CN109263167B - 一种增韧树脂膜制备碳纤维预浸织物的方法 - Google Patents
一种增韧树脂膜制备碳纤维预浸织物的方法 Download PDFInfo
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Abstract
本发明公开了一种增韧树脂膜制备碳纤维预浸织物的方法。所述方法包括：S1.采用短切碳纤维混杂热熔热塑性纤维成型增韧网胎布结构；S2.采用热塑性树脂乳液喷淋所述增韧网胎布结构，制成网胎布增韧树脂胶膜；S3.将网胎布增韧树脂胶膜叠合铺设于碳纤维织物表面，含浸熔融复合成型制得碳纤维预浸织物。本发明采用内含网胎布结构的韧性树脂胶膜，可有效解决热塑性树脂乳液成膜性不稳定的问题，制备的热塑性胶膜的韧性、耐撕裂度；同时采用热熔胶膜叠合、热辊加压熔渗浸渍方式制备碳纤维织物预浸料，浸复合效果稳定，预浸布成型效率高；同时制备工艺简单，生产成本低廉，生产流程短，适合工业化大批量生产。
Description
技术领域
本发明属于碳纤维预浸织物制备技术领域，具体涉及一种增韧树脂膜制备碳纤维预浸织物的方法。
背景技术
碳纤维热塑性预浸料采用碳纤维多向织物含浸热塑性树脂，该预浸料可采用叠层复合热压成型的方式最终制备热塑性碳纤维复合材料的板材，其中碳纤维长丝的高强度、高模量、高冲击强度与热塑性树脂的高韧性和反复成型特性相结合，所得的热塑性碳纤维预浸织物适宜于各种热塑性碳纤维复合材料的制备，得到工业、农业、交通以及航空航天等领域的广泛使用。随着碳纤维热塑性预浸织物的生产工艺技术的发展进步，作为热塑性碳纤维复合材料中间产品的热塑性预浸织物的特种成型结构也不断得到研究。
为了提高热塑性树脂与碳纤维织物的含浸复合效率，各种不同的预浸方法被研究者开发，包括热熔浸渍法、溶液浸渍法、粉末浸渍法以及基于以上三种主要方法的混合使用技术。其中热塑性树脂的溶解难以实现，适宜的溶剂往往毒性较大；熔融浸渍方式需要的热熔加热设备的能耗较大，熔融效率较低；粉末浸渍法在织物含浸过程中由于树脂粉体的包覆分布容易不均匀引起含浸效果的不稳定。鉴于以上三种方式各自存在不足，因此迫切需要开发一种新型的碳纤维预浸织物的含浸成型方法，解决上述预浸织物的成型问题。
发明内容
针对上述现有技术的不足，发明人经长期的技术与实践探索，最终成功研发出一种增韧树脂膜制备碳纤维预浸织物的方法，本发明在制备碳纤维预浸织物中采用内含织物增韧结构的树脂胶膜叠层复合碳纤维多维或多向织物进而制备碳纤维预浸织物，最终浸复合效果稳定，预浸布成型效率高。
本发明的目的之一在于提供一种增韧树脂膜制备碳纤维预浸织物的方法。
本发明的目的之二在于提供上述方法制备得到的碳纤维预浸织物。
本发明的目的之三在于提供上述碳纤维预浸织物的应用。
为实现上述目的，本发明采用如下技术方案：
本发明的第一个方面，提供了一种增韧树脂膜制备碳纤维预浸织物的方法，所述方法包括：
S1.采用短切碳纤维混杂热熔热塑性纤维成型增韧网胎布结构；
S2.采用热塑性树脂乳液喷淋所述增韧网胎布结构，制成网胎布增韧树脂胶膜；
S3.将网胎布增韧树脂胶膜叠合铺设于碳纤维织物表面，含浸熔融复合成型制得碳纤维预浸织物。
进一步的，所述步骤S1中，所述增韧网胎布结构采用短切碳纤维混杂热熔热塑性纤维通过梳理成网制备得到；
所述短切碳纤维选用黏胶基碳纤维，短切纤维的长度控制在5-20cm；
所述热熔热塑纤维选用聚酰胺纤维、聚醚酮纤维、聚醚醚酮纤维、聚氨酯纤维、聚乙烯纤维、聚丙烯纤维中的任意一种；
所述短切碳纤维和热熔热塑性纤维的混杂比例根据最终增韧树脂膜的韧性和最终含浸树脂含量确定，优选短切碳纤维与热熔热塑性纤维的混杂比例为1：1～4；
进一步的，所述步骤S2中，热塑性树脂乳液可选用聚氨酯、聚乙烯、聚丙烯、乙烯基丙烯酸共聚物(EAA)、聚醚酮、聚醚醚酮、聚酰胺中的任意一种，所述热塑性树脂乳液的固含量控制在20-40％范围内；
进一步的，所述步骤S2中，热塑性树脂乳液雾化喷淋在所述增韧网胎布结构基底表面，在50-80℃范围内干燥使乳液成膜，最终制备网胎布增韧树脂胶膜的面密度控制在20-100g/m2范围内，其中网胎布占网胎布增韧树脂胶膜的重量百分含量控制在10-30％范围内；
进一步的，所述步骤S3中，碳纤维织物可选用高强型或高模型碳纤维，如T300、T700、T800、T1000、M40、M60、M40J、M60J其中的任意一种或多种混杂，所用的碳纤维织物的织物结构可选用平纹、斜纹、缎纹、多轴向、单向等多种平面织物结构；
进一步的，所述步骤S3中，采用热辊挤压方式熔融树脂膜，含浸碳纤维预制体结构制备碳纤维预浸织物；
其中，热辊温度控制在高于树脂熔点的10-30℃内，热辊走速控制在1-40m/min，热辊的挤压压强控制在2-10MPa范围内；同时，根据最终树脂含量要求，采用单层或多层树脂胶膜叠合铺设在碳纤维织物表面，通过热辊加压熔融含浸，最终制备碳纤维预浸织物。
本发明的第二个方面，提供上述方法制备得到的碳纤维预浸织物，所述碳纤维预浸织物的面密度控制在50-300g/m2范围内。
本发明的第三个方面，提供上述碳纤维预浸织物在制备热塑性碳纤维复合材料中的应用。
本发明的有益效果：
(1)采用内含网胎布结构的韧性树脂胶膜，可有效解决热塑性树脂乳液成膜性不稳定的问题，制备的热塑性胶膜的韧性、耐撕裂度和最终热熔效果较好；
(2)采用热熔胶膜叠合、热辊加压熔渗浸渍方式制备碳纤维织物预浸料，浸复合效果稳定，预浸布成型效率高；同时制备工艺简单，生产成本低廉，生产流程短，适合工业化大批量生产，使得本发明具有广阔的工业化应用前景和实际应用之价值。
附图说明
图1是本发明碳纤维预浸织物结构示意图，该碳纤维预浸织物采用1-网胎布增韧树脂胶膜、2-碳纤维织物叠层熔渗复合构成，其中1-网胎布增韧树脂胶膜中内含3-黏胶基碳纤维短切丝和4-热熔热塑性纤维混杂梳网构成的5-增韧网胎布结构。
具体实施方式
应该指出，以下详细说明都是例示性的，旨在对本申请提供进一步的说明。除非另有指明，本文使用的所有技术和科学术语具有与本申请所属技术领域的普通技术人员通常理解的相同含义。
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本申请的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。
本发明的一种具体实施中，提供一种增韧树脂膜制备碳纤维预浸织物的方法，所述方法包括：
S1.采用短切碳纤维混杂热熔热塑性纤维成型增韧网胎布结构；
S2.采用热塑性树脂乳液喷淋所述增韧网胎布结构，制成网胎布增韧树脂胶膜；
S3.将网胎布增韧树脂胶膜叠合铺设于碳纤维织物表面，含浸熔融复合成型制得碳纤维预浸织物。
本发明的又一具体实施方式中，所述步骤S1中，所述增韧网胎布结构采用短切碳纤维混杂热熔热塑性纤维通过梳理成网制备得到；
本发明的又一具体实施方式中，所述短切碳纤维选用黏胶基碳纤维，短切纤维的长度控制在5-20cm；
本发明的又一具体实施方式中，所述热熔热塑性纤维选用聚酰胺纤维、聚醚酮纤维、聚醚醚酮纤维、聚氨酯纤维、聚乙烯纤维、聚丙烯纤维中的任意一种；
本发明的又一具体实施方式中，所述短切碳纤维和热熔热塑性纤维的混杂比例根据最终增韧树脂膜的韧性和最终含浸树脂含量确定，优选短切碳纤维与热熔热塑性纤维的混杂比例为1：1～4；
本发明的又一具体实施方式中，所述步骤S2中，热塑性树脂乳液可选用聚氨酯、聚乙烯、聚丙烯、乙烯基丙烯酸共聚物(EAA)、聚醚酮、聚醚醚酮、聚酰胺中的任意一种，所述热塑性树脂乳液的固含量控制在20-40％范围内；
本发明的又一具体实施方式中，所述步骤S2中，热塑性树脂乳液雾化喷淋在所述增韧网胎布结构基底表面，在50-80℃范围内干燥使乳液成膜，最终制备网胎布增韧树脂胶膜的面密度控制在20-100g/m2范围内，其中网胎布占网胎布增韧树脂胶膜的重量百分含量控制在10-30％范围内；
本发明的又一具体实施方式中，所述步骤S3中，碳纤维织物可选用高强型或高模型碳纤维，如T300、T700、T800、T1000、M40、M60、M40J、M60J其中的任意一种或多种混杂，所用的碳纤维织物的织物结构可选用平纹、斜纹、缎纹、多轴向、单向等多种平面织物结构；
本发明的又一具体实施方式中，所述步骤S3中，采用热辊挤压方式熔融树脂膜，含浸碳纤维预制体结构制备碳纤维预浸织物；
本发明的又一具体实施方式中，热辊温度控制在高于树脂熔点的10-30℃内，热辊走速控制在1-40m/min，热辊的挤压压强控制在2-10MPa范围内；同时，根据最终树脂含量要求，采用单层或多层树脂胶膜叠合铺设在碳纤维织物表面，通过热辊加压熔融含浸，最终制备碳纤维预浸织物。
本发明的又一具体实施方式中，提供上述方法制备得到的碳纤维预浸织物，所述碳纤维预浸织物的面密度控制在50-300g/m2范围内。
本发明的又一具体实施方式中，提供上述碳纤维预浸织物在制备热塑性碳纤维复合材料中的应用。
实施例1
制备一种内含织物增韧结构的树脂胶膜叠层复合碳纤维多维或多向织物制备碳纤维预浸织物的方法。
首先采用长度为5cm的短切黏胶基碳纤维混杂聚酰胺热熔热塑纤维，混杂比例为1:1。
之后采用固含量为20％的乙烯基丙烯酸共聚物(EAA)乳液雾化喷淋上述网胎布基底，之后经过80℃范围内干燥成膜，制备面密度控制在20g/m2、树脂含量30％的韧性树脂胶膜。
最终选用T300碳纤维制备平纹预制体织物，采用热辊加压方式，其中热辊温度控制在130℃，热辊走速控制在40m/min，热辊的挤压压强控制在10MPa，最终制备面密度300g/m2的碳纤维预浸织物。
实施例2
制备一种内含织物增韧结构的树脂胶膜叠层复合碳纤维多维或多向织物制备碳纤维预浸织物的方法。
首先采用长度20cm的短切黏胶基碳纤维混杂聚醚酮热熔热塑纤维，混杂比例为1:2。
之后采用固含量为20％的聚氨酯乳液雾化喷淋上述网胎布基底，之后经过70℃范围内干燥成膜，制备面密度控制在40g/m2、树脂含量在30％的韧性树脂胶膜。
最终选用T800碳纤维制备单向预制体织物，采用热辊加压方式，其中热辊温度控制在150℃，热辊走速控制在30m/min，热辊的挤压压强控制在5MPa，最终制备面密度130g/m2的碳纤维预浸织物。
实施例3
制备一种内含织物增韧结构的树脂胶膜叠层复合碳纤维多维或多向织物制备碳纤维预浸织物的方法。
首先采用长度为12cm的短切黏胶基碳纤维混杂聚乙烯热熔热塑纤维，混杂比例为1:4。
之后采用固含量为35％的聚乙烯乳液雾化喷淋上述网胎布基底，之后经过60℃范围内干燥成膜，制备面密度控制在60g/m2、树脂含量在15％的韧性树脂胶膜。
最终选用M60J碳纤维制备缎纹预制体织物，采用热辊加压方式，其中热辊温度控制在140℃，热辊走速控制在30m/min，热辊的挤压压强控制在6MPa，最终制备面密度230g/m2的碳纤维预浸织物。
实施例4
制备一种内含织物增韧结构的树脂胶膜叠层复合碳纤维多维或多向织物制备碳纤维预浸织物的方法。
首先采用长度为16cm的短切黏胶基碳纤维混杂聚丙烯热熔热塑纤维，混杂比例为1:4。
之后采用固含量为35％的聚丙烯乳液雾化喷淋上述网胎布基底，之后经过55℃范围内干燥成膜，制备面密度控制在70g/m2、树脂含量在30％的韧性树脂胶膜。
最终选用T1000碳纤维制备多轴向预制体织物，采用热辊加压方式，其中热辊温度控制在160℃，热辊走速控制在35m/min，热辊的挤压压强控制在4MPa，最终制备面密度200g/m2的碳纤维预浸织物。
以上所述仅为本申请的优选实施例而已，并不用于限制本申请，对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。
Claims (9)
1.一种增韧树脂膜制备碳纤维预浸织物的方法，其特征在于，所述方法包括：
S1.采用短切碳纤维混杂热熔热塑性纤维成型增韧网胎布结构；所述热熔热塑性纤维选用聚酰胺纤维、聚醚酮纤维、聚醚醚酮纤维、聚氨酯纤维、聚乙烯纤维、聚丙烯纤维中的任意一种；
S2.采用热塑性树脂乳液喷淋所述增韧网胎布结构，制成网胎布增韧树脂胶膜，热塑性树脂乳液选用聚氨酯、聚乙烯、聚丙烯、乙烯基丙烯酸共聚物、聚醚酮、聚醚醚酮、聚酰胺中的任意一种；
S3.将网胎布增韧树脂胶膜叠合铺设于碳纤维织物表面，含浸熔融复合成型制得碳纤维预浸织物；
所述步骤S1中，短切碳纤维与热熔热塑性纤维的混杂比例为1：1～4；
所述热塑性树脂乳液的固含量控制在20-40％范围内；
所述步骤S2中，热塑性树脂乳液雾化喷淋在所述增韧网胎布结构基底表面，在50-80℃范围内干燥使乳液成膜，最终制备网胎布增韧树脂胶膜的面密度控制在20-100g/m2范围内，其中网胎布占网胎布增韧树脂胶膜的重量百分含量控制在10-30％范围内。
2.如权利要求1所述的一种制备方法，其特征在于，所述步骤S1中，所述增韧网胎布结构采用短切碳纤维混杂热熔热塑性纤维通过梳理成网制备得到。
3.如权利要求2所述的一种制备方法，其特征在于，所述步骤S1中，所述短切碳纤维选用黏胶基碳纤维，短切纤维的长度控制在5-20cm。
4.如权利要求1所述的一种制备方法，其特征在于，所述步骤S3中，碳纤维织物选用高强型碳纤维或高模型碳纤维。
5.如权利要求1所述的一种制备方法，其特征在于，碳纤维织物为T300、T700、T800、T1000、M40、M60、M40J、M60J其中的任意一种或多种混杂；
所用的碳纤维织物的织物结构选用平纹、斜纹、缎纹、多轴向、单向任意一种。
6.如权利要求1所述的一种制备方法，其特征在于，所述步骤S3中，采用热辊挤压方式熔融树脂膜，含浸碳纤维预制体结构制备碳纤维预浸织物。
7.如权利要求6所述的一种制备方法，其特征在于，热辊温度控制在高于树脂熔点的10-30℃内，热辊走速控制在1-40m/min，热辊的挤压压强控制在2-10MPa范围内。
8.权利要求1-7任一项所述方法制备得到的碳纤维预浸织物。
9.权利要求8所述碳纤维预浸织物在制备热塑性碳纤维复合材料中的应用。
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Effective date of registration: 20240419 Address after: 250061 1001, unit 1, building 1, No. 69, Jingshi Road, Lixia District, Jinan City, Shandong Province Patentee after: Zhu Bo Country or region after: China Patentee after: Cao Weiwei Patentee after: Qiao Kun Patentee after: Zhao Shengyao Patentee after: Wang Yongwei Patentee after: Zhang Min Patentee after: Gao Xueping Address before: 215513 No.9, Sihai Road, Changshu Economic and Technological Development Zone, Suzhou City, Jiangsu Province Patentee before: Huaxia Xingchen (Suzhou) new material technology Co.,Ltd. Country or region before: China |