of 650–900 °C. After performing tests according to the NACE Standard TM 0284 (1987) the specimens were investigated by using quantitative metallography methods. The volume fraction of σ phase was changed with the time of aging and σ phase developed into coarse particles due to the high diffusibility of solute atoms at high temperatures. The variation of size and shape of σ phase particles was obtained by applying different heat treatment conditions to 2205 steel specimens. The results showed that 2205 duplex stainless steel containing nearly 12 vol.% of σ phase in dispersed conditions was resistant to step cracking in wet environments containing hydrogen sulphide. It was highly possible that a crack would propagate faster along the embrittled σ phase. However, very small cracks were found at austenite–ferrite boundaries where o phase particles were also present.     

Cracking behavior of oxide scale formed on Ti3SiC2-based ceramic

The cyclic oxidation and acoustic emission (AE) tests were carried out for studying cracking behavior of oxide scales formed on Ti₃SiC₂-based ceramic at 1100 °C. A duplex oxide scale with an outer layer of pure TiO₂ and an inner layer of a mixture of TiO₂ and SiO₂ was formed. The oxide scale did not spall from substrate during the cyclic oxidation at 1100 °C for 360 times. However, a great number of micro-cracks penetrating whole inner oxide layer were detected. AE test showed that the oxide scale did not crack during the isothermal oxidation at 1100 °C for 1 h, however, the scale cracked during the cooling stage. Comparing the growth rate and thickness between the oxide layers formed during the isothermal oxidation and cyclic oxidation, respectively, indicated that cracks in the inner oxide layer served as paths mainly for outward diffusion of titanium and for inward diffusion of oxygen, resulting in increased growth rate of the outer oxide layer. Because of entire and compact TiO₂ consisted of outer oxide layer, and low thermal stress resulting from small mismatch of thermal expansion coefficients between the oxides and the substrate, Ti₃SiC₂ exhibited excellent cyclic oxidation resistance at 1100 °C for 360 cycles.     

激光铝热还原法制备Al2O3/Ti-Al基复合涂层

利用Al和TiO₂之间的放热化学反应, 采用激光原位合成技术在TC4钛合金基体材料表面制备了Al₂O₃/Ti-Al金属间化合物基复合涂层。对比分析了激光功率、激光束扫描速度和光斑尺寸变化对激光能量密度变化量的影响程度, 借助X射线衍射仪(XRD)、光学显微镜(OM)、能谱仪(EDS)和显微硬度计分别考察了激光束扫描速度对复合涂层表面宏观形貌、截面显微组织结构和显微硬度的影响。结果显示, 扫描速度的变化对激光能量密度变化量的影响程度最大, 光斑尺寸次之, 激光功率的变化影响最弱。随着激光束扫描速度的增大, 复合涂层表面渐趋粗糙, “鱼鳞纹”状形貌特征趋于明显, 复合涂层与基材结合区厚度减小。激光原位复合涂层主要由k-Al₂O₃和α-Al₂O₃增强相与α-Ti和α₂-Ti₃Al基体相组成。随着激光束扫描速度增大, 复合涂层内k-Al₂O₃部分转变为α-Al₂O₃, Al₂O₃增强相有由枝晶状向纤维状转变的趋势; 复合涂层截面显微硬度自基体至涂层表面过度平缓, 且涂层区显微硬度分布均匀, 明显高于基材平均显微硬度。