CN107012721B - 一种超高效碳纤维电磁屏蔽纸的制备 - Google Patents

一种超高效碳纤维电磁屏蔽纸的制备 Download PDF

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CN107012721B
CN107012721B CN201710204473.7A CN201710204473A CN107012721B CN 107012721 B CN107012721 B CN 107012721B CN 201710204473 A CN201710204473 A CN 201710204473A CN 107012721 B CN107012721 B CN 107012721B
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龙柱
桑明珠
陈乐�
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Abstract

本发明公开了一种超高效碳纤维电磁屏蔽纸的制备,属于特种纸领域。本发明方法创新地利用碳纤维、金属导电纤维这两种纤维的优势互补,改变了以往单一的碳纤维纸基材料韧性不够的缺点,优化了碳纤维电磁屏蔽纸的物理性能和导电性能,保证成纸在拥有良好的较高的屏蔽效能的同时具有很好的机械性能和柔韧性。且适用性更广、使用方便,有较高的导电性,较高的电磁屏蔽效能,较好的耐热性以及较好的透气性等,且各项指标都得到有效的控制,可随意剪切使用。

Description

一种超高效碳纤维电磁屏蔽纸的制备
技术领域
本发明涉及一种超高效碳纤维电磁屏蔽纸的制备,属于特种纸领域。
背景技术
目前电磁辐射污染已成为我国乃至整个世界的重要污染。近几年来,因电磁辐射污染而产生的纠纷事件也常常发生。所以,如何减少电磁辐射产生的污染已经成为现在社会的一个热门话题。治理电磁辐射污染主要方法有减少电磁辐射设施和设备的运行时间;距离防护以及电磁屏蔽等。电磁屏蔽的主要作用是降低电磁辐射源所能辐射到的区域内的电磁场效应,阻止电磁辐射从一个区域向另一个区域的传播。电磁辐射屏蔽纸的工作原理是当电磁波辐射到电磁辐射屏蔽纸上时,电磁波在纸张内被多次反射或者吸收,从而衰减电磁辐射的能量,减少电磁辐射的透过量,达到屏蔽的目的。
碳纤维具有较高的强度、良好的导电性能,碳纤维能与入射电磁波产生谐振感应电流,而与碳纤维混合的其它介质则会使电流能量转化为电流,从而可以起到衰减电磁波能量的作用。所以碳纤维近几年来被广泛应用在电磁屏蔽材料中。更因为碳纤维具有一般碳素纤维不具有的各向异性,备受电磁屏蔽材料工作者的青睐。使其在电磁屏蔽领域得到了广泛研究,但仍然存在一些缺陷。
公开号为CN101994275A的专利申请公开了一种新型复相电磁屏蔽功能纸及其制备方法,其使用以未脱墨废纸浆纤维为基体,纤维间分散有碳纤维和炭黑,制备电磁屏蔽纸,但其电磁屏蔽效能、机械强度和耐热性较差。公开号为CN1456750的专利申请公开了碳纸和金属碳纸的制备方法,提出用未经加工的原碳碳粒(木炭、竹炭、活性炭)与加入不锈钢金属纤维,用造纸机生产出碳纸或金属碳纸的方法,但其纸张强度不高、电磁屏蔽效能较差。公开号CN103114503A的专利申请公开了一种镀镍碳纤维屏蔽纸及其制备方法,提出制备镀镍碳纤维的方式,制得镀镍碳纤维屏蔽纸,但工艺过于复杂,且镀Ni的碳纤维发生弯曲时,纤维表面的镀层易开裂,为后续工艺带来诸多不便,影响纸张的屏蔽效果。因此,现有的工艺技术不能满足碳纤维电磁屏蔽纸的应用要求,需要进一步在兼顾其性能基础上,简化制备工艺,为后续产业化提供可能性。
发明内容
本发明所要解决现有技术的缺点和不足,本发明的首要目的是提供一种超高效碳纤维电磁屏蔽纸的制备方法。
本发明的一种超高效碳纤维电磁屏蔽纸的制备方法,包括如下步骤:
(1)活化:除去碳纤维表面的有机涂层,干燥、备用;
(2)复配和助剂添加:将步骤(1)中处理过的碳纤维与金属纤维、水混合得混合浆料,混合成份按重量计,碳纤维:金属纤维为(5-9):(5-1);在混合浆料中加入分散剂、粘合剂,搅拌10-120s,得到纸料;
(3)湿法成型:将步骤(2)所得到的浆料进行湿法成型、脱水、烘干处理,得到原纸;
(4)浸渍和高温热压:用稀释剂将酚醛树脂稀释至质量百分浓度1-15%的酚醛树脂溶液,将步骤(3)得到的原纸在酚醛树脂溶液中做浸渍处理,烘干、然后进行热压、干燥得到碳纤维电磁屏蔽纸。
在一种实施方式中,所述步骤(1)具体是:将碳纤维置于1-3mol/L的NaOH或KOH中预处理1-4h,采用超声辅助处理;超声处理条件如下:温度为20-60℃,超声波频率为20-100kHz,时间为1-60min;取出处理后的碳纤维,用去离子水行洗涤至中性,除去碳纤维表面的有机涂层,干燥、备用;
在一种实施方式中,所述步骤(2)的金属纤维为不锈钢纤维、镍金属纤维、铜纤维、铝纤维、铁纤维中的至少一种,纤维长度为3-6mm,纤维直径2-20μm。
在一种实施方式中,所述步骤(2)中碳纤维和金属纤维共10重量份,碳纤维为5-9重量份。
在一种实施方式中,所述步骤(2)中碳纤维:金属纤维的重量比为(5-9):(5-1)。
在一种实施方式中,所述步骤(2)中碳纤维和金属纤维总重量占混合浆料的0.05~0.2%。
在一种实施方式中,所述步骤(2)分散剂、粘结剂的添加量分别为纤维浆料质量的0.05-5%。
在一种实施方式中,所述步骤(2)分散剂采用聚氧化乙烯(PEO)、羧甲基纤维素(CMC)、阴离子聚丙烯酰胺(APAM)中的一种或两种或三种。
在一种实施方式中,所述步骤(2)粘合剂为聚乙烯醇(PVA)、聚丙烯酰胺(PAM)、水溶性酚醛树脂的一种或两种或三种。
在一种实施方式中,所述步骤(4)稀释剂为:乙醇、丙酮的其中一种,浸渍时间为0.5-5min。
在一种实施方式中,所述步骤(4)的烘干条件为40-80℃、时间为1-5h。
在一种实施方式中,所述步骤(4)的热压条件为:热压温度:50-300℃,热压压力:3-9MPa,热压时间:5-120min。
本发明的第二个目的是提供按照上述制备方法得到的超高效碳纤维电磁屏蔽纸。
本发明的第三个目的是提供所述超高效碳纤维电磁屏蔽纸在电磁屏蔽中的应用。
本发明的超高效碳纤维电磁屏蔽纸需要多种特种纤维合理复配,碳纤维能够显著增强纸张的物理强度,金属导电纤维能作为导电物质,能赋予碳纤维纸一定的柔韧性,聚乙烯醇能够作为有效的粘结剂,采用湿法造纸的工艺技术,再经高温热压处理,最后干燥处理,制备出超高效碳纤维电磁屏蔽纸,将其应用于电磁屏蔽领域。
本发明同现有技术相比具有如下的有益效果:
通过多种特种纤维合理复配且需造纸助剂,由于碳纤维C—C间以非极性共价键相连接,呈乱层石墨结构,导致碳纤维表面光滑,呈现化学惰性,表面能低,缺乏有化学活性的官能团,反应活性低,不易被水润湿,在水中易絮聚,分散性能差,直接影响了复合材料的力学性能,限制了碳纤维高性能的发挥。因而,如何使碳纤维在水相中均匀分散及提高纤维间结合强度,是湿法抄造碳纤维功能纸的关键,添加造纸助剂是至关重要的。
碳纤维表面亲水性差,纤维絮聚上浮快,严重影响着碳纤维在水中的分散性和稳定性。因此单纯依靠降低浓度和减短纤维长度来提高碳纤维的分散性是很难实现纤维的良好分散的,应该考虑加入分散剂。在制备过程中,添加实验所选用的分散剂均不同程度地改善了碳纤维的分散性,其中APAM的分散效果较好,当其加入浆料时,能够使纤维、填料表面形成双分子结构,外层分散剂极端与水有较强亲和力,增加了纤维、填料等固体粒子被水润湿的程度。纤维、填料等固体颗粒之间因静电斥力而远离,从而达到良好的分散效果;碳纤维与金属纤维的黏结性差,界面中存在较多的缺陷,也直接影响复合材料的力学性能,因此考虑添加粘合剂,粘合剂如三聚氰胺甲醛树脂、水溶性酚醛树脂、聚酰胺环氧氯丙烷、聚乙烯醇、聚丙烯酰胺等能够提高碳纤维纸物理指数,本试验采用聚丙烯酰胺、水溶性酚醛树脂、聚乙烯醇作为粘合剂,能显著提高纤维间结合强度,增加纸张的强度和韧性;碳纤维能够显著增强纸张的物理强度,金属导电纤维作为导电物质,并且能赋予碳纤维纸一定的柔韧性,聚乙烯醇能够作为有效的粘结剂,利用湿法成型技术制备出超高效碳纤维电磁屏蔽纸,将其应用于电磁屏蔽领域。且金属导电纤维具有很好的导电性,很低的电阻,具有较好的电磁屏蔽性能,屏蔽电磁波频带宽而且防辐射效果持久,赋予纸张更加良好的屏蔽性能。此外,金属纤维具有较好的机械性能,增强纸张的力学强度。金属纤维耐热性好,如不锈钢纤维在氧化环境下,可以在600℃的高温下一直使用,是热的良导体,增强纸张的耐热性。
该制备方法简单,成本低,适合于工业化生产:所得碳纤维纸具有良好导电性能、电磁屏蔽效能、较高孔隙率、具有适当的柔性和刚性且生产成本低。且湿法成型工艺技术具有成网匀度好,纤维结构合理,水流状态下形成的纤网,纤维在纤网中成三维分布,纤维的杂乱效果好。纤网各向同性显著改善,而且成网均匀度优于干法和纺丝成网法。成网速度快、产量大、劳动生产率高、成本低。其劳动生产率为干法的10-20倍,生产成本只有干法的60-70%。
综上,本发明制备的超高效碳纤维电磁屏蔽纸是利用两种纤维合理复配而获得的,充分的利用了不同纤维的优势,碳纤维能够显著增强纸张的物理强度,金属导电纤维既能作为导电物质,能赋予碳纤维纸一定的柔韧性,改变以往单一碳纤维纸柔韧性不够的特点,且适用性较强,可根据需要,且可根据不同的要求制备不同定量的碳纤维纸,产品灵活多变,且可随意剪切,灵活方便;采用了湿法成形、热压、涂布相结合的生产工艺,具有工艺流程简单、易于控制产品质量,生产过程环保等特点,达到可控生产;多种原料进行功能复配,使产品在导电性、电磁屏蔽、孔隙率分布等各项指标得到有效的控制。
附图说明
图1:本发明的超高效碳纤维电磁屏蔽纸的制备流程。
具体实施方案
下面结合实例对本发明做进一步详细描述:
实施例1
一种超高效碳纤维电磁屏蔽纸的制备,包括以下步骤:
(1)活化:将碳纤维至于2mol/L的NaOH中预处理2h,采用超声辅助处理;超声处理条件如下:温度为40℃,超声波频率为50kHz,时间为30min;取出处理后的碳纤维,用去离子水行洗涤至中性,除去碳纤维表面的有机涂层,烘干、备用;
(2)复配和助剂添加:将步骤(1)中处理过得碳纤维与不锈钢纤维混合,混合成份按重量计,碳纤维:不锈钢纤维为7:3;在混合浆料中加入纤维浆料质量0.12%的APAM、纤维浆料质量1%的PVA,搅拌30s;
(3)湿法成型:将步骤(2)所得到的浆料取一定量的浆浓为0.09%于抄片机进行湿法成型、脱水、烘干处理,得到原纸;
(4)浸渍和高温热压:用乙醇或者丙酮将酚醛树脂稀释至质量百分浓度10%的酚醛树脂溶液,将步骤(3)得到的原纸在酚醛树脂溶液中做浸渍1min,于60℃烘干2h,烘干后,于130℃、6MPa热压30min,之后于160℃、6MPa热压30min干燥得到碳纤维电磁屏蔽纸。
实施例2
一种超高效碳纤维电磁屏蔽纸的制备,包括以下步骤:
(1)活化:将碳纤维至于1mol/L的NaOH中预处理4h,采用超声辅助处理;超声处理条件如下:温度为60℃,超声波频率为100kHz,时间为10min;取出处理后的碳纤维,用去离子水行洗涤至中性,除去碳纤维表面的有机涂层,烘干、备用;
(2)复配和助剂添加:将步骤(1)中处理过得碳纤维与不锈钢纤维混合,混合成份按重量计,碳纤维:不锈钢纤维为7:3;在混合浆料中加入纤维浆料质量0.5%的APAM、纤维浆料质量2%的PVA,搅拌30s;
(3)湿法成型:将步骤(2)所得到的浆料取一定量的浆浓为0.09%于抄片机进行湿法成型、脱水、烘干处理,得到原纸;
(4)浸渍和高温热压:用乙醇或者丙酮将酚醛树脂稀释至质量百分浓度10%的酚醛树脂溶液,将步骤(3)得到的原纸在酚醛树脂溶液中做浸渍1min,于60℃烘干2h,烘干后,于130℃、6MPa热压30min,之后于160℃、6MPa热压30min干燥得到碳纤维电磁屏蔽纸。
实施例3
一种超高效碳纤维电磁屏蔽纸的制备,包括以下步骤:
(1)活化:将碳纤维至于3mol/L的NaOH中预处理1h,采用超声辅助处理;超声处理条件如下:温度为20℃,超声波频率为20kHz,时间为60min;取出处理后的碳纤维,用去离子水行洗涤至中性,除去碳纤维表面的有机涂层,烘干、备用;
(2)复配和助剂添加:将步骤(1)中处理过得碳纤维与不锈钢纤维混合,混合成份按重量计,碳纤维:不锈钢纤维为7:3;在混合浆料中加入纤维浆料质量0.6%的APAM、纤维浆料质量3%的PVA,搅拌30s;
(3)湿法成型:将步骤(2)所得到的浆料取一定量的浆浓为0.09%于抄片机进行湿法成型、脱水、烘干处理,得到原纸;
(4)浸渍和高温热压:用乙醇或者丙酮将酚醛树脂稀释至质量百分浓度10%的酚醛树脂溶液,将步骤(3)得到的原纸在酚醛树脂溶液中做浸渍1min,于60℃烘干2h,烘干后,于130℃、6MPa热压30min,之后于160℃、6MPa热压30min干燥得到碳纤维电磁屏蔽纸。
实施例4:
与实施例1相比,将碳纤维与不锈钢纤维的重量比替换成为6:4,其他步骤或参数与实施例1一致。
实施例5:
与实施例1相比,将碳纤维与不锈钢纤维的重量比替换成为8:2,其他步骤或参数与实施例1一致。
实施例6:
与实施例1相比,将碳纤维与不锈钢纤维的重量比替换成为5:5,其他步骤或参数与实施例1一致。
实施例7:
与实施例1相比,将APAM替换成为PEO,其他步骤或参数与实施例1一致。
实施例8:
与实施例1相比,将PVA替换成为酚醛水溶性树脂,其他步骤或参数与实施例1一致。
实施例9:
与实施例1相比,将PVA替换成为聚丙烯酰胺,其他步骤或参数与实施例1一致。
按照实施例1-9的方法,制备得到的碳纤维电磁屏蔽纸的性能如下表所示。
电磁屏蔽效能/dB 抗张指数/(N·m/g) 体电阻率/(Ω·cm)
实施例1 90 47 0.01
实施例2 89 48 0.013
实施例3 90 48 0.011
实施例4 88 43 0.014
实施例5 82 41 0.018
实施例6 88 39 0.023
实施例7 81 38 0.025
实施例8 79 39 0.028
实施例9 77 40 0.031
其中,电磁屏蔽指标的测定方法是采用法兰同轴设备和安捷伦网络分析仪测试了30~1500MHz的电磁屏蔽效能。
抗张指数指标的测定方法是按照国家标准GB/T453-1989测定。
体电阻率指标的测定方法是纸页导电性测试采用体积电阻,在Agilent高精度表上进行,测量时在两电极上施加2Kg以上的压力以减小接触电阻,提高测量的准确性,体积电阻率计算公式如下:
式中:ρ一材料的体积电阻率,Ω·cm;R一样品电阻的测量值,Ω;h一所测样品截面宽度,cm;d一所测样品截面厚度,cm;L一两测量电极之间距离,cm。
体积电阻率是一个与材料基本尺寸无关的常数,由材料本身性质决定,反映了材料间导电性能的差异。其值越小,材料在相同尺寸条件下的导电性就越高。本实验测试纸张的h和L分别为1.5cm和14.0cm。
虽然本发明已以较佳实施例公开如上,但其并非用以限定本发明,任何熟悉此技术的人,在不脱离本发明的精神和范围内,都可做各种的改动与修饰,因此本发明的保护范围应该以权利要求书所界定的为准。

Claims (9)

1.一种超高效碳纤维电磁屏蔽纸的制备方法,其特征在于,所述方法包括以下步骤:
(1)活化:除去碳纤维表面的有机涂层,干燥、备用;
(2)复配和助剂添加:将步骤(1)中处理过的碳纤维与金属纤维、水混合得混合浆料,混合成份按重量计,碳纤维:金属纤维为(5-9):(5-1);在混合浆料中加入分散剂、粘合剂,搅拌10-120s,得到纸料;
(3)湿法成型:将步骤(2)所得到的浆料进行湿法成型、脱水、烘干处理,得到原纸;
(4)浸渍和高温热压:用稀释剂将酚醛树脂稀释至质量百分浓度1-15%的酚醛树脂溶液,将步骤(3)得到的原纸在酚醛树脂溶液中做浸渍处理,烘干、然后进行热压、干燥得到碳纤维电磁屏蔽纸。
2.根据权利要求1所述的制备方法,其特征在于:所述步骤(1)的金属导电纤维为不锈钢纤维、镍金属纤维、铜纤维、铝纤维、铁纤维中的至少一种,纤维长度为3-6mm,纤维直径2-20μm。
3.根据权利要求1所述的制备方法,其特征在于:所述步骤(2)的分散剂、粘结剂的添加量分别为纤维浆料质量的0.05-5%。
4.根据权利要求1所述的制备方法,其特征在于:所述分散剂采用聚氧化乙烯、羧甲基纤维素、阴离子聚丙烯酰胺中的一种或两种或三种,粘合剂为聚乙烯醇(PVA)、聚丙烯酰胺(PAM)、水溶性酚醛树脂的一种或两种或三种。
5.根据权利要求1所述的制备方法,其特征在于:所述步骤(4)的稀释剂为:乙醇、丙酮的其中一种,浸渍时间为0.5-5min。
6.根据权利要求1所述的制备方法,其特征在于:所述步骤(4)的烘干条件为40-80℃、时间为1-5h。
7.根据权利要求1所述的制备方法,其特征在于:所述步骤(4)的热压条件为:热压温度:50-300℃,热压压力:3-9MPa,热压时间:5-120min。
8.根据权利要求1~7任一所述的制备方法得到的超高效碳纤维电磁屏蔽纸。
9.权利要求8所述的超高效碳纤维电磁屏蔽纸在电磁屏蔽中的应用。
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