摘要
聚酰胺6 (PA6)是一种重要的工程塑料,但因其低温韧性较差等缺点而限制了应用。本论文以三元乙丙橡胶(EPDM)和马来酸酐接枝三元乙丙橡胶(EPDM-g-MAH)的复配共混物为橡胶,纳米碳酸钙(nano-CaCO_3)为无机粒子,通过在PA6基体中构建了EPDM包覆nano-CaCO_3团聚体的“沙袋结构”粒子,制得高韧性的PA6三元复合材料,利用扫描电镜(SEM)、动态力学分析(DMA)等手段观察和研究了“沙袋结构”粒子在基体中的形态及在外力作用下的演变,并进一步探讨了“沙袋结构”粒子对PA6的增韧机理。主要研究内容和结果如下:
1、通过nano-CaCO_3表面处理和EPDM交联,调节EPDM—nano-CaCO_3—PA6间的界面性能,研究了界面性能对PA6/EPDM/nano-CaCO_3三元复合形态与性能的影响。结果表明,采用硬脂酸处理的nano-CaCO_3分散在EPDM相中,形成“沙袋结构”,冲击强度大幅度提高;当过氧化二异丙苯(DCP)含量从0 wt%提高到0.30 wt%时,“沙袋结构”粒子粒径变大,三元复合材料的冲击强度下降。在受到外力作用时,含有均匀分散的“沙袋结构”粒子的三元复合材料通过“沙袋结构”粒子诱发微纤化和“扩张带”耗散外界作用能。
2、共混工艺与注塑工艺对PA6/EPDM/nano-CaCO_3三元复合材料的分散相形态有显著影响。采用两步法工艺制得的三元复合材料形成“沙袋结构”,而一步法工艺制得的三元复合材料中各组分独立分散。通过基本断裂功(EWF)测试发现“沙袋结构”有利于提高复合材料的断裂韧性和抵抗裂纹扩展能力。注射速率很大程度上决定了PA6/EPDM/nano-CaCO_3三元复合材料皮芯层中“沙袋结构”粒子的完整性,随着注射速率的加快,试样皮层的“沙袋结构”粒子发生破裂,出现nano-CaCO_3团聚体,芯层的“沙袋结构”粒子分散性较差,从而导致三元复合材料的冲击强度降低。
3、从空洞和基体的塑性形变能力两方面来定量地研究复合材料的能量耗散。通过体积应变测试和平行于拉伸方向的断面SEM图观察,PA6/EPDM/nano-CaCO_3 (两步法)三元复合材料(E4)的空洞体积大于PA6/nano-CaCO_3二元复合材料(E1)、PA6/EPDM二元复合材料(E2)和PA6/EPDM/nano-CaCO_3 (一步法)三元复合材料(E3)。垂直于拉伸方向的断面SEM图表明E4的基体塑性形变能力大于E1、E2和E3,因此,E4的能量耗散能力大于E1、E2和E3。
Polyamide 6 (PA6) is a kind of widely used engineering plastics, but the application is limited because of its poor toghness under low temperature. In this work, ethylene propylene diene terpolymer rubber (EPDM)/maleated ethylene propylene diene terpolymer rubber (EPDM-g-MAH) was employed as rubber, nano calcium carbonate (nano-CaCO_3) was employed as inorigid particles,“sandbag”microstructure particle embedded nano-CaCO_3 agglomerate into EPDM was constructed in PA6/EPDM/nano-CaCO_3 ternary composites. This“sandbag”microstructure could effectively improve the toughness of PA6. Morphology evolution of“sandbag”microstructure particles in PA6 matrix and under the external force was studied by Scanning Electron Microscope (SEM) and Dynamic Mechanical Analysis (DMA). The toughening mechanism of“sandbag”microstructure particles was further discussed. The main works and conclusions were listed as follows:
1. The effect of interfacial properties controlled by modifing the surface properties of nano-CaCO_3 and crosslinking degree of EPDM on morphology and properties of the ternary composites were studied. It was found that nano-CaCO_3 coated with stearic acid was selectively distributed in EPDM, and“sandbag”microstructure was constructed in the ternary composite of well toughness; When the content of dicumyl peroxide (DCP) in EPDM increased from 0 wt% to 0.30 wt%, the size of“sandbag”microstructure particles dispersed in PA6 matrix became larger, while the impact strength of the ternary composites became smaller. When the ternary composite was impacted, the impact energy applied on the composite was dissipated by the fiber-forming mode and dilataional bands which were induced by“sandbag”microstructure particles finely dispersed in PA6 matrix.
2. The influence of compounding routes and injection molding conditions on morphology and properties of PA6/EPDM/nano-CaCO_3 ternary composites was studied. It was found that the“sandbag”microstructure particles could be constructed only via two-step compounding route, and“sandbag”microstructure particles were effective to improve the fracture toughness and resist the growth of the crake. The structure integrity of“sandbag”microstructure particles dispersed in PA6 matrix markedly depended on the injection rate, when the injection rate increased, there was nano-CaCO_3 agglomerate present in the skin layer, the dispersion of“sandbag”microstructure particles in the core layer became worse, and the impact strength of the ternary composites became smaller.
3. The mechanism of energy dissipation which includes voids and plastic deformation of matrix was studyed. Various modes of voids were observed by scanning electron microscope (SEM). The volume of voids in PA6/EPDM/nano-CaCO_3 (two-step) ternary composites (E4) was larger than PA6/nano-CaCO_3 binary composites (E1), PA6/EPDM binary composites (E2) and PA6/EPDM/nano-CaCO_3 (one-step) ternary composites (E3). The fracture surface along the direction perpendicular to the tensile direction observed by SEM resulted that matrix plastic deformation of E4 was larger than E1, E2 and E3. So energy dissipation of E4 was larger than E1, E2 and E3.
引文
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[1] Kelnar I, Kotek J, Kapralkova L, et al. Polyamide Nanocomposites with Improved Toughness[J]. Journal of Applied Polymer Science, 2005, 96(2): 288-293
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[1] Kelnar I, Kotek J, Kapralkova L, et al. Polyamide Nanocomposites with Improved Toughness[J]. Journal of Applied Polymer Science, 2005, 96(2): 288-293
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[3]王旭波,许向彬,王旭等. PA6基“沙袋结构”复合材料的形态及力学性能[J].塑料工业, 2008, 36(4): 43-45
[4]徐科杰,王晓东,傅李丹等. EPDM/纳米CaCO_3预混料动态力学性能及其对聚丙烯基三元复合材料韧性的影响[J].中国塑料, 2009, 23(6): 45-49
[5] Wang X, Xu KJ, Xu XB, et al. Selective Particle Distribution and Mechanical Properties of Nano-CaCO_3/Ethylene-Propylene-Diene Terpolymer/Polypropylene Composites with High Content of Nano-CaCO_3[J]. Journal of Applied Polymer Science, 2009, 113(4): 2485-2491
[6] Wang X, Wang XD, Xu XB. The Construction of Sandbag Microstructure in Polyamide 6/Ethylene-Propylene-Diene Terpolymer/Nanometer Calcium Carbonate Ternary Composite[J]. Journal of Macromolecular Science, Part B, 2009, 48(6): 1212-1221
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[11]王晓东,徐科杰,王旭等.共混工艺对PA6/EPDM/nano-CaCO3三元复合材料形态与性能的影响[J].塑料, 2009, 38(5): 11-13
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