CN103643231A - 碳酸季铵和碳酸氢季铵作为防腐蚀剂的用途，抑制腐蚀的方法和使用该防腐蚀剂的防腐蚀剂涂料 - Google Patents

碳酸季铵和碳酸氢季铵作为防腐蚀剂的用途，抑制腐蚀的方法和使用该防腐蚀剂的防腐蚀剂涂料 Download PDF

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CN103643231A
CN103643231A CN201310455214.3A CN201310455214A CN103643231A CN 103643231 A CN103643231 A CN 103643231A CN 201310455214 A CN201310455214 A CN 201310455214A CN 103643231 A CN103643231 A CN 103643231A
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quaternary ammonium
carbonic acid
hydrogen
carbonate
mixture
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M·Y·江
L·K·霍尔
J·金勒
J·W·谢布莱恩
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Abstract

公开作为防腐蚀剂的碳酸季铵、碳酸氢季铵和它们的混合物。本发明涉及施用含一种或多种碳酸季铵或碳酸氢季铵的组合物来抑制金属表面腐蚀的方法。公开的内容涉及用于金属基材的含这些化合物的防腐蚀涂料，具有这些防腐蚀涂料的金属基材，还涉及含这些化合物的清洁用水溶液。

Description

碳酸季铵和碳酸氢季铵作为防腐蚀剂的用途,抑制腐蚀的方法和使用该防腐蚀剂的防腐蚀剂涂料
本发明是申请日为2004年5月27日的申请号为200480014534.4、标题为“碳酸季铵和碳酸氢季铵作为防腐蚀剂的用途，抑制腐蚀的方法和使用该防腐蚀剂的防腐蚀剂涂料”的发明专利申请的分案，要求2003年5月28日提交的美国专利申请60/474081的优先权。 
本发明涉及碳酸季铵和碳酸氢季铵作为防腐蚀剂的用途。 
在金属表面与水接触的过程中，无论是液态水还是湿空气，始终存在腐蚀的危险性。特别当金属本身易于腐蚀并且没有涂敷时尤其存在这种危险性。 
发现易于腐蚀的金属的例子有由铁合金制成的压制金属汽车部件、磨损表面如机械加工的钢部件、以及由铸铁制成的机器部件。虽然许多年来已对腐蚀抑制剂(或防腐蚀剂)有所了解，但大多数还不充分。一个关键的不足因素是防腐蚀剂的水溶性。大多数腐蚀抑制剂是由长链脂肪酸和其衍生物制备，水溶性普遍较差。尤其在金属表面与水和油都接触时问题更突出，如在油和气体生产、石油加工以及金属工件的应用中。 
石油化工加工本身对腐蚀抑制剂有宽范围的要求，包括冷却系统、精制系统、管道、蒸汽发生器和油或气体发生装置。 
为降低金属(如金属容器、设备的金属部件、设备表面、管道和储存流体用的设备)，尤其是含铁的那些金属的腐蚀速率，通常在与这些金属接触的流体中加入腐蚀抑制剂。流体可以是气体、浆料或液体。 
近年来，由于涉及到挥发性有机碳(VOCs)，用来清洁金属个金属部件的传统溶剂如溶剂油和煤油已被含水制剂替代。对这种清洁金属部件用的水基制剂的动向并不是没有问题。水不能轻易地溶解油脂或油性残余物，而且水本身能明显增加金属部件本身的腐蚀。此外，这些增加通常以微乳液使用，在清洁过程中微乳液需要使用额外的表面活性剂进行稳定。吗啉被经常用于这些清洁制剂，提供腐蚀防护。然而，吗啉几乎没有清洁作用，并且不能稳定微乳液，因为吗啉并不是 一种优良的表面活性剂。此外，吗啉是一种被管制的产品，因为可用来制备违法药品。 
已发现季铵化合物有限地用作腐蚀抑制剂。U.S.专利No.6,521,028公开使用在丙二醇或丙二醇醚溶剂中的特定吡啶鎓和喹啉鎓盐作为腐蚀抑制剂。 
U.S.专利No.6,080,789和6,297,285公开使用碳酸季铵作为消毒剂。 
U.S.专利No.4,792,417公开一种组合物，用于抑制不锈钢与含有氯离子和任选亚铜离子的水溶液和/或极性有机溶液接触时的胁强腐蚀。该组合物包含特定烷基碳酸季铵或苄基碳酸季铵的水溶液或极性有机溶液。 
仍需要对金属表面具有良好亲合力并且是水溶和油溶的腐蚀抑制剂。此外，还需要能提高清洁能力和表面活性剂能力的新型腐蚀抑制剂。还能对完成的制剂提供抗菌保护的腐蚀抑制剂特别有利。 
目前，已发现碳酸季铵和碳酸氢季铵能抑制金属腐蚀。 
本发明涉及施用(或沉积)抑制腐蚀有效量的一种组合物来抑制金属表面腐蚀的方法，所述组合物包含：(a)至少一种碳酸季铵、碳酸氢季铵或它们的混合物；和(b)任选的溶剂。这种方法对油田井下应用和金属加工特别有用。 
另一个实施方式是用于金属基材的防腐蚀涂层。这种涂层包含至少一种碳酸季铵、碳酸氢季铵或它们的混合物，以及涂布材料。通常，将碳酸季铵、碳酸氢季铵或它们的混合物分散在涂布材料中。根据优选的实施方式，所述涂料还具有抗菌效果。该涂料包含杀菌有效量的防腐蚀的碳酸季铵、碳酸氢季铵或它们的混合物，或不同的抗菌剂。 
另一个实施方式是表面具有本发明防腐蚀涂层的金属基材。 
另一个实施方式是包含抑制腐蚀有效量的至少一种碳酸季铵、碳酸氢盐或它们的混合物的水溶液作为防腐蚀清洁溶液的用途。该清除水溶液可以是水基金属清洁剂。 
另一个实施方式是包含抑制腐蚀有效量的至少一种碳酸季铵、碳酸氢盐或它们的混合物的水溶液或非水溶液作为防腐蚀金属加工流体的用途。 
另一个实施方式是包含抑制腐蚀有效量的至少一种碳酸季铵、碳酸氢盐或它们的混合物的水溶液或非水溶液作为粉末冶金中的腐蚀抑制剂的用途。 
腐蚀抑制剂组合物 
本发明涉及抑制金属基材的腐蚀。在此，术语“抑制腐蚀”包括但不限于， 防止或降低在金属暴露于水或空气，或同时暴露于随和空气时金属表面的氧化速度。金属氧化是一个电化学反应，通常导致金属从表面损失或氧化产物在金属表面积累。在此，术语“金属”包括但不限于：钢、铸铁、铝、金属合金和它们的组合。在一个实施方式中，金属基材是气溶胶罐。 
对本发明有用的碳酸季铵包括但不限于具有下面化学式的那些： 
Figure BDA0000389939260000031
式中，R1和R2各自独立地是C1-20烷基或芳基取代的C1-20烷基(如苄基)。R1和R2可以相同或不同。 
术语“芳基取代的烷基”指被一个或多个芳族碳环取代的烷基，特别是苯环，如苯乙基(烷基连接到氮原子)或苄基。类似地，术语“芳基取代的C1-20烷基”指一个或多个芳族碳环取代的C1-20烷基。 
术语“Cn-m烷基”(例如，“C1-20烷基”)指有n-m(例如1-20)个碳原子的任何直链或支链烷基。 
根据一个实施方式，R1和R2是C4-20烷基或芳基取代的C4-20烷基。 
根据优选的实施方式，R1是C8-12烷基或芳基取代的C8-12烷基。 
优选的碳酸季铵是碳酸二癸基二甲基铵，如碳酸二正癸基二甲基铵。 
碳酸二癸基二甲基铵可以50重量%水溶液获得，含有小于或等于4重量%的醇，如甲醇或乙醇。该溶液为黄色/橙色液体，略带水果味。 
合适的碳酸氢季铵包括但不限于具有下面化学式的那些： 
式中R1和R2具有按对碳酸季铵(I)定义的含义和优选含义。 
优选的碳酸氢季铵是碳酸氢二癸基二甲基铵，如碳酸氢二正癸基二甲基铵。 
上述碳酸季铵和碳酸氢季铵可采用本领域已知的方法，如U.S.专利No.5,438,034和国际公开WO03/006419所述的方法制备。 
碳酸季铵和碳酸氢季铵处于平衡。碳酸氢盐和碳酸盐的浓度随包含它们的溶 液的pH而变化。 
在一个优选实施方式中，碳酸季铵(I)和/或碳酸氢盐(II)中的R1和R2指相同的C1-20烷基。 
在更好的实施方式中，碳酸季铵(I)和/或碳酸氢盐(II)中的R1和R2指C10烷基，最好是正C10烷基。 
另一个优选实施方式中，碳酸季铵(I)和/或碳酸氢盐(II)中的R1指甲基。更好地，R1和R2都指甲基。 
另一个优选实施方式中，碳酸季铵(I)和/或碳酸氢盐(II)中的R1指苄基或苯乙基。 
上述碳酸季铵和碳酸氢季铵可以单独用作腐蚀抑制剂，或配制到腐蚀抑制剂的制剂中。 
与常规的氯化季铵不同，基于在此所述季铵化合物的碳酸盐和碳酸氢盐不仅具有低腐蚀性，而且可用作腐蚀抑制剂。 
碳酸盐和碳酸氢盐在水中能以任何浓度混溶，具有较高的油溶性，并且对金属表面具有亲合力。此外，碳酸盐和碳酸氢盐提高了油，如芳香油和亲油性物质在水溶液中的溶解度。 
适合于碳酸季铵和碳酸氢季铵的溶剂包括极性溶剂(如水和水混溶的极性溶剂)、二醇类、二醇醚(如丙二醇)以及它们的混合物。 
任选地，组合物中可包含一种或多种另外的表面活性剂。合适的表面活性剂包括：非离子型表面活性剂、阳离子型表面活性剂(除在此所述的碳酸季铵和碳酸氢季铵外的其他阳离子型表面活性剂)、阴离子型表面活性剂、两性表面活性剂，和它们的混合物。这样的表面活性剂的非限制性例子有：氧化胺、直链醇乙氧基化物、仲醇乙氧基化物、乙氧基化醚、甜菜碱、含6-22个碳原子的脂肪酸、所述脂肪酸的盐，以及它们的混合物。例如，表面活性剂可以是壬基苯酚乙氧基化物。 
碳酸季铵和碳酸氢季铵腐蚀抑制剂能抑制金属在含水和油环境中，包括水和油混合物(如油田井下应用和金属加工)中的腐蚀。油环境中的油的非限制性例子是石油蒸馏物。石油蒸馏物的例子包括但不限于：煤油、石油溶剂和烃馏份。在金属加工中，经常用水溶液和水-油混合物或乳液进行润滑(如润滑金属加工的工具)。 
在防腐蚀剂组合物可以包含其他常规添加剂，如增效助剂(builder)、着色剂、香料、芳香剂、清洁剂，以及它们的混合物。 
碳酸季铵和/或碳酸氢季铵在金属基材上的施用量是抑制腐蚀有效量，即，防 止或降低金属基材腐蚀速度的量。抑制腐蚀有效量可依据需要的液体变化，并能由本领域技术人员决定。 
不希望受任何特定理论的限制，可以认为在此所述的碳酸季铵/碳酸氢季铵化合物在水溶液中对金属具有固化的亲合力，因为它们也可以用作阳离子表面活性剂，并因此内迁移到金属表面。一旦在表面，碳酸季铵/碳酸氢季铵能阻隔氧气和/或空气进一步氧化金属表面。 
通常，抑制腐蚀组合物以稀浓度或以易于使用的形式供给。一般，易使用的形式包含以组合物总量为100重量%计的约0.005-1.00重量%的碳酸季铵、碳酸氢季铵或它们的混合物。较好地，以组合物总量为100重量%计，易使用形式包含约100ppm至1000ppm的碳酸季铵、碳酸氢季铵或它们的混合物。 
较好地，以使用的总稀释液为100重量%计，最后使用的稀释液含有约100ppm至约500ppm的碳酸季铵、碳酸氢季铵或它们的混合物。 
可采用本领域已知的任何方法将组合物施用到金属基材，包括但不限于：涂布、沉积、浸涂、浸湿、刷涂、喷雾、揩抹(mopping)、洗涤等。 
在优选实施方式中，金属基材选自钢、铸铁、铝、金属合金，以及它们的组合。 
涂料 
上述防腐蚀的碳酸季铵、碳酸氢季铵和它们的混合物可加入用于金属基材的涂料中。本发明的涂料包含涂布材料。较好地，将碳酸季铵、碳酸氢季铵或它们的混合物溶解或分散在涂布材料中。 
合适的涂布材料包括但不限于：有机树脂，如环氧树脂、聚氨酯树脂、乙烯基树脂、缩丁醛树脂、邻苯二甲酸树脂，可固化树脂，如异氰酸酯和丁二烯树脂，以及常规涂料，如清漆、基于聚氨酯的低VOC溶剂涂料，和水基涂料如松香脂肪酸乙烯乳液。这种涂料可采用本领域已知的方法制备。 
本发明的涂料可以是例如漆、底漆和工业涂料。 
涂料中可包含的另外的组分包括但不限于：UV稳定剂、固化剂、硬化剂、阻燃剂，和它们的混合物。 
水溶液和非水溶液(包括清洁溶液和金属加工流体) 
上述腐蚀抑制剂组合物尤其能用作清洁水溶液的组分，用这些溶液清洁能延 缓和使金属部件，特别是钢的腐蚀最小。上述组合物还可用作含水和非含水的金属加工流体，以及用作粉末冶金的腐蚀抑制剂的水溶液或非水溶液中的组分。腐蚀抑制剂组合物还提供对施用该组合物的基材如金属的抗菌保护。为本发明目的，术语“清洁溶液”指用于清洁金属表面，如处理设备的内表面的酸性或碱性水溶液。这些清洁溶液的pH通常在约1-10范围。清洁溶液及其应用的例子在一些专利中公开，如U.S.专利No.3,413,160;4,637,899;Re.30,796和Re.30,714。 
本发明的清洁溶液组合物包含至少一种有机酸，以及抑制与该溶液接触的金属腐蚀的有效量的前述组合物，所述有机酸选自：亚烷基多胺聚羧酸、羟基乙酸、甲酸、柠檬酸，以及它们的混合物或盐。有机酸的例子包括：N,N,N',N'-乙二胺四乙酸(EDTA)、四铵EDTA、二铵EDTA、N-(2-羟乙基)-N,N',N’-乙二胺三乙酸(HEDTA)及其盐。 
这些清洁水溶液的pH通常约1-10范围。腐蚀抑制剂(即，碳酸季铵、碳酸氢季铵或它们的混合物)的示例量约为0.05-1重量%。示例的有机酸清洁溶液包括在U.S.专利No.6,521,028所述的那些。 
本发明的腐蚀抑制剂组合物还可以用于清洁水溶液，抑制金属被次氯酸盐以及被无机酸如硫酸或磷酸的腐蚀。这些清洁溶液包含本发明的腐蚀抑制剂，其量足以抑制金属被这些无机酸的腐蚀。腐蚀抑制剂的示例量约为0.05-1重量%。 
本发明的腐蚀抑制剂能防止化学清洁操作时清洁的基底金属过度腐蚀，或至少使过度腐蚀最小。腐蚀抑制剂组合物较好地可以在宽范围的各种使用有机酸作为清洁剂的清洁溶液中，在宽pH范围使用。 
清洁溶液常用来从含铁金属上除去污垢和锈。但是，该溶液经常与进行清洁系统的整体部件所包含的其他金属接触。这些金属的例子包括铜、铜合金、锌、锌合金等。 
有利地，本发明的腐蚀抑制剂组合物用量为足以抑制金属与清洁溶液接触时由酸引起的腐蚀的量。根据一个实施方式，本发明腐蚀抑制剂组合物的用量为足以使腐蚀速率小于或等于约73.2g·m-2·d-l(0.015lb/ft2/天)。在清洁溶液与被清洁金属接触之前，可将腐蚀抑制剂组合物溶于或分散在清洁溶液中。 
附图描述 
图1是室温下90分钟后冷轧钢板在氯化二癸基二甲基铵(DDAC)溶液或在碳酸二癸基二甲基铵/碳酸氢二癸基二甲基铵(DDACB)溶液中的照片。 
图2是室温下30天后冷轧钢板在氯化二癸基二甲基铵(DDAC)溶液或在碳酸二癸基二甲基铵/碳酸氢二癸基二甲基铵(DDACB)溶液中的照片。 
图3是室温下9个月后冷轧钢板在氯化二癸基二甲基铵(DDAC)溶液或在碳酸二癸基二甲基铵/碳酸氢二癸基二甲基铵(DDACB)溶液中的照片。还示出一个冷轧钢样品5小时后在去离子水中的照片。 
图4是冷轧钢板在氯化二癸基二甲基铵(DDAC)溶液或在碳酸二癸基二甲基铵/碳酸氢二癸基二甲基铵(DDACB)溶液中室温浸泡9个月后的照片。以及在去离子水中室温浸泡5小时后的照片。 
由下面实施例说明本发明，但是这些实施例不构成限制。除非特别指出，所有的份和百分数均以重量给出。 
实施例1 
此试验目的是测试用发动机清洁剂制剂除去油脂污土。加热7.5g植物油(
Figure BDA0000389939260000072
The J.M.Smucker Co.,Orville,OH)和0.1g炭黑的混合物直到液化。将0.5g该加热混合物涂在一个金属试片(钢片，尺寸为0.813×25.4×76.2mm3(0.032"×1”×3")，从Q-Panel Lab Products,Cleveland OH购得)，并使其干燥。然后，将该金属试片部分浸在50ml含吗啉或碳酸二癸基二甲基铵/碳酸氢二癸基二甲基铵(DDACB)的制剂中，如下表1详细列出的。 
1小时后，从制剂中取出金属试片，用水漂洗。肉眼评价从金属试片浸过部分除去多少油脂污土。结果列于表1。 
如表1所示，由碳酸二癸基二甲基铵替代微乳液中的吗啉导致明显提高制剂的稳定性和清洁能力。制剂A和B都含有碳酸二癸基二甲基铵，能从金属试片除去100％的油脂污土，并保持一个相，而制剂C和D，都含有吗啉，但都不含碳酸二癸基二甲基铵，结果只有20%油脂污土被除去，并且相分离为两个不透明相。 
表1 
Figure BDA0000389939260000071
Figure BDA0000389939260000081
Aromatic200TM是芳烃混合物，从ExxonMobil Chemical of Houston,TX购得。 
Figure BDA0000389939260000082
是乙酸氧-庚酯(oxo-heptyl acetate)，从ExxonMobil Chemical of Houston,TX购得。 
Figure BDA0000389939260000083
是二丙二醇正丁基醚，从Dow Chemical of Midland,MI购得。 
Figure BDA0000389939260000084
是乙氧基化C9-11醇的混合物，平均乙氧基化程度为6(6摩尔环氧乙烷/摩尔醇)，从Shell Chemicals of Houston,TX购得。 
实施例2 
将冷轧钢试片(中度钢试片，尺寸为0.813×25.4×76.2mm3(0.032"×1"×3")，(Q-Panel Lab Products,Cleveland OH))置于120ml(4盎司)带螺纹盖的玻璃罐中，完全浸在去离子水含自来水，并浸在含100ppm或1000ppm碳酸二癸基二甲基铵/碳酸氢二癸基二甲基铵(DDACB)混合物的去离子水，或含100ppm或1000ppm碳酸二癸基二甲基铵/碳酸氢二癸基二甲基铵混合物的自来水。每种溶液用两个试片(分别是试片1-10和A-J)。一周后，取出试片，用去离子水或自来水漂洗，并用软尼龙刷轻轻刷除。然后，将试片在氮气流中干燥并称重。结果列于下表2。对重量损失的重量差表示为(-)，或对增重的重量差表示为(+)。所有重量差都以基于各自试片原始重量的百分数给出。 
表2 
Figure BDA0000389939260000085
Figure BDA0000389939260000091
如表2所示，含1000ppm碳酸二癸基二甲基铵/碳酸氢二癸基二甲基铵的溶液1周后没有降解，证据是金属试片的重量基本上没有损失。这些样品上没有观察到形成沉积物。其他测试溶液变成棕色，并在玻璃罐底部有沉积物。冷轧钢试片暴露于去离子水1小时后，观察到腐蚀，而暴露于含1000ppm碳酸二癸基二甲基铵/碳酸氢二癸基二甲基铵1周后，没有观察到腐蚀。 
实施例3 
将去离子水(58.2重量%)、表面活性剂(氧化辛基二甲基胺(40%活性)， 
Figure BDA0000389939260000092
Lonza,Inc.,Fair Lawn,NJ)(8.0重量%)和50%季铵化合物水溶液(氯化二癸基二甲基铵(DDAC)，或碳酸二癸基二甲基铵/碳酸氢二癸基二甲基铵混合物(DDACB))(33.8重量%)混合在一起。 
用该混合物的1:256水稀释液(660ppm活性季铵化合物)来评价DDAC和DDACB的抑制腐蚀性能。将冷轧钢板(钢试片，尺寸为0.813×25.4×76.2mm3(0.032''×1”×3")，(Q-Panel Lab Products,Cleveland OH))室温下浸在各水溶液中9个月，并进行监测。 
图1和图2是钢片分别在室温下水溶液中静置90分钟和30天的照片。由这 些图可知，仅90分钟后，在DDAC溶液中的钢片开始腐蚀，30天后严重腐蚀。相反，在DDACB中的钢片没有腐蚀，即使在30天后。 
图3和图4是钢片在室温下水溶液中静置9个月后的照片。由图可知，在DDACB溶液中的钢片显示没有腐蚀，而在DDAC溶液中的钢片完全腐蚀。为比较目的，还给出浸在不含季铵化合物的去离子水中的同样冷轧钢片的照片。在去离子水中仅5小时后，钢片显示一些腐蚀症状。 

Claims (23)

1.一种抑制金属基材腐蚀的方法，该方法包括使所述基材与一种组合物接触的步骤，该组合物包含：
(a)至少一种选自碳酸季铵、碳酸氢季铵和它们的化合物的季铵化合物；
(b)任选地溶剂。
2.如权利要求1所述的方法，其特征在于，所述碳酸季铵具有下面化学式：
Figure FDA0000389939250000011
式中，R1是任选被芳基取代的C1-20烷基，R2是任选被芳基取代的C1-20烷基。
3.如权利要求1所述的方法，其特征在于，所述碳酸氢季铵具有下面化学式：
Figure FDA0000389939250000012
式中，R1是任选被芳基取代的C1-20烷基，R2是是任选被芳基取代的C1-20烷基。
4.如权利要求2或3所述的方法，其特征在于，R1和R2是相同的C1-20烷基。
5.如权利要求2-4中任一项所述的方法，其特征在于，R1和R2是C10烷基。
6.如权利要求5所述的方法，其特征在于，R1和R2是正-C10烷基。
7.如权利要求5所述的方法，其特征在于，所述碳酸季铵是碳酸二癸基二甲基季铵，所述碳酸氢季铵是碳酸氢二癸基二甲基季铵。
8.如权利要求2或3所述的方法，其特征在于，R1是甲基。
9.如权利要求7所述的方法，其特征在于，R1和R2是甲基。
10.如权利要求2或3所述的方法，其特征在于，R1是苄基或苯乙基。
11.如权利要求1-10中任一项所述的方法，其特征在于，所述组合物还包含选自下列的表面活性剂：氧化胺、直链醇乙氧基化物、仲醇乙氧基化物、乙氧基化醚、甜菜碱、含6-22个碳原子的脂肪酸、含6-22个碳原子的脂肪酸的盐，以及它们的混合物。
12.如权利要求11所述的方法，其特征在于，表面活性剂是壬基苯酚乙氧基化物。
13.如权利要求1-12中任一项所述的方法，其特征在于，金属基材处于油环境中。
14.如权利要求13所述的方法，其特征在于，所述油环境包含石油蒸馏物。
15.如权利要求14所述的方法，其特征在于，石油蒸馏物选自：煤油、石油溶剂、烃馏份，以及它们的混合物。
16.如权利要求1-15中任一项所述的方法，其特征在于，所述组合物还包含至少一种选自下列的组分：增效助剂、着色剂、香料和芳香剂。
17.如权利要求1-16中任一项所述的方法，其特征在于，金属基材选自：钢、铸铁、铝、金属合金，以及它们的组合。
18.一种用于金属基材的防腐蚀涂料，包含：
(a)至少一种碳酸季铵、碳酸氢季铵或它们的混合物；
(b)涂布材料。
19.如权利要求18所述的防腐蚀涂料，其特征在于，碳酸季铵、碳酸氢季铵或它们的混合物分散在涂布材料中。
20.一种金属基材，在其至少一个表面上具有权利要求18所述的防腐蚀涂料。
21.一种包含至少一种碳酸季铵、碳酸氢季铵或它们的混合物的水溶液或非水溶液的用途，用作防腐蚀清洁溶液。
22.一种包含至少一种碳酸季铵、碳酸氢季铵或它们的混合物的水溶液或非水溶液的用途，用作金属加工的防腐蚀流体。
23.一种包含至少一种碳酸季铵、碳酸氢季铵或它们的混合物的水溶液或非水溶液的用途，在粉末冶金中用作腐蚀抑制剂。
CN201310455214.3A 2003-05-28 2004-05-27 碳酸季铵和碳酸氢季铵作为防腐蚀剂的用途，抑制腐蚀的方法和使用该防腐蚀剂的防腐蚀剂涂料 Expired - Fee Related CN103643231B (zh)

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