莫来石晶须的制备及其生长机理

以Al_2O_3和SiO_2为原料、AlF_3·3H_2O为添加剂,采用原位反应法经1 373~1 873 K反应5 h后制备莫来石晶须。研究了添加剂含量及反应温度等对莫来石晶须合成的影响,探讨了莫来石晶须的生长机理。结果表明:AlF_3·3H_2O的最佳添加量为4%(质量分数)时,莫来石晶须的长度和长径比均随合成温度的升高(1 373~1 873 K)先增大后减小,当合成温度为1 673 K时,样品中莫来石晶须的长径比最大(约为54)。莫来石晶须的生长是由气–固反应机理控制。     

以钼酸锂为熔盐制备莫来石晶须

采用非水解溶胶-凝胶法合成莫来石晶种,然后将晶种与钼酸锂熔盐混合制备莫来石晶须。借助XRD、FE-SEM、TEM等测试手段研究熔盐用量、热处理时间等工艺参数对制备莫来石晶须的影响,探讨了莫来石晶须的生长机理以及晶须增强钛酸铝陶瓷的力学性能。结果表明:熔盐用量过多或过少,热处理时间过长或过短均不利于莫来石晶须的制备;莫来石晶种与钼酸盐熔盐的质量比为1∶2,热处理时间为6h能够制得产率高、长径比大于50的莫来石晶须;莫来石晶须用于增强钛酸铝陶瓷,可使其抗折强度提高3.15倍。     

硅酸钠溶液合成托贝莫来石晶须

以硅酸钠为硅质原料,研究了动态水热法合成托贝莫来石的条件及其对产物纯度和形貌的影响。结果表明:硅酸钠和石灰乳直接反应合成的产物主要为针钠钙石;而在苛性碱溶液中反应时,针钠钙石向生成托贝莫来石的方向转化,随苛性碱浓度提高,托贝莫来石生成量增加;加入铝离子且其含量达到钙铝摩尔比为5时,可获得纯的1.1 nm托贝莫来石;溶液中的氯离子可促进晶须生长,当钙氯摩尔比为5时,托贝莫来石晶须的长度为2～13μm,直径为0.2～0.5μm。在优化的合成条件下,以实际含硅碱液为原料,合成出长度为2～10μm、直径为0.2～1.0μm的托贝莫来石晶须。在合成托贝莫来石过程中,苛性碱改变了水化硅酸钙的生成环境,铝离子使硅氧四面体双链无法形成而得到四面体单链,最终合成出纯的1.1 nm托贝莫来石;而氯离子所产生的盐效应促进了托贝莫来石结晶长大,有助于制备组分单一、结晶晶面完整的托贝莫来石晶须。     

莫来石晶须的特性及应用

通过溶胶─凝胶工艺制备了莫来石前驱体,加入适当矿化剂经高温煅烧合成了高纯、单相莫来石晶须。XRD及SEM分析结果显示:晶须直径为50～100nm,长度为3～8μm,晶须尺寸均匀性好,表面光洁,直晶率高。运用所制备的晶须制备了多孔基板试样,并与普通粒子堆积法烧成样品显微结构与性能进行比较,进而分析了低维晶须材料与普通粒子的堆积成孔方式的异同。在此基础上,对莫来石晶须在其它方面的应用进行了展望。     

不同酸对胶凝过程及莫来石晶须形成的影响

以工业纯铝溶胶和硅溶胶为原料,采用溶胶-凝胶工艺制备了莫来石晶须。研究了不同酸对胶凝过程及莫来石晶须形成的影响。结果说明,采用柠檬酸调节溶胶的pH值可以缩短胶凝时间,制备出形貌规则、长径比大的莫来石晶须。     

基于高铝粉煤灰的堇青石-莫来石复合材料制备

为了实现高铝粉煤灰的高值化利用,以高铝粉煤灰为单一铝硅原料,依次对其进行酸、碱预处理,将处理后的高铝粉煤灰与滑石粉混合,通过一步原位烧成制备堇青石-莫来石复合材料,进一步考察原料配比和烧成条件对烧成样品性能的影响规律。结果表明,烧成温度为1 370℃、烧成时间为2 h、堇青石和莫来石理论质量比为50∶50时,可制备出体积密度为1.96 g/cm~3、显气孔率为30.47%、常温抗折强度为66.44 MPa的堇青石-莫来石复合材料,其主要指标均达到YB/T 4549—2016《堇青石-莫来石窑具》的要求,该方法实现了以粉煤灰为主要原料,灵活制备具有不同堇青石和莫来石配比的复合材料,为高铝粉煤灰的高值化利用提供新途径。     

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。     

莫来石晶须的合成与分散

本文以γ-Al_2O_3和SiO_2为主要原料,Al F_3·3H_2O为助剂,采用固相反应法制备了莫来石晶须,对影响莫来石晶须长径比的主要因素(保温时间、烧结温度、氟化铝含量)进行了3因素4水平正交实验,并对实验结果进行了极差分析和方差分析,确定了影响因素的主次、显著性及最优方案。此外,从分散剂和酸腐蚀的影响两方面研究了制备的莫来石晶须的分散性能,获得了较优的晶须分散工艺。     

不同阴离子对固废基铝掺杂托贝莫来石的影响

以粉煤灰(FA)和城市垃圾焚烧飞灰(MSWI)为主要原料,水热合成了固废基铝掺杂托贝莫来石,研究了不同外源阴离子对试样的抗压强度、反应产物、微观形貌和孔结构的影响。结果表明:外加剂的引入提高了固废基铝掺杂托贝莫来石的抗压强度,对于粉煤灰-水泥-生石灰-脱硫石膏(FA-C-T)体系的增强效果从高到低依次为NaCl、NaOH、NaNO_3,粉煤灰-城市垃圾焚烧飞灰-生石灰-脱硫石膏(FA-MSWI-T)体系为NaOH、NaCl、NaNO_3;不同阴离子的引入并没有改变铝掺杂托贝莫来石的矿物组成,只是使得各个矿物相的含量有所差异,表明3种阴离子均是络合在铝掺杂托贝莫来石的表面或者存在于层间;不同阴离子的加入使得托贝莫来石的微观形貌发生了改变,也细化了试样的孔结构。     

高铝粉煤灰合成刚玉莫来石抛光材料的实验研究

采用高铝粉煤灰合成抛光材料刚玉莫来石具有良好发展前景。通过对高铝粉煤灰进行酸碱预处理,提高高铝粉煤灰中的铝与硅的质量比,减少Al2O3的添加量,降低成本。通过对合成的刚玉莫来石进行烧失量以及XED、SEM和激光粒度分析,结果表明:合成温度升高,有利于莫来石相的形成;添加过量的Al2O3,刚玉莫来石相中刚玉相逐渐增加。     

Properties and mechanism of mullite whisker toughened ceramics

High-strength ceramics were prepared from high alumina fly ash (HAFA) and activated alumina as raw materials with magnesia as a sintering additive. The growth kinetics and influence mechanism of secondary mullite whiskers were investigated. Meanwhile, the effects of the Al₂O₃/SiO₂ mass ratio (A/S) and the amount of magnesia on the content and morphology of mullite in the green body were investigated, so as to emphasize the effect of the liquid phase in the sintering process on the growth of secondary mullite whiskers. The results showed that the aspect ratio of secondary mullite whiskers increased significantly after adding activated alumina to increase the A/S ratio of raw materials. When 30 wt% activated alumina was added, the mullite content increased by 5.39%, and the whisker length increased from 1.36 μm to 4.18 μm. The addition of magnesia improved the liquid phase formed during the sintering process and the K value method was used to determine the sintering liquid phase content under various conditions. It was observed that increasing the magnesia level by 1 wt% could raise the liquid phase content by 5–7%. When the total liquid content of the system was 30–40%, the growth activation energy in the diameter direction of the whisker reduced significantly, promoting the growth of secondary mullite whiskers along the C axis. The morphology of mullite gradually developed from fibrous to long columnar crystal, making it combine more densely with the green body matrix. Furthermore, the staggered long columnar mullite crystal structure changes the fracture mode of ceramics from intergranular to transgranular fracture, which fully uses the high mechanical strength of mullite. As a result, the fracture energy and strength of ceramics are significantly improved.     

粉煤灰为基制备耐火材料的研究

以粉煤灰为主要原材料,煤矸石和工业氧化铝为辅料,通过控制物料比例制备了不同Al2O3含量在不同烧结温度下的耐火材料.对所制备材料进行结构性能测试,并借助X射线衍射和扫描电镜对材料进行微观分析.实验结果表明:不同的烧结温度及氧化铝含量对耐火制品的致密性、力学性能、耐火度和晶型状态都有影响.制品在1350 ℃、Al2O3的含量为45%时,其性能指标为:体积密度2.47 g/cm3、常温耐压41 MPa、耐火度1450 ℃、晶型状态以莫来石相和刚玉相为主.该制品的力学性能和使用性能较好,可为进一步利用粉煤灰制备高附加值材料奠定基础.     

The preparation of mullite foamed ceramics reinforced by in-situ SiC whiskers and their reinforcement mechanism

A SiC whisker-bonded mullite foamed ceramic was prepared by using white clay, industrial alumina and silicon powder as raw materials without solid carbon sources. The XRD, SEM, EDS, and Factsage® software were used to investigate the effect of sintering temperature on the phase composition, microstructure, compressive strength, and Young's modulus of foamed ceramics. Additionally, the synthesis reaction of in-situ SiC whiskers and the effect of their formation on the properties of ceramics were studied. The results showed that the in-situ SiC whiskers with dendrite shapes were formed after firing above 1300 °C at the expense of Si/SiO vapors as well as CO vapor, though there were no solid carbon sources in raw materials, which provided a new idea for the synthesis of SiC whiskers. The formation of SiC whiskers was helpful for improving the compressive strength and Young's modulus of mullite foamed ceramics remarkably. Furthermore, the reinforcement mechanism has been investigated systematically.     

Waste recycling of coal fly ash for design of highly porous whisker-structured mullite ceramic membranes

Coal fly ash, a solid state waste massively produced from coal combustion, is considered to be highly hazardous to the environment due to its persistently toxic trace elements. High-value added waste recycling is a promising technique to address this issue. In this work, a waste-to-resource strategy is proposed for design of highly porous whisker-structured mullite ceramic membranes derived from waste coal fly ash and Al(OH)₃ as raw materials and MoO₃ as a single sintering additive. These were characterized in terms of their dynamic sintering behavior, shrinkage, bulk density, porosity, phase evolution, microstructure, pore size distribution, N₂ permeation flux, and mechanical strength. Addition of molybdenum trioxide effectively inhibited the sintering densification of membranes while at the same time forming a metastable low viscosity liquid at lower temperatures. This enables formation of a novel and more highly porous whisker-interlocked structure and accelerates the growth of mullite whiskers with controllable morphologies. Without degradation of mechanical properties, the open porosity increased significantly from 41.65 ± 0.13% to 58.14 ± 0.15% with increasing MoO₃ content from 0 to 20 wt.% without any pore-forming agent, while shrinkage and pore size decreased. The method proposed in this study is expected not only to give a new and facile insight for high-value added recycling of waste coal fly ash but also to fabricate low-cost high performance ceramic membranes with novel structures for further environmental applications.     

高温处理粉煤灰的理化特性研究

为多元化、高附加值利用粉煤灰,以朔州电厂粉煤灰为例,进行了X射线衍射测试、粒度测试和热重分析。结果表明,朔州电厂粉煤灰的w(Al2O3)=41. 09%、w(CaO)=4. 64%,属于高铝低钙型,其平均粒径为108. 1μm;未煅烧的朔州电厂粉煤灰矿物组成为莫来石、石英、石膏;质量损失主要发生在570~750℃和1 100~1 280℃。然后称取未筛选经105℃烘干后的粉煤灰制成Φ40 mm×8. 8 mm的试样,经1 200~1 550℃热处理后,进行劈裂强度试验、XRD分析等。结果表明,随热处理温度升高,试样的强度和密度增大,莫来石含量逐渐增多,1 400℃时性能达到最佳。     

Industrial waste silica-alumina gel recycling: Low-temperature synthesis of mullite whiskers for mass production

The increasing demand for mullite whisker-reinforced, toughened ceramic materials and mullite raw materials that meet industrial requirements has prompted the search for new and alternative sources, as well as effective technologies to obtain the target products. In this work, mullite whiskers of high purity were synthesized by a vapor-liquid–solid (V-L-S) process using industrial waste silica-alumina gel and Al₂(SO₄)₃·18H₂O as raw materials, with AlF₃·3H₂O and Na₂SO₄ as additives. The effects of sintering temperatures on the mullitization reactions and mullite morphology were investigated by XRD, TG-DTA, SEM and so forth. The results suggest that the introduction of AlF₃·3H₂O and Na₂SO₄ alters the mullitization reaction path, which leads to an initial mullitization reaction temperature of 720 °C. The SEM results demonstrate that mullite whiskers transformed from secondary growth to anisotropic growth when the sintering temperature was increased from 720 °C to 825 °C. By analyzing the experimental results, the mechanism of AlF₃·3H₂O-assisted growth of mullite whiskers with Na₂SO₄ as the liquid phase template is proposed based on the “dissolution-precipitation” process. Herein, a novel and feasible solution for the recycling of silica-rich industrial waste is proposed, which offers new and simple insights into the high value-added recycling of industrial waste, which provides new ideas for the actual mass production of mullite whiskers.     

莫来石晶须前驱体原位增强海胆状莫来石材料的性能研究

为了提高粉煤灰的高附加值利用,分别以氢氧化铝和粉煤灰漂珠作为海胆状莫来石前驱体的铝源和硅源,氢氧化铝和粉煤灰为莫来石晶须前驱体增强剂的铝源和硅源,AlF₃和V₂O₅为晶须促进剂和烧结助剂,采用固相法原位制备了莫来石陶瓷材料。主要研究了增强剂与海胆状莫来石前驱体的配比(质量比分别为3:7、4:6、5:5、6:4、7:3)对制备的莫来石陶瓷材料性能、物相组成和显微结构的影响。结果表明,随着增强剂与海胆状莫来石前驱体的配比从3:7增大至7:3,试样中形成的晶相全为莫来石,材料内部更加致密,体积密度和抗压强度逐渐增大,总气孔率逐渐减小,增强剂的引入提高了材料的线变化率和抗热震性能,但降低了材料的重烧线变化率,材料的残余抗压强度及残余强度比先增加后减小。当增强剂与海胆状莫来石前驱体的质量比为6:4时综合性能较佳。     

复合型絮凝剂聚合氯化铝铁的合成

粉煤灰中含有铝、铁,可以用其制备聚合氯化铝铁絮凝剂。但是,粉煤灰中的铝、硅以复杂的玻璃体红柱石形式存在,酸溶性非常差,需要通过焙烧破坏其中的SiO₂-Al₂O₃键,提高其酸溶性。在粉煤灰中通过添加一定量赤泥来调节混合物中铝铁比值关系,然后用改性粉煤灰和盐酸为主要原料,制备聚合氯化铝铁絮凝剂。粉煤灰活化最佳条件：粉煤灰与赤泥的质量比为0.3、焙烧温度为750 ℃、焙烧时间为2 h。粉煤灰中铝铁溶出最佳条件：盐酸浓度为7 mol/L,液固比为3.5 mL/g,反应温度为85 ℃,反应时间为2.0 h,在此条件下铝铁溶出率高达90.5%。将所得溶液陈化18 h即得到聚合氯化铝铁（PAFC）絮凝剂。絮凝实验结果表明：制得的PAFC的絮凝性能优于聚合氯化铝（PAC）、聚合氯化铁（PFC）。     

粉煤灰动态水热合成纳米复合托贝莫来石晶须及其表征

以山西某地普通粉煤灰为原料,采用动态水热法合成纳米复合托贝莫来石晶须,考察了CaO/SiO2摩尔比、反应温度、液固比、反应时间的影响. 结果表明,以预活化的普通粉煤灰为原料,控制CaO/SiO2摩尔比为1.0、液固比为25 mL/g,在220℃下水热反应10 h,可制备出晶须长/径比大于20的纳米复合托贝莫来石晶须,优化条件下晶须可相互缠绕成中空球形颗粒,纯度达80%以上.