CN102762708B - 清洁具有铝组件的传热系统的方法和组合物 - Google Patents
清洁具有铝组件的传热系统的方法和组合物 Download PDFInfo
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- CN102762708B CN102762708B CN201080058311.3A CN201080058311A CN102762708B CN 102762708 B CN102762708 B CN 102762708B CN 201080058311 A CN201080058311 A CN 201080058311A CN 102762708 B CN102762708 B CN 102762708B
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- 229940035048 sorbitan monostearate Drugs 0.000 description 1
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- 239000000600 sorbitol Substances 0.000 description 1
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- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
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- 229960004418 trolamine Drugs 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/06—Phosphates, including polyphosphates
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/2075—Carboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D3/33—Amino carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
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- C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
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Abstract
本文公开的是快速清洁和保护含有控制气氛钎焊铝热交换器的车辆冷却系统的方法和处理系统。该方法和处理系统可以任选地包括老化(钝化)步骤。该处理系统可以包括三个不同部分:(1)清洁剂或清洁溶液;(2)调节剂或调节溶液;和(3)相容的CAB铝保护传热流体。
Description
相关申请的交叉引用
本申请要求2009年7月6日提交的美国临时申请号61/223,272的权益,且其通过引用以其整体并入本文。
发明背景
汽车热交换器,诸如散热器、加热器芯、蒸发器和冷凝器,主要由铝合金制成,以减小车辆的重量。这些热交换器可以是片管式,其中翅片在与气流的方向成直角处是波纹的和/有槽的。
在过去,使用机械膨胀技术用于汽车片管式交换器的大量生产。热交换器现在主要由钎焊操作形成,其中单个组件用钎焊合金永久地结合在一起。
自从20世纪80年代早期,一种知道为控制气氛钎焊(CAB)的钎焊技术被汽车工业越来越流行地使用来制造钎焊铝热交换器。CAB优于先前的钎焊方法,即,真空炉钎焊,由于提高的产率、较低的炉维护需求、更大的钎焊过程坚固性、和所应用设备的较低的资本成本。
当使用CAB工艺制造热交换器式,铝钎料合金(例如,AA 4345或AA 4043)通常预涂层或涂布在芯铝合金板材(或钎焊板)的至少一面上。可选地,预钎焊(prebraze)电弧喷涂Zn涂层施加在没有镀过金属的管上(例如,通过金属电弧喷涂工艺),以提高其抗腐蚀性。片管的铝芯合金典型地为AA 3003、或者各种“长寿命合金”、或改性的AA 3003合金,其中加入少量的元素,典型地选自Cu、Mg、Mn、Ti、Zn、Cu、Cr和Zr。
在CAB工艺中,融合剂施加到被连接的预组装的组件表面。在大约560至575°C钎焊期间,融合剂开始融化,且熔融的熔剂反应、溶解和替换在铝合金表面自然形成的氧化铝层,以及空出来钎料合金。钎料合金在大约575-590°C熔化,并且开始向被钎焊的接头流动。在冷却过程期间,该钎料固化和形成钎焊接头。在表面存在的熔剂也固化,且保留在表面上作为熔剂残留物。
融合剂的另外作用是阻止在钎焊过程中重新形成氧化铝层、增强钎料合金钎料合金的流动和增加基底金属润湿性。融合剂典型地为具有K1-3AlF4-6·xH2O通式的碱金属氟铝酸盐的混合物,其本质上为K3AlF6、K2AlF5和KAlF4的混合物。对于钎焊铝或铝合金,氟基熔剂优于氯基熔剂,因为它们被认为对于铝或其合金是惰性的或者无腐蚀性的,并且在钎焊后基本是水不溶的。当使用推荐的溶剂涂层重量(对于炉钎焊是3–5克每平方米(g/m2)时,CAB工艺据说生成1–2微米(μm)厚紧密粘合的非腐蚀性残留物。因此,相信在钎焊操作后除去熔剂残留物不是必要的。
由于熔剂的报道的非腐蚀性性质、其对于钎焊组件配合的公差和灵活控制,CAB是连接铝热交换器的最低成本方法之一。其现在常常被汽车和制作热交换器的其它行业所使用。
发明概述
由我们最近进行的研究表明显示氟铝酸钾熔剂的残渣在商业的传热流体中是可溶的,和将沥滤出氟和铝离子。这些离子增加了发动机冷却系统中的金属的腐蚀和/或降低了传热流体腐蚀保护作用以及系统的传热性能。释放入传热流体的氟和铝离子的量取决于传热流体的化学成分、熔剂装载的量、使用的熔剂的成分、钎焊工艺涉及的其它参数、暴露时间以及冷却系统的运转条件和设计属性。冷却系统的的传热性能降低和腐蚀的程度往往随着暴露时间的增加而增加。
离子沥滤和随后的腐蚀问题同时影响新的和已用的车辆。在具有最近已经安装或要安装CAB铝组件的车辆中,期望阻止沥滤和腐蚀。在已用的车辆中,其中沥滤和腐蚀已经出现,期望去除腐蚀产物和防止进一步的腐蚀。腐蚀产物的存在可以使传热性能降低。
因此,存在对于清洁和去除腐蚀产物或预防其形成的组合物和方法的需要,以在含有控制气氛钎焊铝组件的车辆冷却系统的运转和寿命期间中,维持或恢复传热流体流动和传热性能,防止腐蚀损害、或阻止或最小化另外的腐蚀损害和维持传热性能。
前述需要通过快速清洁和保护含有控制气氛钎焊铝热交换器的汽车冷却系统的方法和处理系统解决。该方法和处理系统可以任选地包括老化(钝化)步骤。该处理系统可以任选地包括三个不同部分:(1)清洁剂或清洁溶液;(2)调节剂或调节溶液;和(3)相容的CAB铝保护传热流体。明确地考虑是这些三个部分可以组合地使用或者可以独立地使用。
该方法和处理系统在以下更详细地描述。
附图描述
图1-2显示在实施例7中生成的数据。
具体实施方式
已经发现通过CAB制成的铝组件可以在与传热系统中的传热流体接触之前进行清洁,以减少不期望的熔剂的离子沥滤和随后的腐蚀。腐蚀产物可以降低传热效率。为了提高传热流体寿命,也期望在加新的传热流体之前和/或在传热系统中清洁和安装新的部件之后,钝化传热系统。钝化在传热系统的组件的表面上产生保护膜,其防止组件腐蚀。
去除含有CAB铝组件的传热系统的腐蚀产物的方法和组合物也在本文中公开。为了提高传热流体寿命,也期望在加新的传热流体之前、在清洁传热系统之后钝化传热系统。
清洁剂包括25°C具有小于或等于5.0的pKa的有机酸、和吡咯化合物。有机酸可以具有小于或等于4.5的pKa,或更具体地,小于或等于4.0、或更具体地,小于或等于3.5,或更具体地,小于或等于3.0,或更具体地,小于或等于2.5,或更具体地,小于或等于2.0,所有都在25°C。有机酸可以是脂肪族或芳香族有机酸。除了含有碳原子、氢原子和氧原子之外,有机酸分子也可以包含0-4个硫原子、0至4个氮原子和/或0至4个磷原子。有机酸可以包括一个或多个羧酸基团。在选择有机酸的一个考虑是水系统中的溶解度,因为清洁剂与水结合以形成水清洁溶液。因此,有机酸必须具有在水清洁溶液中的足够的溶解度,以这样的量在清洁溶液中存在,使得清洁可以以及时方式完成——典型地为数分钟或数小时的时间量程且通常小于24小时。
选择有机酸的另外考虑是清洁的效率和腐蚀的潜力。在一些实施方式中,期望选择导致短时间(高效率)的清洁的有机酸。然而,清洁的效率必须与产生腐蚀的低潜力平衡。
有机酸包括牛磺酸或2-氨基乙磺酸、磺基丙氨酸、二羟基酒石酸、天冬氨酸、1,1–环丙烷二甲酸、苦味酸、吡啶甲酸、乌头酸、羧基谷氨酸、二异羟肟酸、2,4,6-三羟基苯甲酸、8-喹啉酸、草酸、马来酸和前述羧酸的两种或更多种的组合。也包括前述有机酸的酸酐等同物。考虑可以使用有机酸和有机酸酐的组合。在清洁剂中使用的最优选的有机酸是草酸。草酸和马来酸(或者马来酸酐)混合物也可以在清洁剂中使用。
清洁剂可以包括25°C具有小于或等于5.0的pKa的有机酸的组合。有机酸的组合可以具有小于或等于4.5的pKa,或更具体地,小于或等于4.0的pKa,或更具体地,小于或等于3.5的pKa,或更具体地,小于或等于3.0的pKa,或更具体地,小于或等于2.5的pKa,或更具体地,小于或等于2.0的pKa,所有都在25°C。
清洁剂可以包括基于清洁剂总重量的0.1-99重量%的有机酸(一种或多种)。在这个范围内,清洁剂可以包括基于清洁剂总重量的0.5-97重量%量的有机酸(一种或多种),或更具体地,1-95重量%量的有机酸(一种或多种),或更具体地,2-90重量%量的有机酸(一种或多种)。
清洁剂可以包括单一吡咯化合物或者吡咯化合物的组合。吡咯化合物包括5-或6-员杂环环作为官能团,其中杂环环包含至少一个氮原子。示例性吡咯化合物包括苯并三唑(BZT)、甲苯并三唑、甲基苯并三唑、(例如,4-甲基苯并三唑和5-甲基苯并三唑)、丁基苯并三唑、和其它烷基苯并三唑(例如,含有2-20个碳原子的烷基)、巯基苯并三唑、噻唑和其它取代的噻唑、咪唑、苯并咪唑和其它取代的咪唑、吲唑和取代的吲唑、四唑和取代的四唑、和其混合物。
清洁剂可以包括基于清洁剂总重量的0.001-10重量%的量的吡咯化合物(一种或多种)。在这个范围内,清洁剂可以包括0.01-7重量%的量的吡咯化合物(一种或多种),或更具体地,0.02-6重量%,或,更具体地,0.05-5重量%。
清洁剂可以进一步包括1,2-乙二醇,诸如1,2-亚乙基二醇、丙二醇或其组合。
清洁剂可以包括基于清洁剂总重量的0-约15重量%量的1,2-乙二醇。
清洁剂可以进一步包括作为溶剂的水。水也可以在清洁剂中存在,由于使用含有水的原料,以晶体或非晶体形式。
清洁剂可以进一步包括有机磷酸酯诸如Maxhib AA-0223、Maxhib PT-10T、或其组合。
清洁剂可以包括基于清洁剂总重量的0-约10重量%量的有机磷酸酯。
清洁剂可以进一步包括另外的缓蚀剂。示例性的另外缓蚀剂包括炔醇类、酰胺类、醛类、咪唑类、可溶的碘化物、吡啶类、和胺类。
清洁剂可以包括基于清洁剂总重量的0-10重量%量的另外的缓蚀剂。
清洁剂可以进一步包括丙烯酸或马来酸基聚合物诸如聚丙烯酸、聚马来酸、或其组合。也包括丙烯酸和马来酸二元共聚物和三元共聚物,包括具有磺酸基的那些。示例性物质包括Acumer 2000和Acumer 3100。
清洁剂可以进一步包括表面活性剂,诸如环氧乙烷聚合物或共聚物、1,2-环氧丙烷聚合物或共聚物、C8-C20乙氧基化醇或其组合。示例性表面活性包括PluronicL-61、PM 5150、Tergitol 15-2-9(CAS # 24938-91-8)、Tergitol 24-L-60(CAS #68439-50-9)和Neodol 25-9(CAS # 68002-97-1)。
清洁剂可以进一步包括着色剂诸如非离子着色剂。示例性非离子着色剂从Milliken Chemicals以商品名可得到。
清洁剂可以进一步包括以下的一种或多种:阻垢剂、防泡剂、生物杀伤剂、聚合物分散剂和抗沥滤剂诸如镁质粘土和豆粕。
清洁剂可以是以固体或液体形式。
清洁剂与水结合形成清洁溶液。水可以是去离子水或者干净的自来水。清洁溶液可以提供给最终用户,或者清洁剂可以与制备清洁溶液的说明书一起提供给最终用户。也考虑清洁剂可以是由最终用户用水进一步稀释的浓缩液。
示例性清洁溶液组合物包括水、0.1-99重量%(wt%)的草酸、0.001-4wt%的吡咯化合物、0-10体积%的1,2-亚乙基二醇、0-20wt%的马来酸或马来酸酐、0-20wt%的有机磷酸酯、0-20wt%的25°C具有小于5.0的pKa的有机酸(除了草酸和马来酸之外)、和0-5wt%的丙烯酸或马来酸基聚合物。
清洁溶液可以具有小于或等于5.0的pH,或者更具体地小于或等于4.5,或更具体地,小于或等于3.5,或更具体地,小于或等于2.5,或更具体地,小于或等于2.0,或更具体地,小于或等于1.8,或更具体地,小于或等于1.5。清洁溶液的pH在室温(20-25°C)测定。
典型地,传热系统中存在的任何传热流体在清洁之前排放。传热系统可以用水冲洗,然后加入清洁溶液到传热系统和排放。一些传热系统难于排放和保留显著量的先前循环的流体。传热系统充满清洁溶液。开到发动机和运行可以为持续数分钟至数小时的时间段。清洁溶液可以进行再循环。清洁溶液可以通过内部泵(即,在车辆发动机中的水泵)和/或待清洁的冷却系统中的一个或多个外部泵进行再循环。可选地,清洁溶液可以重力进料至系统中。另外,过滤器,诸如袋滤器,可以在清洁溶液的再循环期间进行使用。过滤器可以在再循环回路的侧流中或在系统的位置中安装,使得其在清洁过程期间可以容易地被去除或交换,没有中断系统的主件中的清洁溶液的循环。过滤器可以具有10微米-200微米的孔径大小的开口。在清洁完成之后,发动机关闭和清洁溶液从系统排放,且系统用水冲洗。
示例性清洁步骤使用外部泵和储液开口至大气压。外部泵和储液室用于通过车辆冷却系统循环流体。传热系统进行传热流体的冲洗和装满水。除去恒温箱和安装改进的恒温箱以模拟“开口”恒温箱条件。该步骤利用使用回流设计通过加热器芯和实现流动通过加热器芯。系统中生成的气体通过系统清除和排放进入储液室。外部泵从储液室中抽清洁溶液,运送其进入加热器芯出口,穿过加热器芯,离开加热器芯进水软管,和进入到发动机上的加热器出口螺纹接套管。输出软管从发动机上的加热器出口螺纹接套管连接返回至储液室。在进入斗中输出软管上可以使用任选的过滤器以捕获任何清洁的碎片。车辆发动机用于在清洁溶液中产生热,但是只可以运行在清洁溶液的温度保持在沸点以下温度的时候。系统可以进行冷却和发动机可以任选地进行重新启动以重新加热溶液,但是同样地发动机只在清洁溶液的温度保持在沸点以下温度的时候运行。在储液室中的清洁溶液可以在加热和冷却循环之间交替。另外的清洁溶液可以在加热循环期间加入以保持清洁溶液的温度在沸点以下。冷却步骤和重新加热步骤可以重复,直到认为系统是清洁的。系统的清洁性可以基于清洁溶液的外观进行评估。在循环清洁溶液之后,传热系统用水冲洗。
在用清洁溶液清洁后,调节剂可以用于钝化传热系统。调节剂可以包括:水,水溶性焦磷酸盐诸如焦磷酸四钾——以0.5-80重量%的量,以0.05-5重量%量的一种或多种吡咯化合物,碱金属磷酸盐诸如磷酸钠或磷酸钾——以0-10重量%的量,碱金属多磷酸盐诸如三聚磷酸钠——以0至5重量%的量,和任选的成分,诸如缓蚀剂、阻垢剂、着色剂、表面活性剂、防泡剂、和止沥滤剂(即,镁质粘土和豆粕)等等。在该段中的量基于调节剂的总重量。
调节溶液的pH在室温(15 to 25°C)可以大于或等于7.5,或更具体地,大于或等于8.0,或更具体地为8.5-11。
调节溶液以与清洁溶液相同或类似的方法引入到传热系统。类似于清洁溶液,调节溶液应该在低于调节溶液的沸点温度的温度循环。调节溶液的温度可以是在环境温度和80°C之间。
在任选的调节剂被去除和从传热系统冲洗后,加入传热流体。
传热流体可以是包含脂肪族羧酸和/或芳香族羧酸的1,2-乙二醇基传热流体。传热流体可以进一步包括吡咯、磷酸盐、或其组合。另外,传热流体也包含水、一种或多种1,2-乙二醇基防冻剂、和任选的调节传热流体的pH至7.5-9.0的pH调节剂。
用于作为车辆冷却系统中的再充填传热流体中的示例性传热流体包括基于传热流体的总重量的10%-90%重量计量的防冻剂;去离子水;和缓蚀剂包装。
适合于使用的防冻剂包括醇或醇的混合物,诸如一元醇或多元醇以及其混合物。醇选自:甲醇,乙醇,丙醇,丁醇,糠醛,糠醇,四氢糠醇,乙氧基化糠醇,1,2-亚乙基二醇,二甘醇,三甘醇,1,2-丙二醇,1,3-丙二醇,双丙甘醇,丁二醇,甘油,甘油-1,2-二甲基醚,甘油-1,3-二甲基醚,甘油的单乙基醚,山梨糖醇,1,2,6–己三醇,三甲醇基丙烷,烷氧基烷醇诸如甲氧基乙醇,和其混合物。醇在组合物中以基于传热流体的总重量的约10%至约99.9%重量的量的存在。在这个范围内,醇可以以30%至99.5%重量的量存在,或者更具体为40%至99%重量。
适合使用的水包括去离子水或软化水。水以基于传热流体的总重量按重量计约0.1%至约90%的量在传热流体中存在,或更具体地,按重量计0.5%至70%,或甚至更具体地为按重量计1%至60%。
缓蚀剂包装可以包括一或二碱价脂肪族(C6至C15)羧酸、其盐、或它们的组合。示例性一或二碱价羧酸包括2-乙基己酸、新癸酸和癸二酸。
缓蚀剂包装可以包括无机磷酸盐,诸如磷酸、正磷酸钠或钾、焦磷酸钠或钾,和多磷酸或六偏磷酸钠或钾。传热流体中的磷酸盐浓度基于传热流体的总重量为按重量计0.002%-5%,或更具体地为按重量计0.01%-1%。
缓蚀剂包装可以包括水溶性镁化合物,诸如硝酸镁和硫酸镁。制剂中镁离子浓度可以为0.5-100ppmMg。
缓蚀剂包装可以包括选自以下的至少一种组分:(1)吡咯化合物或其它铜合金缓蚀剂;(2)膦酰基羧酸混合物诸如Bricorr 288;和(3)膦基羧酸混合物,诸如PSO。
也可以包括铜和铜合金的缓蚀剂。合适的铜和铜缓蚀剂包括含有5-或6-员杂环环作为活性官能团的化合物,其中杂环环含有至少一个氮原子,例如吡咯化合物。具体地,苯并三唑、甲苯基三唑、甲基苯并三唑(例如,4-甲基苯并三唑和5-甲基苯并三唑)、丁基苯并三唑和其它烷基苯并三唑(例如,含有2-20个碳原子的烷基)、巯基苯并三唑、噻唑和其它其它取代的噻唑、咪唑、苯并咪唑和其它取代的咪唑、吲唑和取代的吲唑、四唑和取代的四唑、以及它们的混合物可以用于作为Cu和Cu合金缓蚀剂。铜和铜合金缓蚀剂可以在组合物中以基于传热流体的总重量的约0.01-4%重量计的量在组合物中存在。
传热流体可以进一步包括其它传热流体添加剂,诸如着色剂、在以上没有列出的其它缓蚀剂、分散剂、消泡剂、阻垢剂、表面活性剂、着色剂、和防垢剂、润湿剂和生物杀伤剂等等。
任选的缓蚀剂包括一种或多种水溶性聚合物(MW:200-200,000道尔顿),诸如聚羧酸酯类,例如,聚丙烯酸或聚丙烯酸酯,丙烯酸酯基聚合物、二元共聚物、三元共聚物和四元共聚物,诸如丙烯酸酯/丙烯酰胺共聚物、聚甲基丙烯酸酯,聚马来酸或马来酸酐聚合物、马来酸基聚合物、它们的二元共聚物和三元共聚物,改性的丙烯酰胺基聚合物,包括聚丙烯酰胺、丙烯酰胺基二元共聚物和三元共聚物;一般而言,适合使用的水溶性聚合物包括均聚合物、二元共聚物、三元共聚物和共聚体,所述共聚体具有:(1)至少一种含有C3-C16单烯键不饱和单或双羧酸或它们的盐的单体单元;或(2)至少一种含有C3-C16单烯键不饱和单或双羧酸衍生物诸如酰胺、腈、羧酸酯、酸卤化物(例如,氯化物)、和酸酐以及它们组合的单体单元。适合于在本发明中用于制备水溶性聚合物的单羧酸的实例包括丙烯酸、甲基丙烯酸、乙基丙烯酸、乙烯基乙酸、丙烯基丙酸和巴豆酸。适合于使用的单羧酸酯的实例包括丙烯酸丁酯、丙烯酸正己酯、甲基丙烯酸叔丁基氨基乙酯、丙烯酸二乙基氨基乙酯、甲基丙烯酸羟乙基酯、丙烯酸羟丙基酯、甲基丙烯酸羟丙基酯、甲基丙烯酸二乙基氨基乙酯、甲基丙烯酸二甲基氨基乙酯、丙烯酸二甲基氨基乙酯、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸叔丁基酯、和乙烯乙酸酯。适合于使用的二羧酸的实例包括马来酸、衣康酸、富马酸、柠檬酸、中康酸、和亚甲基丙二酸。适合于使用的酰胺实例包括丙烯酰胺(或2-丙烯酰胺)、甲基丙烯酰胺、乙基丙烯酰胺、丙基丙烯酰胺、叔丁基甲基丙烯酰胺、叔辛基丙烯酰胺、N,N-二甲基丙烯酰胺(或N,N-二甲基-2-丙烯酰胺)、二甲氨基丙基丙烯酰胺、环己基丙烯酰胺、苄基甲基丙烯酰胺、乙烯基乙酰胺、磺甲基丙烯酰胺、磺乙基丙烯酰胺、2-羟基-3-磺丙基丙烯酰胺、磺苯基丙烯酰胺、N-乙烯基甲酰胺,N-乙烯基乙酰胺,2-羟基-3-磺丙基丙烯酰胺,N-乙烯基吡咯烷酮(环状酰胺)、羧甲基丙烯酰胺。适合于使用的酸酐的实例包括马来酸酐(或2,5-呋喃二酮)和琥珀酸酐。适合于使用的腈的实例包括丙烯腈和甲基丙烯腈。适合于使用的酸卤化物的实例包括丙烯酰胺丙基三甲基氯化铵、二丙烯基二甲基氯化铵和甲基丙烯酰胺丙基三甲基氯化铵。另外,含有以下单体的至少一种单体单元的水溶聚合物也可以在本发明中使用。适合于使用的另外单体可以选自:丙烯基羟丙基磺酸盐(酯),AMPS或2-丙烯酰胺-2-甲基丙烷磺酸,聚乙二醇单甲基丙烯酸酯,乙烯磺酸,苯乙烯磺酸,丙烯酰胺甲基丙烷磺酸,甲代烯丙基磺酸,烯丙氧基苯磺酸,1,2-二羟基-3-丁烯,丙烯醇,烯丙基膦酸,二丙烯酸乙二醇酯,天冬氨酸,异羟肟酸,2-乙基恶唑啉,己二酸,二亚乙基三胺,环氧乙烷,环氧丙烷,氨,1,2-乙二胺,二甲胺,邻苯二甲酸二烯丙酯,3-烯丙氧基-2-羟基丙烷磺酸,聚乙二醇单甲基丙烯酸酯,苯乙烯磺酸钠,具有以下结构的烷氧基化烯丙基醇磺酸酯:
其中R1是具有1至约10个碳原子的羟基取代的烷基或烯基,或者具有1至约10个碳原子的非取代的烷基或烯基,或者是(CH2-CH2-O)n、[CH2-CH(CH3)-O]n或两者的混合物,且“n”是约1至约50的整数;R2是H或低级烷基(C1–C3);X,当存在时,是选自SO3、PO3、PO4、COO的阴离子基团;Y,当存在时,是H或氢(多个)、或任何水溶阳离子或阳离子(多个),它们在一起抵消阴离子的化合价;a是0或1。传热流体中的水溶聚合物的量按重量计为约0.005%-10%的范围。水溶聚合物也可以是如在US5,338,477中描述的聚醚聚氨亚甲基膦酸酯或者膦基聚丙烯酸。
任选的缓蚀剂可以包括一种或多种脂肪族三羧酸(例如,柠檬酸)或者脂肪族酸四羧酸,诸如1,2,3,4-烷烃四羧酸,和更优选地为,1,2,3,4-丁烷四-甲酸。也可以使用脂肪族酸四羧酸的水溶盐、酯或酸酐。浓度范围按重量计将是传热流体的约0.001%-5%。
任选的缓蚀剂可以包括以下至少一种:C4–C22脂肪族或芳香族单或双-羧酸,钼酸盐,铜和铜合金缓蚀剂,诸如三唑类、噻唑类、或其它吡咯化合物;亚硝酸盐类,硝酸盐类,膦酸酯类,诸如2-膦酰基-丁烷-1,2,4-三羧酸,胺盐类,和硼酸盐类。
任选的缓蚀剂可以包括选自以下的至少一种金属离子(例如,以水溶盐形式):钙、锶、和/或锌盐、或它们的组合。在传热流体中的水溶金属离子浓度应该是在0.1mg/l至约100mg/l的范围。
考虑的是在一些实施方式中传热流体没有硅酸盐。
一些非离子表面活性剂也可以被包括作为缓蚀剂。适合于使用的非离子表面活性剂包括脂肪酸酯,诸如失水山梨醇脂肪酸酯、聚亚烷基二醇、聚亚烷基二醇酯、环氧乙烷(EO)和环氧丙烷(PO)的共聚物、失水山梨醇脂肪酸酯的聚氧化烯衍生物、以及它们的化合物。非离子表面活性剂的平均分子量将是在约55至约300,000之间,更优选地为约110至约10,000。合适的失水山梨醇脂肪酸酯包括失水山梨醇单月桂酸酯(例如,以商品销售)、失水山梨糖醇单棕榈酸酯(例如,或失水山梨糖醇硬脂酸酯(例如,或失水山梨糖醇单油酸酯(例如,或失水山梨糖醇单倍半油酸酯(例如,或失水山梨糖醇三油酸酯(例如,或失水山梨糖醇三硬脂酸酯(例如,失水山梨糖醇单妥尔油酸酯(例如,合适的聚亚烷基二醇包括聚乙二醇、聚丙二醇以及它们的混合物。适合于使用的聚乙二醇的实例包括CARBOWAXTM聚乙二醇和Dow ChemicalCompany的甲氧基聚乙二醇(例如,CARBOWAX PEG 200,300,400,600,900,1000,1450,3350,4000&8000,等等.)、或BASF Corp.的聚乙二醇(例如,200,300,400,600,1000,2000,3350,4000,6000和8000等等)。合适的聚烷撑二醇酯包括各种脂肪酸的单-和二酯,诸如BASF的的聚烷撑二醇酯(例如,或PEG 200单月桂酸酯或PEG400二油酸酯、或PEG 400单油酸酯、或PEG 600二油酸酯等等)。环氧乙烷(EO)和环氧丙烷(PO)的合适的共聚物包括BASF的各种Pluronic和Pluronic R嵌段共聚物表面活性剂、DOWFAX非离子表面活性剂、UCONTM流体和DOW Chemical的SYNALOX润滑剂。脱水山梨醇脂肪酸酯合适的聚氧化烯包括聚氧乙烯20脱水山梨醇单月桂酸酯(例如,以TWEEN20或T-MAZ 20的商标销售的产品)、聚氧乙烯4脱水山梨醇单月桂酸酯(例如,TWEEN 21)、聚氧乙烯20脱水山梨醇单棕榈酸酯(例如,TWEEN 40)、聚氧乙烯20脱水山梨醇单硬脂酸酯(例如,TWEEN 60或T-MAZ 60K)、聚氧乙烯20脱水山梨醇单油酸酯(例如,TWEEN 80或T-MAZ 80)、聚氧乙烯20三硬脂酸酯(例如,TWEEN 65或T-MAZ 65K)、聚氧乙烯5脱水山梨醇单油酸酯(例如,TWEEN81或T-MAZ 81)、聚氧乙烯20三油酸酯(例如,TWEEN 85或T-MAZ 85K)等等。
另外,传热流体中的缓蚀剂也可以包括一种或多种以下的化合物:衍生自松浆油脂肪酸的环己酮羧酸酯(cyclohexenoic carboxylate)化合物的胺盐,胺化合物,诸如一、二和三乙醇胺、吗啉、苄胺、环己胺、二环己胺、己胺、AMP(或2-氨基-2-甲基-1-丙醇或异丁醇胺)、DEAE(或二乙基乙醇胺)、DEHA(或二乙基羟胺)、DMAE(或2-二甲基氨乙醇)、DMAP(或二甲基氨-2-丙醇)、和MOPA(或3-甲氧基丙胺)。
多种聚二甲基硅氧烷乳液型可以在本发明中使用。它们包括:在Boscawen,NH中的Performance Chemicals,LLC的PC-5450NF;RI中Woonsocket中CNCInternational的CNC消泡剂XD-55NF和XD-56A。适合于在本发明中使用的其它消泡剂包括环氧乙烷(EO)和环氧丙烷(PO)的共聚物,诸如BASF的Pluronic L-61。
一般而言,任选的消泡剂可以包括硅氧烷,例如,由OSI Specialties、DowCorning或其它供应商可得的SAG 10或类似产品;环氧乙烷-环氧丙烷(EO-PO)嵌段共聚物和环氧丙烷-环氧乙烷-环氧丙烷(PO-EP-PO)嵌段共聚物(例如,PluronicL61、Pluronic L81、或其它Pluronic和Pluronic C产品);聚(环氧乙烷)或聚(环氧丙烷),例如,PPG 2000(即,具有2000的平均分子量的聚环氧丙烷);疏水的无定形二氧化硅;聚二有机硅氧烷基产品(例如,含有二甲基硅氧烷(PDMS)的产品等等);脂肪酸或脂肪酸酯(例如,硬脂酸等等);脂肪醇,烷氧化醇和聚乙二醇;聚醚型多元醇乙酸酯,聚醚型乙氧基化山梨醇六油酸酯(hexaoleate),和聚(乙氧烷-丙氧烷)单丙烯醚乙酸酯;石蜡,石脑油,煤油,和芳香油;以及含有一种或多种的前述消泡剂的组合。
示例性传热流体在美国专利公开号2010-0116473A1和2007-0075120-A1中描述,其通过引用以其整体并入。
上述方法和组合物通过以下非限制性实例进一步说明。
实施例
在实施例中,按照描述组合物的平衡是去离子水。
实施例1
取自具有铝CAB组件的传热系统的发动机机体沉积物是暴露于商业可得的传热系统清洁剂。在与沉积物接触之前和之后,由ICP测试清洁溶液。这个实施例是比较实施例。结果在表1中示出。
表1.
实施例1显示具有柠檬酸的商业清洁剂不足以解决该问题。特别地是,清洁溶液的pH大于8。
实施例2
用具有CAB铝组件的汽车传热系统的腐蚀产物封闭的铝热交换器管(型号#1)(它们在安装之前没有进行清洁)暴露于各种评估的清洁溶液,如表2中描述。清洁溶液在暴露于封闭管之前和之后通过电感耦合等离子体质谱(ICP)进行分析。在测试之前,一些管在一侧上切开打开,使得清洁流体通过吸管流溶液施加到打开的管内表面。一些管不切开打开。未打开的管通过缓慢地加入清洁溶液到管的一端(即,入口端)。清洁溶液从另一端(即,出口端)流出该管。“打开”管的外观在清洁之前和之后进行肉眼评估。封闭的管在清洁之后打开就行观察。清洁溶液加热至约90°C,且当热时施加至管,如在表2中描述。
表2
表3继续
*部分封闭闭合管
NA–不可得的
实施例2A证明有机磷酸盐溶液不能够去除管表面的沉积物。剩下的实施例显示使用含有具有pKa小于5的有机酸的清洁溶液去除了沉积物。
实施例3
用具有CAB铝组件的汽车传热系统的腐蚀产物封闭的铝热交换器管(型号#2)(它们在安装之前没有进行清洁)暴露于各种评估的清洁溶液,如表3中描述。清洁溶液在暴露于封闭管之前和之后通过电感耦合等离子体质谱(ICP)进行分析。管的外观在清洁之前和之后进行肉眼评估。清洁溶液加热至约90°C,且当热时施加至管。在清洁溶液与管表面接触之后,由于热交换器管的冷却作用,每个试验的表中列出的温度低于90°C。
表3
实施例4
车辆中使用的散热器的沉积物暴露于各种清洁溶液,其中传热系统包括通过CAB制成的铝组件(其在安装之前不进行清洁)。在暴露之前和暴露之后,通过ICP测试清洁溶液。样品的清洁溶液的测量的温度在表4中示出,其中测量了温度。结果在表5中。
表4
*E-时间:以分钟的所用时间
表5.
*比较实施例
表5.继续
实施例5
取自具有铝CAB组件的传热系统的沉积物暴露于各种溶液,如本文描述。在与沉积物接触之前和之后,清洁溶液通过ICP进行测试。结果在表6中示出。
表6.
实施例6
使用Corr Instruments NanoCorr的具有Corr可视化软件的耦合多电极传感器(CMS)分析仪测定测试溶液中的铸铝的局部腐蚀速率。在该研究中,使用由CorrInstruments提供的25-电极传感器阵列探针。探针的每一个电极由具有1mm2的暴露表面积的铝合金方形制成。密封在环氧中和在1.2×1.2cm矩阵阵列中均匀间隔开的25丝状电极进行电连接。耦合多电极探针模拟具有约1.4cm2的暴露表面积的常规的整块电极表面的腐蚀情况。局部腐蚀速率由探针通过测量探针中每个单独电极的耦合电流和进行测量数据的统计学分析得到作为时间的函数。在该研究中,使用每组数据30秒的取样速度。
容纳500毫升的Pyrex玻璃烧杯作为测试用单元。耦合多电极阵列传感器探针,Ag/AgCl(3M KCl)参比电极放置在具有与多电极传感器探针接近的Lugin探针中,而两个温度探针(即,具有不锈钢外壳的热偶和电阻检测器)安装在特氟龙单元套上并浸没在玻璃烧杯中的溶液中。特氟龙套用于使在试验期间溶液损失最小,并且也用于固定单元中测试探针的位置。在测试期间,使用微处理器控制热板加热溶液到期望的稳定。在测试期间,也使用特氟龙涂布的磁搅拌器棒搅动溶液。在测试期间,溶液暴露于空气。铝合金的腐蚀速率在不同溶液中评估。试验细节和结果在图1和2中示出。
本文所有公开的范围都是包括界限的且是可组合的。虽然本发明参照优选的实施方式进行了描述,但是本领域技术人员应该理解可以做出各种改变和等同物可以用于替换其元件,没有偏离本发明的范围。另外,可以做出多种修改以使本发明的特定状况或者材料适应于本发明的教导,没有偏离其基本范围。因此,意欲本发明不限制于作为被认为实现本发明的最佳实施方式公开的特定实施方式,而是本发明将包括落入附加权利要求的范围内的所有实施方式。
Claims (12)
1.处理系统,包括:
清洁剂,其包括吡咯化合物和在25℃具有小于或等于5.0的pKa的有机酸,其中清洁剂与水结合形成pH小于或等于5的清洁溶液,和
调节剂,所述调节剂包括焦磷酸盐、吡咯、和碱金属磷酸盐,其中所述调节剂与所述清洁剂分离,和
其中所述处理系统是车辆传热处理系统。
2.根据权利要求1所述的处理系统,其中所述有机酸包括草酸。
3.根据权利要求1所述的处理系统,进一步包括有机磷酸酯。
4.根据权利要求1所述的处理系统,其中所述清洁溶液具有小于或等于2.0的pH。
5.根据任一前述权利要求所述的处理系统,进一步包括再充填传热流体。
6.根据权利要求5所述的处理系统,其中所述再充填转移流体没有硅酸盐。
7.根据权利要求6所述的处理系统,其中所述清洁剂是固体。
8.传热系统的处理系统,包括:
清洁剂,其包括吡咯化合物和在25℃具有小于或等于5.0的pKa的有机酸;
调节剂,其与所述清洁剂分离,包括焦磷酸盐、吡咯、和碱金属磷酸盐;
其中所述清洁剂,当用水稀释时,在室温具有小于或等于2.0的pH,而调节剂,当用水稀释时,在室温具有大于或等于7.5的pH。
9.清洁传热系统的方法,包括:
从所述传热系统排放传热流体;
用清洁溶液充满所述传热系统,其中所述清洁溶液包括吡咯化合物和在25℃具有小于或等于5.0的pKa的有机酸,其中清洁溶液具有小于或等于5的pH;
循环所述清洁溶液通过所述传热系统;
从所述传热系统排放所述清洁溶液;
用调节溶液充满所述传热系统,所述调节溶液包括焦磷酸盐、吡咯、和碱金属磷酸盐;和
循环所述调节溶液通过所述传热系统,
其中所述传热系统包括控制气氛钎焊组件。
10.根据权利要求9所述的方法,其中所述清洁溶液具有小于或等于2.0的pH。
11.根据权利要求9或10所述的方法,其中在室温具有大于或等于7.5的pH。
12.根据权利要求11所述的方法,进一步包括排放所述调节溶液和用没有硅酸盐的传热流体充满所述传热系统。
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- 2010-07-06 US US12/830,854 patent/US8216383B2/en not_active Expired - Fee Related
- 2010-07-06 RU RU2012103915/04A patent/RU2012103915A/ru unknown
- 2010-07-06 IN IN614DEN2012 patent/IN2012DN00614A/en unknown
- 2010-07-06 WO PCT/US2010/041059 patent/WO2011005755A2/en active Application Filing
- 2010-07-06 BR BR112012000364A patent/BR112012000364A2/pt not_active IP Right Cessation
- 2010-07-06 EP EP10797714.2A patent/EP2451929A4/en not_active Withdrawn
- 2010-07-06 JP JP2012519666A patent/JP2012532245A/ja active Pending
- 2010-07-06 KR KR1020127002968A patent/KR20120061820A/ko not_active Application Discontinuation
- 2010-07-06 CA CA2767805A patent/CA2767805A1/en not_active Abandoned
- 2010-07-06 CN CN201080058311.3A patent/CN102762708B/zh not_active Expired - Fee Related
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Also Published As
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EP2451929A4 (en) | 2013-08-28 |
EP2451929A2 (en) | 2012-05-16 |
BR112012000364A2 (pt) | 2019-09-24 |
CN102762708A (zh) | 2012-10-31 |
US20110000505A1 (en) | 2011-01-06 |
RU2012103915A (ru) | 2013-08-20 |
US8216383B2 (en) | 2012-07-10 |
IN2012DN00614A (zh) | 2015-06-12 |
CA2767805A1 (en) | 2011-01-13 |
JP2012532245A (ja) | 2012-12-13 |
WO2011005755A3 (en) | 2011-04-28 |
WO2011005755A2 (en) | 2011-01-13 |
KR20120061820A (ko) | 2012-06-13 |
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