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。     

热压法制备Al2O3/TiB2/AlN/TiN复合陶瓷

将金属Al,Al3Ti和TiB2以AlTiB中间合金的形式引入Al2O3基体材料中,利用热压法制备Al2O3/TiB2/AlN/TiN复合陶瓷.探讨了复合陶瓷致密化程度与AlTiB体积含量之间的关系.复合陶瓷在烧结过程中属过渡液相烧结.烧结过程中Al,Ti和N2(保护气氛)通过化学反应生成新相AIN和TiN.对热压烧结后材料的硬度、断裂韧性和抗弯强度进行了测试和分析.分析了复合陶瓷的力学性能随AlTiB体积含量变化的规律.比较了复合陶瓷1500℃和1600℃的相对密度及力学性能.探讨了复合陶瓷断面断裂方式的变化对其力学性能的影响,并分析了AlTiB中间合金的细化特性.     

烧结气氛对合成MgAl2O4-Ti(C,N)复合陶瓷的影响

以金属铝粉、钛白粉和轻烧MgO细粉为原料,通过设计100%焦炭粒(简称C气氛),10%钛白粉 90%焦炭粒(简称TC气氛),以及10%硅微粉 90%焦炭粒(简称SC气氛)3种埋粉条件下的高温烧结还原性气氛,采用X射线衍射仪(XRD)、扫描电镜(SEM)和微区电子探针分析(EPMA)等手段,研究了铝热还原氮化法(1600℃3h)制备MgAl2O4-Ti(C,N)复合陶瓷在不同烧结气氛下的相组成和显微结构的变化。结果表明在不同气氛下,烧后试样的主要物相均为MgAl2O4和Ti(C,N),Ti(C,N)可能会固溶氧,气氛对Ti(C,N)的影响较大。和单纯埋炭气氛下相比,在TC气氛下有助于Ti(C,N)的生成,但晶粒细小;在SC气氛下不利于Ti(C,N)的生成,且有玻璃相存在。     

TiO2-B2O3-C系统反应热力学初步探讨

采用物质吉布斯自由能函数法,对TiO2-B2O3-C系进行了热力学分析.热力学计算结果表明:在采用碳热还原法还原TiO2时, TiO2是按照以下顺序依次被还原:TiO2→Ti4O7→Ti3O5→Ti2O3→TiO→Ti;采用碳热还原法合成TiB2的反应模型为:随着温度逐渐升高,TinO2n-1(n=2～4)被还原为TiO,B2O3被碳还原生成单质B和B4C,随后TiO与B或B4C 进一步反应生成TiB2;采用碳热还原法合成 TiB2时,硼源的选择对于合成温度的高低有直接影响,而采用B2O3作为合成TiB2的硼源,其原料来源充足,合成温度适中,适用于采用此法进行大规模工业生产;为降低反应温度,提高反应的转化率,缩短反应进程,应采用抽真空或在稀有气体气氛下进行,增大稀有气体流速,定时对炉内抽真空换气,以降低炉内CO分压PCO的工艺措施.     

Ti(C0.12 N0.88)粉末的高温合成

本文研究了以TiC和TiN粉末为原料，通过高温反应直接合成Ti(C0.12 N0.88）。实验表明，按设定组成的摩尔比TiC/TiN等12/88，在1500℃，Ar气氛下恒温5小时，能直接反应合成Ti(C0.12 N0.88）粉末。     

TiO2-C体系在不同气氛下的反应

为了解TiO2-C体系在不同气氛下的反应过程,以w(TiO2)≥98.0%的锐钛矿型TiO2和w(C)≥98.8%的活性炭为原料,在热力学计算的基础上,结合室温~1 773 K下的TGA、XRD和SEM分析,研究了m(TiO2)∶m(C)=1∶0.3的TiO2-C体系分别在Ar和N2气氛下热处理过程中的物相变化及显微形貌。结果表明:TiO2的还原反应是分步进行的,随着温度的提高,依次发生反应:TiO2→Ti3O5,TiO2→Ti2O3;在N2条件下,随着温度的升高,TiO2先氮化生成Ti(CON)固溶体,之后转化为TiN。     

碳热还原法合成硼化钛

以金红石型TiO2、石墨和B2O3为原料,采用碳热还原法合成了TiB2粉末。借助X射线衍射、扫描电子显微镜和透射电子显微镜等分析手段,研究了工艺条件对合成TiB2的影响。结果表明:合成温度、球磨时间、保温时间、合成气氛是影响TiB2合成的主要因素。随着合成反应温度升高,TiO2的碳热还原顺序依次为:TiO2→Ti4O7→Ti6O11→Ti5O9→Ti3O5→Ti2O3。TiB2的生成反应温度开始于1300℃左右。真空下合成TiB2的最佳工艺条件为:球磨时间为24h,合成温度为1450℃,保温时间为3h。合成TiB2粉末的纯度达到98%,晶粒发育完整,平均粒径为2～3μm。     

TiB2材料氧化的热力学分析

采用物质吉布斯自由能函数法,对TiB2材料的氧化进行了热力学分析.热力学计算结果表明: TiB2材料从室温到高温均可以与氧发生反应生成TiO2;当温度T＜1450 K时,氧化产物为TiO2固相和B2O3液相,在氧化行为上表现为氧化增重;当温度T＞1450 K时,由于B2O3蒸气挥发,在材料中留下孔隙,增加了TiB2材料与氧气的接触面积,TiB2材料的氧化进程加速,此时,TiB2材料的抗氧化性逐渐下降;在PB2O3=101325 Pa的条件下,TiB2材料由"钝化氧化"向"活化氧化"的转变条件为T=1450 K;在氧化性气氛下,氧化反应的产物为TiO2,而随着氧分压降低,Ti4O7、Ti3O5、Ti2O3、TiO等氧化产物均有可能出现,尤其是在氧分压很低的情况下,TiO生成的可能性增大.     

碳热还原法合成TiB_2的热力学分析与研究

以30μm TiO2(w(TiO2)>99.8%,金红石型)、50 μm B2O3(w(B2O3)>99.5%)及10μm石墨粉(w(C)>99%)为原料,按n(TiO2):n(B2O3):n(C)=1:1:5进行配料后放入不锈钢球磨罐中抽真空球磨24 h,然后将反应混合物移入石墨坩埚内置于热压炉中,分别在1 250、1 350、1 400、1 500、1 600、1 700℃保温4 h进行反应.对以TiO2、B2O3、石墨粉为原料合成TiB2的反应体系进行了热力学计算,并对反应产物进行XRD与SEM分析.热力学计算表明,上述3种原料通过碳热还原反应合成硼化钛的反应开始温度为1 556 K.而合成产物的XRD分析表明,生成硼化钛的开始温度为1 350℃以上.碳热还原TiO2和B2O3合成TiB2的反应机理应为C还原TiO2,其中间产物为Ti3O5、Ti2O3、TiO,然后这些中间产物与B2O3一起逐渐被C还原生成TiB2.SEM分析表明,TiB2颗粒呈不规则短柱状,粒度为5～10m;当反应温度达到1 700℃以上时,硼化钛晶粒有长大的现象.     

(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.     

Effects of TiC/TiN addition on the microstructure and mechanical properties of ultra-fine grade Ti (C, N)–Ni cermets

Two series of Ti (C, N)-based cermets, one with TiC addition and the other with TiN addition, were fabricated by conventional powder metallurgy technique. The initial powder particle size of the main hard phase components (Ti (C, N), TiC and TiN) was nano/submicron-sized, in order to achieve an ultra-fine grade final microstructure. The TiC and TiN addition can improve the mechanical properties of Ti (C, N)-based cermets to some degree. Ultra-fine grade Ti (C, N)-based cermets present a typical core/rim (black core and grayish rim) as well as a new kind of bright core and grayish rim structure. The average metallic constituent of this bright core is determined to be 62 at% Ti, 25 at% Mo, and 13 at% W by SEM–EDX. The bright core structure is believed to be formed during the solid state sintering stage, as extremely small Ti (C, N)/TiC/TiN particles are completely consumed by surrounding large WC and Mo₂C particles. Low carbon activity in the binder phase will result in the formation (Ni₂Mo₂W)C_x intermetallic phase, and the presence of this phase plays a very important role in determining the mechanical properties of TiN addition cermets.     

TiBCN高温陶瓷的XPS分析

本文采用放电等离子烧结法在1700°C、1800°C及1900°C下制备了TiBCN陶瓷,并采用XPS对所制备的TiBCN材料表面组成及元素存在状态进行了详细的分析研究。实验结果表明,不同温度下,钛(Ti)、硼(B)、碳(C)、氮(N)等各元素的存在形式显著不同。1800°C烧结的TiBCN材料主要由高熔点高硬度的TiB_2、TiN和TiBCN三种晶相构成。     

Microstructure–property correlation in nano-diamond and TiN added TiC-based ceramics

In this paper, the effect of TiN and nano-diamond additives on the microstructure and properties of TiC-based composites, produced by spark plasma sintering method, was investigated. The thermal conductivity of TiC ceramic was improved significantly due to the incorporation of nano-diamond additive. Although the introduction of diamond worsened the sintering behavior of the sintered TiC ceramic, it enhanced the formation of continuous network of the graphitized diamond at the grain boundaries. However, the addition of TiN to the TiC-diamond sample led to the formation of nitrogen gas at high temperatures, resulting in a semi-porous ceramic containing ~13% porosity. Furthermore, the unreacted TiN was dissolved in the matrix, creating a solid solution of Ti(C,N). Despite the beneficial influence of nano-diamond on the thermal conductivity of TiC, the incorporation of TiN and nano-diamond in TiC ceramics decreased the flexural strength and hardness.     

Effect of powder size on microstructure and mechanical properties of Ti(C,N) based cermets

Abstract

Effect of the particle size of TiC and TiN on the microstructure and mechanical properties of Ti(C,N) based cermets has been evaluated. Ti(C,N)–WC–Co cermets made from four groups of mixed raw powders of different sizes were manufactured by vacuum sintering. The microstructure and composition were studied using X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectrum (EDX). The result shows that the four samples have the typical microstructures of 'black core/grey rim'. The mechanical properties of the cermet manufactured from submicron TiC and nano TiN are the best among the four samples.     

Repair of spline shaft by laser-cladding coarse TiC reinforced Ni-based coating: Process,microstructure and properties

To repair the surface defects of spline shaft and improve wear resistance, the coarse TiC reinforced Ni-based composite coatings were fabricated on the spline shaft surface by laser cladding with six types of precursors containing Ni45, coarse TiC, and fine TiN powder. The effects of ceramic content and fine TiN addition on the formability, microstructure, and mechanical properties of the coatings were studied comprehensively. In TiC reinforced Ni-based coatings 1–3 without fine TiN addition, the porosity decreased from 20.415 % to 0.571 % with the increase of TiC concentration. The coatings mainly consist of CrB, Cr7C3, Cr23C6, coarse TiC, and γ-Ni. With the addition of fine TiN, the length of the ceramic phases in coatings 1#–3# decreased slightly, while volume fraction and porosity increased. Moreover, the ring-shaped Ti (C, N) phases were also detected at the edges of both undissolved TiC and TiN particles, which improved the bonding force between ceramics and matrix. Besides, these ceramics inhibited the generation of columnar crystals and eliminated the heat-affected zone. The performance test results show that the coating 3# with 30 wt% TiC and 6 wt% TiN exhibits the best wear resistance despite slightly decreased hardness, and its friction coefficient of 0.409 and wear rate of 42.44 × 10⁻⁶ mm³ N⁻¹·m⁻¹ are, respectively, 0.667 and 0.307 times those of the substrate. Based on the additive/subtractive hybrid manufacturing technology, the optimized coatings were ground to obtain the finishing surface, which indicates that the coarse TiC reinforced coating can be employed in repairing the damaged parts.     

cBN–TiN,cBN–TiC composites: chemical equilibria,microstructure and hardness mechanical investigations

This paper summarizes theoretical and experimental studies of cBN–TiN and cBN–TiC of cBN:TiN/TiC molar ratio 1:1 and 2:1. Theoretical calculations show that, at temperatures between 1000 and 1400°C, TiN reacts with BN forming one new phase, TiB₂, and that TiC reacts with cBN forming two new phases, TiB₂ and TiC_0.8N_0.2.. Experimental cBN–TiC/TiN composites were prepared by high pressure hot pressing and the samples were subsequently heat treated.After heat treatment, sinters of cBN–TiN/TiC were characterized using transmission electron microscopy and X-ray diffraction. The samples exhibited a dense polycrystalline structure, and a thin layer of fine TiB₂ was visible at the BN–binder interface. It was found that hardness decreased significantly after heat treatment.     

Comparison of the anti-coking performance of CVD TiN,TiO2 and TiC coatings for hydrocarbon fuel pyrolysis

Previous work has shown that both TiN and TiO₂ coatings can inhibit the metallic catalytic coking effectively, but both of them have their own shortage. In this work, TiC coating was prepared on the surface of SS304 tube using TiCl₄-CH₄-H₂ by CVD method. Its morphology, elemental composition, thickness and oxidation resistance were characterized by SEM, EDX, metalloscopy and TPO tests, respectively. The results show that CVD TiC coating is gray, homogeneous, and dense without cracks or holes. The TiC coating presents a cuboid particle structure with the sizes of about 1.0 µm for the cuboid crystals, and the Ti/C ratio close to 1:1, while the average thickness is about 11.62 µm. TPO results show that the TiC coating begins to react with O₂ and release CO₂ at about 810 °C. Compared with the TiN coating (The initial oxidation temperature of TiN is about 350 °C), the oxidation resistance of TiC coating is improved substantially. As a conclusion, the high oxidation resistance order is TiO₂ coating>TiC coating>TiN coating. Furthermore, the temperature programmed cracking of RP-3 Chinese jet fuel was employed to compare the anti-coking performance of TiN, TiO₂ and TiC coatings. The results show that each of TiN, TiO₂ and TiC coating has obvious anti-coking effect, and the anti-coking performance order is TiN coating=TiC coating>TiO₂ coating.     

C-B4C-SiC与Ti组分的原位反应及热压烧结

以炭黑、炭纤维、Ｂ４Ｃ、ＳｉＣ、Ｓｉ、ＴｉＯ２和ＴｉＣ为原料制备了不同ＴｉＯ２和ＴｉＣ含量的炭／陶复合材料,采用原位合成及热压技术研究了不同ＴｉＯ２和ＴｉＣ含量对多组分炭／陶复合材料的组成、结构和性能的影响。在烧结过程中ＴｉＯ２和ＴｉＣ与Ｂ４Ｃ反应原位生成ＴｉＢ２,Ｓｉ和ＴｉＯ２分别与Ｃ反应生成ＳｉＣ和ＴｉＣ,这些陶瓷相的生成对提高炭／陶复合材料的力学性能有显著作用。加入ＴｉＯ２能使炭／陶复合材料在较低的温度下实现致密化烧结,获得了抗弯强度达４３０ＭＰａ的炭／陶复合材料     

Multicomponent binders for PcBN performance enhancement in cutting tool applications

This study proposes a novel design of binders for polycrystalline cubic boron nitride (PcBN) cutting tool materials. Well-known binder phases TiC and TiN were combined with transitional metal nitrides ZrN, VN, and HfN. Performance screenings of longitudinal turning Inconel 718 and AISI 316 L highlighted the superior performance of PcBN materials with mixed TiC-ZrN and TiC-VN binders. These two systems were further sintered in a wider range of temperatures. XRD and STEM-XEDS analysis confirmed mutual dissolution of both TiC and ZrN, and TiC and VN, thus forming two types of solid solutions (Ti,Zr)(C,N) and (Ti,V)(C,N). Extended performance tests showed that tools with TiC-ZrN binder outperform reference PcBN with TiC binder by up to 20% when machining Inconel 718. When machining hardened Caldie tool steel, the performance of tools with TiC-ZrN and TiC-VN binders were 80–90% higher than the reference tools.