In Situ Thermocouples in Macro-Components Fabricated Using SALD and SALDVI Techniques. II. Evaluation of Processing Parameters

In order to fabricate well-control led in situ SiC/C thermocouples embedded within macro-structural SiC components using an integrated selective area laser deposition (SALD) and the selective area laser deposition and vapor Infiltration (SALDVI) technique, the major processing parameters affecting the crystal structure, the deposition rate, surface morphology of deposits, and shapes and sizes of the cross section of deposited lines are evaluated. It is found that the growth rate of SiC deposits increases with temperature and tetramethy Isilane (TMS) gas pressure over the temperature and pressure range studied. The apparent activation energy for depositing SiC from TMS is 61 kJ/mole in the temperature range from 700 to 1200°C and independent of the TMS gas pressure ranging from 20 to 60 torr. The shape and size of the cross section of SiC lines depend strongly on the deposition temperature. XRD examination indicates that the deposition product using a C₂H₂ precursor at 900°C is crystalline graphite. The crytallinity of Si₃N₄ deposits is affected by the substrate material even though the deposition temperature and other process parameters are the same. These phenomena have been explained in terms of the growth controlling mechanisms of deposits, the temperature distribution induced by an incident laser beam, and the thermal conductivity of the substrate.     

In Situ Thermocouples in Macro-Components Fabricated Using SALD and SALDVI Techniques. I. Thermochemical Modeling

To fabricate macro-structural SiC components containing an In Situ SiC/C thermocouple using an integrated SALD and SALDVI technique, thermodynamic analyses on the involved reactant gases have been performed with the CET89 code based on the minimization of the system free energy. The gaseous precursors considered include tetramethylsilane (TMS) and methyltrichlorosilane (MTS) for the deposition of silicon carbide, and methane, ethylene and acetylene for the deposition of carbon. Reactions between disilane and acetylene and between TMS and ammonia have also been thermodynamically calculated for the deposition of silicon carbide and silicon nitride (for use as an insulation layer between the thermocouple and the matrix), respectively. Based on these analyses, four characteristic temperature zones have been defined for the decomposition of silicon carbide from TMS. A silicon nitride deposition map has been built for the TMS and ammonia system. The deposition temperature range of silicon nitride is found to increase with the total pressure of TMS plus ammonia and the addition of hydrogen, and be affected by the ratio of TMS to ammonia. The addition of hydrogen also introduces a stable silicon carbide and silicon nitride mixture zone that otherwise does not exist. The co-deposition of graphite with silicon carbide and silicon nitride is found in the TMS-containing systems at certain conditions. However, the threshold temperature at which graphite co-deposition occurs can be increased by the addition of hydrogen, thereby eliminating or reducing the graphite co-deposition. Based on these thermodynamic analyses, the gaseous precursors for the deposition of silicon carbide, silicon nitride and carbon have been selected for further experimental evaluation, the result of which is reported in part II of this series.     

Multiple material solid free-form fabrication by selective area laser deposition

Selective Area Laser Deposition (SALD) is a gas phase Solid Free-Form Fabrication approach to the shaping of materials without part specific tooling. SALD uses a laser beam to create a localized heated zone on a substrate surrounded by a reactant gas. Within the localized heated zone, the reactant gas decomposes to produce a solid deposit. Repeated scanning of the beam in a defined pattern builds a three-dimensional shape. The laser-induced temperature distribution within the heated zone coupled with the chemical thermodynamics and kinetics of a reactant gas mixture are shown to give control of both composition and microstructure in ceramic composites. The process for control of composition and microstructure in SALD deposits is demonstrated for titanium oxide–silicon oxide composites deposited from reactant gas mixtures of TiCl₄–SiCl₄–O₂.     

Composites by rapid prototyping technology

The use of rapid prototyping (RP) technology for rapid tooling and rapid manufacturing has given rise to the development of application-oriented composites. The present paper furnishes succinct notes of the composites formed using main rapid prototyping processes such as Selective Laser Sintering/Melting, Laser Engineered Net Shaping, Laminated Object Manufacturing, Stereolithography, Fused Deposition Modeling, Three Dimensional Printing and Ultrasonic Consolidation. The emphasis of the present work is on the methodology of composite formation and the reporting of various materials used.     

Characterization and microstructural evolution of SiC(OAl) fibers to SiC(Al) fibers derived from aluminum-containing polycarbosilane

The SiC(OAl) fibers and the SiC(Al) fibers were fabricated by the use of aluminum-containing polycarbosilane (Al–PCS) precursor. The two types of fibers have been characterized. Chemical element analysis, AES, SEM, XRD, RMS and NMR have been employed. The chemical formula of SiC(OAl) fibers is SiC_1.31O_0.25Al_0.018 with C and O rich on the surface. The microstructure of SiC(OAl) fibers is a mixture of β-SiC nanocrystals, free carbon, and an amorphous silicon oxycarbide (Si–C–O phase), which have been confirmed by an amount of SiC₂O₂, SiCO₃, SiO₄ and SiC₃O units in the ²⁹Si MAS NMR spectrum. A small quantity of aluminum is embedded uniformly in the Si–C–O amorphous continuous phase. For SiC(Al) fibers, nearly stoichiometric composition was confirmed as chemical composition of SiC_1.03O_0.013Al_0.024. The fiber is composed of a large number of β-SiC crystallites, a small amount of -SiC crystalline and SiC amorphous phase. The aluminum in the SiC(Al) fibers mainly exists in two manners: Al–C bonds connected with the surfaces of the β-SiC grains and Al–O bonds, or Al₂O₃, to the amorphous phase.     

原位反应结合碳化硅多孔陶瓷的制备与性能

以碳化硅(SiC)和氧化铝(Al₂O₃)为起始原料、石墨为造孔剂, 通过原位反应结合工艺制备SiC多孔陶瓷. XRD分析表明多孔陶瓷的主相是SiC, 结合相是莫来石与方石英; SEM观察到多孔陶瓷具有相互连通的开孔结构. 坯体在烧结前后具有很小的尺寸变化, 线收缩率约在±1.5%内. 多孔陶瓷的开口孔隙率随烧结温度和成型压力的增大而减小, 随石墨加入量的增加而增大; 而体密度具有相反的变化趋势. 随着石墨粒径的增大, 多孔陶瓷的孔径分布呈现双峰分布. 抗弯强度随烧结温度和成型压力的增大而增大, 随石墨加入量的增大而减小. 于1450℃保温4h烧成的样品在0～800℃的平均热膨胀系数为6.4×10^-6/K. 多孔陶瓷还表现出良好的透气性、抗高温氧化和耐酸腐蚀性, 但耐碱腐蚀性相对较差.     

In situ synthesis mechanism and characterization of ZrB2–ZrC–SiC ultra high-temperature ceramics

The synthesis route, microstructure and properties of ZrB₂–ZrC–SiC composites prepared from a mixture of Zr–B₄C–Si powders by in situ reactive synthesis were investigated. The reactive path and synthesized mechanism of ZrB₂–ZrC–SiC composite were studied through series of pressureless heat treatments ranging from 800 °C to 1700 °C in argon. The in situ ZrB₂–ZrC–SiC composites were fabricated under different synthesis processing. The one with 88.4% relative density performed poorly in mechanical properties due to the occurring of self-propagating high-temperature synthesis (SHS). The fully dense ZrB₂–ZrC–SiC composite was obtained under the optimized synthesis processing without SHS reactions. Its Vickers hardness, flexural strength and fracture toughness were 20.22 ± 0.56 GPa, 526 ± 9 MPa and 6.70 ± 0.20 MPa m^1/2, respectively.     

先驱体法制备的含铝SiC纤维的组成和结构研究

先驱体聚铝碳硅烷经熔融纺丝、空气预氧化处理、1300℃烧成可制得SiC(OAl)纤维(称为KD-A), 该纤?维再经1800℃烧结转变为SiC(Al)纤维(称 为KD-SA). 采用了元素分析、AES、SEM、XRD、RMS以及²⁹Si、¹³C、²⁷Al魔角自?旋固体核磁共振等测试方法对纤维的组成和结构进行了研究. 元素分析结果表?明KD-A的化学组成为SiC_1/31O_0.25Al_0.018, KD-SA为SiC_1.03O_0.013Al_0.024. AES表明, KD-A和KD-SA的表面和内部组成 不同. SEM表明KD-A、KD-SA表面光滑平坦, ?没出现孔洞、裂纹、沟槽等表面缺陷. XRD、RMS以及²⁹Si、¹³C、²⁷Al核磁共振的分析结果表明: KD-A包含较多的不定形游离C, O以不?定形SiC_xO_y复合相的形式存在, Al与复合相中的O相连存在于复合相中, 复合相在纤维中是连续相, 少量 的β-SiC微晶分散在其中, 是非晶SiC纤维; KD-SA含有大量的β-SiC晶粒, 少量的α-SiC和Al₂O₃, 是近化学计量比的多晶SiC纤维.     

Thermal mismatch stress in SiC whisker reinforced aluminium composite: new measurement method by X-ray diffraction

Abstract

A new X-ray diffraction method for characterising thermal mismatch stress (TMS) in SiC_w–Al composite has been developed. The TMS and thermal mismatch strain (TMSN) in SiC whiskers are considered to be axis symmetrical, and can be calculated by measuring the lattice distortion of the whiskers. Not only the average TMS in whiskers and matrix can be obtained, but the TMS components along longitudinal and radial directions in the SiC whiskers can also be deduced. Experimental results indicate that the TMS in SiC whiskers is compressive, and tensile in the aluminium matrix. The TMS and TMSN components along the longitudinal direction in the SiC whiskers are greater than those along the radial direction for a SiC_w–Al composite quenched at 500°C.     

NiCo2O4纳米线/SiC复合纤维制备及其电化学性能

以正硅酸乙酯(TEOS)为硅源,聚乙烯吡咯烷酮(PVP)为助纺剂,采用静电纺丝结合碳热还原制备出结晶度较高的β-SiC纤维,其比表面积为92.6 m2/g,表现出双电层电容储能特征,比电容为155.7 F/g。然后,利用水热法在SiC纤维表面生长出大量直径约为15 nm的NiCo₂O₄纳米线,得到NiCo₂O₄纳米线/SiC复合纤维。测试表明,NiCo₂O₄纳米线/SiC复合纤维中镍和钴元素分别以Ni2+/Ni3+和Co2+/Co3+价态形式存在,由于NiCo₂O₄纳米线与SiC纤维的协同作用,NiCo₂O₄纳米线/SiC复合纤维比电容显著提高,并表现出双电层和赝电容并存的特征,比电容可达300.3 F/g,当功率密度为58.1 W/kg时,NiCo₂O₄纳米线/SiC复合纤维能量密度为60.1 W·h/kg。      

Simulation of SiC Deposition in a Fiber Coating CVD Reactor

A simulation was carried out to study the Chemical Vapor Deposition (CVD) of SiC on a thin cylindrical substrate in a hot wall reactor. The results of this simulation are expected to apply to the process of fiber coating for interface control in fiber reinforced composites. The reactant in this study is methyltrichlorosilane (CH₃SiCl₃) in a background of hydrogen. The simulation was carried out using a commercial code (FLUENT). The simulation results compared well with experimental data from a hot wall reactor. It was determined that the temperature profiles tend to be uniform in the radial direction, and the deposition process is dominated by reaction kinetics.     

Surface oxidation of silicon carbide: quantitative measurement and Rh effect

The oxidation degree of a commercial silicon carbide (SiC) powder was studied by means of Fourier transform infrared spectroscopy, using the intensity of the δ (SiO₂) band at 450 cm⁻¹ for measurements. Results are related to data obtained by LECO and gravimetric measurements. The influence of water in oxygen on the rate of the oxidation process was particularly examined. It was found that water alone had an oxidizing efficiency and that its mixture with oxygen increased the effect of the latter. The presence of Rh particles on SiC promoted the formation of SiO₂. However, as shown by the IR study of CO adsorption, this formation embedded the metal particles. This effect can be avoided by loading Rh on a precalcined SiC sample.     

An experimental study on the in situ strength of SiC fibre in unidirectional SiC/Al composites

In order to investigate the effect of strain rate and high temperature exposure on the mechanical properties of the fibre in the unidirectional fibre reinforced metal-matrix composite, in situ SiC fibre bundles are extracted from two kinds of SiC/Al composite wires, which are heat-treated at two different temperatures (exposed in the air at 400 and 600 °C for 40 min after composition). Tensile tests for these two fibre bundles are performed at different strain rates (quasi-static test: 0.001 s⁻¹, dynamic test: 200, 700, and 1200 s⁻¹) and the stress–strain curves are obtained. The experimental results show that their mechanical properties are rate-dependent, the modulus E, strength σ_b and unstable strain _b (the strain corresponding to σ_b) all increase with increasing strain rate. Compared with the mechanical properties of the original SiC fibre, those of the two in situ fibres degrade to some extent, the degradation of the in situ fibre extracted from the composite wire exposed at 600 °C (hereafter referred to as in situ fibre 2) is more serious than that of the in situ fibre extracted from the composite wire exposed at 400 °C (hereafter referred to as in situ fibre 1). The mechanism of the degradation is investigated. A bi-modal Weibull statistical constitutive equation is established to describe the stress–strain relationship of the two in situ fibre bundles. The simulated stress–strain curves agree well with the experimental results.     

The CVD of Ceramic Protective Coatings on SiC Monofilaments for Use in Titanium Based Composites

TiB₂, TiC and TiN protective coatings have been deposited onto SiC monofilament fibers by the CVD technique using a cold-wall reactor at reduced pressure. The effect of deposition conditions on the morphology, microstructure, phase composition and adherence of the coatings were studied. The physical and chemical compatibility of these ceramic coatings with SiC filaments together with titanium-alloy matrices were assessed and compared. Dense and uniform TiB₂ coatings have been deposited successfully onto SiC monofilaments. The coating is stable on the SiC fiber and acts as an effective: barrier against the vigorous SiC/Ti-6Al-4V interfacial reaction. The adhesion of TiC on SiC fibers is comparatively weaker than the TiB₂ coating. There was no significant reaction found at the interface of TiC/Ti except at the interface of TiC/SiC. Examination of the TiN coatings showed severe cracking and spalling, hence TiN could not provide protection in a Ti-alloy matrix.     

原位反应法制备Cf/SiC复合材料MoSi2-SiC-Si涂层

以C_f/SiC复合材料为基体, 采用原位反应法制备了MoSi₂-SiC-Si涂层, 借助XRD、扫描电镜及能谱对涂层的结构及组成进行了分析研究, 并考查了其高温抗氧化性能. 结果表明, 涂层总厚度约120μm, 主要由MoSi₂、SiC和Si组成. MoSi₂-SiC-Si涂层具有优异的高温抗氧化性能, 在1500℃静态空气中氧化96h, 涂层试样失重仅1.8%. 涂层试样失重的主要原因是由于氧气通过涂层中的贯穿性裂纹与C_f/SiC复合材料基体发生了反应.     

Selective Laser Sintering of Alumina Using Aluminum Binder

Selective Laser Sintering (SLS) process has been used to make shapes from Al₂0₃ using Al as binder. SLS is a rapid manufacturing process that uses data from Solid Modeling systems to guide a laser beam and rapidly form 3-D shapes from powder without any part specific tooling. The aluminum melts under the laser and bonds the alumina particles. Some of the aluminum reacts with the ambient (air) to form alumina. The residual aluminum is oxidized in a subsequent he at-treatment step. The effect of parameters in the SLS step and heat-treating step on the mechanical properties and density of the part is examined. Linear expansion of the parts with oxidation heat-treatment is also examined.     

Comparative study on Pulsed Laser Deposition and Matrix Assisted Pulsed Laser Evaporation of urease thin films

Urease thin films were produced by Matrix Assisted Pulsed Laser Evaporation (MAPLE) and Pulsed Laser Deposition from two types of targets: frozen water solutions of urease with different concentrations (1-10% m/v) and pure urease pellets. The fluence of the ablating KrF excimer laser was varied between 300 and 2200 mJ/cm². Fourier transform infrared spectra of the deposited films showed no difference as compared to the original urease. Morphologic studies proved that the films consist of a smooth “base” layer with embedded micrometer-sized droplets. Absorption-coefficient measurements contradicted the traditional “absorptive matrix” model for MAPLE deposition. The laser energy was absorbed by urease clusters leading to a local heating-up and evaporation of the frozen matrix from the uppermost layer accompanied by the release of dissolved urease molecules. Significant enzymatic activity of urease was preserved only during matrix assisted transfer.     

La(1−x)SrxCoO3 for thin film thermocouple applications

In this study, the LSCO (lanthanum strontium cobalt oxide) family has been investigated for thin film thermocouple applications. Thin films of La_(1−x)Sr_xCoO₃ (x=0.3,0.5,0.7) were prepared on sapphire substrates by pulsed laser deposition. The films were annealed at different temperatures in air and characterized for phase, composition and microstructure to determine their thermal stability. From the phase and composition analyses, it is clear that as the Sr content in LSCO increases, the thermal stability decreases. Among the three compositions studied, x=0.3 had the best phase and chemical stability, and microstructural properties. It was observed that La_0.7Sr_0.3CoO₃ possesses excellent phase, composition and microstructural stability up to 1273 K. Above 1273 K, however, LSCO decomposes resulting in the loss of cobalt and formation of individual oxide phases. Electrical resistivity and Seebeck coefficients were measured in situ as a function of temperature in air up to 1023 K. The electrical and Seebeck coefficient properties were found to be stable for all the three compositions up to 1023 K and studies indicated that electrical conduction occurs through a small polaron hopping mechanism. In conclusion, LSCO possessed good thermal stability in air up to 1273 K and exhibits excellent potential in thin film thermocouple applications.     

碳化硅/碳化钨硬面密封摩擦副的摩擦磨损性能和机理研究

实验研究了干摩擦和水润滑条件下, 常压固相烧结碳化硅陶瓷(SSiC)及常压液相烧结碳化硅陶瓷(LPSiC)分别与碳化钨(WC)组成的硬面配对摩擦副的滑动摩擦磨损性能。在干摩擦条件下, 与LPSiC/WC摩擦副相比, SSiC陶瓷由于具有更大的晶粒尺寸和硬度, 导致SSiC/WC摩擦副具有更大的摩擦系数和更小的磨损量。磨损区域的SEM形貌结合面扫描分析、微区XRD分析结果表明: 微犁沟和微断裂导致SiC陶瓷的磨损, 疲劳损伤导致WC材料的磨损, 而摩擦过程产生的摩擦热导致磨出的WC颗粒氧化成无定型WO₃。在水润滑条件下, 与SSiC/WC摩擦副相比, LPSiC/WC摩擦副具有更大的摩擦系数和更低的磨损率。在干摩擦和水润滑条件下, 与SiC陶瓷作为动摩擦副配对相比, SiC陶瓷作为固定摩擦副的摩擦配对具有更小的摩擦系数和质量损失。     

Benefits of carbon addition on the hydrogen absorption properties of Mg-based thin films grown by Pulsed Laser Deposition

Mg-Ni thin films were grown using Pulsed Laser Deposition. In situ optical changes from shiny metallic to transparent states were observed for films deposited in vacuum and under an Ar/H₂ gas mixture (93/7%), respectively. Optical changes were also achieved by ex situ hydrogenation under hydrogen gas pressure of 15 bars at 200 °C. However, after ex situ hydrogenation, the optical transmittance of the Mg-based hydrogenated thin films did not exceed 25%. Such limitation was attributed to oxygen contamination, as deduced by High Resolution Transmission Electron Microscopy observations, showing the co-existence of both Mg-based and MgO phases for as-deposited films. A significant decrease in oxygen contamination was successfully achieved with the addition of carbon, leading to the preparation of (Mg-based)-C_x (x < 20%) thin films showing a faster and easier hydrogenation.