CN102560490A - 铝及铝合金表面防腐处理方法及其制品 - Google Patents

铝及铝合金表面防腐处理方法及其制品 Download PDF

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CN102560490A
CN102560490A CN2010106092210A CN201010609221A CN102560490A CN 102560490 A CN102560490 A CN 102560490A CN 2010106092210 A CN2010106092210 A CN 2010106092210A CN 201010609221 A CN201010609221 A CN 201010609221A CN 102560490 A CN102560490 A CN 102560490A
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aluminum
silane
aluminium
aluminum alloy
alloy surface
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张新倍
陈文荣
蒋焕梧
陈正士
毛盾
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Hongfujin Precision Industry Shenzhen Co Ltd
Hon Hai Precision Industry Co Ltd
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Hongfujin Precision Industry Shenzhen Co Ltd
Hon Hai Precision Industry Co Ltd
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
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    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
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Abstract

本发明提供一种铝及铝合金表面防腐处理方法，包括以下步骤：提供铝基体；对铝基体进行化学除油；采用溶胶-凝胶法于该铝基体上制备铈盐掺杂硅烷杂化膜；通过真空镀膜方法在铈盐掺杂硅烷杂化膜上形成由难熔化合物组成的陶瓷涂层。经上述铝及铝合金表面防腐处理方法所获得的铝制品，包括铝基体、形成于铝基体表面的铈盐掺杂硅烷杂化膜及形成于该铈盐掺杂硅烷杂化膜上的由难熔化合物组成的陶瓷涂层。

Description

铝及铝合金表面防腐处理方法及其制品
技术领域
本发明涉及一种铝及铝合金表面防腐处理方法及其制品。
背景技术
铝合金具有质量轻、散热性能好等优点，在通讯、电子、交通运输、建筑及航天航空等领域应用广泛。在空气中铝合金表面会形成氧化铝保护膜，在一般的大气环境下，铝合金表面的氧化铝膜能够有效地对铝合金基体进行保护，但在含有电解质的湿气中，例如海洋表面大气环境，铝合金表面容易出现点蚀，严重破环铝合金制品的外观，同时导致制品使用寿命缩短。
耐盐雾侵蚀性能是铝合金耐腐蚀性能的一个重要参数，为了提高铝合金的耐盐雾侵蚀性能，通常需要对铝合金表面进行表面成膜处理，常见的处理手段有阳极氧化处理、烤漆等，但这些工艺都存在较大的环境污染问题。而真空镀膜(PVD)技术虽是一种非常环保的镀膜工艺，且可镀制的膜层种类丰富、耐磨性能优异，但铝合金表面通常具有较多的细小凹陷或孔隙，而PVD工艺沉积的膜层通常具有基体表面的仿形结构，且沉积于这些凹陷或空隙内的膜层往往其它区域的要薄，所以盐雾测试中凹陷或空隙区域往往更容易发生点蚀，导致膜层无法有效地防止盐雾的侵蚀，即防腐蚀性能较差。
发明内容
有鉴于此，有必要提供一种可效提高铝及铝合金防腐性能的防腐处理方法。
另外，还有必要提供一种由上述方法制得的铝制品。
一种铝及铝合金表面防腐处理方法，包括以下步骤：
提供铝基体；
对铝基体进行化学除油；
采用溶胶-凝胶法于该铝基体上制备铈盐掺杂硅烷杂化膜；
通过真空镀膜方法在铈盐掺杂硅烷杂化膜上形成由难熔化合物组成的陶瓷涂层。
上述铝及铝合金表面防腐处理方法所获得的铝制品，包括铝基体、形成于铝基体表面的铈盐掺杂硅烷杂化膜及形成于该铈盐掺杂硅烷杂化膜上的由难熔化合物组成的陶瓷涂层。
本发明的铝及铝合金表面防腐处理方法先通过溶胶-凝胶法对铝基体在铝基体制备一层铈盐掺杂硅烷杂化膜，然后于该铈盐掺杂硅烷杂化膜上镀覆耐磨陶瓷涂层。其中该铈盐掺杂硅烷杂化膜一方面将铝基体表面平整化，另一方面铈盐掺杂硅烷杂化膜自身结构致密，阻挡性好，化学稳定性高，与铝基体结合力强，具有良好的防腐功能。再配合外层耐磨的陶瓷涂层，可保护铈盐掺杂硅烷杂化膜不易受到机械损伤。因此，使该铝制品具有良好的抗腐蚀性能。
附图说明
图1为由本发明一实施例的铝及铝合金表面防腐处理方法所制得的铝合金制品的剖视示意图。
图2为由本发明另一实施例的铝及铝合金表面防腐处理方法所制得的铝合金制品的剖视示意图。
主要元件符号说明
铝制品                    10
铝基体                    20
铈盐掺杂硅烷杂化膜        30
陶瓷涂层                  40
氮氧化铝层                41
氧化铝层                  42
氮化铝层                  43
氮氧化铬层                44
具体实施方式
本发明较佳实施例铝及铝合金表面防腐处理方法主要包括如下步骤：
提供铝基体20，该铝基体的材质可为纯铝或铝合金。
对铝基体20进行化学除油。化学除油是将铝基体20浸渍于60-80℃的除油溶液中30-60s，所用除油溶液为含25-30g/L碳酸钠、20-25g/L磷酸三钠(Na3PO4·12H2O)及1-3g/L乳化剂的水溶液，其中所述乳化剂可用商品名为OP-10的乳化剂，其主要组分为烷基酚与环氧乙烷的缩合物。
于经化学除油处理的铝基体20上制备铈盐掺杂硅烷杂化膜30。本实施例采用溶胶-凝胶法制备该铈盐掺杂硅烷杂化膜30，具体如下：将正硅酸乙酯(TEOS)、γ-环氧丙氧丙基三甲基硅烷(GPTMS)、乙醇、硝酸铈及水按质量比为10-20∶30-40∶10-20∶15-30∶2-5混合，搅拌均匀得到混合液。再用乙酸和乙酸钠将pH值调整到3.8-4.2。将混合液密封后放置于30-60℃左右的恒温水浴中水解8-12小时得到硅烷杂化溶胶。于水解好的硅烷杂化溶胶中加入占硅烷杂化溶胶总质量的2％-4％的乙二胺四乙酸(EDTA)，搅拌均匀后得到制膜溶液。然后，通过浸渍或涂抹的方法将所得制膜溶液于铝基体20上涂膜，将涂膜铝基体20于室温下风干，在铝基体20上形成均匀稳定的凝胶层，接着于120-150℃下进行固化，由此可在铝基体表上形成一层致密的铈盐掺杂硅烷杂化膜30。该铈盐掺杂硅烷杂化膜30的厚度大约为0.1-0.4微米。所述TEOS、GPTMS、乙醇、硝酸铈及水的混合比例按质量较佳为10∶20∶10∶15∶2。所述水解时间较佳为10小时。所述水解温度较佳为40℃。所述固化温度较佳为130℃。
对形成有铈盐掺杂硅烷杂化膜30的铝基体20进行真空镀膜处理，以在铈盐掺杂硅烷杂化膜30上形成由难熔化合物组成的陶瓷涂层40。本实施例中，该陶瓷涂层40包括一层氮氧化铝层41、一层氧化铝(Al2O3)层42及一层氮化铝(AlN)层43，该氧化铝层42直接形成于该铈盐掺杂硅烷杂化膜30上，该氮化铝层43形成于该氧化铝层42上，该氮氧化铝层41形成于该氮化铝层43上。
请参阅图2，在另一实施例中，该陶瓷涂层40也可包括一层氮氧化铝层41及一层氮氧化铬层44。该氮氧化铝层41直接形成于该铈盐掺杂硅烷杂化膜30上，该氮氧化铬层44形成于该氮氧化铝层41上。
该真空镀膜处理可采用现有的真空镀膜方法，比如磁控溅射或电弧离子镀，具体工艺本案不再赘述。
请参阅图1，由上述铝及铝合金表面防腐处理方法所获得的铝制品10，包括铝基体20、形成于铝基体20表面的铈盐掺杂硅烷杂化膜30及形成于该铈盐掺杂硅烷杂化膜30上的由难熔化合物组成的陶瓷涂层40。其中该铈盐掺杂硅烷杂化膜30经稀土铈盐掺杂有机硅烷杂化处理形成，该铈盐掺杂硅烷杂化膜30主要由Si、O、C及H五种元素组成，且原子个数比Si∶O∶C∶H＝0.1-2∶2-3∶2-4∶2-8。该铈盐掺杂硅烷杂化膜30的厚度厚度大约为0.1-0.4微米。本实施例中，该陶瓷涂层40包括一层氮氧化铝层41、一层氧化铝(Al2O3)层42及一层氮化铝(AlN)层43，该氧化铝层42直接形成于该铈盐掺杂硅烷杂化膜30上，该氮化铝层43形成于该氧化铝层42上，该氮氧化铝层41形成于该氮化铝层43上。
请参阅图2，在另一实施例中，该陶瓷涂层40包括一层氮氧化铝层41及一层氮氧化铬层44。该氮氧化铝层41直接形成于该铈盐掺杂硅烷杂化膜30上，该氮氧化铬层44形成于该氮氧化铝层41上。
该陶瓷涂层40的总体厚度大约为2-5微米。
对由本发明的防腐处理方法所制备的铝制品10试样进行35℃中性盐雾(NaCl浓度为5％)测试。结果发现，铝制品10试样在72小时后才出现有腐蚀现象，具有良好的防腐性能。
本发明的铝及铝合金表面防腐处理方法先通过溶胶-凝胶法对铝基体20在铝基体20制备一层铈盐掺杂硅烷杂化膜30，然后于该铈盐掺杂硅烷杂化膜30上镀覆耐磨陶瓷涂层40。其中该铈盐掺杂硅烷杂化膜30一方面将铝基体20表面平整化，另一方面铈盐掺杂硅烷杂化膜30自身结构致密，阻挡性好，化学稳定性高，与铝基体20结合力强，具有良好的防腐功能。再配合外层耐磨的陶瓷涂层40，可保护铈盐掺杂硅烷杂化膜30不易受到机械损伤。因此，使该铝制品10具有良好的抗腐蚀性能。

Claims (10)

1.一种铝及铝合金表面防腐处理方法，包括以下步骤：
提供铝基体；
对铝基体进行化学除油；
采用溶胶-凝胶法于该铝基体上制备铈盐掺杂硅烷杂化膜；
通过真空镀膜方法在铈盐掺杂硅烷杂化膜上形成由难熔化合物组成的陶瓷涂层。
2.如权利要求1所述的铝及铝合金表面防腐处理方法，其特征在于：所述溶胶-凝胶法制备该铈盐掺杂硅烷杂化膜的方法包括：将正硅酸乙酯、γ-环氧丙氧丙基三甲基硅烷、乙醇、硝酸铈及水按质量比为10-20∶30-40∶10-20∶15-30∶2-5混合得到混合液；用乙酸和乙酸钠将混合液的pH值调整至3.8-4.2；将混合液密封后于30-60℃下水解8-12小时得到硅烷杂化溶胶；于水解好的硅烷杂化溶胶中加入预定体积的乙二胺四乙酸得到制膜溶液；将该制膜溶液于该铝基体上涂膜；将该涂膜铝基体于室温下风干，于铝基体上形成凝胶层；接着于120-150℃下进行固化，于铝基体表上形成该铈盐掺杂硅烷杂化膜。
3.如权利要求2所述的铝及铝合金表面防腐处理方法，其特征在于：所述正硅酸乙酯、γ-环氧丙氧丙基三甲基硅烷、乙醇、硝酸铈及水的混合比例按质量为10∶20∶10∶15∶2。
4.如权利要求2所述的铝及铝合金表面防腐处理方法，其特征在于：所述混合液的水解温度为40℃，所述混合液的水解时间为10小时，所述固化温度为130℃。
5.如权利要求1所述的铝及铝合金表面防腐处理方法，其特征在于：该铈盐掺杂硅烷杂化膜由Si、O、C及H五种元素组成，且原子个数比Si∶O∶C∶H＝0.1-2∶2-3∶2-4∶2-8。
6.如权利要求1所述的铝及铝合金表面防腐处理方法，其特征在于：该陶瓷涂层包括一层氮氧化铝层、一层氧化铝层及一层氮化铝层，该氧化铝层直接形成于该铈盐掺杂硅烷杂化膜上，该氮化铝层形成于该氧化铝层上，该氮氧化铝层形成于该氮化铝层上。
7.如权利要求1所述的铝及铝合金表面防腐处理方法，其特征在于：该陶瓷涂层包括一层氮氧化铝层及一层氮氧化铬层，该氮氧化铝层直接形成于该铈盐掺杂硅烷杂化膜上，该氮氧化铬层形成于该氮氧化铝层上。
8.如权利要求1所述的铝及铝合金表面防腐处理方法，其特征在于：所述化学除油是将铝基体浸渍于60-80℃的除油溶液中30-60s，所用除油溶液为含25-30g/L碳酸钠、20-25g/L磷酸三钠及1-3g/L乳化剂的水溶液。
9.如权利要求1所述的铝及铝合金表面防腐处理方法，其特征在于：所述铝基体的材质为纯铝或铝合金。
10.一种由权利要求1-9的任意一项所述的铝及铝合金表面防腐处理方法所制备的铝制品。
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