Preparation and properties of triple shape memory composites based on trans-polyisopren / poly (ethylene-co-vinyl acetate)
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摘要:
三重形状记忆材料以其可调节性、多种刺激和多功能性，广泛应用于传感器、航空航天、4D打印及生物医学等领域。但由于材料内部存在相分离，导致其断裂伸长率较差，严重阻碍了它的实际应用。本文采用TPI和EVA复合，设计过氧化二异丙苯交联反应增强其相容性，制备出具有三重形状记忆功能的复合材料。探究了TPI与EVA比例对TPI-EVA复合材料的力学性能、相结构、结晶性能以及三重形状记忆性能的影响。结果表明，随着EVA质量比增加，TPI的结晶温度(Tc)从14.7℃降低至8.2℃，EVA的Tc略有上升。SEM结果表明，随EVA质量比增加，复合材料的相界面由光滑变为粗糙；DMA测试结果表明，EVA比例的增加使样品的第一临时形状固定率从57.6%提升至88.5%。此外，TPI-EVA复合材料表现出优异的力学强度，其中拉伸强度高达30.3MPa，断裂伸长率达490%。所制备的TPI-EVA复合材料可用于机器人、致动器以及生物医学应用领域。这项工作有助于设计具有良好相容性的三重形状记忆聚合物，为传统商业聚合物的实际应用奠定了基础。 (a) TPI-EVA三重形状记忆复合材料的DMA图，(b) 复合材料力学性能图以及(c)三重形状记忆宏观恢复图 -
关键词:
- 三重形状记忆效应 /
- 反式聚异戊二烯 /
- 乙烯醋酸乙烯酯共聚物 /
- 结晶性能 /
- 力学性能
Abstract: The TPI-EVA triple shape memory composites were prepared by compounding trans-polyisoprene and poly (ethylene-co-vinyl acetate) (TPI-EVA), and designed cross-linking reaction of dicumyl peroxide to connect the two phases. The TPI-EVA composites were characterized by rheometer, universal testing machine, XRD, DSC and dynamic thermomechanical analyzer (DMA). The effects of the mass ratio of EVA on the mechanical properties, phase structure, crystalline properties and triple shape memory properties of TPI-EVA composites were studied. The results showed that with the increase of the mass ratio of EVA, the crystallization temperature (Tc) of TPI decreased from 14.7℃ to 8.2℃, and the Tc of EVA increased slightly. SEM test showed that with the increase of EVA mass ratio, the phase interface of the composites changed from smooth to rough; DMA test showed that the increase of EVA mass ratio increased the first temporary shape memory fixation rate of the samples from 57.6% to 88.5%. Moreover, the TPI-EVA composites exhibit excellent mechanical properties, the tensile strength was as high as 30.3MPa and the elongation at break reached 490%. -
图 1 不同TPI-EVA比例的复合材料室温下的(a)应力应变曲线和(b)拉伸强度和断裂伸长率
Figure 1. (a) Stress-strain curves and tensile strength and elongation at breaking of the TPI-EVA composites with different ratios
图 2 不同TPI-EVA比例的复合材料的XRD图
Figure 2. X-ray diffractograms curves of the TPI-EVA composites with different ratios
图 3 不同TPI-EVA比例的复合材料的DSC曲线：(a)第一次降温曲线和(b)第二次升温曲线
Figure 3. DSC curves of the TPI-EVA composites with different ratios: (a) DSC cooling curves and (b) secondary heating curves
图 4 不同TPI-EVA比例的复合材料的DMA测试图：(a)T9 E1; (b)T8 E2; (c)T7 E3; (d)T6 E4; (e)T5 E5
Figure 4. DMA curves of the TPI-EVA composites with different ratios: (a)T9 E1; (b)T8 E2; (c)T7 E3; (d)T6 E4; (e)T5 E5
图 5 TPI-EVA复合材料的三重形状记忆行为的数码照片：(a)T7 E3;(b)T6 E4
Figure 5. Photographs of the tripe shape memory effect of the TPI-EVA composites: (a)T7 E3;(b)T6 E4
图 6 不同TPI-EVA比例的复合材料的SEM图：(a)T9 E1;(b)T8 E2;(c)T7 E3;(d)T6 E4;(e)T5 E5
Figure 6. SEM photos of the TPI-EVA composites with different ratios: (a)T9 E1; (b)T8 E2; (c)T7 E3; (d)T6 E4; (e)T5 E5
图 7 TPI-EVA复合材料的三重形状记忆机制图
Figure 7. Schematic diagrams of TPI-EVA composites in tripe shape memory process
表 1 TPI-EVA的复合材料配方
Table 1. The formulation of TPI-EVA composites
Sample Code TPI/g EVA/g T10 100 0 T9 E1 90 10 T8 E2 80 20 T7 E3 70 30 T6 E4 60 40 T5 E5 50 50 Notes: 2 g of stearic acid, 8 g of zinc oxide and 1 g of dicumyl peroxide were added. 
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表 2 不同TPI-EVA比例复合材料在175℃下硫化特性参数
Table 2. Vulcanization characteristic parameters of TPI-EVA composites with different ratios at 175℃
Properties T10 T9 E1 T8 E2 T7 E3 T6 E4 T5 E5 MH/(dN·m) 3.77 3.15 2.69 2.53 1.58 1.30 ML/(dN·m) 0.37 0.27 0.14 0.47 0.00 0.00 MH-ML/(dN·m) 3.40 2.88 2.55 2.06 1.58 1.30 T90/min 4.03 4.17 4.39 5:04 5.12 5.39 Cure rate index/min−1 28.4 26.4 24.4 22.6 21.2 21.0
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表 3 不同TPI-EVA比例的复合材料的三重形状记忆性能
Table 3. Tripe shape memory properties of the TPI-EVA composites with different ratios
Sample Code Rf (0→1)/% Rf (1→2) /% Rr (2→1) /% Rr (1→0) (%) T8 E2 57.6 99.0 79.6 99.8 T7 E3 66.9 98.1 79.2 100 T6 E4 77.9 97.6 78.9 99.9 T5 E5 88.5 97.1 77.2 75.1 Notes: Rf—Shape fixity ratio; Rr—Shape recovery ratio.
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