CN109338341B - 一种碳纤维增强树脂基复合材料表面金镀层的制备方法 - Google Patents
一种碳纤维增强树脂基复合材料表面金镀层的制备方法 Download PDFInfo
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Abstract
本发明涉及一种碳纤维增强树脂基复合材料表面金镀层的制备方法，特别涉及电修饰活性点辅助作用下的碳纤维增强树脂基复合材料表面金镀层的制备方法，该方法应用于航天器星载反射面天线、波导阵列天线、喇叭阵列天线表面高精度金镀层，属于表面工程技术领域。本发明能够在碳纤维增强氰酸脂复合材料表面制备外观均匀、可承受‑196℃～120℃高低温冲击100次、电阻率≤0.05μΩ*m的金镀层。
Description
技术领域
本发明涉及一种碳纤维增强树脂基复合材料表面金镀层的制备方法，特别涉及电修饰活性点辅助作用下的碳纤维增强树脂基复合材料表面金镀层的制备方法，该方法应用于航天器星载反射面天线、波导阵列天线、喇叭阵列天线表面高精度金镀层，属于表面工程技术领域。
背景技术
碳纤维增强树脂基复合材料具有密度低、热膨胀系数低、比强度/比刚度高等优点，在航天器星载反射面天线、波导阵列天线、喇叭阵列天线等结构产品中具有广泛的应用前景。
航天器星载反射面天线、波导阵列天线、喇叭阵列天线等为满足电磁波传输功能需求，对其表面的电性能提出了较高的要求，尤其是高频天线，要求表面电阻率尽可能的低。碳纤维增强树脂基复合材料由于树脂的存在，导致其表面电性能较差，无法满足航天器星载天线电磁波传输的功能要求，需在其表面制备电性能优异的金属膜层。
碳纤维增强树脂基复合材料由于表面化学活性较低，导致金属膜层沉积过程中无法与基体材料之间形成有效的化学结合，因此碳纤维增强树脂基复合材料表面金属膜层的结合力较金属基体材料的差。此外，碳纤维增强树脂基复合材料的热膨胀系数较低，而金属膜层的热膨胀系数较大，因此导致两者之间在受热的应用工况下因热膨胀系数的不同而产生较大的内应力，从而引发金属膜层起皮、起泡、脱落等一系列质量问题。航天器星载天线随着卫星的运动将周期性地接受太阳和地球等形体的热辐射，往往要经历温度较大范围的变化，并在结构中产生很大的温度梯度。因此，为满足航天器星载天线在轨应用可靠性要求，对碳纤维增强树脂基复合材料基体表面金属膜层的结合力提出了较高的要求，尤其是需满足真空、高低温交变条件应用需求。由于碳纤维增强树脂基复合材料的材料特点，采用常规方法在其表面制备的金属膜层经高低温交变冲击测试后易出现起皮、起泡、脱落等结合力问题，严重制约了其应用。
发明内容
本发明的技术解决问题是：克服现有技术的不足，提供一种碳纤维增强树脂基复合材料表面金镀层的制备方法，该方法制备的金镀层表观颜色均匀、结合力可承受-196℃～120℃高低温冲击100次，该方法引入电化学沉积修饰活性点的思路，通过化学刻蚀吸附修饰及电化学沉积修饰活性点的协同作用，改善了基体材料界面的化学活性，大幅提高了基体材料与金属膜层之间的结合力。
本发明的目的是通过以下技术方案实现的。
一种碳纤维增强树脂基复合材料表面金镀层的制备方法，该方法是在碳纤维增强氰酸脂复合材料的表面镀金，即该碳纤维增强树脂基复合材料的基体为氰酸脂树脂，具体步骤为：
1)擦拭碳纤维增强树脂基复合材料表面，使碳纤维增强树脂基复合材料表面被水完全润湿且水膜30s内不断；所述碳纤维增强树脂基复合材料中树脂体系为氰酸脂树脂；
2)将步骤1)得到的碳纤维增强树脂基复合材料的表面进行化学粗化，化学粗化溶液配方及操作条件如下：(化学粗化溶液为硫酸和铬酐的混合溶液，硫酸的浓度为650mL/L～750mL/L，铬酐的浓度为150g/L～200g/L)
化学粗化完成后将碳纤维增强树脂基复合材料从溶液中取出；
3)将步骤2)得到的碳纤维增强树脂基复合材料表面上的残留溶液用水清洗；
4)将步骤3)得到的碳纤维增强树脂基复合材料表面进行活性点的电化学修饰，活性点电化学修饰的溶液配方及操作条件如下：(活性点电化学修饰的溶液为氯化钯和盐酸的混合溶液)
活性点电化学修饰完成后将碳纤维增强树脂基复合材料从溶液中取出；
5)将步骤4)得到的碳纤维增强树脂基复合材料表面上的残留溶液用水清洗；
6)将步骤5)得到的碳纤维增强树脂基复合材料的表面进行敏化处理，敏化处理溶液配方及操作条件如下：(敏化处理溶液为氯化亚锡和盐酸的混合溶液)
敏化处理完成后将碳纤维增强树脂基复合材料从溶液中取出；
7)将步骤6)得到的碳纤维增强树脂基复合材料表面上的残留溶液用水清洗；
8)将步骤7)得到的碳纤维增强树脂基复合材料的表面进行活化处理，活化处理的溶液配方及操作条件如下：(活化处理的溶液为氯化钯和盐酸的混合溶液)
活化处理完成后将碳纤维增强树脂基复合材料从溶液中取出；
9)将步骤8)得到的碳纤维增强树脂基复合材料表面上的残留溶液用水清洗；
10)将步骤9)得到的碳纤维增强树脂基复合材料的表面进行还原处理，还原处理的配方及操作条件如下：
次亚磷酸钠 15g/L～25g/L
溶液温度 室温
持续时间 10min～20min
还原处理完成后将碳纤维增强树脂基复合材料从溶液中取出；
11)将步骤10)得到的碳纤维增强树脂基复合材料表面上的残留溶液用水清洗；
12)将步骤11)得到的碳纤维增强树脂基复合材料的表面进行化学镀镍，化学镀镍溶液配方及操作条件如下：(化学镀镍溶液为硫酸镍、次亚磷酸钠、柠檬酸钠、乙酸钠和硫酸镁的混合溶液)
化学镀镍完成后将碳纤维增强树脂基复合材料从溶液中取出；
13)将步骤12)得到的碳纤维增强树脂基复合材料表面上的残留溶液用水清洗；
14)将步骤13)得到的碳纤维增强树脂基复合材料的表面进行镀金，镀金的溶液配方及操作条件如下：(镀金的溶液为金、软纯金K24HF开缸剂、软纯金K24HF补充剂和软纯金K24HF添加剂的混合溶液)
镀金完成后将碳纤维增强树脂基复合材料从溶液中取出；
15)将步骤14)得到的碳纤维增强树脂基复合材料的表面上的残留溶液用水清洗，清洗完成后将碳纤维增强树脂基复合材料的表面吹干，最后得到镀有金层的碳纤维增强树脂基复合材料。
镀金完成后严禁裸手接触镀层，以免留下手印。
有益效果
(1)本发明突破现有传统的化学刻蚀吸附活性点方式，采用化学刻蚀吸附及电化学修饰协同作用的方式，极大的改善了碳纤维增强树脂基复合材料基体界面的表面活性，有效增加了活性点的数量；
(2)本发明采用活性点电化学修饰的方式，巧妙的利用碳纤维增强树脂基复合材料中碳纤维的导电性，采用电化学的方式实现贵金属Pd活性点的沉积，一方面能够大幅增加基材界面处活性点的数量，另一方面可以提高活性点与基材的结合强度；
(3)本发明的化学刻蚀吸附及电化学修饰协同作用的方式，化学刻蚀主要作用于基体材料中树脂成分，能够极大的增加树脂成分的比表面积，从而实现活性点的有效吸附，但基体材料中局部树脂含量较少的区域，化学刻蚀对该区域作用效果较差，导致活性点难以在该区域进行吸附，但该区域导电性较高，利用电化学修饰的方式可以有效的提高该区域活性点的数量，从而实现与化学刻蚀吸附活性点的协同作用；
(4)本发明在碳纤维增强树脂基复合材料基体界面处修饰的活性点的数量较多，在后续化学镀镍过程中可以大幅增加金属膜层与基体界面的结合点，从而提高碳纤维增强树脂基复合材料基体界面表面金属膜层的结合力；
(5)本发明能够在碳纤维增强氰酸脂复合材料表面制备外观均匀、可承受-196℃～120℃高低温冲击100次、电阻率≤0.05μΩ*m的金镀层。
附图说明
图1为实施例1制备的金镀层的截面微观形貌图。
具体实施方式
以下结合实施例对本发明作进一步说明。
实施例
碳纤维增强树脂基复合材料表面金镀层的制备方法，该方法是在碳纤维增强氰酸脂复合材料表面制备金镀层，具体步骤为：
1)擦拭碳纤维增强树脂基复合材料表面，使碳纤维增强树脂基复合材料表面被水完全润湿且水膜30s内不断；
2)将步骤1)得到的碳纤维增强树脂基复合材料的表面进行化学粗化，化学粗化溶液配方及操作条件如下：
化学粗化完成后将碳纤维增强树脂基复合材料从溶液中取出；
3)将步骤2)得到的碳纤维增强树脂基复合材料表面上的残留溶液用水清洗；
4)将步骤3)得到的碳纤维增强树脂基复合材料表面进行活性点的电化学修饰，活性点电化学修饰的溶液配方及操作条件如下：
活性点电化学修饰完成后将碳纤维增强树脂基复合材料从溶液中取出；
5)将步骤4)得到的碳纤维增强树脂基复合材料表面上的残留溶液用水清洗；
6)将步骤5)得到的碳纤维增强树脂基复合材料的表面进行敏化处理，敏化处理溶液配方及操作条件如下：
敏化处理完成后将碳纤维增强树脂基复合材料从溶液中取出；
7)将步骤6)得到的碳纤维增强树脂基复合材料表面上的残留溶液用水清洗；
8)将步骤7)得到的碳纤维增强树脂基复合材料的表面进行活化处理，活化处理的溶液配方及操作条件如下：
活化处理完成后将碳纤维增强树脂基复合材料从溶液中取出；
9)将步骤8)得到的碳纤维增强树脂基复合材料表面上的残留溶液用水清洗；
10)将步骤9)得到的碳纤维增强树脂基复合材料的表面进行还原处理，还原处理的配方及操作条件如下：
次亚磷酸钠 20g/L
溶液温度 室温
持续时间 15min
还原处理完成后将碳纤维增强树脂基复合材料从溶液中取出；
11)将步骤10)得到的碳纤维增强树脂基复合材料表面上的残留溶液用水清洗；
12)将步骤11)得到的碳纤维增强树脂基复合材料的表面进行化学镀镍，化学镀镍溶液配方及操作条件如下：
化学镀镍完成后将碳纤维增强树脂基复合材料从溶液中取出；
13)将步骤12)得到的碳纤维增强树脂基复合材料表面上的残留溶液用水清洗；
14)将步骤13)得到的碳纤维增强树脂基复合材料的表面进行镀金，镀金的溶液配方及操作条件如下：
镀金完成后将碳纤维增强树脂基复合材料从溶液中取出；
15)将步骤14)得到的碳纤维增强树脂基复合材料的表面上的残留溶液用水清洗，清洗完成后将碳纤维增强树脂基复合材料的表面吹干，最后得到镀有金层的碳纤维增强树脂基复合材料。
将得到的镀有金层的碳纤维增强树脂基复合材料采用VK200X激光3D显微镜进行截面微观形貌测试，结果如图1所示；根据QJ479《金属镀覆层结合强度试验方法》中划格法规定，采用英国Elcometer附着力测试仪测定镀层结合力为1级；根据GJB 2502.8《航天器用热控涂层试验方法：第8部分：热循环试验》规定，在120℃保温20min后投入液氮中直至无起泡产生为止，如此循环100次后，按照GJB1941《金电镀层规范》测试金镀层外观，测试后金镀层无起皮、起泡、裂纹以及脱落等现象。通过英国Elcometer附着力测试仪划格法测试、高低温冲击的测试，可知所得金镀层满足QJ479《金属镀覆层结合强度试验方法》中划格法、以及GJB 2502.8《航天器用热控涂层试验方法：第8部分：热循环试验》对金镀层结合力的要求。
本发明未详细说明部分属本领域技术人员公知常识。
Claims (3)
1.一种碳纤维增强树脂基复合材料表面金镀层的制备方法，其特征在于该方法的步骤为：
1)擦拭碳纤维增强树脂基复合材料表面，使碳纤维增强树脂基复合材料表面被水完全润湿且水膜30s内不断；
2)将步骤1)得到的碳纤维增强树脂基复合材料的表面进行化学粗化；化学粗化完成后将碳纤维增强树脂基复合材料从溶液中取出；
3)将步骤2)得到的碳纤维增强树脂基复合材料表面上的残留溶液用水清洗；
4)将步骤3)得到的碳纤维增强树脂基复合材料表面进行活性点的电化学修饰；活性点电化学修饰完成后将碳纤维增强树脂基复合材料从溶液中取出；
5)将步骤4)得到的碳纤维增强树脂基复合材料表面上的残留溶液用水清洗；
6)将步骤5)得到的碳纤维增强树脂基复合材料的表面进行敏化处理；敏化处理完成后将碳纤维增强树脂基复合材料从溶液中取出；
7)将步骤6)得到的碳纤维增强树脂基复合材料表面上的残留溶液用水清洗；
8)将步骤7)得到的碳纤维增强树脂基复合材料的表面进行活化处理，活化处理完成后将碳纤维增强树脂基复合材料从溶液中取出；
9)将步骤8)得到的碳纤维增强树脂基复合材料表面上的残留溶液用水清洗；
10)将步骤9)得到的碳纤维增强树脂基复合材料的表面进行还原处理，还原处理完成后将碳纤维增强树脂基复合材料从溶液中取出；
11)将步骤10)得到的碳纤维增强树脂基复合材料表面上的残留溶液用水清洗；
12)将步骤11)得到的碳纤维增强树脂基复合材料的表面进行化学镀镍，化学镀镍完成后将碳纤维增强树脂基复合材料从溶液中取出；
13)将步骤12)得到的碳纤维增强树脂基复合材料表面上的残留溶液用水清洗；
14)将步骤13)得到的碳纤维增强树脂基复合材料的表面进行镀金，镀金完成后将碳纤维增强树脂基复合材料从溶液中取出；
15)将步骤14)得到的碳纤维增强树脂基复合材料的表面上的残留溶液用水清洗，清洗完成后将碳纤维增强树脂基复合材料的表面吹干，最后得到镀有金层的碳纤维增强树脂基复合材料；
所述的步骤2)中，化学粗化溶液为硫酸和铬酐的混合溶液，硫酸的浓度为650mL/L～750mL/L，铬酐的浓度为150g/L～200g/L，化学粗化中溶液的温度为80℃～90℃，化学粗化时间为5-6h；
所述的步骤4)中，活性点电化学修饰的溶液为氯化钯和盐酸的混合溶液，氯化钯的浓度为3.5g/L～4.5g/L，盐酸的浓度为10mL/L～20mL/L，活性点电化学修饰时的溶液温度为室温，阴极电流密度为8A/dm2～12A/dm2，时间为30min～40min，阳极板为不锈钢板；
所述的步骤6)中，敏化处理溶液为氯化亚锡和盐酸的混合溶液，氯化亚锡的浓度为35g/L～45g/L，盐酸的浓度为80mL/L～120mL/L，温度为室温，时间为30min～40min；
所述的步骤8)中，活化处理的溶液为氯化钯和盐酸的混合溶液，氯化钯的浓度为0.3g/L～0.5g/L，盐酸的浓度为10mL/L～20mL/L，温度为室温，时间为10min～20min；
所述的步骤10)中，还原处理的溶液为次亚磷酸钠溶液，次亚磷酸钠的浓度为15g/L～25g/L，温度为室温，时间为10min～20min；
所述的步骤12)中，化学镀镍溶液为硫酸镍、次亚磷酸钠、柠檬酸钠、乙酸钠和硫酸镁的混合溶液，其中，硫酸镍的浓度为30g/L～35g/L，次亚磷酸钠的浓度为12g/L～15g/L，柠檬酸钠的浓度为8-10g/L，乙酸钠的浓度为8g/L～10g/L，硫酸镁的浓度为16g/L～20g/L，pH值为4.2～4.6，温度为70℃～85℃，时间为40min～50min；
所述的步骤14)中，镀金的溶液为金、软纯金K24 HF开缸剂、软纯金K24 HF补充剂和软纯金K24 HF添加剂的混合溶液，温度为65℃～80℃，pH值为5.5～7.0，阴极电流密度为0.3A/dm2～0.5A/dm2，时间为10min～15min，阳极板为金板。
2.根据权利要求1所述的一种碳纤维增强树脂基复合材料表面金镀层的制备方法，其特征在于：所述的碳纤维增强树脂基复合材料中的基体为氰酸脂树脂。
3.根据权利要求1所述的一种碳纤维增强树脂基复合材料表面金镀层的制备方法，其特征在于：镀金的溶液中金的浓度为5g/L～12g/L，软纯金K24HF开缸剂的浓度为350mL/L～450mL/L，软纯金K24 HF补充剂的浓度为40mL/L～50mL/L，软纯金K24 HF添加剂的浓度为4.5mL/L～5.5mL/L。
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