Research development of fatigue life prediction and damage analysis model of fiber-reinforced composite
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摘要:
随着纤维增强复合材料主承力结构在多领域内的广泛应用,疲劳成为复合材料结构设计必须面对的问题,出现了大量用于复合材料结构疲劳寿命预测及损伤演化的分析模型与方法。目前的复合材料疲劳性能分析模型可以分为疲劳寿命模型、唯象模型和渐进损伤模型。对这3类模型的发展情况进行了综述和对比分析。其中,疲劳寿命模型原理相对简单,适用于工程结构的寿命估算;唯象模型建立了材料剩余强度/刚度与循环数的数学关系,可以预测结构的寿命与材料剩余力学性能;渐进损伤模型不仅可以预测结构寿命和材料剩余力学性能,还能分析结构疲劳损伤机理。对各类疲劳性能分析模型的发展趋势进行了讨论。指出了降低实施成本和提高通用型是各类疲劳性能分析模型有待解决的问题。
Abstract:With the wide application of fiber-reinforced composite primary structures in many fields, fatigue has become a critical problem in composite structural design and analysis. Based on the development of fatigue theory of composite materials, many theoretical methods and numerical models for life prediction and damage analysis have been proposed by scholars. The current composite fatigue performance analysis models can be classified as fatigue life model, phenomenological model and progressive damage model. The development of these three kinds of models is reviewed and compared and their advantages and disadvantages are analyzed. The theory of fatigue life model is relatively simple, and the model is suitable for the life estimation of engineering structures. The mathematical relationship between residual strength/stiffness and fatigue cycle number is established in phenomenological model, which can predict the structure fatigue life and material residual mechanical properties. The progressive damage model can not only predict the structure fatigue life and material residual mechanical properties, but also analyze the fatigue damage mechanism of structures. Finally, the development trends of these fatigue performance analysis models are discussed. It is pointed out that reducing the implementation cost and improving the generality are important problems of these models.
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Key words:
- composites /
- fatigue /
- life prediction /
- phenomenological models /
- progressive damage
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氰酸酯(BADCy)是一类性能优异的热固性树脂,具有较高的玻璃化转变温度和力学性能, 较低的介电常数和介电损耗, 吸湿率低,固化过程无副产物释放, 与各种增强材料的相容性好。因此,氰酸酯作为一种高性能基体树脂在航空航天和微电子等领域得到了广泛的应用。在氰酸酯的分子结构中,苯环和三嗪环之间有一个柔性醚键,使其具有比其他热固性树脂更高的冲击强度,但仍不能满足高性能基体树脂对韧性的要求,通常需要对其进行增韧改性[1-2]。此外,要达到复合材料所需的固化度,纯氰酸酯需要在高温条件下进行长时间的固化,能耗大、工艺成本高,而且会对复合材料的力学性能产生不利的影响。加入金属络合物和小分子酚类助催化剂会降低氰酸酯的固化温度,但同时也会降低其介电性能和热性能[3-4]。因此,在保持氰酸酯优异的力学﹑热学和介电性能的前提下,使氰酸酯同时具有良好的韧性和加工性,是非常具有挑战性的。
与热塑性树脂共混是一种非常有效的对氰酸酯增韧改性的方法。例如,羧基或胺基封端的丁腈橡胶是良好的增韧剂量,Feng等[5]加入10%羧基封端的丁腈橡胶使氰酸酯固化物的冲击强度提高了200%。但是,这类增韧剂由于自身较低的模量和玻璃化转变温度,最终导致氰酸酯固化物的力学和热学性能显著降低。为了克服这种不足,各种高分子量工程塑料如聚醚砜﹑聚苯醚﹑聚醚酰亚胺﹑聚醚醚酮和聚酰亚胺等[6-10],被广泛用于氰酸酯的增韧改性。然而,高分子量工程塑料的加入,会导致氰酸酯树脂的黏度急剧升高,严重影响树脂的加工性能,还会降低树脂对纤维表面的浸润性,影响最终的界面性能。
通过与热固性树脂(如环氧树脂﹑双马来酰亚胺树脂以及聚酰亚胺树脂等)共混形成互穿网络聚合物(Interpenetrating Polymer Network, IPN)是另一种有效的氰酸酯增韧方法。环氧树脂可以与氰酸酯发生共聚反应生成噁唑啉酮环,而环氧树脂中的羟基可以明显催化氰酸酯的聚合,降低固化温度,但环氧树脂自身的综合性能比氰酸酯低,将导致固化产物的玻璃化转变温度、热稳定性和介电性能等明显降低[11-12]。双马来酰亚胺-氰酸酯(BT树脂)可以同时结合两者的优点,具有良好的加工性能、较高的玻璃化转变温度、较低的介电常数和损耗等,但是BT树脂的韧性比纯氰酸酯还低,因为双马来酰亚胺树脂的交联密度更大,性能更脆[13-14]。此外,乙炔基或苯乙炔基封端的热固性聚酰亚胺与氰酸酯的共混研究也有相关报道,Meier等[15]将酚醛型氰酸酯与苯乙炔基封端的聚酰亚胺共混,最终固化物的热学性能与纯氰酸酯相差不大,韧性也只有小幅度的提高。因为苯乙炔基的交联温度过高,需要到370℃,而氰酸酯只要200℃,两者相差太大,导致苯乙炔基的固化过程中链段运动受限制,固化不完全。曲春艳等[16]采用基于乙炔基封端的酰亚胺低聚物与氰酸酯进行共混,由于低聚物的聚合度为2,固化产物交联密度太大,且发生了宏观相分离,致使最终固化产物的玻璃化转变温度、拉伸强度和韧性等没有明显的改善。
本文合成了不同聚合度的乙炔基封端的聚酰亚胺低聚物(BETI),将这种低聚物溶于氰酸酯单体,对改性树脂的固化行为进行了详细探究,对固化产物热学性能、力学性能和介电性能等进行了表征与分析。
1. 实验
1.1 实验原料及试剂
实验所用原料及试剂如表 1所示。
表 1 实验原料及试剂Table 1. Experimental materials and reagents名称 来源 纯化方法 2, 3, 3′, 4′-联苯四甲酸二酐(3, 4-BPDA) 常州阳光药业有限公司 真空熔融 2, 2′-双(三氟甲基)-4′, 4′-联苯二胺(TFMB) 常州阳光药业有限公司 直接使用 4-乙炔基邻苯二甲酸酐(EPA) 瑞典Nexam Chemical公司 直接使用 双酚A型氰酸酯单体(BADCy) 扬州天启新材料有限公司 直接使用 间甲酚 天津市富宇精细化学有限公司 直接使用 无水乙醇 北京化工厂 直接使用 1.2 实验测试仪器及测试条件
红外光谱分析:样品的FTIR谱图采用VERTEX 70型傅里叶变换红外光谱仪在室温下进行测定,样品以粉末形式,采用透过模式。
核磁共振波谱分析:低聚物的1H NMR谱图由Bruker-400型核磁共振波谱仪在室温下测定,四甲基硅烷TMS为内标,低聚物由DMSO-d6溶解。
流变性能分析:采用美国TA公司AR2000ex高级扩展流变仪对低聚物的流变性能进行测试表征,应变为5%,角频率为10 Hz,采用振荡模式,进行恒温和变温测试。
热稳定性分析:采用美国TA公司Q50型热重分析仪对树脂样品的热稳定性进行测试分析,测试温度范围为100~800 ℃,升温速率10 ℃/min,N2氛围。
动态热机械分析:采用美国TA公司Q800型动态热机械分析仪对树脂样品的动态机械性能进行测试分析,升温速率3 ℃/min,频率为1 Hz,单悬臂模式。
力学性能分析:采用美国Instron公司的5982电子万能材料试验机,按GB/T 1040.1—2018对树脂浇铸体的拉伸性能进行测试,加载速率为2 mm/min。树脂样品的冲击强度则采用中国长春JJ-20型计算机控制记忆式冲击试验机进行测试,按GB/T 1843—2008标准。
介电性能分析:采用美国Agilent Technologies公司的4294A阻抗分析仪对树脂的介电常数进行测试分析,测试范围为常温低频段。
1.3 热固性聚酰亚胺低聚物的制备
以二酐单体3, 4′-BPDA,聚合度19的BETI的制备为例:将3, 4-BPDA (27.951 g, 0.095 mol)、TFMB(32.023 g, 0.100 mol)、EPA(1.721 g, 0.01 mol)和500 mL间甲酚加入到带有机械搅拌和分水器的1 L三口瓶中,在N2氛围下80 ℃反应10 h,180 ℃反应12 h,反应过程中加大N2流量,将副产物吹出反应体系外。反应完后,冷却到室温,将黏稠的间甲酚溶液倒入3 L无水乙醇中过滤,用乙醇洗涤6次,置于索氏提取器中,以乙醇为溶剂,索氏提取48 h,真空下,180 ℃烘干,得到浅白色粉末67.4 g,产率为93.2%。其他不同聚合度的BETI的制备方法同上。
1.4 聚酰亚胺树脂改性氰酸酯树脂及浇铸体制备
将氰酸酯粉末加入到烧杯中,100 ℃下融化成透明液体,再将BETI按一定质量分例(10%、20%、30%)加入到氰酸酯中,持续搅拌至均匀透亮液体,浇入到模具中;在120 ℃真空条件下,脱气1 h,移至平板硫化机上,然后按150 ℃/3 h+170 ℃/2 h+190 ℃/2 h+230 ℃/2 h的工艺进行固化;再降温至150 ℃左右脱模,得到不同质量分数(10%、20%、30%)的BETI改性氰酸酯树脂浇铸体,再按测试标准裁剪样条进行测试表征。当BETI质量分数超过30%时,只能部分溶解,而且混合物体系黏度过大,工艺性变差,影响浇铸体的制备和性能,因此未继续加大BETI含量。
2. 结果与讨论
2.1 聚酰亚胺低聚物和固化产物的制备与表征
以乙炔基为末端基团的BETI采用间甲酚为溶剂通过传统的一步法制备,其结构式如图 1所示。通过红外光谱和核磁谱对其结构进行了表征,其中以聚合度2的BETI-2低聚物进行分析。如图 2 FTIR图谱所示,在1 780 cm-1(C=O的不对称伸缩振动吸收峰)、1 730 cm-1(C=O的对称伸缩振动吸收峰)和1 370 cm-1(C-N的伸缩振动吸收峰)附近出现了酰亚胺基团的特征吸收峰;在3 300 cm-1(C-H的伸缩振动吸收峰)附近出现了乙炔基特征吸收峰。如图 3 1H NMR图谱所示,在化学位移为4.7×10-6左右均出现BETI-2低聚物的乙炔基氢质子峰。
BADCy和不同分子量的BETI固化物的玻璃化转变温度和冲击强度如表 2所示。可知,BETI系列固化物的玻璃化转变温度随着聚合度的增大而降低,而冲击强度随着聚合度的增大而升高。当聚合度越低时,固化后产物的交联密度越高,交联网格中的分子链段越短,自由体积越小,运动能力越低,故玻璃化转变温度越高,韧性越低。由于BETI-2和BETI-9本身固化物的冲击强度较低,可以预见其引入很难大幅提升氰酸酯树脂的韧性,而BETI-19固化物的冲击强度远高于纯氰酸酯树脂。继续增大BETI的分子量则会造成端基含量过低,固化过程中乙炔基交联不完全,固化物的热性能和力学性能反而会降低。因此,本文主要采用BETI-19对氰酸酯树脂进行增韧。
表 2 BADCy和BETI固化物的波璃化转变温度和冲击强度Table 2. Glass transition temperature and impact strength of BADCy and BETI固化物 玻璃化转变温度/℃ 冲击强度/(kJ·m-2) BADCy 297 24 BETI-2 441 18 BETI-9 422 26 BETI-19 394 46 2.2 聚酰亚胺低聚物与氰酸酯共混物流变分析
BADCy和BADCy/BETI-19的黏度-温度曲线如图 4所示。可知,随着温度的升高,树脂的复合黏度先降低后升高,在150~250 ℃之间,黏度值维持在20 Pa·s以下,有一个较宽的加工窗口,在制备复合材料过程中有利于对纤维表面的浸润。随着聚酰亚胺加入量的增多,凝胶温度明显降低,避免了过高固化温度带来的高成本以及对复合材料性能的负面影响。
BADCy和BADCy/BETI-19在200 ℃的黏度-时间曲线如图 5所示。可知,即使在200 ℃恒温3 h的条件下,纯氰酸酯黏度也没有明显增长,但加入BETI后,固化速率显著提高,且随着BETI加入量的增多,凝胶时间明显缩短,证明了BETI对氰酸酯聚合的催化作用。
2.3 固化物的热稳定性分析
BADCy、BETI-19及BADCy/BETI-19固化物的TGA曲线如图 6所示。可知,BADCy和BETI-19两种树脂固化物的热失重5%时温度分别为425 ℃和564 ℃。主要是因为双酚A型氰酸酯中含有异丙基和三嗪环,在超过400 ℃就开始发生降解,且结构中含有醚键,故热失重温度较低。而BETI-19树脂分子结构中主要含有刚性的骨架结构,耐温等级高,从而具有良好的热稳定性。而BADCy/BETI-19互穿网络聚合物的热失重5%时温度都与纯氰酸酯的固化物相差不多,均在430 ℃左右,主要是因为共混物的降解过程是两者分别降解,最先降解的都是氰酸酯中的异丙基和三嗪环。
2.4 固化物动态机械性能分析
BADCy、BETI-19及BADCy/BETI-19固化物的DMA曲线如图 7所示。可知,BADCy和BETI-19两种树脂固化物的玻璃化转变温度分别为297 ℃和394 ℃,主要是因为聚酰亚胺主链具有刚性的骨架结构和较强的分子间和分子内作用力。BADCy/BETI-19互穿网络聚合物的储能模量和玻璃化转变温度随聚酰亚胺BETI-19的加入量增多而增大。同时,所有聚合物均具有单一的tan δ峰(δ为模量损耗角),证明互穿网络聚合物未发生明显的相分离。
2.5 固化物力学性能分析
BADCy、BETI-19及BADCy/BETI-19固化物的热和力学性能如表 3所示。可知,BETI-19固化物IPN-10、IPN-20、IPN-30的冲击强度比纯氰酸酯高2倍,向氰酸酯中加入10%、20%和30%的BETI-19后,互穿网络聚合物的冲击强度较纯氰酸酯分别提高了4%、13%和29%。互穿网络聚合物韧性的提高主要归因于聚酰亚胺自身的韧性比氰酸酯高,且聚酰亚胺的混入降低了氰酸酯的交联密度,而分子结构中含有的三氟甲基,降低了分子链的堆积密度,增加了自由体积。此外,互穿网络聚合物的拉伸性能也较纯氰酸酯有所提高,因为引入的聚酰亚胺树脂,其拉伸性能比氰酸酯高,且与氰酸酯固化后形成了互穿网络结构,分子链间的交错互穿和紧密缠结使分子间的作用力增强,从而使拉伸性能得到提高。
表 3 BADCy、BETI-19及其共混固化物热和力学性能Table 3. Thermal and mechanical properties of BADCy, BETI-19 and their blends固化物 玻璃化转变温度/℃ 拉伸强度/MPa 拉伸模量/GPa 断裂伸长率/% 冲击强度/ (kJ·m-2) BADCy 297 76 3.0 2.9 24 IPN-10 303 78 3.2 3.0 25 IPN-20 305 86 3.4 3.3 27 IPN-30 309 94 3.5 3.4 31 BETI-19 394 101 3.8 3.5 46 2.6 固化物介电性能分析
BADCy、BETI-19及BADCy/BETI-19固化物的介电常数-频率曲线如图 8所示。可知,氰酸酯、聚酰亚胺及互穿网络聚合物的介电常数都随频率增加而略有降低,主要归因于高频时,聚合物的极化程度不再有时间达到静态电场值,从而使极化率减小,介电常数降低。由于BETI-19的介电常数高于BADCy,故互穿网络聚合物的介电常数也比纯氰酸酯略高,但增加幅度不大,仍能保证氰酸酯优异的介电性能。
3. 结论
1) 当溶于氰酸酯单体中的BETI聚合度为19时,BETI的增韧效果明显。
2) 乙炔基上的氢原子对氰酸酯的聚合有明显的催化效果,随着BETI加入量的增多,凝胶温度降低、凝胶时间缩短。同纯氰酸酯固化物相比,基于氰酸酯和BETI的互穿网络聚合物的热性能都有一定的提高。
3) 当加入质量分数30%的BETI-19,固化物的玻璃化转变温度从297 ℃提高到309 ℃,5%热失重温度从425 ℃提高到了431 ℃;拉伸强度从76 MPa提高到了94 MPa,冲击强度从24 kJ/m2提高到了31 kJ/m2。
4) 由于BETI固化物本身的介电常数较高,BETI增韧后的互穿网络聚合物介电常数比纯氰酸酯略高,但增加幅度不大,有望作为基体树脂在航空航天等领域获得应用。
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