CN114106377B - 一种热固性电磁屏蔽预浸料、制备方法及制得的复合材料 - Google Patents
一种热固性电磁屏蔽预浸料、制备方法及制得的复合材料 Download PDFInfo
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Abstract
本发明公开了一种热固性电磁屏蔽预浸料的制备方法，包括以下步骤：(1)将磁性粒子用偶联剂处理后，与热固性树脂、固化剂和促进剂混合得到树脂混合物，利用树脂混合物制备上下胶膜，胶膜的面密度为10～250g/m2；(2)将上下胶膜分别贴附在镀镍碳纤维毡两侧面，热熔法双面浸胶得到所述的热固性电磁屏蔽预浸料；所述的镀镍碳纤维毡的面密度为10‑200g/m2。本发明选用镀镍碳纤维毡为增强体，并利用添加有磁性粒子的热固性树脂体系制备预浸料，镀镍碳纤维毡和磁性粒子协同发挥作用，使得制得的预浸料在高频和低频的条件下均具有优异的电磁屏蔽效能，且质轻、可进一步制备轻质、宽频、高电磁屏蔽效能的复合材料。
Description
技术领域
本发明涉及电磁屏蔽材料技术领域，尤其涉及一种热固性电磁屏蔽预浸料、制备方法及制得的复合材料。
背景技术
近年来，由于电子技术的飞速发展，电磁干扰(EMI)已成为日益严重的问题，这极大地危害了电子设备的正常功能和人体健康。为防止电磁辐射干扰精密设备正常工作，必须发展新型高效的电磁屏蔽(EMS)材料以解决这一问题。
通常要获得宽频的电磁屏蔽材料，可以将高磁导率的材料和高电导率的材料进行复合使用。常规的电磁屏蔽材料中添加有导电率较高的金属填料，如银粉、铜粉、镍粉等，在高频波段有较好的屏蔽性能，且应用广泛。然而，由于金属填料的比重高，添加量大，难以满足轻质的需求，因此，开发轻质、宽频、力学性能优异的电磁屏蔽材料是新一代电磁屏蔽材料的发展趋势。
公开号为CN108394148A的中国专利文献公开了一种新型电磁屏蔽复合材料，包括有金属层、热固性树脂和碳纤维编织布，金属层的外表面通过树脂混合溶液设置有碳纤维编织布，金属层、碳纤维编织布均在树脂混合溶液中充分浸润、渗透；树脂混合溶液由热固性树脂与纳米导电填料等组成，该电磁屏蔽复合材料重量轻，结合强度高，耐腐蚀性能较强，使用范围广泛，屏蔽稳定性好，屏蔽波段范围宽。
公开号为CN101531804A的中国专利文献公开了一种三维编织镀镍碳纤维与环氧树脂电磁屏蔽复合材料的制备方法，包括：碳纤维经电镀镍，再编织成镀镍碳纤维织物，采用树脂转移模塑成形(Resin Transfer Molding，RTM)工艺镀镍碳纤维编织物与环氧树脂复合制备得到所述电磁屏蔽复合材料。该电磁屏蔽复合材料具有良好的电磁屏蔽性能，法兰同轴方法测试结果表明，该编织复合材料电磁屏蔽效果达到70～80dB。但该电磁屏蔽复合材料制备过程中需采用三维四向编织，设备成本和工艺成本高。
发明内容
本发明提供了一种热固性电磁屏蔽预浸料，在高频和低频的条件下均具有优异的电磁屏蔽效能，且质轻、制备工艺简单，可作为中间体进一步制备高电磁屏蔽效能的复合材料。
具体采用的技术方案如下：
一种热固性电磁屏蔽预浸料的制备方法，包括以下步骤：
(1)将磁性粒子用偶联剂处理后，与热固性树脂、固化剂和促进剂混合得到树脂混合物，利用树脂混合物制备上下胶膜，胶膜的面密度为10～250g/m2；
(2)将上下胶膜分别贴附在镀镍碳纤维毡两侧面，热熔法双面浸胶得到所述的热固性电磁屏蔽预浸料；所述的镀镍碳纤维毡的面密度为10-200g/m2。
本发明选用镀镍碳纤维毡为增强体，并利用添加有磁性粒子的热固性树脂体系制备预浸料，镀镍碳纤维毡和磁性粒子协同发挥作用，使得制得的预浸料在高频和低频的条件下均具有优异的电磁屏蔽效能，且质轻、可进一步制备性能优异的复合材料。
优选的，所述的磁性粒子包括金属、合金、羰基铁、铁氧体、氮化铁，粒径为1nm～150μm；所述的铁氧体包括Fe3O4、CoFe2O4、MnFe2O4和NiFe2O4等。
优选的，所述的偶联剂包括硅烷偶联剂、钛酸酯偶联剂；偶联剂处理磁性粒子的方法为：将磁性粒子加入至偶联剂溶液中充分混合，待溶剂挥发后，得到偶联剂处理的磁性粒子。采用上述方法可以使偶联剂均匀地附着在磁性粒子表面。
优选的，所述的树脂混合物的制备方法为：将偶联剂处理的磁性粒子、热固性树脂搅拌混匀，搅拌时间为0.1-4h；再加入固化剂、促进剂再次搅拌0.1-4h混匀，得到树脂混合物。
优选的，步骤(1)中，热固性树脂、固化剂和促进剂的质量比为100：10～80：1～10。
磁性粒子占树脂混合物的质量百分比为1％～30％，优选的，磁性粒子占树脂混合物的质量百分比为10％～30％。
所述的热固性树脂包括但不限于双份A型环氧树脂、双份F型环氧树脂、酚醛型环氧树脂、不饱和树脂等。
所述的固化剂包括甲基纳迪克酸酐、双氰胺、4,4-二氨基二苯砜。
所述的促进剂包括2-乙基-4甲基咪唑、3-(3,4-二氯苯基)-1,1-二甲基脲、苯基二甲脲、苄基三乙基氯化铵。
本发明还提供了所述的热固性电磁屏蔽预浸料的制备方法制得的热固性电磁屏蔽预浸料，所述的热固性电磁屏蔽预浸料中，热固性树脂含量为35wt％～70wt％。
优选的，所述的热固性电磁屏蔽预浸料的电磁屏蔽效能为：当电磁波频率为0.1～30MHZ时，电磁屏蔽效能≥30dB；当电磁波频率为30MHz～18GHz时，电磁屏蔽效能≥60dB。
本发明还提供了一种由所述的热固性电磁屏蔽预浸料制得的轻质、宽频、高电磁屏蔽效能的复合材料。
优选的，所述的复合材料为五层复合结构，包括上表层、上连接层、中间层、下连接层和下表层，其中，上表层和下表层分别包括至少一层热固性电磁屏蔽预浸料，上连接层和下连接层分别包括至少一层碳纤维预浸料，中间层为泡沫或蜂窝材料层；将上述各层铺层后，通过热压或模压成型制得轻质、宽频、高电磁屏蔽效能的复合材料。
与现有技术相比，本发明的有益效果在于：
(1)本发明利用镀镍碳纤维毡和磁性粒子的协同作用，使得制得的热固性电磁屏蔽预浸料在高频和低频的条件下均具有优异的电磁屏蔽效能，且质轻、制备工艺简单。
(2)利用所述的热固性电磁屏蔽预浸料制得的复合材料轻质、宽频、且电磁屏蔽效能高，在低频0.1-30MHz范围内，电磁屏蔽效能可达到85dB，在高频30MHz～18GHz范围内，电磁屏蔽效能可达到120dB。
具体实施方式
下面结合实施例，进一步阐明本发明。应理解，这些实施例仅用于说明本发明，而不用于限制本发明的范围。
实施例1～3及对比例1～2中，镀镍碳纤维毡(镀镍CF毡)购买于英国TFP公司，镍含量为47％；单层平纹CF织物/环氧预浸料购买于中复神鹰碳纤维股份有限公司，树脂含量为40％，面密度为200g/m2。
对比例1
(1)将8层平纹CF织物/环氧预浸料+5cm厚的聚氨酯泡沫板+8层平纹CF织物/环氧预浸料进行铺层，通过真空袋压法一体化成型制备电磁屏蔽夹心复合材料。
对比例2
(1)将环氧树脂E51/环性树脂E20按质量比65：35在90℃下搅拌均匀混合，搅拌时间为2h，降温至70℃后，加入固化剂甲基纳迪克酸酐和促进剂2-乙基-4甲基咪唑，再次搅拌1h混合均匀，得到混合物，其中，环氧树脂、固化剂、促进剂的质量比为100：50：2。利用混合物在热熔胶膜机上制备上下胶膜，胶膜的面密度为20g/m2。
(2)将上下胶膜分别贴附在面密度为40g/m2的镀镍CF毡两侧面，采用热熔胶膜预浸机以双面浸胶方式制备得到镀镍CF毡/环氧树脂预浸料；其中，树脂含量为50wt％。
(3)将1层镀镍CF毡/环氧树脂预浸料+8层平纹CF织物/环氧预浸料+5cm厚的聚氨酯泡沫板+8层平纹CF织物/环氧预浸料+1层镀镍CF毡/环氧树脂预浸料进行铺层，通过真空袋压法一体化成型制备电磁屏蔽夹心复合材料。
实施例1
(1)用丙酮将硅烷偶联剂KH560稀释为5％的溶液，然后将平均粒径为20nm的Fe3O4磁性粒子加入至偶联剂溶液中充分混合，待丙酮溶剂挥发后，得到偶联剂处理后的Fe3O4磁性粒子，采用上述方法处理磁性粒子可以得到表面均匀地附着偶联剂的Fe3O4磁性粒子。
(2)将偶联剂处理后的Fe3O4磁性粒子、环氧树脂E51、环性树脂E20(环氧树脂E51与环性树脂E20质量比为65：35)在90℃下搅拌均匀混合，搅拌时间为2h，降温至70℃后，加入固化剂甲基纳迪克酸酐和促进剂2-乙基-4甲基咪唑，再次搅拌1h混合均匀，得到树脂混合物，其中，磁性粒子Fe3O4占树脂混合物的质量百分比为10％；环氧树脂、固化剂、促进剂的质量比为100：50：2。利用树脂混合物在热熔胶膜机上制备上下胶膜，胶膜的面密度为25g/m2。
(3)将上下胶膜分别贴附在面密度为40g/m2的镀镍CF毡两侧面，采用热熔胶膜预浸机以双面浸胶方式制备得到镀镍CF毡/Fe3O4/环氧树脂预浸料(即所述的热固性电磁屏蔽预浸料)，其中，热固性树脂含量为45.6wt％。
(4)将1层镀镍CF毡/Fe3O4/环氧树脂预浸料+8层平纹CF织物/环氧树脂预浸料+5cm厚的聚氨酯泡沫板+8层平纹CF织物/环氧树脂预浸料+1层镀镍CF毡/Fe3O4/环氧树脂预浸料进行铺层，通过真空袋压法一体化成型制备电磁屏蔽夹心复合材料。
实施例2
(1)用丙酮将硅烷偶联剂KH560稀释为5％的溶液，然后将平均粒径为20nm的Fe3O4磁性粒子加入至偶联剂溶液中充分混合，待丙酮溶剂挥发后，得到偶联剂处理后的Fe3O4。
(2)将偶联剂处理后的Fe3O4、环氧树脂E51、环性树脂E20(环氧树脂E51与环性树脂E20质量比为65：35)在90℃下搅拌均匀混合，搅拌时间为2h，降温至70℃后，加入固化剂甲基纳迪克酸酐和促进剂2-乙基-4甲基咪唑，再次搅拌1h混合均匀，得到树脂混合物，其中，磁性粒子Fe3O4占树脂混合物的质量百分比为20％；环氧树脂、固化剂、促进剂的质量比为100：50：2。利用树脂混合物在热熔胶膜机上制备上下胶膜，胶膜的面密度为34g/m2。
(3)将上下胶膜分别贴附在面密度为40g/m2的镀镍碳纤维毡两侧面，采用热熔胶膜预浸机以双面浸胶方式制备得到镀镍CF毡/Fe3O4/环氧树脂预浸料(即所述的热固性电磁屏蔽预浸料)，其中，热固性树脂含量为43wt％。
(4)将1层镀镍CF毡/Fe3O4/环氧树脂预浸料+8层平纹CF织物/环氧树脂预浸料+5cm厚的聚氨酯泡沫板+8层平纹CF织物/环氧树脂预浸料+1层镀镍CF毡/Fe3O4/环氧树脂预浸料进行铺层，通过真空袋压法一体化成型制备电磁屏蔽夹心复合材料。
实施例3
采用实施例2制备的镀镍CF毡/Fe3O4/环氧树脂预浸料，将2层镀镍CF毡/Fe3O4/环氧树脂预浸料+8层平纹CF织物/环氧树脂预浸料+5cm厚的聚氨酯泡沫板+8层平纹CF织物/环氧树脂预浸料+2层镀镍CF毡/Fe3O4/环氧树脂预浸料进行铺层，通过真空袋压法一体化成型制备电磁屏蔽夹心复合材料。
实施例4
(1)用丙酮将硅烷偶联剂KH560稀释为5％的溶液，然后将平均粒径为25μm的坡莫合金(Fe/Ni＝50/50)磁性粒子加入至偶联剂溶液中充分混合，待丙酮溶剂挥发后，得到偶联剂处理后的坡莫合金，采用上述方法处理磁性粒子可以得到表面均匀地附着偶联剂的坡莫合金。
(2)将偶联剂处理后的坡莫合金、环氧树脂E44、环性树脂E20(环氧树脂E44与环性树脂E20质量比为65：35)在90℃下搅拌均匀混合，搅拌时间为2h，降温至70℃后，加入固化剂双氰胺和促进剂3-(3,4-二氯苯基)-1,1-二甲基脲，再次搅拌1h混合均匀，得到树脂混合物，其中，磁性粒子坡莫合金占树脂混合物的质量百分比为10％；环氧树脂、固化剂、促进剂的质量比为100：40：5。利用树脂混合物在热熔胶膜机上制备上下胶膜，胶膜的面密度为25g/m2。
(3)将上下胶膜分别贴附在面密度为40g/m2的镀镍CF毡两侧面，采用热熔胶膜预浸机以双面浸胶方式制备得到镀镍CF毡/坡莫合金/环氧树脂预浸料(即所述的热固性电磁屏蔽预浸料)，其中，热固性树脂含量为45.6wt％。
(4)将1层镀镍CF毡/坡莫合金/环氧树脂预浸料+8层平纹CF织物/环氧树脂预浸料+5cm厚的聚氨酯泡沫板+8层平纹CF织物/环氧树脂预浸料+1层镀镍CF毡/坡莫合金/环氧树脂预浸料进行铺层，通过真空袋压法一体化成型制备电磁屏蔽夹心复合材料。
样品分析
依据GB-T 12190-2006电磁屏蔽室屏蔽效能的测量方法对实施例1～3及对比例1～2的预浸料及夹心复合材料进行电磁屏蔽效能测试，测试结果如表1所示；
表1实施例1～3及对比例1～2的预浸料及复合材料的电磁屏蔽效能
由表1的数据可知，实施例制得的热固性电磁屏蔽预浸料具有较好的电磁屏蔽效能，且随着磁性粒子含量的增加，电磁屏蔽效能随之增加。当树脂混合物中磁性粒子的含量为20wt％时，在低频0.1-30MHz范围内，电磁屏蔽效能高于35dB；在高频30MHz～18GHz范围内，电磁屏蔽效能均高于65dB。
当复合材料铺层相同，随着热固性电磁屏蔽预浸料中磁性粒子含量的增加，在低频0.1-30MHz范围内，电磁屏蔽效能随之增加；采用含有20％的磁性粒子的树脂混合物制得的热固性电磁屏蔽预浸料铺层制备得到的复合材料，在低频0.1-30MHz的电磁屏蔽效能高于45dB；在高频30MHz～18GHz范围内，电磁屏蔽效能均高于80dB。而且随着复合材料中热固性电磁屏蔽预浸料层数的增加，复合材料的电磁屏蔽效能增加。
以上所述的实施例对本发明的技术方案进行了详细说明，应理解的是以上所述的仅为本发明的具体实施例，并不用于限制本发明，凡在本发明的原则范围内所做的任何修改、补充或类似方式替代等，均应包含在本发明的保护范围之内。
Claims (8)
1.一种热固性电磁屏蔽预浸料的制备方法，其特征在于，包括以下步骤：
(1)将磁性粒子用偶联剂处理后，与热固性树脂、固化剂和促进剂混合得到树脂混合物，利用树脂混合物制备上下胶膜，胶膜的面密度为10～250g/m2；
(2)将上下胶膜分别贴附在镀镍碳纤维毡两侧面，热熔法双面浸胶得到所述的热固性电磁屏蔽预浸料；所述的镀镍碳纤维毡的面密度为10～200g/m2；
所述的磁性粒子为坡莫合金、羰基铁、铁氧体或氮化铁，所述的铁氧体包括Fe3O4、CoFe2O4、MnFe2O4和NiFe2O4；
所述的偶联剂包括硅烷偶联剂、钛酸酯偶联剂；偶联剂处理磁性粒子的方法为：将磁性粒子加入至偶联剂溶液中充分混合，待溶剂挥发后，得到偶联剂处理的磁性粒子；
磁性粒子占树脂混合物的质量百分比为10％～30％。
2.根据权利要求1所述的热固性电磁屏蔽预浸料的制备方法，其特征在于，所述的磁性粒子的粒径为1nm～150μm。
3.根据权利要求1所述的热固性电磁屏蔽预浸料的制备方法，其特征在于，步骤(1)中，热固性树脂、固化剂和促进剂的质量比为100：10～80：1～10。
4.根据权利要求1-3任一所述的热固性电磁屏蔽预浸料的制备方法制得的热固性电磁屏蔽预浸料，其特征在于，所述的热固性电磁屏蔽预浸料中，热固性树脂含量为35wt％～70wt％。
5.根据权利要求4所述的热固性电磁屏蔽预浸料，其特征在于，当电磁波频率为0.1～30MHz时，所述的热固性电磁屏蔽预浸料的电磁屏蔽效能≥30dB；当电磁波频率为30MHz～18GHz时，所述的热固性电磁屏蔽预浸料的电磁屏蔽效能≥60dB。
6.根据权利要求5所述的热固性电磁屏蔽预浸料在制备轻质、宽频、高电磁屏蔽效能的复合材料中的应用。
7.根据权利要求6所述的应用，其特征在于，所述复合材料为五层复合结构，包括上表层、上连接层、中间层、下连接层和下表层，其中，上表层和下表层分别包括至少一层所述的热固性电磁屏蔽预浸料，上连接层和下连接层分别包括至少一层碳纤维预浸料，中间层为泡沫或蜂窝材料层。
8.根据权利要求6所述的应用，其特征在于，所述复合材料的制备方法为：将上表层、上连接层、中间层、下连接层和下表层铺层后，通过热压或模压成型制得轻质、宽频、高电磁屏蔽效能的复合材料。
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