CN111620679A - 一种以熔融二氧化硅为硅源制备高纯莫来石材料的方法 - Google Patents

一种以熔融二氧化硅为硅源制备高纯莫来石材料的方法 Download PDF

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CN111620679A
CN111620679A CN202010547921.5A CN202010547921A CN111620679A CN 111620679 A CN111620679 A CN 111620679A CN 202010547921 A CN202010547921 A CN 202010547921A CN 111620679 A CN111620679 A CN 111620679A
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raw material
fused silica
purity
mullite
preparing
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CN111620679B (zh
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赵飞
朱先忠
李可可
刘新红
徐恩霞
杨力远
葛铁柱
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Linyi Lifa Refractory Materials Co.,Ltd.
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Zhengzhou University
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Abstract

一种以熔融二氧化硅为硅源制备高纯莫来石材料的方法，其特征在于：所述方法包括以下步骤：a、按质量百分比将75~94wt%的二氧化硅质原料、4~20wt%的铝硅质原料和0.1~2wt%的烧结助剂混合后，经过球磨、烘干、成型，在1500~1600℃高温炉中煅烧0.5‑1小时，将混合原料烧制成熔融态，冷却后即得熔融二氧化硅原料；b、将步骤a中制备的熔融二氧化硅原料破碎后和氧化铝质原料按Al2O3/SiO2摩尔比为3：2的组成配料，将混合原料共磨后加入上述原料之和4wt%的结合剂，并在80~150MPa压力下成型，经1550~1650℃煅烧3~8小时，冷却后得到高纯莫来石晶体材料。本发明以熔融二氧化硅为硅源，合成高纯莫来石材料的烧结温度低，助烧结剂加入量少，并形成柱状莫来石和板片状莫来石晶体；具有杂质含量少、致密度高和高温力学性能好的特点。

Description

一种以熔融二氧化硅为硅源制备高纯莫来石材料的方法
技术领域
本发明属于高温陶瓷材料技术领域，具体涉及一种以熔融二氧化硅（SiO2）为硅源制备高纯莫来石材料的方法。
背景技术
莫来石作为一种较为理想的高温陶瓷材料，具有良好的抗高温蠕变性，优良的抗热震性能，荷重软化温度高，常温力学性能好、电绝缘性强等特性，被广泛应用于高温工程材料、耐火材料、电力和国防等领域。
采用反应烧结的方法制备高纯莫来石材料是非常困难的，需要较高的烧成温度和较长的烧成时间。如：发明专利“一种高纯莫来石的加工工艺”（专利公开号CN 101314547A）公布了一种以γ-氧化铝和高岭土为原料合成高纯莫来石的方法。虽然该工艺过程较为简单，其成品中的莫来石相含量达到95%以上，但是烧成温度需1700~1850℃，保温时间长达10~30小时，能源消耗较大。为降低高纯莫来石材料的合成温度，一般采用溶胶-凝胶的方法，减少原料的粒度，增加原料的活性，如：Ismail等人（Ismail, et al. Micristrure andmechanical properties of mullite prepared by the sol-gel method [J].J.Am.Ceram.Soc.1987(1):C7）将勃姆石和SiO2制备成溶胶-凝胶，采用二步煅烧的方法，在1650℃煅烧后得理论密度达98%的莫来石材料。张建峰等人公开了“一种高纯莫来石陶瓷及复合材料的制备方法”（专利公开号CN 106064936 B），以Al2O3粉和正硅酸乙酯为原料，在放电等离子体烧结炉中煅烧1400-1500℃得到高纯莫来石材料。采用溶胶-凝胶或放电等离子体烧结的方法能够有效降低高纯莫来石材料的烧成温度，但这些方法制备成本高，生产效率低，很难满足工业化的生产要求。总之，高纯莫来石的合成温度高，提高原料反应活性的方法较为复杂。
发明内容
本发明目的正是针对上述现有的技术中所存在的不足之处而提供一种工艺简单、烧结温度低、助烧结剂加入量少且高温性能优异的高纯莫来石材料的制备方法——以熔融二氧化硅为硅源制备高纯莫来石材料的方法。
本发明的目的可通过下述技术方案来实施：
本发明的以熔融二氧化硅为硅源制备高纯莫来石材料的方法包括以下步骤：
a、按质量百分比将75~94wt%的二氧化硅质原料、4~20wt%的铝硅质原料和0.1~2wt%的烧结助剂混合后，经过球磨、烘干、成型，在1500~1600℃高温炉中煅烧0.5-1小时，将混合原料烧制成熔融态，冷却后即得熔融二氧化硅原料；
b、将步骤a中制备的熔融二氧化硅原料破碎后和氧化铝质原料按Al2O3/SiO2摩尔比为3：2的组成配料，将混合原料共磨后加入上述原料质量之和4wt%的结合剂，并在80~150MPa压力下成型，经1550~1650℃煅烧3~8小时，冷却后得到高纯莫来石材料。
进一步说，本发明步骤a中所述的二氧化硅质原料取自天然石英、硅石或废硅砖中的任意一种，原料中SiO2≥99.0wt%。
步骤a中所述的铝硅质原料取自高纯高岭石、高纯煤矸石、氢氧化铝、工业氧化铝、α-Al2O3和γ- Al2O3中的一种或者两种的组合。
步骤a中所述的烧结助剂混取自锆英石、氧化锰、氧化钇、氧化铈、氧化镧、氧化镁、氧化锌或氧化钙中的一种或两种的组合。
步骤a中经球磨后的混合原料粒径≤325目；所述成型工序是在80~120MPa条件下成型。
步骤b中所述氧化铝质原料取自工业氧化铝、α-Al2O3和γ-Al2O3中的一种或几种的组合，其中Al2O3≥98.0 wt%；原料共磨后的粒径≤325目；所述结合剂取自纸浆废液、聚乙烯醇溶液、硅溶胶或铝溶胶中的任意一种。
本发明中将步骤a中所述的烧结助剂作用在熔融SiO2中，高温下富SiO2液相的粘度下降，提高了原料中Si4+和Al3+间的扩散反应系数，从而降低了材料的烧结温度；所形成的高纯莫来石晶体从富SiO2液相中析出，部分发育成宽大的板片状晶体，提高了材料的高温韧性。
本发明有益效果如下：
本发明的步骤a中，将烧结助剂和少量Al2O3作用在熔融SiO2网络中，降低了富SiO2液相的熔点和粘度，提高了Si4+和Al3+间的扩散反应系数，从而降低了莫来石材料的烧结温度；高温下，熔融SiO2被反应消耗，并生成高温相的莫来石。所生成的莫来石晶体从富SiO2液相中析出，部分发育成宽大的板片状晶体，提高了材料的高温韧性；本发明在制备莫来石的过程中所添加的烧结助剂少，所得到的莫来石材料纯度高，高温力学性能好。同时，本方法工艺简单，生产效率高，能耐满足工业化生产的要求。
附图说明
图1为本发明所制备高纯莫来石材料的显微结构照片；
图2 为本发明所制备高纯莫来石材料的XRD图谱。
具体实施方式
本发明以下将结合实施例作进一步的描述；
实施例1
步骤1）：熔融二氧化硅原料的制备；
按照质量百分比将90.5wt%的天然石英、8.5wt%的高岭石和1.0 wt%的氧化镁混合，放入行星球磨机中（转速280r/min）球磨3小时，粒径≤325目，然后将混合料在100MPa的压力下压制成坯体，将坯体干燥后经1530℃煅烧0.6小时，冷却后即得熔融二氧化硅原料。
步骤2）：利用熔融二氧化硅原料制备高纯莫来石材料；
将步骤1中合成的熔融二氧化硅原料破碎和γ-Al2O3细粉按Al2O3/SiO2摩尔比为3：2的组成配料，原料共磨后（粒径≤325目）加入上述原料质量之和4wt%的聚乙烯醇溶液作为结合剂，在120MPa下成型，经1600℃煅烧3小时即得到高纯莫来石材料。
本实施例所制备的高纯莫来石材料技术指标为：显气孔率<3%，体积密度2.98 g·cm-3，莫来石相含量95.6%，荷重软化开始温度（0.2MPa）为1660℃。
实施例2
步骤1）：熔融二氧化硅原料的制备；
按照质量百分比将94 wt%的硅石、5.5wt%的γ-Al2O3和0.5wt%的氧化钇混合，放入行星球磨机中（转速280r/min）球磨3小时，粒径≤325目，然后将混合料在100MPa的压力下压制成坯体，坯体100℃干燥后经1560℃煅烧0.5小时，冷却后得到熔融二氧化硅原料。
步骤2）：利用熔融二氧化硅原料制备高纯莫来石材料；
将步骤1中合成的熔融二氧化硅原料破碎和α-Al2O3细粉按Al2O3/SiO2摩尔比为3：2的组成配料，原料共磨后（粒径≤325目）加入上述原料质量之和4wt%的硅溶胶作为结合剂，在120MPa下成型，经1630℃煅烧4小时即得到高纯莫来石材料。
本实施例所制备的高纯莫来石材料技术指标为：显气孔率<4%，体积密度3.01 g·cm-3，莫来石相含量96.2%，荷重软化开始温度（0.2MPa）为1675℃。
实施例3
步骤1）：熔融二氧化硅原料的制备；
按照质量百分比将86.6wt%的天然石英、12.8wt%的煤矸石和0.6wt%的氧化锌混合，然后将混合料湿法球磨5小时，粒径≤325目，在120MPa的压力下压制成坯体，坯体100℃干燥后经1550℃煅烧0.6小时，冷却后即得熔融二氧化硅原料。
步骤2）：利用熔融二氧化硅原料制备高纯莫来石材料；
将步骤1中合成的熔融二氧化硅原料破碎和α-Al2O3细粉按照Al2O3/SiO2摩尔比为3：2的组成配料，原料共磨后（粒径≤325目）加入上述原料质量之和4wt%的纸浆废液作为结合剂，在120MPa下成型，经1630℃煅烧5小时即得到高纯莫来石材料。
本实施例所制备的高纯莫来石材料技术指标为：显气孔率<3.5%，体积密度2.96g·cm-3，莫来石相含量97.0%，荷重软化开始温度（0.2MPa）为1665℃。

Claims (7)

1.一种以熔融二氧化硅为硅源制备高纯莫来石材料的方法，其特征在于：所述的方法包括以下步骤：
a、按质量百分比将75~94wt%的二氧化硅质原料、4~20wt%的铝硅质原料和0.1~2wt%的烧结助剂混合后，经过球磨、烘干、成型，在1500~1600℃高温炉中煅烧0.5-1小时，将混合原料烧制成熔融态，冷却后即得熔融二氧化硅原料；
b、将步骤a中制备的熔融二氧化硅原料破碎后和氧化铝质原料按Al2O3/SiO2摩尔比为3：2的组成配料，将混合原料共磨后加入上述原料质量之和4wt%的结合剂，并在80~150MPa压力下成型，经1550~1650℃煅烧3~8小时，冷却后得到高纯莫来石材料。
2.根据权利要求1所述的以熔融二氧化硅为硅源制备高纯莫来石材料的方法，其特征在于：步骤a中所述的二氧化硅质原料取自天然石英、硅石或废硅砖中的任意一种，原料中SiO2≥99.0wt%。
3.根据权利要求1所述的以熔融二氧化硅为硅源制备高纯莫来石材料的方法，其特征在于：步骤a中所述的铝硅质原料取自高纯高岭石、高纯煤矸石、氢氧化铝、工业氧化铝、α-Al2O3和γ- Al2O3中的一种或者两种的组合。
4.根据权利要求1所述的以熔融二氧化硅为硅源制备高纯莫来石材料的方法，其特征在于：步骤a中所述的烧结助剂混取自锆英石、氧化锰、氧化钇、氧化铈、氧化镧、氧化镁、氧化锌或氧化钙中的一种或两种的组合。
5.根据权利要求1所述的以熔融二氧化硅为硅源制备高纯莫来石材料的方法，其特征在于：步骤a中经球磨后的混合原料粒径≤325目；所述成型工序是在80~120MPa条件下成型。
6.根据权利要求1所述的一种以熔融二氧化硅为硅源制备高纯莫来石材料的方法，其特征在于：步骤b中所述氧化铝质原料取自工业氧化铝、α-Al2O3和γ-Al2O3中的一种或几种的组合，其中Al2O3≥98.0 wt%；原料共磨后的粒径≤325目；所述的结合剂取自纸浆废液、聚乙烯醇溶液、硅溶胶或铝溶胶中的任意一种。
7.根据权利要求1所述的以熔融二氧化硅为硅源制备高纯莫来石材料的方法，其特征在于：将步骤a中所述的烧结助剂作用在熔融二氧化硅中，高温下富SiO2液相的粘度下降，提高了原料中Si4+和Al3+间的扩散反应系数，从而降低了材料的烧结温度；所形成的高纯莫来石晶体从富SiO2液相中析出，部分发育成宽大的板片状，提高了材料的高温韧性。
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CN115286368A (zh) * 2022-08-23 2022-11-04 江苏中磊节能科技发展有限公司 一种高强度轻质耐火砖及其制备方法
CN115286368B (zh) * 2022-08-23 2024-01-23 江苏中磊节能科技发展有限公司 一种高强度轻质耐火砖及其制备方法
CN117466635A (zh) * 2023-12-28 2024-01-30 天津包钢稀土研究院有限责任公司 一种稀土改性煤矸石制备致密莫来石的方法
CN117466635B (zh) * 2023-12-28 2024-03-08 天津包钢稀土研究院有限责任公司 一种稀土改性煤矸石制备致密莫来石的方法

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