CN111002678A - 一种低密度复合材料吸波板的制备方法 - Google Patents

一种低密度复合材料吸波板的制备方法 Download PDF

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CN111002678A
CN111002678A CN201911336254.XA CN201911336254A CN111002678A CN 111002678 A CN111002678 A CN 111002678A CN 201911336254 A CN201911336254 A CN 201911336254A CN 111002678 A CN111002678 A CN 111002678A
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carbon nano
resin
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CN111002678B (zh
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刘艳
苏青林
张建东
梁祎
张伟伟
刘鹏
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CETC 33 Research Institute
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Abstract

本发明涉及吸波复合材料制备技术领域，更具体而言，涉及一种低密度复合材料吸波板的制备方法。本发明使用芳纶纤维增强复合材料，利用碳纳米管及镀镍碳纳米管、乙烯基树脂，通过热压罐制备了功能一体化低密度吸波板料。通过碳纳米管、镀镍碳纳米管在铺层阶段不同的含量，将树脂添加到配置好的乙烯基树脂中，在树脂中添加1%、1.2%、1.5%的改性钛酸酯，既可以使吸波剂分散在树脂中，又可以改善树脂与纤维表面，使得树脂很好的浸透于增强纤维，提高复合材料的力学性能；根据吸波原理，以及复合材料低密度要求，通过上述吸波剂的配方设计，经增强纤维铺层设计，采用热压罐制备功能一体化复合材料，该工艺制备的复合树脂含量低，材料致密性好。

Description

一种低密度复合材料吸波板的制备方法
技术领域
本发明涉及吸波复合材料制备技术领域，更具体而言，涉及一种低密度复合材料吸波板的制备方法。
背景技术
随着电子信息技术的快速发展，电子产品超着集成化、微型化、宽频化的方向发展，电子产品的电磁兼容和电磁干扰问题愈发突出，因此对吸波材料提出来更高的要求薄、轻、宽、强。吸波复合材料是一种兼顾吸波和承载防护能力的结构型功能材料，用这种材料工艺制成的复合材料比传统吸波材料力学性能好，吸波频带宽，从而降低目标被雷达探测到的可能性，并且大幅度降低武器装备的重量。吸波复合材料受到了国内外高度重视，并迅速发展进入工程应用阶段。
吸波板材主要由吸收剂、树脂基体、增强纤维布组成。吸收剂主要包括碳纳米管，镀镍碳纳米管。目前复合材料所用吸波剂主要是碳纳米管以及与磁性材料混合，比传统的磁性材料密度有所降低，但是吸波性能与实际使用要求不匹配，并且所用增强纤维大部分为玻璃纤维以及多种纤维混合使用，在特殊的领域，使用密度还比较大，另外在该复合材料基体树脂的选取也很重要，常用的环氧树脂黏度较大，很难使吸波剂均匀的分散到树脂中，即使通过分散剂使得吸波剂分散在树脂，制备工艺难以实施，使得吸波剂局部团聚，导致吸波性能下降，同时力学性能大幅降低。
碳纳米管具有特殊的电磁效应以及较强的宽带吸收性能，但是电磁吸波效能是由介电损耗和磁损耗共同作用，而碳纳米管不具有铁磁性，限制了频率的应用范围，为了拓宽吸波剂的频率，可通过在碳纳米管表面镀磁性金属，该金属不仅需要磁导率好，导电性好，而且抗环境性能好等特点，而金属镍不仅具有导电性好，而且磁导率好，抗氧化性能好，可通过金属镍改善吸波剂的吸收的频率范围。拓宽吸波剂的吸波频率。另外只进行了对镀镍碳纳米管在复合材料中的应用，没有对镀镍碳纳米管的镀镍方式进行说明。
单纯的吸波剂复合成型的材料力学性能差，很难满足新型器件及电磁防护环境的性能要求。为了提高吸波复合材料的力学性能可采用纤维材料进行增强，以往使用玻璃纤维及改性后的玻璃纤维作为增强材料制备吸波复合材料，虽然密度有所降低，但是在特殊的航空领域内难以满足轻质化的需求，本发明使用密度低、电磁透波好的芳纶纤维作为增强材料，密度相对于玻璃纤维可降低20%；即使增强材料密度小，由于镀镍碳纳米管的密度较大，所以镀镍碳纤维的含量直接影响复合材料的密度。
发明内容
为了克服现有技术中所存在的不足，本发明提供一种低密度复合材料吸波板的制备方法，本发明所采用的技术方案为：
一种低密度复合材料吸波板的制备方法，包括以下步骤：
步骤一、制备铺层S1
（1）乙烯基树脂、固化剂、引发剂和分散剂按照质量比100:1:0.5:1混合，得到混合物A1；
（2）将碳纳米管与镀镍碳纳米管按照2:1的比例混合,得到吸波剂B1；
（3）将B1分散到混合物A1中，质量比例4:100，利用行星搅拌机搅拌均匀，搅拌时间不小于30min，得到混合物C1；
（4）乙烯基树脂、固化剂、引发剂和分散剂质量比例100:1:0.5:1.2，得到混合物A2；
（5）将碳纳米管与镀镍碳纳米管按照1:1比例混合，得到吸波剂B2；
（6）将B2分散到混合物A2中，质量比例5:100，利用行星搅拌机搅拌均匀，搅拌时间不小于30min，得到混合物C2；
（7）取混合物C1和混合物C2混合均匀得到C1C2混合物；
（8）模具表面涂刷脱模剂，涂刷2-3次；
（9）将一定尺寸的芳纶纤维布铺设于模具表面，保证纤维布与模具的贴合度，拐角处要开口，多余去掉；
（10）将混合物C1与C1C2混合物分别均匀涂刷到芳纶纤维布两面，得到铺层S1；
步骤二、制备铺层S2
（1）乙烯基树脂、固化剂、引发剂和分散剂质量比例100:1:0.5:1.2，得到混合物A2；
（2）将碳纳米管与镀镍碳纳米管按照1:1比例混合，得到吸波剂B2；
（3）将B1分散到混合物A1中，质量比例5:100，利用行星搅拌机搅拌均匀，搅拌时间不小于30min，得到混合物C2；
（4）将树脂混合物C2均匀涂刷到芳纶纤维布表面，得到铺层S2；
步骤三、制备铺层S3
（1）乙烯基树脂、固化剂、引发剂和分散剂质量比例100:1:0.5:1.5，得到混合物A3；
（2）将碳纳米管与镀镍碳纳米管按照1:3比例混合，得到吸波剂B3；
（3）将B3分散到混合物A3中，质量比例6:100，利用行星搅拌机搅拌均匀，搅拌时间不小于30min，得到混合物C3。
（4）将树脂混合物C3均匀涂刷到芳纶纤维布表面，得到铺层S3；
步骤四、将S1，S2，S3依次叠合；
步骤五、采用热压罐工艺成型。
进一步地，所述固化剂采用双氧水。
进一步地，所述引发剂采用引发剂SW-1305。
进一步地，所述分散剂采用改性钛酸酯。
进一步地，所述脱模剂采用N-770脱模剂。
进一步地，所述脱模剂涂刷方式为顺时针均匀涂刷。
进一步地，每40-60s涂刷一次，共涂刷8次；C1C2混合物在芳纶纤维布涂刷方式为：每40-60s涂刷一次，共涂刷14次；步骤二种混合物C2在芳纶纤维布涂刷方式为：每40-60s涂刷一次，共涂刷6次；步骤一种混合物C3在芳纶纤维布涂刷方式为：每40-60s涂刷一次，共涂刷4次。
与现有技术相比，本发明所具有的有益效果为：
本发明公开了一种低密度吸波复合材料板材的制备，使用芳纶纤维增强复合材料，利用碳纳米管及镀镍碳纳米管、乙烯基树脂，通过热压罐制备了功能一体化低密度吸波板料。通过碳纳米管、镀镍碳纳米管在铺层阶段不同的含量（相对于树脂的总量），将树脂添加到配置好的乙烯基树脂中，在树脂中添加1%、1.2%、1.5%的改性钛酸酯，既可以使吸波剂分散在树脂中，又可以改善树脂与纤维表面，使得树脂很好的浸透于增强纤维，提高复合材料的力学性能，通过配方设计改性酞酸酯还起到分散吸波剂的作用，有利于在所设计的频段内提高复合材料的吸波性能；本发明通过铺层设计了三个阶段吸波剂的含量，确保复合材料的密度不会增大。采用热压罐制备了一种低密度吸波复合板材，该材料吸波性能在8-18GHz频段，反射率≤-10dB，频率为12.5GHz，最大吸收峰为-60dB，复合材料的密度为1.41g/cm3，复合材料的力学性能好于通常的玻璃纤维复合。本发明的吸波材料板材相对于现有技术的制备的复合吸波材料具有密度低，相对于玻璃纤维密度可降低30%，吸波性能好。制备的吸波复合材料力学性能好，能够充分的应用在现代轻质化航天技术中，以及轻质化的防护电磁环境的设备及工程中。不仅为我国节约能约创造价值，同时为防御电磁污染提供了一条制备复合材料的方法。
附图说明
图1为本发明提供的一种低密度复合材料吸波板示意图；
图2为碳纳米管SEM图；
图3为镀镍碳纳米管XRD图；
图4为未加改性酞酸酯碳纳米管在树脂中的分散图；
图5为添加1%改性酞酸酯碳纳米管在树脂中的分散图；
图6为低密度复合材料板材固化参数曲线图
图7为低密度复合材料反射测试结果；
图8为低密度复合材料力学测试数据。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做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。
一种低密度复合材料吸波板的制备方法，包括以下步骤：
步骤一、制备铺层S1
（1）乙烯基树脂、固化剂、引发剂和分散剂按照质量比100:1:0.5:1混合，得到混合物A1；
（2）将碳纳米管与镀镍碳纳米管按照2:1的比例混合,得到吸波剂B1；
（3）将B1分散到混合物A1中，质量比例4:100，利用行星搅拌机搅拌均匀，搅拌时间不小于30min，得到混合物C1；
（4）乙烯基树脂、固化剂、引发剂和分散剂质量比例100:1:0.5:1.2，得到混合物A2；
（5）将碳纳米管与镀镍碳纳米管按照1:1比例混合，得到吸波剂B2；
（6）将B2分散到混合物A2中，质量比例5:100，利用行星搅拌机搅拌均匀，搅拌时间不小于30min，得到混合物C2；
（7）取混合物C1和混合物C2混合均匀得到C1C2混合物；
（8）模具表面涂刷脱模剂，涂刷2-3次；
（9）将一定尺寸的芳纶纤维布铺设于模具表面，保证纤维布与模具的贴合度，拐角处要开口，多余去掉；
（10）将混合物C1均匀涂刷到芳纶纤维布表面，每40-60s涂刷一次，共涂刷8次；将C1C2混合物均匀涂刷到芳纶纤维布另一表面，每40-60s涂刷一次，共涂刷14次，得到铺层S1；
步骤二、制备铺层S2
（1）乙烯基树脂、固化剂、引发剂和分散剂质量比例100:1:0.5:1.2，得到混合物A2；
（2）将碳纳米管与镀镍碳纳米管按照1:1比例混合，得到吸波剂B2；
（3）将B1分散到混合物A1中，质量比例5:100，利用行星搅拌机搅拌均匀，搅拌时间不小于30min，得到混合物C2；
（4）将树脂混合物C2均匀涂刷到芳纶纤维布表面，每40-60s涂刷一次，共涂刷6次，得到铺层S2；
步骤三、制备铺层S3
（1）乙烯基树脂、固化剂、引发剂和分散剂质量比例100:1:0.5:1.5，得到混合物A3；
（2）将碳纳米管与镀镍碳纳米管按照1:3比例混合，得到吸波剂B3；
（3）将B3分散到混合物A3中，质量比例6:100，利用行星搅拌机搅拌均匀，搅拌时间不小于30min，得到混合物C3。
（4）将树脂混合物C3均匀涂刷到芳纶纤维布表面，每40-60s涂刷一次，共涂刷4次，得到铺层S3；
步骤四、将S1，S2，S3依次叠合，如图1所示；
步骤五、采用热压罐工艺成型。
在本实施例中，所述固化剂采用双氧水。
在本实施例中，所述引发剂采用引发剂SW-1305。
在本实施例中，所述分散剂采用改性钛酸酯。在选用芳纶纤维的基础上，通过调试改性钛酸酯子在树脂中的含量，使得吸波剂充分的分散在树脂中，避免了局部团聚，并且改性钛酸酯改善了纤维表面，使得树脂很好的浸透于纤维布之间，提高了复合材料的力学性能。
在本实施例中，所述脱模剂采用N-770脱模剂。
在本实施例中，所述脱模剂涂刷方式为顺时针均匀涂刷。
在本实施例中，图2为碳纳米管SEM图；图3为本实施例中碳纳米管XRD图，碳纳米管中有镍粒子存在，能谱图表示镍元素的含量占比80.36；图5为未加改性酞酸酯碳纳米管在树脂中的分散图，图5为添加1%改性酞酸酯碳纳米管在树脂中的分散图，改性酞酸酯加到树脂中不仅改善纤维表面，而且使得吸波剂充分分散到树脂中；图6为固化参数曲线图，表明了复合材料的特殊成型参数的曲线变化。
图7为本实施例中在高频振动后高功率微波吸收材料反射率测试，图表明芳纶纤维增强复合材料吸波板材8GHz-18GHz频段内，反射率≤-10dB,最大吸收峰为-60dB，频率为12.5GHz。图8为低密度复合材料层间剪切、冲击、压缩和拉伸强度的力学测试数据。
在本实施例中，由于镀镍碳纳米管的密度较大，在不影响复合材料吸波性能的前提下，对镀镍碳纳米管进行不同阶段的配方设计，从而降低了复合材料的密度。密度为1.41g/cm3。本发明的吸波剂为碳纳米管、镀镍碳纳米管难以在树脂中分散，利用改性酞酸酯将吸波剂分散下树脂中，在此过程必须控制分散剂在树脂中的含量，含量过多不仅使得吸波剂难以分散，会造成使分散剂增稠树脂，给制备复合材料带来施工难的麻烦，另外造成吸波剂局部大量团聚，吸波性能下降。所以结合改性酞酸酯既可作为偶联剂又可作为分散剂的功能，改性酞酸酯在树脂中的含量不得超过1.5%（相对树脂的总量），并且因每阶段吸波剂含量不同，改性酞酸酯在S1，S2，S3的比例不同。需要制备密度低，吸波性能好的复合材料，成型工艺也是一种重要的手段，本发明通过成型设计参数，采用热压罐制备了功能一体化吸波复合材料。本发明根据吸波原理，以及复合材料低密度要求，通过上述吸波剂的配方设计，经增强纤维铺层设计，采用热压罐制备功能一体化复合材料，该工艺制备的复合树脂含量低，材料致密性好。根据复合材料基体树脂、改性酞酸酯的特性设置了成型参数凝胶温度80℃，凝胶时间30min，固化温度100℃，固化时间120min，降至60℃，保温时间30min。
上面仅对本发明的较佳实施例作了详细说明，但是本发明并不限于上述实施例，在本领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化，各种变化均应包含在本发明的保护范围之内。

Claims (7)

1.一种低密度复合材料吸波板的制备方法，其特征在于，包括以下步骤：
步骤一、制备铺层S1
（1）乙烯基树脂、固化剂、引发剂和分散剂按照质量比100:1:0.5:1混合，得到混合物A1；
（2）将碳纳米管与镀镍碳纳米管按照2:1的比例混合,得到吸波剂B1；
（3）将B1分散到混合物A1中，质量比例4:100，利用行星搅拌机搅拌均匀，搅拌时间不小于30min，得到混合物C1；
（4）乙烯基树脂、固化剂、引发剂和分散剂质量比例100:1:0.5:1.2，得到混合物A2；
（5）将碳纳米管与镀镍碳纳米管按照1:1比例混合，得到吸波剂B2；
（6）将B2分散到混合物A2中，质量比例5:100，利用行星搅拌机搅拌均匀，搅拌时间不小于30min，得到混合物C2；
（7）取混合物C1和混合物C2混合均匀得到C1C2混合物；
（8）模具表面涂刷脱模剂，涂刷2-3次；
（9）将一定尺寸的芳纶纤维布铺设于模具表面，保证纤维布与模具的贴合度，拐角处要开口，多余去掉；
（10）将混合物C1与C1C2混合物分别均匀涂刷到芳纶纤维布两面，得到铺层S1；
步骤二、制备铺层S2
（1）乙烯基树脂、固化剂、引发剂和分散剂质量比例100:1:0.5:1.2，得到混合物A2；
（2）将碳纳米管与镀镍碳纳米管按照1:1比例混合，得到吸波剂B2；
（3）将B2分散到混合物A2中，质量比例5:100，利用行星搅拌机搅拌均匀，搅拌时间不小于30min，得到混合物C2；
（4）将树脂混合物C2均匀涂刷到芳纶纤维布表面，得到铺层S2；
步骤三、制备铺层S3
（1）乙烯基树脂、固化剂、引发剂和分散剂质量比例100:1:0.5:1.5，得到混合物A3；
（2）将碳纳米管与镀镍碳纳米管按照1:3比例混合，得到吸波剂B3；
（3）将B3分散到混合物A3中，质量比例6:100，利用行星搅拌机搅拌均匀，搅拌时间不小于30min，得到混合物C3；
（4）将树脂混合物C3均匀涂刷到芳纶纤维布表面，得到铺层S3；
步骤四、将S1，S2，S3合叠；
步骤五、采用热压罐工艺成型。
2.根据权利要求1所述的一种低密度复合材料吸波板的制备方法，其特征在于：所述固化剂采用双氧水。
3.根据权利要求1所述的一种低密度复合材料吸波板的制备方法，其特征在于：所述引发剂采用引发剂SW-1305。
4.根据权利要求1所述的一种低密度复合材料吸波板的制备方法，其特征在于：所述分散剂采用改性钛酸酯。
5.根据权利要求1所述的一种低密度复合材料吸波板的制备方法，其特征在于：所述脱模剂采用N-770脱模剂。
6.根据权利要求1所述的一种低密度复合材料吸波板的制备方法，其特征在于：所述脱模剂涂刷方式为顺时针均匀涂刷。
7.根据权利要求1所述的一种低密度复合材料吸波板的制备方法，其特征在于：步骤一种混合物C1在芳纶纤维布涂刷方式为：每40-60s涂刷一次，共涂刷8次；C1C2混合物在芳纶纤维布涂刷方式为：每40-60s涂刷一次，共涂刷14次；步骤二种混合物C2在芳纶纤维布涂刷方式为：每40-60s涂刷一次，共涂刷6次；步骤一种混合物C3在芳纶纤维布涂刷方式为：每40-60s涂刷一次，共涂刷4次。
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