Preparation and thermal conductivity of flexible phase change composite materials with oriented thermal conductivity structure
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摘要: 为解决高分子基复合材料固有热导率较差这一问题，本研究采用简单高效、易工业化的开炼法在聚乙烯辛烯共弹性体(POE)基体中构建有序的取向结构，制备了一种具有优异综合性能的柔性相变复合材料。在开炼机的强剪切场作用下，石蜡(PW)和氮化硼(BN)在POE基体内部沿剪切场方向发生了定向取向排列，促进了导热通路的构建。当石墨烯纳米片(GNPs)和BN添加量分别为2wt%和25wt%时，PW-2wt%GNPs-25wt%BN/POE相变复合材料热导率(λ)从1.01W·m−1·K−1 (PW/POE)提高到2.59 W·m−1·K−1，提高了156%。并且PW-2wt%GNPs-25wt%BN/POE相变复合材料具有优异的拉伸强度(18.3MPa)和断裂伸长率(720%)，在弯曲、折叠成复杂的形状后不会出现任何的破裂，在10次循环往复拉伸测试中具有良好的可回复性。此外，添加30wt%的PW能够赋予PW-2wt%GNPs-25wt%BN/POE一定的焓值44.1 J·g−1；当施加80 mW·cm−2的光照强度时，表面贴有PW-2wt%GNPs-25wt%BN/POE复合材料的瓶内温度高达54.3℃，较未添加GNPs的PW/POE提高了20℃，并且在光照条件下，PW-2wt%GNPs-25wt%BN/POE复合材料具有优异的光驱动可恢复性能，使其具有潜在的光热转换应用前景，在实际应用和工业化生产方面具备巨大潜力。Abstract: To address the issue of poor inherent thermal conductivity in polymer-based composites, this study employed a simple, efficient, and industrially viable kneading method to construct an ordered orientation structure within a polyolefin elastomer (POE) matrix, resulting in a flexible phase-change composite material with outstanding comprehensive performance. Under the strong shear field of the kneader, paraffin wax (PW) and boron nitride (BN) were oriented and arranged along the shear field direction within the POE matrix, facilitating the construction of thermal conduction pathways. When the graphene nanoplatelets (GNPs) and BN content were 2wt% and 25wt%, respectively, the thermal conductivity (λ) of the PW-2wt%GNPs-25wt%BN/POE phase-change composite material increased from 1.01 W·m−1·K−1 (PW/POE) to 2.59 W·m−1·K−1, representing a 156% enhancement. Moreover, the PW-2wt%GNPs-25wt%BN/POE phase-change composite material exhibited excellent tensile strength (18.3 MPa) and elongation at break (720%), with no signs of rupture after bending and folding into complex shapes, and demonstrated good recoverability in 10 cycles of tensile testing. Furthermore, adding 30wt% PW can endow PW-2wt%GNPs-25wt%BN/POE composite material with a certain enthalpy value of 44.1 J·g−1. Under an illumination intensity of 80 mW cm−2, the temperature inside a bottle coated with the PW-2wt%GNPs-25wt%BN/POE composite material reached 54.3°C, which was 20°C higher than that of the PW/POE without GNPs. Moreover, under illumination conditions, the PW-2wt%GNPs-25wt%BN/POE composite material exhibited excellent light-driven recoverable performance, suggesting its potential application in photothermal conversion, and thereby possessing significant potential for practical applications and industrial production.
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图 1 (a)和(b)分别为氮化硼(BN)和石墨烯纳米片(GNPs)的SEM图像
Figure 1. SEM images of (a) boron nitride (BN) and (b) graphene nanosheets (GNPs), respectively
图 2 石蜡(PW)-GNPs-BN/聚乙烯辛烯共弹性体(POE)相变复合材料的制备工艺示意图
Figure 2. Schematic diagram of the preparation process of paraffin wax (PW)-GNPs-BN/ polyolefin elastomer (POE) phase change composite materials
图 3 SEM图像：(a)PW/POE，(a1)高温处理的PW/POE，(b) PW-2wt%GNPs/POE，(c) PW-25wt%BN/POE，(d) PW-2wt%GNPs-5wt%BN/POE，(e) PW-2wt%GNPs-10wt%BN/POE，(f) PW-2wt%GNPs-15wt%BN/POE，(g) PW-2wt%GNPs-25wt%BN/POE以及局部放大图(g1) PW-2wt%GNPs-25wt%BN/POE
Figure 3. SEM images: (a) PW/POE, (a1) thermal heated PW/POE, (b) PW-2wt%GNPs/POE, (c) PW-25wt%BN/POE, (d) PW-2wt%GNPs-5wt%BN/POE, (e) PW-2wt%GNPs-10wt%BN/POE, (f) PW-2wt%GNPs-15wt%BN/POE, (g) PW-2wt%GNPs-25wt%BN/POE and local magnified image (g1) PW-2wt%GNPs-25wt%BN/POE
图 4 PW和PW-GNPs-BN/POE相变复合材料的XRD图像：(a)表面,(b)断面
Figure 4. XRD images of PW and PW-GNPs-BN/POE phase change composite materials: (a) surface, (b) section
图 5 (a)PW-GNPs-BN/POE相变复合材料的DSC熔融曲线,(b)PW-2wt%GNPs-25wt%BN/POE的循环熔融曲线
Figure 5. (a) DSC melting curve of PW-GNPs-BN/POE phase change composite materials, (b) cycle melting curve of PW-2wt%GNPs-25wt%BN/POE
图 6 PW-GNPs-BN/POE相变复合材料的力学性能曲线：(b)：1#、2#、3#、4#、5#、6#和7#分别代表PW/POE、PW-2wt%GNPs/POE、PW-2wt%GNPs-5wt%BN/POE、PW-2wt%GNPs-10wt%BN/POE、PW-2wt%GNPs-15wt%BN/POE、PW-2wt%GNPs-25wt%BN/POE和PW-25wt%BN/POE
Figure 6. Mechanical property curve of PW-GNPs-BN/POE phase change composite materials: (b): 1#, 2#, 3#, 4#, 5#, 6#, and 7# represent PW/POE, PW-2wt%GNPs/POE, PW-2wt%GNPs-5wt%BN/POE, PW-2wt%GNPs-10wt%BN/POE, PW-2wt%GNPs-15wt%BN/POE, PW-2wt%GNPs-25wt%BN/POE, and PW-25wt%BN/POE, respectively.
图 7 PW-GNPs-BN/POE相变复合材料的(a)热扩散系数，(b)λ。其中，1#、2#、3#、4#、5#、6#和7#分别代表PW/POE、PW-2wt%GNPs/POE、PW-2wt%GNPs-5wt%BN/POE、PW-2wt%GNPs-10wt%BN/POE、PW-2wt%GNPs-15wt%BN/POE、PW-2wt%GNPs-25wt%BN/POE和PW-25wt%BN/POE
Figure 7. (a) Thermal diffusion coefficient, (b) λ of PW-GNPs-BN/POE phase change composite materials. Among them, 1#, 2#, 3#, 4#, 5#, 6#, and 7# represent PW/POE, PW-2wt%GNPs/POE, PW-2wt%GNPs-5wt%BN/POE, PW-2wt%GNPs-10wt%BN/POE, PW-2wt%GNPs-15wt%BN/POE, PW-2wt%GNPs-25wt%BN/POE, and PW-25wt%BN/POE respectively.
图 8 POE-PW-GNPS/BN相变复合材料的导热提高率，其中，1#、2#、3#、4#、5#、6#和7#分别代表PW/POE、PW-2wt%GNPs/POE、PW-2wt%GNPs-5wt%BN/POE、PW-2wt%GNPs-10wt%BN/POE、PW-2wt%GNPs-15wt%BN/POE、PW-2wt%GNPs-25wt%BN/POE和PW-25wt%BN/POE
Figure 8. Thermal conductivity enhancement of PW-GNPs-BN/POE phase change composite materials. Among them, 1#, 2#, 3#, 4#, 5#, 6#, and 7# represent PW/POE, PW-2wt%GNPs/POE, PW-2wt%GNPs-5wt%BN/POE, PW-2wt%GNPs-10wt%BN/POE, PW-2wt%GNPs-15wt%BN/POE, PW-2wt%GNPs-25wt%BN/POE, and PW-25wt%BN/POE respectively.
图 9 PW-GNPs-BN/POE相变复合材料的LED灯热管理应用：(a)时间-温度曲线，(b)红外热成像图像
Figure 9. PW-GNPs-BN/POE phase change composite materials for LED lamp thermal management applications: (a) time-temperature curves; (b) corresponding infrared thermography images
图 10 (a)光-热转换测量装置示意图，PW-GNPs-BN/POE相变复合材料分别在(b) 80 mW·cm−2和(c)在不同光照强度下的光热转换曲线图。其中，1#、2#、3#、4#、5#、6#和7#分别代表PW/POE、PW-2wt%GNPs/POE、PW-2wt%GNPs-5wt%BN/POE、PW-2wt%GNPs-10wt%BN/POE、PW-2wt%GNPs-15wt%BN/POE、PW-2wt%GNPs-25wt%BN/POE和PW-25wt%BN/POE
Figure 10. (a) Schematic diagram of the light-to-heat conversion measurement device, photothermal conversion curve of PW-GNPs-BN/POE phase change composite materials (b) under 80 mW cm−2 and (c) under different light intensities. Among them, 1#, 2#, 3#, 4#, 5#, 6#, and 7# represent PW/POE, PW-2wt%GNPs/POE, PW-2wt%GNPs-5wt%BN/POE, PW-2wt%GNPs-10wt%BN/POE, PW-2wt%GNPs-15wt%BN/POE, PW-2wt%GNPs-25wt%BN/POE, and PW-25wt%BN/POE respectively.
图 11 通过模拟热管理应用得到不同样品的时间-温度曲线。其中，1#、2#、6#和7#分别代表PW/POE、PW-2wt%GNPs/POE、PW-2wt%GNPs-25wt%BN/POE和PW-25wt%BN/POE
Figure 11. Time-temperature curves of different samples obtained by simulated thermal management application. Among them, 1#, 2#, 6#, and 7# represent PW/POE, PW-2wt%GNPs/POE, PW-2wt%GNPs-25wt%BN/POE, and PW-25wt%BN/POE respectively.
图 12 在光照强度为80 mW·cm−2时PW-GNPs-BN/POE相变复合材料的红外热成像
Figure 12. Infrared thermography of PW-GNPs-BN/POE phase change composite materials at a light intensity of 80 mW·cm−2
图 13 PW-GNPs-BN/POE相变复合材料的光驱动恢复图像：(a)光照强度为80 mW·cm−2，(b)无光照
Figure 13. Photographs of light-driven recoverability of PW-GNPs-BN/POE phase change composite materials：(a) the light intensity is 80 mW·cm−2, (b) no illumination
表 1 样品配方
Table 1. Sample Formula
Samples POE/wt% PW/wt% Mass ratio of PW/POE GNPs/wt% BN/wt% PW/POE 70 30 7:3 0 0 PW-2wt%GNPs/POE 68.6 29.4 7:3 2 0 PW-2wt%GNPs-5wt%BN/POE 65.1 27.9 7:3 2 5 PW-2wt%GNPs-10wt%BN/POE 61.6 26.4 7:3 2 10 PW-2wt%GNPs-15wt%BN/POE 58.1 24.9 7:3 2 15 PW-2wt%GNPs-25wt%BN/POE 51.1 21.9 7:3 2 25 PW-25wt%BN/POE 52.5 22.5 7:3 0 25 
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表 2 PW-GNPs-BN/POE相变复合材料的取向度
Table 2. Orientation degree of PW-GNPs-BN/POE phase change composite materials
Samples Orientation factor PW-2wt%GNPs-5wt%BN/POE 0.49 PW-2wt%GNPs-10wt%BN/POE 0.51 PW-2wt%GNPs-15wt%BN/POE 0.57 PW-2wt%GNPs-25wt%BN/POE 0.83 PW-25wt%BN/POE 0.55
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表 3 在融化过程中PW和PW-GNPs-BN/POE相变复合材料的相变参数
Table 3. Phase transition parameters of PW and PW-GNPs-BN/POE phase change composite materials during the melting process.
Samples TM/℃ HM/(J·g−1) PW 56.2 141.2 PW/POE 52.3 46.6 PW-2wt%GNPs/POE 49.6 56.6 PW-2wt%GNPs-5wt%BN/POE 50.16 51.9 PW-2wt%GNPs-10wt%BN/POE 49.8 51.9 PW-2wt%GNPs-15wt%BN/POE 49.8 47.5 PW-2wt%GNPs-25wt%BN/POE 49.8 44.1 PW-25wt%BN/POE 49.8 45.1 Notes：TM: Melting temperature; HM: Melting enthalpy.
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