液态金属在陶瓷上铺展时的前驱膜现象

本文采用 Sn 基活性钎料首次在金属-陶瓷润湿系统中发现了润湿前驱膜现象。仔细研究表明,这种前驱膜的形成与活性钎料中活性元素种类、陶瓷材料、第三组元种类及润湿温度有关。扫描电镜观察发现,前驱膜由一层连续的活性元素构成的反应膜和这层表面膜上停驻的细小而分离的 Sn 岛所组成。     

6061铝合金分别在Q235钢和纯钛表面的反应润湿

采用座滴法在高真空条件下研究了熔融6061铝合金在600~700℃分别与Q235钢和纯钛的润湿行为。研究表明两者都为典型的反应润湿,且最终润湿性随着温度的升高而改善;界面反应的自由能变化对最终润湿性及界面结构影响较小,而基板金属在铝中的溶解度不同决定了界面反应层厚度(即溶解度越大则反应层越厚);三相线附近的还原反应诱发了前驱膜的产生,且最终润湿性越好则前驱膜越宽;两者体系的铺展动力学均可以由RPC模型描述:在Al/Ti体系中整个润湿过程分为两个阶段,即先非线性铺展,后线性铺展阶段,两个阶段的铺展活化能分别为72kJ/mol、118kJ/mol,且界面上存在Si的富集;在Al/Q235钢体系中整个润湿过程呈线性铺展,铺展活化能为86kJ/mol,无Si元素在界面富集。     

Mn对熔融Zn-Mn合金与X80钢润湿行为的影响

研究了锌液中0.1%~0.5%(质量分数)Mn对X80钢表面润湿行为的影响。采用改良座滴法获得了450℃时Zn-Mn合金的接触角,通过SEM/EDS观察分析样品表面及界面的组织结构,研究了Zn-χMn(χ=0.1~0.5)合金与X80钢基板的润湿行为和界面反应。结果表明：锰元素对锌合金与钢基体间的润湿性反应起到正吸附作用。在450℃时,当熔体中的锰含量为0.1~0.5时,Zn-χMn合金与钢基间的润湿接触角从85°减小到62°。锌合金熔体/X80钢属于反应性润湿体系,生成的界面产物由FeZn₁₀(δ)、FeZn₁₃(ζ)和Fe₃Zn₁₀(Γ)/Fe₅Zn₂₁(Γ₁)相组成,润湿行为受锌合金界面反应影响。在铺展三相线前沿存在前驱膜,前驱膜的出现能够促进润湿。     

金属/陶瓷润湿性的实验表征和理论预测研究进展

金属/陶瓷体系的润湿性研究在金属与陶瓷的连接、金属液的熔炼和提纯、浸渗法和液相法制备复合材料等领域都有着重要意义。金属熔体在陶瓷表面的润湿过程中,会出现基板在熔体中溶解、界面吸附和互相反应等,是一种较为复杂的物理化学现象。有关金属/陶瓷润湿性的实验和理论研究一直是国际上材料学领域的热点之一。目前金属/陶瓷润湿性主要通过测量接触角θ(借助Young's方程计算)来得出,润湿性表征方法存在较大局限性,特别是接触角对实验条件高度敏感,其往往难以准确反映润湿性,以及适用于高熔点合金与陶瓷体系的方法较为缺乏。因此,除对接触角测试方法进行改进外,很多研究者也试图通过理论计算来考察润湿性,但至今尚未发展出能够很好地应用于所有金属/陶瓷体系的理论预测模型。润湿性实验表征方法的近期研究主要集中在改良座滴法、滴定法、毛细上升法和感应熔化法等。其中,改良座滴法相比传统座滴法能够消除熔体表面氧化膜的影响。感应熔化法可以使高熔点合金(如Ti合金等)熔化,具有独特优势(相比之下其他几种方法只适用于Al系、Mg系等低熔点合金与陶瓷的体系)。在理论预测模型方面,除直接基于Young's方程,根据表面张力模型来研究润湿性外,也有学者尝试结合YoungDupré方程,从热力学和原子键的角度揭示反应界面润湿性的内在规律。同时,将润湿视为一种反应现象,对界面反应吉布斯自由能变化和润湿过程中表面相的能量变化加以考虑,也形成了一种新的定性衡量润湿性的标准。此外,研究者还在润湿铺展动力学方面取得了一些重要成果,包括直接根据金属形核理论来计算润湿角,以及利用如流体动力学模型、分子动力学模型、反应控制模型和扩散控制模型等来预测金属/陶瓷体系的润湿速率。本文主要从润湿过程的机制、接触角的测试方法和用以预测润湿性的理论模型三个方面,综述了金属/陶瓷润湿性领域的实验和理论研究进展。     

金属熔液对氧化镁陶瓷润湿行为研究进展

MgO陶瓷因各种优异性能在轻质高强的金属基复合材料、电子封装材料和涂层材料领域都具有广阔的应用前景,然而研究金属熔液对MgO陶瓷的润湿性是MgO陶瓷能否成功应用于这些领域的基础所在,因此研究金属熔液对MgO的润湿性就显得极为重要.本文通过综述Al/MgO陶瓷反应体系、Mg/MgO陶瓷非反应体系以及其它金属包括稀有金属、贵金属与MgO陶瓷润湿行为的研究进展,将各种金属熔液对于MgO陶瓷的润湿行为分为反应型润湿金属、非反应型润湿金属和非反应型难润湿金属等类型.此外还讨论了目前金属熔液与MgO陶瓷润湿行为研究中尚为存在的一些问题与争论,为金属熔液与MgO陶瓷润湿行为理解的进一步深入提供了支持.     

熔融6061和4043铝合金在纯钛表面的反应润湿

利用改良座滴法研究了高真空条件下熔融6061和4043铝合金在600,650,700℃分别与纯钛(TA2)的反应润湿行为。结果表明:Al/Ti体系属于典型的反应润湿,铝合金中微量的Si元素在界面上产生了明显富集且满足热力学条件;界面上形成了富Si的致密的层片状Ti_7Al_5Si_(12)相,致密层产生后阻碍熔体润湿母材;Ti_7Al_5Si_(12)相的分解及三相线附近疏松的粒状Al_3Ti相产生后能够破除钛表面的氧化膜,进而促进润湿;6061/TA2和4043/TA2两润湿体系铺展动力学均可由反应产物控制(Reaction Product Model)模型描述,整个润湿铺展过程分为两个阶段,即先呈指数铺展、后呈线性铺展;6061铝合金对应两个阶段的铺展活化能分别为56kJ/mol和112kJ/mol,4043铝合金以指数铺展为主,铺展活化能为47kJ/mol,Ti_7Al_5Si_(12)相的分解对应于指数铺展阶段。     

Mo添加对Ni3Al-TiC润湿特性的影响机制研究

采用2AP-LEITZ高温显微镜对TiC-Ni₃Al的润湿接触角进行了实验测定,着重探讨了Ni₃Al对TiC的润湿特性以及Ni₃Al中添加少量Mo的影响机制.结果表明,TiC与Ni₃Al之间具有良好的润湿性能.5wt％Mo的添加使Ni₃Al向TiC基板浸渗的深度增大,并与TiC颗粒发生固溶反应置换出部分Ti,在其周围形成一个含Mo的壳层.在这个壳层里,Ti、Mo进一步与Ni₃Al固溶,这些反应降低了液-固表面张力,导致了润湿接触角的下降,从而改善了TiC-Ni₃Al的润湿性.     

网络陶瓷/金属复合材料的研究进展

介绍了网络陶瓷/金属复合材料近年来的发展.从网络陶瓷/金属复合材料体系出发,介绍了当前主要制备网络陶瓷的多种制备工艺和方法以及各种方法的优缺点;在制备复合材料的工艺中,介绍了无压浸渗和压力浸渗制备网络陶瓷/金属复合材料两种主要的材料复合方法,比较了无压和压力浸渗制备网络陶瓷/金属复合材料各自的优点和弊端;介绍了陶瓷/金属相的润湿类型以及通过添加元素、包覆及热处理等方法来改善金属对陶瓷的润湿;同时也介绍了复合材料中陶瓷与金属结合处的界面结构类型.总结了目前制备的网络陶瓷的不足之处,提出为了满足抗冲击材料的使用,制备网络陶瓷必须要解决的几个关键问题.     

Ag-Cu钎料与双相陶瓷透氧膜的润湿和界面反应研究

用座滴法测试Ag-Cu合金钎料对Ce_0.8Gd_0.2O_2-δ-NdBaCo₂O_5+δ(CGO-NBCO)双相透氧膜的润湿性, 利用SEM-EDS分析润湿和界面反应机理。结果表明: 空气条件下Ag-Cu合金与CGO-NBCO间的润湿遵从界面反应润湿机制。随着Cu含量的增加, Ag-Cu合金对透氧膜润湿性能提高, Cu含量为6.6mol%~15.8mol%时, 润湿角在35°~20°左右。在润湿界面处出现Cu氧化物的富集, 并且在透氧膜侧生成一层由Cu氧化物和CGO-NBCO双相透氧膜反应产生的Ba-Cu-O、Co-Cu-O和Nd-Ce-Cu-O等复杂氧化物相构成的产物层, 新的界面反应层的生成有利于Ag基合金钎料的润湿, 改善了钎料的润湿性能。     

Ag-CuO钎料与BaCo0.7Fe0.2Nb0.1O3-δ透氧膜陶瓷润湿及界面反应机理的研究

利用座滴法润湿实验,借助SEM和EDS测试,研究了Ag-CuO钎料与BaCo0.7Fe0.2Nb0.1O3-δ透氧膜陶瓷润湿及界面反应机理。结果表明Ag-Cu-O/BCFNO间的润湿遵从界面反应润湿机制,随Cu含量增加和温度升高,润湿角快速减小。当Cu含量为3.3%(摩尔分数)时,在界面处BCFNO侧开始生成1层反应层,反应层的存在降低了固液界面能,使界面润湿性得到改善,相互冶金作用增强。反应层产生的原因是界面处发生了界面反应CuOx+BaCoFeNbO→Ba-Cu-O+Co-Cu-O,生成的复杂氧化物Ba-Cu-O、Co-Cu-O在BCFNO基体的晶粒边界上呈岛状分布。     

Precursor film of tin-based active solder wetting on ceramics

The phenomenon of the precursor film in a metal-ceramics wetting system was investigated using tin-based active solder (active element: Ti, Zr, Nb, V, Hf or Ta, the third element Ni, Cu, Ag, In or Al) wetting on the ceramics (sialon, mullite, barium titanate alumina and ZTA-SiC). The results show that the formation of a precursor film in the wetting system is dependent on the following factors. (1) The active metal: the presence of titanium, zirconium or hafnium in the solders induced the formation of a precursor film, but niobium, vanadium and tantalum did not. (2) Temperature: a precursor film will not form unless the critical wetting temperature is reached, while a weak film will form during a second wetting at higher temperature. (3) Ceramics: under the same wetting conditions for Sn-4Ti solder, a precursor film forms on the surface of sialon, ZTA-SiC, and red alumina, but not on white alumina, mullite or barium titanate. (4) The third element; small amounts of nickel (1–3 at %), copper (5 at %), or silver (5 at %) in Sn-5 at % Ti solder will enhance the precursor film. On the other hand, small amounts of Al (5 at %) will completely inhibit the occurrence of precursor film. SEM observation reveals the precursor film to be mainly composed of a continuous film with segregated active metal and some small tin islands on the film. Its thickness is several micrometres, similar to that of the interfacial reaction layer between the solder and the ceramic. Two early theories for the formation of a precursor film, surface diffusion and evaporation-condensation, cannot explain the above phenomenon very well. A new model of rapid absorption then film overflow is proposed here for the first time and some problems with the model are also discussed.     

Preparation of hollow carbon nanospheres via explosive detonation

Hollow carbon nanospheres were prepared via a rapid detonation technique, by using negative-oxygen balance explosive trinitrotoluene and nickel powder as starting materials and inorganic acid as solvent. The carbon/metal nanocomposite particles precursor with core-shell structure was engendered firstly during detonation, and then the metal nickel core was dissolved through inorganic acid to attain the hollow carbon nanospheres. High-Resolution Transmission Electron Microscope, X-ray diffraction and Raman spectrum were used to characterize the precursor and the as-synthesized samples respectively. The results show that the external diameter of the hollow carbon nanospheres is 25-150 nm and the thickness of the wall is about 2-10 nm. The surface of hollow carbon nanosphere displays multilayer wall in structure with 0.35 nm space between the layers. Based on the experimental results, possible formation mechanism was also proposed.     

Fabrication of CuO and Cu2O nanoparticles in a thick polyimide film by post heat treatment in a controlled-atmosphere

We investigated the formation of CuO or Cu2O nanoparticles in the thick polyimide films by oxidizing Cu nanoparticles at various temperatures during the post heat-treatment. Cu nanoparticles of 4-5 nm in diameter were initially formed in the polyimide film by the reaction between a Cu film and a polyimide precursor, polyamic acid, and a following thermal curing in a reducing atmosphere. After the subsequent post heat-treatments in oxidizing atmospheres, X-ray diffraction patterns revealed that initial metallic Cu nanoparticles were transformed to Cu2O or CuO nanoparticles depending on the temperature during the post heat-treatment. Cu nanoparticles were oxidized to Cu2O during the post heat-treatment at low temperature while Cu nanoparticles were oxidized to CuO during the post heat-treatment at high temperature. Cross-sectional TEM studies showed that about 4.7 nm sized Cu2O nanoparticles or 4.7-5.2 nm sized CuO nanoparticles were fabricated in a thick polyimide film depending on the post heat-treatment condition. In the optical absorption measurements, the absorption peak from surface plasmon resonance of Cu nanoparticles disappeared during the post heat-treatment in an oxidizing atmosphere.     

Investigation of CuInS2 thin film formation by a low-temperature chemical deposition method

Copper indium disulfide (CuInS(2), CIS) thin films were prepared by an alternative solution-based coating process adapted from the well-established aqueous metal salt/thiourea precursor system. The temperature for the decomposition of the precursors and the formation of CIS was lowered significantly to 130 °C by using the strongly coordinating solvent pyridine instead of the commonly used water. In addition, the influence of different annealing temperatures and concentrations of thiourea (TU) in the precursor solution on the obtained CIS samples was investigated. The films possess highly beneficial properties for photovoltaic applications, showing a chalcopyrite crystal structure, a high optical absorption (>10(4) cm(-1)) and an optical band gap between 1.45 and 1.51 eV. Chemical and morphological changes during the thin film formation were detected and explained by time-resolved simultaneous grazing incident small- and wide-angle X-ray scattering (GISAXS, GIWAXS) measurements, scanning electron microsccopy (SEM) and simultaneous thermogravimetry/mass spectroscopy (TG/MS).     

Equilibrium and non-equilibrium wetting

The influence of mass transfer and chemical reactions on wetting has been studied using metal systems and aqueous solution systems to determine the equilibrium wetting. The influence of mass transfer on wetting has been studied using Al/Si systems and aqueous solution/NaCl systems and the influence of chemical reactions is discussed using Al/Ni systems and aqueous solution/B₂O₃ systems. The reaction products in the Al/Ni system change with temperature to NiAl₃, Ni₂Al₃ and NiAl, and the reaction product for the aqueous solution/B₂O₃ system is B(OH)₃.We also discuss the influence of relative humidity on wetting in the aqueous solution systems. The results show that the contact angle is highest under equilibrium humidity conditions.     

Characterization of Edge Contact: Atomically Resolved Semiconductor–Metal Lateral Boundary in MoS2

Despite recent efforts for the development of transition‐metal‐dichalcogenide‐based high‐performance thin‐film transistors, device performance has not improved much, mainly because of the high contact resistance at the interface between the 2D semiconductor and the metal electrode. Edge contact has been proposed for the fabrication of a high‐quality electrical contact; however, the complete electronic properties for the contact resistance have not been elucidated in detail. Using the scanning tunneling microscopy/spectroscopy and scanning transmission electron microscopy techniques, the edge contact, as well as the lateral boundary between the 2D semiconducting layer and the metalized interfacial layer, are investigated, and their electronic properties and the energy band profile across the boundary are shown. The results demonstrate a possible mechanism for the formation of an ohmic contact in homojunctions of the transition‐metal dichalcogenides semiconductor–metal layers and suggest a new device scheme utilizing the low‐resistance edge contact.     

Growth of Continuous Diamond Film by Hot Filament C VD Technique on SiC/TiC Pellets, Synthesized Using Combustion Synthesis

β-SiC/TiC composites were synthesized using the process of self propagating-high temperature combustion synthesis (SHS). The heat released during the exothermic reaction between the metal and the carbon powder results in the melting of silicon and the titanium into which the carbon diffuses and then (3-SiC and TiC precipitates out from the supersaturated solution. The composite was characterized using X-ray diffraction techniques, Raman spectroscopy, scanning electron microscopy and transmission electron microscopy. An attempt was made to understand the mechanism of formation of the composite. A theory is proposed for the possible mechanism based on dissolution, diffusion and precipitation from the supersaturated solution. Diamond film was then grown on the pellet by hot filament CVD technique using methane and hydrogen gas as the reactants. The deposition was conducted for a period of four hours. A continuous film of diamond was found to grow on β-SiC/TiC composite using this technique. The diamond film was characterized by using Raman spectroscopy and SEM. The diamond film showed both (001) and (111) facets with an average grain size of 5 μm.     

温度对CPP薄膜润湿张力和摩擦系数变化的影响及其在生产过程检测的应用

简要介绍了CPP薄膜电晕处理原理和添加剂迁移机理，分析了温度对润湿张力和摩擦系数变化的影响，提出生产过程快速检测润湿张力和摩擦系数的方法。