CN111196072A - 一种增材制造用连续纤维增强热塑性预浸料单向带 - Google Patents

一种增材制造用连续纤维增强热塑性预浸料单向带 Download PDF

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CN111196072A
CN111196072A CN201811367767.2A CN201811367767A CN111196072A CN 111196072 A CN111196072 A CN 111196072A CN 201811367767 A CN201811367767 A CN 201811367767A CN 111196072 A CN111196072 A CN 111196072A
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additive manufacturing
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安学锋
闫丽
邓华
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AVIC BASIC TECHNOLOGY RESEARCH INSTITUTE
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Abstract

本发明是一种增材制造用连续纤维增强热塑性预浸料单向带，本发明的增强纤维在单向带内部非均匀分布，该单向带由上部的表面树脂层(1)和下部的纤维层(2)构成，而两部分平均后预浸料整体的纤维含量则与标准预浸料相当。在铺放成型过程中，预浸料富树脂的表面层受热熔融，而后在压力下相邻的两层预浸料粘接为一体，形成均匀致密的复合材料层压结构，成为增材制造的基础。

Description

一种增材制造用连续纤维增强热塑性预浸料单向带
技术领域
本发明是一种增材制造用连续纤维增强热塑性预浸料单向带，属于树脂基复合材料制造技术。
背景技术
以激光快速原型技术为代表的快速制造技术是当前广受关注的材料加工技术。通过将金属、树脂等材料的粉末、液滴自动逐层堆叠，然后按照断层结构选择性粘接、激光烧结，可以高效率地制造出具有精细结构的制件。这种逐层增加材料的成型方法称为“增材制造”；由于其与打印技术具有一定的相似性，又常被俗称为“3D打印”技术。该成型技术以往多应用于快速制造零件原型，所以也常被称为“快速原型”技术；但是近年来其应用范围正迅速向制造日益丰富的实用产品的方向发展，充分体现出低成本、高效率、适于制造复杂结构件的优势。因此，当前各国均对快速制造技术表现出浓厚的兴趣，认为这将是推动新一轮工业技术革新的发展方向。
目前已发展出多种形式的增材制造技术，但是多以金属、聚合物粉末材料为加工对象，连续纤维增强树脂基复合材料方面仍有待进一步研究。目前与此相关的成型技术列举如下：
立体平版印刷(stereolithography，SLA)。其基本原理是利用紫外光、激光等光源选择性地扫描预置在工作台上的光敏聚合物并使之快速固化。工作台上升到液面下一个层厚的位置，激光扫描、固化树脂，然后工作平台下降一个层厚，再重复上述过程，最后形成所需的三维零件。另一种相似工艺是光投影固化成型：将每一层的图像直接投影在液态光敏聚合物表面，使每一层瞬间固化，从而大幅提高成型速度。在各类增材制造工艺中，该方法尺寸精度和表面质量最好，市场份额最大。
选择性激光烧结(selective laser sintering，SLS)及选择性激光熔融(selective laser melting，SLM)。其基本原理是利用热能将聚合物粉末材料粘接或熔合在一起，形成所需的形状。由于聚合物粉末可以起自然支撑作用，因而不需要同步成型支撑结构。在增材制造领域，SLS/SLM是直接快速制造工程零件的最有效方法之一。在快速制造高端工程产品的具有终端用途零件方面，SLS/SLM成型设备是应用最广泛的增材制造设备。利用该技术制造的聚合物零件和高性能复杂结构金属零件正在航空航天、国防和其它高端工程领域获得广泛应用。
熔融沉积成型(fused deposition modeling，FDM)。其原理是在一定压力作用下，丝状聚合物材料通过加热喷嘴软化后，逐点、逐线、逐面、逐层熔化、堆积形成三维结构，成型过程中工作平台下移或喷嘴上移。FDM设备结构非常简单，价格低廉，适合于办公室和家庭环境。低成本FDM设备的推出是增材制造技术近来获得广泛认可和应用的重要原因之一。近期Avero Labs公司宣布推出采用碳纤维和碳纳米管增强的热塑性树脂长纤维，并采用FDM工艺制造出纤维增强树脂基复合材料试验件。
分层实体制造(laminated object manufacturing，LOM)。其原理是根据零件分层几何信息切割箔材，将所获得的层片粘接成三维实体。其工艺过程是首先铺上一层箔材，然后用激光在计算机控制下切出本层轮廓，非零件部分全部切碎以便于去除。当本层完成后，再铺上一层箔材，辊压加热固化黏结剂，使新铺上的一层牢固地粘接在已成形体上，再切割该层的轮廓，如此反复直到加工完毕，最后去除切碎部分以得到完整的零件。该工艺的特点是工作可靠，模型支撑性好，成本低，效率高。
目前连续纤维增强复合材料增材制造的方法是直接利用现有的复合材料自动铺放成型工艺，通过引入在线加热熔融/固化/固结手段，实现传统预浸料材料或专用丝束的快速成型。例如EADS开展的热塑性预浸料自动铺放与前沿快速加热试验，通过制造壁板试验件进行了验证，成型质量良好。试验中使用了两种热源，分别为激光和热空气。这对开展热塑性树脂基复合材料的增材制造技术提供了良好的借鉴。
发明内容
本发明正是针对上述现有技术状况而设计提供了一种增材制造用连续纤维增强热塑性预浸料单向带，其目的是提出一种可与自动铺放工艺相结合的用于增材制造的连续纤维增强热塑性预浸料单向带。
本发明的目的是通过以下技术方案来实现的：
该种增材制造用连续纤维增强热塑性预浸料单向带，其特征在于：该单向带由上部的表面树脂层1和下部的纤维层2构成，该种构成分以下两种形式：
第一种：当增强纤维包括碳纤维时，表面树脂层1由基体树脂制成，厚度为0.05mm～0.50mm，纤维层2由含增强纤维的预浸料制成，该单向带中上部的表面树脂层1和下部的纤维层2平均后的纤维重量百分比含量为50％～65％；
第二种：当增强纤维不包括碳纤维时，表面树脂层1由基体树脂和碳纳米管制成，厚度为0.05mm～0.50mm，碳纳米管在表面树脂层1中的重量百分比含量为0.5％～2.5％，该单向带中上部的表面树脂层1和下部的纤维层2平均后的纤维重量百分比含量为50％～65％。
进一步，下部的纤维层2中增强纤维的重量百分比含量为65％～77％。
进一步，第一种方式中所述增强纤维为碳纤维或碳纤维与玻璃纤维或芳纶纤维的混合物。
进一步，第二种方式中所述增强纤维为玻璃纤维、芳纶纤维中的一种或两种的混合物。
进一步，所述的基体树脂为聚醚醚酮、聚醚酮酮、聚苯硫醚或聚醚酰亚胺。
制备上述单向带的方法是：首先制造高纤维含量的纤维层2，而后将其与表面树脂层1进行复合，形成最终的产品。
在自动铺放过程中，该单向带的表面层受热熔融，而后在铺放辊的压力下将相邻的两层单向带粘接为一体，形成均匀致密的复合材料层压结构。
本发明技术方案的提出是基于对增材制造中连续纤维增强热塑性复合材料出现的问题和更高的要求，所述问题和要求包括：
首先，为满足结构承载的更高要求，单向带中包含的增强纤维应是连续不间断的，理论上与预浸料长度相等；
其次，为了满足结构设计对强度和刚度的要求，单向带中增强纤维的重量百分比含量不低于50％；
再次，为了实现前沿加热自动铺放成型，需要在单向带单侧表面形成树脂富集，确保相邻两层预浸料之间能够形成可靠的粘接；同时还要保证单向带中所有增强纤维丝束都被基体树脂充分浸渍；
最后，为了实现激光加热熔融，对于采用不吸收激光能量的增强纤维例如玻璃纤维、芳纶纤维等的带向带，需要在其内引进可以吸收激光能量的成分，用于加热熔融位于表面的树脂基体。
针对上述问题和要求，本发明技术方案的优点是：
本发明的连续纤维增强热塑性预浸料内部分为两层，包括表面的基体树脂层内部可以添加碳纳米管作为激光吸收剂和其下的纤维层。在保证增强纤维丝束完全浸润的前提下，尽可能将更多的基体树脂富集在预浸料表面，起到层间粘接胶膜的作用，保证相邻铺层间紧密结合。
附图说明
图1为增强纤维为碳纤维的单向带的结构示意图
图2为增强纤维为碳纤维和玻璃纤维的高纤维含量的单向带的结构示意图
图3为增强纤维为芳纶纤维的单向带的结构示意图
具体实施方式
以下将结合附图和实施例对本发明技术方案作进一步地详述：
实施例1
参见附图1所示，该种增材制造用连续纤维增强热塑性预浸料单向带由上部的表面树脂层1和下部的纤维层2构成，增强纤维为碳纤维，表面树脂层1由基体树脂制成，基体树脂为聚醚醚酮，厚度为0.25mm，纤维层2由含增强纤维的预浸料制成，该单向带中上部的表面树脂层1和下部的纤维层2平均后的纤维重量百分比含量为60％，下部的纤维层2中增强纤维的重量百分比含量为70％。
制备该单向带采用热熔挤出预浸机，设计具有上下双入口-单出口的挤出口模，令展开的碳纤维丝束从口模下方入口进入，而挤出的聚醚醚酮熔体则同时进入口模的上下两个入口，完成浸渍后得到碳纤维非均匀分布的单向带。
实施例2
参见附图2所示，该种增材制造用连续纤维增强热塑性预浸料单向带由上部的表面树脂层1和下部的纤维层2构成，增强纤维为碳纤维和玻璃纤维，通过展纱后重新合股制备碳纤维-玻璃纤维混杂丝束，两者的体积比为：碳纤维∶玻璃纤维＝2∶1，表面树脂层1由基体树脂制成，基体树脂为聚苯硫醚，厚度为0.40mm，纤维层2由含增强纤维的预浸料制成，该单向带中上部的表面树脂层1和下部的纤维层2平均后的纤维重量百分比含量为50％。
制备该单向带使用静电粉末预浸机。设定流化床中聚苯硫醚粉末的浓度梯度和混杂丝束通过流化床的速度，使得聚苯硫醚粉末在混杂丝束上表面形成堆积。完成浸渍后得到混杂纤维非均匀分布的单向带。
实施例3
参见附图3所示，该种增材制造用连续纤维增强热塑性预浸料单向带由上部的表面树脂层1和下部的纤维层2构成，增强纤维使用芳纶纤维，由于芳纶纤维对激光无吸收能力，所以，表面树脂层1由基体树脂和碳纳米管制成，基体树脂为聚醚酰亚胺，碳纳米管在表面树脂层1中的重量百分比含量为1.0％，厚度为0.35mm，该单向带中上部的表面树脂层1和下部的纤维层2平均后的纤维重量百分比含量为55％。下部的纤维层2中增强纤维的重量百分比含量为65％。
制备该单向带下部的纤维层2使用热熔预浸机制备。上部的表面树脂层1使用热熔刮涂法制备，首先热熔刮涂制备厚度0.25mm的聚醚酰亚胺胶膜，再将聚醚酰亚胺树脂与碳纳米管混合形成碳纳米管的重量百分比含量为1.5％的混合树脂，热熔刮涂制备厚度为0.15mm的聚醚酰亚胺/碳纳米管胶膜，按照聚醚酰亚胺胶膜-聚醚酰亚胺/碳纳米管胶膜-芳纶纤维/聚醚酰亚胺预浸料的顺序叠放，热压复合，形成芳纶纤维非均匀分布的热熔预浸带，整体芳纶纤维含量为55％，其中底层部分的芳纶纤维含量保持为65％，而上表面0.35mm厚度内为聚醚酰亚胺树脂层，其中含有1％的碳纳米管。将此宽幅预浸料分切后得到自动铺放用窄带。
与现有技术相比，本发明的连续纤维增强热塑性单向带可以通过将碳纤维与玻璃纤维或芳纶纤维混杂的方式，利用碳纤维吸收激光能量加热熔融树脂基体；而对于不含碳纤维的预浸料体系，则通过在富树脂层中引进碳纳米管薄层，实现对激光能量的吸收，加热熔融树脂基体。
本发明的连续纤维增强热塑性预浸料，整体的纤维含量仍可保持在50％～65％，能够达到原有热塑性复合材料的力学性能。

Claims (5)

1.一种增材制造用连续纤维增强热塑性预浸料单向带，其特征在于：该单向带由上部的表面树脂层(1)和下部的纤维层(2)构成，该种构成分以下两种形式：
第一种：当增强纤维包括碳纤维时，表面树脂层(1)由基体树脂制成，厚度为0.05mm～0.50mm，纤维层(2)由含增强纤维的预浸料制成，该单向带中上部的表面树脂层(1)和下部的纤维层(2)平均后的纤维重量百分比含量为50％～65％；
第二种：当增强纤维不包括碳纤维时，表面树脂层(1)由基体树脂和碳纳米管制成，厚度为0.05mm～0.50mm，碳纳米管在表面树脂层(1)中的重量百分比含量为0.5％～2.5％，该单向带中上部的表面树脂层(1)和下部的纤维层(2)平均后的纤维重量百分比含量为50％～65％。
2.根据权利要求1所述的增材制造用连续纤维增强热塑性预浸料单向带，其特征在于：下部的纤维层(2)中增强纤维的重量百分比含量为65％～77％。
3.根据权利要求1所述的增材制造用连续纤维增强热塑性预浸料单向带，其特征在于：第一种方式中所述增强纤维为碳纤维或碳纤维与玻璃纤维或芳纶纤维的混合物。
4.根据权利要求1所述的增材制造用连续纤维增强热塑性预浸料单向带，其特征在于：第二种方式中所述增强纤维为玻璃纤维、芳纶纤维中的一种或两种的混合物。
5.根据权利要求1所述的增材制造用连续纤维增强热塑性预浸料单向带，其特征在于：所述的基体树脂为聚醚醚酮、聚醚酮酮、聚苯硫醚或聚醚酰亚胺。
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