堇青石加入方式对堇青石-莫来石窑具材料性能的影响

为满足锂离子电池正极材料烧成的需要,以堇青石、莫来石、高岭土和氧化铝为原料制备堇青石-莫来石窑具材料,研究了堇青石颗粒和细粉加入量对堇青石-莫来石窑具材料的常温性能、高温抗折强度和抗热震性的影响.并用XRD和SEM分析了试样烧后的物相变化与显微结构.结果表明:随着堇青石颗粒或细粉加入量从0到30％(质量分数),试样的线变化率、显气孔率、高温抗折强度增大,体积密度下降;而对常温抗折强度的影响不大,试样的耐压强度分别呈现下降或提高的趋势,试样的抗热震性先增加后降低,当堇青石颗粒含量为20％,细粉含量为20％时,试样的抗热震性最好.     

黏土的杂质含量对堇青石-莫来石复合材料相组成及性能的影响

以滑石细粉、高铝矾土细粉和两种不同杂质含量的黏土细粉为原料,经配料、加水混练成型后,分别于1300、1350和1400℃保温3h制备了堇青石-莫来石复合材料的试样,用XRD、SEM等研究了黏土中杂质含量对堇青石-莫来石复合材料相组成及性能的影响。结果表明:1)使用高杂质含量的黏土能有效降低试样的烧结温度,促进堇青石和莫来石晶体的生成发育,提高试样的体积密度与常温抗折强度,但对其抗热震性损害较大。2)使用高杂质含量的黏土时,提高MgO含量虽然可增加堇青石的含量,但玻璃相含量增加且黏度降低,不能有效提高材料的抗热震性;而使用低杂质含量的黏土时,通过控制引入MgO的含量与煅烧温度,可调节试样中晶相的含量与组成,从而可提高材料的抗热震性。     

堇青石对莫来石-铝矾土浇注料性能的影响

以莫来石、铝矾土为主要原料,铝酸钙水泥为结合系统,分别研究了不同堇青石含量经过不同热处理温度后对莫来石-铝矾土浇注料性能的影响.试样自然干燥24 h脱模后,再经110 ℃烘干24 h,分别于1000 ℃、1300 ℃和1500 ℃热处理3 h.检测各温度热处理后试样的线变化率(P.L.C)、体积密度(B.D)、抗折强度(M.O.R)、耐压强度(C.C.S)以及试样的热膨胀系数和抗热震性能.结果表明,莫来石-铝矾土浇注料的体积密度随着堇青石含量的增加而减小.经过1000 ℃和1300 ℃热处理后,莫来石-铝矾土浇注料的抗折强度随着堇青石含量的增加而下降.莫来石-铝矾土浇注料随着堇青石含量的增加,有助于改善材料的抗热震性,材料的强度保持率逐渐增大,且较低的体积密度有利于材料获得较高的热震后的强度保持率.     

凝胶注模堇青石-莫来石复相材料的制备及其抗热震性能

采用凝胶注模方法制备堇青石-莫来石复相材料,研究了聚乙烯醇对浆料稳定性、固化时间和表面氧阻聚的影响,分析了堇青石-莫来石复相材料的抗热震性能。结果表明,聚乙烯醇可提高粗颗粒悬浮体系的稳定性,增大浆料黏度,延长固化时间。聚乙烯醇还可以起到消除表面起皮、开裂的作用。通过控制浆料固相含量调节堇青石-莫来石复相材料的气孔分布,从而影响其热震稳定性。当浆料中堇青石-莫来石固相体积分数为41%～44%时,堇青石-莫来石复相材料的热震稳定性最好。     

堇青石-莫来石复相陶瓷的制备与性能

以MgO-Al2O3-SiO2三元相图为依据,采用不同原材料,进行了堇青石—莫来石复相陶瓷材料配料组成的设计,并在高温下合成制备了堇青石—莫来石复相陶瓷材料。研究了堇青石含量、不同原料配方对试样性能的影响。     

陶瓷燃烧器用莫来石-堇青石组合砖的研制

以烧结莫来石、电熔莫来石、合成堇青石和电熔白刚玉为主要原料,通过浇注-离心成型工艺生产了莫来石-堇青石组合砖,并研究了堇青石的加入量和加入形式对莫来石-堇青石组合砖性能的影响。结果表明:采用浇注-离心成型工艺生产的热风炉陶瓷燃烧器用组合砖的性能指标优于机压成型的同类产品;随着试样中堇青石含量的增加,制品的荷重软化开始温度逐渐降低,抗热震性逐渐提高,但在堇青石加入量(质量分数,下同)为15%时,其荷重软化开始温度和抗热震性指标都比较好;当颗粒加入量为12%,细粉加入量为3%时,制品的抗热震性最好,耐压强度也较高。产品在广州钢铁企业集团有限公司等钢厂的陶瓷燃烧器上进行了使用试验,用户反映该组合砖强度高,整体性好,能满足大、中型热风炉燃烧器使用需要,值得大力推广。     

锂电池正极材料LiNixCoyMnzO2承烧用莫来石-堇青石质匣钵的研制

莫来石-堇青石质匣钵对于制备高性能锂电池正极材料尤为重要。本文采用莫来石(1.18～0.6 mm)和堇青石(2～1 mm)为骨料，莫来石(0.074 mm)、煅烧氧化铝(0.044 mm)、佛山黄泥(0.044 mm)和煤矸石(0.044 mm)为基质，在1 380℃下保温3 h烧结制备锂电池正极材料LiNi_xCo_yMn_zO₂(LNCM)承烧用莫来石-堇青石匣钵，并采用埋覆侵蚀法探究了正极材料在烧结过程中对匣钵的侵蚀行为。结果表明：在1 380℃下保温3 h烧结制备的匣钵力学性能和抗热震性均较好，其室温抗折强度为10.02 MPa,经3次热震循环后残余强度保持率在51.52%～53.26%;适当增加粗颗粒(1.18～0.6 mm)莫来石的含量可有效提高莫来石-堇青石匣钵的抗侵蚀性，且经侵蚀25次后匣钵表面的最大反应层厚度为447μm,最小反应层厚度为211μm。     

高温气体过滤器支撑体的抗热震性能改进研究

为了改善高温气体过滤器支撑体的强度及抗热震性能,根据复合材料韧化强化原理,本试验采用陶瓷材料复合技术,制备莫来石-刚玉-钛酸铝-堇青石复合陶瓷材料,探索其作为高温过滤器支撑体的可能性.以粒径小于74μm的高铝矾土熟料、钛酸铝、堇青石为原料,以聚乙烯醇的溶液(质量浓度2％)为结合剂,试样成型压力为50MPa,烧结温度为1360℃,保温3小时制备了莫来石-刚玉-钛酸铝-堇青石复合材料.对烧后试样进行体积密度、气孔率、常温抗折强度、抗热震性的测定及XRD、SEM的分析,研究了配料组成对复合材料烧结及抗热震性能的影响.研究结果表明:具有较好烧结性能与抗热震性能的莫来石-刚玉-钛酸铝-堇青石复合材料支撑体的最佳物料配比(％)为:高铝矾土熟料30％、钛酸铝10％、堇青石60％.     

莫来石–堇青石质匣钵的制备及侵蚀机理

以莫来石、堇青石、α-Al_2O_3、滑石和高岭土为原料制备莫来石–堇青石质匣钵,研究了匣钵的常温力学性能、抗热震性能以及LiCoO_2合成过程对匣钵的侵蚀机理。结果表明:1 350℃烧成匣钵试样的常温力学性能和抗热震性均较好,抗折强度为11.18 MPa,热震循环3次后的残余强度保持率为44.8%。碳酸锂分解产生的Li_2O与试样反应生成LiAlSiO_4、Li_4SiO_4和LiAlO_2。随着反应进行,Li_2O沿气孔向试样内部扩散,反应后的渗透层结构更为致密,可阻碍Li_2O进一步侵蚀试样,匣钵因而具有较强抗侵蚀性。     

原位生成堇青石结合红柱石太阳能热发电储热陶瓷的抗热震性能

为提高储热陶瓷材料的抗热震性能,采用原位生成堇青石增强技术,以红柱石为主要原料,通过半干压成型,无压烧结研制了用于太阳能高温热发电红柱石储热陶瓷材料样品。研究了配方组成、烧成温度、相组成、微观结构对样品抗热震性能的影响。结果表明：红柱石添加量为 70%,经1 400 ℃烧成的样品抗热震性能最佳：30 次热震实验（热震条件：1 100 ℃～室温,风冷）的强度不仅没有损失,反而增加了 26.20%。相组成和微观结构分析表明样品的晶相为堇青石、莫来石、硅线石、α-方石英、α-石英等,原位生成的堇青石晶体均匀分布在由红柱石转化的莫来石晶体之间,赋予样品较好的抗热震性能     

Synthetic mullite and mullite refractories

Refractories and Industrial Ceramics -     

Porous mullite templated from hard mullite beads

Porous mullite bodies were developed by spark plasma sintering (SPS) amorphous mullite beads of about ∼30 μm in diameter at two temperatures, 950 and 1300 °C. Materials showed a close random stacking of solid spheres that retained their original packing but slightly flattened at the contacts in some cases. Depending on the thermal history, the beads were partially or fully crystallized. The thermal conductivity of the different porous mullite materials was analyzed as a function of the microstructure. Owing to the particular porous network, high gas permeability and very low thermal conductivities (1-2 W m⁻¹ K⁻¹) were achieved, among the lowest reported for sintered mullite materials.     

Electrospun mullite nanofibers derived from diphasic mullite sol

Fine‐grained mullite nanofibers derived from the diphasic mullite sol were successfully fabricated by electrospinning and subsequent pyrolysis at 1500°C. Polymethylsiloxane and aluminum tri‐sec‐butoxide were selected as the silicon and aluminum source to synthesize the diphasic sol. Results show that the weight loss of mullite precursor fibers in our work was about 60 wt.%, which is similar with that of fibers fabricated using the monophasic sol. This low weight loss was mainly attributed to the high ceramic yield of polymethylsiloxane and low introduced polyvinylpyrrolidone content, which ensures the integrity of fiber morphology during the sintering process. Mullite fibers with 216 nm average diameter were fabricated after sintered at 1500°C and the corresponding grain size was only ~100 nm, much smaller than that in mullite fibers derived from monophasic sols. Therefore, it can be predicated that mullite fibers in this work should possess a higher mechanical strength than those derived from monophasic sols when the sintering temperature was higher than 1400°C and therefore was an ideal starting materials for the fabrication of mullite nanofibrous ceramics used as the high‐temperature thermal insulation materials.     

莫来石加入量对SiC-莫来石材料性能的影响

以SiC颗粒(2～1mm、≤1mm)、SiC细粉(≤0.066mm)、莫来石细粉(≤0.074mm)和SiO2微粉(≤0.045mm)为原料,在w(SiC细粉)=40%的基础配方中分别以质量分数为5%、10%、15%、20%和25%的莫来石细粉取代相应量的SiC细粉,并外加2%的SiO2微粉,成型后分别在1300℃和1500℃的大气气氛中煅烧3h,测定试样煅烧前后的质量变化率以及烧后试样的显气孔率、常温抗折强度和抗热震性,并用扫描电镜观察试样的显微结构。结果表明:在SiC自保护氧化的作用下,试样的抗氧化性较强,而且随着莫来石加入量的增大,1300℃烧后试样的氧化程度减小,1500℃烧后试样的氧化程度先减小,至15%后又增大;1300℃烧后试样比1500℃具有较高的抗热震性,并且随着试样中莫来石加入量的增大,烧后试样的抗热震性提高。     

Crystallization studies in mullite and mullite–YSZ beads

Mullite and mullite/Y-ZrO₂ (25 and 50 vol.%) beads were produced by thermal spraying in water the corresponding atomised compositions. The amount of amorphous phases in the as-sprayed beads was comparatively determined by X-ray diffraction (XRD) and differential thermal analysis (DTA) methods. Characteristic XRD peaks associated to crystallization of the mullite and Y-ZrO₂ (t) phases were compared with the intensity of the exothermic events in the DTA for each composition. A direct linear relationship between the amount of amorphous phases estimated by XRD methods and the area under DTA peaks per unit mass was found. The crystallization microstructure of the different composition beads after heat treatments was followed by scanning electron microscopy (SEM).     

Mechanochemical synthesis of mullite

The specifics of mechanical activation processes in modifying synthetic corundum powder and gels by silicon alkoxide are considered. As Al₂O₃ is milled with a silicon alkoxide additive, Al₂O₃ and SiO₂ reactants are activated with the formation of an intermediate self-organized complex, in which the mechanochemical interaction proceeds accompanied by the formation of mullite.     

Development of mullite fibers and novel zirconia-toughened mullite fibers for high temperature applications

Polycrystalline mullite fibers and novel zirconia-toughened mullite (ZTM) fibers with average diameters between 9.7 and 10.3 μm containing 3, 7 and 15 wt.-% tetragonal ZrO₂ (ZTM3, ZTM7, ZTM15) in the final ceramic were prepared via dry spinning followed by continuous calcination and sintering in air. A shift in the formation of transient alumina phases and tetragonal ZrO₂ to higher temperatures with increasing amounts of ZrO₂ was observed. Concomitantly, the mullite formation temperature was lowered to 1229 °C for ZTM15 fibers. X-ray diffraction revealed formation of the desired tetragonal crystal structure of ZrO₂ directly from the amorphous precursor. Room temperature Weibull strengths of 1320, 1390 and 1740 MPa and Weibull moduli of 9.5, 7.1 and 9.0 were determined for mullite, ZTM3 and ZTM15 fibers, respectively. Average Young’s moduli ranged from 190 to 220 GPa. SEM images revealed crack-free fiber surfaces and compact microstructures independent of the amount of ZrO₂.     

Effects of in situ synthesized mullite whiskers on compressive strength of mullite fiber brick

The method of in situ synthesis of mullite whiskers by gas-phase deposition and reaction was applied to improve the compressive strength of the mullite fiber brick. During the preparation process, silica sol, Al(NO₃)₃ solution and NH₄F solution were introduced into the fibrous brick in the form of ions or sol through vacuum impregnation and freeze drying, and the silica sol, Al(NO₃)₃ and NH₄F served as the silica sources, aluminum source and catalyst, respectively. Effects of process parameters (concentration of impregnation solutions, holding time, sintering temperature) on compressive strength and elastic modulus of the fibrous brick during the in situ toughening process were analyzed. SEM and XRD analysis results demonstrated that the mullite whiskers were synthesized on the surface of mullite fibers based on the reaction of AlOF and SiF₄. What is more, the whiskers on adjacent fibers intersected with each other and formed many unfixed lap-jointing points, resulting in the increase of compressive strength and elastic modulus. Although the density and thermal conductivity of the sample after the generation of mullite whiskers fabricated with the optimum process were 0.406 g/cm³ and 0.1262 W/(m K), respectively, which were slightly higher than that of the raw fibrous brick (0.375 g/cm³ density and 0.1069 W/(m K) thermal conductivity, respectively), the corresponding compressive strength and elastic modulus of the sample reinforced with the whiskers increased to 1.45 MPa and 42.03 MPa, respectively, which were much higher than that of the raw fibrous brick (0.39 MPa compressive strength and 6.5 MPa elastic modulus).