Preparation of under-liquid superamphiphobic Cu2O films and selective separation performance of oil-water emulsions
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摘要: 为了实现液下超双疏材料选择性分离油水乳液，本文从尺寸筛分、润湿性两方面入手制备Cu2O膜以解决油水乳液难分离现象。采用恒电位电化学沉积法在不锈钢网(SSM)表面沉积氧化亚铜(Cu2O)结构薄膜(Cu2O@SSM)，该膜无需低表面能物质修饰，即可具有液下超双疏特性和良好的乳液选择性分离性能。根据“尺寸筛分”效应，通过在不同目数原始不锈钢网上镀Cu2O，探究不同孔径尺寸的Cu2O@SSM膜对乳液分离效果的影响，得出可实现油水乳液分离的膜孔径尺寸。利用SEM、EDS、XRD、接触角测量仪对其表面微观形貌、成分和润湿性能进行表征，红外光谱含油量分析仪和卡尔费休水分测定仪测定分离前后乳液的油浓度和水浓度。结果表明Cu2O@SSM膜在空气中油、水接触角均为0°，呈现超亲状态，水下油接触角(UWOCA)和油下水接触角(UOWCA)均超过150°，呈现液下超双疏状态，且该自适应润湿性Cu2O@SSM膜用水或油预润湿即可实现油水乳液的选择性分离，即使对含表面活性剂乳液的分离效率仍在96%以上。因此，本文所制备的液下超双疏Cu2O@SSM膜，对油包水乳液和水包油乳液均表现出良好的选择性分离性能，为乳液选择性分离方面的研究提供了新思路。
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关键词:
- 油水乳液分离 /
- 选择性分离 /
- 液下超双疏 /
- 尺寸筛分 /
- 自适应润湿性Cu2O@SSM膜
Abstract: In order to achieve the selective separation of oil-water emulsions by under-liquid superamphiphobic materials, the prepared samples were fabricated by considering two aspects: substrate pore size and wettability, to deal with the phenomenon of difficult separation of oil-water emulsions. In this paper, we used electrochemical constant potential deposition method to deposit the Cu2O film with the rough structure on the surface of stainless steel mesh (SSM), which abbreviated as Cu2O@SSM. The prepared sample of Cu2O@SSM showed the typical characteristics of under-liquid superamphiphobic, and it can easily separate the lotion without the modification of low surface energy materials. According to the size screening effect, the pore size was reduced by coating Cu2O on stainless steel mesh with different meshes, so as to explore the effect of Cu2O@SSM film with different pore sizes on the separation performance of emulsion. Besides, the surface morphology, composition, and wetting performance of the products were characterized using the scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), and contact angle measurement, respectively. The water and oil droplets on the surface of Cu2O@SSM showed both superhydrophilic and superoleophilic state with contact angle near to 0° in air. Moreover, the contact angle of underwater superoleophobic and underoil superhydrophobicity exceeded 150°, indicating an under-liquid dual superlyophobic state. By pre-wetting the prepared sample surface with water or oil, the adaptive wettability Cu2O@SSM sample can realize the selective separation of oil-water lotion, and the separation efficiency of oil-water lotion is more than 96 %. The Cu2O@SSM film shows the typical selective separation behaviors, which provides a new idea for the selective separation of oil/water emulsions. -
图 3 原始不锈钢网(SSM)和Cu2O@SSM复合膜的SEM图像(a-f)及表面形貌放大图像(g)
Figure 3. SEM images (a-f) and enlarged surface topography images (g) of the original stainless steel mesh (SSM) and Cu2O@SSM composite film
图 4 原始不锈钢网和Cu2O@SSM膜XRD图像
Figure 4. XRD results of original stainless steel mesh and Cu2O@SSM films
图 6 原始不锈钢网与Cu2O@SSM膜接触角图像
Figure 6. CA images of original stainless steel mesh and Cu2O@SSM film
图 7 乳液分离图像：(a) 分离过程图(b) Cu2O@SSM膜图 (c) 水包油乳液(d) 油包水乳液
Figure 7. Emulsion separation (a) separation process (b) film (c)water in oil emulsion (d) oil in water emulsion
图 8 有/无表面活性剂水包油乳液分离对比图
Figure 8. Comparison of oil in water emulsion separations with/without surfactant
图 9 有/无表面活性剂油包水乳液分离对比图
Figure 9. Comparison water of in oil emulsion separations with/without surfactant
图 11 Cu2O@SSM膜循环次数与WOCA、分离效率的关系
Figure 11. Relationship between the number of cycles and WOCA and separation efficiency on the Cu2O@SSM film
表 1 不同目数膜分离效果表
Table 1. Separation effect of different mesh films
Sieve pore
size/μmOriginal pore
Size/μmCu2O@SSM pore
size/μmEmulsion separation
effectFlux/
(L·m−2·h−1)Immiscible oil-water
separation effectFlux/
(L·m−2·h−1)36 40 14 × - √ 2120 18 22 8 × - √ 1733 7 10 3 √ 1020 √ 1510 6.4 8 2 √ 901 √ 1458 4.5 3 ~0 × - × - 2.6 2.5 ~0 × - × - Notes: “-” means unmeasured separation flux. 
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