CN114685188A - 一种超疏水碳化硅陶瓷膜及其制备方法 - Google Patents
一种超疏水碳化硅陶瓷膜及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种超疏水碳化硅陶瓷膜及其制备方法，属于陶瓷膜技术领域。包括以下步骤：(1)先用高锰酸钾对碳化硅膜进行表面活化1h；(2)然后采用化学浴沉积的方法在多孔碳化硅膜表面生长ZnO纳米球或纳米花结构；(3)最后对具有ZnO纳米结构的碳化硅膜进行硅烷接枝降低其表面自由能。本发明制备的碳化硅陶瓷膜表面水接触角可在150‑180°进行调控，表现出良好的超疏水性能，将其应用于油包水乳化液的分离，可以明显提升油通量和水截留率。
Description
技术领域
本发明涉及一种超疏水碳化硅陶瓷膜及其制备方法，属于陶瓷膜技术领域。
背景技术
随着工业化的快速发展，能源化工、食品医药、机械制造等行业每年产生数百万吨的含水废油，直接将含水废油排放到水体中将造成严重的资源浪费和环境污染问题。这类以油(脂肪、碳氢化合物或各种石油馏分如柴油、汽油、煤油等)为连续相、水为分散相的油包水乳化液分离问题一直都是困扰世界的难题。传统的陶瓷膜由于表面具有大量羟基具有的亲水特性，无法满足这类油包水乳化液的分离要求。对陶瓷膜进行超疏水改性，使其具有超疏水表面特性，对于提升油包水乳化液分离过程的效率具有非常重要的价值。
中国专利号CN107352980A公开了一种具有超疏水表面的氧化铝平板陶瓷膜及其制备方法，首先将氧化铝微粉和助熔剂混合，以硫酸钛为前驱体，对氧化铝颗粒表面进行修饰；然后采用相转化流延法和高温烧结制备陶瓷膜；最后将陶瓷膜采用微波辅助，表面接枝氟硅氧烷，得到具有超疏水表面的氧化铝平板陶瓷膜。这种方法虽然成功改性得到了超疏水陶瓷膜，但存在操作工序复杂，成本较高的缺点。
中国专利号CN111635258A公开了一种基于陶瓷膜的TiO2超疏水改性方法，通过浸涂-煅烧方法得到二氧化钛种子层，并将其牢牢固定在氧化铝陶瓷衬底上；通过水热反应生成二氧化钛纳米棒；最后，将长有二氧化钛纳米棒的陶瓷膜浸泡在PDTS乙醇溶液中进行疏水化处理，获得稳定的超疏水表面，接触角为152°。中国专利号CN106086197A公开了一种超疏水陶瓷膜材料的制备方法，将聚四氟乙烯粉末均匀地铺展在预处理后的多孔陶瓷膜表面，而后放入高温炉中，在氮气气氛保护下处理12h得到一种超疏水陶瓷膜材料，接触角达155°。上述两种方法虽然都拥有操作简单，成本较低的优点，但疏水程度仍然较低，还不具备优良的超疏水性能。
基于上述问题，亟需开发一种工序简单、低成本、疏水性能强的新型超疏水陶瓷膜材料，以实现油包水乳化液的高效分离。
发明内容
基于工业中油包水乳化液难以分离的问题，本发明提供一种超疏水碳化硅陶瓷膜的制备方法。该超疏水碳化硅陶瓷膜表面具有极强的疏水性能，表面水滴接触角为150-180°且水滴滚动角小于10°，在油包水乳化液的分离过程中表现出良好的分离性能。
一种超疏水碳化硅陶瓷膜的制备方法，其特征在于：碳化硅陶瓷膜的制备方法包括以下步骤：
(1)将多孔碳化硅陶瓷膜置于100℃沸水中进行清洗预处理，干燥，备用；
(2)将经过步骤(1)预处理后的碳化硅膜片置于高锰酸钾溶液中，在室温下表面活化1h-5h，取出后超声清洗，备用；
(3)将步骤(2)处理后的膜片放入装有ZnO化学沉积液的聚四氟乙烯烧杯中，在96℃的油浴下反应0.5h-3h，取出反应后的膜片用去离子水冲洗并烘干；
(4)将步骤(3)得到的膜片置于硅烷改性液中进行接枝，反应温度为40℃，反应时间为12h，反应结束后取出，使用1:1的酒精与水混合溶液冲洗膜表面后，在85℃的烘箱内干燥4h-12h，得到超疏水碳化硅陶瓷膜。
所述的高锰酸钾溶液中需加入体积分数为0.25％的叔丁醇，高锰酸钾浓度为20mM-100mM。所述的ZnO化学沉积液为含Zn2+前驱体、体积分数为5-10％的乙醇胺、体积分数为1％-5％的氨水的混合溶液，含Zn2+前驱体包括硫酸锌、醋酸锌、硝酸锌、氯化锌，浓度为10-100mM。所述的硅烷改性液是浓度为0.2mol/L的正辛基三乙氧基硅烷与无水乙醇的混合溶液。
本发明的有益效果在于：本发明的制备方法工艺简单，制备周期短，制备的超疏水碳化硅膜表面水滴接触角在150-180℃可调控同时具备低于10℃的水滴滚动角，表现出良好的超疏水性能。应用于油包水乳化液的分离过程时，相较于未改性的碳化硅陶瓷膜，能够大幅提升油通量和乳化水截留率。
附图说明
图1是实施例1所制备的超疏水碳化硅陶瓷膜的表面扫描电镜图，插图为该膜与水滴和油滴的接触实验。
图2是制备的三种超疏水碳化硅膜的表面水接触角和滚动角照片。
图3是空白碳化硅膜、实施例1-3所制备的三种超疏水碳化硅膜对于1000ppm水/正己烷乳化液的分离性能。
具体实施方式
下面通过具体实施例对本发明作进一步详细说明。
实施例1：
取平均孔径为250nm的碳化硅陶瓷膜片，膜片直径为41mm，厚度为2mm。首先在100℃沸水中对碳化硅膜片进行煮沸清洗，取出后在100℃下干燥4小时。将洗净后的碳化硅陶瓷膜置于含0.25％叔丁醇的高锰酸钾溶液中室温下反应1h，取出后洗净，得到表面活化的碳化硅膜。将表面活化后的碳化硅膜放入40mL ZnO化学沉积液(75mM硫酸锌、4mL乙醇胺、1mL氨水)中进行膜表面的ZnO化学浴沉积，在96℃的油浴条件下沉积3小时，得到具有ZnO纳米花的ZnO纳米花-碳化硅复合表面结构，参照图1所示。将该膜放入0.2mol/L正辛基三乙氧基硅烷溶液中，在40℃下反应12小时后取出在80℃的烘箱内干燥5小时，得到超疏水碳化硅陶瓷膜，其表面水接触角达到162.1°，滚动角为8°，如图2中a所示。
实施例2：
取平均孔径为250nm的碳化硅陶瓷膜片，膜片直径为41mm，厚度为2mm。首先在100℃沸水中对碳化硅膜片进行煮沸清洗，取出后在100℃下干燥4小时。将洗净后的碳化硅陶瓷膜置于含0.25％叔丁醇的高锰酸钾溶液中室温下反应1h，取出后洗净，得到表面活化的碳化硅膜。将表面活化后的碳化硅膜放入40mL ZnO化学沉积液(75mM醋酸锌、4mL乙醇胺、1mL氨水)中进行膜表面的ZnO化学浴沉积，在96℃的油浴条件下沉积3小时，得到具有ZnO纳米花的ZnO纳米花-碳化硅复合表面结构(图1)。将该膜放入0.2mol/L正辛基三乙氧基硅烷溶液中，在40℃下反应12小时后取出在80℃的烘箱内干燥5小时，得到超疏水碳化硅陶瓷膜，其表面水接触角达到170.3°，滚动角为4°，如图2中b所示。
实施例3：
取平均孔径为250nm的碳化硅陶瓷膜片，膜片直径为41mm，厚度为2mm。首先在100℃沸水中对碳化硅膜片进行煮沸清洗，取出后在100℃下干燥4小时。将洗净后的碳化硅陶瓷膜置于含0.25％叔丁醇的高锰酸钾溶液中室温下反应1h，取出后洗净，得到表面活化的碳化硅膜。将表面活化后的碳化硅膜放入40mL ZnO化学沉积液(75mM硝酸锌、4mL乙醇胺、1mL氨水)中进行膜表面的ZnO化学浴沉积，在96℃的油浴条件下沉积3小时，得到具有ZnO纳米花的ZnO纳米花-碳化硅复合表面结构(图1)。将该膜放入0.2mol/L正辛基三乙氧基硅烷溶液中，在40℃下反应12小时后取出在80℃的烘箱内干燥5小时，得到超疏水碳化硅陶瓷膜，其表面水接触角达到172.8°，滚动角为2°，如图2中c所示。
应用实施例：
参阅图3，将上述实施例1-3所得超疏水碳化陶瓷硅膜用于油包水乳化液的分离过程，对其进行分离性能评价。
在错流过滤装置中，分别装入上述所得超疏水碳化硅膜，以1000ppm水/正己烷乳化液为进料，在室温和1bar跨膜压力下，进行油水分离测试；过程中采用卡尔费休水分测定仪对滤出液进行水分测定。
实验结果表明，本发明所得超疏水碳化硅陶瓷膜均能够大幅提升未经改性的碳化硅膜对于油包水乳化液的分离性能，同时提升了其稳态油通量及对于水的截留率。
Claims (6)
1.一种超疏水碳化硅陶瓷膜，其特征在于，包括对称结构的多孔碳化硅陶瓷膜以及表面的ZnO纳米修饰结构，形成的ZnO修饰的碳化硅膜表面还覆有硅烷分子层。
2.根据权利要求1所述的超疏水碳化硅陶瓷膜，其特征在于，所述的对称结构的多孔碳化硅陶瓷膜是平均孔径为100-1000nm的片式膜，所述的ZnO纳米修饰结构是ZnO纳米球或ZnO纳米花；所述的超疏水为膜表面水滴接触角是150-180°，水滴滚动角小于10°。
3.权利要求1所述的超疏水碳化硅陶瓷膜制备方法包括以下步骤：
(1)将多孔碳化硅陶瓷膜片置于100℃沸水中进行清洗，然后放置在60-100℃的烘箱干燥4-12h备用；
(2)将经过步骤(1)清洗后的碳化硅膜片置于20-100mM高锰酸钾溶液中表面活化1-5h，超声清洗；
(3)将步骤(2)处理后的膜片放入装有ZnO化学沉积液的聚四氟乙烯烧杯中，使用96℃油浴进行加热，反应0.5-3h，取出反应后的膜片，使用去离子水冲洗膜片表面并放置在60-100℃的烘箱干燥4-12h备用；
(4)将步骤(3)得到的碳化硅膜片浸入硅烷改性液进行表面接枝，反应温度为40℃，反应时间为12h，反应结束后取出，使用1:1的酒精与水混合溶液冲洗膜表面后，在85℃的烘箱内干燥4-12h，得到超疏水碳化硅陶瓷膜。
4.根据权利要求3所述的超疏水碳化硅陶瓷膜制备方法，其特征在于，步骤(2)中的高锰酸钾溶液中需加入体积分数为0.25％的叔丁醇。
5.根据权利要求3所述的超疏水碳化硅陶瓷膜制备方法，其特征在于，步骤(3)中的ZnO化学沉积液为含Zn2+前驱体、体积分数为5-10％的乙醇胺、体积分数为1-5％的氨水的混合溶液，含Zn2+前驱体包括硫酸锌、醋酸锌、硝酸锌、氯化锌，浓度为10-100mM。
6.根据权利要求3所述的超疏水碳化硅陶瓷膜制备方法，其特征在于，步骤(4)中硅烷改性液是浓度为0.2mol/L的正辛基三乙氧基硅烷与无水乙醇的混合溶液。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106474947A (zh) * | 2016-12-14 | 2017-03-08 | 中国科学技术大学 | 一种表面疏水多孔陶瓷膜的制备方法 |
| CN112156813A (zh) * | 2020-08-21 | 2021-01-01 | 成都理工大学 | 双层结构的Co2+/ZnO材料及其制备方法 |
| CN112973474A (zh) * | 2019-12-02 | 2021-06-18 | 南京科技职业学院 | 一种碳化硅微滤膜的制备 |
| WO2021229444A1 (en) * | 2020-05-12 | 2021-11-18 | University Of Peradeniya | Novel and improved biodegradable face mask with inherent virucide, hydrophobic and hydrophillic properties with adjustable ear loops |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106474947A (zh) * | 2016-12-14 | 2017-03-08 | 中国科学技术大学 | 一种表面疏水多孔陶瓷膜的制备方法 |
| CN112973474A (zh) * | 2019-12-02 | 2021-06-18 | 南京科技职业学院 | 一种碳化硅微滤膜的制备 |
| WO2021229444A1 (en) * | 2020-05-12 | 2021-11-18 | University Of Peradeniya | Novel and improved biodegradable face mask with inherent virucide, hydrophobic and hydrophillic properties with adjustable ear loops |
| CN112156813A (zh) * | 2020-08-21 | 2021-01-01 | 成都理工大学 | 双层结构的Co2+/ZnO材料及其制备方法 |
Non-Patent Citations (2)
| Title |
|---|
| 李秀秀等: "Al2O3和SiC 微滤膜的疏水改性及其油固分离性能研究", 《化工学报》 * |
| 胡云浩等: "硅橡胶表面原位生长ZnO 纳米花构筑稳固超疏水表面", 《复合材料学报》 * |
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