CN110073032A - 金属组件的防腐和清洁预处理的方法 - Google Patents
金属组件的防腐和清洁预处理的方法 Download PDFInfo
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- CN110073032A CN110073032A CN201780077935.1A CN201780077935A CN110073032A CN 110073032 A CN110073032 A CN 110073032A CN 201780077935 A CN201780077935 A CN 201780077935A CN 110073032 A CN110073032 A CN 110073032A
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Classifications
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/08—Acids
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
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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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/261—Alcohols; Phenols
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/268—Carbohydrates or derivatives thereof
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- C23C22/44—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates containing also fluorides or complex fluorides
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Abstract
本发明涉及金属组件的抗腐蚀和清洁预处理的方法，所述金属组件至少部分地由选自元素铁、锌和/或铝的金属材料制成，使用除了元素Zr和/或Ti的水溶性化合物之外还含有脂族二醇和脂族饱和多羟基化合物的混合物的酸性含水组合物，所述元素Zr和/或Ti的水溶性化合物会导致金属表面的转化。还包含基于上述成分的不含铬(VI)的含水组合物，其在一个方法步骤中在工程金属表面的清洁和同时抗腐蚀转化方面具有优异的结果。
Description
技术领域
本发明涉及一种对金属组件进行抗腐蚀和清洁预处理的方法，所述金属组件至少部分地由元素铁、锌和/或铝的金属材料制成，所述方法使用除了元素Zr和/或Ti的水溶性化合物外还含有脂族二醇和脂族饱和多羟基化合物的混合物的酸性含水组合物，所述元素Zr和/或Ti的水溶性化合物会导致金属表面的转化。还包括基于上述成分的不含铬(VI)的含水组合物，其在一个方法步骤中在工程金属表面的清洁和同时抗腐蚀转化方面提供优异的结果。
在施加保护性涂层和/或装饰性涂层，例如油漆之前，通常将转化涂层施加到金属基材上，特别是含有铁、锌和/或铝材料的金属组件。大量组件的工业涂布需要进行连续预处理，其中每个组件以预定顺序进行多个处理阶段。该连续预处理通常包括分别的清洁和预处理的方法步骤，合适的话，包括涂布，每个工艺步骤始终跟随用于从前述方法步骤中除去活性组分的清洗步骤(rinsing step)。对组件进行湿化学清洁的步骤通常是为了准备组件以基于基材和污染类型进行处理，提供了大量酸洗碱性或酸性清洁剂作为中性清洁剂以除去组件的典型杂质，例如抗腐蚀油、切削油和冷却润滑剂，并调理所述组件的金属表面以用于随后的湿化学预处理步骤。同时，转化处理通常以工业规模进行，并且旨在临时防腐并且提供合适的油漆基料为金属表面提供基于元素Zr和/或Ti的无定形无机涂层。对于所述目的，这种转化处理可以产生基于上述元素的1-100mg/m2的湿化学层沉积物，具有优于基于消耗较少活性组分的磷酸盐的常规部分结晶转化层的优点，并因此，由于较少的方法步骤且在没有磷酸盐的情况下进行配制，在工厂技术方面会节省资源且更有效。现有技术还描述了这样的转化处理方法，其中在一个步骤中进行组件的清洁和组件的金属表面的转化。
WO 2012/178003 A2描述了一种酸性含水组合物，其适用于金属表面的清洁和转化，并含有溶于水中的锆源以及阳离子与非离子表面活性剂的混合物，其中优选将烷基聚乙二醇醚、乙氧基化的脂肪胺和脂肪醇以及EO/PO嵌段共聚物用作非离子表面活性剂，并且将季铵化的烷基铵盐用作阳离子表面活性剂。
鉴于该现有技术，本发明的目的是开发一种替代的转化处理步骤，其中金属组件的清洁可以在一个步骤中与转化同时进行，该方法特别适用于含有铁材料的组件。它还可用于在尽可能低的温度下进行清洁和转化，理想情况下远低于40℃，以避免在由铁制成的表面上形成闪锈，并显著降低工艺中的总能耗。
该目的借助一种用于金属组件的清洁和抗腐蚀预处理的方法实现，所述金属组件至少部分地由主要由金属铁、锌和/或铝中的一种或多种而组成的材料组成，所述方法通过使所述组件与含有如下成分的酸性含水组合物接触而进行，
对金属组件进行清洁和抗腐蚀预处理的方法，所述金属组件至少部分地由主要由金属铁、锌和/或铝中的一种或多种组成的材料组成，所述方法通过使所述组件与含有如下成分的酸性含水组合物接触而进行：
a)至少0.003重量％的具有至少4个碳原子但不多于10个碳原子的脂族二醇；
b)至少0.01重量％的具有至少4个但不多于8个碳原子的脂族饱和多羟基化合物；
c)至少一种元素Zr和/或Ti的水溶性化合物；
d)至少一种水溶性氟离子源。
根据本发明处理的组件可以是来自制造工艺的任何形状和设计的空间结构，特别还包括半成品，例如条带、金属板、棒、管等，以及由所述半成品组装的复合结构，其中所述半成品优选借助粘合、焊接和/或法兰连接(flanging)而相互连接以形成复合结构。
如果材料中的这些元素的原子比例总共大于50原子％，则金属材料主要由元素铁、锌和/或铝组成。
所述金属材料也可以是金属涂布的基材，条件是金属涂层具有至少1μm的层厚度并且由至少50原子％的之前限定的构成元素组成。这种材料都是电镀的铁类材料(ferrousmaterials)，例如电镀或热浸镀锌钢，优选以锌(Z)、铝硅(AS)、锌镁(ZM)、锌铝(ZA)、铝锌(AZ)或锌铁(ZF)的形式电镀。
在本发明的方法中，在一个方法步骤中从金属表面除去来自上游生产阶段的杂质，例如抗腐蚀油、切削油和冷却润滑剂，并且施用呈转化涂层形式的防腐油漆基料。特别地，即使在较低的工作温度下，在本发明的方法中也可以实现金属表面的充分清洁和抗腐蚀转化。总之，本发明的方法还允许在仅有几个处理阶段的***中对组件进行预处理，由于即使在低工作温度下也可以操作的事实，该方法具有额外的经济性。
已经证明，至少部分由铁类材料组成的组件的处理对于本发明的方法是特别有利的。与其他金属材料相比，可以在铁类材料的表面上检测到清洁效果的更大改进和防腐油漆基料的促进。铁类材料的特征在于其铁含量大于50原子％。优选的铁类材料是钢，包括金属材料的钢，所述金属材料的铁的质量分数大于每种其他元素，并且其中不考虑碳化物的碳含量小于2.06重量％。
本发明方法的显著优点在于，从组件的金属表面清洁来自上游生产阶段的基于有机化合物的助剂即使在较低的工作温度下也可成功地进行，所述助剂例如抗腐蚀油、切削油和冷却润滑剂。在本发明方法的一个优选实施方案中，当组合物的温度低于40℃，特别优选低于35℃，更特别优选低于30℃，但优选至少20℃时，发生与酸性含水组合物的接触。在本文中，还优选在本发明方法中所述酸性含水组合物的接触是通过喷雾(Aufspruhen)或喷射(Aufspritzen)，特别优选通过喷射，更特别优选在至少1巴的喷射压力下进行，以实现金属表面的最佳清洁和快速转化。
由于在使组件与酸性含水组合物接触时，表面不含基于有机化合物的助剂，因此可以完全省去前面的清洁步骤。在本发明方法的优选实施方案中，因此在直接优选通过喷雾或喷射而使组件与酸性含水组合物接触之前，不对组件进行湿化学清洁。
根据本发明，湿化学清洁通过与水基组合物接触而进行清洁，其中所述水基组合物总共含有至少0.1重量％的表面活性剂和/或润湿剂，其中表面活性剂和/或润湿剂包括所有在20℃和0.1重量％的比例下会降低水的表面张力的有机化合物，所述表面张力使用Wilhelmy板法测定。
直接在使组件与酸性含水组合物接触之后，在有或者没有中间清洗和/或干燥步骤的情况下，在本发明的方法中，优选将所述组件的先前与酸性含水组合物接触的区域至少部分地进行涂布，优选浸渍涂布，特别是电涂布或粉末涂布。
在本发明的定义中，“清洗步骤”表示仅用于从组件的表面尽可能地去除来自之前的湿化学处理步骤的溶解于粘附于组件上的湿膜中的活性组分的方法，其借助清洗溶液，而不用其他活性组分替换待除去的活性组分。在本申请上下文中的活性组分为包含在液相中的成分，其使得组件的金属表面的可分析检测的涂层具有活性组分的元素成分。
在本发明的定义中，“干燥步骤”是指这样的过程，其中具有湿膜的金属组件的表面意欲借助于技术措施而进行干燥，例如供应热能或通过气流。
本发明方法中使用的组分a)的脂族二醇优选选自其中羟基是通过不多于3个的碳原子而相互连接的二醇，并且特别优选选自具有不多于8个碳原子但优选至少5个碳原子的无环的烷烃二醇，更特别优选2-甲基-2,4-戊二醇。
本发明方法中使用的组分b)的脂族多羟基化合物是具有多于两个的羟基，优选多于三个的羟基的脂族化合物，其中优选地至少两个羟基通过不多于两个的碳原子而相互连接(“邻位羟基”)。特别优选地，组分b)的多羟基化合物是糖醇(alditol)，其优选具有不多于6个的碳原子，特别优选选自赤藓糖醇、苏糖醇、木糖醇、***糖醇、核糖醇、甘露糖醇或山梨糖醇，更特别优选山梨糖醇。
如果组分b)的多羟基化合物与组分a)的二醇的质量比为至少0.4，则会实现优异的清洁性能。因此，在本发明的方法中，优选组分b)的多羟基化合物的这种相对最小量。特别优选地，前述比例为至少1.0，特别优选至少2.0。如果组分b)的多羟基化合物的相对比例太高，则在活性组分a)和b)中的总量恒定的情况下，不能保持高的清洁性能并且金属表面的同时转化也会损失均匀性。因此，在本发明的方法中，优选组分b)的多羟基化合物与组分a)的二醇的质量比不大于20.0，特别优选不大于10.0，更特别优选不大于6.0。
为了使组件的金属表面充分转化，有利的是，组分c)的元素Zr和/或Ti的水溶性化合物在本发明方法的酸性含水组合物中的比例总和至少为0.002重量％，特别优选至少0.005重量％，以Zr的量计算，其中出于经济原因和防止转化层的过度酸洗(overpickling)，优选地，本发明方法的酸性含水组合物中包含总共不超过0.2重量％的Zr和/或Ti的水溶性化合物，以Zr的量计算。
组分c)的元素Zr和/或Ti的水溶性化合物的合适代表为在水溶液中离解成氟复合物的阴离子的化合物。优选的该类化合物例如H2ZrF6、K2ZrF6、Na2ZrF6和(NH4)2ZrF6以及类似的钛化合物。根据本发明，元素Zr或Ti，特别是元素Zr的不含氟的化合物，也可以用作水溶性化合物，例如(NH4)2Zr(OH)2(CO3)2或TiO(SO4)。在本发明方法的优选实施方案中，在酸性含水组合物中含有元素Zr和/或Ti的氟代金属酸盐，及其氟代酸，特别优选六氟代锆酸盐和/或六氟代钛酸盐，及其游离酸。
此外，本发明方法的酸性组合物含有氟离子源作为组分d)，其对于组件的金属表面上的均匀且可重现的抗腐蚀转化涂层是必需的。当溶解或分散在水中时可以释放氟离子的任何无机化合物适用作氟离子源。复合或简单的氟化物为一种优选的氟离子源。本领域技术人员理解简单的氟化物是氢氟酸及其盐，例如碱性氟化物(alkali fluorides)、氟化铵或二氟化铵，而根据本发明，复合氟化物为配位化合物，其中氟化物以配位的方式作为一个或多个中心原子的配体而存在。因此，复合氟化物的优选代表是上述的元素Zr、Ti或Si的含氟复合物。
在本发明方法的酸性含水组合物中作为氟离子源的化合物的比例优选至少足够大，以使所述酸性含水组合物含有至少0.01g/kg量的游离氟化物，但优选不大于0.6g/kg，特别优选不大于0.2g/kg。游离氟化物的含量借助校准的氟化物敏感电极，在20℃下直接在酸性含水组合物中进行测定。
此外，为了通过根据本发明与酸性含水组合物接触而进行最佳转化，特别是由铁制成的表面，优选总氟化物含量与组分c)的元素Zr和/或Ti总量的摩尔比大于4.5，优选大于5.0，特别优选大于5.5。在本发明方法的酸性含水组合物的TISAB缓冲的等分试样部分(TISAB：“总离子强度调节缓冲液”)中使用氟化物敏感电极，在20℃下测定总氟化物比例，缓冲液与酸性含水组合物的等分试样部分的体积混合比为1:1。TISAB缓冲液通过将58gNaCl、1g柠檬酸钠和50mL冰醋酸溶解于500mL去离子水(κ<1μScm-1)中，使用5N NaOH将pH设定为5.3，并再次用去离子水(κ<1μScm-1)将总体积填充至1000mL而制备。
根据本发明，将组件的金属表面清洁和同时转化为基于元素Zr和/或Ti的抗腐蚀涂层在酸性含水组合物中进行。这里，为了最佳的处理结果，必须在一方面的酸洗率和清洁性能与另一方面的活性组件的稳定性之间设定平衡。在这方面已经发现，所述酸性含水组合物的pH优选高于2.0，特别优选高于3.0，更特别优选高于4.0，因为即使低的酸洗率也足以使金属表面实现有效清洁。然而，为了提供均匀的转化涂层，需要特定的酸洗率以在金属表面上形成碱性扩散层，在该金属表面上会发生层组分的沉淀。在这方面，根据本发明，优选其中酸性含水组合物的pH低于6.0，特别优选低于5.5的方法，所述酸性含水组合物优选具有至少1个点(1Punkt)的游离酸含量。通过使用去离子水(κ<1μScm-1)将2mL所述酸性含水组合物稀释至50mL并使用0.1N苛性钠滴定至pH为5.5而测定游离酸。以mL计的酸溶液的消耗量表示游离酸的点数(Punktzahl)。
还发现，本发明方法中酸性含水组合物额外含有钙离子和/或镁离子对清洁性能是有利的，特别优选总共至少0.01重量％的钙和镁离子，更特别优选至少0.01重量％的镁离子。镁和/或钙离子的优选来源是它们的硝酸盐。
在本发明方法的优选实施方案中，为了加速与酸性组合物接触的金属表面的转化，所述酸性含水组合物额外含有至少一种为铜离子源的水溶性化合物，优选呈水溶性盐的形式，例如硫酸铜、硝酸铜和乙酸铜。铜离子的存在对于在转化过程中在组件的金属表面上形成的转化涂层的抗腐蚀性质也是有利的。所述酸性含水组合物中水溶性化合物的铜离子含量优选至少0.001g/kg，特别优选至少0.005g/kg。然而，铜离子的含量优选不高于0.1g/kg，特别优选不高于0.05g/kg，这是因为元素铜的沉积开始在转化涂层的形成中占主导地位。
此外，为了金属表面的快速和可重现的转化，根据本发明，优选本发明方法中的酸性含水组合物额外含有至少一种在pH为0下标准还原电位高于+0.6V(SHE)的水溶性化合物，并且优选选自无机氮化合物，特别优选选自硝酸和/或亚硝酸及其盐。为了加速转化涂层的形成，水溶性化合物的比例优选至少0.001mol/L，更优选至少0.01mol/L，但是，出于经济原因，优选小于0.2mol/L。
在本发明的方法中，金属表面的清洁和同时转化意欲用暂时防止腐蚀的涂层进行，所述涂层仅代表薄且几乎完全无机的无定形涂层，基于元素Zr和/或Ti。在根据本发明的清洁和涂布过程中，不希望给予油漆底漆的性质。因此，在优选的实施方案中，基于有机化合物的总含量，所述酸性含水组合物中不是组分a)和b)的化合物的沸点或分解点高于150℃的有机化合物的重量小于50％，特别优选小于20％，更特别优选小于10％。
本发明进一步包括酸性含水的不含铬(VI)且不含磷酸盐的组合物，用于相应组件的金属表面的清洁和同时转化，所述组合物含有：
a)0.003-2重量％的具有至少4个碳原子但不多于10个碳原子的脂族二醇；
b)0.01-5重量％的具有至少4个但不多于8个碳原子的脂族饱和多羟基化合物；
c)以Zr的量计算，0.002-0.2重量％的元素Zr的水溶性化合物；
d)至少10mg/kg的游离氟离子；和
e)优选0.01-1重量％的钙离子和/或镁离子。
根据本发明，如果溶解于水中的磷酸盐的比例小于100mg/kg，优选小于20mg/kg，以磷的量计算，则组合物为“不含无磷酸盐的”。
根据本发明，如果在氧化阶段中溶解于水中的元素铬+VI的化合物的比例小于100mg/kg，优选小于20ppm，则该组合物是“不含铬(VI)的”。
酸性含水的不含铬(VI)且不含磷酸盐的组合物的优选实施方案类似于之前在本发明方法的内容中关于酸性含水组合物的用于金属组件的清洁和抗腐蚀预处理所描述的那些。
实施方案：
对上油的钢板(MBS 30，Chemetall GmbH)进行清洁转化处理。所述处理在喷射室中在1-2巴的喷射压力下在25℃下进行60秒，并且含水转化溶液的pH为4.6。
所述转化溶液含有：
0.16g/L 六氟锆酸
0.32g/L 六水合硝酸镁
0.3g/L 山梨糖醇
0.1g/L 2-甲基-2,4-戊二醇
在处理后立即进行的水破裂试验中，在用城市用水润湿后，没有观察到自来水膜的破裂，即使在进行清洁转化处理后该金属板在喷射室中储存十分钟之后也是如此，没有检测到闪锈。
Claims (15)
1.对金属组件进行清洁和抗腐蚀预处理的方法，所述金属组件至少部分地由主要由金属铁、锌和/或铝中的一种或多种组成的材料组成，所述方法通过使所述组件与含有如下成分的酸性含水组合物接触而进行：
a)至少0.003重量％的具有至少4个碳原子但不多于10个碳原子的脂族二醇；
b)至少0.01重量％的具有至少4个但不多于8个碳原子的脂族饱和多羟基化合物；
c)至少一种元素Zr和/或Ti的水溶性化合物；
d)至少一种水溶性氟离子源。
2.根据权利要求1所述的方法，其特征在于组分b)的多羟基化合物与组分a)的二醇的质量比至少为0.4，优选至少1.0，特别优选至少2.0，但优选不大于20.0，特别优选不大于10.0，更特别优选不大于6.0。
3.根据前述权利要求一项或两项所述的方法，其特征在于组分a)的脂族二醇选自羟基通过不多于3个的碳原子而相互连接的二醇。
4.根据权利要求3所述的方法，其特征在于组分a)的脂族二醇选自具有不多于8个碳原子但优选至少5个碳原子的无环的烷烃二醇，特别是2-甲基-2,4-戊二醇。
5.根据前述权利要求一项或多项所述的方法，其特征在于组分b)的多羟基化合物具有多于三个的羟基，至少两个羟基优选地通过不多于两个的碳原子而相互连接，并且特别优选地是糖醇，其优选具有不多于6个的碳原子，特别优选选自赤藓糖醇、苏糖醇、木糖醇、***糖醇、核糖醇、甘露糖醇或山梨糖醇，更特别优选是山梨糖醇。
6.根据前述权利要求一项或多项所述的方法，其特征在于以Zr的量计算，所述酸性含水组合物中含有的元素Zr和/或Ti的水溶性化合物总共为至少0.002重量％，优选至少0.005重量％，但以Zr的量计算，优选元素Zr和/或Ti的水溶性化合物总共不为大于0.2重量％。
7.根据前述权利要求一项或多项所述的方法，其特征在于所述酸性含水组合物的pH低于6.0，优选低于5.5，但优选大于2.0，特别优选大于3.0，更特别优选大于4.0，所述酸性含水组合物优选具有至少1个点的游离酸含量。
8.根据前述权利要求一项或多项所述的方法，其特征在于所述酸性含水组合物的水溶性氟离子源的含量使游离氟的比例为至少10mg/kg。
9.根据前述权利要求一项或多项所述的方法，其特征在于所述酸性含水组合物另外含有钙离子和/或镁离子，优选总共至少0.01重量％的钙和镁离子，特别优选至少0.01重量％的镁离子。
10.根据前述权利要求一项或多项所述的方法，其特征在于所述组件至少部分由铁类材料组成。
11.根据前述权利要求一项或多项所述的方法，其特征在于所述接触通过喷雾或喷射，优选通过喷射，特别优选在至少1巴的喷射压力下进行。
12.根据前述权利要求一项或多项所述的方法，其特征在于所述酸性含水组合物在进行接触时的温度低于40℃，优选低于35℃，特别优选低于30℃，但是优选至少20℃。
13.根据前述权利要求一项或多项所述的方法，其特征在于直接在所述组件与所述酸性含水组合物接触之后，在有或者没有中间清洗和/或干燥步骤的情况下，将所述组件的先前与所述酸性含水组合物接触的区域至少部分地进行涂布，优选浸渍涂布或粉末涂布。
14.根据前述权利要求一项或多项所述的方法，其特征在于在喷射过程中在直接使所述组件与所述酸性含水组合物接触之前，不对所述组件进行湿化学清洁。
15.不含铬(VI)且不含磷酸盐的酸性含水组合物，其含有：
a)0.003-2重量％的具有至少4个碳原子但不多于10个碳原子的脂族二醇；
b)0.01-5重量％的具有至少4个但不多于8个碳原子的脂族饱和多羟基化合物；
c)以Zr的量计算，0.002-0.2重量％的元素Zr的水溶性化合物；
d)至少10mg/kg的游离氟离子；和
e)优选0.01-1重量％的钙离子和/或镁离子。
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