CN111822307A - 铝合金蜂窝板 - Google Patents

铝合金蜂窝板 Download PDF

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CN111822307A
CN111822307A CN202010727113.7A CN202010727113A CN111822307A CN 111822307 A CN111822307 A CN 111822307A CN 202010727113 A CN202010727113 A CN 202010727113A CN 111822307 A CN111822307 A CN 111822307A
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aluminum alloy
coating
corrosion inhibitor
coupling agent
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王运雷
曹川川
张�杰
姜中涛
董井忍
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Chongqing University of Arts and Sciences
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Abstract

本发明公开了一种铝合金蜂窝板，包括铝合金面板和设置于铝合金面板之间的铝制蜂窝芯夹层，所述铝制蜂窝芯夹层与铝合金面板之间通过粘接层固定粘接，所述粘接层由三维多孔铝合金纤维浸渍粘接剂形成，所述三维多孔铝合金纤维具有交联互穿网络的多孔结构，所述铝合金面板表面为微观网状粗糙结构，所述微观网状粗糙结构为交联互穿网络结构，在微观网状粗糙结构上涂覆一层具有多重修复功能的涂层；采用特殊的粘接层结合蜂窝夹层结构不仅增强铝合金板材的强度，且层间结构强度更高，增强抗压能力且重量轻，更重要的是，对铝合金板材表面进行特殊处理，提高铝合金板材的抗腐蚀性，达到长效性防护的目的。

Description

铝合金蜂窝板
技术领域
本发明涉及涂层材料，具体涉及一种具有多重修复功能的铝合金蜂窝板。
背景技术
目前在机械产品生产领域中，使用铝合金作为原材料进行产品生产是越来越常见的，但是铝合金作为材料进行产品制造时，铝合金存在强度不足的问题，在收到强压时很容易变形，并且容易被腐蚀，进而造成产品的寿命不长。因此，铝合金产品抗压能力不强且耐腐蚀性不足的问题是亟待解决的问题。金属的涂层防腐是防止金属腐蚀的最有效的方法之一，而防腐涂层在使用过程中，会受到环境因素的影响，在涂层内部产生缺陷，例如固化过程中的有机溶剂挥发、高分子聚合物反应过程的应力产生、不合适的表面预处理工艺等。这些表面微观缺陷会可供腐蚀介质渗透进入的通道，渗入的介质逐渐导致涂层的失效，影响涂层寿命加速金属表面涂层的剥离，进一步加剧金属的腐蚀。而自修复涂层的主要修复机制可分为自主型和非自主型两类。其中自主型分为成膜物质型和缓蚀剂型。而非自主型则分为温度响应和光响应刺激等。现有的大多数自修复涂层都是基于单一的修复机制实现对涂层缺陷的修复。对于自主型修复机制，其主要局限性在于当成膜物质和缓蚀剂耗尽时，涂层难以对金属基材提供长效的防护。非自主型修复机制能够依靠涂层自身物理或化学性质，在常见的外界刺激下，修复涂层的缺陷与屏蔽作用。
发明内容
有鉴于此，本发明的目的在于提供一种铝合金蜂窝板，采用蜂窝结构增强铝合金板的强度却具有减重的目的，更重要的是，在铝合金表面进行处理以解决铝合金的抗腐蚀问题。
本发明的铝合金蜂窝板，包括铝合金面板和设置于铝合金面板之间的铝制蜂窝芯夹层，所述铝制蜂窝芯夹层与铝合金面板之间通过粘接层固定粘接，所述粘接层由三维多孔铝合金纤维浸渍粘接剂形成，所述三维多孔铝合金纤维具有交联互穿网络的多孔结构，所述铝合金面板表面为微观网状粗糙结构，所述微观网状粗糙结构为交联互穿网络结构，在微观网状粗糙结构上涂覆一层具有多重修复功能的涂层，所述涂层原料按重量份包括以下组分：环氧树脂形状记忆成膜物50-100份、碳纤维10-20份、3-氨丙基三甲氧基硅烷5-15份、正硅酸乙酯5-15份、双酚A25-35份、苯胺10-15份、多聚甲醛15-20份、微胶囊40-50份、氧化石墨烯5-10份、聚苯胺5-10份、白云母5-10份、纳米级多孔二氧化硅1-3份、偶联剂2-6份，所述微胶囊为三层包覆结构，其内层为聚脲甲醛包覆的甲基丙烯酸缩水甘油醚，在内层上沉积一层异佛尔酮二异氰酸酯、偶氮聚酯、聚异丁烯(光致引发剂)混合物形成包覆中间层，在中间层上通过溶剂挥发法形成沉积一层石蜡包覆外层；
进一步，涂层原料按重量份包括以下组分：环氧树脂形状记忆成膜物75份、碳纤维15份、3-氨丙基三甲氧基硅烷10份、正硅酸乙酯10份、双酚A30份、苯胺13份、多聚甲醛17份、微胶囊45份、氧化石墨烯7份、聚苯胺7份、白云母7份、纳米级多孔二氧化硅2份、偶联剂4份；
进一步，所述偶联剂为乙烯基三乙氧基硅烷与钛酸酯的混合物；
进一步，所述偶联剂中乙烯基三乙氧基硅烷与太酸酯的质量比为2：1；
进一步，所述纳米级多孔二氧化硅通过低压渗透法负载有复合缓蚀剂；
进一步，所述复合缓蚀剂为咪唑、1，2，4三氮唑和苯并三氮唑的混合物；
进一步，所述复合缓蚀剂的负载量为二氧化硅的60-70％重量百分比；
进一步，所述复合缓蚀剂中咪唑、1，2，4三氮唑和苯并三氮唑的重量比为3：2：1。
本发明的有益效果：本发明的铝铝合金蜂窝板，采用特殊的粘接层结合蜂窝夹层结构不仅增强铝合金板材的强度，且层间结构强度更高，增强抗压能力且重量轻，更重要的是，对铝合金板材表面进行特殊处理，提高铝合金板材的抗腐蚀性，达到长效性防护的目的。
附图说明
图1为本发明的结构示意图。
具体实施方式
本实施例的铝合金蜂窝板，包括铝合金面板1和设置于铝合金面板1之间的铝制蜂窝芯夹层2，所述铝制蜂窝芯夹层2与铝合金面板1之间通过粘接层固定粘接，所述粘接层由三维多孔铝合金纤维浸渍粘接剂形成，所述三维多孔铝合金纤维具有交联互穿网络的多孔结构，所述铝合金面板1表面为微观网状粗糙结构，所述微观网状粗糙结构为交联互穿网络结构，在微观网状粗糙结构上涂覆一层具有多重修复功能的涂层，所述涂层原料按重量份包括以下组分：环氧树脂形状记忆成膜物50-100份、碳纤维10-20份、3-氨丙基三甲氧基硅烷5-15份、正硅酸乙酯5-15份、双酚A25-35份、苯胺10-15份、多聚甲醛15-20份、微胶囊40-50份、氧化石墨烯5-10份、聚苯胺5-10份、白云母5-10份、纳米级多孔二氧化硅1-3份、偶联剂2-6份，所述微胶囊为三层包覆结构，其内层为聚脲甲醛包覆的甲基丙烯酸缩水甘油醚，在内层上沉积一层异佛尔酮二异氰酸酯、偶氮聚酯、聚异丁烯(光致引发剂)混合物形成包覆中间层，在中间层上通过溶剂挥发法形成沉积一层石蜡包覆外层；通过三维多孔铝合金纤维浸渍粘接剂用于蜂窝夹层与面板的连接，铝合金纤维的特殊结构可提高粘接强度，并提高层间结构的强度，铝合金面板1表面的特殊微观网状粗糙结构与特定的表面涂层结合，可增强表面涂层与铝合金面板1之间的界面强度，提高涂层的附着力，通过结合了自主和非自主修复机制多方面互补提升涂层的长效防护能力，实现对铝合金基体进行长效性防护。本发明采用的涂层材料，不仅可以修复涂层的防腐性能和屏蔽性能，还可对涂层机械强度，附着性能以及表面性质进行功能性的多重修复。其中，环氧树脂形状记忆成膜物采用环氧树脂和环氧树脂固化利用现有方法制备获得，采用碳纤维对环氧树脂增韧并结合聚苯胺、白云母和纳米级多孔二氧化硅提高涂层的防腐蚀性能，苯胺插入白云母层间，并在白云母层间发生氧化聚合，不仅耐蚀性高，且热稳定性好；利用3-氨丙基三甲氧基硅烷中的氨基与环氧树脂发生开环交联反应，利用3-氨丙基三甲氧基硅烷和正硅酸乙酯的协同配合作用，进一步他提高涂层的硬度、耐热性和增水性；氧化石墨烯和聚苯胺共同作用，且采用采用原位聚合法使聚苯胺包裹氧化石墨烯后再加入到涂层涂料中使用，可在涂料均匀分散，有效减缓甚至阻碍腐蚀介质渗入涂层内部，提高涂层的防腐性；利用双酚A、苯胺和多聚甲醛经过开环聚合后能够形成交联网络，从而赋予涂层阻隔腐蚀介质的能力，提供良好的屏蔽作用，确保涂层与铝合金面间的黏附力，良好的附着力使得涂层在腐蚀防护过程中不易剥落。对于微胶囊，采用多层结构，且不需要催化剂，采用以上自修复试剂为芯材的微胶囊，在微胶囊破裂并从中释放之后达到自修复的目的。异佛尔酮二异氰酸酯是一种分子式中含有两个－NCO基团的化合物，在水分子或胺类物质存在的条件下可以与之反应，并最终生成高分子聚合物；通过聚异丁烯吸收的长波紫外线使偶氮聚酯从固态向液态的转变，从而使得偶氮聚酯中的破损位点可在光照下实现自我修复，且光照产生的热量会触发涂料的形状记忆效应使涂层破损区域的形状恢复到原始状态。
本发明的涂层材料，利用环氧树脂形状记忆成膜物与微胶囊以及其他助剂的辅助作用，涂层的超疏水能力和屏蔽性均得到了很好的修复，且在户外暴晒环境下，该涂层可利用太阳光短暂照射产生的热量自发的完成对涂层破损的形状记忆自修复过程。
本实施例中，涂层原料按重量份包括以下组分：环氧树脂形状记忆成膜物75份、碳纤维15份、3-氨丙基三甲氧基硅烷10份、正硅酸乙酯10份、双酚A30份、苯胺13份、多聚甲醛17份、微胶囊45份、氧化石墨烯7份、聚苯胺7份、白云母7份、纳米级多孔二氧化硅2份、偶联剂4份；为优选实施例。
本实施例中，所述偶联剂为乙烯基三乙氧基硅烷与钛酸酯的混合物；所述偶联剂中乙烯基三乙氧基硅烷与太酸酯的质量比为2：1；通过钛酸酯分子间的作用力与涂层结合，乙烯基三乙氧基硅烷与涂层的化学键结合，提高涂层的附着力和内聚力。
本实施例中，所述纳米级多孔二氧化硅通过低压渗透法负载有复合缓蚀剂；纳米级多孔二氧化硅既与聚苯胺、白云母、环氧树脂配合作为封闭剂使用，又利用其多孔结构负载复合缓蚀剂。微胶囊和负载又复合缓蚀剂的纳米级多孔二氧化硅共同作用，使涂层能够对自身内部和外部损伤进行修复，延长涂层的使用寿命，实现对铝合金基体进行长效性防护，避免缓释剂释放完毕而导致的防腐能力低下甚至失去防腐能力。
本实施例中，所述复合缓蚀剂为咪唑、1，2，4三氮唑和苯并三氮唑的混合物；所述复合缓蚀剂的负载量为二氧化硅的60-70％重量百分比；所述复合缓蚀剂中咪唑、1，2，4三氮唑和苯并三氮唑的重量比为3：2：1。
实施例一
本实施例的铝合金蜂窝板，原料按重量份包括以下组分：环氧树脂形状记忆成膜物50份、碳纤维10份、3-氨丙基三甲氧基硅烷5份、正硅酸乙酯5份、双酚A25份、苯胺10份、多聚甲醛15份、微胶囊40份、氧化石墨烯5份、聚苯胺5份、白云母5份、纳米级多孔二氧化硅1份、偶联剂2份。
本实施例中，所述偶联剂为乙烯基三乙氧基硅烷与钛酸酯的混合物；所述偶联剂中乙烯基三乙氧基硅烷与太酸酯的质量比为2：1；所述纳米级多孔二氧化硅通过低压渗透法负载有复合缓蚀剂；所述复合缓蚀剂为咪唑、1，2，4三氮唑和苯并三氮唑的混合物；所述复合缓蚀剂的负载量为二氧化硅的60％重量百分比；所述复合缓蚀剂中咪唑、1，2，4三氮唑和苯并三氮唑的重量比为3：2：1。
实施例二
本实施例的铝合金蜂窝板，原料按重量份包括以下组分：环氧树脂形状记忆成膜物100份、碳纤维20份、3-氨丙基三甲氧基硅烷15份、正硅酸乙酯15份、双酚A35份、苯胺15份、多聚甲醛20份、微胶囊50份、氧化石墨烯10份、聚苯胺10份、白云母10份、纳米级多孔二氧化硅3份、偶联剂6份。
本实施例中，所述偶联剂为乙烯基三乙氧基硅烷与钛酸酯的混合物；所述偶联剂中乙烯基三乙氧基硅烷与太酸酯的质量比为2：1；所述纳米级多孔二氧化硅通过低压渗透法负载有复合缓蚀剂；所述复合缓蚀剂为咪唑、1，2，4三氮唑和苯并三氮唑的混合物；所述复合缓蚀剂的负载量为二氧化硅的70％重量百分比；所述复合缓蚀剂中咪唑、1，2，4三氮唑和苯并三氮唑的重量比为3：2：1。
实施例三
本实施例的铝合金蜂窝板，原料按重量份包括以下组分：环氧树脂形状记忆成膜物50份、碳纤维20份、3-氨丙基三甲氧基硅烷5份、正硅酸乙酯15份、双酚A25份、苯胺15份、多聚甲醛15份、微胶囊50份、氧化石墨烯5份、聚苯胺10份、白云母5份、纳米级多孔二氧化硅3份、偶联剂2份。
本实施例中，所述偶联剂为乙烯基三乙氧基硅烷与钛酸酯的混合物；所述偶联剂中乙烯基三乙氧基硅烷与太酸酯的质量比为2：1；所述纳米级多孔二氧化硅通过低压渗透法负载有复合缓蚀剂；所述复合缓蚀剂为咪唑、1，2，4三氮唑和苯并三氮唑的混合物；所述复合缓蚀剂的负载量为二氧化硅的65％重量百分比；所述复合缓蚀剂中咪唑、1，2，4三氮唑和苯并三氮唑的重量比为3：2：1。
实施例四
本实施例的铝合金蜂窝板，原料按重量份包括以下组分：环氧树脂形状记忆成膜物100份、碳纤维10份、3-氨丙基三甲氧基硅烷15份、正硅酸乙酯5份、双酚A35份、苯胺10份、多聚甲醛20份、微胶囊40份、氧化石墨烯10份、聚苯胺5份、白云母10份、纳米级多孔二氧化硅1份、偶联剂6份。
本实施例中，所述偶联剂为乙烯基三乙氧基硅烷与钛酸酯的混合物；所述偶联剂中乙烯基三乙氧基硅烷与太酸酯的质量比为2：1；所述纳米级多孔二氧化硅通过低压渗透法负载有复合缓蚀剂；所述复合缓蚀剂为咪唑、1，2，4三氮唑和苯并三氮唑的混合物；所述复合缓蚀剂的负载量为二氧化硅的68％重量百分比；所述复合缓蚀剂中咪唑、1，2，4三氮唑和苯并三氮唑的重量比为3：2：1。
实施例五
本实施例的铝合金蜂窝板，原料按重量份包括以下组分：环氧树脂形状记忆成膜物80份、碳纤维11份、3-氨丙基三甲氧基硅烷13份、正硅酸乙酯10份、双酚A32份、苯胺13份、多聚甲醛20份、微胶囊45份、氧化石墨烯6份、聚苯胺10份、白云母7份、纳米级多孔二氧化硅1份、偶联剂5份。
本实施例中，所述偶联剂为乙烯基三乙氧基硅烷与钛酸酯的混合物；所述偶联剂中乙烯基三乙氧基硅烷与太酸酯的质量比为2：1；所述纳米级多孔二氧化硅通过低压渗透法负载有复合缓蚀剂；所述复合缓蚀剂为咪唑、1，2，4三氮唑和苯并三氮唑的混合物；所述复合缓蚀剂的负载量为二氧化硅的62％重量百分比；所述复合缓蚀剂中咪唑、1，2，4三氮唑和苯并三氮唑的重量比为3：2：1。
实施例六
本实施例的铝合金蜂窝板，原料按重量份包括以下组分：环氧树脂形状记忆成膜物75份、碳纤维15份、3-氨丙基三甲氧基硅烷10份、正硅酸乙酯10份、双酚A30份、苯胺13份、多聚甲醛17份、微胶囊45份、氧化石墨烯7份、聚苯胺7份、白云母7份、纳米级多孔二氧化硅2份、偶联剂4份。
本实施例中，所述偶联剂为乙烯基三乙氧基硅烷与钛酸酯的混合物；所述偶联剂中乙烯基三乙氧基硅烷与太酸酯的质量比为2：1；所述纳米级多孔二氧化硅通过低压渗透法负载有复合缓蚀剂；所述复合缓蚀剂为咪唑、1，2，4三氮唑和苯并三氮唑的混合物；所述复合缓蚀剂的负载量为二氧化硅的65％重量百分比；所述复合缓蚀剂中咪唑、1，2，4三氮唑和苯并三氮唑的重量比为3：2：1。利用上述实施例的涂层材料，采用现有技术方法处理铝合金片材，将实施例一的涂料用于测试：
1、将铝合金片材对折弯曲70度，用粘性胶带剥离弯曲部分5次，在X20放大镜下检测剥离程度，结果无裂纹。
2、将铝合金片材在沸水中浸泡2小时，在室温下放置24小时后折弯曲70度，用粘性胶带剥离弯曲部分5次，在X20放大镜下检测剥离程度，结果无裂纹。
3、将铝合金片材切开，用浓度为5％的氯化钠溶液喷洒400小时，无鼓泡现象。
4、将样品置于NaCl溶液(3.5wt.％，静态，18天)、NaCl溶液(3.5
wt.％，动态，50小时)及中性盐雾(48小时)环境中测试样品在不同环境中的耐腐蚀稳定性。实验结束后对样品表面的润湿性、微观形貌、表面化学组成成分观察分析。结果表明，样品浸泡在静态的NaCl溶液(3.5wt.％)中18天后，表面的润湿性、微观形貌及化学组成成分均未出现太大的变化；在流动NaCl(3.5wt.％)溶液中，样品的表面润湿性变化加快；并且，随着流速的增加，腐蚀导致的接触角下降、表面形貌变化、表面含氧量增加都大大加快。铝合金表面的原接触角为169.0±2.0°，滚动角为3.8±0.7°)流速为0.5m/s时，50小时后，接触角下降至167.2±1.5°；1.0m/s，下降至165.2±1.4°；2m/s，下降至161.3±1.9°。暴露在中性盐雾环境中48小时后，制备的超疏水样品接触角下降至164.9±2.0°；样品在中性盐雾环境中存储48h后，观察样品表面的润湿性、微观形貌及化学组成成分的变化，结果表明样品能够很好的抵挡自身所处环境中腐蚀介质的侵入，表面具有很好的耐腐蚀稳定性。
最后说明的是，以上实施例仅用以说明本发明的技术方案而非限制，尽管参照较佳实施例对本发明进行了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的宗旨和范围，其均应涵盖在本发明的权利要求范围当中。

Claims (8)

1.一种铝合金蜂窝板，其特征在于：包括铝合金面板和设置于铝合金面板之间的铝制蜂窝芯夹层，所述铝制蜂窝芯夹层与铝合金面板之间通过粘接层固定粘接，所述粘接层由三维多孔铝合金纤维浸渍粘接剂形成，所述三维多孔铝合金纤维具有交联互穿网络的多孔结构，所述铝合金面板表面为微观网状粗糙结构，所述微观网状粗糙结构为交联互穿网络结构，在微观网状粗糙结构上涂覆一层具有多重修复功能的涂层，所述涂层原料按重量份包括以下组分：环氧树脂形状记忆成膜物50-100份、碳纤维10-20份、3-氨丙基三甲氧基硅烷5-15份、正硅酸乙酯5-15份、双酚A25-35份、苯胺10-15份、多聚甲醛15-20份、微胶囊40-50份、氧化石墨烯5-10份、聚苯胺5-10份、白云母5-10份、纳米级多孔二氧化硅1-3份、偶联剂2-6份，所述微胶囊为三层包覆结构，其内层为聚脲甲醛包覆的甲基丙烯酸缩水甘油醚，在内层上沉积一层异佛尔酮二异氰酸酯、偶氮聚酯、聚异丁烯混合物形成包覆中间层，在中间层上通过溶剂挥发法形成沉积一层石蜡包覆外层。
2.根据权利要求1所述的铝合金蜂窝板，其特征在于：所述涂层原料按重量份包括以下组分：环氧树脂形状记忆成膜物75份、碳纤维15份、3-氨丙基三甲氧基硅烷10份、正硅酸乙酯10份、双酚A30份、苯胺13份、多聚甲醛17份、微胶囊45份、氧化石墨烯7份、聚苯胺7份、白云母7份、纳米级多孔二氧化硅2份、偶联剂4份。
3.根据权利要求1所述的铝合金蜂窝板，其特征在于：所述偶联剂为乙烯基三乙氧基硅烷与钛酸酯的混合物。
4.根据权利要求3所述的铝合金蜂窝板，其特征在于：所述偶联剂中乙烯基三乙氧基硅烷与太酸酯的质量比为2：1。
5.根据权利要求4所述的铝合金蜂窝板，其特征在于：所述纳米级多孔二氧化硅通过低压渗透法负载有复合缓蚀剂。
6.根据权利要求5所述的铝合金蜂窝板，其特征在于：所述复合缓蚀剂为咪唑、1，2，4三氮唑和苯并三氮唑的混合物。
7.跟权利要求5所述的铝合金蜂窝板，其特征在于：所述复合缓蚀剂的负载量为二氧化硅的60-70％重量百分比。
8.根据权利要求6所述的铝合金蜂窝板，其特征在于：所述复合缓蚀剂中咪唑、1，2，4三氮唑和苯并三氮唑的重量比为3：2：1。
CN202010727113.7A 2020-07-26 2020-07-26 铝合金蜂窝板 Withdrawn CN111822307A (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113914277A (zh) * 2021-10-19 2022-01-11 中国科学院宁波材料技术与工程研究所 用于修复金属表面损伤的防护涂层、制备方法及复合材料
CN114292426A (zh) * 2021-12-01 2022-04-08 湖南科技大学 超疏水多孔铝合金-环氧树脂防腐复合材料的制备方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113914277A (zh) * 2021-10-19 2022-01-11 中国科学院宁波材料技术与工程研究所 用于修复金属表面损伤的防护涂层、制备方法及复合材料
CN113914277B (zh) * 2021-10-19 2023-11-03 中国科学院宁波材料技术与工程研究所 用于修复金属表面损伤的防护涂层、制备方法及复合材料
CN114292426A (zh) * 2021-12-01 2022-04-08 湖南科技大学 超疏水多孔铝合金-环氧树脂防腐复合材料的制备方法
CN114292426B (zh) * 2021-12-01 2023-02-28 湖南科技大学 超疏水多孔铝合金-环氧树脂防腐复合材料的制备方法

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Application publication date: 20201027