CN114908610A - 一种再生碳纤维纸及其制备方法 - Google Patents
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Abstract
本发明涉及一种再生碳纤维纸及其制备方法,其原料包括以下重量份组分:再生碳纤维50‑80份和可再生木质纤维素50‑90份,其中再生碳纤维是废弃碳纤维复合材料通过热裂解回收得到的碳纤维。将再生碳纤维和可再生木质纤维素通过滤网成纸,压榨,烘干等湿法成纸制备工艺,获得再生碳纤维纸前驱体,通过树脂浸渍、固化对其力学性能进行调节,制得具有良好电磁屏蔽性能的再生碳纤维纸。与现有技术相比,本发明有效利用了高洁净表面的裂解回收碳纤维,构成高导电性的碳纤维纸,有望应用在电磁屏蔽、新能源电极、电化学催化等领域。该碳纤维纸制造流程简单、成本低、能耗低、易工业化放大,为废弃复合材料再生碳纤维提供了应用出口,有效促进了碳纤维复合材料回收产业链的完整闭环。
Description
技术领域
本发明涉及纤维复合材料回收再生利用及碳纤维功能材料领域,具体涉及一种再生碳纤维纸及其制备方法。
背景技术
碳纤维是含碳量95%以上的高强度、高模量的纤维材料,具有良好的力学、热学、电学性能,常被用做各种结构功能复合材料的增强功能体。以碳纤维作为增强体的高性能纤维复合材料,具有高比强度、耐超高温、耐疲劳等特性;越来越广泛地应用在汽车高铁、航空航天和风电产业等领域中。然而,由于碳纤维增强复合材料基体难以分解,基体与功能相键合强,废弃碳纤维复合材料造成的环境污染与资源浪费现已成为了我国严重的环境、社会与经济问题。
碳纤维复合材料热裂解回收,在一定的气氛中将复合材料加热至数百摄氏度,使树脂基体发生裂解,而纤维基本保持原有状态。其过程高效,工业化前景较好。规模化裂解回收技术是国内目前比较成熟的回收技术。如中国专利 ZL201610372900.8、ZL201810803445.1,均是将复合材料中的树脂基体分解为气相小分子,获得表面洁净、无上浆剂的回收纤维,再生纤维虽然基本保持了原生纤维的力学性能与物理特性,但在表面特性、分布状态等方面存在差别。为实现再生纤维再利用与回收技术链和产业链的闭环,专利CN202110793567.9、 CN202010416155.9、CN202110917292.5等将得到的再生纤维通过上浆等表面处理后,用于制备树脂基复合材料,但是目前还没有将回收碳纤维用于制备碳纤维纸的报道。
碳纤维纸一般应用于电磁屏蔽、柔性摩擦、电加热等方面。最近在轨道交通、国防军工、航空航天等领域也有了广泛的应用。现有碳纤维纸的制备过程,通常为商业碳纤维及其他纤维经表面去浆,分散混合,造纸,碳化,石墨化等,存在制备成本高,能耗大的缺点。专利CN103451989A公开了一种碳纤维纸及其制备方法,由碳纤维与芳纶纤维混合浆料经均匀混合分散,成型,压榨,干燥而得。该碳纤维纸原料为商业碳纤维与芳纶纤维,具有制备成本高的缺点。专利CN202010627370.3 公开了一种碳纤维纸及其制备方法和应用,将含有短切碳纤维、短切多孔碳纤维,分散剂,粘合剂和溶剂的混合物经过湿法造纸得到碳纤维纸前驱体,然后固化、碳化和石墨化,该碳纤维纸也存在制备成本高,能耗大的缺点。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种再生碳纤维纸及其制备方法,解决了废弃碳纤维复合材料资源浪费,促进碳纤维复合材料回收产业链闭环,及降低现有碳纤维纸的高制备成本,能耗,得到可用于高效电磁屏蔽等方面的再生碳纤维纸。
本发明的目的可以通过以下技术方案来实现:一种再生碳纤维纸,其原料包括以下重量份组分:再生碳纤维50-80份和可再生木质纤维素50-90份,其中再生碳纤维是通过热裂解回收再生的碳纤维。
进一步地,所述通过热裂解回收再生的碳纤维,所述热裂解为惰性气氛条件下,将纤维复合材料加热至500-800℃,使树脂基体发生裂解,而纤维导电性基本保持原有状态。
进一步地,所述可再生木质纤维素的纤维长度为200-1000um。
本发明还提供一种再生碳纤维纸的制备方法,该方法包括以下步骤:
(1)将再生碳纤维经可控裁切为短切再生碳纤维,其长度为1-10mm,将短切再生碳纤维与分散剂混合,溶解于水中,得到均匀的短切再生碳纤维悬浮液;
(2)将短切再生碳纤维悬浮液与木质纤维素形成纸浆,通过湿法造纸得到再生碳纤维纸前驱体,利用树脂对所述再生碳纤维纸前驱体进行浸渍,树脂固化后得到再生碳纤维纸。
步骤(1)所述分散剂为羟甲基纤维素钠,羟乙基纤维素,十二烷基磺酸钠,十二烷基苯磺酸钠中的至少一种,悬浮液中分散剂浓度为2-10g/L。
所述短切再生碳纤维与分散剂的质量比为1:10-1:2。
将所述木质纤维经打浆机疏解后形成木质纤维素浆粕,然后与短切再生碳纤维悬浮液均匀混合。
所述树脂为聚氨酯、酚醛树脂、环氧树脂、聚二甲基硅氧烷、聚甲基丙烯酸甲酯中的至少一种,浸渍时间为0.5-1h。
所述固化的方式为热压成型,热压温度为100-200℃,热压时间为0.5-2h,热压压力为4-10MPa。为了将热裂解回收过程中得到的再生碳纤维加以利用,本发明通过将再生短切碳纤维与可再生的木质纤维素浆粕均匀混合,采用湿法成纸制备工艺(本发明采用的湿法成纸工艺为现有常规湿法造纸法)、树脂浸渍成型,得到再生碳纤维纸,可用于高精密性、灵敏度的电子仪器设备电磁屏蔽等应用。
本发明利用回收再生的碳纤维和可再生木质纤维素制得具有良好电磁屏蔽性能的再生碳纤维纸。其有效利用了高洁净表面的裂解回收碳纤维,构成高导电性的碳纤维纸。该碳纤维纸制造流程简单、成本低、能耗低、易工业化放大,为废弃复合材料再生碳纤维提供了应用出口,有效实现了碳纤维复合材料回收产业链的完整闭环。
与现有技术相比,本发明的有益效果在于:
(1)本发明所用碳纤维为废弃碳纤维复合材料经环保低耗高温裂解过程制备而成,利用高温裂解获得再生碳纤维保持的导电性,及木质纤维素优良的柔韧性及分散性,混合后形成三维网状结构,从而实现得到环保低碳的电磁屏蔽材料。
(2)本发明通过湿法造纸工艺,将再生碳纤维与木质纤维素浆粕均匀混合形成三维导电网络,得到柔性的再生碳纤维导电纸,通过后续树脂浸渍成型过程,利用高分子树脂材料特点,可形成形状和柔性可调、耐腐蚀的再生碳纤维纸。
(3)本发明制备的再生碳纤维纸复合材料具有高效的电磁屏蔽性能,该碳纤维纸制造流程简单、成本低、能耗低、易工业化放大,为废弃复合材料再生碳纤维提供了应用出口,有效实现了碳纤维复合材料回收产业链的完整闭环。
附图说明
图1为再生碳纤维纸照片;
图2为再生碳纤维纸扫描电子显微镜形貌表征;
图3为实施例4再生碳纤维纸电磁屏蔽性能测试图。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进。这些都属于本发明的保护范围。
本发明再生碳纤维是通过热裂解回收再生的碳纤维,该方法为现有方法,如可采用中国专利ZL201610372900.8、ZL201810803445.1所述方法,通过热裂解回收获得再生碳纤维。
本发明采用的可再生木质纤维素为市售产品,例如可以采用无锡市斯木德工程材料有限公司的建筑用木质纤维等等。
以下是更加详细的实施案例,通过以下实施案例进一步说明本发明的技术方案以及所能够获得的技术效果。
实施例1
称取40g再生短切碳纤维(纤维长度为3mm)、80g分散剂羟乙基纤维素,溶解于溶剂水中,其中分散剂浓度为8g/L;
利用电动搅拌机得到再生短切碳纤维均匀分散的水溶液悬浮液。称取72g木质纤维素经打浆机疏解后形成木质纤维素浆粕,将经打浆机疏解后形成的木质纤维素浆粕与再生碳纤维悬浮液混合均匀得到混合纤维浆。经滤网成纸,压榨,烘缸烘干,得到再生碳纤维纸前驱体。将一层再生碳纤维纸浸渍在聚氨酯树脂中,浸渍完全后,用平板硫化机在压力10MPa下于150℃热压固化40min。得到再生碳纤维纸。
如图1所示,为再生碳纤维纸照片,其中a为再生碳纤维纸,b为再生碳纤维纸的表面组织,从图1可以看出,得到的再生碳纤维纸具有良好的柔性。
如图2所示,为再生碳纤维纸扫描电子显微镜形貌表征,如图2(a)(b)所示,以羟乙基纤维素作为分散剂,得到了再生碳纤维均匀分散的碳纸基体,木质纤维素形成网状结构,将分散的短切碳纤维连结成一个整体。如图2(c)(d)所示,浸渍的树脂将纤维素网络中间的孔隙基本填充完全,并与部分碳纤维有紧密的接触甚至包覆。为再生碳纤维碳纸提供了更高的致密度和力学性能。
对实施例1得到的再生碳纤维复合材料进行电磁屏蔽效能测试,参照GB/T 30142-2013,采用PNA-X N5244a型网络分析仪基于波导法测试S参数,测试频段为X波段8-12GHz.在X波段(8-12GHz)内屏蔽性能为40.8dB。
实施例2
称取40g再生短切碳纤维(纤维长度为3mm)、400g分散剂羟乙基纤维素,溶解于溶剂水中,其中分散剂浓度为10g/L;
利用电动搅拌机得到再生短切碳纤维均匀分散的水溶液悬浮液。称取50g木质纤维素经打浆机疏解后形成木质纤维素浆粕,将经打浆机疏解后形成的木质纤维素浆粕与再生碳纤维悬浮液混合均匀。经滤网成纸,压榨,烘缸烘干,得到再生碳纤维纸前驱体。将三层再生碳纤维纸浸渍在环氧树脂中,浸渍完全后,用平板硫化机在压力4MPa下于100℃热压固化40min。得到再生碳纤维纸。
对实施例2得到的再生碳纤维复合材料进行电磁屏蔽效能测试,在X波段 (8-12GHz)内屏蔽性能达到54.1dB。
实施例3
称取40g再生短切碳纤维(纤维长度为3mm)、150g分散剂羟乙基纤维素,溶解于溶剂水中,其中分散剂浓度为8g/L;
利用电动搅拌机得到再生短切碳纤维均匀分散的水溶液悬浮液。称取25g木质纤维素经打浆机疏解后形成木质纤维素浆粕,将经打浆机疏解后形成的木质纤维素浆粕与再生碳纤维悬浮液混合均匀。经滤网成纸,压榨,烘缸烘干,得到再生碳纤维纸前驱体。将五层再生碳纤维纸浸渍在聚二甲基硅氧烷树脂中,浸渍完全后,用平板硫化机在压力10MPa下于220℃热压固化2h。得到再生碳纤维纸。
对实施例3得到的再生碳纤维复合材料进行电磁屏蔽效能测试,在X波段 (8-12GHz)内屏蔽性能为63.2dB。
实施例4
称取40g再生短切碳纤维(纤维长度为3mm)、200g分散剂羟甲基纤维素钠,溶解于溶剂水中,其中分散剂浓度为7g/L;
利用电动搅拌机得到再生短切碳纤维均匀分散的水溶液悬浮液。称取25g木质纤维素经打浆机疏解后形成木质纤维素浆粕,将经打浆机疏解后形成的木质纤维素浆粕与再生碳纤维悬浮液混合均匀。经滤网成纸,压榨,烘缸烘干,得到再生碳纤维纸前驱体。将一层再生碳纤维纸浸渍在酚醛树脂中,浸渍完全后,用平板硫化机在压力10MPa下于120℃热压固化40min。得到再生碳纤维纸。
对实施例4得到的再生碳纤维复合材料进行电磁屏蔽效能测试,如图3所示,其展示了优良的电磁屏蔽性能,在X波段(8-12GHz)内屏蔽性能为59.4dB。再生碳纤维形成三维导电网络,提升了入射电磁波的反射损耗;同时,电荷位点的积累也带来了更高的偶极极化和界面极化,增强了电磁波的吸收损耗。自由电子在交变电磁场下转移,使电磁能转换为热能。这些增强的电磁波损耗机制带来了优良的电磁屏蔽性能。
实施例5
称取100g再生短切碳纤维(纤维长度为3mm)、200g分散剂十二烷基磺酸钠,溶解于溶剂水中,其中分散剂浓度为2g/L;
利用电动搅拌机得到再生短切碳纤维均匀分散的水溶液悬浮液。称取125g木质纤维素经打浆机疏解后形成木质纤维素浆粕,将经打浆机疏解后形成的木质纤维素浆粕与再生碳纤维悬浮液混合均匀。经滤网成纸,压榨,烘缸烘干,得到再生碳纤维纸前驱体。将五层再生碳纤维纸浸渍在聚氨酯树脂中,浸渍完全后,用平板硫化机在压力10MPa下于150℃热压固化40min。得到再生碳纤维纸。
对实施例3得到的再生碳纤维复合材料进行电磁屏蔽效能测试,在X波段 (8-12GHz)内屏蔽性能为57.2dB。
实施例6
称取80g再生短切碳纤维(纤维长度为3mm)、400g分散剂十二烷基苯磺酸钠,溶解于溶剂水中,其中分散剂浓度为5g/L;
利用电动搅拌机得到再生短切碳纤维均匀分散的水溶液悬浮液。称取90g木质纤维素经打浆机疏解后形成木质纤维素浆粕,将经打浆机疏解后形成的木质纤维素浆粕与再生碳纤维悬浮液混合均匀。经滤网成纸,压榨,烘缸烘干,得到再生碳纤维纸前驱体。将五层再生碳纤维纸浸渍在聚甲基丙烯酸甲酯树脂中,浸渍完全后,用平板硫化机在压力10MPa下于150℃热压固化40min。得到再生碳纤维纸。
对实施例3得到的柔性再生回收碳纤维复合材料进行电磁屏蔽效能测试,在X 波段(8-12GHz)内屏蔽性能为55.7dB。
下面结合具体测试方法对实施例的效果进行测试:
1.参照GB/T 30142-2013,采用PNA-X N5244a型网络分析仪基于波导法测试实施例中材料S参数,测试频段为X波段8-12GHz.
2.采用四探针法(RTS-8,广州四探针科技有限公司)测试电磁屏蔽材料电导率。
实验结果如下表1所示:
表1
实施例 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 |
电磁屏蔽效能(dB) | 40.8 | 54.1 | 63.2 | 59.4 | 57.2 | 55.7 |
电导率(S/m) | 550.7 | 612.4 | 850.6 | 783.3 | 730.8 | 643.6 |
在本说明书的描述中,参考术语“一个实施例”、“示例”、“具体示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中,对上述术语的示意性表述不一定指的是相同的实施例或示例。而且,描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
上述对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (9)
1.一种再生碳纤维纸,其特征在于,其原料包括以下重量份组分:再生碳纤维50-80份和可再生木质纤维素50-90份,其中再生碳纤维是废弃碳纤维复合材料通过热裂解回收得到的碳纤维。
2.根据权利要求1所述的一种再生碳纤维纸,其特征在于,所述通过热裂解回收再生的碳纤维,热裂解为惰性气氛条件下,将纤维复合材料加热至500-800℃,使树脂基体发生裂解,而纤维导电性基本保持原有状态。
3.根据权利要求1所述的一种再生碳纤维纸,其特征在于,所述可再生木质纤维素的纤维长度为200-1000um。
4.根据权利要求1所述的一种再生碳纤维纸的制备方法,其特征在于,该方法包括以下步骤:
(1)将再生碳纤维经可控裁切为短切再生碳纤维,其长度为1-10mm,将短切再生碳纤维与分散剂混合,溶解于水中,机械搅拌得到均匀的短切再生碳纤维悬浮液;
(2)将短切再生碳纤维悬浮液与木质纤维素混合均匀,通过滤网成纸,压榨,烘干得到再生碳纤维纸前驱体,利用树脂对所述再生碳纤维纸前驱体进行浸渍,树脂固化后得到再生碳纤维纸。
5.根据权利要求4所述的一种再生碳纤维纸的制备方法,其特征在于,步骤(1)所述分散剂为羟甲基纤维素钠,羟乙基纤维素,十二烷基磺酸钠,十二烷基苯磺酸钠中的至少一种,悬浮液中分散剂浓度为2-10g/L。
6.根据权利要求4所述的一种再生碳纤维纸的制备方法,其特征在于,所述短切再生碳纤维与分散剂的质量比为1:10-1:2。
7.根据权利要求4所述的一种再生碳纤维纸的制备方法,其特征在于,将所述木质纤维经打浆机疏解后形成木质纤维素浆粕,然后与短切再生碳纤维悬浮液混合后搅拌均匀。
8.根据权利要求4所述的一种再生碳纤维纸的制备方法,其特征在于,所述树脂为聚氨酯、酚醛树脂、环氧树脂、聚二甲基硅氧烷、聚甲基丙烯酸甲酯中的一种或几种,浸渍时间为0.5-1h。
9.根据权利要求5所述的一种再生碳纤维纸的制备方法,其特征在于,所述成型的方式为热压成型,热压温度为100-200℃,热压时间为0.5-2h,热压压力为4-10MPa。
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