CN114437859B - 一种长效缓蚀的铝合金切削液 - Google Patents

一种长效缓蚀的铝合金切削液 Download PDF

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CN114437859B
CN114437859B CN202111274241.1A CN202111274241A CN114437859B CN 114437859 B CN114437859 B CN 114437859B CN 202111274241 A CN202111274241 A CN 202111274241A CN 114437859 B CN114437859 B CN 114437859B
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aluminum alloy
cutting fluid
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CN114437859A (zh
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黄国都
靳永昌
张洪灿
赵凯利
聂晓霖
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Nanjing Kerun Industrial Technology Co ltd
Nanjing Kerun New Material Technology Co ltd
Nanjing Kerun Industrial Media Co ltd
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Nanjing Kerun New Material Technology Co ltd
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Abstract

本发明公开了一种长效缓蚀的铝合金切削液，由如下质量百分比的组分组成：碱度调节剂10％～13％、防锈剂2％～3％、苯并三氮唑0.2％～0.3％、植物油18％～20％、润滑剂10％～12％、植物基合成酯5％～8％、复合磷酸酯2.5％～3％、阴离子乳化剂8％～10％、非离子乳化剂4％～4.5％、铝缓蚀剂0.5％～1％、耦合剂1.5％～2％、消泡剂0.2％～0.3％以及水余量。本发明切削液在使用过程中无需在槽液中额外添加缓蚀添加剂，通过特定比例磷酸酯的复配，并与特种胺、硅氧烷改性物协同发挥铝缓蚀作用，不仅能够在铝工件表面形成致密的缓蚀膜，而且还能在气液界面形成气相防护，从而使航空铝合金在长周期加工时不发生腐蚀变色，并且加工后放置1个月以上也不发生腐蚀变色。

Description

一种长效缓蚀的铝合金切削液
技术领域
本发明涉及一种长效缓蚀的铝合金切削液。
背景技术
航空铝合金材料具有比强度高、加工和成型性好、维护技术成熟以及成本较低等特点，广泛应用于飞机主体结构材料，并通过材料的技术进步，推动航空航天技术的发展。飞机上应用的铝合金主要是2系铝和7系铝，2系铝主要用来制造蒙皮、隔框和翼肋等，7系铝主要用于制造上翼面蒙皮、大梁等。铝合金在商业飞机上的用量已占飞机整体结构材料的70％～80％。
航空铝合金加工的痛点之一是加工周期长，加工和工序间流转过程中易发生腐蚀问题，表现为外观变暗、发黑、发黄、白斑等现象，常常造成返工处理或零件报废，甚至影响后道的浸渗处理。航空铝机械加工过程中为了防止铝合金变色，需要定期在槽边补充缓蚀添加剂，这样操作一方面增加额外的工作量，另一方面不易定时和定量，存在加工质量风险。
发明内容
发明目的：本发明的目的是提供一种无需额外添加铝缓蚀添加剂的铝合金切削液。
技术方案：本发明所述的长效缓蚀的铝合金切削液，由如下质量百分比的组分组成：碱度调节剂10％～13％、防锈剂2％～3％、苯并三氮唑0.2％～0.3％、植物油18％～20％、润滑剂10％～12％、植物基合成酯5％～8％、复合磷酸酯2.5％～3％、阴离子乳化剂8％～10％、非离子乳化剂4％～4.5％、铝缓蚀剂0.5％～1％、耦合剂 1.5％～2％、消泡剂0.2％～0.3％以及水余量。
其中，所述碱度调节剂为：异丙醇胺、三乙醇胺、二甘醇胺、N-甲基乙醇胺或环己基二乙醇胺中的任意两种与3-氨基-4-辛醇的混合物。
其中，胺类与3-氨基-4-辛醇的混合质量比为：6～9：4～5。
其中，所述防锈剂为癸二酸或十二碳二元酸。
其中，所述植物油为环氧大豆油，其环氧值大于6.0％，酸值小于 0.5mgKOH/g。正常的环氧大豆油的参数，否则就环氧化不足，或成为其他产物。
其中，所述润滑剂为环氧植物油的改性物，采用如下方法改性而成：将植物油先进行环氧化反应，然后用氨基醇开环加成，最后进行酰化反应，获得乙酰化的植物油，相比改性前的植物油，改性后的植物油(乙酰化的植物油)的热稳定性和氧化稳定性都明显提高，且保留了良好的生物降解性；其结构式如下：
Figure RE-GDA0003553279500000021
其中，R为-C(CH3)2-CH2-或R＝-CH2-CH(CH3)-。
其中，所述植物基合成酯为三羟甲基丙烷油酸酯。植物基合成酯在体系中的作用为辅助润滑作用，当作基础油用。
其中，所述复合磷酸酯为脂肪醇聚氧乙烯醚磷酸酯与辛基磷酸按质量比为4:1的组合物；其中，脂肪醇聚氧乙烯醚磷酸酯的脂肪醇碳链为C12～C14，EO 数为3.5，单双酯比例为5:5。磷酸酯按照该比例进行复合，具有良好的乳化效果，即使油水混合体系稳定、均一；同时还很好的兼顾了极压润滑和铝缓蚀效果，通过P-O键在铝表面快速成膜，形成P-O-Al键。
其中，所述阴离子乳化剂为妥尔油、油酸、蓖麻油酸和二聚酸中任意一种或两种与四聚蓖麻油酸酯的组合物。
其中，所述非离子乳化剂为碳链为C16-18的聚氧乙烯聚氧丙烯醚与基于聚氧乙烯(20EO)的蓖麻油酸甘油酯的组合物，比例为5:4～3:1，其中C16-18的聚氧乙烯聚氧丙烯醚中EO数为7，PO数为7；优选MTP 070和TAGAT V20。 TAGAT V20对应的就是聚氧乙烯(20EO)的蓖麻油酸甘油酯，MTP 070对应的就是C16-18的聚氧乙烯聚氧丙烯醚中EO数为7，PO数为7。
其中，所述铝缓蚀剂为硅氧烷改性物，其结构式如下：
Figure RE-GDA0003553279500000022
其利用磺化苯乙基三甲氧基对硅烷进行改性，具体采用如下方法制备得到：将氨基硅烷放在烧杯中，边搅拌边加入磺化苯乙基三甲氧基硅烷，并向混合物中缓慢滴加蒸馏水，搅拌半小时后，移入70℃水浴中进行保温6小时，最后制得目标产物。
其中，所述耦合剂为异己二醇、二乙二醇单丁醚、二丙二醇甲醚、苯氧乙醇、 C14和C15单支链伯醇的混合物中的一种或两种，其中C14和C15单支链伯醇优选ISALCHEM 145。耦合剂在体系中的作用为让体系更稳定。
上述航空铝合金用切削液的制备方法，具体为：将碱度调整剂、防锈剂和去离子水搅拌溶解至均匀透明；往其中加入植物油、润滑剂、植物基合成酯，搅拌至均匀的乳白色；加入磷酸酯、阴离子乳化剂、非离子乳化剂和耦合剂，搅拌至均匀透明；最后加入铝缓蚀剂和消泡剂，搅拌至均匀透明。
有益效果：相比于现有技术，本发明的显著优点为：(1)本发明切削液在使用过程中无需在槽液中额外添加缓蚀添加剂，通过特定比例磷酸酯的复配，并与特种胺、硅氧烷改性物协同发挥铝缓蚀作用，不仅能够在铝工件表面形成致密的缓蚀膜，而且还能在气液界面形成气相防护，从而使航空铝合金在长周期加工时不发生腐蚀变色，并且加工后放置1个月以上也不发生腐蚀变色；(2)本发明的硅氧烷经过改性后，能够有效减缓硅氧烷的水解速度，从而提高其在体系中的稳定性，在原液中不会产生沉淀，在工作液中不会因析出而漂浮在液面；(3) 本发明配方无硼、无氯、无硫、无甲醛、无DCHA，环保性能好，不易对操作者产生刺激和过敏；(4)本发明的基础油、润滑剂、合成酯、阴离子乳化剂等均源于植物油基，具有生物可降解性的特点，并且废液中的COD值较常规矿物油基切削液低。
附图说明
图1为使用实施例1切削液配制的质量浓度10％的工作液持续加工飞机铝框体到第15天时，零件外观图；
图2为使用实施例1切削液配制的质量浓度10％的工作液加工飞机铝框体，加工后1个月飞机铝框体的外观图；
图3为使用对比实施例1～3切削液配制的质量浓度10％的工作液持续加工飞机铝框体到第7天时，零件外观图。
具体实施方式
下面结合具体实施例来对本发明技术方案作进一步阐述。
实施例1
本发明具有长效缓蚀效果的航空铝合金切削液，由如下重量百分比的各原料组分组成：3-氨基-4-辛醇5％、三乙醇胺5％、二甘醇胺3％、癸二酸2％、苯并三氮唑0.3％、环氧大豆油20％、润滑剂10％、三羟甲基丙烷油酸酯5％、复合磷酸酯2.5％、蓖麻油酸3％、四聚蓖麻油酸酯5％、MTP 070 3％、TAGAT V20 1％、铝缓蚀剂1％、ISALCHEM 145 0.5％、苯氧乙醇1％、消泡剂Foam Ban MS-575 0.2％以及水余量。
实施例2
本发明具有长效缓蚀效果的航空铝合金切削液，由如下重量百分比的各原料组分组成：3-氨基-4-辛醇4％、N-甲基乙醇胺3％、环己基二乙醇胺3％、十二碳二元酸2％、苯并三氮唑0.3％、环氧大豆油20％、润滑剂10％、三羟甲基丙烷油酸酯5％、复合磷酸酯2.5％、蓖麻油酸3％、四聚蓖麻油酸酯5％、MTP 070 3％、TAGAT V20 1％、铝缓蚀剂1％、苯氧乙醇2％、消泡剂Foam Ban MS-575 0.2％以及水余量。
实施例3
本发明具有长效缓蚀效果的航空铝合金切削液，由如下重量百分比的各原料组分组成：3-氨基-4-辛醇4％、三乙醇胺5％、二甘醇胺4％、癸二酸3％、苯并三氮唑0.2％、环氧大豆油20％、润滑剂10％、三羟甲基丙烷油酸酯8％、复合磷酸酯3.0％、妥尔油3％、蓖麻油酸1％、四聚蓖麻油酸酯4％、MTP 070 2.5％、 TAGAT V20 2％、铝缓蚀剂B 0.5％、ISALCHEM145 1.5％、异己二醇0.5％、消泡剂Foam Ban MS-575 0.2％以及水余量。
对比例1
一种航空铝合金切削液，由如下重量百分比的各原料组分组成：
3-氨基-4-辛醇5％、三乙醇胺5％、二甘醇胺3％、癸二酸2％、苯并三氮唑 0.3％、环氧大豆油20％、润滑剂10％、三羟甲基丙烷油酸酯5％、脂肪醇聚氧乙烯醚磷酸酯2.5％、蓖麻油酸3％、四聚蓖麻油酸酯5％、MTP 070 3％、TAGAT V20 1％、铝缓蚀剂1％、ISALCHEM145 0.5％、苯氧乙醇1％、消泡剂Foam Ban MS-575 0.2％以及水余量。
对比例2
一种航空铝合金切削液，由如下重量百分比的各原料组分组成：
3-氨基-4-辛醇5％、三乙醇胺5％、二甘醇胺3％、癸二酸2％、苯并三氮唑 0.3％、环氧大豆油20％、润滑剂10％、三羟甲基丙烷油酸酯5％、复合磷酸酯2.5％、蓖麻油酸3％、四聚蓖麻油酸酯5％、MTP 070 3％、TAGAT V20 1％、铝缓蚀剂 horlt C101 1％、ISALCHEM145 0.5％、苯氧乙醇1％、消泡剂Foam Ban MS-575 0.2％以及水余量。
对比例3
一种航空铝合金切削液，由如下重量百分比的各原料组分组成：
三乙醇胺5％、二甘醇胺3％、癸二酸2％、苯并三氮唑0.3％、环氧大豆油 20％、润滑剂10％、三羟甲基丙烷油酸酯5％、复合磷酸酯2.5％、蓖麻油酸3％、四聚蓖麻油酸酯5％、MTP 070 3％、TAGAT V20 1％、铝缓蚀剂1％、ISALCHEM 145 0.5％、苯氧乙醇1％、消泡剂Foam Ban MS-575 0.2％以及水余量。
实施例1～3以及对比实施例1～3水性防锈剂的性能指标见表1。
表1
Figure RE-GDA0003553279500000041
Figure RE-GDA0003553279500000051
注①：德国Microtap G8测试仪，3.2163测试块，普通高速钢丝锥，M4F，转速1200rpm，攻丝深度8mm；以市场在售的某铝合金切削液为基准100％，实施例产品润滑值除以现场铝合金切削液润滑值*100％后为最终结果；该值越小，表明相比参照样，检测样品的润滑性能越优异。
由表1可以看出，实施例1～3针对ADC12和7075铝均具有优异的缓蚀性能，具有突出的润滑性能，工作液稳定性好。对比例1中将磷酸酯的组合比例调整后，仅使用脂肪醇聚氧乙烯醚磷酸酯，腐蚀试验表明铝缓蚀性能下降。对比例 2中铝缓蚀剂用其他硅氧烷类铝缓蚀剂替代后，不仅铝缓蚀性能下降，且原液和工作液出现了不稳定状态。对比例3胺类中未加入3-氨基-4-辛醇，铝缓蚀性能下降。
如图1～3所示，实施例1制备的航空铝合金加工液，配制成质量浓度10％的工作液持续加工飞机框体到第15天时，零件未出现腐蚀变色情况，加工后放置1个月仍然未出现变色，而对比例1～3配制的质量浓度10％的工作液在持续加工到第7天时出现了变色情况。

Claims (5)

1.一种长效缓蚀的铝合金切削液，其特征在于，由如下质量百分比的组分组成：碱度调节剂10％～13％、防锈剂2％～3％、苯并三氮唑0.2％～0.3％、植物油18％～20％、润滑剂10％～12％、植物基合成酯5％～8％、复合磷酸酯2.5％～3％、阴离子乳化剂8％～10％、非离子乳化剂4％～4.5％、铝缓蚀剂0.5％～1％、耦合剂1.5％～2％、消泡剂0.2％～0.3％以及水余量；
其中，所述碱度调节剂为：异丙醇胺、三乙醇胺、二甘醇胺、N-甲基乙醇胺或环己基二乙醇胺中的任意两种与3-氨基-4-辛醇的混合物；胺类与3-氨基-4-辛醇的混合质量比为：6～9：4～5；
所述润滑剂为环氧植物油的改性物，其采用如下方法改性而成：将植物油先进行环氧化反应，然后用氨基醇开环加成，最后进行酰化反应，获得乙酰化的植物油；其结构式如下：
Figure FDA0004029817700000011
其中，R为-C(CH3)2-CH2-或-CH2-CH(CH3)-；
所述复合磷酸酯为脂肪醇聚氧乙烯醚磷酸酯与辛基磷酸按质量比为4:1的组合物；
所述非离子乳化剂为碳链为C16-18的聚氧乙烯聚氧丙烯醚与基于聚氧乙烯的蓖麻油酸甘油酯的组合物，比例为5:4～3:1，其中C16-18的聚氧乙烯聚氧丙烯醚中EO数为7，PO数为7；
所述铝缓蚀剂为硅氧烷改性物，其结构式如下：
Figure FDA0004029817700000012
硅氧烷改性物利用磺化苯乙基三甲氧基对硅烷进行改性，具体采用如下方法制备得到：将氨基硅烷放在烧杯中，边搅拌边加入磺化苯乙基三甲氧基硅烷，并向混合物中缓慢滴加蒸馏水，搅拌半小时后，移入70℃水浴中进行保温6小时，最后制得目标产物。
2.根据权利要求1所述的长效缓蚀的铝合金切削液，其特征在于：所述植物油为环氧大豆油，其环氧值大于6.0％，酸值小于0.5mgKOH/g。
3.根据权利要求1所述的长效缓蚀的铝合金切削液，其特征在于：所述植物基合成酯为三羟甲基丙烷油酸酯。
4.根据权利要求1所述的长效缓蚀的铝合金切削液，其特征在于：所述阴离子乳化剂为妥尔油、油酸、蓖麻油酸和二聚酸中任意一种或两种与四聚蓖麻油酸酯的组合物。
5.根据权利要求1所述的长效缓蚀的铝合金切削液，其特征在于：所述耦合剂为异己二醇、二乙二醇单丁醚、二丙二醇甲醚、苯氧乙醇、C14和C15单支链伯醇的混合物中的一种或两种。
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