CN112759416A - 一种六铝酸钙/钛酸铝多孔陶瓷及其制备方法 - Google Patents
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Abstract
本发明涉及一种六铝酸钙/钛酸铝多孔陶瓷及其制备方法。其技术方案是:以55~65wt%的钛铁渣微粉、15~20wt%的氢氧化铝微粉、10~20wt%的勃姆石和5~15wt%的α‑Al2O3微粉为原料,外加所述原料20~25wt%的淀粉和1~2wt%的硼砂,混合,得混合料;将所述混合料在球磨机中干混30~60min,再外加所述原料2~5wt%的有机结合剂,球磨30~35min;在50~55MPa条件下机压成型,在100~110℃条件下干燥12~24h,然后在1350~1500℃条件下保温2~3h,制得六铝酸钙/钛酸铝多孔陶瓷材料。本发明具有成本低廉和和工艺简单的优点,所制备的六铝酸钙/钛酸铝多孔陶瓷气孔率高、热导率低、物相稳定不易分解、常温强度较大和热震稳定性优良。
Description
技术领域
本发明属于多孔陶瓷技术领域。具体涉及一种六铝酸钙/钛酸铝多孔陶瓷及其制备方法。
背景技术
钛铁渣是铝热还原法冶炼铁钛合金时产生的废弃物。据统计,每生产一吨钛铁合金,排放钛铁渣1.1~1.5t。钛铁渣的主要化学成分为Al2O3、CaO和TiO2等,主晶相为六铝酸钙、钛铝酸钙和钛酸钙等。未处理的炉渣会造成一定的环境问题,故对钛铁渣利用的研究已引起本领域技术人员的关注。“一种以钛铁渣为主料的隔热耐火材料及其制备方法(CN106882973A)”、“一种钛铝酸钙隔热耐火材料及其制备方法(CN108558417A)”专利技术,通过溶胶凝胶法和发泡法制备的隔热耐火材料虽然具有较低的导热系数,但是采用溶胶凝胶法和发泡法造孔不仅工艺复杂且增加了制备成本,降低了材料的强度。
钛酸铝多孔陶瓷具有强度高、比表面积大、吸附性好和抗热震性能好等优点,被广泛应用到高温过滤器、催化剂载体和保温材料等领域。“一种多孔钛酸铝陶瓷的制备方法(CN105110813A)”采用溶胶凝胶法制备了多孔钛酸铝陶瓷,但是忽略了钛酸铝在700~1300℃条件下不稳定易分解、失去优良的热震稳定性的缺点。文献(陆洪彬.稳定钛酸铝及钛酸铝—莫来石复相陶瓷的研究[D].南京工业大学,2006.)采用外加添加剂抑制钛酸铝分解,促进钛酸铝的合成,制备了稳定的钛酸铝—莫来石复相陶瓷,但是该材料气孔率低、热导率高,无法应用在多孔陶瓷领域。
发明内容
本发明旨在克服现有技术缺陷,目的在于提供一种成本低廉和工艺简单的六铝酸钙/钛酸铝多孔陶瓷的制备方法,用该方法制备的多孔陶瓷材料的气孔率高、热导率低、物相稳定不易分解、常温强度较大和热震稳定性优良。
为实现上述目的,本发明采用的技术方案是:以55~65wt%的钛铁渣微粉、15~20wt%的氢氧化铝微粉、10~20wt%的勃姆石和5~15wt%的α-Al2O3微粉为原料,外加所述原料20~25wt%的淀粉和1~2wt%的硼砂,混合,得混合料;将所述混合料在球磨机中干混30~60min,再外加所述原料2~5wt%的有机结合剂,球磨30~35min;在50~55MPa条件下机压成型,在100~110℃条件下干燥12~24h,然后在1350~1500℃条件下保温2~3h,制得六铝酸钙/钛酸铝多孔陶瓷材料。
所述钛铁渣微粉的主要化学成分是:Al2O3≥73wt%,CaO≥10wt%,TiO2≥11wt%,Fe2O3≥0.6wt%,MgO≥1.4wt%;所述钛铁渣微粉的密度为3.28g/cm3,钛铁渣微粉的粒度≤60μm。
所述氢氧化铝微粉的Al2O3含量≥65wt%;氢氧化铝微粉的粒度≤10μm。
所述勃姆石微粉的Al2O3含量≥84wt%;勃姆石微粉的粒度≤20μm。
所述α-Al2O3微粉的Al2O3含量≥99.9wt%;α-Al2O3微粉的粒度≤0.025mm。
所述硼砂的Na2B4O7·5H2O含量≥99wt%;硼砂的粒度≤0.6mm。
所述有机结合剂为磷酸二氢钠、聚乙烯醇和树脂中的一种。
由于采用上述技术方案,本发明与现有技术相比具有以下优点:
1、本发明以钛铁渣微粉、氢氧化铝微粉、勃姆石和α-Al2O3微粉为原料,外加淀粉为造孔剂和硼砂为助溶剂,经干混、机压成型、干燥和烧成,工艺简单;所采用的原料钛铁渣的主晶相为钛铝酸钙、六铝酸钙和钛酸钙等,来源丰富,成本低廉,能显著降低六铝酸钙/钛酸铝多孔陶瓷的制备成本。
2、本发明采用的主要原料为钛铁渣,钛铁渣具有高的熔点、较高的常温强度、较低的热膨胀系数和导热系数,显著提高了六铝酸钙/钛酸铝多孔陶瓷的常温力学性能和隔热性能。
3、本发明利用氢氧化铝和勃姆石高温处理过程中的原位分解使材料产生疏松多孔的结构,提高了六铝酸钙/钛酸铝多孔陶瓷的真气孔率,降低了六铝酸钙/钛酸铝多孔陶瓷的导热性能。
4、本发明利用钛铁渣的多相性,如钛铁渣中的钛铝酸钙、二铝酸钙和钛酸钙等能与氢氧化铝和勃姆石分解后产生的氧化铝在热处理后反应生成钛酸铝,显著提高了六铝酸钙/钛酸铝多孔陶瓷的强度和比表面积,同时钛铁渣中的杂质Fe2O3、MgO能提高钛酸铝的稳定性,抑制其高温下的分解。
因此,本发明具有成本低廉和和工艺简单的优点,所制备的六铝酸钙/钛酸铝多孔陶瓷气孔率高、热导率低、物相稳定不易分解、常温强度较大和热震稳定性优良。
具体实施方式
一种六铝酸钙/钛酸铝多孔陶瓷及其制备方法。本具体实施方式所述制备方法是:
以55~65wt%的钛铁渣微粉、15~20wt%的氢氧化铝微粉、10~20wt%的勃姆石和5~15wt%的α-Al2O3微粉为原料,外加所述原料20~25wt%的淀粉和1~2wt%的硼砂,混合,得混合料;将所述混合料在球磨机中干混30~60min,再外加所述原料2~5wt%的有机结合剂,球磨30~35min;在50~55MPa条件下机压成型,在100~110℃条件下干燥12~24h,然后在1350~1500℃条件下保温2~3h,制得六铝酸钙/钛酸铝多孔陶瓷材料。
所述钛铁渣微粉的主要化学成分是:Al2O3≥73wt%,CaO≥10wt%,TiO2≥11wt%,Fe2O3≥0.6wt%,MgO≥1.4wt%;所述钛铁渣微粉的密度为3.28g/cm3,钛铁渣微粉的粒度≤60μm。
所述氢氧化铝微粉的Al2O3含量≥65wt%。
所述勃姆石微粉的Al2O3含量≥84wt%。
所述α-Al2O3微粉的Al2O3含量≥99.9wt%。
所述硼砂的Na2B4O7·5H2O含量≥99wt%。
所述有机结合剂为磷酸二氢钠、聚乙烯醇和树脂中的一种。
本具体实施方式的实施例中:
所述氢氧化铝微粉的粒度≤10μm。
所述勃姆石微粉的粒度≤20μm。
所述α-Al2O3微粉的粒度≤0.025mm。
所述硼砂的粒度≤0.6mm。
实施例中不再赘述。
实施例1
一种六铝酸钙/钛酸铝多孔陶瓷及其制备方法。本实施例所述制备方法是:
以55wt%的钛铁渣微粉、15wt%的氢氧化铝微粉、20wt%的勃姆石和10wt%的α-Al2O3微粉为原料,外加所述原料20wt%的淀粉和2wt%的硼砂,混合,得混合料;将所述混合料在球磨机中干混60min,再外加所述原料5wt%的有机结合剂,球磨35min;在50MPa条件下机压成型,在100℃条件下干燥20h,然后在1350℃条件下保温2h,制得六铝酸钙/钛酸铝多孔陶瓷材料。
所述钛铁渣微粉的主要化学成分是:Al2O3为73.01wt%,CaO为11.85wt%,TiO2为11.87wt%,Fe2O3为0.65wt%,MgO为1.5wt%;所述钛铁渣微粉的密度为3.28g/cm3,钛铁渣微粉的粒度≤60μm。
所述氢氧化铝微粉的Al2O3含量为65wt%。
所述勃姆石微粉的Al2O3含量为84wt%。
所述α-Al2O3微粉的Al2O3含量为99.9wt%。
所述硼砂的Na2B4O7·5H2O含量为99wt%。
所述有机结合剂为磷酸二氢钠。
实施例2
一种六铝酸钙/钛酸铝多孔陶瓷及其制备方法。本实施例所述制备方法是:
以58wt%的钛铁渣微粉、16wt%的氢氧化铝微粉、11wt%的勃姆石和15wt%的α-Al2O3微粉为原料,外加所述原料25wt%的淀粉和1.4wt%的硼砂,混合,得混合料;将所述混合料在球磨机中干混50min,再外加所述原料4wt%的有机结合剂,球磨34min;在52MPa条件下机压成型,在105℃条件下干燥18h,然后在1400℃条件下保温2h,制得六铝酸钙/钛酸铝多孔陶瓷材料。
所述钛铁渣微粉的主要化学成分是:Al2O3为73.45wt%,CaO为11.92wt%,TiO2为11.4wt%,Fe2O3为0.63wt%,MgO为1.45wt%;所述钛铁渣微粉的密度为3.28g/cm3,钛铁渣微粉的粒度≤60μm。
所述氢氧化铝微粉的Al2O3含量为65.1wt%。
所述勃姆石微粉的Al2O3含量为84.2wt%。
所述α-Al2O3微粉的Al2O3含量为99.91wt%。
所述硼砂的Na2B4O7·5H2O含量为99.1wt%。
所述有机结合剂为聚乙烯醇。
实施例3
一种六铝酸钙/钛酸铝多孔陶瓷及其制备方法。本实施例所述制备方法是:
以62wt%的钛铁渣微粉、18wt%的氢氧化铝微粉、12wt%的勃姆石和8wt%的α-Al2O3微粉为原料,外加所述原料23wt%的淀粉和1wt%的硼砂,混合,得混合料;将所述混合料在球磨机中干混40min,再外加所述原料3wt%的有机结合剂,球磨32min;在53MPa条件下机压成型,在110℃条件下干燥24h,然后在1450℃条件下保温3h,制得六铝酸钙/钛酸铝多孔陶瓷材料。
所述钛铁渣微粉的主要化学成分是:Al2O3为74.18wt%,CaO为11.6wt%,TiO2为11.08wt%,Fe2O3为0.61wt%,MgO为1.43wt%;所述钛铁渣微粉的密度为3.28g/cm3,钛铁渣微粉的粒度≤60μm。
所述氢氧化铝微粉的Al2O3含量为65.2wt%。
所述勃姆石微粉的Al2O3含量为84.3wt%。
所述α-Al2O3微粉的Al2O3含量为99.9wt%。
所述硼砂的Na2B4O7·5H2O含量为99.2wt%。
所述有机结合剂为树脂。
实施例4
一种六铝酸钙/钛酸铝多孔陶瓷及其制备方法。本实施例所述制备方法是:
以65wt%的钛铁渣微粉、20wt%的氢氧化铝微粉、10wt%的勃姆石和5wt%的α-Al2O3微粉为原料,外加所述原料22wt%的淀粉和1.8wt%的硼砂,混合,得混合料;将所述混合料在球磨机中干混30min,再外加所述原料2wt%的有机结合剂,球磨30min;在55MPa条件下机压成型,在110℃条件下干燥12h,然后在1500℃条件下保温3h,制得六铝酸钙/钛酸铝多孔陶瓷材料。
所述钛铁渣微粉的主要化学成分是:Al2O3为75.8wt%,CaO为10.05wt%,TiO2为11.03wt%,Fe2O3为0.62wt%,MgO为1.41wt%;所述钛铁渣微粉的密度为3.28g/cm3,钛铁渣微粉的粒度≤60μm。
所述氢氧化铝微粉的Al2O3含量为65.3wt%。
所述勃姆石微粉的Al2O3含量为84.5wt%。
所述α-Al2O3微粉的Al2O3含量为99.91wt%。
所述硼砂的Na2B4O7·5H2O含量为99.3wt%。
所述有机结合剂为磷酸二氢钠。
本具体实施方式与现有技术相比具有以下优点:
1、本具体实施方式以钛铁渣微粉、氢氧化铝微粉、勃姆石和α-Al2O3微粉为原料,外加淀粉为造孔剂和硼砂为助溶剂,经过干混、机压成型、干燥和烧成,工艺简单;所采用的原料钛铁渣的主晶相为钛铝酸钙、六铝酸钙和钛酸钙等,来源丰富,成本低廉,能显著降低六铝酸钙/钛酸铝多孔陶瓷的制备成本。
2、本具体实施方式采用的主要原料为钛铁渣,钛铁渣具有高的熔点、较高的常温强度、较低的热膨胀系数和导热系数,显著提高了六铝酸钙/钛酸铝多孔陶瓷的常温力学性能和隔热性能。
3、本具体实施方式利用氢氧化铝和勃姆石高温处理过程中的原位分解使材料产生疏松多孔的结构,提高了六铝酸钙/钛酸铝多孔陶瓷的真气孔率,降低了六铝酸钙/钛酸铝多孔陶瓷的导热性能。
4、本具体实施方式利用钛铁渣的多相性,如钛铁渣中的钛铝酸钙、二铝酸钙和钛酸钙等能与氢氧化铝和勃姆石分解后产生的氧化铝在热处理后反应生成钛酸铝,显著提高了六铝酸钙/钛酸铝多孔陶瓷的强度和比表面积,同时钛铁渣中的杂质Fe2O3、MgO能提高钛酸铝的稳定性,抑制其高温下的分解。
因此,本具体实施方式具有成本低廉和和工艺简单的优点,所制备的六铝酸钙/钛酸铝多孔陶瓷气孔率高、热导率低、物相稳定不易分解、常温强度较大和热震稳定性优良。
Claims (8)
1.一种六铝酸钙/钛酸铝多孔陶瓷的制备方法,其特征在于:以55~65wt%的钛铁渣微粉、15~20wt%的氢氧化铝微粉、10~20wt%的勃姆石和5~15wt%的α-Al2O3微粉为原料,外加所述原料20~25wt%的淀粉和1~2wt%的硼砂,混合,得混合料;将所述混合料在球磨机中干混30~60min,再外加所述原料2~5wt%的有机结合剂,球磨30~35min;在50~55MPa条件下机压成型,在100~110℃条件下干燥12~24h,然后在1350~1500℃条件下保温2~3h,制得六铝酸钙/钛酸铝多孔陶瓷材料。
2.根据权利要求1所述的六铝酸钙/钛酸铝多孔陶瓷的制备方法,其特征在于所述钛铁渣微粉的主要化学成分是:Al2O3≥73wt%,CaO≥10wt%,TiO2≥11wt%,Fe2O3≥0.6wt%,MgO≥1.4wt%;所述钛铁渣微粉的密度为3.28g/cm3,钛铁渣微粉的粒度≤60μm。
3.根据权利要求1所述的六铝酸钙/钛酸铝多孔陶瓷的制备方法,其特征在于所述氢氧化铝微粉的Al2O3含量≥65wt%;氢氧化铝微粉的粒度≤10μm。
4.根据权利要求1所述的六铝酸钙/钛酸铝多孔陶瓷的制备方法,其特征在于所述勃姆石微粉的Al2O3含量≥84wt%;勃姆石微粉的粒度≤20μm。
5.根据权利要求1所述的六铝酸钙/钛酸铝多孔陶瓷的制备方法,其特征在于所述α-Al2O3微粉的Al2O3含量≥99.9wt%;α-Al2O3微粉的粒度≤0.025mm。
6.根据权利要求1所述的六铝酸钙/钛酸铝多孔陶瓷的制备方法,其特征在于所述硼砂的Na2B4O7·5H2O含量≥99wt%;硼砂的粒度≤0.6mm。
7.根据权利要求1所述的六铝酸钙/钛酸铝多孔陶瓷的制备方法,其特征在于所述有机结合剂为磷酸二氢钠、聚乙烯醇和树脂中的一种。
8.一种六铝酸钙/钛酸铝多孔陶瓷,其特征在于所述六铝酸钙/钛酸铝多孔陶瓷是根据权利要求1~7项中任一项所述的六铝酸钙/钛酸铝多孔陶瓷的制备方法所制备的六铝酸钙/钛酸铝多孔陶瓷。
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