VO2@KH550/570@PS复合薄膜的制备及其热致相变性能

doi:10.11949/0438-1157.20240329

化工学报 ›› 2024, Vol. 75 ›› Issue (9): 3348-3359.DOI: 10.11949/0438-1157.20240329

• 材料化学工程与纳米技术 • 上一篇下一篇

VO₂@KH550/570@PS复合薄膜的制备及其热致相变性能

张丽萍¹(), 孟晓荣¹^,²(), 宋锦峰³, 杜金晶⁴

^1.西安建筑科技大学化学与化工学院，陕西西安 710000
^2.陕西省膜分离技术研究院，陕西西安 710054
^3.陕西环保产业集团有限责任公司，陕西西安 710000
^4.西安建筑科技大学冶金工程学院，陕西西安 710000

收稿日期:2024-03-21 修回日期:2024-04-20 出版日期:2024-09-25 发布日期:2024-10-10
通讯作者: 孟晓荣
作者简介:张丽萍（2000—），女，硕士研究生，zhangliping0108@163.com
基金资助:
陕西省科技创新引导专项(2022QFY10-04)

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

Liping ZHANG¹(), Xiaorong MENG¹^,²(), Jinfeng SONG³, Jinjing DU⁴

^1.School of Chemistry and Chemical Engineering，Xi’an University of Architecture and Technology，Xi’an 710000，Shaanxi，China
^2.Shaanxi Academy of Membrane Separation Technology，Xi’an 710054，Shaanxi，China
^3.Shaanxi Environmental Protection Industry Group Co. , Ltd. , Xi’an 710000, Shaanxi，China
^4.School of Metallurgy Engineering，Xi’an University of Architecture and Technology，Xi’an 710000，Shaanxi，China

Received:2024-03-21 Revised:2024-04-20 Online:2024-09-25 Published:2024-10-10
Contact: Xiaorong MENG

摘要/Abstract

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

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

中图分类号:

TQ 050.4⁺3

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.

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.

图/表 14

图1 VSPS聚合物复合薄膜的制备流程图

Fig.1 Preparation flow chart of VSPS polymer composite film

图2 隔热性能检测装置示意图

Fig.2 Schematic diagram of thermal insulation testing device

图3 VSPS的XRD谱图(a)， DSC图(b)， FTIR谱图[(c)、(d)]

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

图4 VSPS的TEM图：（a）VS550PS，（b）VS570PS；HRTEM图：（c）VS550PS，（d）VS570PS

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

图5 VSPS粉体的SEM图：(a) VO2， (b) VS550PS， (c) VS570PS， (g) VS550， (h) VS570， (i) VO2@PS；水接触角：(d) VO2， (e)VS550PS，(f) VS570PS， (j) VS550， (k) VS570， (l) VO2@PS

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

图6 粉体耐酸性测试图[从左到右依次为VO2 (M)、VS550、VS570、VS550PS、VS570PS]

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

图7 粉体耐氧化性测试图[从左到右依次为VO2 (M)、VS550、VS570、VS550PS、VS570PS]

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

图8 有无交联剂MBA的VS570PS在Et、THF、DMAC溶液中静置图

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

图9 复合薄膜的SEM图[（a）~（c）]、对应的局部放大SEM图[（d）~（f）]和水接触角[（g）~（i）]

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

图10 复合薄膜热致变色性能：(a)、(b) 不同VSPS复合薄膜；(c) 不同VS570PS用量下复合薄膜的光透过率和全红外阻隔率；(d) 不同VSPS用量下复合薄膜的紫外-可见-近红外透射谱图

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

表1 VO2/PVB和VSPS聚合物复合薄膜的Tlum和ΔTsol值（A为高低温可见光透过率平均值）

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

图11 VSPS复合薄膜的光透过率、全红外阻隔率（a）及隔热性能（b）

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

表2 VSPS复合薄膜升温速率K

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

图12 不同膜厚的VSPS复合薄膜的光透过率（a）和全红外阻隔率（b）

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

参考文献 37

1	Pachano J E, Fernández-Vigil Iglesias M, Saiz J C, et al. Two-stage multi-step energy model calibration of the cooling systems of a large-space commercial building[J]. Applied Thermal Engineering, 2023, 230: 120638.
2	Sirvent P, Perez G, Guerrero A. VO₂ sprayed cementitious materials for thermochromic building envelopes[J]. Solar Energy, 2022, 243: 13-21.
3	Zhao Y, Ji H N, Lu M Y, et al. Thermochromic smart windows assisted by photothermal nanomaterials[J]. Nanomaterials, 2022, 12(21): 3865.
4	Chen G Q, Zhang Y T, Chen Y M, et al. Energy efficient thermochromic smart windows based on polymers and metal oxides[J]. Journal of Polymer Science, 2024, 62(2): 229-240.
5	Feng Y Q, Lv M L, Yang M, et al. Application of new energy thermochromic composite thermosensitive materials of smart windows in recent years[J]. Molecules, 2022, 27(5): 1638.
6	Lee D, Chung B, Shi Y, et al. Isostructural metal-insulator transition in VO₂ [J]. Science, 2018, 362(6418): 1037-1040.
7	Raveendran S V, Unni A K A, Mohanan J. Photocatalytic dye degradation, self-cleaning, and chromogenic properties of VO₂thin films for eco-friendly smart window application[J]. Applied Nanoscience, 2023, 13(3): 1841-1854.
8	Kayani Z N, Iqbal A, Bashir Z, et al. Effect of K contents on the efficiency of K-doped TiO₂ thin films for smart window applications[J]. Inorganic Chemistry Communications, 2023, 151: 110560.
9	Dang Y Y, Zhao L R, Liu J C. Preparation and optical properties of W-doped VO₂/AZO bilayer composite film[J]. Ceramics International, 2020, 46(7): 9079-9085.
10	Basso M, Colusso E, Carraro C, et al. Rapid laser-induced low temperature crystallization of thermochromic VO₂ sol-gel thin films[J]. Applied Surface Science, 2023, 631: 157507.
11	Rajeswaran B, Pradhan J K, Ramakrishna S A, et al. Annealing enhanced phase transition in VO₂ thin films deposited on glass substrates via chemical vapor deposition[J]. Thin Solid Films, 2023, 778: 139918.
12	Bleu Y, Bourquard F, Barnier V, et al. Towards room temperature phase transition of W-doped VO₂ thin films deposited by pulsed laser deposition: thermochromic, surface, and structural analysis[J]. Materials, 2023, 16(1): 461.
13	Li J G, An Z W, Zhang W L, et al. Thermochromatic vanadium dioxide (VO₂) thin films synthesized by atomic layer deposition and post-treatments[J]. Applied Surface Science, 2020, 529: 147108.
14	Xygkis M, Gagaoudakis E, Zouridi L, et al. Thermochromic behavior of VO₂/polymer nanocomposites for energy saving coatings[J]. Coatings, 2019, 9(3): 163.
15	Huang X J, Zeng X F, Wang J X, et al. Transparent dispersions of monodispersed ZnO nanoparticles with ultrahigh content and stability for polymer nanocomposite film with excellent optical properties[J]. Industrial & Engineering Chemistry Research, 2018, 57(12): 4253-4260.
16	Haruna M A, Wen D S. Stabilization of polymer nanocomposites in high-temperature and high-salinity brines[J]. ACS Omega, 2019, 4(7): 11631-11641.
17	Ji H N, Liu D Q, Zhang C Y, et al. VO₂/ZnS core-shell nanoparticle for the adaptive infrared camouflage application with modified color and enhanced oxidation resistance[J]. Solar Energy Materials and Solar Cells, 2018, 176: 1-8.
18	Chiozzi V, Rossi F. Inorganic–organic core/shell nanoparticles: progress and applications[J]. Nanoscale Advances, 2020, 2(11): 5090-5105.
19	Du Z Y, Li M, Zou F X, et al. VO₂@SiO₂ nanoparticle-based films with localized surface plasmon resonance for smart windows[J]. ACS Applied Nano Materials, 2022, 5(9): 12972-12979.
20	Salamati M, Kamyabjou G, Mohamadi M, et al. Preparation of TiO₂@W-VO₂ thermochromic thin film for the application of energy efficient smart windows and energy modeling studies of the produced glass[J]. Construction and Building Materials, 2019, 218: 477-482.
21	Chen Y X, Zeng X Z, Zhu J T, et al. High performance and enhanced durability of thermochromic films using VO₂@ZnO core-shell nanoparticles[J]. ACS Applied Materials & Interfaces, 2017, 9(33): 27784-27791.
22	Zhao S W, Tao Y, Chen Y X, et al. Room-temperature synthesis of inorganic-organic hybrid coated VO₂ nanoparticles for enhanced durability and flexible temperature-responsive near-infrared modulator application[J]. ACS Applied Materials & Interfaces, 2019, 11(10): 10254-10261.
23	Tong K, Li R, Zhu J T, et al. Preparation of VO₂/Al-O core-shell structure with enhanced weathering resistance for smart window[J]. Ceramics International, 2017, 43(5): 4055-4061.
24	Li R, Ji S D, Li Y M, et al. Synthesis and characterization of plate-like VO₂(M)@SiO₂ nanoparticles and their application to smart window[J]. Materials Letters, 2013, 110: 241-244.
25	Saini M, Dehiya B S, Umar A. VO₂(M)@CeO₂ core-shell nanospheres for thermochromic smart windows and photocatalytic applications[J]. Ceramics International, 2020, 46(1): 986-995.
26	Zhu Z Z, Zhu K Z, Guo J H, et al. Preparation and durability evaluation of vanadium dioxide intelligent thermal insulation films[J]. Colloid and Interface Science Communications, 2022, 48: 100619.
27	赵立英, 刘长生. 硅烷偶联剂对聚甲基丙烯酸甲酯/二氧化硅纳米复合材料结构与性能的影响[J]. 化工学报, 2005, 56(11): 2223-2227.
	Zhao L Y, Liu C S. Influence of silane coupler on structure and properties of PMMA/SiO₂ nanocomposites materials[J]. Journal of Chemical Industry and Engineering(China), 2005, 56(11): 2223-2227.
28	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.
	Hu X, Li W T, Fu Q W, 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.
29	Zhao X X, Sun J H, Ma J C, et al. Combining reversible addition-fragmentation chain transfer polymerization and thiol-ene click reaction for application of core-shell structured VO₂@polymer nanoparticles to smart window[J]. Sustainable Materials and Technologies, 2022, 32: e00420.
30	张少鸿, 付娟, 苏秋成, 等. 超细VO₂粉末的制备及其可逆相变的原位表征[J]. 稀有金属材料与工程, 2015, 44(3): 738-742.
	Zhang S H, Fu J, Su Q C, et al. Preparation of VO₂ superfine powders by a redox method and in situ characterization on the reversible phase transition[J]. Rare Metal Materials and Engineering, 2015, 44(3): 738-742.
31	Zhao X X, Sun J H, Guo Z Y, et al. One-step hydrothermal synthesis of monoclinic vanadium dioxide nanoparticles with low phase transition temperature[J]. Chemical Engineering Journal, 2022, 446: 137308.
32	Fan S J, Fan L L, Li Q, et al. The identification of defect structures for oxygen pressure dependent VO₂ crystal films[J]. Applied Surface Science, 2014, 321: 464-468.
33	Chen W, Luan J D, Yu X K, et al. Preparation of core-shell structured polystyrene @ graphene oxide composite microspheres with high adsorption capacity and its removal of dye contaminants[J]. Environmental Technology, 2021, 42(24): 3840-3851.
34	Domenichelli I, Banerjee S, Taddei S, et al. Styrene and substituted styrene grafted functional polyolefins via nitroxide mediated polymerization[J]. Polymer Chemistry, 2018, 9(3): 307-314.
35	Jijie R, Barras A, Teslaru T, et al. Aqueous medium-induced micropore formation in plasma polymerized polystyrene: an effective route to inhibit bacteria adhesion[J]. Journal of Materials Chemistry B, 2018, 6(22): 3674-3683.
36	Le P T P, Hofhuis K, Rana A, et al. Tailoring vanadium dioxide film orientation using nanosheets: a combined microscopy, diffraction, transport, and soft X-ray in transmission study[J]. Advanced Functional Materials, 2020, 30(1): 1900028.
37	Wang X, Li M, Wang Q S, et al. Effect of Mie scattering on thermochromic performance of branched VO₂ prepared by one-step hydrothermal method[J]. European Journal of Inorganic Chemistry, 2020, 2020(18): 1783-1789.

[1]	夏东, 黄朋, 李恒. 水热法制备三维导电石墨烯气凝胶及其焦耳热性能研究[J]. 化工学报, 2021, 72(7): 3839-3848.
[2]	张洁, 庞丽萍, 曲洪权, 王天博. 基于随机配置网络的机载电子吊舱多工况热模型[J]. 化工学报, 2020, 71(S1): 441-447.
[3]	张琳琳, 赵蕾, 杨柳. 分层土壤中竖直埋管换热器传热特性[J]. 化工学报, 2015, 66(12): 4836-4842.
[4]	王坤, 李金波, 程林. 阿尔法磁谱仪在轨运行异常温度及热响应分析[J]. 化工学报, 2014, 65(z2): 155-161.
[5]	董如林，刘淑赟，陈智栋，金长春，王彩霞. TiO2/SiO2复合薄膜的制备及其自清洁性能[J]. 化工进展, 2013, 32(03): 645-651.
[6]	沈江南，裘俊红，郑幸存，吴礼光，高从堦. 微乳液聚合在分离膜制备中的应用研究进展 [J]. CIESC Journal, 2008, 27(4): 515-.
[7]	尹辉斌，高学农，丁静，张正国. 热适应复合材料应用于电子器件散热的研究进展 [J]. CIESC Journal, 2007, 26(6): 830-.
[8]	李晓;夏声平;张卫英;肖娴华;任文成;董声雄 . 甲基丙烯酸甲酯/丙烯酸/水反相无皂微乳液体系的聚合 [J]. CIESC Journal, 2006, 57(7): 1582-1587.
[9]	许涌深;刘颖;赵宁;袁才登 . 硅氧烷的微乳液聚合动力学 [J]. CIESC Journal, 2006, 57(6): 1464-1467.
[10]	邢志祥,蒋军成,赵晓芳. 液化石油气储罐在喷射火焰作用下的热响应模型[J]. CIESC Journal, 2004, 12(5): 639-646.

VO₂@KH550/570@PS复合薄膜的制备及其热致相变性能

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

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 14

参考文献 37

相关文章 10

编辑推荐

Metrics

本文评价