Fabrication and properties of multifunctional CeO2/cellulose nanofibers composite superhydrophobic coating
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摘要: 自然界超疏水现象因独特的润湿性能被广泛关注,超疏水涂层的制备与应用尤为迫切。采用硝酸铈六水合物(Ce(NO3)3·6H2O)共沉淀法于纤维素纳米纤维(CNFs)表面合成二氧化铈(CeO2),通过十八烷基三甲基硅氧烷(OTMS)对其进行疏水改性,喷涂构筑得到超疏水涂层。探讨了CNFs、Ce(NO3)3·6H2O和OTMS不同质量比对超疏水涂层形貌和疏水性能的影响。结果表明:CNFs和Ce(NO3)3·6H2O质量比为1∶5和1∶7涂层具有实现超疏水特性的微/纳结构,其中CNFs、Ce(NO3)3·6H2O和OTMS质量比为1∶5∶10涂层接触角为(159.7±1.1)°,滚动角为(5.7±1.8)°,经过150°C高温处理3 h和UV照射36 h后接触角仍大于150°,同时具有良好的pH稳定性和一定的力学强度。涂层应用于玻璃、纸、木材和海绵等基体均可构筑超疏水表面并赋予其优异的自清洁性能,其中超疏水玻璃涂层对UV-A和UV-B紫外透过率分别为12.6%和0.1%,超疏水海绵吸油效率达94%左右。该超疏水涂层有望被用作保护材料并且拓展了稀土金属氧化物在纤维素基超疏水涂层领域的应用。Abstract: The superhydrophobic phenomenon in nature has attracted more attention due to its unique wettability. It is urgent that the preparation and application of superhydrophobic coating. Cerium dioxide (CeO2) was in situ synthesized on the surface of cellulose nanofibers (CNFs) by co-precipitation method using cerium nitrate hexahydrate (Ce(NO3)3·6H2O), following modified by octadecyltrimethoxysilane (OTMS) and the coating was constructed by spraying method. It investigated the effects of different mass ratios of CNFs, Ce(NO3)3·6H2O, and OTMS on coating morphology and hydrophobicity. The results show that the coatings consisting of CNFs, and Ce(NO3)3·6H2O with the mass ratios of 1∶5 and 1∶7 can construct the micro/nanostructure contributing to achieving superhydrophobic properties. When the mass ratios of CNFs, Ce(NO3)3·6H2O, and OTMS is 1∶5∶10, the coating static contact angle is (159.7±1.1)° and the sliding angle is (5.7±1.8)°. Its static contact angle can remain greater than 150° after the 150°C heating for 3 h and UV illumination for 36 h, meanwhile, possesses excellent pH stability and certain mecha-nical durability. When applied to glass, paper, wood, sponge, and other substrates, superhydrophobic surfaces can be constructed with excellent self-cleaning performance. The UV transmittance of superhydrophobic glass coating to UV-A and UV-B is 12.6% and 0.1%, respectively. The oil absorption efficiency of the superhydrophobic sponge is about 94%. This superhydrophobic coating is expected to use as a protective material and extends the application of rare earth metal oxidate in the cellulose-based superhydrophobic coating field.
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Key words:
- superhydrophobic /
- cellulose nanofibers /
- cerium dioxide /
- coating /
- in-situ synthesis /
- UV-shielding
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图 6 ((a)~(d)) CeO2/CNFs-X-Glass (X=1、3、5和7)的SEM图像;((e)~(h)) 10-O-CeO2/CNFs-X-Glass (X=1、3、5和7)的SEM图像;((i)~(l)) CNFs-Glass、CeO2-Glass、O-B-CeO2/CNFs-Glass和O-CeO2-Glass的SEM图像
Figure 6. ((a)-(d)) SEM images of O-CeO2/CNFs-X-Glass (X=1, 3, 5 and 7); ((e)-(h)) SEM images of 10-O-CeO2/CNFs-X-Glass (X=1, 3, 5 and 7); ((i)-(l)) SEM images of CNFs-Glass, CeO2-Glass, O-B-CeO2/CNFs-Glass and O-CeO2-Glass
图 7 Y-O-CeO2/CNFs-1-Glass (a)、Y-O-CeO2/CNFs-3-Glass (b)、 Y-O-CeO2/CNFs-5-Glass (c)和 Y-O-CeO2/CNFs-7-Glass (d) (Y=0、5、10和15)的接触角和滚动角
Figure 7. Static contact angle and sliding angle of Y-O-CeO2/CNFs-1-Glass (a), Y-O-CeO2/CNFs-3-Glass (b), Y-O-CeO2/CNFs-5-Glass (c), andY-O-CeO2/CNFs-7-Glass (d) (Y=0, 5, 10, and 15)
图 8 10-O-CeO2/CNFs-5-Glass在不同温度(a)、UV辐照(b)和不同pH值(c)处理一定时间后接触角变化;((d)~(i)) 在UV处理36 h和不同pH下处理10 h滴有亚甲基蓝的涂层照片
Figure 8. Change of static contact angle under different temperatures (a), UV illumination (b) and different pH treatment (c) of 10-O-CeO2/CNFs-5-Glass for a certain time; ((d)-(i)) Photographs of the coating with methylene blue droplets after treated with UV for 36 h and different pH for 10 h
图 10 球形亚甲基蓝液滴在10-O-CeO2/CNFs-5-Glass (a)、10-O-CeO2/CNFs-5-Paper (b)、10-O-CeO2/CNFs-5-Wood (c) 和水滴在10-O-CeO2/CNFs-5-Sponge (d) 表面照片及其接触角和滚动角 (f);(e) 10-O-CeO2/CNFs-5-Glass表面液滴撞击照片
Figure 10. Photographs of spherical methylene blue aqueous dye on the surface of 10-O-CeO2/CNFs-5-Glass (a), 10-O-CeO2/CNFs-5-Paper (b), 10-O-CeO2/CNFs-5-Wood (c), and water droplets on the surface of 10-O-CeO2/CNFs-5-Sponge (d) as well as static contact angle and sliding angle (f); (e) Photographs of water droplet impact on the 10-O-CeO2/CNFs-5-Glass surface
图 12 Glass、CNFs-Glass和10-O-CeO2/CNFs-5-Glass的 (a) 紫外线透过率曲线和 (b) 紫外线透过率;Paper、CNFs-Paper和10-O-CeO2/CNFs-5-Paper的 (c) 紫外线透过率曲线和 (d) 紫外线透过率
Figure 12. UV transmittance curves (a) and UV transmittance (b) of Glass, CNFs-Glass, and 10-O-CeO2/CNFs-5-Glass; UV transmittance curves (c) and UV transmittance (d) of Paper, CNFs-Paper, and 10-O-CeO2/CNFs-5-Paper
表 1 Y-O-CeO2/纤维素纳米纤维(CNFs)-X复合材料配方
Table 1. Y-O-CeO2/cellulose nanofibers (CNFs)-X composite formulations
Mass ratio Sample Ce(NO3)3·6H2O∶CNFs 1∶1 CeO2/CNFs-1 3∶1 CeO2/CNFs-3 5∶1 CeO2/CNFs-5 7∶1 CeO2/CNFs-7 X∶1 CeO2/CNFs-X OTMS:CeO2/CNFs-X 5∶1 5-O-CeO2/CNFs-X 10∶1 10-O-CeO2/CNFs-X 15∶1 15-O-CeO2/CNFs-X Y∶1 Y-O-CeO2/CNFs-X Notes: Y—Mass ratio of OTMS to CeO2/CNFs-X; X—Mass ratio of Ce(NO3)3·6H2O to CNFs. -
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