Preparation of VO2@KH550/570@PS composite film and its thermally induced phase change properties

doi:10.11949/0438-1157.20240329

Abstract

Abstract:

Low-cost and large-scale thin-film production technology is the key to the popularization of thermally induced phase change vanadiam dioxide VO₂(M) in the field of energy-saving windows. In this study, silane coupling agent KH550/KH570 was used to modify the surface of VO₂(M) powder synthesized by solid phase method, and then polystyrene (PS) modified VO₂@KH550/570@PS microspheres (VSPS) were obtained by microemulsion polymerization to systematically study the effect of surface modification on the properties and optical and thermal insulation performance of VO₂(M)-based polymer composite films on the properties of VO₂(M) based polymer films and the influence of optical and thermal insulation properties. The results show that the premodification of coupling agent is conducive to enhance the combination of PS and VO₂ during emulsion polymerization, and the introduction of cross-linking agent MBA enhances the chemical stability of VSPS, which improves the dispersing ability of VO₂ inorganic powders in the polymer solution system, and obtains more homogeneous polymer composite films. Among them, VS₅₇₀PS/PVB has a high T_lum of 86.64%, a 12-fold improvement in ΔT_sol compared to VO₂/PVB, and the temperature difference between the blank glass is 16℃. This preparation technique of VSPS polymer composite film with both high light transmittance and heat insulation performance provides a useful idea for the application of VO₂(M) as a smart window material.

Key words: thermo-responsive, VO₂@KH550/570@PS, composite film, microemulsion polymerization

摘要：

低成本和规模化的薄膜化生产技术是热致相变性二氧化钒VO₂（M）普及应用于节能窗领域的关键。采用硅烷偶联剂γ-氨丙基三乙氧基硅烷/γ-甲基丙烯酰氧基丙基三甲氧基硅烷KH550/KH570对固相法合成的VO₂（M）粉体进行表面改性，再经微乳液聚合得到聚苯乙烯（PS）修饰的VO₂@KH550/570@PS微球（VSPS），以聚乙烯醇缩丁醛（PVB）、聚氯乙烯（PVC）、聚偏二氟乙烯（PVDF）为聚合物共混基材，系统研究表面修饰对VO₂（M）基聚合物复合薄膜的性质及光学、隔热性能的影响规律。结果表明：偶联剂预修饰有利于提升乳液聚合过程中PS与VO₂结合，交联剂亚甲基双丙烯酰胺（MBA）的引入增强了VSPS的化学稳定性。相比VO₂，VSPS在聚合物溶液体系中的分散能力增加，得到更加均匀的聚合物复合薄膜。其中VS₅₇₀PS/PVB的可见光透光率T_lum高达86.64%，太阳能调制效率ΔT_sol较VO₂/PVB提升了12倍，与空白玻璃温差达16℃。这种兼具高透光性和隔热性能的VSPS聚合物复合膜制备技术为VO₂（M）的智能窗材料应用提供了有益的思路。

关键词: 热响应, VO₂@KH550/570@PS, 复合薄膜, 微乳液聚合

CLC Number:

TQ 050.4⁺3

Liping ZHANG, Xiaorong MENG, Jinfeng SONG, Jinjing DU. Preparation of VO₂@KH550/570@PS composite film and its thermally induced phase change properties[J]. CIESC Journal, 2024, 75(9): 3348-3359.

张丽萍, 孟晓荣, 宋锦峰, 杜金晶. VO₂@KH550/570@PS复合薄膜的制备及其热致相变性能[J]. 化工学报, 2024, 75(9): 3348-3359.

Figures/Tables 14

Fig.1 Preparation flow chart of VSPS polymer composite film

Fig.2 Schematic diagram of thermal insulation testing device

Fig.3 XRD patterns (a), DSC curves (b), FTIR spectra [(c),(d)] of VSPS

Fig.4 TEM image of VSPS:（a）VS550PS，（b）VS570PS；HRTEM image:（c）VS550PS，（d）VS570PS

Fig.5 SEM images of VSPS powder： (a) VO2， (b) VS550PS， (c) VS570PS, (g) VS550， (h) VS570， (i) VO2@PS; water contact angle of modified powder: (d) VO2， (e)VS550PS， (f) VS570PS, (j) VS550， (k) VS570， (l) VO2@PS

Fig.6 Acid resistance test diagram of powder [from left to right: VO2 (M)， VS550， VS570， VS550PS， VS570PS]

Fig.7 Powder oxidation resistance test diagram [from left to right: VO2 (M)， VS550， VS570， VS550PS， VS570PS]

Fig.8 Static diagrams of VS570PS with or without cross-linking agent MBA in Et， THF， DMAC solution

Fig.9 SEM images of composite film [(a)—(c)], corresponding local enlarged SEM images [(d)—(f)], water contact angle [(g)—(i)] of composite film

Fig. 10 Thermochromic properties of composite films: (a),(b) different VSPS composite films； (c) VL transmittance full IR rejection of composite film under different VS570PS dosage; (d) transmittance spectra of composite films with different amounts of VSPS

Table 1 Tlum and Tsol of VO2/PVB and VSPS polymer composite films，（where A is average transmittance of high and low temperature visible light）

Sample	T_lum/%		A-T_lum/%	T_sol/%		ΔT_sol/%
Sample	20℃	90℃	A-T_lum/%	20℃	90℃	ΔT_sol/%
VO₂/PVB	57.60	59.65	58.63	57.28	56.94	0.34
VS₅₅₀PS/PVB	81.35	83.03	82.19	80.73	78.84	1.89
VS₅₇₀PS/PVB	84.87	88.42	86.64	84.80	80.46	4.34
VS₅₇₀PS/PVDF	68.07	70.66	69.36	70.58	69.15	1.43
VS₅₇₀PS/PVC	85.84	84.97	85.41	86.00	83.79	2.21

Fig.11 VL transmittance, full IR rejection (a) and heat insulation properties (b) of VSPS composite films

Table 2 Heating rate K of VSPS composite film

Sample	K1 （0—180 s）	K2 （210—380 s）	K3 （410—600 s）
blank glass	0.607	0.159	0.0760
VO₂/PVB	0.552	0.153	0.0710
VS₅₅₀PS/PVB	0.357	0.139	0.0610
VS₅₇₀PS/PVB	0.335	0.149	0.0630
VS₅₇₀PS/PVC	0.428	0.147	0.0670
VS₅₇₀PS/PVDF	0.450	0.096	0.0610

Fig.12 Light transmittance (a) and total infrared blocking rate (b) of VSPS composite films with different film thicknesses

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Preparation of VO₂@KH550/570@PS composite film and its thermally induced phase change properties

VO₂@KH550/570@PS复合薄膜的制备及其热致相变性能

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