添加剂及底膜对溶胶—凝胶法制备ZrO_2超滤膜的影响研究
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摘要
本文以解决溶胶—凝胶法路线制备陶瓷超滤膜关键技术为背景,针对溶胶—凝胶法制备氧化锆超滤膜这一具体的制备过程,开展有关研究工作,以期为实现陶瓷超滤膜的工业化提供必要的技术基础。
稳定的制膜液是制备出完整、无缺陷溶胶膜的首要条件。本文采用以无机锆盐(Zr(NO_3)_4·5H_2O)为前驱体制备的稳定锆溶胶为原料,详细研究了增稠剂和干燥控制剂的种类及加入量对制膜液稳定性的影响,并进一步考察了制膜液的稳定性对成膜过程的影响,同时考察了晶型稳定剂对成膜过程的影响。结果表明,在本文所采用的锆溶胶体系中,以PVA为增稠剂、丙三醇等中性物质为干燥控制剂最为合适;研究发现,通过控制PVA的加入量在2～3%,可以防止内渗透且获得较为完整的溶胶膜层,添加中性干燥控制剂能够有效地防止膜层开裂;在溶胶中引入晶型稳定剂硝酸钇(Y:Zr=0.08:0.92),可以防止氧化锆由于晶型的转变而可能导致的膜层开裂和缺陷。
底膜对溶胶—凝胶成膜过程的影响十分显著。本文从底膜的微结构和材料性质两方面入手,分析底膜微结构对所形成膜的微结构的影响以及底膜与膜之间的材料性质匹配问题,从而确定适合的底膜条件。采用EDX分析制膜液在不同孔径底膜下的内渗透行为,结果表明,底膜孔径越小,越能防止溶胶的内渗透现象且越易在底膜表面形成膜层;提出通过在相同功率超声相同时间下,膜层质量损失率来表征膜层与底膜材质间性质匹配问题,结果表明,在ZrO_2底膜上所形成的溶胶膜层质量损失率最小;但是在平均孔径为0.2μm的ZrO_2、Al_2O_3、TiO_2三种材质底膜上浸浆涂膜5次后,大孔缺陷问题依然存在。
针对溶胶—凝胶法制备陶瓷超滤膜制膜工艺控制参数优化问题,对浸浆时间,干燥条件和烧结制度等工艺参数进行系统的优化研究。结果表明一次涂膜后膜厚与浸浆时间的平方根成正比,浸浆时间控制在60s左右较为合适;随着涂膜次数的增加,膜厚有所增加且增加的趋势逐渐变缓,最后膜厚趋于一定。涂膜5次以后(600℃下烧结2小时),膜层基本达到完整,纯水通量大约为100 L·m~(-2)·h~(-1),对500000D和70000D葡聚糖截留率分别为80%和20%;干燥过程中增加湿度有效防止了膜层的开裂现象;孔径随着烧结温度的升高而增大,从而导致截留性能的下降;采用压汞仪表征氧化锆超滤膜的孔径分布,其最可几孔径在40～50nm;采用SEM表征氧化锆超滤膜的微观形貌,膜的表面较为完整光滑,顶层氧化锆溶胶膜厚度约为1μm。
With the solution to the crucial technique in the preparation of ceramic ultrafiltration membrane by means of Sol-Gel method as the groud work, this paper studies the concrete preparation of zirconia ultrafiltration membrane so as to provide necessary technique foundations for the realization of the industrialization of ceramic ultrafiltration membrane.Suspension stability is the primary factor to prepare integrated membrane without defect. With stable zirconium sol prepared by Zr(NO_3)_4·5H_2O as raw materials, this paper studies in details the effects of the types and doses of organic binders and Drying Control Chemical Additives (DCCA) upon the stability of the suspension. Meanwhile, the effect of stability of suspension and crystal phase stabilizer upon the process of membrane is explored as well. It shows that PVA and neutral DCCA such as glycerol are most suitable for zirconium sol system selected in this paper. It also indicates that sol is not absorbed by the support and the surface of membrane is homogeneous throughout by controlling the amount of PVA with 2~3%. Membrane is crack-free by adding neutral DCCA. Yttrium nitrate(Y:Zr=0.08:0.92) could avoid membrane defect caused by crystal phase transformation.Substrate has a distinct effect on membrane preparation by Sol-Gel method. In this paper, the effect of substrate micro-structure on membrane micro-structure and material property matching problem between substrate and membrane are discussed at length in order to choose suitable substrate for suspension. EDX analysis is introduced to observe suspension absorbed into substrates with different pore diameter. It shows that the smaller the substrate pore diameter, the easier the fact that membrane could form on it. Membrane mass loss rate under the same ultrasound power and ultrasound time is raised to represent material property matching problem. It shows membrane mass loss rate is the least on zirconia substrate. However, after dip-coating for 5 times on three different substrates, large pore size defects still exists.Influences of the dip-coating time, dry conditions and sintering program are investigated systemically. It is found the thickness of the top layer increases linearly with the square root of the dip-coating time after coating for 1 time. It is suitable to control dip-coating time at 60s. With the increase of coating frequency, membrane thickness also increases and then goes to a constant gradually. After coats for 5 times (600℃ for 2h), membrane almost reaches intergrity. Pure water flux is about 100 L·m~(-2)·h~(-1) and rejection rate of 500000D dextran and 70000D dextran are 80% and 20% respectively. Membrane
crack is avoided effectively by introducing humidity during dry process. Pore diameter increases with the increase of the sintering temperature , which leads to a decrease in rejection rate. Pore diameter distribution is measured between 40nm and 50nm by mercury porosimetry. Surface and cross-sectional SEM of zirconia ultrafiltration membrane show that membrane surface is smooth and the top membrane thickness is about lum.
稳定的制膜液是制备出完整、无缺陷溶胶膜的首要条件。本文采用以无机锆盐(Zr(NO_3)_4·5H_2O)为前驱体制备的稳定锆溶胶为原料,详细研究了增稠剂和干燥控制剂的种类及加入量对制膜液稳定性的影响,并进一步考察了制膜液的稳定性对成膜过程的影响,同时考察了晶型稳定剂对成膜过程的影响。结果表明,在本文所采用的锆溶胶体系中,以PVA为增稠剂、丙三醇等中性物质为干燥控制剂最为合适;研究发现,通过控制PVA的加入量在2～3%,可以防止内渗透且获得较为完整的溶胶膜层,添加中性干燥控制剂能够有效地防止膜层开裂;在溶胶中引入晶型稳定剂硝酸钇(Y:Zr=0.08:0.92),可以防止氧化锆由于晶型的转变而可能导致的膜层开裂和缺陷。
底膜对溶胶—凝胶成膜过程的影响十分显著。本文从底膜的微结构和材料性质两方面入手,分析底膜微结构对所形成膜的微结构的影响以及底膜与膜之间的材料性质匹配问题,从而确定适合的底膜条件。采用EDX分析制膜液在不同孔径底膜下的内渗透行为,结果表明,底膜孔径越小,越能防止溶胶的内渗透现象且越易在底膜表面形成膜层;提出通过在相同功率超声相同时间下,膜层质量损失率来表征膜层与底膜材质间性质匹配问题,结果表明,在ZrO_2底膜上所形成的溶胶膜层质量损失率最小;但是在平均孔径为0.2μm的ZrO_2、Al_2O_3、TiO_2三种材质底膜上浸浆涂膜5次后,大孔缺陷问题依然存在。
针对溶胶—凝胶法制备陶瓷超滤膜制膜工艺控制参数优化问题,对浸浆时间,干燥条件和烧结制度等工艺参数进行系统的优化研究。结果表明一次涂膜后膜厚与浸浆时间的平方根成正比,浸浆时间控制在60s左右较为合适;随着涂膜次数的增加,膜厚有所增加且增加的趋势逐渐变缓,最后膜厚趋于一定。涂膜5次以后(600℃下烧结2小时),膜层基本达到完整,纯水通量大约为100 L·m~(-2)·h~(-1),对500000D和70000D葡聚糖截留率分别为80%和20%;干燥过程中增加湿度有效防止了膜层的开裂现象;孔径随着烧结温度的升高而增大,从而导致截留性能的下降;采用压汞仪表征氧化锆超滤膜的孔径分布,其最可几孔径在40～50nm;采用SEM表征氧化锆超滤膜的微观形貌,膜的表面较为完整光滑,顶层氧化锆溶胶膜厚度约为1μm。
With the solution to the crucial technique in the preparation of ceramic ultrafiltration membrane by means of Sol-Gel method as the groud work, this paper studies the concrete preparation of zirconia ultrafiltration membrane so as to provide necessary technique foundations for the realization of the industrialization of ceramic ultrafiltration membrane.Suspension stability is the primary factor to prepare integrated membrane without defect. With stable zirconium sol prepared by Zr(NO_3)_4·5H_2O as raw materials, this paper studies in details the effects of the types and doses of organic binders and Drying Control Chemical Additives (DCCA) upon the stability of the suspension. Meanwhile, the effect of stability of suspension and crystal phase stabilizer upon the process of membrane is explored as well. It shows that PVA and neutral DCCA such as glycerol are most suitable for zirconium sol system selected in this paper. It also indicates that sol is not absorbed by the support and the surface of membrane is homogeneous throughout by controlling the amount of PVA with 2~3%. Membrane is crack-free by adding neutral DCCA. Yttrium nitrate(Y:Zr=0.08:0.92) could avoid membrane defect caused by crystal phase transformation.Substrate has a distinct effect on membrane preparation by Sol-Gel method. In this paper, the effect of substrate micro-structure on membrane micro-structure and material property matching problem between substrate and membrane are discussed at length in order to choose suitable substrate for suspension. EDX analysis is introduced to observe suspension absorbed into substrates with different pore diameter. It shows that the smaller the substrate pore diameter, the easier the fact that membrane could form on it. Membrane mass loss rate under the same ultrasound power and ultrasound time is raised to represent material property matching problem. It shows membrane mass loss rate is the least on zirconia substrate. However, after dip-coating for 5 times on three different substrates, large pore size defects still exists.Influences of the dip-coating time, dry conditions and sintering program are investigated systemically. It is found the thickness of the top layer increases linearly with the square root of the dip-coating time after coating for 1 time. It is suitable to control dip-coating time at 60s. With the increase of coating frequency, membrane thickness also increases and then goes to a constant gradually. After coats for 5 times (600℃ for 2h), membrane almost reaches intergrity. Pure water flux is about 100 L·m~(-2)·h~(-1) and rejection rate of 500000D dextran and 70000D dextran are 80% and 20% respectively. Membrane
crack is avoided effectively by introducing humidity during dry process. Pore diameter increases with the increase of the sintering temperature , which leads to a decrease in rejection rate. Pore diameter distribution is measured between 40nm and 50nm by mercury porosimetry. Surface and cross-sectional SEM of zirconia ultrafiltration membrane show that membrane surface is smooth and the top membrane thickness is about lum.
引文
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