TiB2-TiC复合粉的自蔓延高温还原合成

热分析结果表明,对于B₂O₃-TiO₂-Mg-C体系,可利用SHS还原技术合成出TiB₂-TiC陶瓷复合粉。其化学反应机理为:Mg先还原B₂O₃和TiO₂,新生的Ti与B和C反应生成TiB₂和TiC; TiO₂的还原经历了TiO₂→TiO→Ti的逐步过程。采用一定的酸洗工艺得到了纯净的TiB₂-TiC陶瓷复合粉。复合粉中包含六方片状TiB₂和圆球状TiC;复合粉中1μm以下颗粒质量百分数超过45%,87%以上的颗粒大小在3μm以下。在TiB₂-TiC中,TiC_<em>y以一种贫碳结构存在,物料中Ti被B或C结合形成TiB₂和TiC_<em>y,y的值为0.7483。     

Microstructure Evolution and Isothermal Compaction in TiO2-Al-C Combustion Reaction

Combustion reaction in the TiO₂-Al-C system was investigated by the combustion wave freezing technique with a wedge-shaped copper-made quenching block. The combustion reaction was a combined process in which the aluminothermic reduction of TiO₂ (3TiO₂ + 4Al 2Al₂O₃ + 3Ti) and TiC formation reaction (Ti + C TiC) occur in series. First, the aluminothermic reduction was activated by wet spreading of molten Al into interspaces between TiO₂ particles to produce rounded Al₂O₃ grains embedded in the Ti-rich liquid phase. In the later combustion stage, the Ti-rich phase reacted with the reactant C to produce TiC grains in the Ti-rich liquid phase. The three-dimensionally interconnected Al₂O₃ structure typically shown in this system mainly originated from interconnection between the rounded Al₂O₃ grains due to the high combustion temperature from the high exothermic TiC formation reaction. With decreasing the combustion temperature and controlling the C and TiC content, the interconnected Al₂O₃ structure changed to isolated. The isolated Al₂O₃ structure showed superior isothermal compaction behavior to the interconnected. Finally, it is suggested that the microstructure of combustion reaction should be one of the important factors in the SHS compaction process.     

微波烧结TiC/Ti6Al4V复合材料的高温氧化行为

采用微波烧结法制备TiC/Ti6Al4V复合材料,研究TiC/Ti6Al4V复合材料在550、650和750℃空气中的恒温氧化行为,并对氧化膜的表面、截面形貌及相组成进行了分析。结果表明:TiC/Ti6Al4V复合材料由TiC、ɑ-Ti+β-Ti三种物相组成。随着氧化温度的增加,TiC/Ti6Al4V复合材料的氧化规律由抛物线型转变为直线型,在650℃温度以下,复合材料的氧化产物主要由TiO_2组成,而750℃时氧化层主要有外层极薄的TiO_2、中间层Al_2O_3和TiO_2混合区及大部分内层TiO_2三部分组成。随着TiC含量增加,氧化激活能增大,氧化物粒径减小,TiC/Ti6Al4V复合材料的抗氧化性能也越好。     

金刚石表面形成Ti3SiC2的反应机理

采用Ti、Si、TiC、金刚石磨料为原料,通过放电等离子烧结(SPS),制备了Ti3SiC2陶瓷结合剂金刚石材料.研究结果表明,Ti-Si-2TiC试样经SPS加热的过程中位移、位移率和真空度在1200℃时发生明显变化,表明试样发生了物理化学变化.XRD分析结果表明1200℃时试样发生化学反应生成了Ti3SiC2.随着温度升高,试样中Ti3SiC2含量逐渐增加.当烧结温度为1200℃、1300℃、1400℃和1500℃时,产物中Ti3SiC2含量分别为65.9%、79.97%、87.5%和90.1%.在Ti/Si/2TiC粉料中添加适量的金刚石5%和10%进行烧结,并未抑制Ti3SiC2的反应合成.SEM观察表明,金刚石与基体结合紧密,同时其表面生长着发育良好的Ti3SiC2板条状晶粒.提出了一种金刚石表面形成Ti3SiC2的机制,即金刚石表面的碳原子首先与周围的Ti反应生成TiC,然后TiC再与Ti-Si相发生化学反应,生成Ti3SiC2.     

Coating of titanium carbide films on stainless steel by chemical vapour deposition and their corrosion behaviour in a Br2-O2-Ar atmosphere

Stainless steel (SUS304) plates were coated with TiC films using chemical vapour deposition (CVD) as a candidate material for UT-3 which is a promising process of hydrogen production through the thermal decomposition of water. The corrosion behaviour of the TiC film-coated SUS304 plates was examined in a Br₂-O₂-Ar atmosphere. The effects of CVD conditions on the surface texture, deposition rates and preferred orientation of the TiC films were investigated, and the optimum CVD conditions determined. Corrosion of the TiC film-coated SUS304 plates in the Br₂-O₂-Ar atmosphere was mainly caused by oxidation of the TiC film and SUS304 substrate. Microcracks in the TiC films lead to corrosion of the SUS304 substrate. At oxygen partial pressures below 0.1 kPa, weight loss was observed due to the formation of volatile titanium and iron bromides. At oxygen partial pressures greater 0.1 kPa, the time dependence of weight increase was parabolic due to the formation of oxide scale. The oxide scales were mixtures of TiO₂, Fe₂O₃ and Fe₃O₄. The corrosion mechanism is discussed thermodynamically.     

In-situ production of Fe-TiC composite

A TiC/Fe composite was produced by a novel process which combines in situ with powder metallurgy techniques. The microstructure of the Fe-TiC composite was studied by scanning electron microscopy (SEM) and X-ray diffraction (XRD); with the help of differential thermal analysis (DTA), the reaction path of the Fe-Ti-C system was discussed. The results show that the production of an iron matrix composite reinforced by TiC particulates using the novel process is feasible. TiC particles exhibit homogeneous distribution in the α-Fe matrix. The reaction path is as follows: first, allotropic change Fe_α → Fe_γ at 765.6 °C; second, formation of the compound Fe₂Ti at 1078.4 °C because of the eutectic reaction between Ti and Fe; third, reaction between carbon and melted Fe₂Ti causing formation of TiC at 1138.2 °C; finally, Fe₃C formation due to the eutectic reaction between remanent C and Fe at 1146.4 °C.     

Preparation of various titanium suboxide powders by reduction of TiO2 with silicon

Various titanium suboxide powders have been produced by solid-state reaction between TiO2 powders or TiO2 coated mica and silicon as reducing agent at temperatures below 1000°C in an inert atmosphere. The process leads to blue-grey powders with colour characteristics depending on the composition and the structure of the materials. Titanium suboxides like Ti2O3, -Ti3O5, Ti4O7, Ti7O13, Ti8O15 or Ti9O17 are formed during the reduction processes. Calcium chloride as an additive, type of atmosphere as well as temperature have an important influence on the composition and on the colour of the powders. The titanium suboxide powders were characterized by XRD.     

金刚石表面的Ti、Mo、W镀层及界面反应对抗氧化性能的影响

为了提高工业金刚石的抗氧化能力,本文用XRD、SEM、DTA和TGA等方法研究了Ti、Mo、W镀层与金刚石界面反应过程、结构特征及对金刚石抗氧化性能的影响.结果表明:Ti在高于600℃、Mo在高于650℃、W在高于650℃与金刚石界面发生固相反应,通过反应扩散过程在金刚石表面外延生长成相应的TiC、MoC+Mo₂C及WC+W₂C碳化物层.该致密连续的碳化物层具有较高的抗氧化能力,延缓了金刚石表面的氧化.镀Ti、Mo、W金刚石在空气中的氧化温度达958℃、871℃和880℃.Ti、Mo、W镀层经真空碳化处理后,抗氧化温度分别达1024℃、977℃和986℃.而未镀金刚石在780℃以上即开始氧化.     

Formation of Ti<Subscript>3</Subscript>SiC<Subscript>2</Subscript> from Ti-Si-TiC powders by pulse discharge sintering (PDS) technique

Ti/Si/TiC powder mixture with molar ratios of 2:2:3 were sintered at various temperatures from 700–1300 °C for 15 min by PDS technique. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used for the evaluation of phase composition in different samples for the understanding of the sintering mechanism for this system. Results showed that Ti₅Si₃ formed as the intermediate phase during sintering. The reaction between Ti₅Si₃ and TiC as well as Si induces the formation of Ti₃SiC₂, and TiSi₂ appears as the byproduct in this process. At temperature above 1000 °C, TiSi₂ reacts with TiC to form Ti₃SiC₂. High Ti₃SiC₂ phase content bulk material can be synthesized at 1300 °C for 15 min.     

添加TiC和Ti3AlC2对燃烧合成Ti3AlC2粉体的影响

Ti、Al、C和TiC组成的Ti:Al:C=3:1.1:1.8（摩尔比）体系的燃烧合成实验结果表明，当在体系中未加入TiC时，得到的主要是TiC，但加入TiC后燃烧合成产物主要是Ti3AlC2，且Ti3AlC2量随TiC加入量的增加而增加，随燃烧反应体系温度的降低而增加；加入晶种Ti3AlC2有利于合成Ti3AlC2相物质。     

A thermogravimetric study of the oxidation of CuFeO2

The oxidation kinetics of CuFeO₂ have been studied between 500 and 1000° C under various oxygen partial pressures using thermogravimetric analysis (TGA). The oxidation rate was found to increase as the oxygen partial pressure was increased, and for a given partial pressure of oxygen it was found to be maximum at 700° C. The enthalpy and activation energy for the oxidation of CuFeO₂ were calculated to be 26.6±2 and 18±2 kcal mol^–1 respectively. The oxidation of CuFeO₂ resulted in the formation of CuFe₂O₄ and CuO, and the rate of reaction followed an S-type curve as found in the pearlitic transformation in steels.     

Fabrication of Monolithic Ti3SiC2 Ceramic Through Reactive Sintering of Ti/Si/2TiC

Fabrication of monolithic Ti₃SiC₂ has been investigated through the route of reactive sintering of Ti/Si/2TiC mixtures. Significant phase differences existed between the surface and the interior of as-synthesized products due to the evaporation of Si during the reaction process. The use of a 3Ti/SiC/C mixture as a powder bed could control the evaporation of Si and develop monolithic Ti₃SiC₂. A reaction model for the formation of Ti₃SiC₂ in the Ti/Si/2TiC system is discussed.On leave from     

A new synthesis reaction of Ti3SiC2 from Ti/TiSi2/TiC powder mixtures through pulse discharge sintering (PDS) technique

Ti/TiSi₂/TiC powder mixtures with molar ratios of 1:1:4 (M1) and 1:1:3 (M2) were first employed for the synthesis of Ti₃SiC₂ through pulse discharge sintering (PDS) technique in a temperature range of 1100–1325 °C. It was found that Ti₃SiC₂ phase began to form at the temperature above 1200 °C and its purity did not show obvious dependence on the sintering temperature at 1225–1325 °C. The TiC contents in M2 samples is always lower than that of the M1 samples, and the lowest TiC contents in the M1 and M2 samples were calculated to be about 7 wt% and 5 wt% when the sintering was conducted at the temperature near 1300 °C for 15 minutes. The relative density of the M1 samples is always higher than 99% at sintering temperature above 1225 °C, indicating a good densification effect produced by the PDS technique. A solid-liquid reaction mechanism between Ti-Si liquid phase and TiC particles was proposed to explain the rapid formation of Ti₃SiC₂. Furthermore, it is suggested that Ti/TiSi₂/TiC powder can be regarded as a new mixture to fabricate ternary carbide Ti₃SiC₂. Received: 5 September 2001 / Accepted: 11 September 2001     

Solid-state synthesis and characterization of the ternary phase Ti3SiC2

Ti₃SiC₂ is the only true ternary compound in the Ti-Si-C system. It seems to exhibit promising thermal and mechanical behaviour. With the exception of its layered crystal structure, most of its properties are unknown, owing to the great difficulty of synthesis. A new procedure of solid-state synthesis with several steps is proposed, which results in Ti₃SiC₂ with less than 5 at % of TiC. Ti₃SiC₂ is stable at least up to 1300 °C. Beyond this temperature, it can decompose with formation of non-stoichiometric titanium carbide and gaseous silicon, with kinetics highly dependent on the nature of the surroundings. As an example, graphite can initiate this process by reacting with silicon, while alumina does not favour the decomposition which remains very slow. The oxidation of Ti₃SiC₂ under flowing oxygen starts at 400 °C with formation of anatase-type TiO₂ film, as studied by TGA, XRD, SEM and AES. Between 650 and 850 °C both rutile and anatase are formed, rapidly becoming protecting films and giving rise to slow formation of SiO₂ and more TiO₂. The oxidation kinetics is slower than for TiC, owing to a protecting effect of silica. By increasing the temperature, both oxidation processes (i.e. direct reaction and diffusion through oxide layers) are activated and an almost total oxidation is achieved between 1050 and 1250 °C resulting in titania (rutile) and silica (cristobalite).     

Formation of Ti3AlC2 by mechanically induced self-propagating reaction in Ti–Al–C system at room temperature

Abstract

The formation of Ti₃AlC₂ was first investigated by mechanically induced self-propagating reaction (MSR) in Ti–Al–C system at room temperature. The effects of the milling parameters on the formation of Ti₃AlC₂ were discussed. The phase composition and microstructure were analysed and observed by using X-ray diffraction and scanning electron microscopy, respectively. The formation mechanism of Ti₃AlC₂ was analysed. An MSR was ignited during mechanical alloying of Ti, Al and C powders after a short time. An exothermic reaction between Ti and Al in the Ti–Al–C system first occurred after a certain milling time. Then, Ti–C reaction was induced at high temperature. All of the above reactions were exothermic that resulted in Ti–Al liquid formation. The previously formed TiC dissolved into and nucleated in the Ti–Al liquid. At last, Ti₃AlC₂ formed between the Ti–Al melt and the TiC. The final products consist of Ti₃AlC₂, TiC and Al₃Ti.     

Formation of mixed TiC/Al2O3 layers and αa- and κ-Al2O3 on cemented carbides by chemical vapour deposition

Al₂O₃ and Ti(C, O) were codeposited as a mixed chemical vapour deposition (CVD) layer from AlCl₃-TiCl₄-CH₄-CO₂-H₂ gas mixtures on cemented carbides and pure alumina substrates. A thermodynamical approach of this CVD system is presented. The coatings were described by SEM and X-ray diffraction analysis. They consist of large facetted-Al₂O₃ crystals containing some titanium and surrounded by a fine grained Ti(C, O) matrix. Carbon diffusing from the cemented carbide substrate can considerably influence the morphology and the composition of the mixed coating.Methane in a AlCl₃-CO₂-H₂ environment stabilizes the-Al₂O₃ phase which can be deposited as a compact layer without whisker formation on a WC-Co substrate even without a TiC underlayer.     

液硅渗透法制备Ti3SiC2改性C/CSiC复合材料

采用浆料浸渗结合液硅渗透法原位生成高韧性Ti₃SiC₂基体, 制备Ti₃SiC₂改性C/C-SiC复合材料。研究了TiC颗粒的引入对熔融Si浸渗效果的影响, 分析了Ti₃SiC₂改性C/C-SiC复合材料的微结构和力学性能。实验结果表明: TiC与熔融Si反应生成Ti₃SiC₂是可行的, 而且C的存在更有利于生成Ti₃SiC₂; 在含TiC颗粒的C/C预制体孔隙(平均孔径22.3 μm)内, 熔融Si的渗透深度1 min内可达10.8 cm; Ti₃SiC₂取代残余Si后提高了 C/C-SiC复合材料的力学性能, C/C-SiC-Ti₃SiC₂复合材料的弯曲强度达203 MPa, 断裂韧性达到8.8 MPa·m1/2; 对于厚度为20 mm的试样, 不同渗透深度处材料均具有相近的相成分、 密度和力学性能, 无明显微结构梯度存在, 表明所采用的浆料浸渗结合液硅渗透工艺适用于制备厚壁Ti₃SiC₂改性C/C-SiC复合材料构件。      

Preparation of spherical Pb(Zr,Ti)O3 powders by ultrasonic spray pyrolysis

Spherical Pb(Zr,Ti)O₃ powders were prepared from the aqueous acetate-base solution by ultrasonic spray pyrolysis. The raw materials were Pb(C₂H₃O₂)-3H₂O, ZrO(C₂H₃O₂)₂ and a mixture of Ti(C₃H₇O)₄ and C₅H₇O₂. A single-phase PZT was formed at 900 C in air and at 700 C in O₂ atmosphere. The PbTiO₃ phase, as an intermediate product, was observed in the formation of PZT and no PbZrO₃ phase was detected under our experimental conditions. The intensity of the PbTiO₃ peak decreased with increasing reaction temperature in air, while the reverse effect of reaction temperature was observed in O₂. Spherical and irregular-shaped particles coexisted in the powder containing the minor PbTiO₃ phase, while the particles of a single-phase PZT have spherical morphology with little evidence of irregular-shaped particle formation.     

Reactive sintering mechanism of Ti + Mo<Subscript>2</Subscript>C and Ti + VC powder compacts

TiC reinforced Ti-matrix composites have been synthesized successfully by reactive sintering of Ti-1.5%Fe-2.25%Mo (wt%) powder compacts with addition of Mo₂C and VC particles. The reactions for the formation of TiC particles start at 600 °C, but the distribution of TiC particles and the densification behavior in the two compacts are significantly influenced by the metal carbides (Mo₂C or VC). The compact with addition of Mo₂C has a relative density of 98% after sintering at 1300 °C for 1.5 h, but TiC particles are agglomerated in the Ti matrix. The compact with addition of VC has a relative density of about 91% after sintering at 1300 °C for 1.5 h, but TiC particles distribute more homogenously in the Ti matrix. Different TiC particle distribution and densification behaviors are attributed to the reaction rates between Ti and metal carbides and the subsequent diffusion process.     

XD 法合成TiC/Al 复合材料的机制

本文研究了XD 法合成TiC/Al 复合材料的机理。结果表明: 在铝基体中, 首先形成Al₃Ti相, 然后,Al₃Ti 相与C 粉发生反应, 生成TiC 增强相。分析认为:Al 在TiC 相形成过程中起触媒作用, 降低激活能, 加速反应进行。