自生TiCp/Ti复合材料中TiC的生长习性

利用配位多面体生长基元理论研究了自生TiCp/Ti复合材料中TiC的生长习性。TiC晶体的配位多面体生长基元为TiC6。生长基元进入{100}面时为4个棱边同时联结，生长速率最快，不易显露；进入{111}面时为共面联结，生长速率最慢，容易显露。因此，TiC晶体的理想形态为{111} 面为显露面的八面体。TiC晶胚在熔体中生长时，受传热传质过程的影响，6个顶角所处的{100}方向生长速率加快，形态失稳，从{100}方向顶角部位生长出二次枝晶臂，最终形成棱面枝晶状TiC。如枝晶形成时低生长速度的晶面上形成大量的晶体缺陷，则它们的生长速度加快，棱面消失，成为光滑枝晶。     

钛合金中TiC晶体的生长基元及平衡形态

运用负离子配位多面体生长基元理论，对钛合金中自由生长的TiC晶体的生长基元及平衡形态进行了研究。根据TiC晶体结构特点及Ti晶体d轨道能级分裂、晶体键合轨道等角度分析研究，并通过TiC晶体中形成不同生长基元时可能释放的键能大小来验证等手段，分析和推断出TiC晶体在Ti熔体中自由生长时生长基元为TiC6。对TiC6生长基元的堆垛方式的研究表明TiC晶体的平衡形态应为八面体。在实际试样制备过程中，由于存在较大的过冷度和溶质分布的不均匀性，TiC晶体可能形成各种不同的形态。浮区定向凝固实验结果证明上述分析结果是正确的。     

Grain refining action of Al–5Ti–C and Al–TiC master alloys with Al–5Ti master alloy addition for commercial purity aluminium

Al–Ti–C master alloys have a great potential as efficient grain refiners for aluminium and its alloys. In the present work, the Al–5Ti–C, Al–TiC and Al–5Ti master alloys have been successfully prepared by a method of liquid solidification reactions. While the Al–5Ti–C master alloy consists of some strip- or needle-like TiAl₃, and in addition to TiC particles in the Al matrix, the Al–TiC master alloy revealed the presence of only TiC particles, and the Al–5Ti master alloy consists of only some blocky TiAl₃ particles. A united refinement technology by Al–5Ti–C+Al–5Ti and Al–TiC+Al–5Ti master alloys was put forward in this paper. The blocky TiAl₃ particles in Al–5Ti master alloy can not only improve the grain refinement efficiency of Al–5Ti–C and Al–TiC master alloys but also reduce the consumption because the blocky TiAl₃ particles improve the grain refinement efficiency of TiC particles in Al–5Ti–C and Al–TiC master alloys.     

RELATIONSHIP BETWEEN PRIMARY MORPHOLOGY AND CRYSTAL STRUCTURE OF CARBIDES GROWING IN SUPERALLOYS

The SEM analysis of decply etched specimens of Ni-base superalloys K38 and K19H+Ta in-dicates that both the primary morphologies under normal growth conditions and the finalmorphologies near equilibrium of MC carbides are octahedral blocks.The classification ofMC crystal faces by means of PBC(Periodic Bond Chains)theory confirms that{100},{110}and{111}are F faces,and that{212}are S faces.The calculations of the attachmentenergy for each F face show that{111}are most easily appeared.It has also been inferred thatone of the MC growth units is a coordination octahedron composed of one metal atom sur-rounded by six carbon atoms.The octahedral growth units can be attached to the growth sur-faces of MC carbides through laver stacking mechanism on the{111}faces.     

Microstructure and refinement performance of Al-Ti-C master alloy: Effect of excess Ti on the growth and nucleating ability of TiC particles

Al-5Ti-0.2C, Al-0.8Ti-0.2C, Al-8Ti-2C, and Al-10Ti master alloys were prepared and used to investigate the influence of excess Ti on the growth of TiC particles and its ability to nucleate Al-grains. The results of a microstructure analysis of TiC-containing alloys and refined CPAl were interrelated to the results of a refinement test. It was found that the presence of excess Ti is essential at the stage of master alloy preparation, as it facilitates the growth and uniform distribution of TiC within the structure. In Al-5Ti-0.2C alloy containing excess Ti, carbide particles grow faster and to a higher extent (from 0.29 μm to 0.44 μm) compared to Al-0.8Ti-0.2C alloy produced without excess Ti (from 0.29 μm to 0.32 μm). The results support the “Ti-transition zone theory” as the mechanism of grain refinement by TiC-containing master alloys. The refinement performance of Al-5Ti-0.2C is superior compared to the one achieved by adding Al-8Ti-2C and Al-10Ti master alloys in corresponding concentrations. For the TiC particles to become favourable nucleating sites, they must undergo certain interaction with excess Ti at the stage of master alloy preparation.     

Growth mechanism of reinforcements in in-situ synthesized (TiB TiC)/Ti composites

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钛合金成分对共晶碳化钛形貌的影响

自生TiC颗粒增强钛基复合材料中的TiC存在着两种形态 ,即初生TiC和共晶TiC ,它们的形态和尺寸都会对合金的性能产生影响 ,目前对初生枝晶状TiC研究较多 ,而对共晶TiC形态和生长研究很少 ,利用SEM、XRD、EDX等手段研究了钛合金中共晶TiC的形态及碳和铝对共晶TiC形态的影响。在亚共晶范围内 ,不同的含碳量时TiC具有不同的形态 ,含碳量远离共晶成分时形成的共晶TiC为羽毛状 ,而含碳量接近或达到共晶成分时TiC形态为短棒状或块状 ,合金中含有铝时会促使羽毛状TiC的形成和共晶点左移 ,使得在更低含碳量时出现初生TiC ,而且TiC颗粒中固溶少量的Al;还从凝固过程中TiC的生长环境的变化分析了出现上述现象的原因     

Precipitation phenomenon in stoichiometric Nd2Fe14B alloys modified with titanium and titanium with carbon

Precipitation phenomenon has been investigated in stoichiometric Nd₂Fe₁₄B alloys modified with Ti and Ti with C. Precipitates can be used to inhibit grain growth and understanding the precipitation process is important in order to form the most effective dispersion. In the Nd---Fe---B---Ti system, TiB₂, and in the Nd---Fe---B---Ti---C system. TiC are found to be the precipitating phases. Depending on composition, the precipitates can form at high temperatures in the liquid, during cooling after solidification, and during heat treatment. The precipitates form on grain or phase boundaries. The TiC precipitates typically form as discrete particles while the TiB₂ precipitates form generally in a globular bunched-up fashion. After a homogenization heat treatment, the equilibrium solubilities of Ti and Ti with C in the Nd₂Fe₁₄B phase are found to be 0.47 wt.% and 0.06 wt.% respectively. This means that almost all of the alloyed Ti and C can be precipitated as TiC which returns the excellent intrinsic magnetic properties of the hard magnetic phase. Both the carbides and the borides are found to have excellent high-temperature stability and resist coarsening and dissolution at least to 1000°C. Since Ti and C react to form TiC the amount of hard magnetic phase is not reduced while Ti addition alone reacts with boron and reduces the amount of hard magnetic phase if extra boron is not added.     

激光熔覆原位合成TiC/Al陶瓷基复合涂层增强Ti6Al4V研究

采用Ti-C-Al体系激光点火自蔓延合成TiC/Al材料的同时,在Ti6Al4V钛合金表面形成均匀厚度的涂层。实验所用设备为2kWNd:YAG脉冲固体激光器;原料中钛碳原子比1:1,铝含量范围10%~40%(质量分数)。原料中的铝含量对原位合成的TiC颗粒形态和大小影响较大,通过实验确定了原料中合适的铝含量。利用扫描电镜对涂层与基体结合界面微观结构进行表征,测试涂层的显微硬度和耐磨性。结果表明,涂层和基体有良好的冶金结合;TiC颗粒在涂层表面处主要以树枝晶状存在,而在涂层与基体连接处主要为近球状晶粒;涂层显微硬度可达到8000MPa(HV0.5),约为基材的2~3倍。     

反应火焰喷涂TiC/Fe复合涂层组织及形成机理

以TiFe粉和碳的前驱体（石油沥青）为原料通过前驱体碳化复合技术制备了Ti-Fe-C系反应喷涂复合粉末,并用普通火焰喷涂技术制备了TiC/Fe陶瓷金属复合涂层.观测了喷涂粉末、淬熄实验获取的飞行粒子以及涂层的形态、相和组织结构.结果表明：前驱体碳化复合Ti-Fe-C系喷涂粉末有非常紧密的结构;可有效的解决反应喷涂过程中原料粉末分离的问题.在反应火焰喷涂过程中,每一个喷涂粉末颗粒构成独立的微小反应单元,原料之间反应充分.在整个喷涂过程中喷涂粉末经历了熔化扩散、物相形成、碰撞后快速凝固三个阶段.所得涂层由TiC和Ti2O3共生聚集片层和细小TiC颗粒弥散分布于金属基体所形成的内晶型复合强化片层交替叠加而成.     

MC碳化物非平衡凝固液/固界面结构及生长机制

在冷却速度为10^2-10^5K/s的激光快速凝固条件下，对Jackson因子约为5－7的TiC型MC碳化物典型小面晶体液／固界面结构、生长形态及生长机制进行了系统的实验研究和理论分析。结果表明，尽管MC碳化物的生长形态随着凝固冷却速度的变化而发生显著变化，但其液／固界面始终保持原子尺度上光滑，其微观生长机制始终为台阶侧向生长，在10^2-10^5K/s凝固冷却速度条件下，MC碳化物生长机制并未发生由侧向生长机制向连续生长机制的转化。     

银基钎料钎焊金刚石的界面结构及TiC生长机制

在合适的工艺下,采用Ag-Cu-Ti钎料实现了金刚石与钢基体的高强度连接,并剖析了Ag-Cu-Ti钎料与金刚石的界面微区结构.通过对界面处的成分分布和深腐蚀后碳化物TiC形貌的观察,分析了Ti的作用机理、新生化合物TiC的形貌及生长规律.结果表明:在一定的条件下,Ti元素与组成金刚石的碳元素发生反应形成TiC层;碳化物层使钎料与金刚石之间产生冶金结合,并在其界面上形成了金刚石/TiC/钎料/钢基体的梯度结合层.     

The solidification path related columnar-to-equiaxed transition in Ti–Al alloys

Columnar-to-Equiaxed Transition (CET) of binary Ti–Al alloys and multi-component Ti–48Al–2Cr–2Nb alloys is studied using Bridgman solidification technique. The effect of aluminum concentration and growth rate on CET is determined. It is found in Ti–46Al and Ti–50Al alloy ingots equiaxed grains develop ahead of the moving solid–liquid interface with a growth rate of 500 μm/s; microstructures in Ti–49Al alloy stay columnar dendrites with the same growth rate. CET in Ti–Al alloys are not only influenced by growth rate, but also by the solidification path that is related to alloying composition. CET in Ti–Al alloys is predicted using the dendritic growth model based on the criterion of growth at marginal stability. According to the calculated results and directionally solidified microstructures, values of the nucleation undercooling for α and β phases are given. The growth rates to avoid CET in Ti–48Al–2Cr–2Nb alloy are suggested.     

深过冷Si-Al合金的凝固过程和组织特征研究

用高速摄影和扫描电镜研究了电磁悬浮熔炼条件下,Si-20%Al合金的凝固过程及其组织特征.结果发现,将Si-20%Al合金在氩气中进行电磁悬浮熔炼可使其获得375K的过冷度.过冷合金先结晶相的形貌和尺寸与其形核过冷度有关.在小过冷度下,合金的初生硅为粗大的长片多面体;过冷度增大到1 26 K后,初生硅变为均匀细小的等轴多面体.在过冷度小于328 K以前,初生硅的表面有明显棱角,表现出小平面生长的特征;过冷度大于328 K后,初生硅变为细小均匀表面有圆滑钟乳石状凸起、没有明显棱角的不规则多面体,表现出了非小平面生长的特征.     

热液环境下氢氧化镁结晶形态机理研究

研究了热液环境下氢氧化镁结晶形态形成机理。根据负离子多面体配位生长理论,构造了氢氧化镁的生长基元,计算了相应于不同维数和多重数n的水镁石生长基元稳定能。根据不同生长基元稳定能的计算结果,发现氢氧化镁的生长基元稳定能在1维方向(n×1×1),随着n值的增大而较快地增大,而二维方向生长基元稳定能为负值,这说明:氢氧化镁晶体是在1维方向(此方向平行于氢氧化镁晶体结构的基本层)优先生长,形成氢氧化镁针状或纤维状结晶形态。并由此推断,陕南黑木林的天然纤维状水镁石矿最初应该是在地壳局部形成的1种热压的环境里,在1种热液状态下生成的。     

Ag—Cu—Ti钎料中Ti元素在金刚石界面的特征

研究了金刚石钎焊接头中碳化物形成元素Ti与金刚石（或石墨）之间的相互作用行为。通过对接头界面处的成分分布和断口形貌观察,分析了Ti的作用机理、新生儿合物TiC的断口形及生长规律,结果表明：在一定的条件下,Ti元素与组成金刚石（或石墨）的碳元素发生反应形成TiC层;碳化物层使钎料与金刚石之间产生冶金结合;TiC与金刚石之间存在有明显的界面,TiC断口的微观表面形态呈韧窝状;在金刚石表面初始形成的TiC的生长方向与金刚石的晶向指数有关。     

钛微合金钢连铸中TiN与TiC析出热力学研究

连铸过程中夹杂物的析出对铸坯的组织性能有重要影响。为研究钛微合金化Q345钢中TiN 、TiC夹杂物的析出规律，对TiN 、TiC的生成热力学进行了计算，计算了Q345钢的固/液相线温度、碳氮化物的析出温度、不同温度下TiN、TiC的平衡/实际溶度积和析出时所需的Ti、N初始浓度，分析了高钛钢在凝固过程中TiN 、TiC的析出规律。结果表明：TiN 、TiC在液相线温度以上不能析出；由于Ti、N、C在凝固前沿的富集，当两相区fs＞0.56时，TiN开始析出，当两相区fs＞0.92时，TiC开始析出；在固相奥氏体中有TiN粒子析出，而TiC的析出温度较TiN低，在铁素体中析出。     

制备多物相AlTiC合金的Ti与C熔体反应法

将Ti与C同时加入Al熔体可制备出Ti与C摩尔比分别大于、等于、小于4的3种含不同物相的Al—TiC合金：Al—TiAl3-TiC、Al—TiC、Al-Al4C3-TiC。对纯铝的细化实验表明：不含过量Ti的后两种合金的细化效果相近，Al4C3在Al—TiC合金中的大量出现不会进一步降低合金的细化能力；含TiAl3的第一种合金的细化效率远高于后两者的；TiC物相在基体中以离散颗粒或聚集团形式在Al基体中分布；Al4C3相极脆，易与空气中的水蒸汽反应而分解。分析表明Ti与C在Al熔体中反应生成TiC是通过两条途径同时进行的：熔体中的固体C颗粒与溶解态的Ti直接反应；固体C颗粒和Al反应生成的A4C3与溶解态的Ti发生反应。     

聚丙烯酰胺凝胶法制备纳米BeO粉体前驱体的热分解过程及结晶机理

采用聚丙烯酰胺凝胶法制备纳米BeO粉体,通过TG-DSC、XRD和SEM等测试手段研究凝胶前驱体的热分解过程和所得粉体的性能,并借助负离子配位多面体生长基元理论分析热分解过程中纳米BeO的结晶机理。结果表明:随着温度的升高,凝胶前驱体内的有机凝胶逐渐分解,同时凝胶前驱体内的硫酸铍盐脱除结晶水;当温度达到600℃左右时,有机凝胶完全分解,得到纳米级的无水硫酸铍;继续升高温度,纳米级的无水硫酸铍分解得到纳米BeO;热分解过程中,纳米硫酸铍通过生长基元Be(SO4)6断键形成纳米BeO,成核过程为受迫状态下的非均匀成核。     

Influence of carbon on martensitic phase transformations in NiTi shape memory alloys

In the present paper we show how carbon affects martensitic transformations in Ni-rich NiTi shape memory alloys. During vacuum induction melting in graphite crucibles, NiTi melts dissolve carbon and TiC particles form during solidification. Differential scanning calorimetry (DSC) shows that this is associated with a decrease in the phase transition temperatures. We provide new experimental evidence for increasing temperature intervals between the start and the end of the martensitic transformations (from B2 to B19′) with increasing C content in as-cast and solution-annealed (850 °C) microstructures. The nucleation and growth of TiC particles in intercellular/interdendritic regions causes variations in the local Ni/Ti ratios. This results in wider transformation temperature intervals (DSC peak broadening) in as-cast and solution-annealed microstructures. Subsequent intense heat treatments (1000 °C) homogenize the alloy and re-establish sharp DSC peaks during martensitic transformations.