VO<sub>2</sub>@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

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

呼啸¹,
李文婷^1, ,,
付勍玮¹,
徐慧妍¹,
聂永¹,
杨帅军¹,
蒋绪川^{1, 2, ,}

1.
济南大学　智能材料与工程研究院，济南 250022
2.
济南大学　材料科学与工程学院，济南 250022

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
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出版历程
- 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
- 刊出日期: 2023-08-15

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

HU Xiao¹,
LI Wenting^{1
, ,},
FU Qingwei¹,
XU Huiyan¹,
NIE Yong¹,
YANG Shuaijun¹,
JIANG Xuchuan^{1, 2
, ,}

1.
Institute for Smart Materials & Engineering, University of Ji'nan, Ji'nan 250002, China
2.
School of Materials Science and Engineering, University of Ji'nan, Ji'nan 250002, China

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

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(T_lum)为77.89%时涂层的太阳光调制能力(ΔT_sol)高达10.12%，具有优异的光学性质，满足智能窗的应用需求。
- 二氧化钒 /
- 聚甲基丙烯酸甲酯 /
- 原位聚合 /
- 球磨法 /
- 稳定性 /
- 分散性 /
- 智能窗
Abstract: Vanadium dioxide (VO₂) can change infrared transmittance in response to external temperature changes, and has become the preferred material for thermochromic smart windows. The facile ball milling method is simple, easy to operate, short reaction time, less pollution, suitable for industrial production. However, there are still some problems with vanadium dioxide that may hinder large scale production and practical applications, such as poor stability and easily agglomeration. Here we report on the preparation of thermochromic coating based on VO₂@polymethyl methacrylate (PMMA) microcapsule synthesized through in-situ polymerized method. Uniform VO₂@PMMA microcapsules was obtained by in situ polymerization of double bonds on the surface of VO₂ and methyl methacrylate (MMA) monomer. The space barrier effect of in-situ polymerized PMMA is used to prevent VO₂ agglomeration. With good compactness PMMA prevent air and moisture from contacting VO₂, which improve VO₂ stability. VO₂@PMMA films prepared by a roll coating method not only has good acid resistance and oxidation resistance, but also has excellent optical properties with the solar modulation efficiency (ΔT_sol) 10.12% at 77.89% visible light transmittance (T_lum), which meets the application requirements of smart windows.
- vanadium dioxide /
- polymethyl methacrylate /
- in-situ polymerization /
- ball milling /
- stability /
- dispersibility /
- smart windows

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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

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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

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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))

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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

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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))

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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))

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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)

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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)

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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

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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

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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

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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

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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

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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 T_lum/%		Solar transmittance T_sol/%		Solar regulation efficiency ΔT_sol/%
	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

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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

Condition	VO₂	VO₂@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

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