Oxidation of porous nanocrystalline titanium nitride. III. Oxidation mechanism

The air oxidation mechanism of nanocrystalline TiN at 500 to 900 °C is examined. It is shown that at t ≤ 800 °C the oxidation of titanium nitride is controlled by the diffusion of oxygen and at t > 800 °C the interdiffusion of titanium ions is observed. The oxidation properties of porous TiN are determined by the chemical interaction of oxygen and the reaction surface, which includes the external surface of samples and the internal surface of the pores into which oxygen penetrates. The time and temperature dependence of the weight increment complies with the porous material oxidation model. Active initial oxidation is due to the interaction of oxygen and large internal surface. Short-term self-heating of porous samples is also possible. At t ≤ 800 °C, the pores are obliterated with oxides with time, the internal reaction surface reduces, an external oxide film is formed, the oxygen diffusion and weight increment slow down, and the process stabilizes. With temperature increase, these processes are activated and lead to a smaller weight increment at the final stage (2 to 4 h) at 800 °C as compared with 600 °C. At t > 800 °C the pore obliteration rate increases, but due to the interaction of oxygen and titanium ions that diffuse into the external scale surface, weight increment continuously increases with both time and oxidation temperature. The phase composition of the scale also affects the oxidation mechanism of porous TiN. Oxynitride of terminal composition plays a protective role; the transformation of anatase into rutile is accompanied by a decrease in the oxygen diffusion rate; Ti₂O₃ formed in pores accelerates their obliteration. __________ Translated from Poroshkovaya Metallurgiya, Vol. 46, No. 3–4 (454), pp. 95–104, 2007.     

Oxidation of porous nanocrystalline titanium nitride. I. Kinetics

We used the continuous weighing method to study the oxidation kinetics in air for TiN specimens pressed and sintered from nanocrystalline powders with particle size ≤55 nm. Oxidation was carried out at 500–1000 °C for 240 min. By comparing with the oxidizability of compact titanium, we estimated the total reaction surface S of the porous specimens as a function of their oxidation conditions. The mass of absorbed oxygen Δm was calculated from the mass gain ΔP, taking into account the volatile component N₂. We have shown that the maximum mass gain Δm at 600 °C is due to reaction of oxygen with the largest reaction surface. Within 120 min, external pores close up, S decreases, and then a continuous oxide layer forms in which diffusion of oxygen is slowed down. At 700–800 °C, the process of closing up of the pores is activated, and S decreases by an order of magnitude compared to 600 °C. After the first 40–50 min, a continuous oxide film forms and virtually no further mass gain occurs. As the temperature increases, the oxidation rate increases. At 900 °C, the reaction surface becomes equal to the external surface of the specimen, but the thickness of the scale increases linearly. We hypothesize that for T > 850 °C, counterdiffusion of titanium ions is superimposed on diffusion of oxygen. __________ Translated from Poroshkovaya Metallurgiya, Nos. 1–2(447), pp. 98–103, January–February, 2006.     

轴承钢中TiN夹杂物的控制研究

研究了轴承钢中TiN夹杂物的形成热力学,以及钢中Ti和N的控制理论,并在某钢厂进行了GCr15轴承钢的生产实验.结果表明,在凝固过程中钢中Ti或N的含量越高,TiN夹杂物开始析出温度就越高,析出物的尺寸就越大;使用低Ti合金原料能够有效降低钢中的Ti含量;采用低Ti铁水,初炼渣中的TiO₂降到1.0%以下,能有效控制钢水中的Ti含量;采用低钛合成渣过程回钛量显著减少,钢中Ti含量由原来的37×10^-6下降至30×10^-6;优化改进精炼工艺和大包保护浇铸可以降低钢中N含量为33×10^-6;降低凝固偏析,能降低TiN夹杂析出.     

Hardening of compact and porous titanium in asymmetric rolling

The hardening of materials deformed by shear rolling between rolls of different diameters is examined. The effect of the rolling conditions on structure-formation and hardening mechanisms is studied. The process of consolidation within porous titanium billets subjected to conventional and asymmetric rolling is examined. It is established that asymmetric rolling increases the strength of compact and porous titanium. __________ Translated from Poroshkovaya Metallurgiya, Vol. 46, No. 1–2(453), pp. 15–22, 2007.     

The composition,structure, and properties of calcium-hydride powder of titanium carbide

The technology of obtaining titanium carbide powders by reduction-carbidization of titanium dioxide with calcium hydride and carbide at temperatures up to 1200°C is developed. The dispersity of the TiC particles is determined by thermal desorption and scanning electron microscopy: the average size of crystals is no larger than 1 μm. It is revealed by the methods of coulometry and energy dispersive spectrometry that calcium-hydride titanium carbide is characterized by a high content of bound carbon and a low content (0.01–0.03 wt %) of free carbon. It is established by X-ray structural analysis and transmission electron microscopy that TiC particles are uniform (their composition is close to stoichiometric TiC_1.0) and are single crystals. The investigation of the structure and properties of hard alloys of the compositions 60% TiC + 29.6% Ni + 10.4% Mo and 72% TiC + 18.3% Ni and 9.7% Mo, which were obtained on the basis of calcium-hydride titanium carbide powders, showed that they completely satisfy the requirements to tungsten-free hard alloys.     

超低氧车轮钢中TiN夹杂析出的热力学分析及控制

通过对高速车轮钢中TiN夹杂物析出进行热力学分析,得到了车轮钢的液相线和固相线温度及1873K时Ti、N的活度.对TiN生成反应和钢中Ti、N溶度积进行了计算.结果表明:TiN只能在固相中生成,但在本车轮钢Ti、N含量下,固相中也没有TiN生成的条件,只有在钢液凝固前沿,由于Ti、N在两相区的富集,TiN夹杂物的生成反应得以进行.因此,在生产中,适当提高连铸二冷的冷却速率,使钢液快速凝固,减少凝固前沿Ti、N的富集时间,可减少纯TiN的析出.对本实验车轮钢中TiN夹杂的检测结果进行计算分析可知,在正常生产时铸坯冷却速率条件下,将钢中Ti的质量分数控制在3.5×10^-5以下、N的质量分数控制在3.1×10^-5以下,理论上可以消除TiN夹杂物的析出,改善车轮钢的疲劳性能,提高车轮的使用寿命.     

钛矿石化学成分及物相分析方法研究进展

钛矿石是一种较难分解的矿石,由于含钛量很高,而钛易水解形成难溶的偏钛酸析出,给分析测试带来较大困难。综述总结了近10年来钛铁矿、钒钛磁铁矿、金红石等钛矿石化学成分分析方法、化学物相分析方法和标准物质研制等方面取得的进展情况:化学成分分析包括样品分解方法、滴定法、分光光度法、电感耦合等离子体原子发射光谱法(ICP-AES)、电感耦合等离子体质谱法(ICP-MS)和X射线荧光光谱法(XRF)等;对钛矿石中含钛及含铁矿物相的分离方法进行了讨论;对国内研制的钛矿石化学成分及物相分析标准物质进行了简要介绍。结合目前国内钛矿石分析方法的现状,对钛矿石分析测定技术的发展前景提出了建议。     

Preparation and characterization of perovskite REFeO3 nanocrystalline powders

Combustion of nitrate-citrate gel was employed to prepare REFeO3(RE=Y,La and Gd) nanocrystalline powders.The samples were characterized with X-ray diffraction(XRD) analysis,thermal analysis(TG/DTA) and transmission electron microscopy(TEM).LaFeO3 crystallites were directly obtained by the sol-gel combustion process,and orthorhombic YFeO3 and GdFeO3 were formed when annealed at 800 oC.The investigation of magnetic properties showed that YFeO3 and LaFeO3 exhibited ferromagnetic behavior,while GdFeO3 presented...     

以金红石为主的钛矿石中钛的物相分析方法研究

建立了以金红石为主的钛矿石中钛的化学物相分析方法 ,通过溶剂选择 ,实现了金红石与钛铁矿、钛磁铁矿、榍石等含钛硅酸盐的分离与测定 ,获得满意结果。     

超细氮化硅粉的组成分析和评估

采用X荧光光谱、等离子发射光谱、原子吸收光度、气相色谱以及重量法、容量法等多种分析技术对超细氮化硅粉中硅、氮、氧、氯根、水分及金属杂质等组成进行了分析方法研究。确定了测值可信且再现性好的分析方法。通过程序升温、红外检测及微机解卷重叠峰形,探讨了氮化硅中不同状态的氧量,进而对主相量作出评估。国内用高频等离子法和激光诱导合成的氮化硅超细粉,主相量均达97％以上,其组成式接近为Si_(30)N_(10)O。     

CaO-ZrO2-TiO2-BN材料的热力学分析及实验验证

从Ca-O-N、Zr-O-N、Ti-O-N及B-O-N的叠加的优势区图可以看出CaO-ZrO₂-TiO₂-BN体系在1823K下可以稳定存在.XRD分析结果表明氧化物之间高温下形成了复杂的化合物或固溶体.应用FactSage软件计算CaO-ZrO₂-TiO₂三元相图得出,通过控制TiO₂的加入量,能够将体系控制在高温固相区,可用作水口材料.由于钢水中[Al]的存在,BN在连铸过程中不会被水口内部达到平衡时的游离O₂以及钢中溶解[O]所氧化.     

联合法生产海绵钛过程中氧含量的控制研究

分析了联合法生产海绵钛过程中氧杂质的来源,以及造成海绵钛中氧杂质含量高的主要原因。指出降低海绵钛产品中氧含量的关键在于降低精TiCl4中的TiOCl2含量,而采用铝粉除钒工艺可降低精TiCl4中TiOCl2的含量。此外,对粗TiCl4进行密封保护,并采用降温储存的方法(降低TiOCl2在TiCl4中的溶解度),可有效降低精TiCl4中的氧杂质含量,从而生产出氧杂质含量低的高品质海绵钛产品。     

钛粉粒度对轧制烧结多孔钛板力学性能的影响

对不同粒度钛粉的流动性、松装密度和振实密度进行分析, 经轧制和烧结制备出满足湿法冶金需求的多孔钛板, 研究了钛粉粒度对轧制烧结多孔钛板力学性能的影响。结果表明: 轧制烧结多孔钛板的最大孔径和孔隙度随钛粉粒度的减小而减小, 钛板密度、剪切强度、抗弯强度、抗拉强度及伸长率均随钛粉粒度的减小有所增加; 当钛粉粒度范围为89~104 μm时, 粉末轧制烧结多孔钛板的综合力学性能较高。     

钛精粉氧化过程中物相转变

采用热重分析和恒温实验法研究了攀枝花钛精粉氧化过程中相的存在形式及其转变规律.X射线衍射结果和微观形貌分析表明:温度低于500℃,钛精粉未发生氧化反应;600℃时产生Fe₂Ti₃O₉和TiO₂相,其和原相Fe₂O₃相衍射峰强度均随温度的升高而增强;900℃时,Fe₂Ti₃O₉相完全转变为Fe₂TiO₅相,且随温度的升高,TiO₂相和Fe₂O₃相衍射峰强度逐渐减弱;在整个氧化过程中存在四个化学反应,其与烧结作用相互关联,使得氧化产物表面形成较多孔隙,变得凹凸不平且疏松.     

电解钛氢化脱氢制备超细高纯钛粉工艺

以电解钛为原料,采用氢化、球磨破碎和脱氢的工艺,制备超细高纯钛粉。采用激光衍射粒度分析、SEM及氢和氧元素分析等手段,研究各工艺过程所得的TiH2粉和Ti粉的粒度及其分布、粉末形貌和氧含量的变化趋势。结果表明:电解钛经420℃氢化后,初次球磨得到中位径(D50)为9.81μm的超细TiH2粉,再经600℃保温脱氢,最后经球磨分散得到D50为11.04μm,氧含量为0.48%(质量分数)的不规则形状超细高纯钛粉。在各个工艺过程中,氧含量(质量分数)增加量由低到高依次是TiH2粉脱氢、TiH2球磨制粉、脱氢钛粉球磨和电解钛氢化。     

汽车用粉末冶金钛合金零件的开发与应用

粉末冶金钛合金具有优良的综合性能,逐步在汽车工业中得到了广泛的应用。简要介绍了 粉末冶金钛合金在汽车零部件中的应用,并对其发展前途加以展望。     

Role of Nitrogen during Oxidation of Titanium Diboride in Air

We have studied the effect of nitrogen on oxidation of titanium diboride in air. By thermodynamic analysis of the reaction in the TiB₂ – air system, we have established that the oxide film is layered. When the air content in the system is less than 50 mass%, the predominant reaction products are boron and titanium nitrides, which suggests a special role for nitrogen during oxidation.     

氢化钛氧化处理及其热分解行为

在大气条件下进行氢化钛的氧化处理试验,利用扫描电镜和X射线衍射仪研究氧化处理后氢化钛的形貌与相组成,通过TG/DSC热分析,研究氧化处理对氢化钛热分解行为的影响规律。结果表明,氧化处理后氢化钛颗粒形貌无明显变化,随温度升高和时间延长,其颜色经历了灰黑色—蓝色—浅灰色的转变,且颗粒表面形成了Ti3O和TiO2的氧化物薄膜。与此同时,随氧化处理温度升高和时间延长,氢化钛热分解的质量损失率降低,但氢化钛的热分解温度显著提高,以AlSi12合金为基体,应用粉末冶金法制备泡沫铝,其氢化钛的氧化处理工艺为480℃/1h。     

液相烧结非晶纳米氮化硅陶瓷粉体结晶与相变行为研究

以Y2 O3 和Al2 O3 纳米陶瓷粉体作为烧结助剂 ,液相烧结非晶纳米Si3 N4陶瓷粉体 ,研究了不同温度下烧结体的结晶与相变行为。 1 5 0 0℃烧结 ,烧结体为非晶与晶体混合态 ,结晶相主要为α Si3 N4和 β Si3 N4,结晶度达到 70 %。温度超过 1 6 0 0℃以后 ,烧结体已经完全结晶 ,为 β Si3 N4和Si2 N2 O双相陶瓷。当温度达到1 6 5 0℃ ,Si2 N2 O的体积分数达到最大值 ,说明烧结体中的O2 与Si3 N4已经反应完全。烧结温度超过 1 70 0℃时 ,Si2 N2 O的体积分数开始减小 ,烧结体中没有SiO2 出现 ,证明反应 2Si3 N4(s) +1 5O2 (g) =3Si2 N2 O(s) +N2(g)为可逆反应。 1 6 0 0℃烧结体的典型结晶形貌分析表明 :粒径尺寸基本分布在两个区域 ,大部分较大晶粒粒径在 1 5 0～ 2 5 0nm之间 ,小部分晶粒粒径 <1 0 0nm ,个别晶粒的长径比达到 1 5。