Effects of Annealing on Atomic Interdiffusion and Microstructures in Fe/Si Systems

Pure metal Fe films with thickness of about 100nm were deposited on Si （100） substrates by DC magnetron sputtering. Annealing was subsequently performed in a vacuum furnace in the temperature range of 600-1000℃ for 2h. The samples were characterized by means of Rutherford backscattering （RBS） with 3MeV carbon ions. The RBS data were fitted with SIMNRA 6.0, and the results show the atomic interdiffusion in Fe/Si systems. The microstructures and crystal structures were characterized by scanning electron microscope and X-ray diffrac- tion. The effects of annealing on atomic interdiffusion, silicide formation, and microstructures in Fe/Si systems were analyzed.

Atomic interdiffusion in Ni-Cu system under high magnetic field

The effect of high magnetic field on the atomic interdiffusion in Ni-Cu system was studied using the Cu/Ni/Cu diffusion couples. During the atomic interdiffusion in Ni-Cu system, it was found that the interdiffusion coefficients increased with the increase of molar fraction of Ni atoms in the interdiffusion zones when the couples were annealed with or without the magnetic field. It was noted that all corresponding interdiffusion coefficients under the magnetic field are smaller than those without the magnetic field. The results demonstrate that the magnetic field retards the atomic interdiffusion in Ni-Cu system. This retardation is achieved through reducing the frequency factors but not changing the interdiffusion activation energies.

Interdiffusion behavior between Cr and Zr and its effect on the microcracking behavior in the Cr-coated Zr-4 alloy

High-temperature chromium(Cr)-zirconium(Zr)interdiffusion commonly occurs in Cr-coated zircaloys applied for enhanced accident-tolerant fuel(ATF)claddings.Such interdiffusion changes the interfacial microstructure and thus the fracture mechanism of the coating under external loading.In this study,the interdiffusion behavior in a magnetron sputtered Cr coating deposited on a Zr-4 alloy was studied in a vacuum environment at 1160C.In addition,the effect of interdiffusion on the microcracking behavior of the Cr coating was determined by in situ three-point bending tests.The experimental results show that the interdiffusion behavior resulted in the formation of a ZrCr2 layer,accompanied by the consumption of Cr coating and interfacial roughening.The growth of the diffusion layer followed a nearly parabolic law with respect to annealing time,and the residual stress of the annealed coating decreased with increasing annealing time.Under external loading,a large number of cracks were generated in the brittle interlayer,and some interfacial cracks were formed and grew at the ZrCr2/Zr-4 interface.Despite the remarkable microcracks in the ZrCr2 layer,the vacuum-annealed Cr coating has significantly fewer cracks than the original coating,mainly because of the recrystallization of the coating during annealing.

Oxidation and interdiffusion behavior of a germanium-modified silicide coating on an Nb–Si-based alloy

To investigate the interdiffusion behavior of Ge-modified silicide coatings on an Nb–Si-based alloy substrate,the coating was oxidized at 1250°C for 5,10,20,50,or 100 h.The interfacial diffusion between the(Nb,X)(Si,Ge)_2(X = Ti,Cr,Hf) coating and the Nb–Si based alloy was also examined.The transitional layer is composed of(Ti,Nb)_5(Si,Ge)_4 and a small amount of(Nb,X)_5(Si,Ge)_3.With increasing oxidation time,the thickness of the transitional layer increases because of the diffusion of Si from the outer layer to the substrate,which obeys a parabolic rate law.The parabolic growth rate constant of the transitional layer under oxidation conditions is 2.018 μm×h^(-1/2).Moreover,the interdiffusion coefficients of Si in the transitional layer were determined from the interdiffusion fluxes calculated directly from experimental concentration profiles.

Interdiffusion in the Fe_2O_3-TiO_2 system

Interdiffusion in the Fe203-TiO2 system was investigated by the diffusion couple method in the temperature range of 1323 to 1473 K. The diffusion concentration curves of Ti4＋ cations were obtained by electron probe microanalysis, according to which the Boltzmann-Matano method optimized by Broeder was used to calculate the interdiffusion coeffi- cients. The interdiffusion coefficients almost increased linearly with the mole fraction of Ti4＋ cations increasing, and they were in the range of 10-12-10-11cm2-s-1. The increase of temperature could also lead to the increase of the interdiffusion coefficients at a constant concentration of Ti4＋ cations. It was also found that the thickness growth of the diffusion layer obeyed the parabolic rate law.

Effect of Substrate Characteristics on Interdiffusion Coefficients of Ni and Al Atoms in β-NiAl Phase of Aluminide Coatings

Interdiffusion coefficients at 950℃ and 1050℃ are calculated by Wagner analysis method as a function of composition of β-NiAI phase. The β-NiAI phase is formed by pack cementation on surface of superalloy. Results of the calculation show that interdiffusion coefficients in β-NiAI phase strongly depend on the compositions and vary over several orders of magnitude. Compared with the interdiffusion coefficients in the stoichiometric β-NiAI phase, the interdiffusion coefficients in β-NiAI phase formed on superalloy is obviously small, probably due to the composition, complicated microstructure and precipitates. However, it could be seen clearly that the shapes of the diffusivity curves are very similar to each other. The similarity of the diffusion curves and the difference between interdiffusion coefficients imply that the compositions, microstructures and precipitates of superalloy have a distinctly adverse effect on the interdiffusion of Ni and Al atoms during aluminization, but do not change the essential characteristics of β-NiAI phase.

A repeated interdiffusion method for efficient planar formamidinium perovskite solar cells

A repeated interdiffusion method is described for phase-stable and high-quality （FA,MA）PbI3 film. The crys- tallization and growth of the perovskite films can be well controlled by adjusting the reactant concentrations. With this method, dense, smooth perovskite films with large crystals have been obtained. Finally, a PCE of 16.5% as well as a steady-state efficiency of 16.3% is achieved in the planar perovskite solar cell.

Phase-field simulation of the effect of interaction among ordered domains on interdiffusion in Ni-Al-Cr alloys

The effect of interaction among γ′ ordered domains on the interdiffusion process in γ＋γ′ and γ＋γ′/γ＋γ′ diffusion couples is investigated by using the phase-field method, in which bulk free energy and mobility are linked with thermodynamic and kinetic databases. Simulated results show that the interaction among γ′ ordered domains has great influence on the microstructure, the interdiffnsion velocity and the volume fraction ofγ′ phase on both sides of the diffusion couples.

Fundamental Concept of Interdiffusion Problems

In accordance with the definition of diffusivity, the origin of coordinate system of the original diffusion equation is set at a point in the solvent material. Kirkendall revealed that Cu atoms, Zn atoms and vacancies move simultaneously in the interdiffusion region. This indicates that the original diffusion equation is a moving coordinate system for the experimentation system outside the diffusion region. The diffusion region space which means vacancies and interstices among atoms plays an important role in the diffusion phenomena. The theoretical equation of the Kirkendall effect is reasonably obtained as a shift between coordinate systems of the diffusion equation. The situation is similar to the well-known Doppler effect in the wave equation. Boltzmann transformed the original diffusion equation of a binary system into the nonlinear ordinary differential equation in accordance with the parabolic law. In the previous works, the solutions of the diffusion equation transformed by Boltzmann were analytically obtained and we found that the well-known Darken equation is mathematically wrong. In the present study, we found that the so-called intrinsic diffusivity corresponds in appearance to the physical solution obtained previously. However, the intrinsic diffusivity itself conceived in the diffusion research history is essentially nonexistent.

New Analytical Method of Interdiffusion Problems

The nonlinear diffusion equation for a binary system interdiffusion was analytically solved in the previous work. The theoretical relation of Kirkendall effect was also derived in the previous work. These new results have not yet been concretely applied to actual diffusion problems. In the present work, it is revealed that the previous results reproduce the experimental concentration profile by taking account of the movement of diffusion region space. It is thus actually confirmed that any problems of binary system interdiffusion can be solved by the new analytical method if even diffusivities of self-diffusion and impurity diffusion in the materials concerned are given. The method for solving interdiffusion problems of many elements system, which is extremely important for the development of new useful materials, is also reasonably discussed. Further, it is revealed that the concept of intrinsic diffusion is unsuitable for the diffusion theory. The fundamental theory of diffusion discussed here will be useful for analyzing actual diffusion problems in future.

Interdiffusion of Na, K, and Ca Between Granitic Melts and NaCl Liquid

This study is aimed at determining the diffusion coeffcient of net-work modifiers（mainly Na, K, and Ca） in a two-phase melt-NaCl system, in which the melts are granitic andthe system is NaCl-rich in composition. The diffusion coefficients of Na, K, and Ca were measured at the temperatures of 750 -1400℃, pressures of 0. 001×108 - 2×108 Pa, and initialH2O contents of O wt% - 6. 9 wt% in the granitic melts. The diffusion coefficients of Fe andMg were difficuIt to resolve. In all experiments a NaCl melt was present as well. In the absence of H2O, the diffusion of net-work modifiers folows an Arrhanious equation at 1 ×105 Pa:lgDCa= - 3. 88 - 5140/ T, lgDK = - 3. 79 - 4040/ T, and lgDNa=- 4.99 - 3350/ T,where D is in cm2/s and T is in K. The diffusion coefficients of Ca, Na, K, and Fe increasenon-linearly with increasing H2O cOntent in the melt. The presence of about 2 wt% H2O inthe melt will lead to a dramatical increase in diffusivity, but higher H2O content has only a minor effect. This change is probably the result of a change in the melt structure when H2O ispresent. The diffusion coefficients measured in this study are significantly different from thosein previous woks. This may be understood in terms of the "transient two-liquid equilibrium"theory. Element interdiffusion dapends not only on its concentration, but also on its activity coefficient gradient, which is reflected by the distribution coefficient, of the two contactingmelts.

Effect of Cu additions on interdiffusion behavior in the Al-Zn solid solution

After diffusion couples were annealed at 260-360 ℃, the concentration profiles of Zn element were measured by EPMA. It has been first quantitatively determined by Matano method that the interdiffusion coefficient in A1-Zn fee solid solution containing high Zn contents is remarkably decreased due to the small addition of Cu. Also, the interdiffusion coefficient in A1-Zn fee solid solution clearly increases with the increasing of Zn concentration. The interdiffusion activity energy remarkably decreases with the increasing of Zn contents. On the other hand, the interdiffusion activity energy markedly increases due to the small addition of Cu in the A1 Zn fcc solid solution containing high Zn contents.

铝化物涂层拓扑密排相的研究进展

铝化物涂层因其良好的抗高温氧化能力而被应用于航机和燃机叶片的高温防护。在涂层制备与服役过程中,涂层与基体元素互扩散,使基体的相结构发生转变,导致在涂层/基体界面形成互扩散区(IDZ),并析出富含Re、W、Cr、Mo等元素的细小拓扑密排相(TCP相)。TCP相的析出导致固溶强化效果减弱,同时作为一种脆性相促进了裂纹的产生,此外,互扩散区的形成减小了基体的承载面积,导致基体的高温蠕变性能下降。针对涂层TCP相的析出及IDZ的形成机理进行了介绍,分析了TCP相的类型(σ相、μ相、P相)、特点及对基体性能的危害。添加铂族改性元素和预沉积Ni层是抑制TCP相析出的主要方法,添加改性元素可以增大固溶元素的固溶度,并抑制TCP相的生长和成核,而预沉积Ni层可以减小固溶强化元素的扩散。最后,展望了未来可通过添加多元改性元素或元素改性与预沉积Ni相结合的方法来抑制铝化物涂层TCP相的析出。

热障涂层与单晶高温合金互扩散控制方法研究进展

目前,二代及更高级单晶涡轮叶片的表面服役温度已达到1050℃以上,因此涂层与基体间的元素互扩散十分严重。互扩散不仅会消耗涂层中的有益元素,降低涂层服役寿命,而且会在单晶基体中形成二次反应区,严重损害单晶基体的力学性能。扩散障和低互扩散性涂层是控制热障涂层与单晶基体间元素互扩散的有效方法。结合国内外最新研究进展,本文首先对扩散障的设计原理、基本特性以及分类作简要介绍,并具体分析了金属扩散障、陶瓷扩散障和活性扩散障存在的主要问题以及针对这些问题开展的相关研究工作;其次,对低互扩散性涂层在热障涂层领域中的应用与最新发展动态进行综述,详细讨论了纳米晶涂层、相平衡涂层和γ′基涂层的高温防护性能和阻扩散机制。在此基础上,指出了扩散障和低互扩散性涂层的未来发展方向。

应用于三维集成的金铟键合技术研究

由于埋置芯片耐受温度的限制,圆片级低温键合技术是MEMS三维集成的关键工艺之一。金属In凭借自身熔点低而金属间化合物(Intermetallic compound, IMC)熔点高且性质稳定的特点,使得Au-In固液扩散键合法成为颇具前景的低温键合技术之一。本文采用Au-In二元共晶化合物进行圆片级低温键合,在键合衬底上先后制备了0.4μm的SiO/SiN介质层、3.5μm的Au层和1.7μm的In层,然后分别研究了先预加热键合极板再贴合圆片和先贴合再加热两种键合方式。电性能测试、An/In组分分析和剪切试验结果表明:先贴合再加热的键合样品芯片形成了性质稳定的IMC组分,具有良好的电学互连特性稳定性,且剪切强度达到100 MPa。一定样本容量的实验结果证明隔绝键合前Au-In的相互扩散能够有效增强键合的可靠性。

低压等离子喷涂NiCoCrAIYTa涂层的抗燃气热冲击性能研究

为了保障涡轮叶片材料的抗高温氧化与耐热腐蚀性能,采用低压等离子喷涂技术在航空发动机涡轮叶片试验件上成功制备了NiCoCrAlYTa涂层。通过对不同粉末制备的NiCoCrAlYTa涂层进行1000℃/75 h燃气热冲击试验,研究了带涂层叶片尺寸、涂层表面形貌、相组成和显微组织、涂层厚度和均匀性等性能参数的变化。结果表明:热冲击试验后,不同涂层叶片的整体尺寸未发生显著变化,表明涂层在高温环境下具有稳定的尺寸;涂层表面形成了Al_(2)O_(3)膜和NiAl_(2)O_(4)尖晶石,保留了较好的结构完整度,这有助于提高涂层的耐腐蚀性能;涂层的物相组成主要包括γ-Ni、γ’-Ni_(3)Al和少量的β-NiAl,形成了贫Al区、互扩散区、二次反应区等典型微区结构,析出的TCP相为R相,表明在热冲击过程中涂层发生了相变;不同粉末制备的NiCoCrAlYTa涂层均表现出了良好的抗热冲击性能,为航空发动机涡轮叶片的高温应用提供了可行的涂层方案。

Re扩散障厚度对铂改性铝化物涂层1200℃氧化行为影响

铂改性铝化物(PtAl)涂层具有良好的抗高温氧化和抗热腐蚀综合性能,被广泛用于单晶航空发动机高温合金叶片的高温防护。添加扩散障可阻止高温合金中难熔元素(W,Mo)向外扩散,提高涂层/基体结构稳定性,以及PtAl涂层抗氧化和高温力学性能。为探究Re扩散障厚度对PtAl涂层性能的影响,采用电镀与高温低活性渗铝技术,在Ni3Al基单晶高温合金表面制备了无Re扩散障和3种不同厚度Re扩散障的PtAl涂层,开展了1200℃恒温氧化实验,对比分析了PtAl涂层的抗高温氧化性能。利用场发射-扫描电镜、能谱仪和X射线衍射仪,对涂层微观组织结构和成分进行了详细表征,对其氧化行为及失效机制进行了深入探讨。研究表明,未添加Re扩散障的制备态PtAl涂层呈现双层结构,包括外层和互扩散区。添加Re扩散障后,PtAl涂层转变为3层结构,包括外层、扩散障层和互扩散区。添加了Re扩散障的PtAl涂层,经1200℃氧化后涂层表面呈现出更少的剥落面积,氧化膜相对致密完整,表明Re扩散障的添加可以显著提升PtAl涂层的抗高温氧化性能。随着Re扩散障厚度的增加,涂层的氧化增重进一步降低;然而,当Re扩散障厚度超过一定程度后,涂层抗氧化性能的提升并不明显。其原因是过厚的电镀Ni-Re层在氧化过程中导致了Re扩散障致密度和连续性的下降,降低了扩散障对Al元素的阻扩散效果。本研究深入揭示了Re扩散障厚度对PtAl涂层抗氧化性能的影响机理,为含Re扩散障的PtAl涂层的设计提供了重要理论基础。

热处理过程中Hg_(1-x)Cd_xTe/CdTe界面互扩散研究

对ＨｇＣｄＴｅ／ＣｄＴｅ／ＧａＡｓ结构热处理后的样品进行深度剥层腐蚀，并用椭偏光谱测量方法，获得了样品在４９０℃经０．５ｈ和２ｈ热处理后不同深度下的组份分布．根据实验结果对Ｚａｎｉｏ等人提出的扩散系数公式进行了修正，得到４９０℃热处理条件下的组份扩散系数ＤＨｇ１－ｘＣｄｘＴｅ（４９０℃）＝４×１０－３×１０－３·ｘ．

NiCrAlYSi涂层与镍基高温合金基体互扩散行为研究

采用电弧离子镀方法在镍基高温合金DZ125上沉积NiCrAlYSi涂层,通过对不同氧化时间后Al和Cr原子浓度分布曲线的分析,运用Boltzmann-matano方法,计算了Al和Cr元素在1373K分别加热0.5,2h和5h的互扩散系数,并拟合了这三个时间段的计算结果。结果表明:相同温度下,Al和Cr的互扩散系数分别随Al和Cr的原子浓度增加而增大。随氧化时间的延长,Al的互扩散系数随原子浓度的变化先增大然后基本不变,Cr的互扩散系数则逐渐减小;伴随着元素间互扩散行为的增强,涂层中的Al和Cr向基体扩散,基体合金元素Ni,Co,Mo,Ti和W则向涂层扩散,但涂层中Mo和Ti的含量相对较少。由于元素间互扩散行为,涂层中各元素的含量将趋向于更加均匀。

NiCrAlY涂层/Ni基单晶高温合金的元素扩散及界面特性

采用磁控溅射方法在Ni基单晶高温合金上沉积NiCrAlY涂层,研究了真空热处理及高温氧化过程中,NiCrAlY涂层/Ni基单晶合金界面显微结构的变化及元素扩散行为。结果表明,原始涂层成分分布比较均匀,各元素分布在涂层/基体界面呈陡然变化。真空热处理时,涂层与基体间发生互扩散,NiCrAlY涂层的显微结构和相结构发生变化:涂层/基体界面区出现互扩散层(内、外扩散层);出现g-Ni3Al 和a-Cr两新相,导致涂层局部区域富Cr。1 000℃氧化200h后,涂层/基体界面区的互扩散层增厚,并且在其下的基体中出现扩散影响层。Ta在涂层中扩散时,置换了部分g-Ni3Al相中的Al,导致g相的晶格常数a0增大。