CN103415651B - 从含铁类的表面除锈的方法 - Google Patents
从含铁类的表面除锈的方法 Download PDFInfo
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- CN103415651B CN103415651B CN201280010699.9A CN201280010699A CN103415651B CN 103415651 B CN103415651 B CN 103415651B CN 201280010699 A CN201280010699 A CN 201280010699A CN 103415651 B CN103415651 B CN 103415651B
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- 238000000034 method Methods 0.000 title claims abstract description 56
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- 229910052742 iron Inorganic materials 0.000 title abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 38
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 229910000831 Steel Inorganic materials 0.000 claims description 12
- 239000010959 steel Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 6
- ROBFUDYVXSDBQM-UHFFFAOYSA-N hydroxymalonic acid Chemical compound OC(=O)C(O)C(O)=O ROBFUDYVXSDBQM-UHFFFAOYSA-N 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
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- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
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- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
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- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 7
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- XFTRTWQBIOMVPK-UHFFFAOYSA-N citramalic acid Chemical compound OC(=O)C(O)(C)CC(O)=O XFTRTWQBIOMVPK-UHFFFAOYSA-N 0.000 claims 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 2
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- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims 1
- 229910052901 montmorillonite Inorganic materials 0.000 claims 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 7
- 239000002253 acid Substances 0.000 description 14
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 14
- 229940094522 laponite Drugs 0.000 description 12
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- -1 N-butyric acie Chemical compound 0.000 description 8
- 238000013019 agitation Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000004927 clay Substances 0.000 description 6
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- 238000003756 stirring Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000009974 thixotropic effect Effects 0.000 description 4
- GLDQAMYCGOIJDV-UHFFFAOYSA-N 2,3-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1O GLDQAMYCGOIJDV-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- 239000005995 Aluminium silicate Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
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- 239000008273 gelatin Substances 0.000 description 3
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- YQUVCSBJEUQKSH-UHFFFAOYSA-N protochatechuic acid Natural products OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 description 3
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- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 2
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- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
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- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
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- C—CHEMISTRY; METALLURGY
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
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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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Landscapes
- Chemical & Material Sciences (AREA)
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Abstract
披露了从含铁类的表面除锈的方法。这些方法包括使该表面与包含羧酸、合成锂蒙脱石粘土、和水的组合物接触。
Description
发明领域
本发明涉及从含铁类的表面除锈的方法等。
发明背景
在加工期间，或只是暴露于大气期间，金属氧化物层，即锈，经常会形成在铁类金属表面的全部或一部分上，从而损害其外观和/或进一步使用的适应性。一个例子是钢，例如在多种制品的制造中使用的低碳钢。因此，经常期望除去该金属氧化物层。一般来说，这样的去除通过用强酸例如硝酸、硫酸、盐酸或磷酸处理锈蚀的金属表面来完成。然而，这些高酸性的、腐蚀性和剧烈的化学品从环境和安全性方面来看通常是不期望的。
在一些情况中，待处理的铁类是以基本上竖直的方向定位的，例如可以是例如大的结构(例如储罐、船和其它交通工具、和桥梁等)的情况。此外，为了方便有效使用，通常期望可喷洒的产品。
因此，期望提供一种通过使用不含环境上不期望的强酸的可喷洒的组合物从含铁类的表面(包括以基本上竖直方式定位的那些)除锈的方法。
发明概述
在某些方面，本发明涉及从含铁类的表面除锈的方法。该方法包括使该表面与包含：(a)羧酸；(b)合成锂蒙脱石粘土；和(c)水的组合物接触。本发明还涉及通过前述方法处理的含铁类的表面等。
发明实施方式的详细说明
为了以下详细说明的目的，应理解，本发明可涵盖各种替换变型和步骤顺序，除非有明确的相反说明。此外，除了在任何操作实施例中，或另有说明，所有表达例如说明书和权利要求书中使用的成分的量的数都应理解为在所有情况下被术语“约”修饰。因此，除非另有说明，以下说明书和所附权利要求书中给出的数值参数是近似值，并且可根据本发明所获得的期望性质而改变。最起码，并且不视图限制等同原则适用于权利要求的范围，各数值参数应至少根据所报告的有效数字的数量并适用一般的死四舍五入技术来理解。
虽然限定本发明的宽泛范围的树脂范围和参数是近似值，但具体实施例中给出的数值是尽可能精确地报道的。然而，任何数值固然含有由它们各自的测量方式参数的标准偏差必然导致的误差。
此外，应理解，本文引述的任何数值范围意图包括所有其中的子范围。例如，“1-10”的范围意图包括在所引述的最小值1和所引述的最大值10之间的所有子范围(并且包括端点值)，也就是说，最小值等于或大于1且最大值等于或小于10。在本申请中，单数形式的使用包括复数形式，并且复数形式涵盖单数形式，除非另有具体说明。此外，在本申请中，除非另有具体说明，使用“或”表示“和/或”，但“和/或”可能明确地在某些情形中使用。
如前所述，本发明的某些实施方式涉及从含铁类的表面除锈的方法。本文使用的“锈”是指通过氧化或腐蚀在金属上形成的涂层或膜。在一些情况下，在本发明的方法中除去的锈是“红锈”，本文使用的“红锈”是指通过氧化(例如在暴露于空气和/或湿气期间)在铁或钢上形成的涂层或膜，其包含铁(II)氧化物(FeO，方铁矿)，α相铁(III)氧化物(α-Fe2O3，赤铁矿)，β相铁(III)氧化物(β-Fe2O3)，γ相铁(III)氧化物(γ-Fe2O3，磁铁矿)，ε相铁(III)氧化物(ε-Fe2O3)，铁(II)氢氧化物(Fe(OH)2)，铁(III)氢氧化物(Fe(OH)3，bernalite),和/或任意前述物质的水合形式和组合。在一些实施方式中，在本发明的方法中除去的铁氧化物通常被称作“轧屑”，本文使用的“轧屑”是指氧化(例如暴露于空气、湿气、和/或热期间)在铁或钢上形成的涂层或膜，其包含铁(II,III)氧化物(Fe3O4，磁铁矿)，α相铁(III)氧化物(α-Fe2O3，赤铁矿)，铁(II)氢氧化物Fe(OH)2，(III)氢氧化物(Fe(OH)3，bernalite),和/或任意前述物质的水合形式和组合。
可在本发明的方法中处理的金属表面包括，但不限于，由以下构成的表面：冷轧钢，热轧钢，用锌金属、锌化合物、或锌合金涂覆的钢，例如电镀锌钢、热浸镀锌钢、热镀锌钢，和用锌合金电镀的钢。由低碳钢构成的表面可在本发明的方法中处理。本文使用的低碳钢是指含小于0.25wt%碳的低碳钢。
在本发明的方法中，金属表面与包含羧酸的组合物接触。在某些实施方式中，选用于本文所述的组合物中的羧酸在20℃的水溶解度>1g/L。适用于本发明的方法中使用的组合物的羧酸包括，例如，单羧酸，例如甲酸、乙酸、丙酸、甲基乙酸、丁酸、乙基乙酸、正戊酸、正丁酸、丙烯酸、丙炔酸、甲基丙烯酸、棕榈酸、硬脂酸、油酸、亚油酸、和亚麻酸；二羧酸，例如草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、lepargilic酸、癸二酸、马来酸、和富马酸；脂族羟基酸，例如乙醇酸、乳酸、丙醇二酸、甘油酸、苹果酸、酒石酸、柠苹酸、柠檬酸、异柠檬酸、亮氨酸、甲羟戊酸、泛解酸、蓖麻油酸、反蓖麻油酸、脑酮酸、奎宁酸，和莽草酸；芳族羟基酸，例如水杨酸、萘酚油酸、香草酸、丁香酸、焦儿茶酸、二羟基苯甲酸、原儿茶酸、龙胆酸、苔色酸、没食子酸、扁桃酸、二苯乙醇酸、阿卓乳酸、草木犀酸、根皮酸、香豆酸、伞形酸、咖啡酸、阿魏酸、和芥酸。也可使用任何前述物质的混合物。
在某些实施方式中，羧酸以至少1重量%，例如至少10重量%，或在一些情况下,至少15重量%的量存在于本发明的方法中使用的组合物中，其中该重量百分比基于所述组合物的总重量计。在某些实施方式中，羧酸以不超过50重量%，例如不超过30重量%，或在一些情况下不超过25重量%的量存在于本发明的方法中使用的组合物中，其中该重量百分比基于所述组合物的总重量计。
在本发明的方法中，与含铁类的表面接触的组合物还包含合成锂蒙脱石粘土。本文所述的组合物中合成锂蒙脱石粘土的存在产生了具有高剪切变薄、触变流变性的增稠组合物。因此，该组合物是利用普通喷洒设备(包括下述的那些)可喷洒的，并且，已经发现，保留在含铁类的表面上足以有效除锈的时间，即使该表面基本上竖直地定向。本文使用的术语“基本上竖直地”表示基本上垂直(即垂直±20%以内)于设置有的含铁类的表面地面或其它表面。实际上，令人惊奇地发现，与其他增稠剂，包括其它触变粘土(例如高岭土和膨润土粘土)相反，使用合成锂蒙脱石粘土产生了即在环境条件下可喷洒、又可以有效地从含铁类的表面除锈(即使当该表面基本上竖直地定向时)的组合物。目前认为，会需要产生从基本上竖直地定向表面除锈的有效组合物的其它触变粘土的量是在环境条件下不可喷洒的。本文使用的“环境条件”是指23℃和大气压。
适用于本文所述的组合物的合成锂蒙脱石粘土包括，例如，LAPONITE RD、LAPONITE RDS、和LAPONITE JS，包括它们的组合。如能够领会的，各个这些均为根据化学式NaO3(Mg,Li)3Si4O10(F,OH)2的层结构化的含水硅酸镁。LAPONITE RD是自由流动的合成层状硅酸盐，其堆密度为1,000kg/m3，表面积(BET)为370m2/g，在水中2%悬液的pH为9.8，其中该组合物以干重量计为59.5%SiO2、27.5%MgO、0.8%Li2O、和2.8%Na2O。LAPONITE RDS也是合成层合成层状硅酸盐，其堆密度为1,000kg/m3，表面积(BET)为330m2/g，在水中2%悬液的pH为9.7其中该组合物以干重量计为54.5%SiO2、26.0%MgO、0.8%Li2O、5.6%Na2O、和4.1%P2O5。合成锂蒙脱石，例如上述那些，的粒度典型地为1-30纳米的平均直径。
在某些实施方式中，该合成锂蒙脱石粘土以至少1重量%，例如至少2重量%，或在一些情况下至少3重量%的量存在于本发明的方法中使用的组合物中，其中该重量百分比基于所述组合物的总重量计。在某些实施方式中，该合成锂蒙脱石粘土以不超过10重量%，例如不超过6重量%，或在一些情况下不超过5重量%的量存在于本发明的方法中使用的组合物中，其中该重量百分比基于所述组合物的总重量计。
在某些实施方式中，本发明的方法中使用的组合物进一步包含氯离子源。当需要或期望除去轧屑时，氯离子源的存在可以是特别有利的。合适的氯离子源包括，例如，盐酸、氯化钙、氯化钠、氯化铵、和氯化钾等。
在某些实施方式中，该氯离子源以至少1重量%，例如至少2重量%，或在一些情况下至少3重量%的量存在于本发明的方法中使用的组合物中，其中该重量百分比基于所述组合物的总重量计。在某些实施方式中，该氯离子源以不超过10重量%，例如不超过8重量%，或在一些情况下不超过6重量%的量存在于本发明的方法中使用的组合物中，其中该重量百分比基于所述组合物的总重量计。
在某些实施方式中，本发明的方法中使用的组合物进一步包含有机溶剂，例如水混溶的有机溶剂。合适的此类溶剂包括乙二醇或二乙二醇的单烷基或二烷基醚，或三乙二醇及其乙酸酯衍生物的单、二、或三烷基醚。烷基基团通常范围在1-4个碳原子。合适的实例有含至少四个碳原子的饱和二醇或含式I的化合物：
其中：R独立地选自氢、1-4碳原子的烷基和-(O)C-CH3；R1独立地选自-CH2、-CH2-CH-、-CH2-CH(CH3)-、和-CH(CH2OH)-；R2独立地选自1-4碳原子的烷基，羟基取代的1-4碳原子的烷基和-(O)C-CH3。
示例溶剂有溶纤剂(乙二醇的单乙基醚的商标)，甲基溶纤剂，丁基溶纤剂，异丁基溶纤剂，己基溶纤剂，卡必醇(二乙二醇的单乙基醚的商标)，丁基卡必醇，己基卡必醇，丙二醇的单丁基醚，丙二醇的单丙基醚，丙二醇的单甲基醚，二丙二醇的单甲基醚，丁氧基三甘醇C4H9O(C2H4-O)3H，甲氧基三甘醇CH3O(C2H4-O-)3H，乙氧基三甘醇C2H5O(C2H4O)3H，1,丁氧基乙氧基-2-丙醇，二乙二醇，三乙二醇，四乙二醇，丙二醇，二丙二醇，三丙二醇，聚丙二醇(分子量至多2000)，己二醇，2-乙基-1,3-己二醇；1,5-戊二醇，酯二醇-204(2,2-二甲基-3-羟基丙酸2,2-二甲基-3-三羟基丙基酯)等。
可用于本发明的合适的水混溶的醇具有1-8个碳原子，例如甲醇、乙醇、丙醇、丁醇、异丁醇、戊醇、己醇、庚醇、辛醇、甲基戊醇等
可用于本发明的合适的水混溶的脂族酮有丙酮、甲基乙基酮、二乙基酮、甲基丙基酮、甲基异丁基酮、甲氧基丙酮、环己酮、甲基正戊基酮、甲基异戊基酮、乙基丁基酮、二异丁基酮、异氟尔酮、乙酰基丙酮(2,4-戊二酮)、二丙酮醇(CH3)2C(OH)CH2C(O)CH3。
在某些实施方式中，该有机溶剂以至少1重量%，例如至少2重量%，或在一些情况下至少3重量%的量存在于本发明的方法中使用的组合物中，其中该重量百分比基于所述组合物的总重量计。在某些实施方式中，该氯离子源以不超过10重量%，例如不超过8重量%，或在一些情况下不超过6重量%，的量存在于本发明的方法中使用的组合物中其中该重量百分比基于所述组合物的总重量计。
本发明的方法中使用的组合物还可以包含任意多种任选成分，例如着色剂、表面活性剂、腐蚀抑制剂、防腐剂、填料、磨蚀剂、缓冲剂、香料等。
本发明的方法中使用的组合物的其余部分典型地为水，例如去离子水。
在某些实施方式中，本发明的方法中使用的组合物基本上不含、完全不含产生环境上不期望的副产物的强酸，例如磷酸和/或硫酸。本文使用的“基本上不含”当用于本文所述的组合物中不含强酸时，表示该组合物包含小于1wt%，例如小于0.1wt%的强酸。本文使用的“完全不含”表示组合物中完全没有强酸。
在某些实施方式中，本发明的方法中使用的组合物具有低剪切粘度(本文使用的“低剪切粘度”是指用Physica MCR301粘度计利用CP50-1/TG纺锤体在0.01s(-1)的剪切速率和在23℃下70秒测量的粘度。)为至少1,000Pa·s，例如至少2,000Pa·s，或在一些情况下至少4,000Pa·s，或至少5,000Pa·s。在某些实施方式中，本发明的方法中使用的组合物具有高剪切粘度(本文使用的“高剪切粘度”是指用Physica MCR301粘度计利用CP50-1/TG纺锤体在10(4)s(-1)的剪切速率下在23℃下5秒钟测量的粘度。)为不超过0.50Pa·s，例如不超过0.1Pa·s，或在一些情况下不超过0.01Pa·s。
在某些实施方式中，本发明的方法中使用的组合物的pH为不超过6.0，例如2.0-5.0，或在一些情况下3.0-4.0。
在本发明的方法中，组合物通过任意各种方法与含金属表面接触，例如通过刷涂、喷洒、或浸渍等方法。本文所述的组合物特别适合于利用常规压力罐设备或HVLP设备喷洒施用。由于本文所述组合物的触变特性，本发明的方法可以适用于基本上竖直地定向含铁类的表面，例如可以是具有例如大型结构体的情况，例如储罐、桥梁、船和其它交通工具等。
施用后，使该组合物保留在含金属表面上以以期望和需要的程度除锈。接触时间通常为至少5分钟至数小时，通常至少30分钟，在一些情况下至少3或4小时，这取决于锈蚀程度和进行清洁的温度。然后可用水洗涤经除锈的表面以除去本文所述的组合物、松弛的锈和溶解的锈。在一些情况下，可能需要一次以上施用本文所述的组合物。还可期望例如在施用本文所述的组合物前，通过金属丝刷以机械方式除去松弛的锈和垢。
本发明还特别涉及通过本发明的方法处理过的金属表面。
以下实施例说明本发明，但不应视为限制本发明为其细节。实施例以及整个说明书中的份数和百分比都以重量计，除非另有说明。
实施例1
用表1中列出的成分和量(以克计)制备5种溶液。锈蚀板通过用市售碱性清洁剂(CK2010，可商购自PPG Industries，Inc.)清洗3x4英寸冷轧钢裸板(可购自ACT TestPanels LLC273Industrial，Dr.Hillsdale，MI49242)，然后将该板放在盐雾室4小时来准备。将该板用去离子水漂洗并环境条件下空气干燥，然后施用溶液。
表1
| 成分 | 实施例1A | 实施例1B | 实施例1C | 实施例1D | 实施例1E |
| Laponite RD1 | 6 | -- | -- | -- | -- |
| Klucel M2 | -- | 1.5 | -- | -- | -- |
| Klucel H3 | -- | -- | 1.5 | -- | -- |
| 聚乙烯基吡咯烷酮4 | -- | -- | -- | 15 | -- |
| 明胶(小牛皮)5 | -- | -- | -- | -- | 15 |
| 去离子水 | 114 | 118.5 | 118.5 | 105 | 105 |
| 柠檬酸 | 30 | 30 | 30 | 30 | 30 |
1Laponite RD is可商购自Southern Clay Products，Inc。在实施例1A中，根据制造商的推荐方式将Laponite RD加入水中。然后在搅拌溶液时将柠檬酸缓慢加入。
2Klucel M是羟基丙基纤维素(Mw为约850,000)，可购自Hercules Inc。在实施例1B中，将Klucel M材料在搅拌下撒在水中。该材料溶解后，在搅拌下缓慢加入柠檬酸。
3Klucel H是羟基丙基纤维素(Mw为约1,150,000)，可购自Hercules Inc。在实施例1C中，将Klucel H材料在搅拌下撒在水中。该材料溶解后，在搅拌下缓慢加入柠檬酸。
4聚乙烯基吡咯烷酮，可商购自Sigma-Aldrich Co.，其平均Mw为约1,300,000。在实施例1D中，将聚乙烯基吡咯烷酮在搅拌下撒在水中。该材料溶解后，在搅拌下缓慢加入柠檬酸。
5明胶可商购自Sigma-Aldrich Co。在实施例1E中，将明胶在搅拌下撒在水中。该材料溶解后，在搅拌下缓慢加入柠檬酸。
测试基材
用试管将各上述溶液的一部分施涂在一组以与水平成大约80°角放置的锈蚀钢板上。2小时后，将该板用去离子水漂洗并检查被除去锈的近似百分比。结果见于表2。
表2
| 实施例 | 除去的锈的大致% |
| 1A | 100 |
| 1B | 80 |
| 1C | 90 |
| 1D | 50 |
| 1E | 30 |
实施例2
用表3中列出的成分和量(以克计)制备三种溶液。在各实例中，将粘土在搅拌下撒到水中。含Laponite RD的材料在掺入几分钟后显示出提高的粘度。在20分钟内，溶液变透明，并且没有可见颗粒。膨润土溶液在加入水后显示非常轻微的粘度改变，该材料保持不透明的蓝绿色。高岭土材料在加入后没有显示出任何粘度改变。各种粘土加入后，将溶液搅拌大约20分钟，加入柠檬酸，并将所得混合物搅拌约10分钟。
表3
| 成分 | 实施例2A | 实施例2B | 实施例2C |
| 去离子水 | 380 | 380 | 380 |
| Laponite RD1 | 20 | -- | -- |
| 膨润土2 | -- | 20 | -- |
| 高岭土2 | -- | -- | 20 |
| 柠檬酸 | 100 | 100 | 100 |
1可商购自Southern Clay Products，Inc。
2可商购自VWR International，LLC。
锈蚀板如实施例1中所述制备。用园艺喷雾器将三种溶液喷洒施用到以与水平成大约80°角放置的板上。1小时后，用水漂洗该板，并目视评估锈的去除量。大约100%的锈被实施例2A的溶液除去，而实施例2B和2C都没有显示出任何除去锈。
三种溶液的流变性使用Paar-Physica MCR301流变计用CP50-1/TG纺锤体在23℃和各种剪切速率下测量。结果示于表4。
表4
| 剪切速率(1/s) | 实施例2A(Pa·s) | 实施例2B(Pa·s) | 实施例2C(Pa·s) |
| 0.01 | 5,040 | 35.8 | 8.92 |
| 0.1 | 457 | 4.65 | 1.03 |
| 1 | 54.2 | 0.551 | 0.115 |
| 10 | 4.42 | 0.0678 | 0.0295 |
| 100 | 0.319 | 0.0141 | 0.00693 |
| 1000 | 0.0683 | 0.00641 | 0.00328 |
实施例3
使用表5中列出的成分和量(以克计)制备含相同理论量的氯离子的三种溶液。在各情形中，根据制造商的推荐方式将Laponite RD加入水中。然后在搅拌溶液下将柠檬酸缓慢加入。对于实施例3A，然后在搅拌下逐滴加入盐酸。对于实施例3B，然后在搅拌下加入氯化钠。对于实施例3C，然后在搅拌下加入氯化铵。
表5
| 成分 | 实施例3A | 实施例3B | 实施例3C |
| 去离子水 | 317.5 | 342.9 | 346.1 |
| Laponite RD | 20 | 20 | 20 |
| 柠檬酸 | 100 | 100 | 100 |
| 37%HCl1 | 62.5 | -- | -- |
| NaCl1 | -- | 37.1 | -- |
| NH4Cl1 | -- | -- | 33.9 |
1可商购自VWR International，LLC。
锈蚀板如实施例1制备。将三种溶液施涂至与水平呈大约80°角放置的板。1小时后，用水漂洗该板，并目视评估锈的去除量。用三种溶液都除去了大约100%的锈。
实施例4
使用表6中列出的成分和量(以克计)制备含相同理论量的含羧酸化合物的三种溶液。在各情形中，根据制造商的推荐方式将LaponiteRD加入水中。然后在搅拌溶液下将酸缓慢加入。
表6
| 成分 | 实施例4A | 实施例4B | 实施例4C |
| 去离子水 | 106.5 | 106.5 | 116 |
| Laponite RD | 6 | 6 | 6 |
| 乳酸(80%，H2O中)1 | 37.5 | -- | -- |
| 酒石酸(80%，H2O中)1 | -- | 37.5 | -- |
| 柠檬酸 | -- | -- | 30 |
1可商购自VWR International，LLC。
锈蚀板如实施例1制备。将三种溶液施涂至与水平呈大约80°角放置的板。1小时后，用水漂洗该板，并目视评估锈的去除量。用三种溶液都除去了大约100%的锈。
本领域技术人员将领会，对上述实施方式可进行改变而不会背离本发明的宽泛概念。因此，应理解，本发明不限于所披露的特定实施方式，而是意图涵盖在本发明主旨和范围内的改型，如所附权利要求中所限定。
Claims (15)
1.从含铁类金属的表面除锈的方法，包括使该表面与包含以下的组合物接触：
(a)羧酸，其中所述羧酸包括草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、马来酸、富马酸、丙醇二酸、苹果酸、酒石酸、柠苹酸、柠檬酸、异柠檬酸或它们的混合物；
(b)合成锂蒙脱石粘土，所述合成锂蒙脱石粘土基于所述组合物的总重量计以至少3重量％且不超过10重量％的量存在；和
(c)水。
2.权利要求1的方法，其中所述锈包含铁氧化物和/或铁氢氧化物。
3.权利要求1的方法，其中所述铁类金属包括钢。
4.权利要求3的方法，其中所述钢包括低碳钢。
5.权利要求1的方法，其中所述羧酸基于所述组合物的总重量计以至少10重量％且不超过30重量％的量存在于所述组合物中。
6.权利要求1的方法，其中所述合成锂蒙脱石粘土的化学式为NaO3(Mg,Li)3Si4O10(F,OH)2。
7.权利要求1的方法，其中所述合成锂蒙脱石的平均直径为1-30纳米。
8.权利要求1的方法，其中所述组合物进一步包含氯离子源。
9.权利要求1的方法，其中所述组合物的低剪切粘度为至少1,000Pa·s且高剪切粘度为不超过0.50Pa·s。
10.权利要求9的方法，其中所述组合物的低剪切粘度为至少4,000Pa·s且高剪切粘度为不超过0.01Pa·s。
11.权利要求1的方法，其中所述组合物的pH为不超过6.0。
12.权利要求1的方法，其中所述接触包括将所述组合物喷洒到含铁类金属的表面上。
13.权利要求12的方法，其中所述含铁类金属的表面基本上竖直地定向。
14.从含铁类金属的表面除锈的方法，包括将组合物喷洒施用到所述含铁类金属的表面的至少一部分上，所述组合物包含：
(a)羧酸，其中所述羧酸包括草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、马来酸、富马酸、丙醇二酸、苹果酸、酒石酸、柠苹酸、柠檬酸、异柠檬酸或它们的混合物；
(b)合成锂蒙脱石粘土，所述合成锂蒙脱石粘土基于所述组合物的总重量计以至少3重量％且不超过10重量％的量存在；和
(c)水，
其中(i)所述含铁类金属的表面基本上竖直地定向，以及(ii)所述组合物的低剪切粘度为至少1,000Pa·s且高剪切粘度为不超过0.50Pa·s。
15.权利要求14的方法，其中所述组合物进一步包含氯离子源。
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| Application Number | Priority Date | Filing Date | Title |
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| US13/011,151 | 2011-01-21 | ||
| US13/011,151 US20120189485A1 (en) | 2011-01-21 | 2011-01-21 | Methods of removing rust from a ferrous metal-containing surface |
| PCT/US2012/022004 WO2012100146A1 (en) | 2011-01-21 | 2012-01-20 | Methods of removing rust from a ferrous metal-containing surface |
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| US8852357B2 (en) | 2011-09-30 | 2014-10-07 | Ppg Industries Ohio, Inc | Rheology modified pretreatment compositions and associated methods of use |
| CN103898529B (zh) * | 2014-04-22 | 2017-02-15 | 东北大学 | 一种除锈方法 |
| JP6727019B2 (ja) * | 2016-04-22 | 2020-07-22 | ショーボンド建設株式会社 | 鋼材の下地処理方法、および下地処理剤 |
| CN109628940B (zh) * | 2019-01-21 | 2021-11-12 | 常熟理工学院 | 一种多羟基苯甲酸型水基中性除锈剂 |
| KR102166122B1 (ko) | 2020-04-13 | 2020-10-15 | 케이알건설 주식회사 | 강 교량의 녹 또는 페인트 제거방법 |
| MX2022015215A (es) * | 2020-06-10 | 2023-01-04 | Chemetall Gmbh | Composiciones de decapado acuosas y sin fosfonato, y su uso. |
| JP7426641B1 (ja) | 2023-09-18 | 2024-02-02 | スズカファイン株式会社 | 既設鋼材の錆の除去方法 |
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| US20020037822A1 (en) * | 2000-07-19 | 2002-03-28 | Foley Peter Robert | Cleaning composition |
| US6514350B1 (en) * | 2000-09-15 | 2003-02-04 | Ashland Inc. | Process for removing rust from metal surfaces |
| US20040149311A1 (en) * | 2002-11-15 | 2004-08-05 | The Procter & Gamble Company | Method for cleaning cookware and tableware with film-forming liquid dishwashing compositions, and compositions therefore |
| US20060076299A1 (en) * | 2004-10-08 | 2006-04-13 | The Hong Kong University Of Science And Technology | Synthesis of bentonite clay-based iron nanocomposite and its use as a heterogeneous photo fenton catalyst |
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| US20060079424A1 (en) * | 2004-09-23 | 2006-04-13 | Perry Stephen C | Buffered acid cleaner and method of production |
| US20090197792A1 (en) * | 2008-02-05 | 2009-08-06 | Amcol International Corporation | Drip resistant acidic compositions for sprayable and non-sprayable application |
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| US20120189485A1 (en) | 2012-07-26 |
| BR112013018680A2 (pt) | 2016-10-18 |
| SG192055A1 (en) | 2013-08-30 |
| TR201807940T4 (tr) | 2018-06-21 |
| KR20130117853A (ko) | 2013-10-28 |
| EP2665845B1 (en) | 2018-03-07 |
| WO2012100146A1 (en) | 2012-07-26 |
| MX2013008465A (es) | 2013-12-06 |
| AU2012207164B2 (en) | 2015-08-20 |
| JP5693754B2 (ja) | 2015-04-01 |
| CA2825284A1 (en) | 2012-07-26 |
| NZ613553A (en) | 2015-11-27 |
| EP2665845A1 (en) | 2013-11-27 |
| PL2665845T3 (pl) | 2018-08-31 |
| ES2666452T3 (es) | 2018-05-04 |
| JP2014508220A (ja) | 2014-04-03 |
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