自蔓延高温合成Ti3AlC2 和Ti2AlC及其反应机理研究

以Ti,Al和C的粉体混合物为原料，在纯氩气气氛，25MPa压力，1600℃保温4h条件下，自蔓延高温合成了Ti3AlC2和Ti2AlCT，利用X射线衍射分析（XRD）和扫描电镜（SEM）等手段对反应产物进行了研究，提出了自蔓延高温合成Ti3AlC2和Ti2AlC应具备的条件，并探讨了Ti，Al和C自蔓延高温合成Ti3AlC2和Ti2AlC的反应机理，结果表明，Ti3AlC2和Ti2AlC能够由Ti,Al和C元素经高温自蔓延合成反应来制备，其制备的必要条件是需要极快的加热速率以防止铝熔化并且改变钛的转移路线，Ti3AlC和Ti2AlC综合了金属材料和陶瓷材料的优点，成功的应用自蔓延高温方法合成Ti2AlC2和TiAlC必将成为该类材料纯块体的合成和制备提供好的原料，从而这类材料的实际应用将起到极大的推动作用。     

工艺调控对原位合成Ti3AlC2陶瓷的影响

以TiC、Ti和Al粉为原材料,采用冷压预成型-热压辅助工艺原位制备Ti3 AlC2陶瓷.借助反应吉布斯自由能分析TiC-Ti-Al体系的合成机制,采用XRD和SEM分析工艺因素如升温速率、Al含量、烧结温度和压坯尺寸对原位合成Ti3 AlC2陶瓷的影响.结果表明,通过调控工艺,成功合成了高纯度Ti3 AlC2陶瓷,Ti3 AlC2具有典型的层状结构.该反应体系的最佳升温速率为:1000℃之前,20℃/min; 1000℃之后,10℃/min.用纳米TiC粉替代微米TiC粉,烧结温度由1450℃降至1350℃,且Ti3 AlC2的合成纯度更高.当采用大尺寸压坯时,发生了“热爆”现象,非平衡相较多,Ti3 AlC2的生成含量较低,且样品开裂严重.Ti3 AlC2的合成过程为:Ti与Al反应生成TiAl金属间化合物,接着TiAl与TiC反应生成Ti3AlC2.     

原位热压2TiC/Ti/Al合成Ti3AlC2陶瓷

以2TiC/Ti/Al为组分采用原位热压技术制备Ti3AlC2陶瓷。采用XRD和SEM分析不同工艺时合成产物的物相组成和显微结构。结果表明：恰当的加压工艺和升温速率控制,能够合成高纯Ti3AlC2陶瓷。用TiC粉替代C和部分Ti粉有利于Ti3AlC2的原位合成。     

热压烧结工艺制备Ti2AlC/Ti3AlC2陶瓷材料

以Ti，Al，C为原料，采用热压工艺制备出相组成为Ti2AlC/Ti3AlC2块体材料，合成材料的X—射线衍射和扫描电镜(SEM)分析的结果表明：当烧结温度为1400℃时，材料中的主晶相为Ti2AlC,大小为10μm的板状多晶体；而在1500℃的温度下烧结所得材料的主晶相为Ti3AlC2，其板状多晶体的晶粒尺寸平均约为20μm。     

Ti3AlC2材料的制备及其高温抗氧化性能研究

以TiC粉、Ti粉和Al为原料,按TiC:Ti:Al=2:1:1(原子比)混合,采用真空热压烧结法制备Ti3AlC2材料.XRD和SEM分析表明,合成产物中几乎全为Ti3AlC2相,TiC含量极少,层片状的Ti3AlC2发育良好,晶粒细小,分布均匀.该材料在900 ℃宅气中断续氧化30 h后的氧化动力学遵循抛物线规律,氧化层主要成分为TiO2和Al2O3,与基体粘结紧密,起到良好的保护作用.     

Ti_3AlC_2陶瓷的热压合成

以TiC-Ti-Al为反应体系,采用原位热压技术制备Ti3AlC2陶瓷。借助XRD分析相组成,并对实验现象进行分析。结果表明,TiC的加入,避免了Ti和C粉之间强烈的放热反应。通过降低初始压坯尺寸抑制了"热爆行为",有利于合成高纯Ti3AlC2。用大压坯时,"热爆行为"明显,产物由Ti3AlC2、TiC和Ti3Al相组成,Ti3AlC2含量少;用小压坯时,未发生"热爆行为",产物由Ti3AlC2和TiC相组成,Ti3AlC2相含量较高。     

放电等离子烧结工艺制备Ti2A1C材料的研究

以元素粉钛、铝、碳为原料,采用放电等离子烧结工艺在1100℃的温度下成功地制备了高纯、致密Ti2AlC材料.合成材料的X-射线衍射(XRD)和扫描电镜(SEM)分析的结果表明:多晶体Ti2AlC形貌为板状结晶,晶粒大小平均约为20μm,厚度在3～5μm.     

放电等离子烧结工艺制备Ti_2AlC材料的研究

以元素粉钛、铝、碳为原料 ,采用放电等离子烧结工艺在 1 1 0 0℃的温度下成功地制备了高纯、致密Ti2 AlC材料。合成材料的X -射线衍射 (XRD)和扫描电镜 (SEM)分析的结果表明 :多晶体Ti2 AlC形貌为板状结晶 ,晶粒大小平均约为 2 0 μm ,厚度在 3～ 5 μm。     

原料体系对Ti3SiC2合成过程中相组成和显微结构演变的影响

分别以粉末钛粉、硅粉、石墨和钛粉、碳化硅、石墨为原料,采用热压烧结法制备了Ti3SiC2材料,借助XRD和SEM手段研究了原料体系和烧成温度对试样相组成、致密化程度和显微结构的影响,并分析了反应烧结机理。结果表明:(1)随着温度的升高,钛粉-硅粉-石墨体系较钛粉-碳化硅-石墨体系合成出的Ti3SiC2块体材料纯度更高;(2)钛粉-硅粉-石墨体系在烧结温度低于1300℃时,主要以Ti5Si3、TiC和残余的硅粉、石墨反应生成Ti3SiC2,在烧结温度为1300～1600℃时,主要以形成的液相Ti-Si(L)与TiC反应生成了Ti3SiC2;钛粉-碳化硅-石墨体系在1485℃液相出现之后,颗粒经历重排和溶解再析出的过程,在液相中生成Ti3SiC2。     

热压工艺制备高纯致密Ti3AlC2材料

原料配比为n(TiC)：n(Ti)：n(Al)：n(Si)=2：1：1：0．2的起始混合粉料在1300--1500℃温度下，30MPa压力下热压2h制得高纯致密Ti3AlC2块体材料。添加适量硅作助剂显加快Ti3AlC2的反应合成，使Ti3AlC2在1200℃的温度下大量生成，能谱仪分析表明Si在材料中均匀分布。1300℃和1400℃烧结所得Ti3AlC2颗粒均呈六方板状结晶形貌，其在平面内尺寸大小分别为3～6μm和10～20μm。     

Synthesis of single-phase Ti3SiC2 powder

In this study, free 2Ti/2Si/3TiC powder mixture was heated at high temperatures in vacuum, in order to reveal the possibility for the synthesis of high Ti₃SiC₂ content powder. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used for the evaluation of phase identities and the morphology of the powder after different treatments. Results showed that almost single phase Ti₃SiC₂ powder (99.3 wt.%) can be synthesized by heat treatment with free 2Ti/2Si/3TiC powders in vacuum at 1210°C for about 3 h. The nucleation and growth of Ti₃SiC₂ within TiC particles was observed. The typical appearance of the formed Ti₃SiC₂ is equiaxed with particle size of 2–4 μm. Effects of temperature and heating time on the morphology and the particle sizes of the synthesized Ti₃SiC₂ powders are not obvious.     

Effect of Ti5Si3 on wear properties of Ti3Si(Al)C2

Near-fully dense Ti₃Si(Al)C₂/Ti₅Si₃ composites were synthesized by in situ hot pressing/solid–liquid reaction process under a pressure of 30 MPa in a flowing Ar atmosphere at 1580 °C for 60 min. Compared to monolithic Ti₃Si(Al)C₂, Ti₃Si(Al)C₂/Ti₅Si₃ composites exhibit higher hardness and improved wear resistance, but a slight loss in flexural strength (about 26% lower than Ti₃Si(Al)C₂ matrix). In addition, Ti₃Si(Al)C₂/Ti₅Si₃ composites maintain a high fracture toughness (K_IC = 5.69–6.79 MPa m^1/2). The Ti₃Si(Al)C₂/30 vol.%Ti₅Si₃ composite shows the highest Vickers hardness (68% higher than that of Ti₃Si(Al)C₂) and best wear resistance (the wear resistance increases by 2 orders of magnitude). The improved properties are mainly ascribed to the contribution of hard Ti₅Si₃ particles, and the strength degradation is mainly due to the lower Young's modulus and strength of Ti₅Si₃.     

Effect of Ti3AlC2 precursor on the electrochemical properties of the resulting MXene Ti3C2 for Li-ion batteries

The presented work compared the etching behavior between combustion synthesized Ti₃AlC₂ (SHS-Ti₃AlC₂) and pressureless synthesized Ti₃AlC₂ (PLS-Ti₃AlC₂). Because the former had a more compact structure, it was harder to be etched than PLS-Ti₃AlC₂ under the same conditions. When served as anode material for Li-ion batteries, SHS-Ti₃C₂ showed much lower capacity than PLS-Ti₃C₂ at 1?C (52.7 and 87.4?mAh?g^?1, respectively) due to the smaller d-spacing. Furthermore, Potentiostatic Intermittent Titration Technique (PITT) was used to determine the Li-ion chemical diffusion coefficient (${\mathrm{D}}_{{\mathrm{Li}}^{+}}$) of Ti₃C₂ in the range of 10^?10 ??10^?9 cm² s^?1, indicating that Ti₃C₂ could exhibit an excellent diffusion mobility for Li-ion.     

Preparation and characterization of Ti3SiC2 powder

Pressureless sintering in vacuum was applied to synthesize Ti₃SiC₂ from elemental powders of Ti, Si and C. Based on the phase compositions and purities of the products obtained by X-ray diffraction, the elemental powders composition and sintering condition were optimized. It was found that the sample sintered at 1450 °C for 240 min from a mixture of 3Ti/1.75Si/2C (molar ratio) contained Ti₃SiC₂ with the volume fraction as high as 93%. It was proposed that loss of Si through gaseous vaporization and contamination of C might be the main obstacles against obtaining high-purity material by this way.     

Effect of Al2O3 on mechanical properties of Ti3SiC2/Al2O3 composite

The effect of Al₂O₃ on mechanical properties of Ti₃SiC₂/Al₂O₃ composite fabricated by SPS was studied systematically. The results show that the hardness of the Ti₃SiC₂/Al₂O₃ composite can reach 10.28 GPa, 50% higher than that of pure Ti₃SiC₂. However, slight decrease in the other mechanical properties was observed with Al₂O₃ addition higher than 5–10 vol.%, which is believed to be due to the agglomeration of Al₂O₃ in the composite.     

熔盐法合成Ti3SiC2粉体

以NaCl为熔盐介质,利用熔盐法在真空条件下合成了Ti3SiC2粉体。研究了煅烧温度和原料中Si的含量对合成Ti3SiC2粉体成分及形貌的影响。研究发现使用熔盐法可以在相对较低的温度下合成的Ti3SiC2粉体,当Ti∶Si∶C的摩尔配比为3∶1.3∶2时,在1200℃保温2h可以获得质量分数为97%的Ti3SiC2粉体,且所获得粉体形貌较为均匀,无明显团聚现象。     

氯化 Ti3AlC2 陶瓷制备碳化物衍生碳的结构表征

以三元碳化物陶瓷Ti_3AlC_2为原料,在500°C~1000°C温度范围内氯化制备具有纳米孔结构的碳化物衍生碳(Ti_3AlC_2-CDC)。高温氯化制备得到的Ti_3AlC_2-CDC由无定形碳和石墨组成。氯化温度越高,石墨化程度越明显,石墨有序度越高。Ti_3AlC_2-CDC的结构与前驱体Ti_3AlC_2的层状结构保持一致。但随着温度升高,Ti_3AlC_2-CDC会逐渐裂解为单片层或多片层。采用N2吸附技术研究了700°C、800°C和1000°C下制备的Ti_3AlC_2-CDC的孔隙结构特征,通过分析试样的吸附等温线特征和孔径分布探讨了温度对CDC孔结构的影响。     

纯Ti2O3中Ti3+含量的测定

使用容量法和重量法，测定了TiO     

Reactive synthesis for porous Ti3AlC2 ceramics through TiH2, Al and graphite powders

Porous Ti₃AlC₂ ceramics were fabricated by reactive synthesis. The process of fabrication involved five steps: (i) the pyrolysis of stearic acid at 450 °C; (ii) the decomposition of TiH₂ at 700 °C, which leads to the conversion of TiH₂ to Ti; (iii) the solid–liquid chemical reaction of solid Ti and molten Al at 800–1000 °C, which converts the mixture to Ti–Al compounds; (iv) the newly synthesized Ti–Al compounds that react with surplus Ti and graphite to form ternary carbides and TiC at 1100–1200 °C; and (v) reactive synthesized ternary carbides and TiC that yield porous Ti₃AlC₂ at 1300 °C.     

Effect of TiO2 on sinterability and physical properties of pressureless sintered Ti3AlC2 ceramics

TiO₂ was selected as effective sintering aid for pressureless sintering of Ti₃AlC₂ ceramics in this study. The addition of only 5?wt% TiO₂ largely promotes the densification and nearly dense Ti₃AlC₂ ceramic was obtained by pressureless sintering at 1500?°C. Significant strengthening and toughening effects were observed with the addition of TiO₂. High Vickers hardness, flexural strength and fracture toughness of 3.22?GPa, 298?MPa and 6.2?MPa?m^?1/2, respectively, were achieved in specimen pressureless sintered with 10?wt% TiO₂. Additionally, the addition of 5?wt% TiO₂ had no deleterious effect on the excellent oxidation resistance of Ti₃AlC₂ ceramic under 1200?°C water vapor atmosphere, while addition of 10?wt% TiO₂ accelerates the oxidation rate by two orders of degree.