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

VO₂@PMMA微胶囊的原位制备及其热致变色涂层性能

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资助

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: 2022-11-07
- 刊出日期: 2023-08-15

In situ preparation of VO₂@PMMA microcapsule and their thermochromic properties

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 Jinan, Jinan250002, China
2.
School of Materials Science and Engineering, University of Jinan, Jinan250002, China

Funds: Natural Science Foundation of Shandong Province(No. ZR2022 QE017); Science and Technology Program of University of Jinan (XKY2065); the Major Subject Project of the University of Jinan

摘要

摘要: 球磨法制备二氧化钒粉体工艺设备简单、反应时间短、能耗低、无废液产生适合工业化大规模生产，但由于磨球的强烈冲击使VO₂(M)粉体分散性和稳定性较差，且与有机基体相容性不好，导致其涂层太阳光调制能力较差，在实际应用中面临重大挑战。本文利用γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)对球磨VO₂进行修饰得到VO₂-KH570，VO₂-KH570粉体均匀分散在低黏度甲基丙烯酸甲酯(MMA)单体中，加热条件下MMA单体原位聚合得到分散性好、平均粒径为55 nm的VO₂@PMMA微胶囊，不仅可以利用PMMA的空间阻隔作用防止VO₂团聚，而且PMMA具有良好的致密性可以防止空气、湿气等接触VO₂，提高其稳定性。除此之外，VO₂@PMMA微胶囊表面的PMMA可以与基体中的PMMA发生物理缠绕，提高VO₂与有机基体之间的相容性。因此，所制得的VO₂@PMMA微胶囊涂层抗酸和抗氧化能力显著提高(> 24 h，而纯VO₂ < 30 min)，而且光学性质明显改善(T_lum =77.89%，ΔT_sol =10.12%，而纯VO₂的T_lum =78%，ΔT_sol =5.25%)。1VO₂@PMMA微胶囊的合成示意图(a)及其涂层紫外-可见-近红外透射光谱(b)
- 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@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 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 (T_lum =77.89%, ΔT_sol =10.12%), which meets the application requirements of smart windows.
- vanadium dioxide /
- polymethyl methacrylate /
- in-situ polymerization /
- stability /
- ball milling /
- dispersibility /
- smart windows

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

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

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

Figure 2. FTIR spectra (a), TGA curves (b), XRD pattern (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)SEM图像

Figure 3. image of VO₂ (a), VO₂-KH570 (b) and VO₂@PMMA microcapsule (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) image 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 image 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 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, d), VO₂-KH570 coating (b, e) and VO₂@PMMA microcapsule coating (c, f)

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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)紫外-可见-近红外透射光谱

Figure 8. UV–Vis-NIR transmittance spectra of VO₂ coating, VO₂-KH570 coating and VO₂@PMMA microcapsule coating (a), UV-vis-NIR transmission spectra of coatings 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花样；(c)VO₂和VO₂@PMMA微胶囊涂层未浸泡和在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-近红外透射光谱

Figure 9. From left to right pictures of VO₂, VO₂-KH570 and VO₂@PMMA microcapsule nanoparticle (a) and coating (c) dispersed in H₂SO₄ solution, XRD patterns of VO₂@PMMA microcapsule nanoparticle dispersed in H₂SO₄ solution for 48 h (b), UV–Vis-NIR transmittance spectra of VO₂ coating and VO₂@PMMA microcapsule coating dispersed in H₂SO₄ solution for 24 h (d)

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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花样；(c)VO₂(左)和VO₂@PMMA微胶囊(右)涂层未浸泡和在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溶液后紫外-可见-近红外透射光谱

Figure 10. From left to right pictures of VO₂, VO₂-KH570 and VO₂@PMMA microcapsule nanoparticle (a) and coating (c) dispersed in H₂O₂ solution, XRD patterns of VO₂@PMMA microcapsule nanoparticle dispersed in H₂O₂ solution for 48 h (b), UV–Vis-NIR transmittance spectra of VO₂ coating and VO₂@PMMA microcapsule coating dispersed in H₂O₂ solution for 24 h (d)

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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-近红外透射光谱

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十个月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)涂层常温放置十个月紫外-可见-近红外透射光谱

Figure 12. From left to right pictures of VO₂, VO₂-KH570 and VO₂@PMMA microcapsule nanoparticle (a) and coating (c) 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) The photograph of small house for test of thermal insulation effect of coated glass; (b) the relation curves between the temperature and time of different coating glasses

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表 1 VO₂、VO₂-KH570和VO₂@PMMA微胶囊涂层的光学性能

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表

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

	VO₂	VO₂@PMMA
Before acidification	8.52	9.99
Acidification for 24 h	−5.8	9.9
Before oxidation	5.24	11.05
Oxidation for 24 h	1.95	8.63
Before UV ageing	8.2	9.3
UV ageing for 48 h	7.11	10.33

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