水泥窑用低导热多层复合砖的研究(Ⅱ):原料对工作层硅莫砖性能的影响

为了克服非均质天然铝矾土熟料给低导热多层复合砖工作层用硅莫砖性能带来的波动,以粒度均为5~3、3~1和1 mm的M60或M70矾土基烧结莫来石为骨料,以粒度均0.074 mm的M60莫来石、M70莫来石、80均化料、85均化料为细粉,掺入碳化硅、红柱石、白泥等原料,在1 490℃保温3 h制备了硅莫砖试样,并研究了各原料对试样显气孔率、体积密度、烧后线变化率、常温耐压强度、抗热震性、荷重软化温度等性能的影响。结果表明:采用M60或M70矾土基烧结莫来石为骨料,分别以M60、M70、80均化料、85均化料为细粉,掺入碳化硅和红柱石的试样性能比较稳定,可以避免以天然矾土为原料引起的试样高温性能波动的问题;以M70为骨料,80均化料为细粉,加入12%(w)的碳化硅细粉,加入10%~12%(w)的红柱石细粉的试样经高温煅烧后的主晶相为莫来石和碳化硅,莫来石柱状晶粒发育完好,且形成了网络交错的微观结构,碳化硅和玻璃相均匀分布在莫来石晶粒周围,具有良好的力学性能和较高的荷重软化温度。     

以矾土和煤矸石烧结合成刚玉和莫来石

为了提高高铝矾土资源的综合利用率,并促使矾土熟料在质量、品种和价格上升级,以高铝矾土和煤矸石为原料,配制成w(Al2O3)分别为90%、80%、70%和60%的试样,通过均化(细磨、混练)、成型、烘干后,分别在1450℃、1500℃、1550℃、1600℃、1650℃和1700℃保温3h煅烧,测定煅烧后试样的显气孔率、体积密度和烧后线变化率,以此确定各试样的烧结温度;还测定了烧结试样的荷重软化开始温度,并采用XRD和SEM分析了烧结试样的相组成和显微结构。结果表明:w(Al2O3)为90%、80%、70%和60%的试样的烧结温度分别为1550℃、1550℃、1700℃和1650℃,各烧结试样的荷重软化开始温度分别为1450℃、1500℃、1600℃和1550℃,并且烧结试样的纯度和密度均很高(w(Al2O3 SiO2)>93.5%,显气孔率<3%)。由于w(Al2O3)为70%和60%的试样在煅烧过程中二次莫来石化较多,玻璃相含量较少,因此其烧结温度相对较高;同时,由于这两个试样烧结后有发育良好的棱柱状莫来石构成的连续的网络结构,因此其荷重软化开始温度相对较高。     

以矾土碎矿和煤矸石合成莫来石均质料

采用Ⅰ等高铝矾土碎矿、Ⅱ等高铝矾土碎矿分别与煤矸石配合,并加入活性Al2O3调整m(Al2O3)/m(SiO2),按照矾土基莫来石均质熟料w(Al2O3)=68%～72%的要求,共配成6个混合料,将混合料湿磨至粒度≤0.044mm以均化化学成分,经成型、干燥后分别在1550℃、1600℃、1650℃和1700℃煅烧3h,冷却后测定其显气孔率和体积密度,以确定它们的烧结温度。结果表明:均质料的烧结温度为1700℃;在1700℃烧结制成的矾土基莫来石均质熟料的Al2O3含量为68%～72%,显气孔率<2.5%,体积密度≥2.75g·cm-3,其莫来石晶体发育良好,构成网络结构。同时,还将部分试样分别在800℃、1000℃、1200℃、1300℃、1400℃、1500℃、1600℃、1650℃和1700℃保温3h,测量其烧后线收缩率和显气孔率,并用XRD分析其相组成,据此分析试样在不同温度下所发生的反应。结果表明,试样在1000～1700℃加热过程中的变化可分为3个阶段:1000～1200℃的一次莫来石形成阶段,1200～1500℃的二次莫来石化阶段,以及1500～1700℃的液相烧结阶段。     

助烧剂对Al2O3-SiC-C捣打料烧结性的影响

以高铝矾土、棕刚玉为骨料 ,矾土粉、SiC粉、石墨为基质料 ,以磷酸二氢铝和沥青粉为复合结合剂 ,另加少量α Al2 O3微粉 ,制成了Al2 O3-SiC-C捣打料。研究了硅粉、硼酸、SiO2 微粉以及硼酸 SiO2 微粉 4种助烧剂对捣打料烧结性的影响。结果表明 ,这些助烧剂均对捣打料有助烧结作用 ,且有抗氧化作用 ,其中以加入硼酸 SiO2 微粉的复合助烧剂的助烧结和抗氧化作用效果最佳。     

原位合成莫来石晶须-氧化铝复合体系

为改善氧化铝陶瓷的韧性,以Al_2O_3、Si O2和AlF_3·3H_2O为原料,原位合成了莫来石晶须-氧化铝复合体系。探讨了AlF_3·3H_2O加入量(质量分数分别为2.9%、9.1%和16.6%)和热处理温度(1 400、1 500和1 600℃)对在Al_2O_3为80%~90%(w)的粉体中原位合成莫来石晶须的影响,并研究了莫来石晶须的生长机制。结果表明:原位合成莫来石晶须-氧化铝复合体系的最佳工艺条件是Al F3·3H2O加入量为9.1%(w),热处理条件为1 600℃保温5 h;生成的莫来石晶须长度可达50μm,长径比可达25;莫来石晶须的原位生长遵循气-固(VS)机制。     

新一代矾土基耐火材料

可以期望在新世纪我国根据丰富的高铝矾土资源特点,新一代矾土基耐火材料将会兴起--优质合成原料和高效耐火新产品.优质合成原料包括:(1)Al2O3含量为50%～90%的均质矾土熟料(均质类);(2)矾土基烧结和电熔锆刚玉莫来石和锆刚玉尖晶石系合成料(改性类);(3)矾土基Sialon和Alon(转型类).利用这些合成料开发的矾土基高效新产品为:(1)高温性能优良的高品位高铝砖和浇注料,(2)矾土基刚玉系材料,(3)矾土基Al2O3-Sialon(Alon)复合材料.     

助烧剂和造孔剂对真空烧结SiC多孔陶瓷性能的影响

以粒度≤0.063mm的SiC为主要原料,分别加入30%(质量分数)的Al2O3-Y2O3与10%的Al2O3-高岭土复合助烧剂,并外加不同量(分别为12.8%、26.3%、30.0%和36.4%)的造孔剂羧甲基纤维素钠(CMC),制样后首先在空气炉中经过300℃2h或1100℃4h的预烧,然后在真空炉中于1550℃4h真空烧结而制备成SiC多孔陶瓷,并研究了助烧剂种类以及造孔剂CMC外加量对SiC多孔陶瓷显微组织、显气孔率及抗折强度的影响。结果显示:采用Al2O3-Y2O3作为助烧剂的SiC多孔陶瓷比Al2O3-高岭土作助烧剂的具有较高的抗折强度,显气孔率稍有减小;随着羧甲基纤维素钠量的增加,加入两种助烧剂的SiC多孔陶瓷均表现为显气孔率增加,抗折强度降低。     

制备矾土基莫来石均质料加热过程变化的研究

研究了矾土为原料,部分配以适量煤矸石及加入少量Al2O3,制备矾土基莫来石均质料的加热过程线收缩率、显气孔率、相组成和显微结构的变化。结果表明,其加热过程一般分为三个阶段:(1)1000℃～1200℃,一次莫来石已经形成,试样收缩、气孔率降低。(2)1200℃～1500℃,二次莫来石化阶段,液相已经出现。其中,1300℃～1400℃,二次莫来石大量生成,试样膨胀、气孔率增加。(3)1500℃～1700℃,液相烧结阶段,试样收缩和气孔率下降较快。根据XRD图谱可判断低温阶段(<1400℃)形成的莫来石的结晶度,而对高温阶段则较困难,原因为高温形成的莫来石衍射峰变化很小;显微结构观察表明,随温度升高,莫来石晶体发育不断完善,从片状晶体(1200℃)到发育较差的柱状(1500℃),直至发育完善长大柱状晶体(1700℃),并由其构成交错连续的网络结构。     

ρ-Al2O3加入量对莫来石-刚玉浇注料性能的影响

以烧结莫来石(w(Al2O3)>45%)、电熔莫来石(w(Al2O3)>70%)、刚玉(w(Al2O3)>99%)、α-Al2O3微粉(w(Al2O3)>99.5%)、SiO2微粉(w(SiO2)>92%)、ρ-Al2O3微粉(w(Al2O3)>83.0%)等为主要原料,制备了莫来石-刚玉浇注料试样,经110℃24 h、1 000℃3 h和1 400℃3 h处理,研究了ρ-Al2O3加入量(w)分别为1%、2%、3%、4%和5%对莫来石-刚玉浇注料性能的影响。结果表明:随着ρ-Al2O3加入量的增加,莫来石-刚玉浇注料的体积密度下降,显气孔率增大,抗热震性和抗渣性逐渐变好。110℃24 h处理后强度逐渐增大;1 000℃和1 400℃处理后强度和永久线变化率则是先增加后减小,当ρ-Al2O3加入量为2%时达最大;试样的高温抗折强度先增加后减小,以ρ-Al2O3加入量为3%时最大。     

环保型快速烧结转炉大面修补料的研制及应用

为了减少对环境的污染,提高转炉大面修补料的使用寿命,采用中档镁砂、电熔镁砂为主要原料,引入结合剂、助烧剂、防氧化剂,多元醇为助流剂,环保无烟油类物质作为润湿剂制备了修补料。研究了助烧剂(铁红粉、Al粉和镁橄榄石细粉)、防氧化剂(Al粉、Si粉和Si C粉)及结合剂(高温改性沥青、中温改性沥青)的种类对转炉大面修补料性能的影响。结果表明:以中档镁砂、电熔镁砂为主原料,0.5%(w)的Al粉和1.5%(w)的Si粉复合作为防氧化剂和助烧剂,高温改性沥青与中温改性沥青分别为8.5%、4%(w)作为结合剂时,辅以少量的液体润湿剂和助流剂生产的转炉大面修补料,其环保性好,能快速烧结,强度高,寿命长(平均寿命超过34炉)。     

Flash microwave sintering of zirconia by multiple susceptors cascade strategy

In the field of flash sintering, microwave energy represents an interesting way to densify ceramics complex shapes, thanks to a contactless volumetric heating. Attaining a fast and homogeneous heating is a critical parameter and hybrid heating, using silicon carbide susceptors, is generally used. In this study, an original multiple susceptors cascade strategy is developed, using both SiC and 3D-printed ZrO₂ susceptors. This novel configuration follows perfectly the flash heating scheme, even for high heating rates up to 1000 K.min^-1 and leads to a high stability of the “flash” hybrid heating. Flash microwave sintering produced dense (97 % relative density) microstructures within 45 s. Based on comprehensive multiphysics simulations of the overall process, in-situ dilatometry measurements, kinetics method analysis and microstructural characterizations, this work highlights the sintering behavior of zirconia and the temperature distribution during flash microwave sintering.     

An interface nucleation rate limited sintering kinetic model applied to in situ sintering Al2O3-SmAlO3 composites

A nucleation rate limited sintering model was recently developed based on observations of bicrystal sintering. This work validates the applicability of this model for sintering of polycrystalline clusters of Al₂O₃-SmAlO₃ at high temperature in the range of 1130–1610 ℃. The model fits the data well and agrees with trends observed during bicrystal sintering. A temperature dependence to the dominant sintering strain deformation modes is observed from in situ heating experiments performed in a transmission electron microscope (TEM). The observations provide insights into how temperature influences the early stages of sintering by affecting the pore size distribution through local de-sintering. This provides insights into the role heating rate and sintering schedule play in microstructural evolution that influences the grain size versus density trajectory.     

热压烧结金刚石工具用石墨模具抗氧化研究

采用氧化失重实验,对热压烧结金刚石工具用石墨模具的氧化腐蚀性能进行了研究。着重讨论了抗氧化剂组分、总磷酸盐浓度和抗氧化浸渍工艺等因素对石墨模具抗氧化性能的影响。结果表明:以复合磷酸盐为主体,添加金属氟化物和氮化物制备出的抗氧化剂,对石墨模具的抗氧化性和抗压强度有明显提高。当抗氧化剂总磷酸盐浓度大于25%,采用真空加压抗氧化浸渍工艺,对石墨模具的抗氧化效果最好。     

添加物对LaCrO3材料烧结的影响

以钙质铬酸镧微粉为主原料,研究了分别添加ZrO2、CaO、MgO、SiO2或Al2O3五种微粉对铬酸镧材料烧结的影响。通过测定试样的体积密度、显气孔率,并借助电镜观察分析,对铬酸镧材料的烧结性进行了探讨。结果表明:在铬酸镧材料中分别添加ZrO2、CaO、MgO、SiO2或Al2O3,均能促进材料的烧结,使材料达到致密,并能使烧结温度降到1650℃。从显微结构看,添加ZrO2、MgO或CaO的铬酸镧烧结体,晶粒以固-固结合为主,而添加SiO2或Al2O3的铬酸镧烧结体晶粒间则以液相结合为主,且结构中有较多的封闭气孔。当温度再升高时,由于铬离子的挥发以及具有较低体积密度的相的生成,反而会使铬酸镧材料的密度下降。     

ZnO and CuO crystal precipitation in sintering Cu-doped Ni-Zn ferrites. II. Influence of sintering temperature and sintering time

This paper presents a study of the precipitation of ZnO and CuO crystals during the sintering of Cu-doped Ni-Zn ferrites. The nature of the resulting crystal precipitates were analysed using scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) analysis, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), confirming the findings of a previous paper (Part I). This study examines the influence of sintering temperature and sintering time of the thermal cycle on their formation, and on their microstructure and electromagnetic properties. The same two consecutive chemical reactions proposed in Part I can be used to explain the bulk precipitation and subsequent re-dissolution of the zinc and copper oxides observed during sintering. The effect of these crystal precipitates on the final properties of this type of soft ferrite was also analysed, revealing a deterioration in its electromagnetic performance.     

Vapor-phase assisted sintering of lutetium oxide

Conventional methods of green-body formation of powder compacts, along with temperature/pressure processing methods, were optimized to sinter and post-HIP Lu₂O₃ compacts to optical transparency (99.1 % of theoretical transparency at 1100 nm). Fissures between remnants of spray-dried granules, yielding opaque spheroids around them, were eliminated by lower temperature heat treatment schedules which minimized fissure coarsening via preferential intragranular densification. A key development was the use of LiF vapor produced adjacent to the compact in the furnace environment, which physisorbed onto particle surfaces of the pre-sintered compact. This acted as a grain growth inhibitor and hence sintering aid.     

Effective diffusion distance for isothermal sintering of hydroxyapatite

Abstract

The microstructural evolution of hydroxyapatite (HAp) was quantified for isothermal sintering at 1100°C. The aggregated state of the powder particles is thought to be responsible for the relatively high value of the average pore separation throughout isothermal sintering. The measured grain size exponent of 6·7 is not compatible with the values expected for volume diffusion or grain boundary diffusion under the assumptions of the Combined Stage Sintering Model and hence the Master Sintering Curve. The measured exponent for a previously defined flux weighted effective diffusion distance gave a more reasonable value of 3·4. The theoretical exponent in the Combined Stage Sintering Model was then corrected to accommodate a non-linear relationship between the effective diffusion length and pore size. The results demonstrate how the effective lengthscale in the Combined Stage Sintering Model can be corrected to accommodate aggregation in the microstructure.     

复合烧结剂对高铝质干式料烧结性能的影响

以粒度3～5mm,1～3mm,≤1mm,≤0.088mm的高铝矾土为主要原料,以粒度≤0.1mm的硼酸(H3BO3>99.6%)、粒度≤0.05mm的粘土、粒度≤0.1mm的钾长石和粒度≤0.1μm的硅灰(SiO2>90%)为复合烧结剂,按m(骨料)∶m(细粉)=65∶35的配比配料。将混合料在陶瓷模具中手工捣打成型,将成型好的试样分别在600℃、700℃、800℃、900℃和1000℃下均保温2h后脱模。测量热处理后各试样的耐压强度和显气孔率;采用XRD分析了试样的物相组成。结果表明:复合烧结剂中钾长石和硼酸在中温、低温下具有良好的烧结作用,在700～800℃热处理后,试样耐压强度和显气孔率明显增加。硼酸含量为2%的试样,在800～1000℃热处理后,显气孔率增幅较大。添加硅灰可以降低钾长石烧结温度;而复合烧结剂中的粘土在中温、低温下不利于干式料的烧结,低于800℃热处理后的试样,耐压强度和显气孔率没有随粘土含量增加而变化;900～1000℃热处理后的试样,耐压强度随粘土含量的增加而降低,显气孔率增加不大。     

Flash sintering of ceramics

Flash sintering is a novel densification technology for ceramics, which allows a dramatic reduction of processing time and temperature. It represents a promising sintering route to reduce economic, energetic and environmental costs associated to firing. Moreover, it allows to develop peculiar and out-of-equilibrium microstructures.The flash process is complex and unusual, including different simultaneous physical and chemical phenomena and their understanding, explanation and implementation require an interdisciplinary approach from physics, to chemistry and engineering. In spite of the intensive work of several researchers, there is still a wide debate as for the predominant mechanisms responsible for flash sintering process.In the present review, the most significant and appealing mechanisms proposed for explaining the “flash” event are analyzed and discussed, with the aim to point out the level of knowledge reached so far and identify, at least, possible shared theories useful to propose future scientific activities and potential technological implementations.