Microsoft Word - 02Revised.doc CHEMICAL ENGINEERINGTRANSACTIONS VOL. 55, 2016 A publication of The Italian Association of Chemical Engineering Online at www.aidic.it/cet Guest Editors:Tichun Wang, Hongyang Zhang, Lei Tian Copyright © 2016, AIDIC Servizi S.r.l., ISBN978-88-95608-46-4; ISSN 2283-9216 Preparation, Characterization and Properties of SiO2 Aerogel Composite Thermal Insulation Coating Zhaohui Liu, Yidong Ding*, Xin Shu, Na Liu Department of Chemistry & Materials Engineering, LEU, Chongqing, China 419659327@qq.com Probing into the preparation and thermal insulation mechanism of SiO2 aerogel composite thermal insulation coating, it is discovered that the thermal insulation and heat control of the coating are realized by means of reducing the thermal conductivity, increasing the reflectivity and radiance, etc. The author obtains the content of each filler by single-doped experiments, acquires the optimal coating formula by orthogonal experiment, and gets the characteristics of the coating with self-made thermal insulation test equipment, scanning electron microscope (SEM), fourier translation infrared spectrum (FT-IR), X-ray diffractometer (XRD) and other analytical methods. The results show that the SiO2 aerogel composite thermal insulation coating has the best performance when 5ωt% SiO2 aerogel, 5ωt% titanium dioxide, 5ωt% hollow glass beads, and 10ωt% far- infrared ceramic powder are added. Besides, the high temperature performance of the coating improves with the increase of mass fraction of SiO2 aerogel. When the fraction is 5ωt%, the SiO2 aerogel composite thermal insulation coating performs well at 300°C. Therefore, the author concludes that the SiO2 aerogel significantly improves the thermal insulation and high temperature performance of the thermal insulation coating. The conclusion lays a good foundation for the application of SiO2 aerogel in the coating industry. 1. Introduction The rapid socio-economic development has spurred an increase in energy consumption and raised the awareness of building energy efficiency. Fortunately, there are many innovations in the field of building energy conservation that have significantly improved energy efficiency. The R&D and application of new thermal insulation materials are not to be ignored (Lang, 2002). As one of the ten most promising new materials, SiO2 aerogel boasts broad prospects in building thermal insulation (Buratti et al., 2016l Cheng and Cheng, 2012). Thanks to its unique nano-pore and 3D network structure, the material can effectively reduce the heat transfer, thereby protecting the environment and reducing energy consumption (Boulaoued et al., 2016; De Angelis et al., 2016; Luca et al., 2016; Mario et al., 2013; Zhou and chen, 2016; Woignier et al., 1990; Pierre and Pajonk, 2002; Roselli et al., 2016). Insulation coating refers to the functional coating with thermal insulation effect. By the mechanism of action, insulation coating is mainly divided into reflective insulation coating, thermal barrier coating, and radiant insulation coating. Due to the stricter requirements on insulation performance nowadays, the R&D of composite thermal insulation coating material has become a new hotspot (Xia et al., 2001; Lu and Chen, 2005). The so-called composite thermal insulation coating material stands for the thermal insulation coating material of two or more insulation mechanisms. Different thermal insulation materials are combined into one so that several insulation mechanisms can act at the same time. With the synergic effect of various insulation measures, the composite coating material has a better effect than coating materials of only one insulation mechanism. However, the multiple thermal insulation effect of the composite coating material depends on the low thermal conductivity, high reflectivity and radiance of the functional fillers. Normally, two or more fillers should be mixed together. If SiO2 aerogel is applied, the thermal conductivity of the insulation coating would decrease dramatically, thereby improving the insulation effect (Qu et al., 2014; Zhao et al., 2014). This paper optimizes the formula of the coating by using SiO2 aerogel as the barrier filler, titanium dioxide and hollow glass beads as the reflective filler, and far-infrared ceramic powder as reflective powder. In this way, the author obtains SiO2 aerogel composite thermal insulation coating with excellent thermal insulation performance, and explores its high temperature performance. DOI: 10.3303/CET1655044 Please cite this article as: Liu Z.H., Ding Y.D., Shu X., Liu N., 2016, Preparation, characterization and properties of sio2 aerogel composite thermal insulation coating, Chemical Engineering Transactions, 55, 259-264 DOI:10.3303/CET1655044 259 2. Test 2.1 Raw materials Hydrophobic SiO2 aerogel (Guangdong Alison Hi-Tech Co. ,Ltd.); silicone-based wetting agent Silok 7117, Alkyl ammonium salt dispersant Silok 7195 (Silok); water-based acrylic resin, film-forming additives (Jelee Chemical Industry); titanium dioxide (Huntsman); hollow glass beads (3M); far-infrared ceramic powder (Lingshou County Xunhang Mineral Distribution Co., Ltd.); defoamer 681-F (Rhodia); deionized water (lab made). 2.2 Coating preparation The SiO2 aerogel composite thermal insulation coating material is prepared in the following process: Firstly, mix the SiO2 aerogel particles with multi-grade zirconium beads, grind the particles into nano powder with a high-energy ball mill (speed: 500r/min; duration: 5min; cycle: 1). Secondly, add wetting agent, dispersant, deionized water and a certain amount of zirconium beads into a beaker and stir the mixture evenly (speed: 300~500r/min; duration: 3 minutes). Thirdly, add some defoamer dropwise into the beaker, add the SiO2 aerogel powder, and let the mixture disperse for 3h (speed: 1,800r/min); To prevent the powder from flying at the beginning, the beaker cup should be sealed. Meanwhile, reduce the speed to 700r/min to remove the bubbles in the coating material. While adding the rest of the defoamer, prepare evenly dispersed and stable SiO2 aerogel slurry by slowing down the speed in stages. Fourthly, mix the SiO2 aerogel slurry with resin and additives, add titanium dioxide, far-infrared ceramic powder and hollow glass beads in turn, mix and stir the materials to get the coating material. After the addition of titanium dioxide and far-infrared ceramic powder, high-speed shear dispersion can be adopted (speed: 1,000r/min; duration: 20m); Before the addition of hollow glass beads, the speed should be reduced to 500r/min to prevent excessive shear force from breaking the outer wall of hollow glass beads, causing damages to the hollow insulation structure of the hollow glass beads. 2.3 Performance test The test is performed in accordance with the Roofing Products from Metal Sheet with Reflect Thermal Coating. In light of actual needs, the author improves the standard test device by making a thermal insulation test device with polystyrene foam (thickness: 30mm; thermal conductivity: 0.025 W/(m•K)) for the sample coating. The coating is characterized with scanning electron microscope (SEM), fourier translation infrared spectrum (FT-IR), and X-ray diffractometer (XRD). With different sized wire rod coaters, the author prepares coatings of different film thicknesses, and characterizes their insulation performance. In addition, the author heats the coatings to 200°C, 300°C and 400°C in a muffle furnace, and analyzes their high temperature performances with XRD and FT-IR. 3. Results and discussion 3.1 Thermal insulation performance of SiO2 aerogel composite thermal insulation coating 3.1.1 Formula optimization of SiO2 aerogel composite thermal insulation coating By the mechanism of action, insulation coating is mainly divided into reflective insulation coating, thermal barrier coating, and radiant insulation coating. In the test, the insulation coating is prepared with functional fillers like SiO2 aerogel, titanium dioxide, hollow glass beads, and far-infrared ceramic powder. When the insulation coating is made of a single kind of filler, it has the best performance when 5ωt% SiO2 aerogel, 5ωt% titanium dioxide, 5ωt% hollow glass beads, and 8ωt% far-infrared ceramic powder are added respectively. In the experiment, the functional fillers are added in combinations so that the coating features low thermal conductivity, high reflectivity and high radiance. Besides, the author optimizes the formula of SiO2 aerogel composite thermal insulation coating based on the equilibrium temperature of the bottom of the sample coating in the orthogonal test. Table 1 records the data of the test, where the ωt% of titanium dioxide and hollow glass beads are obtained after the two fillers are mixed at the ratio of 1:1. According to Table 1, the values in the column of SiO2 aerogel are greater than those in other columns within the range R, indicating that the SiO2 aerogel consumption of the coating formula has the most significant impact on the thermal insulation performance of the optimized SiO2 aerogel thermal insulation coating, followed by the consumption of titanium dioxide and the consumption of hollow glass beads. The far-infrared ceramic powder has the lowest impact to the thermal insulation performance of the coating. The optimal ratio between the fillers is SiO2 aerogel: titanium dioxide: hollow glass beads: far-infrared ceramic powder= 5: 5: 5: 10. At this ratio, the bottom temperature of the sample coating is 44.4°C, 14.8°C lower than the equilibrium temperature at the bottom of the uncoated blank sample. This means the ratio has a good insulation effect. 260 Table 1: Orthogonal test of L9(3 4) Number Content (ωt%) SiO2 aerogel TiO2 and Hollow glass beads Far-infrared ceramic powder Temperature (°C) 1 4 8 6 47.2 2 4 10 8 46 3 4 12 10 46.6 4 5 8 8 45.5 5 5 10 10 44.4 6 5 12 6 45 7 6 8 10 48.2 8 6 10 6 47.8 9 6 12 8 49.5 K1 139.8 140.9 140 K2 134.9 138.2 141 K3 145.5 141.1 139.2 k1 46.6 46.9667 46.6667 k2 44.9667 46.0667 47 k3 48.5 47.0333 46.4 Range R 3.5333 0.9666 0.6 3.1.2 The effect of film thickness on thermal insulation performance According to the test results in Section 2.1.1, the author prepares coatings at the thickness of 50μm, 80μm, 100μm, 150μm and 200μm with a coater and in light of the optimal formula of five materials. In other words, the author adopts the optimal ratio between the fillers SiO2 aerogel: titanium dioxide: hollow glass beads: far- infrared ceramic powder= 5: 5: 5: 10. After the coatings are solidified at room temperature, the author measures the equilibrium temperatures of the sample coatings. See Figure 1 for the test results. As shown in Figure 1, the equilibrium temperatures of the sample coatings gradually decrease with the increase of the coating thickness, but the downward trend gradually slows. The phenomenon is interpreted as follows: the thicker the coating, the more functional fillers in a unit area, leading to a decrease in thermal conductivity, and an increase in reflectivity and radiance. As a result, the thermal insulation performance of the coating gets better as the thickness grows. When the wet film thickness is 100μm, 150μm and 200μm, the equilibrium temperature of the sample coating is 44.6°C, 44.2°C and 44°C respectively. This indicates that the thermal insulation performance of the coating is not significantly improved after the thickness exceeds a certain degree due to the lack of sufficient decrease of thermal conductivity or increase of solar reflectance and radiance. Figure 1: The change curve of temperatures of sample coatings of different thicknesses 3.2 Analysis and characterization of SiO2 aerogel composite thermal insulation coating 3.2.1 Micro-morphology analysis Figure 2 displays the SEM images of the SiO2 aerogel composite thermal insulation coatings of formula 5 and formula 6, which have better thermal insulation performance than the coatings of other formulas. As shown in the figure, the hollow glass beads form a continuous solar barrier layer and reflective layer, featuring low 261 thermal conductivity and reflection effect. Due to their small particle sizes, SiO2 aerogel, titanium dioxide and far-infrared ceramic powder fill up the gaps of the coating, which enhances the continuity of filler and improves the barrier efficiency of the coating; some of these materials are attached to the surface of the hollow glass beads, acting as a reflector and radiator of sunlight (Garbarino et al., 2013; Liang, 2014; Feng et al., 2017). (a) Coating of formulation 5 (b) Coating of formulation6 Figure 2: SEM images of SiO2 aerogel composite thermal insulation coatings of different formulas 3.2.2 FT-IR analysis Figure 3 displays the infrared images of SiO2 aerogel composite insulation coatings of different formulas. As show in the figure, in spite of the difference in mass fraction of functional fillers, the coatings exhibit basically the same characteristic peaks. Among them, 2960 cm-1 and 1453 cm-1 are respectively the absorption peaks of asymmetric stretching vibration, symmetrical stretching vibration, and asymmetric edges of methyl (CH3) in acrylic resin; 1731 cm-1 is the absorption peak of stretching vibration of carbonyl (C=O) in acrylic resin; 770 cm-1and 705 cm-1 are the absorption peaks of variable angular vibration of COO－ in acrylic resin; 3300 cm-1 is the absorption peak of stretching vibration of –NH of secondary amide in alkyl ammonium salt dispersant; 2854 cm-1and 2925 cm-1 are the absorption peaks of symmetrical stretching and a symmetrical stretching of CH2; 1636cm -1 is the absorption peak of stretching vibration of C=O in secondary amide; 1095 cm-1 is the absorption peak of the asymmetric stretching vibration of Si-O-Si; 847 cm-1 is the absorption peak of bending vibration of Si-OH; 470 cm-1 is the absorption peak of bending vibration of Si-O-Si. The last three absorption peaks are the characteristic absorption peaks of SiO2 aerogel. 3.2.3 XRD analysis Figure 4 displays the XRD images of SiO2 aerogel composite insulation coatings of different formulas. As show in the figure, the coatings contain basically the same substances. The wide dispersion peak near 22° belongs to SiO2 aerogel, the peaks near 27°, 36°, 42° and 54° probably belongs to titanium dioxide, the sharp peak near 22° may belong to hollow glass beads, and the peaks near 29° and 56° may come from the far- infrared ceramic powder. All of these peaks come from the raw materials of the coatings. Figure 3: FT-IR images of SiO2 aerogel composite thermal insulation coatings of different formulas Figure 4: XRD images of SiO2 aerogel composite thermal insulation coatings of different formulas 3.3. High temperature performance analysis of SiO2 aerogel composite thermal insulation coatings 3.3.1 XRD analysis Figure 5 displays the XRD images of SiO2 aerogel composite insulation coatings after being burned at different temperatures. As show in the figure, the characteristic peaks of the coatings of different formulas largely remains at the original location after being burned at 200°C, indicating that the coatings do not undergo chemical changes and products no new substance at the temperature. This means all of the coatings can withstand the temperature of 200°C. After being burned at 300°C, the coating of formula 2 exhibits characteristic peaks near 43°, 70° and 75°. In contrast, the same does not happen to the coatings of formulas 262 4, 5 & 6 for which the same peaks appear only after the coatings are burned at 400°. The reason is that cracks appear in the coatings as the temperature rises so that the characteristic peaks of low-carbon steel substrate materials appear in XRD images. Plus, as the mass fraction of SiO2 aerogel in the coatings of formulas 4, 5 & 6 is higher than the coating of formula 2, indicating that the SiO2 aerogel is conducive to the heat resistance of coating. What is more, the wide dispersion peak near 22° disappears after the coatings are burned at 400°C. This is probably caused by the formation of SiO2 crystals after the coatings are burned at 400°C. Figure 5: XRD images of the optimized coatings burn at different temperatures 3.3.2 FT-IR analysis Figure 6 displays the FT-IR of SiO2 aerogel composite insulation coatings of different formulas after being burned at different temperatures. In comparison with Figure 3, the characteristic peaks are not changed significantly after the coatings are burned at 200°C, but the intensity of some peaks are enhanced as the temperature rises. In light of the analysis of Figure 5, the intensity of the characteristic peak of Si-O-Si is greatly enhanced due to the formation of crystals, which is demonstrated by the sharp peaks at 1095 cm-1and 470 cm-1. Besides, through analysis of the images, the organics are not greatly affected by the firing at 200°C. However, when the temperature rises to 300°C, the characteristic peaks of organics in all coatings are reduced, indicating that some of the organics in the coatings are decomposed. When the temperature rises to 400°C, the characteristic peaks of organics almost disappear while those of inorganic substances become sharp and prominent. Figure 6: FT-IR images of the optimized coatings burn at different temperatures 4. Conclusion 1) Through the orthogonal experiment, the SiO2 aerogel composite thermal insulation coating has the best performance when 5ωt% SiO2 aerogel, 5ωt% titanium dioxide, 5ωt% hollow glass beads, and 10ωt% far- infrared ceramic powder are added. Besides, the thermal insulation performance of the coating gradually improves with the increase in wet film of the coating. 263 2) The hollow glass beads of the coatings form a continuous solar barrier layer and reflective layer, and SiO2 aerogel, titanium dioxide and far-infrared ceramic powder further enhance the barrier efficiency of the coating and act as a reflector and radiator of sunlight, thereby greatly improving the thermal insulation performance of the coatings 3) The thermal insulation and high temperature performance of the thermal insulation coating increase with the mass fraction of the SiO2 aerogel. When the SiO2 aerogel is 5ωt%, the coating can withstand the temperature as high as 300°C. 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