Preparation of boehmite sol modified HGMs and properties of water-based composite coatings
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摘要: 保温隔热对节能减排、减少能源消耗有着重大战略意义。本文以勃姆石溶胶对空心玻璃微球(Hollow glass microspheres，HGMs)进行表面改性，引入气腔结构以提高涂层保温隔热性能，制备可连续生产的高性能水性复合涂层。通过FTIR、XRD、SEM等表征手段对复合微球的微观形貌及结构进行分析。采用热失重分析、热导率、红外热成像等技术手段，系统研究涂层的微观结构、综合性能、保温隔热机制。结果表明：勃姆石溶胶成功对HGMs进行表面改性，HGMs@Al2O3保留HGMs的基本结构与特征，增强与水性聚合物基体的界面相容性，解决HGMs与水性基体界面粘结性差、致使其热导率波动大的实际问题。与未添加隔热填料的复合涂层相比，当HGMs@Al2O3含量为7wt%时达逾渗阈值，涂层综合性能最佳，显著提高复合涂层保温隔热性，导热系数降低58.7%；复合涂层最大热分解温度提高11%，在100℃热场环境下，能达到温度差为18.1℃的隔热效果，应用潜力及商业化前景巨大。Abstract: Thermal insulation is of great strategic importance for energy saving and emission reduction, and energy consumption. In this paper, the surface modification of hollow glass microbeads (HGMs) with boehmite sol was used to introduce the air cavity structure to improve the thermal insulation performance of the coating and to prepare a high-performance water-based composite coating that can be produced continuously. The microscopic morphology and structure of the composite microspheres were analyzed by FTIR, XRD, SEM and other characterization methods. Thermal weight loss analysis, thermal conductivity, infrared thermography and other technical means were used to systematically study the microstructure, comprehensive performance, thermal insulation and heat preservation mechanism of the coating. The results show that the surface modification of HGMs is successfully carried out by boehmite sol, and HGMs@Al2O3 retains the basic structure and characteristics of HGMs, enhances the interfacial compatibility with the aqueous polymer matrix, and solves the practical problem of poor interfacial bonding between HGMs and the aqueous matrix, resulting in large fluctuations of its thermal conductivity. Compared with the composite coating without added thermal insulation filler, when the content of HGMs@Al2O3 is 7wt%, it reaches the over-permeability threshold, and the comprehensive performance of the coating is the best, which significantly improves the thermal insulation of the composite coating and reduces the thermal conductivity by 58.7%. The application potential and commercialization prospect are huge.
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图 1 空心玻璃微球(HGMs)@Al2O3水性复合涂层的制备示意图
PVP—Polyvinylpyrrolidone; AIP—Aluminium isopropoxide
Figure 1. Preparation diagram of hollow glass microspheres (HGMs)@Al2O3 water-based composite coating
图 2 聚乙烯吡咯烷酮(PVP)改性HGMs的FTIR图谱
Figure 2. FTIR spectra of polyvinylpyrrolidone (PVP) modified HGMs
图 4 HGMs与HGMs@Al2O3微球的SEM及TEM图像：(a) 纯HGMs；(b) PVP活化HGMs；(c) HGMs@Al2O3微球；(d) HGMs@Al2O3的TEM图像
Figure 4. SEM and TEM images of HGMs and HGMs@Al2O3 microspheres: (a) Pure HGMs; (b) PVP activated HGMs; (c) HGMs@Al2O3 microspheres; (d) TEM image of HGMs@Al2O3
图 5 HGMs、HGMs@Al2O3涂层的硬度(a)及耐冲击高度(b)测试
Figure 5. Hardness (a) and impact resistance height (b) tests of HGMs and HGMs@Al2O3 coatings
图 6 HGMs和HGMs@Al2O3涂层水接触角(CA)照片
Figure 6. Photographs of water contact angle (CA) of HGMs and HGMs@Al2O3 coatings
图 7 7wt%HGMs@Al2O3含量的涂层浸水前后照片
Figure 7. Photos of coating with 7wt%HGMs@Al2O3 content before and after immersed in water
图 9 HGMs、HGMs@Al2O3涂层的磨损质量(a)及摩擦系数(b)
Figure 9. Wear quality (a) and friction coefficient (b) of HGMs and HGMs@Al2O3 coatings
图 10 HGMs、HGMs@Al2O3涂层的拉伸强度(a)及断裂伸长率(b)
Figure 10. Tensile strength (a) and elongation at break (b) of HGMs and HGMs@Al2O3 coatings
图 11 HGMs@Al2O3涂层的TG曲线(a)及DTG曲线(b)
Figure 11. TG curves (a) and DTG curves (b) of HGMs@Al2O3 coating
图 12 不同HGMs@Al2O3含量复合涂层的断口SEM图像：(a) 0wt%；(b) 4wt%；(c) 5wt%；(d) 6wt%；(e) 7wt%；(f) 8wt%
Figure 12. SEM images of fracture of composite coatings with different HGMs@Al2O3 contents: (a) 0wt%; (b) 4wt%; (c) 5wt%; (d) 6wt%; (e) 7wt%; (f) 8wt%
图 13 HGMs、HGMs@Al2O3涂层的导热系数(a)及热导率变化指数(b)
Figure 13. Thermal conductivity (a) and thermal conductivity change index (b) of HGMs and HGMs@Al2O3 coatings
图 14 HGMs、HGMs@Al2O3涂层的红外热成像图(a)及温度平衡时3D图(b)
Figure 14. Infrared thermograms (a) and 3D diagrams at temperature equilibrium (b) for HGMs and HGMs@Al2O3 coatings
图 15 HGMs@Al2O3涂层圆片中心点温度随时间变化曲线
Figure 15. Temperature variation curves of HGMs@Al2O3 coated disc center point with time
表 1 添加不同隔热填料及含量的水性复合涂层在马口铁片镀锡板上的基本性能
Table 1. Basic properties of composite coatings with different fillers and contents at normal temperature and pressure
Test item Thickness/μm Adhesive force (ISO) Pencil hardness Bending strength/mm Impact resistance/cm 0wt% 300±2.7 1 HB ≤ 2 <50 4wt%HGMs 308±1.7 0 2H ≤ 2 <50 4wt%HGMs@Al2O3 307±3.2 0 3H ≤ 2 >50 5wt%HGMs 305±2.1 0 3H ≤ 2 <50 5wt%HGMs@Al2O3 307±1.8 0 4H ≤ 2 >50 6wt%HGMs 304±2.8 0 3H 5 50 6wt%HGMs@Al2O3 305±1.2 0 5H ≤ 2 >50 7wt%HGMs 306±1.5 0 3H 5 50 7wt%HGMs@Al2O3 304±1.8 0 6H ≤ 2 >50 8wt%HGMs 307±1.5 1 3H 5 50 8wt%HGMs@Al2O3 307±0.7 1 6H 5 >50 
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