CN116286157A - 一种长寿命镁合金微乳切削液及其制备方法 - Google Patents

一种长寿命镁合金微乳切削液及其制备方法 Download PDF

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CN116286157A
CN116286157A CN202310192241.XA CN202310192241A CN116286157A CN 116286157 A CN116286157 A CN 116286157A CN 202310192241 A CN202310192241 A CN 202310192241A CN 116286157 A CN116286157 A CN 116286157A
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cutting fluid
magnesium alloy
long
life
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文建清
黄晓剑
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Huizhou Disaien Lubrication Technology Co ltd
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Huizhou Disaien Lubrication Technology Co ltd
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Abstract

本申请涉及切削液领域，具体公开了一种长寿命镁合金微乳切削液及其方法。该切削液包括有以下原料组分：PH值稳定剂；有机酸防锈剂；无氯二元羧酸盐；有色金属缓蚀剂；无机磷酸酯；有机膦酸酯；特种胺；阴离子乳化剂；基础油；自乳化酯；醇醚羧酸；非离子表面活性剂；耦合剂；杀菌剂；水。本申请通过加入包含无机磷酸酯、有机磷酸酯和阴离子乳化剂在内的镁合金的阳极和阴极复合钝化剂，有效的降低了镁合金中镁离子的析出，既可以有效的抑制镁合金腐蚀，又最大限度的降低了因为镁离子析出导致水硬度过高导致切削液失效的情况，从而提高了镁合金切削液的使用寿命。换液周期从之前的3个月提高到现在的24个月以上。

Description

一种长寿命镁合金微乳切削液及其制备方法
技术领域
本申请涉及金属加工液领域，更具体地说，它涉及一种长寿命镁合金微乳切削液及其制备方法。
背景技术
镁作为结构材料中最轻的金属，其合金具有密度轻、比强度和比刚度高、良好的导电导热性能、优秀的磁屏蔽性能和加工性能。镁合金还具有热疲劳性能好，不易老化，相对密度小，导热压铸性好等一系列优点。镁合金强度与铝合金相近，但比强度比铝合金和钢都要高；而比刚度与铝合金及钢没有明显区别。镁合金是代替钢铁、铝合金和工程塑料的新一代结构材料。作为本世纪最具生命力的绿色工程材料，已经广泛应用于3C、汽车、航天航空、交通、化工行业。
镁合金的加工过程中，往往要用到切削液。但镁及其合金化学性质活泼，耐腐蚀性能差，加工过程中常出现工件发黑的情况。而且，随着镁离子不断的析出，切削液中水的硬度越来越高，导致切削液的工作液出现破乳化而失效的情况，表现为切屑液的寿命较短。
发明内容
为了改善因镁离子析出导致水硬度过高从而导致切屑液失效的情况，提高切屑液的寿命，以及改善镁合金工件加工过程中工件发黑的情况，本申请提供一种长寿命镁合金微乳切削液及其制备方法。
第一方面，本申请提供一种长寿命镁合金微乳切削液，采用如下的技术方案：
一种长寿命镁合金微乳切削液，按重量百分比，包括有以下原料组分：
Figure BDA0004105980370000011
Figure BDA0004105980370000021
现有的切削液往往是通过加入镁合金缓蚀剂以减少镁合金的腐蚀和提高切削液的抗硬水性能来增加工作液的使用寿命。而本申请通过加入镁合金的阳极和阴极复合钝化剂，有效的降低了镁合金中镁离子的析出，既可以有效的抑制镁合金腐蚀，又最大限度的降低了因为镁离子析出导致水硬度过高导致切削液失效的情况，从而提高了镁合金切削液的使用寿命。换液周期从之前的3个月提高到现在的24个月以上。具体地，阳极和阴极复合钝化剂包含无机磷酸酯、有机膦酸酯和阴离子乳化剂，成膜初期用无机磷酸酯来防止镁变色，属于阳极钝化，抑制镁离子的析出，3～5分钟后依靠阴离子乳化剂及有机膦酸酯的复合成膜将镁钝化，属于阴极钝化，抑制镁离子的析出。
可选的，按重量百分比，包括有以下原料组分：
Figure BDA0004105980370000022
各原料组分的配比影响切削液的性能，当各原料组分的配比在上述范围内时，切削液降低镁合金中镁离子析出，抑制镁合金腐蚀，改善水硬度过高导致失效，提高切削液使用寿命的效果更加显著。
可选的，所述有机膦酸酯选自2-乙基己基磷酸2-乙基己基酯、二(2-乙基己基)辛基膦酸酯、2-氧代-4-苯丁基磷酸二甲酯中的一种或几种。优选二(2-乙基己基)辛基膦酸酯。
有机膦酸酯的膦酸是磷酸(HO)3PO分子中一个或两个羟基为烷基或芳基置换的化合物，是有机酸。采用上述有机膦酸酯能够很好地配合阴离子乳化剂发挥阴极钝化的效果。
可选的，所述阴离子乳化剂可以采用羧酸盐型，例如硬脂酸钠，也可以采用磺酸盐型，例如烷基苯磺酸钠，也可以采用硫酸盐型，例如十二烷基硫酸钠。
上述羧酸盐型、磺酸盐型以及硫酸盐型的阴离子乳化剂均能够很好的配合上述有机酸发挥阴极钝化的效果。
可选的，所述无机磷酸酯选自磷酸三甲酯、磷酸三丁酯、磷酸三(丁氧基乙基)酯中的一种或几种。
无机磷酸酯的磷酸是无机酸，上述无机磷酸酯呈弱酸性，均可用于本申请中。
可选的，所述基础油选自石蜡基基础油、环烷基基础油中的一种或几种。
石蜡基基础油具有粘温性能好，润滑性和抗氧化性好的特点，环烷基基础油具有低温流动性好，电绝缘性好的特点，均可用作本申请的基础油。
可选的，所述特种胺选自异佛尔酮二胺、4,4'-二仲丁氨基二苯甲烷中的一种或几种。
上述特种胺具有耐高温，耐腐蚀，绝缘性好，柔韧性佳，耐化学品的特点，有利于提升本申请的切削液的综合性能。
可选的，所述无氯二元羧酸盐选自庚二酸钙、壬二酸钙、壬二酸锌中的一种或几种。
上述无氯二元羧酸盐具有热稳定性佳的特点，有利于提升本申请的切削液的热稳定性。
可选的，所述PH值稳定剂采用三乙醇胺，与其他原料组分具有良好的相容性。
可选的，所述有机酸防锈剂选自葵二酸、三元羧酸中的一种或几种，均具有良好的防锈性、低泡性、硬水稳定性，有利于提升本申请的切削液的综合性能。
可选的，所述有色金属缓蚀剂可选自硼酸钠、铬酸钠、亚硝酸钠中的一种或几种，均具有良好的缓蚀性能。
可选的，所述自乳化酯采用自乳化酯ML-955，具有良好的润滑、乳化以及硬水稳定性。
可选的，所述醇醚羧酸可采用脂肪醇聚氧乙烯醚羧酸，具有良好的乳化性能，有利于保持切削液的稳定性。
可选的，所述非离子表面活性剂可以选自十二醇、十六碳醇、脂肪酸聚氧乙烯酯中的一种或几种，有利于维持切削液的稳定性。
可选的，所述耦合剂采用异构醇耦合剂，例如异构十三醇，有利于维持切削液的稳定性。
可选的，所述杀菌剂选自苯氧乙醇、1,2-苯并异噻唑-3-酮、羟乙基六氢均三嗪中的一种或几种，有利于提升切削液的防腐性。
第二方面，本申请提供一种上述长寿命镁合金微乳切削液的制备方法，采用如下的技术方案：
一种长寿命镁合金微乳切削液的制备方法，包括有以下步骤：将水、PH值稳定剂、有机膦酸酯和无机磷酸酯混合，加热至45～55℃反应直至完全溶解，然后继续加入剩余原料组分，混合均匀，即得长寿命镁合金微乳切削液。该种制备方法有利于各组分之间的融合分散。
综上所述，本申请具有以下有益效果：
本申请通过加入包含无机磷酸酯、有机磷酸酯和阴离子乳化剂在内的镁合金的阳极和阴极复合钝化剂，有效的降低了镁合金中镁离子的析出，既可以有效的抑制镁合金腐蚀，又最大限度的降低了因为镁离子析出导致水硬度过高导致切削液失效的情况，从而提高了镁合金切削液的使用寿命。换液周期从之前的3个月提高到现在的24个月以上。
附图说明
图1是切削液对镁合金的防腐性能检测结果。
具体实施方式
以下对本申请作进一步详细说明。
实施例
以下实施例中的长寿命镁合金微乳切削液的制备方法包括有以下步骤：将水、PH值稳定剂、有机膦酸酯和无机磷酸酯混合，加热至45～55℃反应直至完全溶解，然后继续加入剩余原料组分，混合均匀，即得长寿命镁合金微乳切削液。
实施例1～5
实施例1～5的原料组分、重量百分比及制备参数如表1～表2所示，其中，实施例4～5与实施例2的区别在于原料的重量百分比不同。
表1实施例1～3的原料组分、重量百分比及制备参数
Figure BDA0004105980370000051
Figure BDA0004105980370000061
表2实施例2和实施例4～5的原料组分的重量百分比
Figure BDA0004105980370000062
实施例6
一种长寿命镁合金微乳切削液，与实施例2的区别在于：有机膦酸酯采用2-乙基己基磷酸2-乙基己基酯。
实施例7
一种长寿命镁合金微乳切削液，与实施例2的区别在于：有机膦酸酯采用2-氧代-4-苯丁基磷酸二甲酯。
实施例8
一种长寿命镁合金微乳切削液，与实施例2的区别在于：阴离子乳化剂采用硬脂酸钠。
实施例9
一种长寿命镁合金微乳切削液，与实施例2的区别在于：阴离子乳化剂采用十二烷基硫酸钠。
对比例
对比例1
一种切削液，与实施例2的区别在于：不添加有机膦酸酯。
对比例2
一种切削液，与实施例2的区别在于：不添加阴离子乳化剂。
对比例3
一种切削液，与实施例2的区别在于：不添加有机膦酸酯和阴离子乳化剂。
对比例4
一种现有的用于镁合金加工的切削液，某德资品牌。
性能检测
切削液在使用过程中的镁离子浓度检测
分别将实施例1～9以及对比例1～3的切削液样品用于同批镁合金切削加工，其中，切削液按1:10的重量比兑水稀释后使用，加工设备为CNC机床，加工类型包含切削、攻牙、铣削、钻孔等。期间，分别在使用开始、3个月、6个月、9个月、12个月、24个月时取过程样，检测过程样的镁离子浓度，检测结果如表3所示。
表3各实施例和对比例的切削液样品在使用过程中的镁离子浓度
Figure BDA0004105980370000071
Figure BDA0004105980370000081
根据表3，对比例4的现有镁合金切削液在使用3个月后，镁离子浓度就已经达到750ppm，不适合继续使用。而本申请实施例1～9的样品连续使用24个月后的镁离子浓度为500ppm～750ppm，这说明本申请的切削液的使用寿命可达24个月以上。
进一步结合实施例4～5可以看出，各原料组分的配比对切削液的性能存在影响，当配比在实施例2和实施例4～5的范围内时，切削液抑制镁离子析出的能力更强。
由实施例2和对比例1～2可以看出，当有机膦酸酯和阴离子乳化剂去掉其中一种时，切削液抑制镁离子析出的能力则大幅下降，这说明有机膦酸酯和阴离子乳化剂之间存在协同作用。本申请的作用机理在于，成膜初期用无机磷酸酯来防止镁变色，属于阳极钝化，抑制镁离子的析出，3～5分钟后依靠阴离子乳化剂及有机膦酸酯的复合成膜将镁钝化，属于阴极钝化，抑制镁离子的析出。
进一步结合实施例6～7可以看出，有机膦酸酯的种类选择对切削液的性能存在一定的影响，当有机膦酸酯选择二(2-乙基己基)辛基膦酸酯时，切削液抑制镁离子析出的能力更加突出。而进一步结合实施例8～9可以看出，阴离子乳化剂的选择对切削液的性能的影响相对较小。
切削液对镁合金的防腐性能检测
将实施例1～3、实施例6、对比例3和对比例4的切削液按1:10的重量比兑水稀释得到切削液样品，对切削液样品采用纯镁进行常温72小时浸泡测试，结果如附图1所示，其中，实施例1～3、实施例6、对比例3和对比例4分别对应一排左图、一排有右图、二排左图、二排右图、三排左图(纯镁片下半部分为浸泡部位)、三排右图(纯镁片下半部分为浸泡部位)。
由附图1可以看出，采用本申请的切削液的纯镁片无腐蚀，纯镁片浸泡过后的表面依旧光亮如新，且在表面已经成膜。而对比例中的纯镁片的浸泡部位已经出现发黄腐蚀。这说明，本申请的切削液能够有效抑制纯镁片的腐蚀，从而能够有效抑制镁合金的腐蚀。
切削液的综合性能检测
检测实施例1～3的切削液样品的综合性能，结果列于表4。
表4实施例1～3的切削液样品的综合性能
Figure BDA0004105980370000091
由表4可以看出，本申请的切削液的外观优良；PH值适宜，接触操作人员的手也不会出现伤手、皮肤过敏的现象；浓度恰当，切削液的稳定性较佳；防腐性能优异，能够有效避免镁合金加工过程中的腐蚀；产生气泡后10秒钟内剩余气泡的体积即可低于2ml，消泡性能优异，能够有效避免加工过程中泡沫的产生，从而保障切削液与镁合金的接触；切削液加入到200ppm的硬水中放置24小时不会出现分层和浮油的情况，硬水稳定性优异。可见，本申请的切削液具备优秀的综合性能。
本具体实施例仅仅是对本申请的解释，其并不是对本申请的限制，本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改，但只要在本申请的权利要求范围内都受到专利法的保护。

Claims (10)

1.一种长寿命镁合金微乳切削液，其特征在于，按重量百分比，包括有以下原料组分：
PH值稳定剂 4.0%～10.0%；
有机酸防锈剂 2.0%～10.0%；
无氯二元羧酸盐 0.5%～5.0%；
有色金属缓蚀剂 0.5%～5.0%；
无机磷酸酯 1.0%～6.0%；
有机膦酸酯 0.5%～5.0%；
特种胺 1.0%～7.0%；
阴离子乳化剂 8.0%～16.0%；
基础油 20.0%～30.0%；
自乳化酯 2.0%～8.0%；
醇醚羧酸 1.0%～7.0%；
非离子表面活性剂 2.0%～6.0%；
耦合剂 0.5%～3.0%；
杀菌剂 0.5%～6.0%；
水 余量。
2.根据权利要求1所述的一种长寿命镁合金微乳切削液，其特征在于：
PH值稳定剂 6.0%～8.0%；
有机酸防锈剂 4.0%～6.0%；
无氯二元羧酸盐 1.0%～3.0%；
有色金属缓蚀剂 1.0%～3.0%；
无机磷酸酯 2.0%～4.0%；
有机膦酸酯 1.0%～3.0%；
特种胺 3.0%～5.0%；
阴离子乳化剂 10.0%～13.0%；
基础油 25.0%～28.0%；
自乳化酯 4.0%～6.0%；
醇醚羧酸 2.0%～4.0%；
非离子表面活性剂 3.0%～5.0%；
耦合剂 0.5%～1.5%；
杀菌剂 1.0%～3.0%；
水 余量。
3.根据权利要求1所述的一种长寿命镁合金微乳切削液，其特征在于：所述有机膦酸酯选自2-乙基己基磷酸2-乙基己基酯、二(2-乙基己基)辛基膦酸酯、2-氧代-4-苯丁基磷酸二甲酯中的一种或几种。
4.根据权利要求1所述的一种长寿命镁合金微乳切削液，其特征在于：所述阴离子乳化剂选自羧酸盐型、磺酸盐型、硫酸盐型中的一种或几种。
5.根据权利要求1所述的一种长寿命镁合金微乳切削液，其特征在于：所述无机磷酸酯选自磷酸三甲酯、磷酸三丁酯、磷酸三(丁氧基乙基)酯中的一种或几种。
6.根据权利要求1所述的一种长寿命镁合金微乳切削液，其特征在于：所述基础油选自石蜡基基础油、环烷基基础油中的一种或几种。
7.根据权利要求1所述的一种长寿命镁合金微乳切削液，其特征在于：所述特种胺选自异佛尔酮二胺、4,4'-二仲丁氨基二苯甲烷中的一种或几种。
8.根据权利要求1所述的一种长寿命镁合金微乳切削液，其特征在于：所述无氯二元羧酸盐选自庚二酸钙、壬二酸钙、壬二酸锌中的一种或几种。
9.根据权利要求1所述的一种长寿命镁合金微乳切削液，其特征在于：所述PH值稳定剂采用三乙醇胺；所述有机酸防锈剂选自葵二酸、三元羧酸中的一种或几种；所述有色金属缓蚀剂选自硼酸钠、铬酸钠、亚硝酸钠中的一种或几种；所述自乳化酯采用自乳化酯ML-955；所述醇醚羧酸采用脂肪醇聚氧乙烯醚羧酸；所述非离子表面活性剂选自十二醇、十六碳醇、脂肪酸聚氧乙烯酯中的一种或几种；所述耦合剂采用异构醇耦合剂；所述杀菌剂选自苯氧乙醇、1,2-苯并异噻唑-3-酮、羟乙基六氢均三嗪中的一种或几种。
10.一种权利要求1～9任意一项所述的一种长寿命镁合金微乳切削液的制备方法，其特征在于，包括有以下步骤：将水、PH值稳定剂、有机膦酸酯和无机磷酸酯混合，加热至45～55℃反应直至完全溶解，然后继续加入剩余原料组分，混合均匀，即得长寿命镁合金微乳切削液。
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CN111909767A (zh) * 2020-09-16 2020-11-10 江苏赢新润滑科技有限公司 一种高性能的水基镁合金加工液
CN112500915A (zh) * 2020-12-15 2021-03-16 常州畅锐元材料科技有限公司 绿色环保水基石墨烯量子点切削液的制备方法
CN114317084A (zh) * 2021-12-31 2022-04-12 广州米奇化工有限公司 切削液及其应用

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