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VO2@PMMA微胶囊的原位制备及其热致变色涂层性能

呼啸 李文婷 付勍玮 徐慧妍 聂永 杨帅军 蒋绪川

呼啸, 李文婷, 付勍玮, 等. VO2@PMMA微胶囊的原位制备及其热致变色涂层性能[J]. 复合材料学报, 2023, 40(8): 4587-4600. doi: 10.13801/j.cnki.fhclxb.20221102.004
引用本文: 呼啸, 李文婷, 付勍玮, 等. VO2@PMMA微胶囊的原位制备及其热致变色涂层性能[J]. 复合材料学报, 2023, 40(8): 4587-4600. doi: 10.13801/j.cnki.fhclxb.20221102.004
HU Xiao, LI Wenting, FU Qingwei, et al. In situ preparation of VO2@PMMA microcapsule and thermochromic properties of its coating[J]. Acta Materiae Compositae Sinica, 2023, 40(8): 4587-4600. doi: 10.13801/j.cnki.fhclxb.20221102.004
Citation: HU Xiao, LI Wenting, FU Qingwei, et al. In situ preparation of VO2@PMMA microcapsule and thermochromic properties of its coating[J]. Acta Materiae Compositae Sinica, 2023, 40(8): 4587-4600. doi: 10.13801/j.cnki.fhclxb.20221102.004

VO2@PMMA微胶囊的原位制备及其热致变色涂层性能

doi: 10.13801/j.cnki.fhclxb.20221102.004
基金项目: 山东省自然科学基金青年项目(ZR2022 QE017);济南大学科技计划项目(XKY2065);济南大学学科重大课题项目
详细信息
    通讯作者:

    李文婷,博士,讲师,研究方向为有机-无机复合材料及抗菌高分子材料 E-mail: ism_liwt@ujn.edu.cn

    蒋绪川,博士,教授,博士生导师,研究方向为光、热、电、磁等外界刺激响应型无机功能材料,隔热节能玻璃的功能化 E-mail: ism_jiangxc@ujn.edu.cn

  • 中图分类号: TB332

In situ preparation of VO2@PMMA microcapsule and thermochromic properties of its coating

Funds: Natural Science Foundation of Shandong Province (ZR2022 QE017); Science and Technology Program of University of Ji'nan (XKY2065); Major Subject Project of the University of Ji'nan
  • 摘要: M相二氧化钒(VO2(M))能够响应外界温度变化而改变红外波段透过率,成为热致变色智能窗涂层的首选材料。球磨法工艺设备简单、易于操作、反应时间短、无废液产生,适合工业化生产,但球磨VO2稳定性差、易团聚在实际应用中面临重大挑战。本文基于原位聚合法制备了二氧化钒@聚甲基丙烯酸甲酯(VO2@PMMA)微胶囊并辊涂构建热致变色涂层。甲基丙烯酸甲酯(MMA)单体在球磨法制备的VO2颗粒表面通过共价键原位聚合得到尺寸均匀、耐酸抗氧化能力强的VO2@PMMA微胶囊。VO2@PMMA热致变色涂层不仅具有良好的抗酸和抗氧化能力,而且可见光透过率(Tlum)为77.89%时涂层的太阳光调制能力(ΔTsol)高达10.12%,具有优异的光学性质,满足智能窗的应用需求。

     

  • 图  1  二氧化钒@聚甲基丙烯酸甲酯(VO2@PMMA)微胶囊的合成示意图

    KH570—3-methacryloxypropyltrimethoxysilane; KPS—Potassium persulfate

    Figure  1.  Schematic diagram of the preparation of vanadium dioxide@polymethyl methacrylate (VO2@PMMA) microcapsule

    图  2  VO2、VO2-KH570和VO2@PMMA微胶囊的FTIR图谱(a)、TGA曲线(b)、XRD图谱(c)和DSC曲线(d)

    Figure  2.  FTIR spectra (a), TGA curves (b), XRD patterns (c) and DSC curves (d) of VO2, VO2-KH570 and VO2@PMMA microcapsule

    图  3  VO2 (a)、VO2-KH570 (b)和VO2@PMMA微胶囊粉体((c)、(d))的SEM图像

    Figure  3.  SEM images of VO2 (a), VO2-KH570 (b) and VO2@PMMAmicrocapsule ((c), (d))

    图  4  VO2@PMMA微胶囊的TEM (a)和HRTEM (b)图像

    Figure  4.  TEM (a) and HRTEM (b) images of VO2@PMMA microcapsule

    图  5  VO2 ((a)、(d))、VO2-KH570 ((b)、(e))和VO2@PMMA微胶囊((c)、(f))涂层表面的SEM图像

    Figure  5.  SEM images of VO2 coating ((a), (d)), VO2-KH570 coating ((b), (e)) and VO2@PMMA microcapsule coating ((c), (f))

    图  6  VO2 ((a)、(d))、VO2-KH570 ((b)、(e))和VO2@PMMA微胶囊((c)、(f))涂层断面的SEM图像

    Figure  6.  Cross sectional SEM images of VO2 coating ((a), (d)), VO2-KH570 coating ((b), (e)) and VO2@PMMA microcapsule coating ((c), (f))

    图  7  VO2 (a)、VO2-KH570 (b)和VO2@PMMA微胶囊(c)涂层断面粉体的线分析

    Figure  7.  Ingredient linear scan analysis on the cross sectional of VO2 coating (a), VO2-KH570 coating (b) and VO2@PMMA microcapsule coating (c)

    图  8  VO2、VO2-KH570和VO2@PMMA微胶囊涂层(a)和不同含量VO2@PMMA微胶囊涂层(b)的紫外-可见-近红外透射图谱

    Figure  8.  UV-Vis-NIR transmittance spectra of VO2 coating, VO2-KH570 coating, VO2@PMMA microcapsule coating (a) and with different content VO2@PMMA microcapsules (b)

    图  9  (a)从左向右依次为VO2、VO2-KH570和VO2@PMMA微胶囊在0.5 mol/L的H2SO4溶液中浸泡不同时间的实物照片;(b) VO2@PMMA微胶囊未浸泡和浸泡H2SO4溶液48 h后粉体的XRD图谱;(c) VO2 (左)和VO2@PMMA微胶囊(右)涂层浸泡在0.5 mol/L的H2SO4溶液中浸泡24 h的实物照片;(d) VO2和VO2@PMMA微胶囊涂层浸泡H2SO4溶液24 h后紫外-可见-近红外透射图谱

    Figure  9.  (a) From left to right pictures of VO2, VO2-KH570 and VO2@PMMA microcapsule nanoparticle dispersed in 0.5 mol/L H2SO4 solution for different times; (b) XRD patterns of VO2@PMMA microcapsule nanoparticle before and after dispersed in H2SO4 solution for 48 h; (c) Pictures of VO2 (left) and VO2@PMMA (right) coating dispersed in 0.5 mol/L H2SO4 solution for 24 h; (d) UV-Vis-NIR transmittance spectra of VO2 coating and VO2@PMMA microcapsule coating after dispersed in H2SO4 solution for 24 h

    图  10  (a)从左向右依次为VO2、VO2-KH570和VO2@PMMA微胶囊在0.1 mol/L的H2O2溶液中浸泡不同时间的实物照片;(b) VO2@PMMA微胶囊未浸泡和浸泡H2O2溶液48 h后粉体的XRD图谱;(c) VO2 (左)和VO2@PMMA微胶囊(右)涂层浸泡在0.1 mol/L的H2O2溶液中浸泡24 h的实物照片;(d) VO2和VO2@PMMA微胶囊涂层浸泡H2O2溶液24 h后紫外-可见-近红外透射图谱

    Figure  10.  (a) From left to right pictures of VO2, VO2-KH570 and VO2@PMMA microcapsule nanoparticle dispersed in 0.1 mol/L H2O2 solution for different times; (b) XRD patterns of VO2@PMMA microcapsule nanoparticle before and after dispersed in H2O2 solution for 48 h; (c) Pictures of VO2 (left) and VO2@PMMA (right) coating dispersed in 0.1 mol/L H2O2 solution for 24 h; (d) UV-Vis-NIR transmittance spectra of VO2 coating and VO2@PMMA microcapsule coating after dispersed in H2O2 solution for 24 h

    图  11  VO2 (a)、VO2-KH570 (b)和VO2@PMMA微胶囊(c)涂层紫外老化48 h紫外-可见-近红外透射图谱

    Figure  11.  UV-Vis-NIR transmittance spectra of VO2 coating (a), VO2-KH570 coating (b) and VO2@PMMA microcapsule coating (c) after UV ageing for 48 h

    图  12  从左向右依次为常温放置10个月VO2、VO2-KH570和VO2@PMMA微胶囊涂料(a)和涂层(b)实物照片; VO2 (c)、VO2-KH570 (d)和VO2@PMMA微胶囊(e)涂层常温放置10个月紫外-可见-近红外透射图谱

    Figure  12.  From left to right pictures of VO2, VO2-KH570 and VO2@PMMA microcapsule nanoparticle (a) and coating (b) after ageing for 10 months, UV-Vis-NIR transmittance spectra of VO2 coating (c), VO2-KH570 coating (d) and VO2@PMMA microcapsule coating (e) after ageing for 10 months

    图  13  (a)构建简易测试涂层玻璃隔热效果的小房子实物图;(b)温度随照射时间的变化曲线

    Figure  13.  (a) Photograph of small house for test of thermal insulation effect of coated glass; (b) Relation curves between the temperature and time of different coating glasses

    表  1  VO2、VO2-KH570和VO2@PMMA微胶囊涂层的可见光透过率和太阳光调制能力汇总

    Table  1.   Summary of luminous transmittance and solar modulation efficiency for VO2 coating, VO2-KH570 coating and VO2@PMMA microcapsule coating

    Luminous transmittance Tlum/%Solar transmittance Tsol/%Solar regulation efficiency ΔTsol/%
    20℃90℃20℃90℃
    VO2-1 77.23 79.22 82.02 76.77 5.25
    VO2-2 68.24 68.73 73.53 66.56 6.97
    VO2-3 41.16 43.02 50.88 42.03 8.85
    VO2-KH570-1 74.74 74.92 80.11 75.12 4.99
    VO2-KH570-2 69.97 73.37 77.21 74.02 3.19
    VO2-KH570-3 45.04 45.83 56.06 47.22 8.84
    VO2@PMMA-1 78.29 77.48 83.16 73.04 10.12
    VO2@PMMA-2 64.80 64.07 73.60 60.30 13.30
    VO2@PMMA-3 57.29 56.72 68.08 50.58 17.50
    下载: 导出CSV

    表  2  VO2和VO2@PMMA微胶囊涂层耐酸、抗氧化和紫外老化后太阳光调制能力汇总

    Table  2.   Summary of solar modulation efficiency of VO2 coating and VO2@PMMA microcapsule coating after acid resistance, oxidation resistance and UV ageing

    ConditionVO2VO2@PMMA
    Before acidification 8.52 9.99
    Acidification for 24 h −5.80 9.90
    Before oxidation 5.24 11.05
    Oxidation for 24 h 1.95 8.63
    Before UV ageing 8.20 9.30
    UV ageing for 48 h 7.11 10.33
    下载: 导出CSV
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  • 收稿日期:  2022-08-15
  • 修回日期:  2022-09-22
  • 录用日期:  2022-10-16
  • 网络出版日期:  2022-11-02
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