CN109291575A - 一种表面防护型导电复合材料及其制备方法 - Google Patents
一种表面防护型导电复合材料及其制备方法 Download PDFInfo
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Abstract
本发明是一种表面防护型导电复合材料及其制备方法,该复合材料由树脂基复合材料、胶粘层、导电层、增强层、防护层经复合模压而成。胶粘层为无机或有机胶粘剂;导电层为纯导电金属网或者高分子树脂导电胶膜或者高分子树脂绝缘胶膜/导电金属网复合胶膜或者高分子树脂导电胶膜/导电金属网复合胶膜;增强层为织物;防护层为橡胶材料。制备前首先将预浸料、胶粘层、导电层、增强层、防护层按照复合材料制件的形状、尺寸逐层裁切,然后将导电层与树脂基复合材料进行一体化固化成型,接着将树脂基复合材料与胶粘层、增强层、防护层制作成坯料,最后模压成型。
Description
技术领域
本发明是一种表面防护型导电复合材料及其制备方法,属于导电复合材料技术领域。
背景技术
纤维增强树脂基复合材料具有可设计性强、比强度高、耐腐蚀、结构尺寸稳定性好、抗疲劳断裂性能好等特点,广泛应用于航空和航天领域,已迅速发展成为飞机等航空器的重要结构材料,其用量已成为飞机先进性的重要标志之一。但是,相比于传统的金属材料,虽然复合材料中的碳纤维具有较好的导电性,但绝缘性树脂阻隔了导电通路;当飞机遭到雷击时,雷电电流难以通过材料表面导出而生成大量的热量,结果对复合材料产生烧蚀作用,大大降低其强度和刚度,从而对飞机结构的安全性和经济性带来了极大挑战。
目前改善复合材料雷击保护以及电磁屏蔽应用效果,已通过不同的方法来增强复合结构的导电性。此类方法包括整体或分段式的避雷针、电弧喷涂或火焰喷涂金属、金属丝网状物、实体箔/扩展箔、穿孔箔包覆、表面喷涂含导电粒子的导电漆等。如波音787飞机复合材料机身结构的防雷击措施是在复合材料机身制造过程中加入金属网,将雷击电流引走。但是,高密度的金属材料直接暴露于环境中易发生腐蚀,使得与复合材料之间的表面容易出现间隙,当雷击电流经过时产生电弧和火花,严重时甚至可能引燃结构中的油箱造成飞机***;因此需要对导电金属材料进行表面防护。此外,网箔包覆型复合材料在服役过程中可能因冰雹、飞机跑道上飞起的碎石、或维修人员不慎跌落的工具及粗暴踩踏等而发生破坏,结果破坏了金属网中电路的连续性,甚至内部的复合材料也可能发生损伤,从而影响服役性能。
发明内容
本发明正是针对上述现有技术中存在的不足而设计提供了一种表面防护型导电复合材料及其制备方法,其目的是提高导电复合材料的密封防护和抗损伤性能。
本发明的目的是通过以下技术方案来实现的:
本发明技术方案提出了一种表面防护型导电复合材料,其特征在于:该复合材料的基材(1)是纤维增强树脂基复合材料,在基材(1)的表面依次制备导电层(2)、胶粘层(3)与防护层(5),其中:
所述的导电层(2)为纯导电金属网、高分子树脂导电胶膜、高分子树脂绝缘胶膜/导电金属网复合胶膜或高分子树脂导电胶膜/导电金属网复合胶膜;
所述的胶粘层(3)为无机或有机胶粘剂,该胶粘剂应可与橡胶同步固化,且可以与高分子树脂、橡胶、织物产生良好的粘接效果,以180°剥离强度为例,该剥离强度大于0.1kN/m;
所述的防护层(5)为天然橡胶、合成橡胶或天然橡胶与合成橡胶的并用胶。
进一步,在胶粘层(3)与防护层(5)之间或在防护层(5)上面加入增强层(4),增强层(4)为涤纶织物、芳纶织物、锦纶织物、聚酯织物、玻璃布、棉布或碳纤维布的一种或者几种;
最外层如果是防护层(5),在其之上再铺贴增强层(4)或交替铺贴增强层(4)、防护层(5),最外层如果是增强层(4)的,在其之上再铺贴防护层(5)或交替铺贴防护层(5)、增强层(4);
所述纤维增强树脂基复合材料所用增强纤维为碳纤维、玻璃纤维、芳纶纤维、玄武岩纤维、氧化铝纤维或碳化硅纤维中的一种或几种,增强纤维的结构形式为织物或者单向带。
所述纤维增强树脂基复合材料所用的基体树脂为热塑性树脂或热固性树脂,其中:
热塑性树脂为聚醚酮、聚砜、聚醚砜、热塑性聚酰亚胺、聚醚酰亚胺、聚碳酸酯、聚苯醚或聚酰胺中的一种或几种混合树脂;
热固性树脂为环氧树脂、双马来酰亚胺树脂、热固性聚酰亚胺树脂、聚苯并噁嗪树脂、酚醛树脂、氰酸酯树脂或不饱和聚酯树脂中的一种或几种混合树脂。
所述合成橡胶为丁苯橡胶、顺丁橡胶、氯丁橡胶、乙丙橡胶、丁腈橡胶、氢化丁腈橡胶、丁基橡胶、氯醚橡胶、聚硫橡胶、氟硅橡胶、硅橡胶或氟橡胶的一种或几种的混合物。
所述高分子树脂导电胶膜中的树脂为环氧树脂、双马来酰亚胺树脂、热固性聚酰亚胺树脂、聚苯并噁嗪树脂、酚醛树脂、氰酸酯树脂、不饱和聚酯树脂中的一种或几种混合树脂;
所述高分子树脂导电胶膜中用的导电粒子为碳纳米管、石墨烯、炭黑、石墨、银粉、镍粉、铝粉、铁粉、铜粉、金粉中的一种或几种的混合物。
所述纯导电金属网为铜网、铝箔网中的一种或两种的混合体。
本发明技术方案还提供了一种制备所述的表面防护型导电复合材料的方法,该方法的步骤如下:
步骤一、导电复合材料预制件的制备
将导电层2的材料铺贴于纤维增强树脂基复合材料的预浸料坯料的单面或双面上,然后采用成型工艺进行固化,得到预制件;
步骤二、预制件的预处理
对预制件的表面进行预处理,预处理方法为喷砂或打磨,然后清洁,随后在预制件的单面或双面上喷涂、刷涂或铺贴胶粘层3;
步骤三、表面防护型导电复合材料的制备
将防护层5铺贴于胶粘层3上,铺贴完成后模压成型得到表面防护型导电复合材料。
进一步,步骤一中所述的预制体的固化方法为热压罐、RTM、真空袋法、液体成型工艺或树脂膜浸渗工艺。
进一步,所述表面防护型导电复合材料的结构为平板或者曲面形状。
进一步,步骤一中所述的预制体的固化的固化度超过30%。
本发明具有的优点和有益效果是:
本发明利用橡胶作为导电层的表面防护层,具有厚度可调、性能可设计的优点,从而有效隔离了导电层与外界环境的接触,避免了导电层中的导电粒子或金属网的环境腐蚀;此外,还可以起到包覆减振缓冲防护作用,极大地改善复合材料的冲击阻抗和损伤容限。另外,本发明所制备的结构受到气动加热时,外层橡胶还可起到热防护作用,避免复合材料受到热冲击破坏。
本发明通过树脂基复合材料的基材、导电层和采用橡胶制成防护层的结构一体化制备技术,工艺便利,有效避免了常规导电复合材料繁琐的二次喷涂防护工艺;此外,本发明在导电层与防护层间引入了化学胶粘层,极大地改善了常规导电复合材料与表面涂层界面粘接不足的缺点,延长了防护层的服役寿命,可达到与导电复合材料同等寿命。
所得复合材料具有高刚度、高强度、耐湿热环境、耐疲劳,同时又抗冲击、阻尼减震的优点。不仅如此,本发明还可以通过导电层的铺贴位置以及厚度的控制,实现对复合材料导电特性的设计,满足飞行器不同部位的雷击保护以及电磁屏蔽需求,特别适合应用在航空航天领域。
附图说明
图1是本发明实施例一铺层示意图;
图2是本发明实施例二铺层示意图;
图3是本发明实施例三铺层示意图;
图4是本发明实施例四铺层示意图;
具体实施方式
以下实施例用来具体说明本发明,但本发明不限于此,本领域技术人员可以在权利要求的范围内做出各种变形或修改,这并不影响本发明的实质内容。
实施例一
参见附图1所示,生产表面防护型导电复合材料平面板材:长度为660mm±5mm,宽度为120mm±5mm,厚度为3.5mm±0.2mm,步骤如下:
(1)首先铺贴3mm±0.2mm厚度的T700S/5228高温环氧树脂基复合材料预浸料坯料,尺寸为长度670mm,宽度130mm,然后将厚度为0.2mm±0.04mm高分子导电树脂膜作为导电层2铺贴在预浸料单侧表面,然后在150℃下预固化30min,得到导电复合材料预制件;
(2)裁切预制件1的尺寸为长度660mm,宽度120mm,打磨铺有导电层的预制件的单侧表面,用丙酮清理,然后在该表面均匀喷涂高分子胶粘剂胶液作为胶粘层3,胶粘剂厚度为0.02mm~0.04mm;
(3)在胶粘层3上铺贴高阻尼丁苯橡胶作为防护层5,厚度为0.5mm±0.1mm,其裁切尺寸为长度660mm,宽度120mm。
将上述铺层形成的坯料,在(180℃±5℃)×(10MPa±2MPa)×(150min±5min)模压成型,取模后修边,即得一种复合板材,且经无损检测证实,其内部不存在明显的缺陷界面。
实施例二
参见附图2所示,生产表面防护型导电复合材料曲面板材:长度为660mm±2mm,宽度为120mm±2mm,厚度为4.5mm±0.2mm,步骤如下:
(1)首先铺贴3mm±0.2mm厚度的SW280/苯并噁嗪树脂预浸织物坯料,尺寸为长度670mm,宽度130mm,然后将厚度为0.2mm±0.04mm高分子导电树脂膜作为导电层2铺贴在预浸料双侧表面,然后在150℃下预固化30min,得到导电复合材料预制件;
(2)裁切预制件1的尺寸为长度660mm,宽度120mm,打磨预制件的双侧表面,用丙酮清理,然后在该表面均匀喷涂高分子胶粘剂胶液作为胶粘层3,胶粘剂厚度为0.02mm~0.04mm;
(3)在导电复合材料预制件的一侧,于胶粘层3上铺贴高分子聚酯织物作为增强层4,厚度为0.3mm±0.05mm,其裁切尺寸为长度660mm,宽度120mm;在增强层4上铺贴高阻尼氢化丁腈橡胶作为防护层5,厚度为0.5mm±0.05mm,其裁切尺寸同增强层4;
(4)在导电复合材料预制件的另一侧,于胶粘层3上铺贴高阻尼丁腈橡胶作为防护层5,厚度为0.5mm±0.05mm,裁切尺寸为长度660mm,宽度120mm。
将上述铺层形成的坯料,按照(185℃±5℃)×(10MPa±2MPa)×(180min±5min)模压成型,取模后修边,即得一种复合板材,且经无损检测证实,其内部不存在明显的缺陷界面。
实施例三
参见附图3所示,生产表面防护型导电复合材料平面板材:长度为1200mm±2mm,宽度为200mm±2mm,厚度为3.3mm±0.2mm,步骤如下:
(1)首先铺贴3mm±0.2mm厚度的DP328/3233芳纶纤维预浸织物坯料,尺寸为长度1210mm,宽度210mm,然后将厚度为0.05mm~0.08mm纯金属铝箔导电网作为导电层2铺贴在预浸料双侧表面,然后在125℃下预固化20min,得到导电复合材料预制件;
(2)裁切预制件的尺寸为长度1200mm,宽度200mm,打磨预制件的单侧表面,用丙酮清理,然后在该表面均匀喷涂高分子胶粘剂胶液作为胶粘层3,胶粘剂厚度为0.02mm~0.04mm;
(3)在胶粘层3上铺贴高阻尼乙丙橡胶作为防护层5,厚度为0.3mm±0.05mm,其裁切尺寸为长度1200mm,宽度200mm。在防护层5上铺贴高分子聚酯织物作为增强层4,厚度为0.15mm±0.05mm,其裁切尺寸同防护层5。
将上述铺层形成的坯料,在(160℃±5℃)×(10MPa±2MPa)×(60min±3min)下模压成型,取模后修边,即得一种复合板材,且经无损检测证实,其内部不存在明显的缺陷界面。
实施例四
参见附图4所示,生产表面防护型导电复合材料曲面板材:长度为1200mm±2mm,宽度为200mm±2mm,厚度为3.6mm±0.3mm,步骤如下:
(1)首先在模具中铺贴厚度为3mm±0.2mm的碳纤维预成型体,尺寸为长度为1210mm,宽度为210mm;接着将厚度为0.05mm~0.08mm纯金属铜导电网作为导电层2铺贴于在碳纤维预成型体单侧表面;然后将环氧树脂、固化剂三乙烯四胺按比例100:13搅拌均匀,然后通过RTM工艺注射入模具内,注射压力位0.15MPa。注射完毕后,按照130℃/3h+150℃/2h+170℃/2h+180℃/2h+200℃/2h的固化梯度进行固化操作以制备导电复合材料预制件;
(2)裁切预制件的尺寸为长度1200mm,宽度200mm,打磨铺有导电层的预制件的表面,用丙酮清理,然后在该表面均匀喷涂高分子胶粘剂胶液作为胶粘层3,胶粘剂厚度为0.02mm~0.04mm;
(3)在胶粘层3上铺贴高阻尼丁腈橡胶作为防护层5,厚度为0.2mm±0.05mm,其裁切尺寸为长度1200mm,宽度200mm。在防护层5上铺贴高分子聚酯织物作为增强层4,厚度为0.3mm±0.05mm,其裁切尺寸同防护层5。在增强层4上铺贴高阻尼丁腈橡胶作为防护层5,厚度为0.3mm±0.05mm,其裁切尺寸同增强层4。
将上述铺层形成的坯料,在(160℃±5℃)×(10MPa±2MPa)×(30min±5min)下模压成型,取模后修边,即得一种复合板材,且经无损检测证实,其内部不存在明显的缺陷界面。
与现有技术相比,本发明成型方法简单易行,所得导电复合材料电性能可设计,具有高刚度、高强度、耐湿热环境、耐疲劳,避免了金属导电层存在的腐蚀问题,同时又有热防护、抗冲击、阻尼减震的优点,可满足飞行器不同部位的雷击保护以及电磁屏蔽需求,特别适合应用于航空航天领域。
Claims (12)
1.一种表面防护型导电复合材料,其特征在于:该复合材料的基材(1)是纤维增强树脂基复合材料,在基材(1)的表面依次制备导电层(2)、胶粘层(3)与防护层(5),其中:
所述的导电层(2)为纯导电金属网、高分子树脂导电胶膜、高分子树脂绝缘胶膜/导电金属网复合胶膜或高分子树脂导电胶膜/导电金属网复合胶膜;
所述的胶粘层(3)为无机或有机胶粘剂;
所述的防护层(5)为天然橡胶、合成橡胶或天然橡胶与合成橡胶的并用胶。
2.根据权利要求1所述的表面防护型导电复合材料,其特征在于:在胶粘层(3)与防护层(5)之间或在防护层(5)上面加入增强层(4),增强层(4)为涤纶织物、芳纶织物、锦纶织物、聚酯织物、玻璃布、棉布或碳纤维布的一种或者几种。
3.根据权利要求2所述的表面防护型导电复合材料,其特征在于:最外层如果是防护层(5),在其之上再铺贴增强层(4)或交替铺贴增强层(4)、防护层(5),最外层如果是增强层(4)的,在其之上再铺贴防护层(5)或交替铺贴防护层(5)、增强层(4)。
4.根据权利要求1所述的表面防护型导电复合材料,其特征在于:所述纤维增强树脂基复合材料所用增强纤维为碳纤维、玻璃纤维、芳纶纤维、玄武岩纤维、氧化铝纤维或碳化硅纤维中的一种或几种,增强纤维的结构形式为织物或者单向带。
5.根据权利要求1所述的表面防护型导电复合材料,其特征在于:所述纤维增强树脂基复合材料所用的基体树脂为热塑性树脂或热固性树脂,其中:
热塑性树脂为聚醚酮、聚砜、聚醚砜、热塑性聚酰亚胺、聚醚酰亚胺、聚碳酸酯、聚苯醚或聚酰胺中的一种或几种混合树脂;
热固性树脂为环氧树脂、双马来酰亚胺树脂、热固性聚酰亚胺树脂、聚苯并噁嗪树脂、酚醛树脂、氰酸酯树脂或不饱和聚酯树脂中的一种或几种混合树脂。
6.根据权利要求1所述的表面防护型导电复合材料,其特征在于:合成橡胶为丁苯橡胶、顺丁橡胶、氯丁橡胶、乙丙橡胶、丁腈橡胶、氢化丁腈橡胶、丁基橡胶、氯醚橡胶、聚硫橡胶、氟硅橡胶、硅橡胶或氟橡胶的一种或者几种混合物。
7.根据权利要求1所述的表面防护型导电复合材料,其特征在于:所述高分子树脂导电胶膜中的树脂为环氧树脂、双马来酰亚胺树脂、热固性聚酰亚胺树脂、聚苯并噁嗪树脂、酚醛树脂、氰酸酯树脂、不饱和聚酯树脂中的一种或几种混合树脂;
所述高分子树脂导电胶膜中用的导电粒子为碳纳米管、石墨烯、炭黑、石墨、银粉、镍粉、铝粉、铁粉、铜粉、金粉中的一种或几种的混合物。
8.根据权利要求1所述的表面防护型导电复合材料,其特征在于:所述纯导电金属网为铜网、铝箔网中的一种或两种的混合体。
9.制备权利要求1所述的表面防护型导电复合材料的方法,其特征在于:该方法的步骤如下:
步骤一、导电复合材料预制件的制备
将导电层(2)的材料铺贴于纤维增强树脂基复合材料的预浸料坯料的单面或双面上,然后采用成型工艺进行固化,得到预制件;
步骤二、预制件的预处理
对预制件的表面进行预处理,预处理方法为喷砂或打磨,然后清洁,随后在预制件的单面或双面上喷涂、刷涂或铺贴胶粘层(3);
步骤三、表面防护型导电复合材料的制备
将防护层(5)铺贴于胶粘层(3)上,铺贴完成后模压成型得到表面防护型导电复合材料。
10.根据权利要求9所述的制备表面防护型导电复合材料的方法,其特征在于:步骤一中所述的预制体的固化方法为热压罐、RTM、真空袋法、液体成型工艺或树脂膜浸渗工艺。
11.根据权利要求9所述的制备表面防护型导电复合材料的方法,其特征在于:所述表面防护型导电复合材料的结构为平板或者曲面形状。
12.根据权利要求9所述的制备表面防护型导电复合材料的方法,其特征在于:步骤一中所述的预制体的固化的固化度超过30%。
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