CN111572115B - 具有高疲劳强度的cf/peek复合材料及其制备方法 - Google Patents
具有高疲劳强度的cf/peek复合材料及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种具有高疲劳强度的CF/PEEK复合材料及其制备方法，制备方法包括以下步骤：(1)将CF表面原有的上浆剂高温分解；(2)在饱和水蒸气环境中，对CF同时进行微波辐射和紫外光辐照，产物记为ACF；(3)将ACF浸入聚醚酰亚胺/二氯甲烷/碳纳米管悬浮液，取出后干燥，得到上浆改性碳纤维MCF；(4)将MCF与PEEK材料叠层热压；即得具有高疲劳强度的CF/PEEK复合材料；最终制得的CF/PEEK复合材料的弯曲强度为700‑800MPa，107次循环弯曲疲劳强度为360‑440MPa，弯曲模量为55‑62GPa，层间剪切强度为87‑100MPa，冲击后的剩余压缩强度为220‑260MPa。本发明的方法特点为高效、环保、可实现规模化生产，制得的复合材料可替代金属用于航空航天、医疗、机械、汽车和轨道交通、石油运输等领域。
Description
技术领域
本发明属碳纤维增强聚醚醚酮(CF/PEEK)复合材料技术领域，涉及一种具有高疲劳强度的CF/PEEK复合材料及其制备方法。
背景技术
近年来，热塑性复合材料由于具有良好的可回收性、可二次加工性、高抗冲韧性、高比强度和高比模量等优势，受到广泛关注。在各种热塑性复合材料中，CF/PEEK具有高刚度、高热稳定性、耐化学腐蚀性、耐磨性、生物相容性等优异性能，有望作为结构材料，代替工艺成熟的金属或热固性复合材料，广泛应用于航空航天、医疗、机械、汽车和轨道交通、石油运输等领域。
然而，CF/PEEK热塑性复合材料的实际应用情况不容乐观。主要问题在于其层间剪切强度(ILSS)较低，导致弯曲强度也较低，当承受垂直于面板的力矩时，尤其是当无限多次交变载荷作用的疲劳力矩作用时，材料容易分层或发生其他形式的损伤、破坏。造成该性能缺陷的主要原因在于碳纤维与PEEK基体的界面相互作用较弱、浸润性很差，在复合材料成型加工过程中容易产生孔隙。其根本原因是CF呈较稳定的六元环结构，表面由非极性的且由高度有序的石墨基面构成，使得纤维表面含有较少的活性官能团，而PEEK熔体粘度高，因此碳纤维与PEEK树脂间浸润性较差，界面粘结强度较弱。作为纤维与树脂基体间载荷传递的纽带，界面层的结合强度很大程度上影响整体复合材料的力学性能，低界面强度的复合材料在受到破坏时，裂纹沿界面扩展，纤维的增强作用得不到良好发挥，从而使复合材料强度远低于理论值。
对CF进行表面改性处理，可以解决上述问题，提高复合材料层间剪切强度等性能。已知技术有两类，一是“活化(有时也称氧化)”，二是“上浆”。可以单一使用，也可组合叠加使用。活化改性的原理是在纤维表面引入活性官能团，增加纤维与聚合物基体间化学键或氢键的数量，通过强大的化学作用提高复合材料的界面粘结强度。上浆改性的原理是通过溶液或乳液涂层，使聚合物(可不同于基体)薄层附着到纤维表面，利用其能够同时与纤维和基体间产生强相互作用的特性，在原本相互作用弱的纤维和基体间架起一座桥梁，增强两者关联性。
现有活化技术包括等离子体处理、阳极电解或电沉积处理、强酸处理、臭氧处理、微波超声共处理等。活化的过程可能会降低CF单丝强度，需要寻找活性基团数量和CF单丝强度的平衡，让CF表面产生尽量多的羟基和羧基等基团，产生尽量多的沟槽以便增加与基体间的接触面积，但同时要尽量低程度损失单丝强度。
现有上浆技术包括反应型上浆剂和涂层型上浆剂等。
现有技术虽然在某些方面取得效果，但存在各种缺陷或不足，导致在针对PEEK这种需要～400℃高温成型加工的基体时，难以实现工业化生产。
如等离子体处理CF时，丝束外层与内层效果差异显著，外层的活性基团多、单丝强度损伤很大时，内层CF的活性往往还未被改善。因此稳定性差，离散度大，不适宜工业化生产。
阳极电解或电沉积处理工艺处理丝束有效，但处理织物比较困难，单丝强度降低幅度较大。
强酸处理由于大量废酸废液产生，所以环境污染较大；多为间歇操作，所需处理时间较长，与CF生产线相匹配有困难；且对设备耐腐蚀性要求很高，操作危险系数高，因此在工业化生产中几乎不被考虑。
臭氧处理会产生大量的对人体有害的臭氧，对含臭氧废气的处理会大幅增加成本，这种不环保的方式也正在被逐渐摒弃。
微波超声共处理对CF单丝强度损伤较大，且损伤程度难以控制。
反应型上浆剂(表面接枝、偶联剂等)的反应速率低，且需通过搭配前面几种活化技术共同使用。
涂层型上浆剂(依靠范德华力作用)可以提高基体对纤维的浸润性，但对界面相互作用的提升效果有限。
上述已知技术制备的CF/PEEK复合材料的107次循环弯曲疲劳强度通常不超过300MPa，少数超过300MPa，但制备过程中或使用强酸，或使用等离子体处理，均难以实现工业化生产。CF表面活化之后的氧/碳(O/C)含量比提高幅度为40％左右。
发明内容
本发明旨在提供一种无酸环境制备的CF/PEEK复合材料的方法，制得的复合材料具有疲劳强度高等优点。
本发明的目的之一是提供一种具有高疲劳强度的CF/PEEK复合材料。
本发明的目的之二是提供一种具有高疲劳强度的CF/PEEK复合材料的制备方法，是一种完全无酸的环境条件的制备方法，环保，可实现规模化生产；CF表面的活性基团羧基和羟基在～400℃高温下稳定；所采用的针对PEEK基体的上浆剂PEI可溶性好且耐热性好，在CF/PEEK复合材料成型的～400℃高温下稳定；PEI与PEEK因为均含大量苯环，两者间存在较强的π-π键相互作用；PEI上的羰基与CF上的羧基和羟基可形成氢键，相互作用较强；上浆剂中加入含量适中、分散良好的羧基化CNT，可以通过其与PEEK基体的钉扎效应进一步增强界面相互作用；PEI是无定型高分子，其自身通常发生韧性断裂且屈服强度较高，使得复合材料疲劳强度较高。
本发明的具有高疲劳强度的CF/PEEK复合材料的制备方法，包括以下步骤：
(1)将CF表面原有的上浆剂高温分解；
(2)在饱和水蒸气环境中，对CF同时进行微波辐射和紫外光辐照，产物记为活化-CF(ACF)；该步骤对CF进行了无酸的活化改性处理，因此环保、具备产业化规模生产的可能性；
(3)将ACF浸入聚醚酰亚胺(PEI)/二氯甲烷(DCM)/碳纳米管(CNT)悬浮液，取出后干燥，得到上浆改性碳纤维(MCF)；
(4)将MCF与PEEK材料叠层热压；PEEK基体从固体变为熔体，并在压力下，发生剪切流动，浸润MCF丝束内部中。
降温至室温，脱模即得具有高疲劳强度的CF/PEEK复合材料。
作为优选的技术方案：
如上所述的制备方法，CF为缎纹织物形式，当CF为其他形式时，如短切纤维、长纤维、纤维毡、连续纤维丝束，或平纹、斜纹、无屈曲织物，同样也能采用本发明的方法将其与PEEK复合，但是制得的复合材料的性能相对较差。
如上所述的制备方法，所述高温分解是指在300-420℃下烧结5-180min。通过高温分解，去除原有的上浆剂。这些上浆剂附着于商业级碳纤维的表面，成分通常为环氧树脂类，出厂时必须上浆才能实现纤维卷绕，否则会产生毛丝，甚至导致纤维断裂。然而，这些上浆剂若不去除，将不利于CF和PEEK的复合，因为这些上浆剂在PEEK成型的高温(～400℃)下会发生分解，在复合材料中形成孔隙，降低材料强度等力学性能。若偏离建议的参数区间将不利于高温分解过程的有效控制。例如，如果高温分解的温度太低或时间太短，则无法彻底去除原有的上浆剂，残留的部分仍将在CF/PEEK复合材料成型加工的高温下分解，影响复合材料各项力学性能；如果高温分解的温度太高或时间太长，则将使部分CF的表面结构因氧化反应而受到损伤，CF表面出现沟壑，单丝强度下降超过一定幅度(如10％)，复合材料各项力学性能指标也会随着大幅下降。在高温分解的过程中，若能建立真空环境或氮气、氦气等惰性气体氛围，则效果更好，可以抑制CF自身的氧化反应，使CF单丝强度保持率更高。
如上所述的制备方法，饱和水蒸气的相对湿度大于95％；微波辐射时间为3-30min，微波频率为300MHz-10 GHz；辐照紫外光波长为290-340nm，紫外辐照度为20-50W/m2。该步骤具有三方面作用：1)微波辐照可促进碳纤维表面石墨化，弥补/抵消单丝强度的损失；2)紫外辐照，进一步清洁碳纤维表面凹槽中不耐高温的原有上浆剂残留，因为紫外可通过氧化反应打断CF表面残留有机物的双键；3)紫外光和水蒸气共同作用，在CF表面激发羟基和羧基等基团。
特别强调的是，在紫外和饱和水蒸气作用的同时加入微波作用很有必要，因为在氧化过程中，微波辐照可以使CF均匀加热，促进羟基化和羧基化进行。对比有微波和无微波的样品可知，有微波的样品中，O/C比更高，暗示含氧基团的含量更高。而且，微波辐照可促进碳纤维表面石墨化，弥补/抵消单丝强度的损失。
如果湿度过小、微波辐射时间过短、微波频率过低、紫外光波长过长或辐照度过低，则羟基和羧基被激发的数量较少，CF活化度较低，能与上浆剂形成的氢键数量也较少，ACF与上浆剂相互作用较小；如果微波辐射时间过长、微波频率过高、紫外光波长过短或辐照度过高，则可能过多破坏CF表面的六元环结构，CF单丝强度下降过多，从而导致复合材料各项力学性能下降。
同样的活化改性方法(在表面产生羟基、羧基，且尽量少的影响自身内部结构)，也可适用于碳纳米管(CNT)、石墨烯、氧化石墨烯(GO)、炭黑(CB)、碳纳米纤维(CNF)等碳材料。
PEI/DCM/CNT悬浮液中，PEI完全溶解且含量为0.2-3wt.％，CNT含量为0.01-0.1wt.％，通过5-60min超声分散制备稳定的悬浮液，CNT为羧基改性的单壁或多壁CNT，PEI的重均分子量大于50000；浸入时间为10-180min；干燥至含水量小于0.5wt.％。
PEI是无定型高分子，可溶性良好，且PEI上的羰基与ACF上的羟基及羧基之间可形成大量氢键，因此PEI溶液能够有效涂覆到ACF表面；因为CNT上的羧基与PEI上的羰基也可以发生氢键作用，所以CNT可以稳定分散于PEI溶液；PEI与PEEK基体的化学结构相似，且因为各自的大量苯环而发生π-π键相互作用，因此两者的浸润性和相容性良好；PEI热稳定性良好，在CF/PEEK复合材料成型加工的高温(～400℃)下不发生降解；并且，PEI不需要像PAA一样经过热处理转化为耐热性好的材料组分，因此在成型加工过程中不会发生明显的收缩，也不会产生较强的内应力；CNT的存在一方面使MCF表面粗糙度增加，CNT可以像许多钉子一样扎在PEEK基体中，通过大量的接触面积增加摩擦力总和，另一方面CNT还增强了PEI/CNT这一界面层本身的强度；PEI是无定型高分子，其自身通常发生韧性断裂且屈服强度较高，使得CF/PEEK复合材料疲劳强度较高。
如果PEI溶液浓度过低或浸入时间过短，则无法涂覆足够量的上浆剂到ACF表面；如果PEI溶液浓度过高，则ACF表面包裹的上浆剂过多，由于PEI是无定型高分子，在高温下会发生较大蠕变，导致复合材料在高温下的力学性能降低；如果浸入时间过长，则影响生产效率、增加成本。如果PEI分子量过低，则作为过渡层的PEI层自身强度过低，复合材料受力时容易发生界面层破坏，整体力学性能下降。如果CNT含量过低，CNT与PEEK基体间能发生钉扎效应的CNT数量过小，钉扎效应不明显，MCF与PEEK的相互作用力不够大；如果CNT含量过高或超声分散时间过短，则引起CNT分散不够、发生团聚，影响PEEK对MCF的浸润；如果超声时间过长，不仅浪费能耗、降低效率，还可能损伤CNT的结构完整性。如果干燥后的含水量过大，会在复合材料成型过程中因水蒸气挥发而形成孔隙，影响复合材料力学性能。
如上所述的制备方法，PEEK材料的形态为薄膜、无纺布毡、粉末或纤维；PEEK材料的重均分子量为30000-150000；叠层热压的工艺参数：温度370-420℃，压力0.5-5MPa，加载时间3-30min。在这个过程中，由于PEEK与MCF相互作用增强，因此PEEK熔体对MCF的浸润性能大幅提升，复合材料内部形成孔隙的可能性降低，且复合材料在受到外力破坏时，PEEK与MCF的界面粘结强度增加，材料失效模式从纤维拔出转变为基体断裂。
如果PEEK材料分子量过低，则基体中的分子链缠结较少，基体自身强度过小，复合材料整体强度受限；如果分子量过高或热压温度过低，则熔体粘度过大，复合材料的孔隙率增大；如果热压温度过高或保温加载时间过长，则PEEK容易在高温下发生降解、变色、老化等，树脂强度下降；如果压力较小或加载时间过短，熔体受到的剪切作用较小，对CF浸润不完全，复合材料的孔隙率增大；如果压力过大，将有更多树脂从模具缝隙中流出，复合材料出现贫胶等缺陷。
本发明制备方法制得的具有高疲劳强度的CF/PEEK复合材料，弯曲强度为700-800MPa，107次循环弯曲疲劳强度为360-440MPa，弯曲模量为55-62GPa，层间剪切强度(ILSS)为87-100MPa，冲击后的剩余压缩强度(CAI)为220-260MPa。
由于采用以上技术方案，本发明具有以下有益效果：
通过本发明制备的高疲劳强度的CF/PEEK复合材料，其原理是先通过高温分解CF表面原有的上浆剂。这些上浆剂附着于商业级碳纤维的表面，以保证纤维可以卷绕，然而这些上浆剂在PEEK成型的高温(～400℃)下会发生分解，在复合材料中形成孔隙，降低材料强度等力学性能。其次，再在饱和水蒸气环境中，对CF同时进行微波辐射和紫外光辐照。一方面微波辐照可促进碳纤维表面石墨化，弥补或抵消单丝强度的损失；第二方面紫外可通过氧化反应打断CF表面残留有机物的双键，因此紫外辐照可进一步清洁碳纤维表面凹槽中不耐高温的原有上浆剂残留；第三方面紫外光和水蒸气共同作用，在CF表面激发羟基和羧基等基团。因此通过无酸的活化改性处理使CF表面接枝羟基和羧基等活性基团，环保，具备产业化规模生产的可能性。接着，采用PEI/DCM/CNT悬浮液对ACF进行浸渍上浆。PEI可溶性良好，且PEI上的羰基与ACF上的羟基及羧基之间可形成大量氢键，因此PEI溶液能够有效涂覆到ACF表面；因为CNT上的羧基与PEI上的羰基也可以发生氢键作用，所以CNT可以稳定分散于PEI溶液；PEI与PEEK基体的化学结构相似，且因为各自的大量苯环而发生π-π键相互作用，因此两者的浸润性和相容性良好；PEI热稳定性良好，在CF/PEEK复合材料成型加工的高温(～400℃)下不发生降解；并且，PEI不需要像PAA一样经过热处理转化为耐热性好的材料组分，因此在成型加工过程中不会发生明显的收缩，也不会产生较强的内应力；CNT的存在一方面使MCF表面粗糙度增加，CNT可以像许多钉子一样扎在PEEK基体中，通过大量的接触面积增加摩擦力总和，另一方面CNT还增强了PEI/CNT这一界面层本身的强度；PEI是无定型高分子，其自身通常发生韧性断裂且屈服强度较高，使得CF/PEEK复合材料疲劳强度较高。最后，通过叠层热压制备CF/PEEK复合材料。PEEK基体在加热下从固体变为熔体，并在压力下，发生剪切流动、浸润MCF丝束内部中。在这个过程中，由于PEEK与MCF相互作用增强，因此PEEK熔体对MCF的浸润性能大幅提升，复合材料内部形成孔隙的可能性降低，且复合材料在受到外力破坏时，PEEK与MCF的界面粘结强度增加，材料失效模式从纤维拔出转变为基体断裂。
本发明方法的优点之一在于CF表面活化过程是无酸处理，环保，具备产业化可能性，且活化效果与使用强酸进行活化的效果相当。
通过本发明制备方法制备的具有高疲劳强度的CF/PEEK复合材料，弯曲强度为700-800MPa，107次循环弯曲疲劳强度为360-440MPa，弯曲模量为55-62GPa，层间剪切强度(ILSS)为87-100MPa，冲击后的剩余压缩强度(CAI)为220-260MPa。其中疲劳强度高于其他的环保、具备产业化条件的已知技术。
附图说明
图1为未处理CF的XPS曲线和氧元素/碳元素(O/C)含量，其中O/C含量比值越大代表活化效率越高；
图2为饱和水蒸气环境中进行紫外辐照处理CF的XPS曲线和氧元素/碳元素(O/C)含量；
图3为饱和水蒸气环境中同时进行微波和紫外辐照处理CF的XPS曲线和氧元素/碳元素(O/C)含量。
图4为饱和水蒸气环境中同时进行微波和紫外辐照处理、再经过含有0.01wt.％CNT的悬浮液上浆处理后得到碳纤维的扫描电镜照片；
图5为饱和水蒸气环境中同时进行微波和紫外辐照处理、再经过含有0.05wt.％CNT的悬浮液上浆处理后得到碳纤维的扫描电镜照片；
图6为饱和水蒸气环境中同时进行微波和紫外辐照处理、再经过含有0.1wt.％CNT的悬浮液上浆处理后得到碳纤维的扫描电镜照片。
具体实施方式
下面结合具体实施方式，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
具有高疲劳强度的CF/PEEK复合材料的制备方法，步骤如下：
(1)将CF的T300级3K5枚缎纹织物在300℃下烧结180min使其表面原有的上浆剂高温分解；
(2)在相对湿度为95.3％的饱和水蒸气环境中，对CF同时进行微波辐射和紫外光辐照，产物记为ACF；微波辐射的时间为30min，微波频率为300MHz；辐照紫外光波长为290nm，紫外辐照度为20W/m2；
(3)将ACF浸入聚醚酰亚胺/二氯甲烷/碳纳米管悬浮液中180min，聚醚酰亚胺的重均分子量为51000，取出后干燥至含水量为0.48wt.％，得到上浆改性碳纤维MCF，扫描电镜照片如图4所示；聚醚酰亚胺/二氯甲烷/碳纳米管悬浮液中，聚醚酰亚胺含量为0.2wt.％，碳纳米管含量为0.01wt.％，通过5min超声分散制备稳定的悬浮液，碳纳米管为羧基改性的单壁碳纳米管；
(4)将MCF与重均分子量为30000的PEEK粉末叠层热压；叠层热压的工艺参数：温度370℃，压力5MPa，加载时间3min；
降温至室温，脱模即得具有高疲劳强度的CF/PEEK复合材料。
最终制得的具有高疲劳强度的CF/PEEK复合材料的弯曲强度为700MPa，107次循环弯曲疲劳强度为368MPa，弯曲模量为55GPa，层间剪切强度为87MPa，冲击后的剩余压缩强度为220MPa。
对比例1
CF/PEEK复合材料的制备方法，基本同实施例1，相对于实施例1省略了步骤(1)和(2)，同时将步骤(3)中浸入聚醚酰亚胺/二氯甲烷/碳纳米管悬浮液中的材料由ACF变为CF的T300级3K5枚缎纹织物，其他过程和参数同实施例1。
最终制得的CF/PEEK复合材料的弯曲强度为501MPa，107次循环弯曲疲劳强度为248MPa，弯曲模量为47GPa，层间剪切强度为63MPa，冲击后的剩余压缩强度为186MPa。
将实施例1与对比例1对比可以看出，实施例1制得的CF/PEEK复合材料的弯曲强度、107次循环弯曲疲劳强度、弯曲模量、层间剪切强度、冲击后的剩余压缩强度远高于对比例1，对比例1中未处理CF的XPS曲线和氧元素/碳元素(O/C)含量如图1所示，实施例1中在饱和水蒸气环境中同时进行微波和紫外辐照处理CF的XPS曲线和氧元素/碳元素(O/C)含量如图3所示，对比可以看出，未处理的CF的O/C比为0.0700，其中O元素的含量不高，说明CF呈现惰性，而紫外+水蒸气+微波处理的CF的O/C比为0.1782，其中O元素的含量明显提高，与未处理的CF相比，O/C比提高了155％(提高至原有的255％)，说明在紫外+水蒸气的同时采用微波处理很重要，这正是为什么用未处理的CF制备的CF/PEEK复合材料的弯曲强度、107次循环弯曲疲劳强度、弯曲模量、层间剪切强度、冲击后的剩余压缩强度均较低的原因。
对比例2
CF/PEEK复合材料的制备方法，基本同实施例1，相对于实施例1步骤(2)进行了调整，具体为在饱和水蒸气环境中，对CF仅进行紫外光辐照，而不进行微波辐射，其他过程和参数同实施例1。
最终制得的CF/PEEK复合材料的弯曲强度为508MPa，107次循环弯曲疲劳强度为251MPa，弯曲模量为46GPa，层间剪切强度为64MPa，冲击后的剩余压缩强度为201MPa。
将实施例1与对比例2对比可以看出，实施例1制得的CF/PEEK复合材料的弯曲强度、107次循环弯曲疲劳强度、弯曲模量、层间剪切强度、冲击后的剩余压缩强度远高于对比例2，对比例2中在饱和水蒸气环境中进行紫外辐照处理CF的XPS曲线和氧元素/碳元素(O/C)含量如图2所示，实施例1中在饱和水蒸气环境中同时进行微波和紫外辐照处理CF的XPS曲线和氧元素/碳元素(O/C)含量如图3所示，对比可以看出，紫外+水蒸气处理的CF的O/C比为0.0765，其中O元素的含量提高并不明显，说明仅使用紫外+水蒸气，效果并不太好，而紫外+水蒸气+微波处理的CF的O/C比为0.1782，其中O元素的含量明显提高，说明在紫外+水蒸气的同时采用微波处理很重要，这正是为什么用紫外+水蒸气处理的CF制备的CF/PEEK复合材料的弯曲强度、107次循环弯曲疲劳强度、弯曲模量、层间剪切强度、冲击后的剩余压缩强度均较低的原因。
实施例2
具有高疲劳强度的CF/PEEK复合材料的制备方法，步骤如下：
(1)将CF的T300级3K5枚缎纹织物在350℃下烧结138min使其表面原有的上浆剂高温分解；
(2)在相对湿度为95.8％的饱和水蒸气环境中，对CF同时进行微波辐射和紫外光辐照，产物记为ACF；微波辐射的时间为27min，微波频率为820MHz；辐照紫外光波长为299nm，紫外辐照度为50W/m2；
(3)将ACF浸入聚醚酰亚胺/二氯甲烷/碳纳米管悬浮液中175min，聚醚酰亚胺的重均分子量为55000，取出后干燥至含水量为0.45wt.％，得到上浆改性碳纤维MCF；聚醚酰亚胺/二氯甲烷/碳纳米管悬浮液中，聚醚酰亚胺含量为0.9wt.％，碳纳米管含量为0.03wt.％，通过10min超声分散制备稳定的悬浮液，碳纳米管为羧基改性的单壁碳纳米管；
(4)将MCF与重均分子量为60000的PEEK粉末叠层热压；叠层热压的工艺参数：温度378℃，压力4.7MPa，加载时间7min；
降温至室温，脱模即得具有高疲劳强度的CF/PEEK复合材料。
最终制得的具有高疲劳强度的CF/PEEK复合材料的弯曲强度为742MPa，107次循环弯曲疲劳强度为379MPa，弯曲模量为56GPa，层间剪切强度为94MPa，冲击后的剩余压缩强度为241MPa。
实施例3
具有高疲劳强度的CF/PEEK复合材料的制备方法，步骤如下：
(1)将CF的T300级3K5枚缎纹织物在420℃下烧结5min使其表面原有的上浆剂高温分解；
(2)在相对湿度为95.9％的饱和水蒸气环境中，对CF同时进行微波辐射和紫外光辐照，产物记为ACF；微波辐射的时间为24min，微波频率为1GHz；辐照紫外光波长为305nm，紫外辐照度为35W/m2；
(3)将ACF浸入聚醚酰亚胺/二氯甲烷/碳纳米管悬浮液中142min，聚醚酰亚胺的重均分子量为59050，取出后干燥至含水量为0.42wt.％，得到上浆改性碳纤维MCF；聚醚酰亚胺/二氯甲烷/碳纳米管悬浮液中，聚醚酰亚胺含量为1.3wt.％，碳纳米管含量为0.04wt.％，通过15min超声分散制备稳定的悬浮液，碳纳米管为羧基改性的单壁碳纳米管；
(4)将MCF与重均分子量为75000的PEEK无纺布毡叠层热压；叠层热压的工艺参数：温度381℃，压力3.4MPa，加载时间11min；
降温至室温，脱模即得具有高疲劳强度的CF/PEEK复合材料。
最终制得的具有高疲劳强度的CF/PEEK复合材料的弯曲强度为765MPa，107次循环弯曲疲劳强度为391MPa，弯曲模量为59GPa，层间剪切强度为93MPa，冲击后的剩余压缩强度为248MPa。
实施例4
具有高疲劳强度的CF/PEEK复合材料的制备方法，步骤如下：
(1)将CF的T300级3K5枚缎纹织物在335℃下烧结168min使其表面原有的上浆剂高温分解；
(2)在相对湿度为96.3％的饱和水蒸气环境中，对CF同时进行微波辐射和紫外光辐照，产物记为ACF；微波辐射的时间为20min，微波频率为1.5GHz；辐照紫外光波长为313nm，紫外辐照度为24W/m2；
(3)将ACF浸入聚醚酰亚胺/二氯甲烷/碳纳米管悬浮液中110min，聚醚酰亚胺的重均分子量为60020，取出后干燥至含水量为0.41wt.％，得到上浆改性碳纤维MCF，扫描电镜照片如图5所示；聚醚酰亚胺/二氯甲烷/碳纳米管悬浮液中，聚醚酰亚胺含量为1.8wt.％，碳纳米管含量为0.05wt.％，通过50min超声分散制备稳定的悬浮液，碳纳米管为羧基改性的单壁碳纳米管；
(4)将MCF与重均分子量为82000的PEEK纤维叠层热压；叠层热压的工艺参数：温度389℃，压力2.9MPa，加载时间15min；
降温至室温，脱模即得具有高疲劳强度的CF/PEEK复合材料。
最终制得的具有高疲劳强度的CF/PEEK复合材料的弯曲强度为784MPa，107次循环弯曲疲劳强度为418MPa，弯曲模量为61GPa，层间剪切强度为96MPa，冲击后的剩余压缩强度为255MPa。
实施例5
具有高疲劳强度的CF/PEEK复合材料的制备方法，步骤如下：
(1)将CF的T300级3K5枚缎纹织物在360℃下烧结104min使其表面原有的上浆剂高温分解；
(2)在相对湿度为96.8％的饱和水蒸气环境中，对CF同时进行微波辐射和紫外光辐照，产物记为ACF；微波辐射的时间为16min，微波频率为2.3GHz；辐照紫外光波长为320nm，紫外辐照度为31W/m2；
(3)将ACF浸入聚醚酰亚胺/二氯甲烷/碳纳米管悬浮液中121min，聚醚酰亚胺的重均分子量为61825，取出后干燥至含水量为0.38wt.％，得到上浆改性碳纤维MCF；聚醚酰亚胺/二氯甲烷/碳纳米管悬浮液中，聚醚酰亚胺含量为2.3wt.％，碳纳米管含量为0.07wt.％，通过28min超声分散制备稳定的悬浮液，碳纳米管为羧基改性的多壁碳纳米管；
(4)将MCF与重均分子量为90000的PEEK薄膜叠层热压；叠层热压的工艺参数：温度395℃，压力2.3MPa，加载时间19min；
降温至室温，脱模即得具有高疲劳强度的CF/PEEK复合材料。
最终制得的具有高疲劳强度的CF/PEEK复合材料的弯曲强度为800MPa，107次循环弯曲疲劳强度为440MPa，弯曲模量为62GPa，层间剪切强度为100MPa，冲击后的剩余压缩强度为260MPa。
实施例6
具有高疲劳强度的CF/PEEK复合材料的制备方法，步骤如下：
(1)将CF的T300级3K5枚缎纹织物在383℃下烧结92min使其表面原有的上浆剂高温分解；
(2)在相对湿度为97.1％的饱和水蒸气环境中，对CF同时进行微波辐射和紫外光辐照，产物记为ACF；微波辐射的时间为12min，微波频率为3.9GHz；辐照紫外光波长为330nm，紫外辐照度为45W/m2；
(3)将ACF浸入聚醚酰亚胺/二氯甲烷/碳纳米管悬浮液中85min，聚醚酰亚胺的重均分子量为62385，取出后干燥至含水量为0.35wt.％，得到上浆改性碳纤维MCF；聚醚酰亚胺/二氯甲烷/碳纳米管悬浮液中，聚醚酰亚胺含量为2.5wt.％，碳纳米管含量为0.08wt.％，通过35min超声分散制备稳定的悬浮液，碳纳米管为羧基改性的多壁碳纳米管；
(4)将MCF与重均分子量为113000的PEEK薄膜叠层热压；叠层热压的工艺参数：温度405℃，压力1.2MPa，加载时间23min；
降温至室温，脱模即得具有高疲劳强度的CF/PEEK复合材料。
最终制得的具有高疲劳强度的CF/PEEK复合材料的弯曲强度为791MPa，107次循环弯曲疲劳强度为429MPa，弯曲模量为58GPa，层间剪切强度为97MPa，冲击后的剩余压缩强度为239MPa。
实施例7
具有高疲劳强度的CF/PEEK复合材料的制备方法，步骤如下：
(1)将CF的T300级3K5枚缎纹织物在412℃下烧结20min使其表面原有的上浆剂高温分解；
(2)在相对湿度为97.5％的饱和水蒸气环境中，对CF同时进行微波辐射和紫外光辐照，产物记为ACF；微波辐射的时间为8min，微波频率为6.8GHz；辐照紫外光波长为336nm，紫外辐照度为41W/m2；
(3)将ACF浸入聚醚酰亚胺/二氯甲烷/碳纳米管悬浮液中63min，聚醚酰亚胺的重均分子量为63500，取出后干燥至含水量为0.32wt.％，得到上浆改性碳纤维MCF；聚醚酰亚胺/二氯甲烷/碳纳米管悬浮液中，聚醚酰亚胺含量为2.7wt.％，碳纳米管含量为0.09wt.％，通过48min超声分散制备稳定的悬浮液，碳纳米管为羧基改性的多壁碳纳米管；
(4)将MCF与重均分子量为136000的PEEK纤维叠层热压；叠层热压的工艺参数：温度411℃，压力1MPa，加载时间27min；
降温至室温，脱模即得具有高疲劳强度的CF/PEEK复合材料。
最终制得的具有高疲劳强度的CF/PEEK复合材料的弯曲强度为727MPa，107次循环弯曲疲劳强度为407MPa，弯曲模量为60GPa，层间剪切强度为90MPa，冲击后的剩余压缩强度为234MPa。
实施例8
具有高疲劳强度的CF/PEEK复合材料的制备方法，步骤如下：
(1)将CF的T300级3K5枚缎纹织物在404℃下烧结50min使其表面原有的上浆剂高温分解；
(2)在相对湿度为98.2％的饱和水蒸气环境中，对CF同时进行微波辐射和紫外光辐照，产物记为ACF；微波辐射的时间为3min，微波频率为10GHz；辐照紫外光波长为340nm，紫外辐照度为39W/m2；
(3)将ACF浸入聚醚酰亚胺/二氯甲烷/碳纳米管悬浮液中10min，聚醚酰亚胺的重均分子量为64630，取出后干燥至含水量为0.28wt.％，得到上浆改性碳纤维MCF，扫描电镜照片如图6所示；聚醚酰亚胺/二氯甲烷/碳纳米管悬浮液中，聚醚酰亚胺含量为3wt.％，碳纳米管含量为0.1wt.％，通过60min超声分散制备稳定的悬浮液，碳纳米管为羧基改性的多壁碳纳米管；
(4)将MCF与重均分子量为150000的PEEK无纺布毡叠层热压；叠层热压的工艺参数：温度420℃，压力0.5MPa，加载时间30min；
降温至室温，脱模即得具有高疲劳强度的CF/PEEK复合材料。
最终制得的具有高疲劳强度的CF/PEEK复合材料的弯曲强度为718MPa，107次循环弯曲疲劳强度为360MPa，弯曲模量为57GPa，层间剪切强度为89MPa，冲击后的剩余压缩强度为229MPa。
Claims (4)
1.具有高疲劳强度的CF/PEEK复合材料的制备方法，其特征是包括以下步骤：
（1）将CF表面原有的上浆剂高温分解；高温分解是指在300-420 ℃下烧结5-180 min；
（2）在饱和水蒸气环境中，对CF同时进行微波辐射和紫外光辐照，产物记为ACF；饱和水蒸气的相对湿度大于95%；微波辐射时间为3-30 min，微波频率为300 MHz-10 GHz；辐照紫外光波长为290-340 nm，紫外辐照度为20-50 W/m2；
（3）将ACF浸入聚醚酰亚胺/二氯甲烷/碳纳米管悬浮液，取出后干燥，得到上浆改性碳纤维MCF；
聚醚酰亚胺/二氯甲烷/碳纳米管悬浮液中，聚醚酰亚胺含量为0.2-3 wt. %，碳纳米管含量为0.01-0.1 wt. %，通过5-60 min超声分散制备稳定的悬浮液，碳纳米管为羧基改性的单壁或多壁碳纳米管，聚醚酰亚胺的重均分子量大于50000；浸入时间为10-180 min；干燥至含水量小于0.5 wt. %；
（4）将MCF与PEEK材料叠层热压；PEEK材料的重均分子量为30000-150000；叠层热压的工艺参数：温度370-420 ℃，压力0.5-5 MPa，加载时间3-30 min；
即得具有高疲劳强度的CF/PEEK复合材料。
2.根据权利要求1所述的具有高疲劳强度的CF/PEEK复合材料的制备方法，其特征在于，CF为缎纹织物形式。
3.根据权利要求1所述的具有高疲劳强度的CF/PEEK复合材料的制备方法，其特征在于，PEEK材料的形态为薄膜、无纺布毡、粉末或纤维。
4.根据权利要求1~3中任一项所述的具有高疲劳强度的CF/PEEK复合材料的制备方法制得的具有高疲劳强度的CF/PEEK复合材料，其特征是：弯曲强度为700-800 MPa，107次循环弯曲疲劳强度为360-440 MPa，弯曲模量为55-62 GPa，层间剪切强度为87-100 MPa，冲击后的剩余压缩强度为220-260 MPa。
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