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。     

碳还原硫酸锶反应的热力学分析

研究了碳还原法制备碳酸锶过程中碳还原反应的机理.通过热重分析初步确定了主反应发生的温度范围在800～1 100 ℃,选用Gibbs-Helmholtz方程、Van′t Hoff方程和Kirchhoff方程对反应过程中的热力学函数随温度的变化情况进行了探讨,从而判断该反应过程的反应机理.对影响反应的反应时间、反应温度、反应物粒度这3个因素进行了考察.结果表明,反应温度越高,反应物粒度越小,反应速度越快,反应时间越短;但反应温度过高、反应时间过长均不利于反应的进行.适宜的反应条件为:反应温度为1 050 ℃,反应时间为45 min,反应物粒度为130 μm.在此条件下,水溶性锶产率达到92.87%.     

碳热还原法合成硼化锆粉体影响因素探究

以氧化锆(ZrO2)、硼酸(H3 BO3)和碳(C)粉为原料,研究了不同碳粉(活性炭、石墨)与前驱体粒度、温度及保温时间对碳热还原法制备硼化锆(ZrB2)粉体的影响.通过X射线衍射(XRD)分析合成粉体物相,扫描电镜(SEM)观察合成粉体形貌,并通过化学方法分析了合成粉体中的C、O含量.结果表明:以活性炭为碳源合成的粉体形貌呈条棒状,以石墨为碳源合成的粉体形貌呈规则的块状;合成粉体的粒度随前驱体粒度减小而减小,形貌由规则的块状逐渐转变为圆滑的不规则形貌,合成ZrB2粉体最小平均粒度约为1.69μm,产物中C含量随前驱体粒度减小而减少,O含量随前驱体粒度减小而增加,氧含量最低为0.54wt％;碳热还原法合成ZrB2粉体在1500℃下是可行的,但直到1900℃碳热还原反应合成ZrB2才进行完全;碳热还原反应合成ZrB2粉体最佳的反应条件为1900℃保温30 min.     

溶胶-凝胶和碳热还原法合成碳化硅晶须的研究

以工业硅溶胶和炭黑为主要原料，用溶胶－凝胶和碳热还原法合成了SiC晶须，获得的产物中碳化硅质量分数高于95％，碳化硅晶须质量分数高于74％，碳化硅晶须为直线形，具有光滑的表面，直径为0．2－0．5μm，长径比约为50－200，对影响碳化硅晶须产率和微观结构的主要因素进行了研究，结果表明：采取原料中碳含量稍多于理论值，并且严格控制反应温度，使得碳化硅的生成速度与碳化硅晶须的形成速度相匹配的措施对于提高产物中的碳化硅晶须含量是非常有效的。     

硼热还原法制备LaB6粉末

研究了采用硼热还原法制备LaB6粉末的反应合成工艺,La2O3-B系反应热力学分析表明,气体分压对LaB6的形成有重要影响,减小气体分压可以明显降低LaB6的合成温度,结合DTA测定结果,确定了制备LaB6粉末的合成温度,同时,对不同温度的和保温时间条件下所生成的LaB6粉末的相组成、颗粒尺寸与形貌以及纯度进行了测试分析,实验结果表明,La2O3-B系制备LaB6粉末的优化工艺是真空度133Pa,1923K保温6h,所合成的LaB6粉末平均粒径为6um,纯度达99.2%,颗粒形态比较规整,多数呈氨似团块状。     

硼酐碳热法合成碳化硼的研究

用Ｘ－射线衍射分析方法，研究了温度及反应物中Ｂ２Ｏ３摩尔量对碳热合成Ｂ４Ｃ粉末中残留含量的影响，同时探讨其反应机理，实验表明，碳化硼粉末中的残留碳含量不仅取决于反应而且与Ｂ２Ｏ３的摩尔量有关。在碳管炉内合成Ｂ４Ｃ的反应以液固反应为主，在反应时间一定条件下Ｂ２Ｏ３摩尔量为５－６ｍｏｌ的反应物料，在１６５０℃Ａｒ气氛中反应，其残留碳含量最低，其相对量为１０％左右。     

碳热还原法合成Si3N4的研究

研究了碳热还原法合成Ｓ３Ｎ４粉末中原料配比、Ｎ２流量，反应压力、反应莳晶种等因素对氮化的影响，获得了较佳的工艺参数，研制出氮含量大于３７％，平均粒径小于１．５μｍ的α－Ｓｉ３Ｎ４粉末。     

碳热还原镁橄榄石合成MgO-SiC复合粉体的热力学研究

本文对碳热还原镁橄榄石合成MgO-SiC复合粉体进行了热力学研究,结合实验,分析了反应的中间过程,对合成粉体具有重要的指导意义.热力学分析表明:当T=1923 K时,所形成的产物,从容易到困难排序依次为:MgO+SiC,MgO+Si,MgO+SiO,Mg+SiC,Mg+Si,Mg+SiO,Mg+SiO2;增大惰性气体流速,降低CO的分压,可以降低镁橄榄石解构温度.在不同氩气流量下的实验证明,增大氩气流量,促进了镁橄榄石的碳热还原反应,有益于MgO-SiC复合粉体的合成.以镁橄榄石与炭黑物质的量比为1∶5配料,混合均匀后,在氩气保护下,在气体流量分别为100 mL/min,300 mL/min,500 mL/min时,1650℃保温3h合成粉体.用X射线衍射仪(XRD)测试合成的物相,用扫描电子显微镜(SEM)观察各物相形貌.实验结果表明,合成的产物MgO为八面体,SiC为条形.过程分析表明,碳还原镁橄榄石生成MgO和SiO,是合成复合粉体的重要中间过程.     

溶胶--凝胶碳热还原法制备硼化锆超细粉体

以氧氯化锆、硼酸、葡萄糖等为原料,在柠檬酸和乙二醇的螯合作用下,采用溶胶--凝胶、碳热还原工艺合成了ZrB2超细粉体。研究了原料配比及合成温度对合成超细粉体的影响。结果表明:不同的B/Zr及C/Zr摩尔比显著影响ZrB2超细粉体的合成,其最佳摩尔比为:n(B)/n(Zr)=2.5,n(C)/n(Zr)=6.5;当热处理温度为1 773K时能够合成纯相的ZrB2超细粉体;1 773K保温2h条件下合成的ZrB2超细粉体的颗粒尺寸为1~2μm,晶粒尺寸为55nm。     

反应热压法制备TiB_2-Ti(C,N)复相陶瓷研究

采用反应热压法制造TiB_2-Ti(C, N)复相陶瓷,用Ti,TiH_2,BN,B_4C,C,B等为原料,通过化学反应设计可以制备出不同相组成及碳氮比的复相陶瓷。这种方法工艺简单、制造成本低。由SEM发现这种复相陶瓷在TiB_2和TiC_(0.5)N_(0.5)颗粒内部,分別分散着非常细小(一般为几十纳米)的Ti(C,N)和TiB_2颗粒,这种结构可能对材料的性能发挥着重要的作用。如何通过工艺控制这种结构的形成值得深入研究。断口分析发现较租的TiB_2晶粒发生穿晶断裂现象。     

Influence of SiC on phase and microstructure of ZrB2 powders synthesized via carbothermal reduction at different temperatures

ZrB₂ powders were successfully prepared via carbothermal reduction of ZrO₂ with H₃BO₃ and carbon black under flowing argon. By introducing SiC species into reaction mixtures, the effects of SiC addition on phase composition and morphology of ZrB₂ powders thermally treated at different temperatures were investigated. The resultant samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and energy dispersive spectrometer (EDS). The highly pure ZrB₂ with the mean size of 5?µm could be obtained at 1600?°C for 90?min and the grains presented columnar shapes. After addition of SiC, ZrB₂ revealed relatively better crystallinity and finer particle size. Regular columnar ZrB₂ grains ranging from 1 to 2?µm were seen existing after reaction at 1500?°C for 90?min.     

碳热还原氮化法制备碳氮化钛粉末

以物质的量比为1∶2.5的TiO_2粉和活性炭粉为原料,于N2气氛下采用碳热还原氮化法在不同的合成温度(分别为1500℃、1600℃、1650℃、1700℃、1750℃,N2压力固定为0.1MPa)和N2压力(分别为0.05MPa、0.1MPa、0.15MPa、0.2MPa,温度1700℃)下保温3h合成了碳氮化钛粉末。研究结果表明提高合成温度和降低N2压力有利于合成碳含量高的碳氮化钛粉末;在N2压力为0.1MPa的条件下,于1700℃保温3h热处理后,可以获得平均粒径为2μm的碳氮化钛粉末。     

Low temperature synthesis of Titanium diboride by carbothermal method

Titanium diboride powders have been synthesized by means of carbothermal reduction method utilizing Titanium oxide, Boric acid and Graphite. The effect of mechanical activation of mixed raw materials and the use of additional Boric acid on the final phases have been studied. The resultant powders were characterized by X-ray diffraction (XRD) analyzer and Field Emission Scanning Electron Microscope (FESEM). XRD patterns showed that TiB₂, TiC and C phases after heat treatment at stoichiometric ratio of reactants. By increasing the milling time, the unwanted phases such as C and TiC will be reduced. Pure TiB₂ could be synthesized with mechanical activation of raw materials for 24?h at non-stoichiometric ratio (using additional Boric acid) and heat treatment at low temperature of 1380?°C. In this condition, Titanium diboride could be achieved with residual carbon of 0.92 0.09wt% and mean average particle size of 3.28µm. Thermal analysis (TGA-DTA) was used to determine the reaction progress and mechanism. Results revealed that the intermediate phase, TiBO₃, played an important role in getting to lower temperature synthesis. This phase was identified after mechanical milling of raw materials and heat treatment at temperature of 1250?°C.     

碳热还原氮化制备Ti(C,N)技术的现状与发展

简单概述了Ti(C,N)的结构、性质、应用及其制备方法,并从热力学和动力学方面对碳热还原氮化制备Ti(C,N)技术进行了论述,分析了其制备过程中的工艺因素(如C/Ti摩尔比,原料种类及粒度大小,原料混合方式,气体流速,燃烧温度,添加剂等)的影响,同时还对碳热还原氮化制备Ti(C,N)技术的发展方向进行了展望。     

碳热还原氮化合成TiN的研究

以锐钛矿(中位径0.38μm)、金红石(中位径4.58μm)和鳞片石墨(粒度<0.15mm)、炭黑(平均粒度0.02μm)、可膨胀石墨(粒度<0.15mm)为原料,固定配比nC∶nTiO2为5∶1时分别组成不同的原料组合,并以锐钛矿和鳞片石墨为原料,改变配比nC∶nTiO2分别为3∶1、4∶1、5∶1、6∶1、7∶1和8∶1进行配料,在管式电炉、流动N2中分别于1300℃和1400℃制备了TiN,并进行了合成产物的氧化脱碳试验;采用XRD测定TiN的特征峰(d200=0.212nm)强度,以表征TiN的合成率,研究了原料粒度、反应物活性、反应温度等因素对TiN合成率的影响。结果表明:选用粒度较细或晶格活性大的原料,提高反应温度,均有利于提高TiN粉末的合成率;合成TiN粉末的最佳原料组合是可膨胀石墨和锐钛矿;以鳞片石墨和锐钛矿为原料时,其配比为nC∶nTiO2=6∶1时TiN合成率最高;合成产物中均含有一定量的碳,采用普通的加热氧化法不能除碳,其原因是TiN的氧化温度低于石墨的。     

碳热还原锆英石合成ZrO2-SiC复合材料

以锆英石(粒度≤44μm)和炭黑(粒度≤30μm)为原料,按m(锆英石)∶m(炭黑)=100∶20的比例配料,于球磨罐中混匀后,以100MPa的压力压制成20mm×5mm的试样,在120℃下干燥12h后置于Ar气流量为1.5L·min-1的气氛炉内,分别在1450℃、1500℃、1550℃、1600℃和1650℃煅烧4h,自然冷却至室温后,通过化学分析测定SiC含量并计算SiO2的转化率,采用XRD分析试样的相组成,采用SEM观察试样的显微结构,并对碳热还原反应过程进行热力学分析。研究结果表明:1)以锆英石和炭黑为原料,利用碳热还原反应在Ar气氛下可以合成出ZrO2-SiC复合材料;2)通过控制煅烧温度或炉内CO气体分压,可以获得不同组成的复合材料;3)在本试验条件下,合成ZrO2-SiC复合材料的适宜温度为1600℃。     

Carbothermal reduction synthesis of TiB2 ultrafine powders

Submicrometric TiB₂ powders were synthesized by carbothermal reduction process using titanium dioxide, boron carbide and carbon black as the starting materials. The influence of different amount of boron carbide (22.0–26.8 wt%), calcination temperature (1400–1900 °C) and holding time (15–90 min) on the composition and microstructure of the product was investigated. The resultant powders were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). Results showed that hexagonal impurity-free TiB₂ crystalline powders with the grain size below 1.0 μm could be successfully prepared at 1600 °C for 30 min in Ar atmosphere when the amount of boron carbide was 25.3 wt%. The increase in temperature contributed to reaction completion and grain growth, but the abnormal grain growth and oversintering took place above 1800 °C.     

TiO2 碳热还原氮化反应的热力学分析

通过热力学计算和分析,绘制了Ti-C-N-O系中氮化物、碳化物与氧化物稳定存在区域图(即优势区相图);讨论了碳热还原氮化法合成TiN和TiC粉末过程中的主要影响因素及最佳条件.     

Characterization of SnO2 nanowires synthesized from SnO by carbothermal reduction process

In this paper, single-crystalline SnO₂ nanowires have been successfully prepared by a carbothermal reduction process employing SnO as the starting material and CuO as the catalyst. Their morphologies, purity and sizes of the products were characterized by transmission electron microscopy (TEM), selected area electron diffraction, X-ray diffraction, field emission scanning electron microscopy (FESEM) and Raman spectroscopy, respectively. The FESEM images reveal wire-like and rod-shaped nanowires of about 100–800 μm in length and 30–200 nm in the transverse dimensions. The three observed Raman peaks at 474, 634 and 774 cm⁻¹ indicate the typical rutile phase of the SnO₂ which is in agreement with the X-ray diffraction results. The influence of some reaction parameters, including the temperature and the reaction duration, on the forming, morphology and particle size of SnO₂ crystallize is discussed.     

Investigation of the conditions required for the formation of V(C,N) during carburization of vanadium or carbothermal reduction of V2O5 under nitrogen

Phase stability diagrams of V–C–N and V–O–C–N systems were constructed as a function of carbon activity, nitrogen partial pressure, oxygen partial pressure, and solution formation characteristics to determine the conditions for the formation of V(C,N) via the carburization of vanadium or carbothermal reduction of V₂O₅ under nitrogen. The diagram showed that only V, V₂C, and V(C,N) phases would be stable in the V–C–N system. From the diagram, it was also observed that only V(C,N) exists after the carburization of vanadium under nitrogen atmosphere more than 10^?5 atm. The diagram of V–O–C–N system suggests that V₂O₅ can be reduced to V(C,N) without forming VO, owing to the high stability of the V(C,N) phase. Using these stability diagrams, the conditions for preparing V(C,N) from vanadium or V₂O₅ were deduced and the validity of the diagrams was verified using the experimental results.