Intermediate Phases in Ti3SiC2 Synthesis from Ti/SiC/C Mixtures Studied by Time-Resolved Neutron Diffraction

The reactive sintering of 3Ti/SiC/C to form the layered ternary carbide Ti₃SiC₂ was studied in situ by time-resolved neutron powder diffraction. A number of intermediate processes occur during the synthesis beginning with the α-β transition in Ti. Concurrent with the α-β transition, two intermediate phases, TiC _x and Ti₅Si₃C _x ( x ≤ 1), form. These phases account for almost the entire sample in the range 1500–1600°C beyond which they react with each other and a small amount of free C to form the product phase Ti₃SiC₂.     

Self-Propagating High-Temperature Synthesis of Ti3SiC2: I, Ultra-High-Speed Neutron Diffraction Study of the Reaction Mechanism

In situ neutron diffraction at 0.9 s time resolution was used to reveal the reaction mechanism during the self-propagating high-temperature synthesis (SHS) of Ti₃SiC₂ from furnace-ignited stoichiometric 3Ti + SiC + C mixtures. The diffraction patterns indicate that the SHS proceeded in five stages: (i) preheating of the reactants, (ii) the α→β phase transformation in Ti, (iii) preignition reactions, (iv) the formation of a single solid intermediate phase in <0.9 s, and (v) the rapid nucleation and growth of the product phase Ti₃SiC₂. No amorphous contribution to the diffraction patterns from a liquid phase was detected and, as such, it is unlikely that a liquid phase plays a major role in this SHS reaction. The intermediate phase is believed to be a solid solution of Si in TiC such that the overall stoichiometry is ∼3Ti:1Si:2C. Lattice parameters and known thermal expansion data were used to estimate the ignition temperature at 923 ± 10°C (supported by the α→β phase transformation in Ti) and the combustion temperature at 2320 ± 50°C.     

可加工陶瓷Ti3SiC2的合成和性能

可加工的Ti3SiC2陶瓷属于六方晶体结构。空间群为R63／mmc。它有许多独特的优良性能。如很好的导电、导热能力。高温延展性、抗热震，高强度。抗氧化。耐腐蚀。超低摩擦性。良好的自润滑性等。制备该化合物的方法主要有CVD,SHS,HP/HIP等方法。作者以元素粉为原料。用等离子放电烧结(SPS)方法成功地制备了高纯的Ti3SiC2陶瓷。     

Microstructure and Mechanical Properties of (TiB2 + SiC) Reinforced Ti3SiC2 Composites Synthesized by In Situ Hot Pressing

Fully dense (TiB₂ + SiC) reinforced Ti₃SiC₂ composites with 15 vol% TiB₂ and 0–15 vol% SiC were designed and synthesized by in situ reaction hot pressing. The increase in SiC content promoted densification and significantly inhibited the growth of Ti₃SiC₂ grains. The in situ incorporated TiB₂ and SiC reinforcements showed columnar and equiaxed grains, respectively, providing a strengthening–toughening effect by the synergistic action of particulate reinforcement, grain's pulling out, “self‐reinforcement,” crack deflection, and grain refining. A maximum bending strength of 881 MPa and a fracture toughness of 9.24 MPam^1/2 were obtained at 10 vol% SiC. The Vickers hardness of the composites increased monotonously from 9.6 to 12.5 GPa.     

Ti3SiC2陶瓷粉末的制备

新型层状陶瓷材料Ti3SiC2集金属和陶瓷的优良性能于一身,如低密度、高熔点、良好的导电导热性、高弹性模量、高断裂韧性、耐氧化、耐热震、易加工且有良好的自润滑性。在高温结构陶瓷、电刷和电极材料、可加工陶瓷材料、自润滑材料等领域有着广泛的应用前景。本文综合介绍了Ti3SiC2粉求制备的研究进展。最近,作者以Ti／Si／C／Al元素粉为原料,采用无压烧结的方法制备出纯度较高的Ti3SiC2陶瓷粉末。为Ti3SiC2基复合材料的发展开辟了一条新途径。     

Ti3SiC2陶瓷粉末的制备

新型层状陶瓷材料Ti3SiC2集金属和陶瓷的优良性能于一身,如良好的导电导热性、耐氧化、耐热震、高弹性模量、高断裂韧性等,在高温结构陶瓷、电刷和电极材料、可加工陶瓷材料、自润滑材料等领域有着广泛的应用前景。本文综合介绍了Ti3SiC2粉末制备的研究进展。此外,作者以Ti／Si／C／Al元素粉为原料,采用无压烧结的方法制备出纯度较高的Ti3SiC2陶瓷粉末,为Ti3SiC2基复合材料的发展开辟了一条新途径。     

放电等离子烧结工艺合成Ti3SiC2的研究

以元素单质粉为原料，当原料配比为n(Ti):n(Si):n(Al):n(C)=3:(1.2-x):x:2，其中：x=0.05-0.2时，在1200－1250℃温度下经放电等离子烧结成功制备了高纯、致密Ti3SiC2固溶体材料。原料中掺加适量Al能改善Ti3SiC2的合成反应并提高制备材料的纯度。当x=0.2时，所合成的固溶体形貌为板状结晶，分子式近似为Ti3Si0.8Al0.2C2，晶格参数a=0.3069nm,c=1.767nm。在1250℃温度下烧结，得到平均厚度达5μm，发育完善均匀的致密多晶体材料。材料Vickers硬度为3.5-5.5GPa，具有与石墨相似的加工性能。     

低温合成Ti3SiC2陶瓷

采用机械合金化和放电等离子烧结技术制备了纯度较高的Ti3SiC2陶瓷,研究了微量Al对Ti3SiC2的机械合金化和放电等离子烧结过程的影响.结果表明:添加适量的Al可以显著提高机械合金化及放电等离子烧结产物中Ti3SiC2的含量,并显著降低高纯度Ti3SiC2的烧结温度.机械合金化10h,成分为3Ti/Si/2C/0.2Al(摩尔比)的混合粉体,经850℃放电等离子烧结可获得质量分数(下同)高达96%的Ti3SiC2块体,烧结温度提高到1 100℃,可获得纯度为99.3%、相对密度高达98.9%的Ti3SiC2致密块体.     

热压烧结制备原位复合（TiB2+TiC）/Ti3SiC2复相陶瓷

采用热压烧结法制备了原位复合(TiB2+TiC)/Ti3SiC2复相陶瓷。采用X射线衍射、扫描电镜和透射电镜对材料的物相组成和显微结构进行了表征,研究了烧结温度对材料物相组成、烧结性能、显微结构与力学性能的影响。结果表明:烧结温度在1 350～1 500℃范围内,随着烧结温度的升高,合成反应进行逐渐完全,材料的密度、抗弯强度和断裂韧性显著提高。1 500℃烧结可得到致密的原位复合(TiB2+TiC)/Ti3SiC2复相陶瓷,材料晶粒发育较完善,层片状Ti3SiC2、柱状TiB2与等轴状TiC晶粒清晰可见,增强相晶粒细小,晶界干净,材料的抗弯强度、断裂韧性和Vickers硬度分别达到741 MPa,10.12 MPa.m1/2和9.65 GPa。烧结温度达到1 550℃时Ti3SiC2开始发生分解,材料的密度和力学性能又显著下降。     

Synthesis and formation mechanism of high-purity Ti3AlC2 powders by microwave sintering

High-purity titanium aluminum carbide (Ti₃AlC₂) powders were synthesized by a microwave sintering method using different titanium sources as raw materials. The prepared products were characterized by differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results indicated that the synthesized Ti₃AlC₂ powders have high purity (97.5%) and even distribution of the grain size when using a 3TiH₂/1.2Al/2C mixture as raw materials when the microwave sintering temperature and time were 1300°C and 30 minutes, respectively. The formation mechanism of the Ti₃AlC₂ is described as proceeding via four stages. The solid-phase reaction between titanium and aluminum occurs below the melting point of aluminum and the main product is a Ti₃Al phase, which is an observed intermediate compound for the formation of Ti₂AlC and Ti₃AlC₂. Thus, this study provides a beneficial approach to low-temperature synthesis of high-purity Ti₃AlC₂ materials.     

Ti3SiC2陶瓷的制备及性能研究

层状陶瓷材料Ti，SiC2结合了金属和陶瓷的许多优异性质，既具有与金属相似的良好的导热、导电性，良好的可加工性，相对柔软，抗热震性好，可塑性变形等性能，同时又具有与陶瓷相似的抗氧化、耐腐蚀、耐高温等特性；并且还有很好的自润滑性和超低磨擦系数，被认为在许多领域有着广泛的应用前景。     

Synthesis of Ti3SiC2 MAX phase powder through molten salt method

Titanium silicon carbide (Ti₃SiC₂) MAX phase powder was synthesized from elemental reactants using the molten salt synthesis (MSS) method. Optimum experimental parameters were also investigated to determine the purity and synthesis pathway of the Ti₃SiC₂ MAX phase. The results showed that Ti₃SiC₂ was not synthesized using carbon black as the carbon source in the starting materials because of the high quantity of TiC formed along with the TiSi₂ silicide phase. However, Ti₃SiC₂ was successfully synthesized in a relatively high purity (93%) at 1200°C for 2 h using graphite as the source of carbon because of the formation of TiC and Ti₅Si₃ intermediate phases. The Ti₅Si₃ silicide phase was found to play a crucial role in the formation of the Ti₃SiC₂ MAX phase using the MSS method. Moreover, applying a pressure of 150 MPa to the prepared samples and using the eutectic mixture of NaCl–KCl (molar ratio: 1:1) instead of NaCl also resulted in the higher formation of the Ti₃SiC₂ MAX phase. The formation mechanism of Ti₃SiC₂ was determined to be the reaction among Ti₅Si₃, TiC, and residual carbon through the template-growth and dissolution–precipitation mechanisms that occurred at different stages of the synthesis process.     

Mechanical-Alloying-Assisted Synthesis of Ti3SiC2 Powder

Mechanical alloying (MA) has been used to synthesize Ti₃SiC₂ powder from the elemental Ti, Si, and C powders. The MA formation conditions of Ti₃SiC₂ were strongly affected by the ball size for the conditions used. MA using large balls (20.6 mm in diameter) enhanced the formation of Ti₃SiC₂, probably via an MA-triggered combustion reaction, but the Ti₃SiC₂ phase was not synthesized only by the MA process using small balls (12.7 mm in diameter). Fine powders containing 95.8 vol% Ti₃SiC₂ can be obtained by annealing the mechanically alloyed powder at relatively low temperatures.     

Low-Temperature Chemical Synthesis of Nanocrystalline MgAl2O4 Spinel Powder

Nanocrystalline MgAl₂O₄ spinel powder was synthesized by pyrolysis of complex compounds of aluminum and magnesium with triethanolamine (TEA). The soluble metal ion–TEA complexes formed the precursor material on complete dehydration of the complexes of aluminum–TEA and magnesium–TEA. Single-phase MgAl₂O₄ spinel powder resulted after heat treatment of the precursor material at 675°C. The precursor and the heat-treated powders were characterized by X-ray diffractometry (XRD), differential thermal and thermogravimetric analysis, and transmission electron microscopy (TEM). The average crystallite size as measured from the X-ray line broadening was around 14 nm and the average particle size from TEM studies was around 20 nm.     

Synthesis of Ti3SiC2 coatings onto SiC monoliths from molten salts

Coatings with composition close to Ti₃SiC₂ were obtained on SiC substrates from Ti and Si powders with the molten NaCl method. In this work, the growth of coatings by reaction in the salt between monolithic SiC substrates and titanium powder is obtained between 1000 and 1200 °C. At 1000 °C, a coating of 8 µm thickness is formed in 10 h whereas a thin coating of 0.5 µm has been grown in 2 h. A lack in silicon was first found in the coatings prepared at 1100 and 1200 °C. For these temperatures, the addition of silicon powder in the melt had a favorable effect on the final composition, which is found very close to the composition of Ti₃SiC₂. The reaction mechanism implies the formation of TiC_x layers in direct contact with the SiC substrate and the presence of more or less important quantities of Ti₃SiC₂ and Ti₅Si₃C_x in the upper layers.     

Fabrication of Titanium Carbide Ceramics by High-Pressure Self-Combustion Sintering of Titanium Powder and Carbon Fiber

Titanium carbide ceramics have been fabricated from the reactants titanium powder and carbon fiber by the highpressure self-combustion sintering method (HPCS) under two pressure conditions (65 MPa and 3 GPa). Porous TiC with a density of about 50% of theoretical was obtained under a pressure of 65 MPa. A possible model accounting for the formation mechanism of TiC is proposed on the basis of observation of the microstructure of the products formed from the incomplete reaction. On the other hand, dense TiC (>95% of theoretical) was fabricated under 3 GPa. The mean grain size varied, depending on the mixing molar ratio of the reactants. The influence of differences in the carbon (powder and fiber forms) on the structure of TiC compacts is discussed.     

In Situ Neutron Diffraction Study of a Liquid Nitrogen-Quenched Mg-PSZ Under Load: A Microcrack-Dominated System?

The mechanical response of liquid nitrogen-quenched 9.4 Mg-PSZ in which the orthorhombic ( o ) phase is the major constituent (46 wt%) was investigated using in-situ neutron diffraction during uniaxial compression. The material remains elastic below 1 GPa with a Young's modulus of∼242 GPa, second highest of all zirconia-based materials and highest of all zirconia-based ceramics. Beyond 1 GPa, the material develops small plastic strains in a time-dependent manner (i.e., by room temperature creep) although the strains were generally much smaller than the unquenched material, which contains no o phase. As for standard Mg-PSZ, the creep was accompanied by a volume change usually indicative of tetragonal to monoclinic ( m ) phase transformation; however, the amount of m phase apparent in the neutron diffraction patterns increased only marginally. The magnitude of the volume increase could not be accounted for by the observed increase in the m phase and hence, microcracking is believed to be responsible for most of the volume change. There is some evidence for a small amount of o to m transformation at the detection limit of the phase analysis technique.     

Ti_3SiC_2可加工材料的研究现状

Ti3SiC2陶瓷具有很好的高温强度、热稳定性和耐腐蚀性能,同时它还具有很好的导电、导热能力,优良的可加工性,又具备金属良好的高的抗氧化性、抗热震性和高温塑性、良好的自润滑性。本文对其结构、性能以及制备方法和应用前景进行了综合评述。     

Synthesis of Ti3SiC2 Phase from Polycarbosilane Precursor

Ti₃SiC₂ phase was synthesized by reactive pyrolysis of three different polycarbosilane, [Si(H)₂CH₂]_m·[(H)Si(Vi)CH₂]_n·[(H)Si(Me)CH₂]_p (AHPCS), [Si(CH₃)₂CH₂]_x·[Si(H)(CH₃)CH₂]_y (PCS), and [Me(H)SiC≡C]_n, filled with metal Ti powder. The pyrolysis was carried out in argon atmosphere between 1200°C and 1400°C. The metal–precursor reactions and phase evolution during the pyrolysis were studied by means of X-ray diffraction and scanning electron microscopy. The results indicated that PCS/Ti system was more beneficial for the synthesis of Ti₃SiC₂. In addition, the high-purity Ti₃SiC₂ could be synthesized through the pyrolysis of green compact of the PCS/Ti system with CaF₂ at 1400°C.     

Al对等离子放电烧结法合成Ti3SiC2的影响研究

以元素为原料，Al为助剂，采用等离子放电烧结(SPS)工艺合成Ti3SiC2块体材料，通过X射线衍射分析和对SPS过程参数的研究表明：适量A1能促进Ti3SiC2的反应合成，提高合成材料的纯度，但Al也会使Ti3SiC2的热稳定性降低。