自蔓延高温合成Ti2SnC粉体及反应机理的研究

采用自蔓延高温合成技术制备了Ti_2SnC粉体材料,利用XRD、SEM、EDS、TEM及DTA等分析手段对其形貌结构进行表征,在室温条件下其晶格参数a和c分别为3.186和13.630。分析了Ti2SnC的形成机制。在Ti-Sn-C反应体系中,Sn在232℃时熔化为液态,随着温度的升高,钛包裹在碳的外面形成钛碳层,继续加热Ti和Sn反应生成Ti-Sn金属间化合物TixSny,如Ti_6Sn_5和Ti_5Sn_3,在800℃左右钛碳层形成了TiC,在1100℃左右TiC与TixSny发生反应生成类盘状的Ti_2SnC。     

三元层状陶瓷Ti2SnC的研究进展

MAX相化合物由于兼具陶瓷和金属的综合性能而引起了广大研究者的关注,Ti_2SnC与其他M2AX相化合物相比很少被研究。Ti_2SnC具有高的韧性及模量、高的损伤容限、良好的导热导电性能及抗热震和抗氧化性能等。这些优异的性能使其成为高温结构和功能应用的潜在材料。文章主要综述了三元层状陶瓷Ti_2SnC的晶体结构、理论研究、合成方法、性能的研究进展,分析了利用不同方法合成Ti_2SnC的机理,并展望了其应用前景。     

无压烧结Ti3SiC2/铝基复合材料组织与性能

MAX相具有独特的层状晶体结构,不但具备常用铝基复合材料外加陶瓷颗粒的性能特征,同时具有可与石墨媲美的摩擦性能.本文以Al粉、Si粉和典型MAX相Ti_3SiC_2为原料,采用冷压成型-无压烧结方法制备了Ti_3SiC_2/Al-Si复合材料,并通过金相显微镜、X射线衍射仪(XRD)、扫描电镜(SEM)、能谱仪(EDS)等分析手段,研究了烧结温度、Si元素含量对复合材料组织与性能的影响.研究表明:随着烧结温度从500℃提高到700℃,复合材料致密度先上升后下降,摩擦系数先降低后上升,硬度逐渐增大至最大值并基本保持稳定;随着Si质量分数从0增加到20.7%,复合材料的致密度逐渐降低,硬度逐渐增大,摩擦系数先降低后增大,晶粒尺寸随之下降,12.5%Si晶粒最为细小;烧结温度为650℃,Si元素质量分数为12.5%的铝基复合材料具有最低的摩擦系数0.18,相应的硬度为62 HV,致密度为92.12%.XRD物相和扫描电镜组织分析表明,复合材料的主要相组成为Al、Ti_3SiC_2,及由界面反应产生的Al_4C_3和Al的氧化产物Al_2O_3.     

Synthesis of Ti3Si0.8Al0.4C1.8 solid solution from Ti-Si-Al-C powder mixture

In this study, free Ti/Si/Al/C powder mixtures with molar ratios of 3:0.8:0.4:1.8 were heated in argon with various schedules, in order to reveal the possibility for the synthesis of high Ti₃Si_0.8Al_0.4C_1.8 content powder. X-ray diffraction (XRD) was used for the evaluation of phase identities of the powder after different treatments. Scanning electron microscopy (SEM) was used to observe the morphology of the Ti₃Si_0.8Al_0.4C_1.8 solid solution. XRD results showed that predominantly single phase samples of Ti₃Si_0.8Al_0.4C_1.8 were prepared after heating at 1450 °C for 5 min in argon and the lattice parameters of Ti₃Si_0.8Al_0.4C_1.8 lay between those of Ti₃SiC₂ and Ti₃AlC₂. SEM observation showed that the grains of Ti₃Si_0.8Al_0.4C_1.8 solid solution exhibited a lamellar shape, which is a characteristic feature of Ti₃SiC₂ and Ti₃AlC₂.     

烧结温度对(Ti5Si3+TiC+TiB)/Ti复合材料组织和力学性能的影响

为了获得性能优异的钛基复合材料和解决单一增强相对性能提升有限等问题,以Ti粉、SiC粉、TiB₂粉、C粉为原料,采用粉末冶金法,在不同烧结温度下原位自生制备了(Ti₅Si₃+TiC+TiB)/Ti复合材料。通过XRD、SEM、万能试验机等设备表征了复合材料的微观组织和力学性能。结果表明:随烧结温度的升高,复合材料的致密度提高,平均晶粒尺寸逐渐增大;烧结温度的升高使增强相数量增加的同时减少了较低烧结温度下的团聚现象。复合材料的洛氏硬度、屈服强度、抗拉强度随烧结温度的升高先增大后减小,断裂应变下降不显著。在1 300 ℃下,(Ti₅Si₃+TiC+TiB)/Ti具有最佳的综合力学性能,烧结态试样的抗压强度达到最高2 435 MPa,屈服强度1 649 MPa,洛氏硬度49.1HRC,断裂应变28.7%。分析可知,微米尺寸的TiC、TiB和亚微米尺寸的Ti₅Si₃增强相的协同作用在显著提高复合材料强度的同时也保持了一定的塑性。(Ti₅Si₃+TiC+TiB)/Ti复合材料的增强方式以细晶强化、弥散强化和载荷传递强化为主。     

Polycarbosilane derived Ti3SiC2

Titanium silicon carbide (Ti₃SiC₂) ceramic was synthesized by in-situ reaction of metal titanium and polycarbosilane. Reaction mechanisms which lead to the formation of Ti₃SiC₂ were suggested on the basis of XRD analysis. The content of Ti₃SiC₂ reached 93% in products obtained from heating the Ti/polycarbosilane green compact at 1400 °C in Ar. The morphology and compositions of the products were examined by SEM equipped with EDX. The typical laminate structure of Ti₃SiC₂ particles with 1-4 μm in thickness and 4-15 μm in length was observed. EDX results showed that the atomic ratio of Ti:Si:C of grains is close to 3:1:2, which agrees with Ti₃SiC₂ composition.     

Microstructure and boundary phases of Lu–Al-doped silicon nitride by pressureless sintering

Various silicon nitride materials were fabricated by pressureless sintering using lutetia and alumina as sintering additives. Densification behavior, microstructure, strength and formation of secondary crystalline phases were investigated. The combination of Lu₂O₃/Al₂O₃ sintering aids can promote the densification and evolution of a fine grain microstructure of Lu–Al-doped silicon nitride because of the low viscosity of the liquid. The J′ phase given by Lu₄Si_2−xAl_xO_7+xN_2−x was considered to be secondary crystalline phase at the grain pockets. The composition with a Lu₂O₃/Al₂O₃ weight ratio 10/10 had highest strength of 690 ± 50 MPa.     

Synthesis and microstructure of layered-ternary Ti2AlC ceramic by high energy milling and hot pressing

Fully dense and single-phase Ti₂AlC ceramic was successfully synthesized by a high energy milling and hot pressing using Ti, C and Al as starting materials. The effects of composition of the initial elemental powders and sintering temperatures on the purity and formation of Ti₂AlC were examined. The formation mechanism for the single-phase Ti₂AlC ceramics was investigated by XRD in details, which could be described as follows: the most of initial elements reacted to form TiC and Ti–Al intermetallics; the intermetallics and the residual Ti and Al transformed to TiAl phase; and finally the TiAl intermetallics and the TiC reacted to yield Ti₂AlC.     

Synthesis reactions of Cr2AlC from Cr-Al4C3-C by pulse discharge sintering

The reaction process of ternary compound Cr₂AlC synthesis was studied. Powder mixture of Cr, Al₄C₃ and graphite at the composition of Cr:Al:C = 2:1.1:1 was processed by pulse discharge sintering in vacuum in the temperature range of 850 to 1350 °C. The synthesized materials were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM) equipped with an energy dispersive spectrum (EDS) system. It was found that the amount of Cr₂AlC phase increased significantly in the temperature range of 950 to 1150 °C at the consumption of Cr and Al₄C₃ as well as an intermediate phase Cr₂Al. Predominantly single-phase Cr₂AlC with small amount of Cr₇C₃ was obtained as the sintering temperature is above 1250 °C. It is presumed that Cr₂AlC phase is formed near Al₄C₃ particle by the diffusion of Cr and the reaction of the diffused Cr with Al₄C₃.     

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     

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     

Densification and grain growth during pressureless sintering of TiO2 nanoceramics

Anatase titania nanopowders with mean particle sizes of 7, 15, 26 and 38 nm synthesized by sol–gel method were used to sinter bulk TiO₂ nanoceramics. The relative densities and average grain sizes of the TiO₂ nanoceramics were studied as a function of the compaction pressure on green sheet, sintering temperature, and mean particle size of the starting TiO₂ nanopowders. The relative density of the TiO₂ nanoceramics increases rapidly and average grain size increases slowly with increasing sintering temperature below 800 °C. Sintering at higher temperatures above 800 °C enhances the densification of the TiO₂ nanoceramics and leads to a increase of the grain size. Bulk TiO₂ nanoceramics with an average grain size of less than 60 nm and relative density over 95% was obtained by a phase-transformation-assisted pressureless sintering at a relatively low temperature (800 °C).     

Synthesis and phase evolution of Si-C-Ti powder derived from poly(methylsilaacetylene) and Ti

Si-C-Ti powder was synthesized by reactive pyrolysis of poly(methylsilaacetylene)(PSCC) precursor mixed with metal Ti powder. Pyrolysis of PSCC/Ti mixture with certain atomic ratio was carried out in argon atmosphere between 1300 °C and 1500 °C. The metal-precursor reactions, and phase evolution were studied using X-ray diffraction and scanning electron microscopy equipped with EDX. Ti₃SiC₂ phase was obtained from reaction of PSCC and Ti for the first time. Ti₃SiC₂ formation started at 1300 °C and its amount increased significantly at 1400 °C. In addition, liquid formed by additive CaF₂ could promote the formation of Ti₃SiC₂ phase.     

Joining of SiC ceramic-based materials with ternary carbide Ti3SiC2

The joining of two pieces of SiC-based ceramic materials (SiC or C_f/SiC composite) was conducted using Ti₃SiC₂ as filler in vacuum in the joining temperatures range from 1200 °C to 1600 °C. The similar chemical reactions took place at the interface between Ti₃SiC₂ and SiC or C_f/SiC, and became more complete with joining temperature increases, and with the consequent increased joining strengths of the SiC and C_f/SiC joints. Based on the XRD and SEM analyses, it turns out that two reasons are most important for the high joining strengths of the SiC and C_f/SiC joints. One is the development of layered Ti₃SiC₂ ceramic, which has plasticity in nature and can contribute to thermal stress relaxation of the joints; the other is the chemical reactions between Ti₃SiC₂ and the base materials which result in good interface bonding.     

Synthesis reactions for Ti3SiC2 through pulse discharge sintering TiH2/Si/TiC powder mixture

Ternary compound Ti₃SiC₂ was rapidly synthesized by pulse discharge sintering the powder mixture of 1TiH₂/1Si/1.8TiC without preliminary dehydrogenation. Almost single-phase dense Ti₃SiC₂ was synthesized at 1400 °C for 20 min. The grain size of synthesized Ti₃SiC₂ strongly depends on sintering temperature. The synthesis mechanism of Ti₃SiC₂ was revealed to be completed via the reactions among the intermediate phases of Ti₅Si₃, TiSi₂ and the other reactants in the starting powder. The Ti-Si liquid reaction occurring above the Ti-Ti₅Si₃ eutectic temperature at 1330 °C was found to assist the synthesis reaction and densification of Ti₃SiC₂. The dehydrogenation of TiH₂ was accelerated by the synthesis reactions.     

无压烧结合成纯Ti3SiC2及其晶体生长机理

在1400℃,用Ti,Si,C,Al,NaCl原料,氩气保护下无压烧结合成出纯净的、层状的Ti3SiC2陶瓷。用X射线衍射、扫描电子显微镜,透射电子显微镜对Ti3SiC2陶瓷的物相、表面形貌、微观结构进行表征。对合成出的Ti3SiC2陶瓷的微观形貌进行观察,发现Ti3SiC2晶体中有规整的六方形状的层状晶体,提出了Ti3SiC2晶体的自由生长的机理。Ti3SiC2晶体的生长机理由二维成核理论控制,台阶状晶体生长的形貌表明(002)晶面的生长要经过两个独立的过程。添加NaCl,有助于生成高纯度的层状Ti3SiC2陶瓷。     

Current Status in Layered Ternary Carbide Ti3SiC2, a Review

This article provides a review of current research activities that concentrate on Ti₃SiC₂. We begin with an overview of the crystal and electronic structures, which are the basis to understand this material. Followings are the synthetic strategies that have been exploited to achieve, and the formation mechanism of Ti₃SiC₂. Then we devote much attentions to the mechanical properties and oxidation/hot corrosion behaviors of Ti₃SiC₂ as well as some advances achieved recently. At the end of this paper, we elaborate on some new discoveries in the Ti₃SiC₂ system, and also give a brief discussion focused on the "microstructure -property" relationship.     

Preparation of Gd2O2S:Pr Scintillation Ceramics by Pressureless Reaction Sintering Method

Fabrication of Gd₂O₂S:Pr scintillation ceramics by pressureless reaction sintering was investigated. The 2Gd₂O _3˙(Gd,Pr)2(SO ₄)_3˙mH₂O precursor was made by hydrothermal reaction using commercially available Gd₂O₃, Pr₆O₁₁ and H₂SO₄ as the starting materials. Then single phase Gd₂O₂SO₄:Pr powder was obtained by calcining the precursor at 750°C for 2 h. The Gd₂O₂SO₄:Pr powder compacts can be sintered to single phase Gd₂O₂S:Pr ceramics with a relative density of 99% and mean grain size of 30 μm at 1750°C for 2 h in flowing hydrogen atmosphere. Densification and microstructural development of the Gd₂O₂S:Pr ceramics were examined. Luminescence spectra of the Gd₂O₂S:Pr ceramic under 309 nm UV excitation and X-ray excitation show a green emission at 511 nm as the most prominent peak, which corresponds to the ³P₀-³H₄ transition of Pr³⁺ ions.     

Preparation of Lu2Ti2O9 nano-powders from oxides by molten salt method

Nano-sized Lu₂Ti₂O₇ powders have been prepared successfully using TiO₂ and Lu₂O₃ oxides as precursors based on a modified molten salt technique. The results of XRD and SEM analysis show that two-step calcinations retards the grain growth and accelerates the phase transformation of Lu₂Ti₂O₇ more effectively in comparison with single-step calcinations. The spherical Lu₂Ti₂O₇ powders with a particle size of 50 nm are achieved by heating the precursors up to 1100 °C followed by holding at 800 °C for 30 min. Based on the above observations, a possible particle growth mechanism of two-step calcinations under molten salt conditions is also given in this paper, in which it is suggested that a high temperature (T1) can increase nucleation rate and contribute to Lu₂Ti₂O₇ phase transformation while at the same time, the growth process is limited at the lower temperature (T2 ) of the second calcinations step.     

Microscale meshes of Ti3O5 nano- and microfibers prepared via annealing of C-doped TiO2 thin films

A new technique to produce microscale Ti₃O₅ nano- and microfiber meshes is proposed. When a 3 wt% carbon-doped TiO₂ film on Si(1 0 0) was annealed at 1000 °C in wet nitrogen (0.8%H₂O), the amorphous TiO₂ phase gave rise to crystalline phases of λ-Ti₃O₅ (75%) and rutile + trace of TiO_2−xC_x (25%). From Raman and FTIR Spectroscopy results, it was concluded that rutile is formed at the inner layer located at the interface between the mesh and the Si that was located away from the surface such that the meshes of nano- and microfibers are predominantly composed of Ti₃O₅ grown from the reaction of rutile with Si to form Ti₃O₅ and SiO₂. On the other hand, it was noteworthy that the microscale mesh of nano- and microfibers showed increased photoluminescence compared with amorphous TiO₂. The PL spectrum which had a broad band in the visible spectrum, fitted as three broad Gaussian distributions centered at 571.6 nm (∼2.2 eV), 623.0 nm (∼2.0 eV) and 661.9 nm (∼1.9 eV).