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多功能CeO2/纤维素纳米纤维复合超疏水涂层的制备与性能

樊鑫炎 黄俊雅 杨炎晓 宋丽丽 王永贵 肖泽芳 王海刚 谢延军

樊鑫炎, 黄俊雅, 杨炎晓, 等. 多功能CeO2/纤维素纳米纤维复合超疏水涂层的制备与性能[J]. 复合材料学报, 2023, 40(5): 3002-3017. doi: 10.13801/j.cnki.fhclxb.20220622.002
引用本文: 樊鑫炎, 黄俊雅, 杨炎晓, 等. 多功能CeO2/纤维素纳米纤维复合超疏水涂层的制备与性能[J]. 复合材料学报, 2023, 40(5): 3002-3017. doi: 10.13801/j.cnki.fhclxb.20220622.002
FAN Xinyan, HUANG Junya, YANG Yanxiao, et al. Fabrication and properties of multifunctional CeO2/cellulose nanofibers composite superhydrophobic coating[J]. Acta Materiae Compositae Sinica, 2023, 40(5): 3002-3017. doi: 10.13801/j.cnki.fhclxb.20220622.002
Citation: FAN Xinyan, HUANG Junya, YANG Yanxiao, et al. Fabrication and properties of multifunctional CeO2/cellulose nanofibers composite superhydrophobic coating[J]. Acta Materiae Compositae Sinica, 2023, 40(5): 3002-3017. doi: 10.13801/j.cnki.fhclxb.20220622.002

多功能CeO2/纤维素纳米纤维复合超疏水涂层的制备与性能

doi: 10.13801/j.cnki.fhclxb.20220622.002
基金项目: 国家自然科学基金(31901247)
详细信息
    通讯作者:

    王永贵,博士,教授,博士生导师,研究方向为生物质复合材料 E-mail: wangyg@nefu.edu.cn

  • 中图分类号: TB332

Fabrication and properties of multifunctional CeO2/cellulose nanofibers composite superhydrophobic coating

Funds: National Natural Science Foundation of China (31901247)
  • 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。

     

  • 图  1  O-CeO2/CNFs超疏水涂层的制备示意图

    TEMPO—2, 2, 6, 6-tetramethylpiperidine-1-oxy; OTMS—Octadecyl trimethoxysilane

    Figure  1.  Schematic diagram of the preparation of O-CeO2/CNFs superhydrophobic coating

    图  2  (a) 纤维素的SEM图像;(b) CNFs的TEM图像;CeO2/CNFs-5 ((c)~(f)) 和10-O-CeO2/CNFs-5 ((g)~(i)) 不同分辨率TEM图像

    Figure  2.  (a) SEM image of cellulose; (b) TEM image of CNFs; TEM images of CeO2/CNFs-5 ((c)-(f)) and 10-O-CeO2/CNFs-5 ((g)-(i))with different resolutions

    图  3  各样品的XRD图谱

    Figure  3.  XRD patterns of samples

    图  4  各样品的FTIR图谱

    Figure  4.  FTIR spectra of samples

    图  5  (a) 各样品的XPS图谱;(b) CeO2/CNFs-5和10-O-CeO2/CNFs-5的Si2p高分辨图谱;(c) C1s图谱;(d) O1s图谱

    Figure  5.  (a) XPS survey spectra of samples; (b) High-resolution spectra of Si2p of CeO2/CNFs-5 and 10-O-CeO2/CNFs-5; (c) High-resolution spectra of C1s; (d) High-resolution spectra of O1s

    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  9  10-O-CeO2/CNFs-5-Glass在不同磨损次数下接触角(a)及磨损10次前((b), (c))和后((d), (e))的SEM图像

    Figure  9.  Static contact angle (a) of 10-O-CeO2/CNFs-5-Glass under different abrasion cycles and SEM images of coating before ((b), (c))and after ((d), (e)) 10 abrasion cycles

    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  11  10-O-CeO2/CNFs-5-Paper自清洁过程

    Figure  11.  Self-cleaning process of 10-O-CeO2/CNFs-5-Paper

    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

    图  13  ((a)~(e)) 10-O-CeO2/CNFs-5-Sponge正己烷/水分离过程;(f) 油水分离后的海绵表面润湿性

    Figure  13.  ((a)-(e)) n-hexane/water separation process of 10-O-CeO2/CNFs-5-Sponge; (f) Wettability of sponge surface after oil/water separation

    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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  • 收稿日期:  2022-05-09
  • 修回日期:  2022-06-05
  • 录用日期:  2022-06-11
  • 网络出版日期:  2022-06-23
  • 刊出日期:  2023-05-15

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