CN110588100B - 一种汽车板材用碳纤维复合材料及其制备工艺 - Google Patents

一种汽车板材用碳纤维复合材料及其制备工艺 Download PDF

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CN110588100B
CN110588100B CN201910724982.1A CN201910724982A CN110588100B CN 110588100 B CN110588100 B CN 110588100B CN 201910724982 A CN201910724982 A CN 201910724982A CN 110588100 B CN110588100 B CN 110588100B
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韩一博
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Nanjing Aerospace 3D Intelligent Technology Co.,Ltd.
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Abstract

本发明提出了一种汽车板材用碳纤维复合材料及其制备工艺，该碳纤维复合材料，包括高强叠板层、补偿增韧层，高强叠板层包括复合热压的CFPR板以及蜂窝型稀土铝合金板，补偿增韧层采用上、中、下三层含矿物掺杂的不饱和聚酯碳纤维增强板，高强叠板层、补偿增韧层厚度比为1:0.4‑0.7，本发明对材料、结构双方面进行改进，不仅提高了力学性能，同时具有优异的防护抗压、减震回复性，且层间结合力强，安全稳定，整体轻质高强，应用推广性高。

Description

一种汽车板材用碳纤维复合材料及其制备工艺
技术领域
本发明涉及碳纤维复合材料技术领域，具体涉及一种汽车板材用碳纤维复合材料及其制备工艺。
背景技术
碳纤维是指含炭量在90％以上的高强度高模量纤维，用腈纶和粘胶纤维做原料，经高温氧化碳化而成，其耐高温居所有化纤之首。碳纤维具有耐高温、抗摩擦、导电、导热及耐腐蚀等特性，外形呈纤维状、柔软、可加工成各种织物，由于其石墨微晶结构沿纤维轴择优取向，因此沿纤维轴方向有很高的强度和模量，而且碳纤维的密度小，因此比强度和比模量高。碳纤维的主要用途是作为增强材料与树脂、金属、陶瓷及炭等复合，制造先进复合材料。
汽车车身的轻量化，对于降低汽车能耗具有重要意义。尤其是对于新能源汽车中的纯电动车，在目前电池性能远不如人意的情况下，在保证车身安全性的前提下，降低车身重量，更具有现实意义。宝马i3在这方面进行了率先尝试。外表并不瘦小的宝马i3，因为采用碳纤维复合材料车身，自重仅1224kg。
宝马i3的碳纤维复合材料车身是由若干碳纤维复合材料构件组合而成，生产一个碳纤维复合材料车身，首先要生产若干碳纤维复合材料构件，然后再将所有碳纤维复合材料构件组合而成。
当下碳纤维复合材料正处于热门研究中心，为满足不断提高的工业需求，对碳纤维复合材料进行优化改进是未来很长时间内的一种研究趋势。对此，本发明提出了一种汽车板材用的碳纤维复合材料，具有优异的强韧性、抗压恢复性，力学性能强，综合性能显著提高。
发明内容
针对上述存在的问题，本发明提出了一种汽车板材用碳纤维复合材料及其制备工艺，对材料、结构双方面均进行了改进，不仅提高了力学性能，同时具有优异的防护抗压、减震回复性，且层间结合力强，安全稳定，整体轻质高强，应用推广性高。
为了实现上述的目的，本发明采用以下的技术方案：
一种汽车板材用碳纤维复合材料，包括高强叠板层、补偿增韧层，高强叠板层包括复合热压的CFPR板以及蜂窝型稀土铝合金板，补偿增韧层包括复合热压的上、中、下三层含矿物掺杂的不饱和聚酯碳纤维增强板；高强叠板层、补偿增韧层厚度比为1:0.4-0.7。
作为本发明的进一步优化，补强增韧层的上、下层的含矿物掺杂的不饱和聚酯纤维增强板相向侧面开设有若干卡接槽，且上、下卡接槽开口朝向相反，中层的含矿物掺杂的不饱和聚酯纤维增强板的上、下侧面设有与卡接槽对应适配的凸沿。
作为本发明的进一步优化，CFPR板、蜂窝型稀土铝合金板以及含矿物掺杂的不饱和聚酯纤维增强板间均设有粘结层，粘结层为胶粉层或高分子胶膜层或胶粉-高分子胶膜复合层，粘结层厚度为0.15-0.25mm。
作为本发明的进一步优化，CFRP板采用聚丙烯腈碳纤维/海泡石纤维与聚氨酯树脂固化成型的板材，蜂窝型稀土铝合金板采用Al-Zn-Mg-Cu系铝合金为基础合金，添加RE和Mn元素，蜂窝型稀土铝合金板孔隙率为45-50％。
作为本发明的进一步优化，CFRP板制备方法为，采用静电纺丝法先制备聚丙烯腈碳纤维/海泡石纤维的复合纤维毡，然后采用树脂传递模塑成型工艺以复合纤维毡为增强材料、以聚氨酯树脂为树脂体系，同时添加适量填料，制得CFRP层；其中，
复合纤维毡中聚丙烯腈碳纤维与海泡石纤维质量比为1:0.1-0.2；填料为滑石粉与玻璃微珠组合物，两者质量比为1:4；
复合纤维毡、填料、聚氨酯树脂的质量百分比分别为18-25％、25-40％、余量。
作为本发明的进一步优化，蜂窝型稀土铝合金板中RE为Ce、Y两种元素组合物，以基础合金为计量基础，RE元素添加量为0.05wt％＜RE≤0.2wt％，且Ce/Y的摩尔比为1:0.6-0.8，Mn元素添加量为Mn≤0.3wt％。
作为本发明的进一步优化，蜂窝型稀土铝合金板制备方法为，先将Al-Zn-Mg-Cu系铝合金加热熔融，然后将Mn元素与50wt％的稀土Ce加入金属溶液中，精炼除渣，剩余的稀土元素一半随流添加，另一半纳入包底随流出包，采用注射成型技术对熔融金属液进行相应形状的固化成型。成型后产品采用高低温循环时效处理，有利于提高综合力学性能。作为一个优选，先在280-350℃加热保温30min，然后在460-550℃加热保温30min，并以此为一个预热处理单元，循环至少2次。
作为本发明的进一步优化，补偿增韧层制备方法为，采用静电纺丝法先制备复合纤维毡，然后采用树脂传递模塑成型工艺，以复合纤维毡为增强材料、以不饱和聚酯树脂为树脂体系、以掺杂矿物为补强材料，同时添加适量填料，制得补偿增韧层；其中，
复合纤维毡为聚丙烯腈碳纤维/玻璃纤维复合纤维毡，两者质量比为1:0.5-1；不饱和聚酯树脂采用双酚A不饱和聚酯树脂；掺杂矿物为埃洛石和丝光沸石组合物，两者质量比为1:0.1-0.5；填料为玻璃微珠、云母粉组合物，两者质量比为1:0.5；
增强纤维、补强材料、填料、树脂基体质量百分比分别为15-18％、4-10％、22-40％、余量。
作为本发明的进一步优化，汽车板材用碳纤维复合材料，制备方法为：
1)取高强叠板层、补偿增韧层原料，对不饱和聚酯纤维增强板、CFRP板材进行表层预处理；
2)将三层不饱和聚酯纤维增强板拼接组合，层间放置粘结层材料，复合热压后备用，然后同样将CFPR板以及蜂窝型稀土铝合金板复合热压后备用；
3)将两个热压后的组合板再次复合热压，且不饱和聚酯纤维增强板与蜂窝型稀土铝合金板相邻设置，即得最终成品。
作为本发明的进一步优化，所述表层预处理为先用酸碱洗活化，然后在板材表层分散粘附聚醚醚酮粉末，聚醚醚酮分散量为1-3g/m2。
本发明碳纤维复合材料在汽车板材中的应用，使用时，以现有聚氨酯泡沫板为基板，然后将本发明碳纤维复合材料对称热压于基板两侧(高强叠板层朝外)，然后再在外侧复合热压无纺布即可。
由于采用上述的技术方案，本发明的有益效果是：
1、本发明对材料、结构双方面进行改进，不仅提高了力学性能，同时具有优异的防护抗压、减震回复性，层间结合力强，安全稳定，整体轻质高强，综合性价比显著提高，值得推广应用。
2、本发明碳纤维复合材料分为三个部分，分别是CFRP板、蜂窝型稀土铝合金板、含矿物掺杂的不饱和聚酯碳纤维增强板，三个部分配合作用，在保证足够强度的同时，抗震抗压性明显提高，且结构韧性、回弹性、缓冲性高，具有优异的抗冲击效果，同时，结构比重低，成本低，轻质高强，综合性价比高。
3、补偿增韧层由三个配合组合的含矿物掺杂的不饱和聚酯碳纤维增强板热压复合而成，通过卡接槽、凸沿上下反方向插接扣合，层间自锁固定性好，既保证了一体的稳固性，同时多层分散的胶黏结构也有利于提高抗压性，而阵列排布的凸沿与卡接槽也避免了应力集中，具有良好的受力传递性。不饱和聚酯碳纤维增强板本身的树脂塑性强，与CFRP板配合，对中间夹持的金属层具有良好的防护性，应力分散性好，承重均匀，同时中部的蜂窝型结构也有利于分散各个方向上的受力，同时对板材隔热、消音也具有优异的促进效果。
4、蜂窝型铝合金板，以稀土和Mn元素掺杂，有效细化晶粒，提高强韧性的同时，有利于后期加工成型，有效避免了蜂窝成型的组织变质裂纹等，结构稳定性、强韧性增强。
5、本发明碳纤维复合材料用于汽车板材制备，特别是汽车顶板，其抗压性能提高了50％以上(雪压测试)，同时具有良好的防水、耐磨、防锈效果，拉伸强度、弯曲强度、断裂伸长率均具有显著的提高。
附图说明
图1为本发明层间结构示意图(分离状态)；
图中：1高强叠板层、11 CFRP板、12蜂窝型稀土铝合金板、2补偿增韧层、21a上层不饱和聚酯纤维增强板、21b中层不饱和聚酯纤维增强板、21c下层不饱和聚酯纤维增强板、22卡接槽、23凸沿、3粘结层。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述。基于本发明的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1：
一种汽车板材用碳纤维复合材料，包括高强叠板层、补偿增韧层，高强叠板层包括复合热压的CFPR板以及蜂窝型稀土铝合金板，补偿增韧层包括复合热压的上、中、下三层含矿物掺杂的不饱和聚酯碳纤维增强板；高强叠板层、补偿增韧层厚度比为1:0.4-0.7。
补强增韧层的上、下层的含矿物掺杂的不饱和聚酯纤维增强板相向侧面开设有若干卡接槽，且上、下卡接槽开口朝向相反，中层的含矿物掺杂的不饱和聚酯纤维增强板的上、下侧面设有与卡接槽对应适配的凸沿。
CFPR板、蜂窝型稀土铝合金板以及含矿物掺杂的不饱和聚酯纤维增强板间均设有粘结层，粘结层为胶粉层或高分子胶膜层或胶粉-高分子胶膜复合层，粘结层厚度为0.15-0.25mm。
该汽车板材用的碳纤维复合材料分为三个部分，含碳纤维才材料分层分散设置，且结构优化改进，具有良好的递进辅助效果，相较于传统的纯CFRP材料，成本更低，性价比高。
由外向内，先由CFRP层保证足够的化学防护性和一定的力学性能，逐步向内，中层金属部分为蜂窝设置，有效保证了轻质高强、受力稳定，同时附有减震消能、隔音隔热的效果，与同比重的CFRP板材，综合性能更为优异(结合成本、性能考察)，然后最内层的补强增韧层，以矿物/纤维补强掺杂，力学性能优异，同时塑性效果好，且为相互锁合的多层结构，为抗压卸力、缓冲消能提供了有效支持，采用不饱和聚酯树脂，与汽车板材基板(聚氨酯)具有良好的结合效果，在制备过程中，对树脂基体表面进行一定的活化处理，即可获得高强结合的(化学键合)高稳定性复合板，简单高效。
实施例2：
CFRP板采用聚丙烯腈碳纤维/海泡石纤维与聚氨酯树脂固化成型的板材；
蜂窝型稀土铝合金板采用Al-Zn-Mg-Cu系铝合金为基础合金，添加RE和Mn元素，蜂窝型稀土铝合金板孔隙率为45-50％(该孔隙率为大量实验下获得的保证强度和比重的最优范围值)。蜂窝型稀土铝合金板中RE为Ce、Y两种元素组合物，以基础合金为计量基础，RE元素添加量为0.05wt％＜RE≤0.2wt％，且Ce/Y的摩尔比为1:0.6-0.8，Mn元素添加量为Mn≤0.3wt％。
含矿物掺杂的不饱和聚酯碳纤维增强板采用含埃洛石/丝光沸石掺杂补强的聚丙烯腈碳纤维/玻璃纤维-双酚A不饱和聚酯树脂复合材料。
对各层板材材料进行优化改进，保证了板材物化性能的同时，有利于层间的稳定结合，在粘结层材料热压的过程中，层间界面除了与粘结材料粘附连接外，还具有一定的活化效果，对其中的纤维骨架具有诱导作用，有利于分子间的架桥结合。
如外层CFRP板材中海泡石纤维在与连续碳纤维交联结合后，其本身的高离子交换性以及催化性能能够有效促进与其他树脂活性基团反应连接(-OH、-NH2等)，同时可作为高活性的连接桥梁，为层间离子迁移做稳固导向，有效保证了层间的结合强度，有利于稳定组织结构。埃洛石与沸石组合，能够有效协助填料提高板材的强韧性，而且能够形成良好的助分散网络结构，与纤维协同作用，整体力学性能强，结构稳定度高，同样具有易活化效果，有利于外层活性基团反应结合，催化促进效果好，层间结合稳定。
实施例3(单层板材制备)：
①CFRP板制备方法为，采用静电纺丝法先制备聚丙烯腈碳纤维/海泡石纤维的复合纤维毡，然后采用树脂传递模塑成型工艺以复合纤维毡为增强材料、以聚氨酯树脂为树脂体系，同时添加适量填料，制得CFRP层；其中，
复合纤维毡中聚丙烯腈碳纤维与海泡石纤维质量比为1:0.1-0.2；填料为滑石粉与玻璃微珠组合物，两者质量比为1:4；
复合纤维毡、填料、聚氨酯树脂的质量百分比分别为18-25％、25-40％、余量。
②蜂窝型稀土铝合金板制备方法为，先将Al-Zn-Mg-Cu系铝合金加热熔融，然后将Mn元素与50wt％的稀土Ce加入金属溶液中，精炼除渣，剩余的稀土元素一半随流添加，另一半纳入包底随流出包，采用注射成型技术对熔融金属液进行相应形状的固化成型。稀土分多次添加，有效保证了孕育和均质效果，结构晶粒细化稳定性强，综合性能提高。
③补偿增韧层制备方法为，采用静电纺丝法先制备复合纤维毡，然后采用树脂传递模塑成型工艺，以复合纤维毡为增强材料、以不饱和聚酯树脂为树脂体系、以掺杂矿物为补强材料，同时添加适量填料，制得补偿增韧层；其中，
复合纤维毡为聚丙烯腈碳纤维/玻璃纤维复合纤维毡，两者质量比为1:0.5-1；不饱和聚酯树脂采用双酚A不饱和聚酯树脂；掺杂矿物为埃洛石和丝光沸石组合物，两者质量比为1:0.1-0.5；填料为玻璃微珠、云母粉组合物，两者质量比为1:0.5；
增强纤维、补强材料、填料、树脂基体质量百分比分别为15-18％、4-10％、22-40％、余量。
实施例4(复合板材制备)：
汽车板材用碳纤维复合材料，制备方法为：
1)取高强叠板层、补偿增韧层原料，对不饱和聚酯纤维增强板、CFRP板材进行表层预处理，表层预处理为先用酸碱洗活化，然后在板材表层分散粘附聚醚醚酮粉末，聚醚醚酮分散量为1-3g/m2；
2)将三层不饱和聚酯纤维增强板拼接组合，层间放置粘结层材料，复合热压后备用，然后同样将CFPR板以及蜂窝型稀土铝合金板复合热压后备用；
3)将两个热压后的组合板再次复合热压，且不饱和聚酯纤维增强板与蜂窝型稀土铝合金板相邻设置，即得最终成品。
板材原料在热压复合强进行预处理，对表层界面具有一定的活化效果，有利于层间结合，同时，还撒施有聚醚醚酮，有效提高了界面柔性和强韧度，对纤维以及活化分子的嵌入渗移具有良好的促进效果，同时，柔性界面对应力的传递具有积极作用，保证了材料强度的提升。
实施例5：
按本发明实施例制备碳纤维复合材料板，性能如下表：
拉伸强度，MPa 弯曲强度，MPa 断裂伸长率，％ 剪切强度，MPa
样品1 2536 1583 175 116
样品2 2470 1561 160 118
样品3 2455 1503 182 103
对照品1 2322 1496 215 99
对照品2 2411 1482 151 112
对照品3 1344 1306 203 72
样品1：高强叠板层：补偿增韧层＝1:0.5(厚度比)；CFRP板：蜂窝型稀土铝合金板＝1:1(厚度比)；CFRP板中聚丙烯腈碳纤维：海泡石纤维＝1:0.1(质量比)；蜂窝型稀土铝合金板孔隙率＝48.2％；单层粘结层(高分子胶膜层)：0.2mm；聚醚醚酮分散量为2g/m2；补偿增韧层中埃洛石：丝光沸石＝1:0.3(质量比)，聚丙烯腈碳纤维：玻璃纤维＝1:0.5(质量比)。
样品2：高强叠板层：补偿增韧层＝1:0.4(厚度比)；CFRP板：蜂窝型稀土铝合金板＝1:0.75(厚度比)；CFRP板中聚丙烯腈碳纤维：海泡石纤维＝1:0.2(质量比)；蜂窝型稀土铝合金板孔隙率＝50％；单层粘结层(高分子胶膜层)：0.2mm；聚醚醚酮分散量为3g/m2；补偿增韧层中埃洛石：丝光沸石＝1:0.5(质量比)，聚丙烯腈碳纤维：玻璃纤维＝1:0.5(质量比)。
样品3：高强叠板层：补偿增韧层＝1:0.6(厚度比)；CFRP板：蜂窝型稀土铝合金板＝1:0.5(厚度比)；CFRP板中聚丙烯腈碳纤维：海泡石纤维＝1:0.2(质量比)；蜂窝型稀土铝合金板孔隙率＝45％；单层粘结层(高分子胶膜层)：0.15mm；聚醚醚酮分散量为2.5g/m2；补偿增韧层中埃洛石：丝光沸石＝1:0.1(质量比)，聚丙烯腈碳纤维：玻璃纤维＝1:1(质量比)。
对照品1：与样品1同厚度的纯CFRP板；
对照品2：与样品1同厚度的高强叠板层；
对照品3：与样品1同厚度的补偿增韧层。
本发明对材料、结构双方面进行改进，不仅提高了力学性能，同时具有优异的防护抗压、减震回复性，层间结合力强，安全稳定，整体轻质高强，综合性价比显著提高，值得推广应用。
需要说明的是，在本文中，诸如第一和第二等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来，而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。而且，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。在没有更多限制的情况下，由语句“包括一个……”限定的要素，并不排除在包括要素的过程、方法、物品或者设备中还存在另外的相同要素。
以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。

Claims (8)

1.一种汽车板材用碳纤维复合材料，其特征在于：包括高强叠板层、补偿增韧层，高强叠板层包括复合热压的CFPR板以及蜂窝型稀土铝合金板，补偿增韧层包括复合热压的上、中、下三层含矿物掺杂的不饱和聚酯纤维增强板；高强叠板层、补偿增韧层厚度比为1:0.4-0.7；
所述补偿增韧层的上、下层的含矿物掺杂的不饱和聚酯纤维增强板相向侧面开设有若干卡接槽，且上、下卡接槽开口朝向相反，中层的含矿物掺杂的不饱和聚酯纤维增强板的上、下侧面设有与卡接槽对应适配的凸沿；
所述CFPR板、蜂窝型稀土铝合金板以及含矿物掺杂的不饱和聚酯纤维增强板间均设有粘结层，粘结层为胶粉层或高分子胶膜层或胶粉-高分子胶膜复合层，粘结层厚度为0.15-0.25mm。
2.根据权利要求1所述的汽车板材用碳纤维复合材料，其特征在于：所述CFRP板采用聚丙烯腈碳纤维/海泡石纤维与聚氨酯树脂固化成型的板材，蜂窝型稀土铝合金板采用Al-Zn-Mg-Cu系铝合金为基础合金，添加RE和Mn元素，蜂窝型稀土铝合金板孔隙率为45-50％。
3.根据权利要求2所述的汽车板材用碳纤维复合材料，其特征在于：所述CFRP板制备方法为，采用静电纺丝法先制备聚丙烯腈碳纤维/海泡石纤维的复合纤维毡，然后采用树脂传递模塑成型工艺以复合纤维毡为增强材料、以聚氨酯树脂为树脂体系，同时添加适量填料，制得CFRP层；其中，
复合纤维毡中聚丙烯腈碳纤维与海泡石纤维质量比为1:0.1-0.2；填料为滑石粉与玻璃微珠组合物，两者质量比为1:4；
复合纤维毡、填料、聚氨酯树脂的质量百分比分别为18-25％、25-40％、余量。
4.根据权利要求2所述的汽车板材用碳纤维复合材料，其特征在于：所述蜂窝型稀土铝合金板中RE为Ce、Y两种元素组合物，以基础合金为计量基础，RE元素添加量为0.05wt％＜RE≤0.2wt％，且Ce/Y的摩尔比为1:0.6-0.8，Mn元素添加量为Mn≤0.3wt％。
5.根据权利要求4所述的汽车板材用碳纤维复合材料，其特征在于：所述蜂窝型稀土铝合金板制备方法为，先将Al-Zn-Mg-Cu系铝合金加热熔融，然后将Mn元素与50wt％的稀土Ce加入金属溶液中，精炼除渣，剩余的稀土元素一半随流添加，另一半纳入包底随流出包，采用注射成型技术对熔融金属液进行相应形状的固化成型。
6.根据权利要求1所述的汽车板材用碳纤维复合材料，其特征在于：所述补偿增韧层制备方法为，采用静电纺丝法先制备复合纤维毡，然后采用树脂传递模塑成型工艺，以复合纤维毡为增强材料、以不饱和聚酯树脂为树脂体系、以掺杂矿物为补强材料，同时添加适量填料，制得补偿增韧层；其中，
复合纤维毡为聚丙烯腈碳纤维/玻璃纤维复合纤维毡，两者质量比为1:0.5-1；不饱和聚酯树脂采用双酚A不饱和聚酯树脂；掺杂矿物为埃洛石和丝光沸石组合物，两者质量比为1:0.1-0.5；填料为玻璃微珠、云母粉组合物，两者质量比为1:0.5；
增强纤维、补强材料、填料、树脂基体质量百分比分别为15-18％、4-10％、22-40％、余量。
7.根据权利要求1-6任一项所述的汽车板材用碳纤维复合材料，其特征在于，制备方法为：
1)取高强叠板层、补偿增韧层原料，对不饱和聚酯纤维增强板、CFRP板材进行表层预处理；
2)将三层不饱和聚酯纤维增强板拼接组合，层间放置粘结层材料，复合热压后备用，然后同样将CFPR板以及蜂窝型稀土铝合金板复合热压后备用；
3)将两个热压后的组合板再次复合热压，且不饱和聚酯纤维增强板与蜂窝型稀土铝合金板相邻设置，即得最终成品。
8.根据权利要求7所述的汽车板材用碳纤维复合材料，其特征在于：所述表层预处理为先用酸碱洗活化，然后在板材表层分散粘附聚醚醚酮粉末，聚醚醚酮分散量为1-3g/m2。
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