不同硅源对溶胶凝胶法制备莫来石纤维可纺性和结构的影响

采用铝粉和结晶氯化铝作为铝源,分别加入硅溶胶、硅溶胶与纳米氧化硅(7 nm、15 nm)的混合物作为硅源,采用溶胶-凝胶法,制备莫来石纤维。研究了不同硅源对莫来石前驱体溶胶纺丝性能、并对纤维晶化温度和结构的影响。结果表明加入纳米氧化硅后,溶胶纺丝性能下降;全部加硅溶胶制备的溶胶,纺丝性能最好,凝胶纤维长度大于500 cm。不同硅源凝胶纤维,在1200℃煅烧后主要物相为莫来石。加入纳米氧化硅(7 nm和15 nm)的试样,在1600℃煅烧后,有硅线石生成。加入纳米二氧化硅为硅源,纤维致密度明显增高,晶粒得到细化,孔隙率降低。     

铝硅混合凝胶对刚玉-莫来石制品性能的影响

按莫来石骨料占65%(质量分数),刚玉和黏土组成的混合粉占35%(质量分数)配料,分别外加占原料总质量4%的水、硅溶胶、铝硅混合凝胶作结合剂,研究了结合剂种类对刚玉-莫来石材料经1 100、1 400和1 600℃分别保温3 h烧后的性能及显微结构的影响,并在此基础上研究了铝硅混合凝胶加入量(分别为1%、2%、3%、4%)及配比(m(Al2O3):m(SiO2)分别为8:2、7:3、4:6)对刚玉-莫来石制品常温性能的影响.结果表明:以铝硅混合凝胶为结合剂的刚玉-莫来石试样,经1 400、1 600℃烧后的常温、高温抗折强度和抗热震性均比仅加硅溶胶或水的好,但显气孔率偏大;当铝硅混合凝胶加入量为2%且m(Al2O3):m(SiO2)=7:3时,烧后试样的常温强度最高.     

硅源对无定形硅铝物化性能的影响

以硅溶胶和九水硅酸钠为硅源,九水硝酸铝为铝源,采用分步沉淀法制备一系列不同硅铝比的无定形硅铝,通过XRD、BET和NH₃-TPD等考察硅源对无定形硅铝物化性能的影响。结果表明,以九水硅酸钠为硅源制备的无定形硅铝比表面积和酸性均明显优于以硅溶胶为硅源制备的无定形硅铝;以九水硅酸钠为硅源,在SiO2质量分数为55%时,该无定形硅铝呈现出最大酸量和高的比表面积,作为性能优异的催化材料将具有良好的应用价值。     

镝铝石榴石(DAG)粉体的溶胶凝胶法制备工艺研究

以Dy2O3、Al（NO3）3.9H2O和HNO3为原料,柠檬酸为络合剂,通过溶胶凝胶法制备了纯相镝铝石榴石（DAG）纳米粉体,采用XRD和SEM手段对DAG粉体进行了表征。结果表明：纯相的DAG粉体在900℃、保温2h形成,在1200℃完全晶化。通过谢乐公式计算,得到经各种温度处理后粉体的平均晶粒尺寸范围为30-50nm。对比烧结温度和保温时间对粉体粒度的影响,发现在粉体晶化完全前,延长保温时间对晶粒尺寸的影响比升高烧结温度要大;在粉体完全晶化后,烧结温度的提高比保温时间的延长更能影响晶粒尺寸。     

铝源对溶胶凝胶法制备锂辉石相微晶玻璃特性的影响

采用溶胶-凝胶法制备了具有β锂辉石配比的锂铝硅微晶玻璃,采用3种不同铝源,分别为硝酸铝、硝酸铝与异丙醇铝,硝酸铝与异丙醇铝的摩尔比为1:1,或者完全采用异丙醇铝.在Ai(NO3)3·9H2O为铝源的样品中,在1 300℃煅烧处理后,得到样品的主晶相为β锂霞石相.而完全采用异丙醇铝或部分采用异丙醇铝为铝源的样品中,最终得到的是B-锂辉石相.采用不同铝源制备的样品的热膨胀系数并没有明显差别.800℃煅烧处理得到的样品具有正的膨胀系数,而1 300℃煅烧处理后样品具有负的膨胀系数,合理的设计煅烧处理温度,可以得到在某一测量温度范围内热膨胀系数为零的样品.采用不同铝源制备的锂铝硅微晶玻璃微观结构都为球形晶体颗粒,晶粒尺寸为2～4μm.     

非水解溶胶-凝胶Al2O3碳热还原氮化合成AlN超细粉

以无水氯化铝和异丙醚为原料,利用非水解溶胶-凝胶法制备出高活性Al2O3凝胶,以其作为铝源,引入炭黑作为碳源,利用碳热还原氮化技术低温合成AlN超细粉体。研究了凝胶未经煅烧以及预煅烧温度分别为300、500℃,按n(C)/n(Al2O3)为3.9、7.8和9.6分别加入不同量的炭黑,1 400、1 450和1 500℃的合成温度以及N2流量分别为40和80 mL·min-1时对AlN粉体合成的影响。结果表明:Al2O3凝胶经300℃预煅烧后,按n(C)/n(Al2O3)=7.8与炭黑混合,在流量为80 mL·min-1的高纯N2中于1 450℃保温2 h后可以合成出高纯AlN超细粉体。FE-SEM分析表明,AlN超细粉体平均粒径在400 nm左右,分散较为均匀。     

溶胶-凝胶法低温合成莫来石的研究

以去离子水和无水乙醇为分散介质,以六水合氯化铝为铝源、正硅酸乙酯为硅源,通过1,2-环氧丙烷调凝,采用溶胶-凝胶法合成了莫来石前驱体凝胶。考察了环氧丙烷用量以及水浴温度对凝胶时间及莫来石合成的影响。研究表明,水浴温度65℃、1,2-环氧丙烷与铝的摩尔比为3:1时可以较快的制备出均匀稳定的莫来石前驱体凝胶。利用TG-DTA、XRD、FT-IR对干凝胶热处理过程中的结构变化及相演变进行了分析,结果表明,前驱体凝胶为第一类莫来石凝胶,在热处理过程中没有形成γ-Al_2O_3、铝硅尖晶石等中间相,在990℃左右凝胶晶化放热直接转变成单相莫来石。干凝胶经1000℃煅烧1h后可形成莫来石,1200℃煅烧后莫来石晶相发育良好。在热处理之前凝胶中已经形成Si-O-Al结构,这是莫来石低温合成的最主要原因。     

溶胶-凝胶法制备纳米镁铝尖晶石纳米粉

以硝酸镁和硝酸铝为原料,柠檬酸为络合剂,混合后制得柠檬酸盐先驱体,并将脲加到柠檬酸盐先驱体中,得到另一种新的含脲柠檬酸盐先驱体.两种先驱体分别经800 ℃和1000 ℃煅烧,可得到镁铝尖晶石纳米粉.XRD分析表明,800 ℃煅烧已有镁铝尖晶石形成,镁铝尖晶石结晶化程度随煅烧温度的升高而提高,而在同一热处理温度下,含脲柠檬酸盐前驱体比柠檬酸盐前驱体制得的纳米镁铝尖晶石颗粒细.TEM结果表明:800 ℃煅烧含脲柠檬酸盐可得到的镁铝尖晶石纳米粉体,颗粒大小均匀,粒径尺寸在20～30 nm.     

纳米莫来石的制备及其对氧化铝陶瓷性能的影响

以硝酸铝和硅溶胶为原料,采用溶胶-凝胶法合成了纳米莫来石粉体,进而探讨了纳米莫来石对氧化铝陶瓷烧结性能、抗弯强度以及抗热震性能的影响.结果发现,在1100 ℃煅烧硝酸铝与硅溶胶先驱体时仅有少量Al2O3生成,当将煅烧温度升高到1200 ℃时,获得了单一的莫来石晶相,粉体的平均粒径在50～60 nm之间;在氧化铝中添加2wt%～10wt%的纳米莫来石,可以有效促进陶瓷体的致密烧结,并获得良好的抗弯强度与抗热震性能;纳米莫来石含量为5wt%的陶瓷,在1650 ℃烧结后的抗弯强度为247.49 MPa,经过1200 ℃热震后的抗弯强度为218.52 MPa;当纳米莫来石的添加量超过10wt%时,将降低陶瓷的饱和体积密度,并恶化陶瓷的抗弯强度与抗热震性能.     

Sol-Gel-SPD制备超细Al2O3-SiO2二元粉体材料

以硝酸铝(Al(NO3)3·9H2O)和正硅酸乙酯(TEOS)为原料,采用溶胶-凝胶(Sol-Gel)技术并结合喷雾干燥(SPD)技术制得超细Al2O3-SiO2二元复合粉体材料,并分别于400℃、800℃、1000℃、1150℃和1200℃煅烧2 h;采用全自动比表面积与孔隙率分析仪、TEM、TG-DSC及XRD等仪器研究了热处理温度、pH值(分别为5.5、7和8)以及干燥方法对粉体材料的表面性能、显微形貌、物相组成及Al2O3-SiO2二元系晶体转变过程的影响.结果表明由Sol-Gel-SPD制备的超细Al2O3-SiO2二元粉体材料的比表面积＞448 m2·g-1,而经1200℃煅烧2 h后所得的超细莫来石的比表面积34.05m2·g-1;TG-DSC分析表明采用Sol-Gel-SPD制得的Al2O3-SiO2二元粉体材料的质量损失主要发生在500℃之前;XRD分析表明粉体试样的开始莫来石化温度为1000℃,铝硅尖晶石(6Al2O3·SiO2)与非晶态SiO2在1150～1200℃完全转化为莫来石;比较不同pH值试样经1200℃煅烧后的TEM照片发现,当pH=7时,得到的超细莫来石粉体粒径最小,为50 nm.     

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.     

Effects of precursor pH and sintering temperature on synthesizing and morphology of sol–gel processed mullite

Needlelike mullite, which shows high aspect ratios, has been synthesized by coprecipitation from aluminum nitrate enneahydrate and colloidal silica sols. The effects of precursor pH and sintering temperature on the synthesizing behavior and the morphology of the needlelike mullite have been investigated. The equilibrium mullite phase appeared in the samples, which had been sintered at and above 1200 °C for each precursor pH. Crystallization of cristobalite from excessive SiO₂ occurred during sintering from 1200 °C, and the amount of cristobalite increased with sintering temperature up to 1400 °C. However, resorption of cristobalite into mullite decreased the amount of the phase from 1500 °C. The mullite synthesized with precursor pH2 (acidic sample) displayed high aspect ratios at high sintering temperature. However, morphology of the mullite synthesized with precursor pH8 (basic sample) transformed to rodlike or granular shape with increasing sintering temperature.     

Preparation of nano-AlN powder by sol–gel foaming and its sintering properties

Uniformly dispersed nano-sized aluminum nitride powders were prepared by the sol–gel foaming method using aluminum nitrate as the aluminum source, sucrose as the carbon source, and ammonium chloride as the foaming agent. The effects of ammonium chloride content on the particle size and the sintering properties of aluminum nitride were investigated. The results showed that when the molar ratio of ammonium chloride to aluminum nitrate was .5, the colloidal foams were uniform, large, and fluffy, and amorphous alumina precursors with uniform particles could be prepared. Aluminum nitride powder with a particle size of 22–27 nm can be obtained by calcining these precursors in nitrogen atmosphere at 1400°C for 2 h. At the same time, aluminum nitride bulk material with a relative density of 95% can be obtained by sintering the compact samples in nitrogen atmosphere at 1700°C for 2 h.     

以粉煤灰和赤泥为原料烧结陶瓷工艺与性能研究

本文研究了在1050 ℃至1200 ℃之间温度对以粉煤灰赤泥为原料烧结陶瓷的物相和烧结性能的影响.结果表明:实验用粉煤灰原料的主要矿相组成为石英(SiO_2)和莫来石(3Al_2O_3·2SiO_2),赤泥原料的主要矿相组成有钙铝黄长石(Ca_2Al_2SiO_7)、石英(SiO_2)、钙铁榴石(Ca_3Fe_2+3(SiO_4)_3)和钙钛榴石(Ca_3TiFeSi_3O_(12));以粉煤灰赤泥为原料的5组不同配比试样在1200 ℃时试样气孔率相对降低,体积密度和抗压强度相对程度增大;其中5#试样在经1200 ℃烧结后的气孔率为1.67%,体积密度为2.10 g·cm~(-3),抗压强度为123.23 MPa,达到较好的烧结致密状态,试样主要物相是钙钠长石和莫来石.试样内莫来石的形成及玻璃液相的增加促进烧结并在1200 ℃达到致密烧结状态.     

Colloidal processing of a mullite matrix material suitable for infiltrating woven fibre preforms using electrophoretic deposition

Commercially available alumina and silica precursors for the preparation of mullite ceramic via colloidal processing and viscous transient sintering have been identified, including fumed nanosize powders and colloidal suspensions. These materials were chosen due to the fact that they can be used in the form of a sol, as mullite matrix precursors, to infiltrate woven fibre preforms using electrophoretic deposition. The sintered density of the mullite matrices sintered for 2 h, at the upper temperature for fabricating SiC-fibre reinforced composites (1300 °C) is only ≈ 90% of theoretical. However, by exploiting a viscous flow densification mechanism, it is envisaged that hot-pressing can be used to produce fully dense mullite matrix composites at the required temperatures. Additionally. using a simple pressureless sintering route, almost fully dense (98% of theoretical density) monolithic mullite has been obtained from the pre-mullite powders. A very homogeneous and fine microstructure was achieved by sintering for 5 h at a temperature of ≈ 1450 °C.     

Synthesis of Mullite Powders Through a Suspension Combustion Process

This work reports on the synthesis of mullite powders by a suspension combustion process. Aluminum nitrate, as a source of Al, and a colloidal silica suspension, as a source of Si, are used as reagents, and urea serves as the fuel. This colloidal suspension allows a complete mixing of the reactants, thus promoting a core-shell reaction to produce the mullite. The powders obtained need to be treated at a high temperature to form the mullite. However, when ammonium nitrate is also added as a combustion aid, the mullite phase is directly obtained without any further treatment. A chemical reaction involving all these compounds is proposed, and the thermodynamic parameters are calculated in order to predict the temperature reached during the combustion process. The addition of ammonium nitrate reduces the temperature of the reaction by ca. 150°C. Once the conditions for the combustion reaction are optimized, the Al/Si ratio is modified in an attempt to obtain monophasic mullite.     

The Effect of La2O3 Addition on Sol–Gel Derived Mullitization

Monophasic gel with stoichiometric 3Al₂O₃·2SiO₂ composition and gels with 0.99, 1.96, and 2.91 mol% La₂O₃ added were sol–gel derived. The crystallization path, structure evolution, microstructure, and morphology of calcined premullite powders and sintered ceramic bodies have been investigated as a function of La₂O₃ content and sintering temperature. In addition to mullite, spinel phase at about 980°C, and α‐alumina at above 1000°C were determined; however, neither La₂O₃ nor La‐related compounds had crystallized. The La₂O₃ predominately incorporated into the glassy phase, enhanced with La₂O₃ level, which affected both mullite structure and composition, as confirmed by electron microscopy, Rietveld structure refinement, determination of unit cell parameters, electron microscopy, and achieved density of the sintered bodies. Increased thermal treatment changes the alumina/silica ratio in mullite (towards 3:2 below 1200°C, and toward 2:1 above), and decreases the mullite/amorphous ratio. Sintered dense ceramic bodies revealed a positive densification effect and increased sinterability as a result of the lanthanum‐induced increase in glassy phase.     

Acid Corrosion Behavior of Sol–Gel‐Prepared Mullite Ceramics With and Without Addition of Lanthanum

The corrosion behavior of pure and lanthanum doped, sol – gel‐derived, mullite ceramics in nitric acid aqueous solutions with various concentrations was investigated and compared. Samples sintered at a temperature of 1600°C for 4 h were characterized using powder X‐ray diffraction, SEM, and energy dispersive X‐ray spectroscopy. The corrosion behavior was explored by measuring the amount of eluted ions using atomic absorption spectrophotometry and inductively coupled plasma optical emission spectrometry (ICP‐OES). The doped sample was found to be more susceptible to dissolution in the corrodent, having higher leaching rates. The amounts of eluted lanthanum ions were in order of magnitude higher than amounts of silicon and aluminum. Those phenomena were attributed to the incorporation of lanthanum in the glassy phase, forming SiO₂ – La₂O₃‐rich glassy phase, which can dissolve in corrodent more easily than SiO₂‐rich glassy phase in the pure sample.     

溶胶凝胶法制备锆-钴高温防氧化粉体

在调节剂柠檬酸铵的作用下,采用溶胶凝胶法制备了Y稳定的Zr-Co粉体,经高温烧结制得致密陶瓷薄膜。利用场发射扫描电镜（SEM）表征了Zr-Co粉体的形貌特征和烧结后的陶瓷薄膜结构,热重（TG／DTA）分析了Zr-Co粉体烧结过程的失重和相转变吸放热过程,X射线衍射（XRD）分析跟踪了不同温度段烧结体系的组成变化趋势,在此基础上对粉体烧结后陶瓷薄膜的防氧化效果进行了分析,结果表明：温度对粉体的颗粒形貌和晶相结构有较大的影响,高温烧结的粉体性质稳定,经过1200℃烧结后的陶瓷膜层具有很好的致密性,具有很好的防氧化效果。     

莫来石纺丝溶胶的流变特性及可纺性研究

本文以氢氧化铝为铝源,以硅溶胶为硅源,采用溶胶-凝胶技术制备了莫来石纺丝溶胶,采用稳态及动态两种测试模式,研究了纺丝溶胶的粘度及流变性能,并采用干法纺丝制备连续莫来石凝胶纤维,评价了溶胶的可纺性。结果表明,温度对溶胶的非牛顿指数及结构粘度指数影响不大,这将有利于纺丝工艺的调节;高固含量有利于莫来石凝胶纤维的纺丝成纤,制备的凝胶纤维更细,纺丝稳定性更好。