TiB_2的价电子结构及其性能研究

根据固体与分子经验电子理论 ,对TiB2 的价电子结构进行了定量分析 ,通过键距差 (BondLengthDifference)方法计算了TiB2 晶胞中各键上的共价电子数。结果表明 :B -B原子键最强 ,其共价电子数nA =0 .56561,键能EA =93.0 7kJ·mol-1,B -Ti原子键为次强键 ,其共价电子数的nB=0 .2 0 4 81,键能EB=33.12kJ·mol-1,从nA、nB 的大小及键络的分布特征对TiB2 的一些性能进行了分析。     

Sr,Mg掺杂的LaGaO3的离子导电性与价电子结构判据

应用固体与分子经验电子理论(EET理论)计算了Sr,Mg掺杂的镓酸镧固体电解质材料的价电子结构,探讨了价电子结构与离子电导率间的关系.提出了离子导电性的价电子结构判据关系式,得到了与实验规律一致的结果.     

Fe3C型碳化物与人造金刚石晶面价电子结构分析

基于高温高压合成金刚石过程中铁基触媒及其金属包膜中存在大量Fe3C型碳化物的实验结果,利用余氏理论(empirical electron theory of solid and molecule,EET)分析了Fe3C型碳化物内C-C键组成晶面和与之对应的金刚石晶面的共价电子密度,发现它们在一级近似下存在连续性,满足程氏理论(improved Thomas-Fermi-Dirac theory advanced by Cheng,TFDC)提出的原子界面边界条件.分析结果表明:高温高压下的金刚石单晶生长与Fe3C型碳化物的分解有关.在4种Fe3C型碳化物中,(Fe,Ni)3C内的C-C键组成晶面和与之对应的金刚石晶面的共价电子密度连续的组数最多.因而认为:合成金刚石过程中使用含镍的铁基触媒,在高温高压下形成的(Fe,Ni)3C作为碳源,最容易转变为金刚石.     

高温高压下Fe-Ni-C系合成金刚石单晶的机理研究(上)

从三个方面综合介绍了本课题组近几年来采用Fe-Ni-C系在高温高压下合成优质金刚石单晶的研究成果:1)采用单质金属铁、镍粉和石墨粉以及粉末冶金方法制备出新型铁基触媒,利用六面顶压机合成了高品位的金刚石单晶;2)采用现代分析测试方法对金刚石单晶外的金属包覆膜物相结构进行了系统表征和分析;3)基于固体与分子经验电子理论(EET理论)和托马斯-费米-狄拉克-程开甲理论(TFDC理论)对金刚石合成过程中相关物相(金刚石、石墨、Fe3C((Fe,Ni)3C)和γ-(Fe,Ni)等)的价电子结构进行了计算和论证。实验分析与理论研究结果表明,单质金属粉辅以粉末冶金方法同样可以实现高品位金刚石单晶的合成;金属包覆膜中存在大量的Fe3C、(Fe,Ni)3C类型的金属碳化物和γ-(Fe,Ni)型金属中间相,且γ-(Fe,Ni)与金属碳化物的对应晶面之间存在相互平行的位向关系;金刚石与石墨主要晶面间的平均共价电子密度在一级近似条件下均不连续,而Fe3C与金刚石或Fe3C与γ-(Fe,Ni)之间存在界面电子密度连续性,因此证明Fe3C/金刚石界面能够满足金刚石生长的边界条件。研究结果表明,金刚石单晶生长的碳源并非直接来源于石墨,而来源于在金属中间相的催化作用下,由金属碳化物过渡相中脱溶出的、具有类SP3杂化态的C-C原子团,因此从实验和理论上进一步支持了金刚石合成的"溶剂-催化"理论。     

Cr3C2和VC对Ti(C,N)基金属陶瓷中环形相的价电子结构和性能的影响

根据固体与分子经验电子理论，计算了Ti(C，N)基金属陶瓷中界面环形相的价电子结构，讨论了其价电子结构与塑性间的关系。当材料晶体结构相同时，Σna可用来比较其塑性的相对高低。Cr在环形相(Ti，Mo)(C，N)中的固溶，可使其塑性增强，V在环形相中的固溶将使其塑性变差。在计算的基础上进行实验，实验结果表明：Cr3C2的适量加入确实有利于提高金属陶瓷的强度，最终所制备出金属陶瓷的强度比典型成分体系材料的提高了1倍以上；尽管VC的加入能使材料的晶粒得到有效地细化，但它使环形相塑性降低，使金属陶瓷的抗弯强度略有增加。     

熔体缓冷形成玻璃的经验判据

本文提出了单元组分熔体冷却形成玻璃的结构参数图。它不同于已有的键参数图,而是综合考虑了影响结构的电子因素和几何因素。实际表明结构参数图在反映玻璃形成能力上更有合理性。本文还在结构参数图基础上总结出形成玻璃的经验判据式,即: G(R.φ)=(3.922R-2.902)~2+(2.597φ-4.545)~2<1凡满足该式的单组分化合物熔体可以缓冷生成稳定玻璃。式中尺寸参数R=(γ_c/γ_o)_(cor),γ。为配位多面体中心元素的共价半径,γ_c为配位多面体顶点元素的共价半径;键参数函数φ=(0.15∑Z/γ_(cov)-0.18△X),Z为元素的价电子数。△X为两元素的电负性差,此判据与实际结果基本相符。     

温度对Cr基钎料钎焊金刚石界面微观形貌影响的研究

选用含Cr活性钎料,适当控制钎焊工艺,实现了金刚石与基体的高强度连接.采用扫描电子显微镜(SEM)和能谱仪(EDS)分析了真空加热条件下,不同钎焊温度对钎焊后金刚石表面微观形貌的影响,探讨了钎料与金刚石界面处碳化物的形成机理.分析结果表明,活性钎料中的Cr能在金刚石表面富集并与金刚石中的C生成枝状的碳化物,碳化物形貌与钎焊温度存在很大关系.     

用自相关拓扑指数估算链烷烃的热力学性质

以碳原子的价电子能级值 (εi)为参数 ,建构了自相关拓扑指数 ( tT) ,其中0 T =Σεi,1T =Σ(εi.εj) 0 .5,1T不仅对链烷烃分子呈现良好的结构选择性 ,而且与 85种链烷烃的热力学性质 (p,标准生成焓、标准熵、标准生成自由能 )具有高度相关性 ,P与1T及N(或P3)的复相关系数依次为 0 .995 3,0 .9992 ,0 .992 5。优于文献值 ,预测结果令人满意     

Ti(C,N)基金属陶瓷抗弯强度的价电子判据研究

利用固体分子经验电子理论,计算了金属陶瓷中三元复合陶瓷相（Ｔｉ,Ｍｏ,Ｗ）Ｃ,四元复合陶瓷相（Ｔｉ,Ｍｏ,Ｗ,Ｎｂ）Ｃ和（Ｔｉ,Ｍｏ,Ｗ,Ｔａ）Ｃ五元复合陶瓷相（Ｔｉ,Ｎｏ,Ｗ,Ｎｂ,Ｔａ）Ｃ的价电子结构,探讨陶瓷相的价电子结构与金属陶瓷抗弯强度关系,提出判据关系式,此外,还进行了抗弯强度的实验验证。     

陶瓷相（Ti,W）C的价电子结构与力学性能的关系

计算了陶瓷相（Ｔｉ，Ｗ）Ｃ的价电子结构，比较了陶瓷相（Ｔｉ，Ｗ）Ｃ，ＴｉＣ，ＴｉＮ，ＴｉＯ之间的价电子结构与力学性能之间的关系，指出陶瓷相价电子结构中的最强键ｎＡ的大小在晶体结构相同时可作为硬度高低的比较标准，陶瓷相的强度可由η＝ｎｃ／ｎＴ来衡量。     

Carburization and wear behavior of self-lubricating Ti(C,N)-based cermets with various secondary carbides

Self-lubricating Ti(C,N)-based cermets were manufactured using vacuum sintering and solid carburizing in this study, and the effects of various carbides on the carburization and wear behavior of the cermets were investigated. The findings demonstrate that solid carburizing resulted in strong graphite precipitation in all the Ti(C,N)-based matrices. Refractory carbides significantly affect the morphological characteristics of graphite in cermets. The activated carbon atoms in the cermet matrix are consumed in two ways: rearrangement followed by precipitation in the form of graphite and combination with metal atoms followed by precipitation in the form of carbides or carbonitrides. As the amount of refractory carbide dissolved in the binder phase increases, more carbon atoms are consumed by bonding with metal atoms, and less graphite is precipitated. The precipitation of carbides and carbonitrides in the ceramic phase increases the rim phase thickness. After carburization, the mechanical properties of the cermets were noticeably degraded owing to the introduction of graphite and the coarsening of ceramic particles. However, the presence of graphite significantly reduced the friction coefficient of the cermet material owing to its good lubrication effect. The decreased mass loss and better wear morphology suggest that the wear deterioration of all the cermets is remarkably mitigated by carburization. The wear properties of cermets are determined by the mechanical properties and the lubrication conditions of the contact surfaces, and good lubrication conditions can partially compensate for the degradation of the mechanical properties of cermets in the sliding wear process.     

Assessment of mechanical properties at microstructural length scale of Ti(C,N)–FeNi ceramic-metal composites by means of massive nanoindentation and statistical analysis

It is well known the interest of the scientific community in substituting the traditional cemented carbides (WC–Co) by alternative ceramic-metal systems. In this regard, Ti(C,N)-based cermets arise as excellent candidates due to their exceptional mechanical, tribological and thermal properties. In this work, microstructurally different Ti(C,N)–FeNi cermets were processed using a combination of colloidal and powder metallurgy techniques. Three distinct ceramic/metal phase ratios were used: 85/15, 80/20 and 70/30 (volume fraction) of Ti(C,N) and FeNi respectively. Microstructural parameters and micromechanical properties (hardness and stiffness) of the three composite systems and their constitutive phases were assessed. Small-scale hardness was evaluated by means of massive nanoindentation testing and statistical analysis of the gathered data, under the consideration of three mechanically different phases: Ti(C,N) particles, metallic binder and a composite-like one, corresponding to probing regions containing both constitutive phases. It is found that values of local hardness for both composite-like and metallic phases increase as the ceramic/metal phase ratio rises. In particular, local hardness values are determined to be significantly distinct for the metallic binder in the three cermets investigated. Results are discussed and rationalized on the basis of the constrained deformation imposed for the harder phase to the softer and more ductile one. Estimated effective flow stress values for the metallic binder as well as detailed inspection of crack-microstructure interaction and fractographic features point out the effectiveness of FeNi as reinforcement phase and toughening agent for Ti(C,N)-base cermets.     

Micropillar compression of Ti(C,N)-FeNi cermets: Microstructural,processing, and scale effects

The influence of microstructure and processing route on the small-scale mechanical response as well as on the deformation and failure mechanisms of Ti(C,N)-FeNi cermets were investigated by uniaxial compression of micropillars milled by focused ion beam with different sizes. Stress-strain curves were determined and associated deformation mechanisms were observed in-situ using scanning electron microscopy. The appropriate micropillars dimension was assessed, based on the microstructural characteristics of studied cermets, to overcome scale effect issues. A direct relationship was observed between yield strength and ceramic/metal ratio for colloidal samples. Meanwhile, deformation of metallic binder and glide between Ti(C,N)/Ti(C,N) particles were evidenced as dominant mechanisms during the compression for colloidal cermets with 70 and 80 vol% of ceramic phase, respectively. The obtained results illustrate that samples processed from powder attained by colloidal route provide superior mechanical behavior, as compared to that exhibited by specimens shaped following a conventional powder metallurgy one (wet ball-milling/drying).     

Effect of Cr3C2 on Valence-Electron Structure and Plasticity of Rim Phase in Ti(C,N)-Based Cermets

Based on the empirical electron theory of solids and molecules, the valence-electron structure (VES) of the rim phase in Ti(C,N)-based cermets was calculated, and the relationship between the VES and plasticity was determined. The results indicated that the plasticity of the rim phase in a Ti(C,N)-based cermet could be defined using the sum of the n _a values for the covalent bonds, and that chromium dissolution in the rim phase improved the plasticity of the rim phase. Moreover, a series of experiments showed that adding Cr₂C₃ to a typical Ti(C,N)-based cermet strengthened the interface. Based on those results, a Ti(C,N)-based cermet with added Cr₃C₂ was manufactured; the new cermet had more than twice the transverse rupture strength of a typical cermet.     

Ti(C,N)-based cermets containing uniformly dispersed ultrafine rimless grains: Effect of VC additions on the microstructure and mechanical properties

Difference in lattice parameters and physical properties of core-rim structure leads to mismatch at the core-rim interfaces. In this respect, VC was adopted to shrink the lattice of rims and intended to reduce the lattice misfit. Small amount of VC (0.8 wt%) effectively decreased the grain size from 0.77 μm to 0.57 μm, with an increased lattice parameter of the core-rim phase. Higher VC content accelerated the dissolution and precipitation process, resulting in the formation of thicker rims and smaller lattice parameters of core-rim structure. The same lattice parameters of core-rim phases were achieved with 4.8 wt% of VC addition. A distortion zone with a thickness of 3–5 atomic layers was confirmed, which located at the boundary of binder and gray rim. VC induced the formation of spherical rimless grains, which were uniformly dispersed in the binder and usually attached to the coarse core-rim grains. Black ultrafine rimless grains exhibited larger lattice parameters than Ti(C,N) cores due to the increased C/N ratios. Ti(C,N)-based cermets with uniformly dispersed rimless grains were achieved, which showed effectively improved the bending strength of cermets, with in-situ formed dimples inside the binders during the fracture.     

Ti(C,N)-based cermets with strengthened interfaces: Roles of secondary cubic carbides

Core-rim structure, concerning its interface structure and internal stress, plays an important role in mechanical performance of Ti(C,N)-based cermets. Four types of cermets containing equimolar TaC, VC, ZrC, and NbC were fabricated, in order to reveal the synergetic relationship between core-rim structure and mechanical properties. VC and ZrC effectively inhibited the grain growth, while TaC and NbC favored for coarser core-rim grains. A thin distortion layer at the rim-binder interface was confirmed, formed during the solidifying stage. Compared to the TaC, ZrC and NbC, VC shrunk the lattice parameters of rims and effectively decreased the lattice misfit of the distortion zone from around 4.0%-0.8%. Cermets containing VC showed satisfactory bending strength of 2099 MPa and toughness of 10. 3 MPa m^1/2, owing to the strengthened rim-binder interface. TaC and NbC exhibited the similar roles in cermets with comparable mechanical properties, while addition of ZrC increased the lattice misfit of core-rim structure, resulting in poor mechanical performance. Decreased lattice misfit of rim-binder interface changed the fracture mode of cermets from intergranular to transgranular fracture, with in-situ formed dimples.     

Influence of ZrC addition on the microstructure,mechanical properties and oxidation resistance of Ti(C,N)-based cermets

In this study, Ti(C,N)-WC-NbC-ZrC-Co-Ni cermets were prepared by sintering-hip at 1450?°C. The effect of ZrC addition on the microstructure, mechanical properties, oxidation resistance and wear resistance of Ti(C,N)-WC-NbC-Co-Ni cermets were explored in detail. The results show that ZrC addition plays the role of inhibitor in the dissolution–reprecipitation process, which can increase the wear-resistant carbide phases and inhibit the precipitation of brittle (Ti,W,Nb)(C,N) rim phase. Therefore, the core-rim structures are refined and the Nb content in binder increases, which enhance mechanical properties and oxidation resistance of cermets. With the increasing ZrC content, the oxidation resistance of cermets can be improved constantly, while the transverse rupture strength, fracture toughness and wear resistance of these cermets increase first and then decrease. The cermet with 1?wt% ZrC exhibits the transverse rupture strength of 2549?MPa and highest fracture toughness of 13.0?MPa?m^1/2. The oxidation weight gain of cermets containing 5?wt% ZrC after holding 100?h at 750?°C in air is 2.8?×?10^?6 g?mm^?2, which is only 22% of that in the cermets without ZrC addition.     

Effect of WC-Co granules on mechanical properties and microstructure of Ti(C,N)-based cermets

The effect of WC-Co granules addition on the microstructure and mechanical properties of TiC(nm)-TiN(nm)-Co-Mo-C cermets (shown as Ti(C,N)-based cermets in other part of the paper) was studied in this paper. The results show that the WC-Co granules distribute homogeneously in the matrix of Ti(C,N) based cermets. There was a transitional layer containing intermetallic compound between the WC-Co granules and the matrix of Ti(C,N) based cermets. Transverse rupture strength(TRS) and fracture toughness increase with the increase of WC-Co granules, reach a peak value at 15 vol% addition in comparing with that of without WC-Co granules addition. The toughening mechanisms were crack deflection, branching and trapping. However, when the content of WC-Co granules was higher than 15 vol%, the excessive content of WC-Co granules leaded to voids in the cermets, which decreased the mechanical properties of the cermets.     

Effect of WC content on the microstructures and corrosion behavior of Ti(C,N)-based cermets

The influence of WC content on the microstructure and corrosion behavior of Ti(C, N)-based cermets in 2 mol/L nitric acid solution was studied in this paper. There exists typical core/rim structure in the cermets. The cores appear black or white, and the rim is divided into white inner rim and grey outer rim. The undissolved Ti(C, N) particles normally appear as black cores, while the white core, inner rim and outer rim are (Ti, W, Mo) (C, N) solid solution formed at different sintering stages. The inner rim and white core appear brighter atomic contrast than the outer rim and black core, which is attributed to their higher W and Mo content. The thickness of the inner rim increases with WC addition, but the grain size of core/rim phase becomes finer. Meanwhile, the amount of white cores increases and that of black cores decreases. WC is more easily oxidized and dissolved in the nitric acid solution, compared with Ti(C, N). Therefore, the degradation of inner rim phase and the white core becomes more considerable with the increase of WC content. Consequently, the corrosion rate of cermets increases and the corrosion resistance of Ti(C, N)-based cermets is deteriorated with the increase of WC content.