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。     

Thermal and electrical properties of spark plasma sintered (Ti,Cr)B2 ceramics

Thermal and electrical properties were measured for TiB₂ ceramics containing varying CrB₂ contents up to 33 mol%. The room-temperature thermal diffusivity decreased with increasing Cr content from 0.330 ± 0.003 cm²/s for pure TiB₂ to 0.060 ± 0.003 cm²/s for (Ti_0.66Cr_0.33)B₂. The amount of anisotropy in the coefficients of thermal expansion increased with increasing Cr content and the c-axis had the greatest dependence on Cr addition, with an increase of more than 25% in the thermal expansion for 33 mol% CrB₂ compared to TiB₂, whereas the a-axis only increased by about 8%. The electrical conductivity was the lowest for (Ti_0.66Cr_0.33)B₂ at ∼8.5 × 10³ S/cm compared to ∼106.1 × 10³ S/cm for nominally pure TiB₂. Overall, the addition of CrB₂ as a sintering aid for TiB₂ was shown to have a significant effect on the thermal and electrical properties of TiB₂ for additions as small as 5 mol% CrB₂.     

Combustion of Ti+0.5C and Ti+C mixtures of bulk density in inert gas coflow

The combustion of Ti-C mixtures of bulk density under inert gas blowing conditions produced by evacuation of one end of the reaction cell was studied for the first time. The experiments showed that the tested mixtures in quartz cups were not ignited and did not burn without the inert gas (argon) flow. Increasing the rate of gas evacuation from the sample increased the rate of steady-state combustion of the mixture of titanium with carbon black, and for the mixture of titanium with graphite, stabilization of the flat combustion front was observed. It is shown that the presence of small pressure difference (up to 105 Pa) allows control of the combustion process and confirms the basic postulates of the convective-conductive theory of combustion for heterogeneous condensed systems. __________ Translated from Fizika Goreniya i Vzryva, Vol. 45, No. 1, pp. 30–37, January–February, 2009.     

Green Density of a Powder Compact and Its Influence on the Steady-State Wave Velocity in Combustion Synthesis of Condensed Phase

Various experimental evidence indicates that the porosity of a compact has a pronounced effect on the steady-state velocity in combustion synthesis of condensed phases, hut no simple and explicit treatment for it is available in the literature. Utilizing an existing model of the effective thermal conductivity in a porous media, a simple model for the steady-state velocity of the combustion front has been developed. As ob- served in experiments, the model also predicts a decrease in combustion velocity with increasing porosity. The developed equation can be helpful in the analysis and interpretation of experimental results in self-propagating high-temperature synthesis of condensed phase.     

放电等离子制备Ti3AlC2/TiB2复合材料及性能

采用放电等离子烧结(spark plasma sintering,SPS)工艺制备了Ti3AlC2/TiB2复合材料,并研究了复合材料的性能.研究表明:在1 250℃,30MPa烧结8min,可以获得相对密度达98%以上的致密Ti3AlC2/TiB2块体材料;在Ti3AlC2中添加TiB2能大幅度提高材料性能,当TiB2含量为30%(体积分数,下同)时,Ti3AlC2/30%TiB2复合材料的Vickers硬度达到10.39GPa,电导率为3.7×106 S/m;当TiB2含量为10%时,抗弯强度为696MPa,断裂韧性为6.6MPa·m1/2.用电子显微镜对复合材料的显微结构分析表明:Ti3AlC2/TiB2复合材料的晶粒为层状结构.     

Simultaneous Synthesis and Densification of Titanium Nitride/ Titanium Diboride Composites by High Nitrogen Pressure Combustion

Composites of TiN/TiB₂ were synthesized by a combustion process of BN, Ti in a nitrogen atmosphere. The effect of the BN/Ti ratio and the nitrogen gas pressure on the synthesis of these composites was investigated. Dense TiN/TiB₂ composites with relatively high hardness and toughness were fabricated by combustion synthesis from Ti and BN under a nitrogen pressure of 4.0 MPa. The Vickers microhardness of the products obtained from reactants with a BN/Ti mole ratio of 0.11 increased with an increase in nitrogen pressure and had a maximum value of ∼25 GPa. Fracture toughness, K _IC, of the products increased from 3.1 to 5.9 MPa·m^1/2 as the BN/Ti ratio increased from 0.11 to 0.20. However, products formed under nitrogen pressures higher than 6.0 MPa exhibited circumferential macrocracks due to thermal shock.     

Dynamic modes of Ti combustion in a coflow of N<Subscript>2</Subscript>-Ar mixture

Combustion of bulk density Ti powder (containing 20 wt % TiN as a diluent) in a coflow of N₂-Ar mixture was investigated upon variation in the nitrogen content of the gaseous mixture. The obtained data are believed to open up new horizons for fabrication of layered and composite ceramics by infiltration-mediated combustion.      

Al2O3陶瓷基体中原位生成TiB2和Ti（C,N）研究

采用原位反应法结合热压工艺制备Ａｌ２Ｏ３－ＴｉＢ２－Ｔｉ（Ｃ，Ｎ）复相陶瓷，用ＴｉＯ２，Ｂ４Ｃ，ＢＮ，Ａｌ及Ａｌ２Ｏ３为原料，通过组成设计可以制备出不同相组成及碳氮比的复相陶瓷。由ＳＥＭ及ＴＥＭ发现在Ａｌ２Ｏ３晶粒中分布着亚微米至微米级的近圆形Ｔｉ（Ｃ，Ｎ）颗粒，而在ＴｉＢ２晶粒中分布着纳米级的板状Ｔｉ（Ｃ，Ｎ）晶体，并对这种显微结构的形成机理及化学反应过程作用初步分析。     

Synthesis of Dense TiB2-TiN Nanocrystalline Composites through Mechanical and Field Activation

The synthesis of dense nanometric composites of TiN-TiB₂ by mechanical and field activation was investigated. Powder mixtures of Ti, BN, and B were mechanically activated through ball milling. Some powders were milled to reduce crystallite size but to avoid initiating a reaction. In other cases powders were milled and allowed to partially react. All these were subsequently reacted in a spark plasma synthesis (SPS) apparatus. The products were composites with equimolar nitride and boride components with relative densities ranging from 90.1% to 97.2%. Crystallite size analyses using the XRD treatments of Williamson-Hall and Halder-Wagner gave crystallite sizes for the TiN and TiB₂ components in the range 38.5–62.5 and 31.2–58.8 nm, respectively. Vickers microhardness measurements (at 2 N force) on the dense samples gave values ranging from 14.8 to 21.8 GPa and fracture toughness determinations (at 20 N) resulted in values ranging from 3.32 to 6.50 MPa·m^1/2.     

TiB_2材料的研究现状及其应用

ＴｉＢ_２材料具有熔点高、硬度大、耐磨、耐腐蚀、抗氧化性、导电性和导热性好等优点，是一种有广泛应用前景的新型陶瓷材料。本文介绍了ＴｉＢ_２材料的制备、烧结及其复相陶瓷的研究现状，对其力学性能、抗氧化性能和摩擦学性能进行了评价。     

(SiC,TiB2)/B4C复合材料的微观结构及性能

以B4C与Si3N4和少量SiC,TiC为原料,Al2O3和Y2O3为烧结助剂,烧结温度为1 800～1 880℃,压力为30 MPa的热压条件下制备(SiC,TiB2)/B4C复合材料.用透射电子显微镜、扫描电子显微镜和能谱分析进行显微结构分析.结果表明:在烧结过程中反应生成了SiC,TiB2和少量的BN.复合材料的主晶相之间有长棒状架构弥散相和束状弥散相,在部分B4C晶粒内部出现了内晶结构.结合对复合材料性能的分析表明:新形成相、均匀细晶和棒状结构对提高材料的性能具有重要作用.通过对材料断口形貌和裂纹扩展模式分析认为,复合材料的断裂机制主要为裂纹偏转.     

二硼化钛在氟化钾溶液中的放电行为

研究了二硼化钛电极在20%(质量分数)KF溶液中的放电性能及其影响因素。试验发现,当放电速率为100 mA/g时,二硼化钛电极总的放电容量可达2000 mA.h/g。二硼化钛电极在20%(质量分数)KF溶液中的放电曲线上出现了4个放电平台,结合循环伏安曲线、ICP及XRD等分析手段对相应的电化学过程进行了分析,提出了二硼化钛发生电化学氧化反应的可能机理。     

Combustion of mechanically activated 3Ti + 2BN mixtures

Laws of self-propagating high-temperature synthesis in 3Ti + 2BN reactive mixtures after preliminary mechanical activation in a planetary ball mill are studied. A discontinuity caused by specific features of the dynamics of formation of mechanocomposites is observed on the plots of the burning rate and temperature versus time. Regimes of preliminary activation are determined, which ensure the solid-phase combustion regime. Results of x-ray diffraction phase analysis and electron microscopy of combustion products and initial mixtures for different times of mechanical activation are presented.     

Combustion synthesis of titanium aluminides via co-reduction of oxides

In this study, Ti-50Al and Ti-48Al-2Cr powders were produced via reduction of TiO₂/Al₂O₃ and TiO₂/Al₂O₃/Cr₂O₃ mixtures with Ca. Upon addition of KClO₄ to the above mixtures, a combustion synthesis process was initiated in the systems. In the presence of KClO₄, the reduction temperature decreased from 1000 to 550°C.      

Fracture and property relationships in the double diboride ceramic composites by spark plasma sintering of TiB2 and NbB2

Bulk titanium diboride–niobium diboride ceramic composites were consolidated by spark plasma sintering (SPS) at 1950°C. SPS resulted in dense specimens with a density exceeding 98% of the theoretical density and a multimodal grain size ranging from 1 to 10 μm. During the SPS consolidation, the pressure was applied and released at 1950 and 1250°C, respectively. This allowed obtaining a two-phase composite consisting of TiB₂ and NbB₂. For these ceramics composites, we evaluated the flexural strength and fracture toughness and room and elevated temperatures. Room-temperature strength of thus produced bulks was between 300 and 330 MPa, at 1200°C or 1600°C an increase in strength up to 400 MPa was observed. Microstructure after flexure at elevated temperatures revealed the appearance of the needle-shape subgrains of NbB₂, an evidence for ongoing plastic deformation. TiB₂–NbB₂ composites had elastic loading stress curves at 1600°C, and at 1800°C fractured in the plastic manner, and strength was ranged from 300 to 450 MPa. These data were compared with a specimen where a (Ti,Nb)B₂ solid solution was formed during SPS to explain the behavior of TiB₂–NbB₂ ceramic composites at elevated temperatures.     

B2O3-TiO2-Mg-C体系燃烧反应热力学与产物结构变化过程研究

对B2O3-TiO2-Mg-C体系的燃烧反应热力学进行了研究，结果表明，该体系化学反应机理为:Mg先还原B2O3和TiO2，新生的Ti与B的C反应生成TiB2和TiC；TiO2的还原经历了TiO2→Ti3O2→TiO→Ti2O→Ti的逐步过程，对燃烧合成的产物结构形成机理进行了研究，表明当燃烧区的能量传到预反应区时，B2O3首先熔化并均匀地包裹在Mg,TiO2和C周围，Mg熔化后通过扩散与B2O3和TiO2反应，随着预反应区温升的升高，B2O3与Mg作用还原出B，TiO2与Mg作用还原出Ti，然后Ti与B或C反应形成TiB2或TiC晶核，最后TiB2与TiC及MgO在持续高温下长大。     

Spark plasma sintering of TiB2-based ceramics with Ti3AlC2

A TiB₂–Ti₃AlC₂ ceramic was manufactured by spark plasma sintering at 1900 °C temperature for 7 min soaking time under 30 MPa biaxial pressure. The role of Ti₃AlC₂ additive on the microstructure development, densification behavior, phase evolution, and hardness of the ceramic composite were studied. The phase characterization and microstructural investigations unveiled that the Ti₃AlC₂ MAX phase decomposes at the initial stages of the sintering. The in-situ formed phases, induced by the decomposition of Ti₃AlC₂ additive, were identified and scrutinized by XRD and FESEM/EDS techniques as well as thermodynamics principles. The sintered TiB₂–Ti₃AlC₂ ceramic approached a near full density of ~99% and a hardness of ~28 GPa. The densification mechanism and sintering phenomena were discussed and graphically illustrated.     

Growth behavior of TiB2 hexagonal plates prepared via a molten-salt-mediated carbothermal reduction

TiB₂ powders were successfully synthesized by a molten-salt-mediated carbothermal reduction method. The products obtained at 1300°C for 2 hours were hexagonal plates with side length of 3-8 μm and thicknesses of 200-500 nm. The microstructural evolution with temperature confirmed that the growth of TiB₂ hexagonal plates was a layer-by-layer growth controlled by a two-dimensional nucleation. No-uniform grains were observed attached on side and step edges of TiB₂ plates, which became finer and disappeared during the growth. This indicated that layer growth and growth on the side of TiB₂ plates followed the surface adsorption growth model.     

Self‐propagating mechanosynthesis of HfB2 nanoparticles by a magnesiothermic reaction

A mechanically induced self‐sustaining reaction (MSR) was used to synthesize hafnium diboride nanoparticles. Along this route, magnesium was selected as a robust reducing agent for co‐reduction in boron and hafnium oxides in a combustive manner. Combustion occurred after a short milling period of 12 minutes. The hafnium diboride nanoparticles had a polygonal faceted morphology and were 50‐250 nm in diameter. The assessment of the processing mechanism revealed that the initial combustive reduction in B₂O₃ to elemental B by Mg was the major step for progressing the overall reaction. After that, HfO₂ can be reduced to elemental Hf, followed by the synthesis of HfB₂ phase.