杜仲胶基形状记忆复合材料的制备与性能研究

发布时间：2018-01-17 18:18

本文关键词：杜仲胶基形状记忆复合材料的制备与性能研究　出处：《青岛科技大学》2017年硕士论文　论文类型：学位论文

【摘要】：形状记忆聚合物是一种刺激响应型智能材料,它们可以“记忆”一种或多种预先设定的形状,在受到热、电、磁、光、湿度或化学刺激等外界刺激时,材料能够发生较大的可回复变形。形状记忆聚合物具有可回复形变量大,密度低,加工成型容易,性能可调节范围大,回复行为可控性强,成本低等优点,被广泛应用于生物医用材料、航天航空、汽车、纺织以及自修复等领域。杜仲胶便是最典型的一种形状记忆聚合物,以其为基体的新材料开发应用具有很高的战略意义。本文以杜仲橡胶为基体材料制备了一系列热致型形状记忆复合材料,并研究了材料的内部结构、组成与物理机械性能、形状记忆性能之间的关系。本文的主要研究内容如下:首先,我们研究了门尼粘度对杜仲胶材料物理机械性能、形状记忆性能的影响。结果表明:高门尼粘度的杜仲胶与低门尼粘度的杜仲胶相比,在硫化方面,高门尼粘度的杜仲胶的焦烧时间和硫化时间明显较大,最小转矩和最大转矩也明显提高,这说明高门尼材料的加工安全性比低门尼的好,但硫化时间较长;在物理机械性能方面,随硫黄用量的增加,高、低门尼材料的撕裂强度、定伸应力、扯断伸长率的变化趋势类似,但拉伸强度变化正好相反;在热性能方面,升、降温曲线规律一致,但从材料的结晶、熔融焓来看,低门尼材料的结晶度要好;在形状记忆方面,高门尼粘度材料的形状回复率最高可达98.9%,而低门尼粘度材料的形状回复率最高才达到81.4%。其次,我们研究了填料的种类和用量对杜仲胶材料物理机械性能、形状记忆性能的影响,并研究了复合材料的单向和双向形状记忆行为。实验表明:随甲壳素用量的增大,拉伸强度、撕裂强度、扯断伸长率和形状回复率都有所降低;适当的加入碳化硅或炭黑填料能明显提高TPI材料的力学性能和形状记忆性能,加入碳化硅为10份时形状回复率可达到95.6%,加入炭黑为5份时形状回复率可达到90.4%。最后,我们采用共混的方法制备杜仲胶/聚丁二酸丁二醇酯(TPI/PBS)形状记忆复合材料,我们研究了杜仲胶/聚丁二酸丁二醇酯共混比以及相容剂的加入对复合材料力学性能、形状记忆性能的影响。结果表明:在共混比方面,随PBS用量的增大,复合材料的力学性能有逐渐减小的趋势,热刺激响应温度逐渐减小,材料的形状回复率先增加后降低,当共混比为90/10时,形状回复率最大,达到92.5%;在硫化体系方面,研究了硫黄(S)、过氧化物(DCP)、硫黄/过氧化物(S/DCP)并用对TPI/PBS形状记忆复合材料性能的影响,结果表明:随硫化剂用量的增大,材料的力学性能都有逐渐减小的趋势,但硫黄/过氧化物并用作硫化剂的体系的拉伸强度、撕裂强度、定伸应力明显比其他两个体系好,拉伸强度提高了1-2MPa,撕裂强度提高了1-4KN/m,定伸应力也提高了1-3MPa左右;从形状记忆性能来看,在硫黄作硫化剂的复合材料中,当硫黄用量为1.6phr时,复合材料的形状记忆性能最佳,在过氧化物作硫化剂的复合材料中,当DCP用量为1.2phr时,材料的形状记忆性能最佳,在硫黄/过氧化物并用作硫化剂的复合材料中,当DCP用量为0.4phr时,复合材料的形状记忆性能最佳。
[Abstract]:The shape memory polymer is a stimulus response type of smart materials, they can be "memory" of one or more predetermined shape by heat, electricity, magnetism, light, humidity or chemical stimulation of external stimuli, the material can occur large recoverable deformation. The shape memory polymer has the recovery of large deformation. Low density, easy processing, performance can be adjusted in a wide range, recovery behavior of strong controllability and low cost advantages, has been widely used in biomedical materials, aerospace, automotive, textile and other fields. The self repairing of Eucommia ulmoides gum is a kind of typical shape memory polymers, the new materials development and application of matrix has a high strategic significance. This paper prepared a series of thermally induced shape memory composite materials with eucommia rubber is studied and the internal structure of materials, and the physical and mechanical properties, shape memory The relation between energy. The main research contents of this paper are as follows: firstly, we study the Mooney viscosity on the mechanical performance of Eucommia rubber material physical properties, shape memory effect. The results showed that: compared with gutta percha gutta and low Mooney viscosity of high Mooney viscosity, curing, high Mooney viscosity of gutta percha and scorch time the curing time is relatively obvious, the minimum torque and the maximum torque is obviously improved, indicating that the processing safety of high Mooney material than low Mooney good, but the curing time longer; in the physical and mechanical properties, with the increase of amount of sulfur, high tear strength, low Mooney material, tensile stress, the change trend of elongation similar, but the tensile strength variation is on the contrary; in terms of thermal properties, rise, cooling curve, but the material from the crystallization, melting enthalpy, low Mooney material crystallinity in better shape memory; The shape of the material, high Mooney viscosity recovery rate up to 98.9%, while the low Mooney viscosity material shape recovery rate was the highest to 81.4%.. Secondly, we study on the mechanical properties of rubber materials physics of Eucommia type and amount of filler, influence the shape memory properties, and the research of composite unidirectional and bidirectional shape memory behavior. The experimental results show that with increasing chitin dosage of tensile strength, tear strength, elongation and shape recovery rate is reduced; amount of silicon carbide or carbon black filler can improve the mechanical properties and shape memory properties of TPI materials with silicon carbide, 10 was the shape recovery rate can reach 95.6%, the addition of carbon black was 5 phr the shape recovery rate can reach 90.4%.. Finally, we use the method of blending preparation of Eucommia ulmoides gum / poly butylene succinate (TPI/PBS) shape memory composite materials, we studied the Du Secondary glue / polybutylene succinate blend ratio and compatibilizer on properties of composite material mechanics, influence the shape memory properties. The results showed that: in the blend ratio, with the increase of PBS content, the mechanical properties of the composites has a gradually decreasing trend, Tottenham response temperature decreases, the shape of the material response the first increased and then decreased, when the blend ratio is 90/10, the shape recovery rate is the largest, reaching 92.5%; in the curing system, the influence of sulfur (S), peroxidase (DCP), peroxidase (S/DCP) and sulfur / write memory effect, the properties of the composite materials of TPI/PBS shape results show that with increasing the amount of curing agent that has gradually decreased the mechanical properties of the material, but the sulfur / peroxide and used as vulcanizing agent system, tensile strength, tear strength, tensile stress was significantly better than the other two systems, the tensile strength increased 1-2MPa, tear Improve the strength of 1-4KN/m, tensile stress also increased about 1-3MPa; from the point of view of shape memory properties, composite curing agent in sulfur, when the sulfur amount is 1.6phr, the composite shape memory performance, as a composite material in the peroxide vulcanizing agent, when the content of DCP is 1.2phr, material the shape memory performance is the best in the sulfur / peroxide and used as curing agent in composite materials, when the dosage of DCP was 0.4phr, the composite shape memory performance is the best.

【学位授予单位】：青岛科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB381

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