Design of functionally graded thermal barrier coatings based on a nonlinear micromechanical approach

This study presents the methodology of analysis and design of functionally graded thermal barrier coatings (FG TBCs) consisting of ceramics and metals based on a mean-field micromechanical approach taking into account the time-independent and dependent inelastic deformation, such as plasticity of metals, creep of metals and ceramics, and diffusional mass flow at the ceramic/metal interface. Ni–ZrO₂ systems were numerically studied and the effect of the compositional gradation patterns and time-dependent inelastic deformation on the micro- and macro-stress states in the FG TBCs were examined. The suitable compositional gradation patterns were proposed for typical thermo-mechanical boundary conditions. It was shown that the creep deformation near the ceramic surface can introduce large tensile stresses, potentially leading to thermal fracture, which is possibly reduced by controlling the ability of creep of the ceramics.     

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.     

Void formation in metal matrix composites by solidification and shrinkage of an AlSi7 matrix between densely packed particles

Particle reinforced metals are developed as heat sink materials for advanced thermal management applications. Metal matrix composites combine the high thermal conductivity of a metal with a low coefficient of thermal expansion of ceramic reinforcements. SiC and carbon diamond particle reinforced aluminum offer suitable thermal properties for heat sink applications. These composites are produced by liquid metal infiltration of a densely packed particle preform. Wettability, interface bonding strength and thermal mismatch are critical for void formation which leads to thermal fatigue damage under operation. The evolution of voids in AlSiC and AlCD has been studied by in-situ high resolution synchrotron tomography during matrix solidification. Large irregularly shaped matrix voids form during eutectic solidification. These voids help alleviate thermal expansion mismatch stresses by visco-plastic matrix deformation during cooling to RT after solidification, if sufficient interface bonding strength is assumed.     

Ceramic-metal reaction welding

In bonding ceramic oxides to metals, two reaction mechanisms have been utilized. These are (1) a surface or microscopic reaction, between close-packed ceramic oxides, quartz, and glasses and the noble metals (e.g. Pt, Pd, Au, Ag), maintaining a sharp discontinuity at the interface, (2) a bulk or macroscopic reaction between the same oxides and other transition metals (e.g. Fe, Co, Ni) producing a diffusional type interface. Both have common reaction conditions and occur: (a) below the melting point of the lowest melting component, (b) in any atmosphere compatible with all components at the operating temperature, (c) under little or no pressure, and (d) without deformation.The progress of several Type 1 reactions has been followed by direct observation at elevated temperatures and high resolution in a modified transmission electron microscope. It has thereby been established that this reaction proceeds with the formation of an intermediate phase, liquid-like at temperatures below the melting point of any of the components.Bonds have also been examined using electron scanning microscopy, electron probe microanalysis, and optical microscopy. Vacuum tight bonds can be produced and shear tests indicate that strength is generally limited by the strength of oxide components.     

Nanoscale Oxide Formation at α-Al2O3–Nb Interfaces

Parts for metallurgical applications made from refractory metal–ceramic composites offer improved thermal shock resistance due to their capability for resistive heating compared to ones made solely from ceramics such as Al₂O₃. The combination of Al₂O₃ and Nb is intriguing as both show similar thermal expansion behavior over a wide temperature range. The high affinity of Nb for O to form nonprotective oxides, however, hampers its use in oxidative environments. Formation of such phases at the ceramic–metal interface can have detrimental effects on the cohesion of the composites. For this work, nanocrystalline Nb films are deposited on sapphire substrates by magnetron sputtering to study diffusion of O and high-temperature phase formation at a refractory metal–ceramic interface during heat treatment under Ar at 1600 °C. A combined approach of atom probe tomography and transmission electron microscopy for compositional and crystallographic analyses reveals that at triple junctions of the sapphire–Nb interface with Nb grain boundaries, heterogeneous nucleation of nanoscale NbO₂ occurs, which further reacts with Al₂O₃ to form AlNbO₄, while the Nb film itself remains metallic. Fast O transport through grain boundaries leads to internal oxidation at the interface, whereas regions further away from Nb grain boundaries remain unchanged.     

固体氧化物燃料电池阳极材料成份的优化规律

本研究借助第一性原理总能量计算法, 针对可能用于固体氧化物燃料电池阳极材料的3~6周期金属元素及其氧化物, 进行了稳定性、电学性能及力学性能等方面的研究。对工作条件下(高温、还原性气氛)阳极的结构形态、综合性能等的演化情况进行了研究分析, 得到了金属/氧化物体系体模量、禁带宽度的变化趋势, 及其与稳定性的关系。结果显示, 位于生成趋势图中部区域的金属/氧化物稳定性适中, 易于发生氧化/还原反应, 可能是阳极工作条件下综合性能较优的原因, 其中靠近金属区的元素更能为体系提供电子电导和催化活性, 靠近氧化物区的元素更能为体系提供氧离子并增加稳定性, 这些结果为不同条件下的阳极选择提供了理论指导。     

Studies of ceramic-liquid metal reaction interfaces

An investigation has been made of the nature and extent of chemical reactions between various liquid metals and a range of engineering-grade ceramics typically used as cutting tool inserts. Such possible reactions are relevant to chemical wear effects during metal cutting but also relate to liquid metal containment by ceramics and ceramic-metal joining. The experimental procedure has involved immersing pre-polished ceramic sections in liquid metals for controlled times with subsequent sectioning and examination of the reaction interface. The ceramics studied were two alumina-based materials and five silicon nitrides and sialons. The metals were pure iron, pure nickel and four iron-nickel alloys (a mild steel, a stainless steel and two nickel-based superalloys) and span a range of Fe-Ni compositions. The reaction rates of the alumina materials were found to be much lower than those of the silicon nitride-based materials and reflect the chemical stability of the Al-O bond array. Zirconia-toughened alumina showed little evidence of reaction with clean iron alloys but substantial attack by oxygen-containing iron-based materials was found resulting in the formation of iron-aluminium spinel reaction products. Al₂O₃-TiC/N exhibited preferential metal attack of the carbonitride phase with dissolution and/or replacement of the TiC/N dispersion. Within the silicon nitride-based group, ferrous alloys were found to be more damaging than mainly nickel alloys and silicon nitrides were more readily attacked than sialons. The difference in behaviour between the sialons and silicon nitrides is attributed to alumina additions in the former group of materials increasing resistance to attack by molten metals. A detailed mechanism of attack for these mixed-phase ceramics is proposed whereby a silicon concentration gradient is established from the crystalline ceramic phases, through the glassy binding phase, to the metal. The result is dissolution of the crystalline phase and an increase in volume fraction of the glassy binder at the metal-ceramic interface with concomitant progressive disruption of the ceramic microstructure.     

The effects of residual stresses and degradation on the response of viscoplastic functionally graded materials

Functionally graded materials (FGMs), having ceramic and metallic constituents, are commonly used for extreme temperature applications. Under extreme temperature changes, the mismatches in the thermo-mechanical properties of the ceramics and metallic constituents could cause pronounced thermal stresses and could lead to degradation in the properties of the constituents. High stresses in the metallic constituent lead to plastic deformations and high tensile stresses in the ceramic constituent induce cracking. An elastic–viscoplastic micromechanical model is formulated for analyzing residual stresses and strains and degradation in ceramic–metal FGMs undergoing temperature changes due to conduction of heat. A degradation parameter that depends on the temperature and strain is introduced in order to determine the level of material degradation in the ceramics and metallic constituents. The Perzyna viscoplastic model is considered for the metallic constituent while the ceramic constituent is assumed linear elastic. The material parameters in these constituents change with the degradation. The problem leads to time-dependent coupled thermal, deformation, and degradation behaviors. The micromechanical model is implemented in a displacement based finite element (FE), which is used to determine the performance of the viscoplastic functionally graded structures subject to external thermo-mechanical stimuli.     

Review Room-temperature reactions in thin metal couples

Results of a 40 year-long investigation of room-temperature formation of compounds in 144 thin-film couples obtained by combining 23 metals (Ag, Al, Au, Bi, Cd, Co, Cr, Cu, Ga, Ge, In, Mg, Mn, Ni, Pb, Pd, Pt, Sb, Sm, Sn, Te, Ti, Zn) are presented. The data from published papers of the present and other authors have been complemented by unpublished data of the present authors. The systematized results and their analysis point to the following. In 39 couples, a total of 65 compounds are formed. The reactions of compound formation last from 1 min to 10 y, depending on the specimen type and procedure of film deposition. In the bulk–film specimens, the number of compounds formed is smaller and the reaction is slower than in the film–film specimens prepared by thermal evaporation. In the specimens with the sputtered top layer, a greater number of compounds is formed and the compound formation reaction proceeds more rapidly than in the couples prepared by thermal evaporation of both metals. The compounds formed can be transformed into others containing higher percentage of one of the constituents, until the specimen contains an excess of that constituent, provided that such compounds exist in the respective phase diagram. At the beginning of the reaction, compounds are formed in a broad concentration range, while at the reaction end the range is narrowed down, becoming close to that in the corresponding phase diagram. The optimum conditions for compound formation exist in the couples consisting of a high-melting metal and a low-melting one, provided that the potential compound is not high-melting. If the potential compound is high-melting, or if both metals in the couple have melting points in the same temperature range, no compound formation takes place at room temperature. In the couples consisting of a given high-melting metal and one of the low-melting metals, a linear relationship exists between the interdiffusion coefficient and the melting point of the low-melting metal. If, for a couple consisting of a high-melting metal and a low-melting one, there is a solid solubility range of the low-melting metal, during the course of long ageing, the compound formed is decomposed and the low-melting metal is amorphized. During the long ageing, the ambient atmosphere acts on the metal films (alone or in a couple) leading to formation of oxides, hydroxides or carbonates. The results obtained complement the low-temperature range results in the respective phase diagrams.     

碳纳米管增强金属基复合材料的研究进展

碳纳米管增强金属基复合材料由于高的比强度、比模量以及优异的热、电性能在航空航天领域具有很好的应用潜力,本文在分析大量文献的基础上,评述该类材料的制备技术和界面研究进展,对其典型性能进行归纳,指出碳纳米管的分散技术以及碳管、基体之间的界面特性应该是今后本领域的重点研究方向。     

热震中7YSZ热障涂层结构演变

采用低温超音速等离子喷涂(LT-HVOF)在镍基高温合金基体上制备了NiCoCrAlYTa粘结层, 使用大气等离子喷涂(APS)在粘结层上`制备了7wt%Y₂O₃-ZrO₂ (7YSZ) 陶瓷层。基于动态试验即热震实验研究了粘结层的扩散氧化机制, 探讨了陶瓷层的烧结及相变过程并观察了涂层的结构演变。实验结果表明: 动态热循环下随着热震次数的增加, 粘结层组元扩散氧化形成热生长氧化物(TGO)且厚度逐渐增加。此外, 粘结层组元在温度梯度下沿陶瓷层内部裂纹向高温区扩散, 最终在陶瓷层表面裂纹区域出现大量的金属氧化物, 同时粘结层组元的扩散有助于陶瓷层的烧结, 导致其显微硬度逐渐增大, 而粘结层由于Kirkendall效应, 其内部出现大量的孔洞导致其显微硬度逐渐降低。另外, 陶瓷层在相变及热循环应力的作用下表面出现了大尺度的宏观裂纹。     

Zirconia-toughened hydroxyapatite ceramic obtained by wet sintering

A toughened hydroxyapatite (HA) ceramic has been obtained through the incorporation of magnesia partially stabilized zirconia (Mg-PSZ) under uniaxial pressing and sintering in wet oxygen at 1250 °C for 4 h. The powder X-ray diffraction (XRD) patterns and infrared spectra (FT-IR) show that HA is the only calcium phosphate phase present. The composite (MgPSZ-HA) has a density of 94% the theoretical value. The bending strength and the fracture toughness are around 50% higher for Mg-PSZ reinforced than for HA. The grain size and the fracture surface were studied by scanning electron microscopy (SEM). The influence of the Mg-PSZ particles on the fracture mechanism of the HA ceramic is discussed.     

Factorial experimental design for recovering heavy metals from sludge with ion-exchange resin

Wastewaters containing heavy metals are usually treated by chemical precipitation method in Taiwan. This method can remove heavy metals form wastewaters efficiently, but the resultant heavy metal sludge is classified as hazardous solid waste and becomes another environmental problem. If we can remove heavy metals from sludge, it becomes non-hazardous waste and the treatment cost can be greatly reduced. This study aims at using ion-exchange resin to remove heavy metals such as copper, zinc, cadmium, and chromium from sludge generated by a PCB manufacturing plant. Factorial experimental design methodology was used to study the heavy metal removal efficiency. The total metal concentrations in the sludge, resin, and solution phases were measured respectively after 30 min reaction with varying leaching agents (citric acid and nitric acid); ion-exchange resins (Amberlite IRC-718 and IR-120), and temperatures (50 and 70 degrees C). The experimental results and statistical analysis show that a stronger leaching acid and a higher temperature both favor lower heavy metal residues in the sludge. Two-factors and even three-factor interaction effects on the heavy metal sorption in the resin phase are not negligible. The ion-exchange resin plays an important role in the sludge extraction or metal recovery. Empirical regression models were also obtained and used to predict the heavy metal profiles with satisfactory results.     

Effect of active metal coatings on the mechanical properties of silicon nitride-based ceramics

The effects of titanium, zirconium, hafnium and tantalum coatings on the mechanical properties of three silicon nitride ceramics were studied. The titanium coatings was found to cause a 50% decrease in the four-point bend strength of one of the silicon nitride ceramics while the effects of the zirconium, hafnium and tantalum coatings on all three silicon nitride ceramics were moderate. The reactions at a high temperature (940–980°C) between titanium and the grain-boundary glassy phase was the major cause for the degradation of the ceramic properties by the titanium coating. Residual tensile stress developed at the reaction interface replaced the glassy grain-boundary phase. Analytical electron microscopy showed the formation of a 180 nm thick Ti₅Si₃ layer and the crystallization of the amorphous grain-boundary phase. An indentation technique was used to measure qualitatively the residual stress developed at the reaction interface.     

New promising Co-free thermoelectric ceramic based on Ba–Fe–oxide

Thermoelectric ceramics are based in a limited number of transition metal oxides (Co, Mn, Ni,…) which produce materials with high thermoelectric performances. Based on previously existing thermoelectric phases, the phase diagram equilibrium can help to design new thermoelectric ceramics based on other transition metals (for example, Fe). In this work, BaFeO_x ceramics have been prepared by the classical solid state method using different sintering temperatures. The produced materials have shown promising thermoelectric properties when treatment temperatures are in the perovskite zone domain of the phase equilibrium diagram. In spite of the good values for the Seebeck coefficients, power factor is low due to the high resistivities measured in all cases.     

Simulation of the effect of material properties and interface roughness on the stress distribution in thermal barrier coatings using finite element method

A Finite Element Model (FEM) was developed to evaluate the stresses induced by the thermal cycling in a typical plasma-sprayed thermal barrier coating system (TBCs). The thermo-mechanical model of this multi-layer system takes into account the effects of thermal and mechanical properties, morphology of the top-coat/bond-coat interface and oxidation on the local stresses that are responsible for the micro-crack nucleation during cooling, especially near the metal/ceramic interface.Two top-coat/bond-coat geometries corresponding to different interfacial asperity morphologies (semicircle or sinusoidal) are modeled considering a two dimensional and periodic geometry. The effect of the geometry and the amplitude of asperities on stress distribution are examined to study the cause of the subsequent delamination of the TBCs system. Moreover, the effect of the creep in all layers and plastic deformation in the bond-coat as well as the oxidation in the perpendicular direction of the top-coat/bond-coat interface are examined toward the stress development and critical sites with respect to possible crack paths. In addition, crack initiation and propagation at the system was predicted.     

The behaviour of Al in MSW incinerator fly ash during thermal treatment

Fly ash from municipal solid waste (MSW) incinerators contains leachable metals, including potentially hazardous heavy metals. The metal content of the fly ash can be reduced by thermal treatment, which vaporizes the volatile metal compounds. After heat treatment of fly ash at 1000 degrees C for 3 h, less metal was able to be leached from the thermally treated ash than from the ash without thermal treatment. Al and Cr were the exceptions. These metals were more soluble in the ash that had been thermally treated. This paper focuses on the leaching behaviour of Al only. Both simple and sequential extraction leaching tests showed that the leachable Al for the heat-treated fly ash is about twice that of the untreated fly ash. The sequential test further revealed that (i) the majority of the leachable Al is associated with Fe-Mn oxides in the fly ash, and (ii) most of the unleachable Al resides in the silicate matrices of the heat-treated and untreated fly ash. Pure chemicals, Al(2)O(3), CaO and CaCl(2), simulating the relevant ingredients in the fly ash, were used for studying their reactions at 1000 degrees C. The aluminum compounds were identified by X-ray Diffraction (XRD). Two new chemical phases produced by the thermal treatment were identified; Ca(AlO(2))(2) and 12CaO.7Al(2)O(3). Their formation suggests a mechanism whereby thermal treatment of fly ash would produce more soluble Al.     

Topotactic Metal–Insulator Transition in Epitaxial SrFeOx Thin Films

Topotactic phase transformation enables structural transition without losing the crystalline symmetry of the parental phase and provides an effective platform for elucidating the redox reaction and oxygen diffusion within transition metal oxides. In addition, it enables tuning of the emergent physical properties of complex oxides, through strong interaction between the lattice and electronic degrees of freedom. In this communication, the electronic structure evolution of SrFeO_x epitaxial thin films is identified in real‐time, during the progress of reversible topotactic phase transformation. Using real‐time optical spectroscopy, the phase transition between the two structurally distinct phases (i.e., brownmillerite and perovskite) is quantitatively monitored, and a pressure–temperature phase diagram of the topotactic transformation is constructed for the first time. The transformation at relatively low temperatures is attributed to a markedly small difference in Gibbs free energy compared to the known similar class of materials to date. This study highlights the phase stability and reversibility of SrFeO_x thin films, which is highly relevant for energy and environmental applications exploiting the redox reactions.     

Thermal oxidation and native oxide-substrate reactions on InAs and InxGa1−xAs

The condensed phase portion of the In-As-O phase diagram has been used in conjuction with Raman scattering and photoemission studies to examine certain compositional aspects of native oxide-substrate reactions and thermal oxidation patterns on InAs and In_xGa_1?xAs. Elemental arsenic is found to be an intrinsic interfacial phase in native oxides grown under conditions close to thermodynamic equilibrium. Thermally driven oxide-substrate reactions yielding elemental arsenic can also be induced in anodic films which initially contained no elemental arsenic.     

Reduction reactions applied for synthesizing different nano-structured materials

Different materials have been synthesized by alternative routes: nitrates thermal decomposition to prepare oxide or co-formed oxides and reduction by hydrogen or graphite to obtain mixed oxides, composites or alloys. These chemical-based synthesis routes are described and thermodynamics studies and kinetics data are presented to support its feasibility. In addition, selective reduction reactions have been applied to successfully produce metal/ceramic composites, and alloys. Structural characterization has been carried out by X-ray Diffraction and, more extensively, Transmission Electron Microscopy operating in conventional diffraction contrast (CTEM) and high-resolution mode (HRTEM), indicated the possibility of obtaining oxide and alloy crystals of sizes ranging between 20 and 40 nm.