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CN102560491A - 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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CN102560491A
CN102560491A CN2010106147853A CN201010614785A CN102560491A CN 102560491 A CN102560491 A CN 102560491A CN 2010106147853 A CN2010106147853 A CN 2010106147853A CN 201010614785 A CN201010614785 A CN 201010614785A CN 102560491 A CN102560491 A CN 102560491A
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aluminium
aluminum
alloy surface
layer
anticorrosion treatment
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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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Priority to CN2010106147853A priority Critical patent/CN102560491A/zh
Priority to US13/191,598 priority patent/US8852358B2/en
Publication of CN102560491A publication Critical patent/CN102560491A/zh
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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；采用以钼酸盐为主要成膜剂的成膜溶液对铝基体进行化学转化处理，以于铝基体上形成一层钼酸盐转化膜；通过真空镀膜方法在该钼酸盐转化膜上形成由难熔化合物组成的陶瓷涂层。本发明提供一种上述防腐处理方法制得的铝制品。

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，同时导致采用铝或铝合金制做的产品的使用寿命缩短。
为了提高铝合金的耐腐蚀性能，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，所以在使用过程中，所述凹陷或空隙区域往往更容易发生点蚀，使膜层无法有效地防止铝合金基体被防腐。
发明内容
有鉴于此，有必要提供一种可有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；
采用以钼酸盐为主要成膜剂的成膜溶液对铝基体进行化学转化处理，以于铝基体上形成一层钼酸盐转化膜；
通过真空镀膜方法在该钼酸盐转化膜上形成由难熔化合物组成的陶瓷涂层。
由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钼酸盐转化膜及形成于该钼酸盐转化膜上的由难熔化合物组成的陶瓷涂层，该钼酸盐转化膜是采用以钼酸盐为主要成膜剂的成膜溶液对铝基体进行化学转化处理形成。
本发明的铝及铝合金表面防腐处理方法先通过化学转化处理于铝基体上沉积一层钼酸盐转化膜，然后于该钼酸盐转化膜上镀覆防腐、耐磨的陶瓷涂层。其中该钼酸盐转化膜一方面将铝基体表面平整化，另一方面钼酸盐转化膜自身结构致密，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。配合外层防腐、耐磨的陶瓷涂层，可保护铈盐转化膜不易受到机械损伤，使制备的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。
图3为本发明一实施例的铝及铝合金表面防腐处理方法中所用镀膜设备示意图。
主要元件符号说明
铝制品                10
铝基体                20
钼酸盐转化膜          30
陶瓷涂层              40
氧化铝层              41
氮化铝层              42
氮氧化铝层            43
氮氧化铬层          44
磁控溅射设备        1
真空室              2
真空泵              3
转架                4
铝靶                5
铬靶                6
气源通道            7
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包括如下步骤：
请参阅图1，提供铝基体20。该铝基体20的材质可以为纯铝或铝合金。
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(Na2CO3)、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OP-10乳化剂，其主要组分为烷基酚与环氧乙烷的缩合物。
对铝基体20进行碱蚀处理。该碱蚀处理步骤是将铝基体20浸渍于40-50℃的碱性蚀刻液中3-5s。所用碱性蚀刻液为含40-70g/L氢氧化钠(NaOH)、10-20g/LNa3PO4·12H2O、25-30g/LNa2CO3及40-50g/L氟化钠(NaF)的水溶液。该碱蚀处理一方面用于溶解消低铝基体20上突出的部位，使铝基体20表面趋于平整，另一方面可进一步去除铝基体20表面的油污。
采用以钼酸盐为主要成膜剂的成膜溶液对铝基体20进行化学转化处理，以于铝基体20上形成钼酸盐转化膜30。该成膜溶液可为含8-15g/L钼酸钠(Na2MnO4)、1-3g/L氟化钠及6-10g/L高锰酸钾的水溶液，该成膜溶液的pH值为2-4。较佳地，该成膜溶液为含10g/L钼酸钠、1g/L氟化钠及8g/L高锰酸钾的水溶液，其pH值为3。处理方法可将经上述碱蚀处理的铝基体20浸泡于25-40℃的该成膜溶液中4-7分钟，浸泡过程中可搅拌成膜溶液。较佳地，浸泡过程中该成膜溶液的温度保持为30℃，浸泡时间为5-6分钟。
然后，对形成有所述钼酸盐转化膜30的铝基体20进行真空镀膜处理，以在钼酸盐转化膜30上形成由难熔化合物组成的陶瓷涂层40。该陶瓷涂层40包括一层或多层金属难熔化合物层，该金属难熔化合物可选自钛、铝、铬、锆及钴的氮化物、氧化物、氮碳化物及氮氧化物中的一种或几种的组合。在一个实施例中，该陶瓷涂层40包括一层氧化铝(Al2O3)层41、一层氮化铝(AlN)层42及一层氮氧化铝(AlON)层43，该氧化铝层41直接形成于该钼酸盐转化膜30上，该氮化铝层42形成于该氧化铝层41上，该氮氧化铝层43形成于该氮化铝层42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(AlON)层43及一层氮氧化铬(CrON)层44。该氮氧化铝层43直接形成于该钼酸盐转化膜30上，该氮氧化铬层44形成于该氮氧化铝层43上。
该真空镀膜处理可采用磁控溅射或电弧离子镀，下面以磁控溅射制备该氮氧化铝层43及该氮氧化铬层44为例对该真空镀膜处理进行说明。
请参阅图3，提供一磁控溅射设备1，磁控溅射设备1包括一真空室2、用以对真空室2抽真空的真空泵3以及与真空室2相通的气源通道7。该真空室2内设有转架4及相对设置的铝靶5和铬靶6。转架4带动铝基体20做圆周运行，且铝基体20在随转架4运行的同时也进行自转。镀膜时，溅射气体与反应气体经由气源通道7进入真空室2。
在该钼酸盐转化膜30上溅射该氮氧化铝层43。将形成有该钼酸盐转化膜30的铝基体20放置于磁控溅射设备1的转架4上，对真空室2抽真空至6.0×10-3～8.0×10-3Pa后通入溅射气体氩气，氩气流量为150～300sccm(标准状态毫升/分钟)，同时通入反应气体氮气和氧气，氧气流量为30～60sccm，氮气流量为15～40sccm，铝基体20施加偏压至-100～-300V，开启铝靶5，铝靶5的功率为8～10kw，调节真空室2内温度为100～150℃，转架4的转速为0.5～1.0rpm(revolution per minute，转/分钟)，对铝基体20溅射0.5～1小时，以于钼酸盐转化膜30表面形成该氮氧化铝层43。
在氮氧化铝层43上溅射该氮氧化铬层44。关闭铝靶5，开启铬靶6，铬靶6的功率为8～10kw，调节氧气流量为40～100sccm，氮气流量为30～60sccm，其它参数保持不变，溅射0.5～2小时，以在该氮氧化铝层43上沉积一层氮氧化铬层44。
镀膜结束后，关闭负偏压及铬靶6电源，停止通入氩气和氮气，待所述氮氧化铬层44冷却后，向真空室2内通入空气，打开真空室门，取出镀覆好的铝制品10。
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表面的钼酸盐转化膜30及形成于该钼酸盐转化膜30上的由难熔化合物组成的陶瓷涂层40。该钼酸盐转化膜30是采用以钼酸盐为主要成膜剂的成膜溶液对铝基体20进行化学转化处理形成。该陶瓷涂层40包括一层或多层金属难熔化合物层，该金属难熔化合物可选自钛、铝、铬、锆及钴的氮化物、氧化物、氮碳化物及氮氧化物中的一种或几种的组合。本实施例中，该陶瓷涂层40包括一层氧化铝(Al2O3)层41、一层氮化铝(AlN)层42及一层氮氧化铝(AlON)层43，该氧化铝层41直接形成于该钼酸盐转化膜30上，该氮化铝层42形成于该氧化铝层41上，该氮氧化铝层43形成于该氮化铝层42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(AlON)层43及一层氮氧化铬(CrON)层44。该氮氧化铝层43直接形成于该钼酸盐转化膜30上，该氮氧化铬层44形成于该氮氧化铝层43上。
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化学转化处理于铝基体20上沉积一层钼酸盐转化膜30，然后于该钼酸盐转化膜30上镀覆防腐、耐磨的陶瓷涂层40。其中该钼酸盐转化膜30一方面将铝基体20表面平整化，另一方面钼酸盐转化膜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。配合外层防腐、耐磨的陶瓷涂层40，可保护铈盐转化膜30不易受到机械损伤，使制备的铝制品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；
采用以钼酸盐为主要成膜剂的成膜溶液对铝基体进行化学转化处理，以于铝基体上形成一层钼酸盐转化膜；
通过真空镀膜方法在该钼酸盐转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：该化学转化处理是将该铝基体浸泡于25-40℃，含8-15g/L钼酸钠、1-3g/L氟化钠及6-10g/L高锰酸钾的成膜溶液中4-7分钟，该成膜溶液的pH值为2-4。
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：该化学转化处理是将该铝基体浸泡于30℃，含10g/L钼酸钠、1g/L氟化钠及8g/L高锰酸钾的成膜溶液中5-6分钟，该成膜溶液的pH值为3。
4.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或多层金属难熔化合物层，该金属难熔化合物选自钛、铝、铬、锆及钴的氮化物、氧化物、氮碳化物及氮氧化物中的一种或几种的组合。
5.如权利要求4所述的铝及铝合金表面防腐处理方法，其特征在于：所述陶瓷涂层包括一层氧化铝层、一层氮化铝层及一层氮氧化铝层，该氧化铝层直接形成于该钼酸盐转化膜上，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。
6.如权利要求4所述的铝及铝合金表面防腐处理方法，其特征在于：所述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钼酸盐转化膜上，该氮氧化铬层形成于该氮氧化铝层上。
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：所述真空镀膜方法为磁控溅射或电弧离子镀中的一种。
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：该铝合金表面防腐处理方法还包括在所述浸锌处理前对铝基体进行碱蚀处理的步骤，该碱蚀处理是将该铝基体浸渍于40-50℃，含40-70g/LNaOH、10-20g/LNa3PO4·12H2O、25-30g/LNa2CO3及40-50g/LNaF的水溶液中3-5s。
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：所述化学除油是将铝基体浸渍于60-80℃，含25-30g/LNa2CO3、20-25g/LNa3PO4·12H2O及1-3g/L乳化剂的水溶液30-60s。
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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