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.     

Direct diffusion bonding of Ti3SiC2 and Ti3AlC2

Two typical layered ternary compounds, Ti₃SiC₂ and Ti₃AlC₂, were joined directly by solid-state diffusion bonding method. By various bonding tests at 1100-1300 °C for 30-120 min under 10-30 MPa, and characterizing the microstructure and diffusion reactive phases of the joints by scanning electron microscopy (SEM), energy dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and X-ray diffraction (XRD), the optimal condition for direct joining of Ti₃SiC₂ and Ti₃AlC₂ was obtained. Strong joints of Ti₃SiC₂/Ti₃AlC₂ can be achieved via diffusion bonding, which is attributed to remarkable interdiffusion of Si and Al at the joint interface. The shear strength of the Ti₃SiC₂/Ti₃AlC₂ joints was determined.     

TaC/Ti3SiC2复合材料的制备与性能

采用反应热压烧结法制备了TaC/Ti₃SiC₂复合材料,借助XRD、SEM、能谱仪以及热重分析等,研究了TaC含量对TaC/Ti₃SiC₂复合材料的相组成、显微结构、力学性能和抗氧化性的影响。结果表明: 采用反应热压烧结法可以制备出致密的TaC/Ti₃SiC₂复合材料,该复合材料的主晶相为Ti₃SiC₂和TaTiC₂,还含有少量的TiC;随着TaC含量的增加,TaC/Ti₃SiC₂复合材料的弯曲强度和断裂韧性呈现先增大后降低的变化趋势,当TaC含量为30wt%时,二者均达到最大值,此时弯曲强度为404 MPa,断裂韧性为4.10 MPa·m^1/2;TaC的引入,使TaC/Ti₃SiC₂复合材料抗氧化性能明显优于Ti₃SiC₂材料。     

层状Ti3SiC2陶瓷的组织结构及力学性能

利用热压烧结TiH₂,Si和C粉获得了致密度大于98%的层状Ti₃SiC₂陶瓷。利用压痕法,在不同的载荷下测定了材料的维氏硬度, 发现其硬度值随载荷的增加而降低,在最大载荷30kg时,硬度值为4GPa。压痕对角线没有发现径向裂纹的出现。 这归因于多重能量吸收机制——颗粒的层裂、裂纹的扩展、颗粒的变形等。利用三点弯曲法和单边切口梁法测定了材料的强度和韧性分别为270MPa和6.8MPa·m1/2。Ti₃SiC₂材料的断口表现出明显的层状性质,大颗粒易于发生层裂和穿晶断裂,小颗粒易被拔出。当裂纹沿平行于Ti₃SiC₂基面的方向扩展造成颗粒的层裂,当裂纹沿垂直于基面的方向扩展时,裂纹穿过颗粒的同时,在颗粒内部发生偏转,使裂纹的扩展路径增加。裂纹的扩展路径类似人们根据仿生结构设计的层状复合材料。裂纹在颗粒内的多次偏转、裂纹钉扎以及颗粒的层裂和拔出等是材料韧性提高的主要原因。此外,在室温下得到的荷载-位移曲线,说明Ti₃SiC₂材料不象其它陶瓷材料的脆性断裂,而是具有金属一样的塑性。     

TiC/Ti_3SiC_2泡沫陶瓷的制备和性能

采用聚氨酯泡沫为原始骨架,用高频感应加热反应熔渗制备TiC/Ti_3SiC_2泡沫陶瓷,研究了在制备过程中不同阶段泡沫体的Ti含量对其相组成、微区化学成分、显微组织以及抗压缩性能的影响。结果表明,随着泡沫体中Ti含量的增加,在其骨架中柑继生成TiC、Ti_3SiC_2及少量的Ti_5Si_3.骨架的致密度提高,泡沫材料...     

Ti3SiC2/Cu复合材料的制备与摩擦磨损性能

以Ti₃SiC₂陶瓷粉和Cu粉作为原料,采用放电等离子烧结(SPS)工艺制备Ti₃SiC₂/Cu块体复合材料,研究不同Ti₃SiC₂添加含量及烧结温度对Ti₃SiC₂/Cu复合材料的组织、致密度和显微硬度的影响,研究SPS后Ti₃SiC₂/Cu复合材料的摩擦磨损性能。研究表明:采用SPS工艺制备的Ti₃SiC₂/Cu复合材料的Ti₃SiC₂在Cu中分布均匀,但随着Ti₃SiC₂含量的增加和烧结温度的升高,组织中出现团聚趋势,部分Ti₃SiC₂与Cu在界面处发生互溶现象,互溶增强了Ti₃SiC₂与基体的结合能力;Ti₃SiC₂含量和烧结温度对Ti₃SiC₂/Cu复合材料的致密度和显微硬度影响较大,当烧结温度为900℃时,Ti₃SiC₂/Cu复合材料的致密度达到99.7%,接近完全致密,Ti₃SiC₂/Cu复合材料的硬度较纯Cu提高了2倍左右;对于不同Ti₃SiC₂含量的Ti₃SiC₂/Cu复合材料的磨损机制也有所差异,当Ti₃SiC₂含量较低时(1vol%~5vol%),磨损机制为磨粒磨损和黏着磨损;随着Ti₃SiC₂含量的增加(10vol%~15vol%),Ti₃SiC₂发挥了本身的自润滑性,Ti₃SiC₂/Cu复合材料的摩擦磨损性能有所改善,磨损机制转为犁削磨损和轻微黏着磨损;当Ti₃SiC₂含量增加到20vol%时,Ti₃SiC₂/Cu复合材料的磨损表面变得均匀而平整,表明Ti₃SiC₂/Cu复合材料的耐磨性提高。      

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.     

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.     

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.     

机械球磨法制备Ti3SiC2 / Al 纳米复合材料

研究了用微米级Ti₃SiC₂ 陶瓷颗粒与Al 粉复合球磨制备纳米复合材料的工艺过程。结果表明, 在其他实验参数相同的条件下, 不同材质的磨球对陶瓷颗粒的细化作用差异很大。采用氧化锆磨球可以使Ti₃SiC₂ 的颗粒更好地细化且均匀分散在Al 基体中, 而用钢球和玛瑙球则易产生混合粉的团聚。用氧化锆球进行球磨后的复合粉在550 ℃的温度及20 MPa 的压力下成功地制备了组织成分均匀的大块纳米复合材料。与同成分的非纳米材料相比, Ti₃SiC₂ / Al 纳米复合材料的硬度从HV60 提高到HV80 , 强度则从110 MPa 提高到150 MPa 。      

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 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.     

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。      

High-power impulse magnetron sputtering of Ti-Si-C thin films from a Ti3SiC2 compound target

We have deposited Ti-Si-C thin films using high-power impulse magnetron sputtering (HIPIMS) from a Ti₃SiC₂ compound target. The as-deposited films were composite materials with TiC as the main crystalline constituent. X-ray diffraction and photoelectron spectroscopy indicated that they also contained amorphous SiC, and for films deposited on inclined substrates, crystalline Ti₅Si₃C_x. The film morphology was dense and flat, while films deposited with direct-current magnetron sputtering under comparable conditions were rough and porous. We show that, due to the high degree of ionization of the sputtered species obtained in HIPIMS, the film composition, in particular the C content, depends on substrate inclination angle and Ar process pressure.     

Cracking behavior of oxide scale formed on Ti3SiC2-based ceramic

The cyclic oxidation and acoustic emission (AE) tests were carried out for studying cracking behavior of oxide scales formed on Ti₃SiC₂-based ceramic at 1100 °C. A duplex oxide scale with an outer layer of pure TiO₂ and an inner layer of a mixture of TiO₂ and SiO₂ was formed. The oxide scale did not spall from substrate during the cyclic oxidation at 1100 °C for 360 times. However, a great number of micro-cracks penetrating whole inner oxide layer were detected. AE test showed that the oxide scale did not crack during the isothermal oxidation at 1100 °C for 1 h, however, the scale cracked during the cooling stage. Comparing the growth rate and thickness between the oxide layers formed during the isothermal oxidation and cyclic oxidation, respectively, indicated that cracks in the inner oxide layer served as paths mainly for outward diffusion of titanium and for inward diffusion of oxygen, resulting in increased growth rate of the outer oxide layer. Because of entire and compact TiO₂ consisted of outer oxide layer, and low thermal stress resulting from small mismatch of thermal expansion coefficients between the oxides and the substrate, Ti₃SiC₂ exhibited excellent cyclic oxidation resistance at 1100 °C for 360 cycles.     

无压熔渗制备TiC/Ti3SiC2复合材料高速载流摩擦磨损性能

采用无压熔渗反应烧结技术制备了TiC/Ti₃SiC₂复合材料,通过HST-100型载流摩擦磨损试验机,在60~90 m/s滑动速度范围内,对TiC/Ti₃SiC₂复合材料的高速载流摩擦磨损性能进行了研究。结果表明：当与HSLA80配副时,TiC/Ti₃SiC₂的摩擦磨损性能与摩擦速度和TiC含量呈现出一定的相关性。当摩擦速度小于80 m/s时,摩擦表面出现具有减磨作用的熔融状态的均匀分布氧化膜（FeTiO₃和Fe_2.35Ti_0.65O₄）,呈现山脊及犁沟状形貌,磨损机制以磨粒切削磨损、氧化磨损及粘着磨损为主;当摩擦速度超过80 m/s时,摩擦表面出现不均匀分布的氧化膜,呈现孤峰状形貌,磨损机制以氧化磨损及电弧烧蚀磨损为主。相同实验条件下,摩擦系数随着TiC含量的增加而增大,磨损率随之降低。     

Electronic structure of Ti2CAl and Ti2NAl

The electronic structure and chemical bonding mechanism of Ti₂CAl and Ti₂NAl are studied on the basis of charge density and total density of states and band structure calculations using the full potential linearized augmented plane-wave method (FP-LAPW). Results demonstrate the features of the anisotropic behavior in these compounds.     

Layered growth of Ti2AlC and Ti3AlC2 in combustion synthesis

In Ti-Al-C system two ternary carbides of Ti₂AlC and Ti₃AlC₂ were prepared by combustion synthesis. Laminated grain morphology and a terraced structure consisting of several parallel laminated layers were observed. On the basis of SEM and TEM results, a layered growth mechanism was proposed to describe the formation of the terraced structure. In this mechanism, the ternary carbide grains will undergo a preferential growth, i.e. each layer grows fast and expands quickly in the basal plane and all the layers are successively stacked along the normal direction identical to the c-axis in the hexagonal structure. This preferential growth characterized by the terraced structure was widely observed in this study and hence may be a common behavior during the growth of Ti₂AlC and Ti₃AlC₂ crystals in combustion synthesis.     

The crystal structure of LiScS2 and NaScS2

LiScS₂ and NaScS₂ were prepared and the structure was determined by X-ray powder work. The observed α-NaFeO₂ structure for these compounds is discussed in relation to other ABS₂ compounds.