基于真空热压扩散法的金刚石/Ti界面生成机制

采用真空热压扩散法在聚晶金刚石表面制备Ti层,探究金刚石表面金属化过程中的界面生成机制。利用扫描电子显微镜和X射线衍射仪,分析了钛层的表面形貌、界面结构和界面间的物相组成,采用能谱仪对界面进行了元素分析,计算了聚晶金刚石与Ti层之间界面的扩散带宽度及生成TiC的化学反应吉布斯自由能变。研究结果表明:在聚晶金刚石表面形成了平整、致密的Ti层,在聚晶金刚石与Ti层界面之间存在C、Ti和Co元素的扩散,在结合界面处产生了一定宽度的元素扩散带,同时在金刚石表面生成了点状TiC。真空热压扩散法实现了金刚石与Ti层的化学结合,可以提高金刚石与Ti层的结合强度。      

Physico‐chemical and mathematical modeling of phase interaction taking place during fusion welding processes

The quality of metallic materials depends on their composition and structure and these are determined by various physico‐chemical and technological factors. To effectively prepare materials with required composition, structure and properties, it is necessary to carry out research in two parallel directions: 1. Comprehensive analysis of thermodynamics, kinetics and mechanisms of the processes taking place at the solid‐liquid‐gaseous phase interface during welding processes. 2. Development of mathematical models of specific welding technologies. We have developed a unique method of mathematical modeling of phase interaction at high temperatures. This method allows us to build models taking into account: thermodynamic characteristics of the processes, influence of the initial composition and temperature on the equilibrium state of the reactions, kinetics of heterogeneous processes, influence of the temperature, composition, hydrodynamic and thermal factors on the velocity of the chemical and diffusion processes. The model can be implemented in optimization of various technological processes in welding, surfacing, casting as well as in manufacturing of steels and non‐ferrous alloys, materials refining, alloying with special additives, removing of non‐metallic inclusions.     

Development of the microstructure during gradient sintering of a cemented carbide

A gradient sintered WC–Ti(C,N)–Co-based cemented carbide has been studied. The material was sintered in a nitrogen-free atmosphere, resulting in an outward diffusion of nitrogen. Due to the strong thermodynamic coupling between nitrogen and titanium, an inward diffusion of titanium is created. As a result of the diffusion processes the material develops a cubic carbide depleted and binder phase enriched surface zone, and inside this zone a region enriched in cubic carbide. The structure of the gradient surface zone has been studied, where variations in volume fractions of the different phases present have been investigated by scanning electron microscopy (SEM) and image analysis, and elemental variations have been studied with electron probe microanalysis (EPMA). Computer simulations of the gradient formation, based on diffusion and thermodynamic properties, show good agreement with the experimental results, and the gradient formation can be reasonably well predicted. Also studies of grain composition have been performed. In the rim of the cubic carbide grains, variations in composition are found which can be related to the sintering process. The composition of cubic carbide grains has been studied with SEM and analytical electron microscopy.     

Non-equilibrium thermodynamics and variational principles for fully coupled thermal–mechanical–chemical processes

In this paper, the chemical Gibbs function variational principle, the Helmholtz function variational principle and the internal energy variational principle based on irreversible thermodynamics are proposed for the thermal–chemical–mechanical fully coupling problems. The complete fully coupling governing equations, including the heat conduction, mass diffusion and chemical reactions, are derived from the variational principles. The convective effect can also be derived in the diffusion and energy equations from the variational principles naturally. Moreover, the concentrations and entropy jump conditions on the moving interface between the products due to chemical reactions and the matrix can be derived from the variational principles naturally. This work provides the basis for the analyses and computations of thermochemomechanical coupling problems.     

镀锡银钎料扩散过渡区的物相和形成机制

采用温度梯度法对镀锡银钎料进行热扩散处理,形成了扩散过渡区。为了揭示镀锡银钎料扩散过渡区的形成机制和主要物相的形成过程,借助金相显微镜、扫描电镜(SEM)、能谱分析仪(EDS)、X射线衍射分析仪(XRD)对扩散过渡区的显微组织、Sn元素的面扫描分布、物相组成及形貌进行分析。研究表明,Sn元素在镀锡银钎料中分布均匀、无偏析,在扩散过渡区主要以棒状Ag_3Sn相和块状Cu_3Sn相存在。随着热扩散温度升高,Ag_3Sn相和Cu_3Sn相的相对衍射强度逐渐增大。Ag_3Sn相的形成过程分为三个阶段:Ag_3Sn颗粒相弥散分布、Ag_3Sn颗粒相互相接触合并、生成大块棒状化合物相。Cu_3Sn相主要是锡晶须生长冲破镀层的氧化膜,在张应力和压应力协同作用下形成。镀锡银钎料扩散过渡区的形成机制为"钎接、互扩散、亚稳态、合金化"。     

Cathodes Coating Layer with Li-Ion Diffusion Selectivity Employing Interactive Network of Metal-Organic Polyhedras for Li-Ion Batteries (Small 5/2023)

Surface modification of cathodes using Ni-rich coating layers prevents bulk and surface degradation for the stable operation of Li–ion batteries at high voltages. However, insulating and dense inorganic coating layers often impede charge transfer and ion diffusion kinetics. In this study, the fabrication of dual functional coating materials using metal–organic polyhedra (MOP) with 3D networks within microporous units of Li–ion batteries for surface stabilization and facile ion diffusion is proposed. Zr-based MOP is modified by introducing acyl groups as a chemical linkage (MOPAC), and MOPAC layers are homogenously coated by simple spray coating on the cathode. The coating allow the smooth transport of electrons and ions. MOPAC effectively suppress side reactions between the cathode and electrolyte and protect active materials against aggressive fluoride ions by forming a Li–ion selective passivation film. The MOPAC-coated Ni-rich layered cathode exhibited better cycle retention and enhanced kinetic properties than pristine and MOP-coated cathodes. Reduction of undesirable gas evolution on the cathode by MOPAC is also verified. Microporous MOPAC coating can simultaneously stabilize both the bulk and surface of the Ni-rich layered cathode and maintain good electrochemical reaction kinetics for high-performance Li–ion batteries.     

NbSi基原位复合材料表面包埋渗制备SiCrY共渗涂层

通过热力学计算分析了分别使用NH₄Cl和CrCl₃·6H₂O两种不同激活剂时, 各个共渗元素的卤化物蒸汽压分压的变化, 得到了实现Nb-Si基原位复合材料上Si-Cr-Y三元包埋共渗的最佳条件。采用包埋共渗法在Nb-Si基原位复合材料表面制备了Si-Cr-Y共渗涂层, 研究了涂层的组织形貌、 成分及其相组成。结果表明: 使用NH₄Cl做激活剂, 通过调整包埋渗料的成分, 可以在适当的温度下实现Si-Cr-Y的三元共渗。当渗料成分为12Cr-6Si-0.75Y₂O₃-5NH₄Cl-76.25Al₂O₃(质量分数)时, 在1350℃可以实现Si-Cr-Y三元共渗。制备的涂层具有多层结构, 分为外层、 内层和明显的互扩散层。互扩散层的存在, 表明涂层的形成是一个连续生长过程, 伴随着Cr、 Si、 Y元素向基体内的扩散。涂层的主要成分由Cr₂(Nb,Ti)、 (Nb,Ti)₅Si₃和HfSi₂组成, Y元素的添加起到了细化涂层的作用。     

Proposal for photothermal characterization of boundaries between layer and substrate

The accurate measurement of frequency dependent photothermal phase angle curves allows the characterization of the boundary layer between substrate and coating. Regarding the measurable quantities phase extremum and the ratio of the abscissa for the zero crossing and the extremum we can classify the boundary type as a jump in material properties, as a delamination or as a diffusion zone between substrate and coating.     

Mikrostrukturelle und röntgenographische Analysen an einem plasmanitrierten Schnellarbeitsstahl

Microstructural analysis of a plasmanitrided tool steel by means of metallography and X‐ray diffraction Nitriding leads to improved tribological and corrosive properties of iron alloy components. In order to study the effect of plasma nitriding parameters on the structure of compound layer and diffusion zone, a systematic variation of process parameters, temperature and process gas atmosphere has been carried out. Metallographic inspection, X‐ray diffraction and Glow Discharge Optical Spectroscopy analysis (GDOES) were used in this investigation. The results clarified that depending on the amount of nitrogen in the gas atmosphere nitrided layers with and without compound layer can be generated in the surface of M2 tool steel for temperatures from 350°C to 500°C. For plasma nitriding in 5 vol.% Nitrogen and 95 vol.% Hydrogen no compact compound layer was formed. The gas mixture of 76 vol.% Nitrogen resulted in compound layer formation for all temperatures from 350°C to 500°C. X‐ray phase analysis indicated an almost 100% ε‐(carbo)nitride phase but the existence of the γ′‐(carbo)nitride could not be excluded completely from the X‐ray phase diagrams. After corrections to account for the nitrogen gradient, high compressive surface residual stresses have been measured in the diffusion zone. They increased with temperature. After a qualitative correction for chemical composition gradients high tensile residual stresses were found probably existing in the ε‐(carbo)nitride phase for the investigated plasma nitrided tool steel samples.     

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。      

Diffusion processes and mechanics of materials

Within the framework of continuum mechanics, we investigate the interdependent processes of strain and diffusion. By solving a wide class of initial-value and boundary-value problems concerning a physicomechanical state of elastic and viscoelastic bodies, we establish kinetic regularities of the interaction of structural and functional materials with working and technological media. We propose approaches to the calculation of residual stresses under conditions of multicomponent diffusion, phase transformations, and chemical reactions. We emphasize the importance of a consistent and rigorous consideration of properties of structural materials for the construction of their physicomathematical models. Tendencies and prospects of the development of investigations in this direction are evaluated. Karpenko Physicomechanical Institute, Ukrainian Academy of Sciences, L'viv. Tranlated from Fizyko-Khimichna Mekhanika Materialiv, Vol. 34, No. 3, pp. 13–23, May–June, 1998.     

Polysilazane‐Type Coatings on Mo–Si–B Alloys: A Thermodynamic Assessment of the Phase Composition

Thermodynamic analysis is conducted to identify the most probable phase composition of a polysilazane‐type coating system on Mo–Mo₃Si(A15)–Mo₅SiB₂(T2) alloy. The Free Gibbs Energy of chemical reactions between these constituents and resulting phases are calculated. Silicon nitrides, silicon oxynitrides, and molybdenum silicides have been found in the phase equilibrium between the gas phase and condensed species of the proposed coating system. Silicon oxynitride and silica as components in the coating system are potential candidates for Mo–Si–B alloy oxidation protection in air at high temperatures.

     

激光熔覆法制备Al2O3-TiO2涂层的显微组织与性能研究

采用预置粉末式激光熔覆法在钛合金(Ti-6Al-4V)表面开展了Al_2O_3-13%(质量分数)TiO_2涂层的研究。利用光学显微镜(OM)、扫描电子显微镜(SEM)、X射线衍射分析仪(XRD)和显微硬度计研究了激光熔覆熔池的特征和涂层的显微结构,分析了涂层的成分分布、相组成和显微硬度分布情况。预置粉末激光熔覆制备的Al_2O_3-13%(质量分数)TiO_2涂层界面结合良好,涂层组织均匀,没有明显的裂纹和气孔。激光熔覆涂层表现出明显流线型特征,熔覆层截面分为热影响区、扩散结合区和涂层区。涂层由Ti、AlTi_3、α-Al_2O_3和γ-Al_2O_3等相组成。涂层的显微硬度达到1000~1300HV_(0.3),比基体硬度360~390HV_(0.3)高2倍。     

Interface Interactions of Dissimilar Materials at Elevated Temperatures

This paper reviews some of the chemical interactions that occurred at the interface of ceramic/molten metal liquids. Control of interfacial reactions between dissimilar materials is an important issue in numerous technological applications, such as brazing of ceramics to metals, design of ceramic–metal composites, coatings of ceramics on metal substrates, and development of crucibles for melting of refractory metals. In ceramic/metal systems, wetting of the ceramic surface by the liquid metal is typically accompanied to some extent by interfacial reactions. The chemical incompatibility between the metal and non‐metallic materials can result in the formation of undesirable phases, due to the chemical and metallurgical reactions that take place during processing or in service. There is a need, therefore, to characterize the governing factors and reaction pathways at these interfaces. So, when the reaction products obtained during interdiffusion processing are not favorable, the diffusion pathway can be modified to control their formation.     

等离子喷涂A12O3＋13%TiO2陶瓷涂层的组织结构及其耐磨性

本文用Ｘ射线衍射、扫描电镜等研究了等离子喷涂Ａ１２Ｏ３＋１３％ＴｉＯ２（质量分数）陶瓷涂层的相结构、相组成及其组织特征。陶瓷涂层孔隙率低,致密程度较高,以亚稳相ｒ－Ａ１２Ｏ３为主要相,同时存在α－Ａ１２Ｏ３和金红石ＴｉＯ２。富Ａ１２Ｏ３区与富ＴｉＯ２区呈明显相互交迭的层状结构,且存在相互成分扩散,另外涂层设计对硬度有一定影响,ＴｉＯ２的引入提高了涂层的耐磨性。     

注入氮离子的SiC涂层阻氢性能研究

利用离子束混合－离子注入（Ar^ ）和磁控溅射相结合的实验技术在HR－1不锈钢基体上制备了注入N^ 的SiC涂层，并用表面分析手段对所制备涂层的表面形貌，剖面形貌、相结构，表面成分，表面元素的化学态进行了分析，结果表明：制备的涂层结构致密，表面平整、膜层成分均匀；涂层与基体之间形成了一明显的过渡层，增强了涂层和基体之间的结合力，用二次离子质谱（SIMS）对充氘涂层的阻氢性能进行了定性分析，结果表明，涂层元素与氢形成稳定的化学键，抑制了氢的扩散和迁移，使得涂层具有一定的阻氢能力。     

Microstructure and composition evolution of a single-crystal superalloy caused by elements interdiffusion with an overlay NiCrAlY coating on oxidation

MCrAlY(M=Ni and/or Co) overlay coating is widely used as a protective coating against high temperature oxidation and corrosion. However, due to its big difference in chemical composition with the underlying superalloy, elements interdiffusion occurs inevitably. One of the direct results is the formation of interdiffusion zone(IDZ) and secondary reaction zone(SRZ) with a high density of fine topological closed-packed phases(TCPs), weakening dramatically the mechanical properties of the alloy substrate. It is by now the main problem of modern high-temperature metallic coatings, but there are still hardly any reports studying the formation, growth and transformation of IDZ and SRZ in deep, as well as the precipitation of TCPs.In this work, a typical NiCrAlY coating is deposited by arc ion plating on a single-crystal superalloy N5.Elements interdiffusion between them and its relationship on microstructure were clarified. Cr rather than Al from the coating diffuses into the alloy at high temperatures and segregates immediately beneath their interface, contributing largely to the formation of IDZ. Simultaneously, diffusion of Ni from the deep alloy to IDZ leads to the formation and continuous expansion of SRZ.     

Solid lubricants: a review

The fundamental mechanisms of solid lubrication are reviewed with examples from well-known solid lubricants like the transition metal dichalcogenides and diamond-like carbon families of coatings. Solid lubricants are applied either as surface coatings or as fillers in self-lubricating composites. Tribological (friction and wear) contacts with solid lubricant coatings typically result in transfer of a thin layer of material from the surface of the coating to the counterface, commonly known as a transfer film or tribofilm. The wear surfaces can exhibit different chemistry, microstructure, and crystallographic texture from those of the bulk coating due to surface chemical reactions with the surrounding environment. As a result, solid lubricant coatings that give extremely low friction and long wear life in one environment can fail to do so in a different environment. Most solid lubricants exhibit non-Amontonian friction behavior with friction coefficients decreasing with increasing contact stress. The main mechanism responsible for low friction is typically governed by interfacial sliding between the worn coating and the transfer film. Strategies are discussed for the design of novel coating architectures to adapt to varying environments.     

Mechanical behavior of metaphosphate glasses used as coating on metals in relation to their structure and preparation method

The purpose of the present work was to investigate the mechanical behavior of metaphosphate glass coatings of the Na₂O-CaO-P₂O₅ system on steel substrates. These coatings may be used as thermal barriers or to give anti-corrosion protection. Coacervates of glasses under consideration were obtained by a coacervation process, from Graham's salt and deposited on aluminized steel substrate. Chemical composition of coacervate phases was improved by the choice of cations and addition of a filler to reduce the residual stresses in glass metal joints due to the thermal expansion coefficient mismatch. The chemical and mechanical properties of both the coating and the interface were studied by energy dispersive spectrometry (EDS) and hardness measurements. It was shown that an alumina layer is formed by the reaction between the phosphates compounds during curing. This layer acts as a barrier for the iron diffusion. The fracture toughness of the glass coating was investigated by Vickers indentations. Inasmuch the cracks are of the Palmqvist form, the Evans and Charles formula holds for calculating K_IC. A value near 0.85 MPa m^1/2 was found for all the glasses investigated. Residual stress distribution was calculated. The glass coating was in compression and residual stresses were reduced by the interlayer formation. A good adhesion was found since cracks produced by indentation near the glass steel interface propagated in the coating rather than along the interface.