CN109626979B - 一种孔形可调的硅酸钙多孔陶瓷膜的制备方法 - Google Patents

一种孔形可调的硅酸钙多孔陶瓷膜的制备方法 Download PDF

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CN109626979B
CN109626979B CN201910117174.9A CN201910117174A CN109626979B CN 109626979 B CN109626979 B CN 109626979B CN 201910117174 A CN201910117174 A CN 201910117174A CN 109626979 B CN109626979 B CN 109626979B
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胡月
肖珍
叶灿
武雨茜
王兴明
王焕平
徐时清
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Abstract

本发明公开了一种孔形可调的硅酸钙多孔陶瓷膜的制备方法，包括：将碳类物质均匀分散在无水乙醇中，获得碳的悬浮液；硝酸钙溶解在去离子水中，同时将正硅酸乙酯溶于无水乙醇后缓慢滴加至硝酸钙溶液中，混合均匀；再将碳悬浮液滴加至混合溶液中，经超声分散均匀；调节pH值至酸性，并缓慢加入一定浓度的聚乙二醇(PEG)溶液，搅拌混合使其成为溶胶；经成化、干燥后获得干凝胶；将干凝胶研磨成粉模压成型，保温去除有机物，经冷却后放入等静压机中进行等静压，烧结，即可获得硅酸钙多孔陶瓷膜。本发明制备的多孔陶瓷膜具有孔隙分布均匀、孔的形貌可控、孔径细小、弯曲强度高等特点，在污水过滤、空气净化等领域具有重要的应用前景。

Description

一种孔形可调的硅酸钙多孔陶瓷膜的制备方法
技术领域
本发明涉及一种制备多孔材料的方法，具体涉及一种孔形可调的硅酸钙多孔陶瓷膜的制备方法，属于材料科学技术领域。
背景技术
多孔陶瓷是近年来广泛受到关注的一种新型材料，因其独特的孔隙结构可实现多种功能特性，所以又称气孔功能材料。多孔陶瓷不仅具有优异的稳定性、耐高温腐蚀性，而且还具有较大的比表面积、高孔隙率、高渗透性、较低的电导率等优点，可用作过滤材料、催化剂载体、保温隔热材料、生物功能材料等,目前已经广泛应用于化工、能源、冶金、生物医药、环境保护、航空航天等诸多领域。
目前，多孔陶瓷的孔径一般在3～5μm左右，很难将孔径做到更小，要想获得更好的过滤效果，必须将孔径做到更小甚至达到纳米级。硅酸钙是一种具有极好生物活性和介电性能的材料，目前已被应用到生物医学、介电材料等领域；早在Pan(J.Mech.Behavior.Biomed.Mater.2016,55:120-126)等人研究表明高温烧结获得的硅酸钙结构不致密之前，林开利(无机材料学报,2005,20:962)等人就已经成功制备出了硅酸钙生物微球并用于体外活性及降解性研究，但这种多孔陶瓷孔径很大，在200～500μm之间；有最新专利表示(李明辉，中国计量学院，ZL201610014543.8，2018-4-20)，利用固相法能制备出孔径小于100nm的硅酸钙多孔陶瓷，大大促进了硅酸钙多孔陶瓷的发展；然而，孔径更小的硅酸钙多孔陶瓷膜还鲜见报道；此外，通过加入不同的碳类物质来调节孔的形状，从而获得不同孔型的硅酸钙多孔陶瓷膜的研究未见报道。
发明内容
本发明的目的在于提供一种孔形可调的硅酸钙多孔陶瓷膜的制备方法，为实现上述目的，本发明采用的技术方案如下：
一种孔形可调的硅酸钙多孔陶瓷膜的制备方法，采用湿化学结合固相烧结法实现，主要包括以下步骤：
(1)称取碳类物质于无水乙醇中，经超声分散，获得均匀的碳悬浮液；所述的碳类物质选自炭黑、碳纳米纤维、碳纳米管、石墨烯、活性炭；
(2)称取摩尔比为1：1的硝酸钙和正硅酸乙酯；将硝酸钙于去离子水中溶解，同时将正硅酸乙酯溶于无水乙醇；并在磁力搅拌的条件下，将正硅酸乙酯溶液滴加至硝酸钙溶液中，磁力搅拌使其混合均匀；
(3)将第(1)步获得的碳悬浮液与第(2)步获得的混合溶液在磁力搅拌的条件下混合，随后进行超声震荡，使碳类物质在混合溶液中分散均匀；
(4)调节溶液的pH值至酸性，并加入浓度为10～30g/L的聚乙二醇(PEG)溶液，搅拌混合使其成为溶胶；经成化、干燥后获得干凝胶；
(5)等静压成型：在干凝胶中加入少量粘结剂进行造粒，待其完全均匀分散后，先于10MPa的压力下成型，然后于500度保温2小时，以排除有机物，冷却后再放入等静压机中，于200MPa下等静压成型；
(6)烧结：将等静压后的样品置于高温炉中，在800～950℃条件下保温2～6小时，随后升温至1250～1350℃保温2～6小时，最后随炉冷却至室温，获得硅酸钙多孔陶瓷膜。
本发明具有以下有益效果：
(1)本发明采用湿化学法先制得干凝胶再结合固相烧结成型获得多孔硅酸钙陶瓷膜，通过采用不同的碳类物质可以有效调控孔的形貌结构和孔径大小，从而获得不同性能的硅酸钙多孔陶瓷膜，应用到多个领域；尤其是当碳类物质采用炭黑时，制得的多孔陶瓷膜其孔隙均匀细密，孔径可达10～30nm。
(2)采用湿化学方法获得的硅酸钙多孔陶瓷膜，孔隙分布均匀、孔径可控、强度高；将该陶瓷膜制成实物(如净水器、防雾霾口罩等)应用在污水处理和空气净化等领域，具有重要的应用前景。
附图说明
图1是实施例1采用湿化学方法制备的硅酸钙多孔陶瓷膜的XRD图谱；
图2是实施例2采用湿化学方法制备的硅酸钙多孔陶瓷膜的SEM照片；
具体实施方式
下面结合实例对本发明作进一步描述。
实施例1：
将炭黑溶于无水乙醇中，经超声分散，获得质量分数为5％的均匀的炭黑悬浮液；按摩尔比1:1称取硝酸钙和正硅酸乙酯，将硝酸钙于去离子水中溶解，同时，将正硅酸乙酯于无水乙醇中溶解后，缓慢滴加到硝酸钙溶液中，经磁力搅拌成均匀混合溶液；随后，将炭黑悬浮液滴加到硝酸钙/正硅酸乙酯的混合溶液中，经超声震荡，使其分散均匀；调节溶液的pH值至酸性，随后加入20g/L的PEG溶液，搅拌混合使其成为溶胶；经成化、干燥后获得干凝胶；在干凝胶中加入少量粘结剂进行造粒，待其完全均匀分散后，先于10MPa的压力下成型，然后于500度保温2小时，以排除有机物，冷却后再放入等静压机中，于200MPa下等静压成型；将等静压后的产物放在高温炉中，升温到850℃保温4小时，接着继续升温到1260℃保温3小时，最后随炉冷却至室温，获得具有圆形多孔的硅酸钙多孔陶瓷膜。陶瓷膜中孔径为10～30nm。
实施例2：
将活性炭于无水乙醇中，经超声分散，获得质量分数为2％的均匀的活性炭悬浮液；按摩尔比1:1称取硝酸钙和正硅酸乙酯，将硝酸钙于去离子水中溶解，同时，将正硅酸乙酯于无水乙醇中溶解后，缓慢滴加到硝酸钙溶液中，经磁力搅拌成均匀混合溶液；随后，将活性炭悬浮液滴加到硝酸钙/正硅酸乙酯的混合溶液中，经超声震荡，使其分散均匀；调节溶液的pH值至酸性，随后加入10g/L的PEG溶液，搅拌混合使其成为溶胶；经成化、干燥后获得干凝胶；在干凝胶中加入少量粘结剂进行造粒，待其完全均匀分散后，先于10MPa的压力下成型，然后于500度保温2小时，以排除有机物，冷却后再放入等静压机中，于200MPa下等静压成型；将等静压后的产物放在高温炉中，升温到800℃保温2小时，接着继续升温到1340℃保温2小时，最后随炉冷却至室温，获得具有球形不规则多孔的硅酸钙多孔陶瓷膜。
实施例3：
将碳纳米管于无水乙醇中，经超声分散，获得质量分数为3％的均匀的碳纳米管悬浮液；按摩尔比1:1称取硝酸钙和正硅酸乙酯，将硝酸钙在去离子水中溶解，同时，将正硅酸乙酯于无水乙醇中溶解后，缓慢滴加到硝酸钙溶液中，经磁力搅拌成均匀混合溶液；随后，将碳纳米管悬浮液滴加到硝酸钙/正硅酸乙酯的混合溶液中，经超声震荡，使其分散均匀；调节溶液的pH值至酸性，随后加入20g/L的PEG溶液，搅拌混合使其成为溶胶；经成化、干燥后获得干凝胶；在干凝胶中加入少量粘结剂进行造粒，待其完全均匀分散后，先于10MPa的压力下成型，然后于500度保温2小时，以排除有机物，冷却后再放入等静压机中，于200MPa下等静压成型；将等静压后的产物放在高温炉中，升温到750℃保温6小时，接着继续升温到1300℃保温4小时，最后随炉冷却至室温，获得具有狭长隧道状多孔的硅酸钙多孔陶瓷膜。
与现有制备硅酸钙多孔陶瓷膜的方法相比，本发明采用湿化学和固相烧结相结合的方法，不仅实现了超细孔径的制备(孔径可达到10～30nm级别)，而且可以实现对孔径形貌的调节，获得隧道状多孔、层片状多孔的陶瓷膜，可以满足不同应用需求。

Claims (4)

1.一种孔形可调的硅酸钙多孔陶瓷膜的制备方法，其特征在于，采用湿化学结合固相烧结法实现，具体包括以下步骤：
(1)称取碳类物质于无水乙醇中，经超声分散，获得均匀的碳悬浮液；所述的碳类物质选自炭黑、碳纳米纤维、碳纳米管、石墨烯、活性炭；
(2)称取摩尔比为1：1的硝酸钙和正硅酸乙酯；将硝酸钙于去离子水中溶解，同时将正硅酸乙酯溶于无水乙醇；并在磁力搅拌的条件下，将正硅酸乙酯溶液滴加至硝酸钙溶液中，磁力搅拌使其混合均匀；
(3)将第(1)步获得的碳悬浮液与第(2)步获得的混合溶液在磁力搅拌的条件下混合，随后进行超声震荡，使碳类物质在混合溶液中分散均匀；
(4)调节溶液的pH值至酸性，并加入浓度为10～30g/L的聚乙二醇(PEG)溶液，搅拌混合使其成为溶胶；经成化、干燥后获得干凝胶；
(5)等静压成型：在干凝胶中加入粘结剂进行造粒，待其完全均匀分散后，先于10MPa的压力下成型，然后于500℃保温2小时，以排除有机物，冷却后再放入等静压机中，于200MPa下等静压成型；
(6)烧结：将等静压后的样品置于高温炉中，在800～950℃条件下保温2～6小时，随后升温至1250～1350℃保温2～6小时，最后随炉冷却至室温，获得硅酸钙多孔陶瓷膜。
2.一种硅酸钙多孔陶瓷膜，其特征在于，采用如权利要求1所述的方法制得，其中碳类物质采用炭黑，所制得的硅酸钙多孔陶瓷膜的孔径为10～30nm。
3.一种硅酸钙多孔陶瓷膜，其特征在于，采用如权利要求1所述的方法制得，其中碳类物质采用碳纳米纤维或碳纳米管，所制得的硅酸钙多孔陶瓷膜的孔为隧道状多孔。
4.一种硅酸钙多孔陶瓷膜，其特征在于，采用如权利要求1所述的方法制得，其中碳类物质采用石墨烯，所制得的硅酸钙多孔陶瓷膜的孔为层片状多孔。
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