CN104294348B - 用于钝化带状的黑铁皮的方法 - Google Patents
用于钝化带状的黑铁皮的方法 Download PDFInfo
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- CN104294348B CN104294348B CN201410337358.3A CN201410337358A CN104294348B CN 104294348 B CN104294348 B CN 104294348B CN 201410337358 A CN201410337358 A CN 201410337358A CN 104294348 B CN104294348 B CN 104294348B
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- steel band
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- steel
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- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 claims description 5
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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
-
- 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
- C23C22/07—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 phosphates
- C23C22/08—Orthophosphates
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
-
- 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
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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
- C23C22/73—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 characterised by the process
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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
- C23C22/73—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 characterised by the process
- C23C22/74—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 characterised by the process for obtaining burned-in conversion coatings
-
- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及一种用于钝化带状黑铁皮的方法，具有以下步骤：通过将黑铁皮引导穿过电解液进行电化学处理来构造惰性的钢表面，冲洗黑铁皮，将水状的、无铬的处理溶液施加到黑铁皮的至少一个表面上来构造防腐的转换层和用于漆和有机涂层材料的附着层。根据本发明处理的黑铁皮的特征在于高抗腐蚀性，并且对漆和有机涂层具有良好的附着能力，因此非常适合代替无锡的钢片和白铁皮用来制造包装，特别是罐子。与传统的用于无锡的钢片和白铁皮的生产及钝化法不同，在根据本发明的方法中不使用危害环境和健康的铬‑VI。
Description
技术领域
本发明涉及一种用于钝化带状的黑铁皮的方法，其中，在第一个步骤中通过电化学处理黑铁皮在黑铁皮表面上形成惰性层，并且在进一步的步骤中在黑铁皮的至少一个表面上涂覆上水状的、无铬的处理溶液，用于构造防腐蚀的转化层，转化层此外还构成用于漆和有机涂层材料的附着层。钝化这个概念在这里要理解为在黑铁皮上有针对性地产生保护层(这里：转化层)，保护层能防止或者至少大幅度减缓黑铁皮的腐蚀。本发明还涉及将根据本发明被处理的黑铁皮用作包装钢材。
背景技术
为了保护金属制表面不被腐蚀，公知许多方法，其中，金属制表面配上由另一种、通常是非贵金属的金属(例如锌和铬)制成的涂层。因此，例如公知的黑铁皮都要用锌或铬或者也可以用锡(然而锡相比钢来说更稀有)涂层。为了特别是在食品领域生产包装，例如广泛使用的镀锡的薄金属片(白铁皮)。白铁皮的特征在于很强的抗腐蚀性和良好的可塑性以及可焊接性，因此非常适合用于制造包装，例如饮料罐。
为了也能够保护金属涂层(例如白铁皮中的锡涂层)不被腐蚀，并且为漆和人工材料涂层制造良好的附着基底，通常在金属涂层的表面上涂覆上转化层。
转化层这个概念要理解为金属表面上非金属的、大部分是无机的、极薄的层，它们通常是通过水状的处理溶液与金属基底发生化学反应制造而成的。转换涂层尤其是在金属箔中确保了非常有效的防腐保护效果，为漆和人工材料提供了良好的附着基底，并且它们能减少表面摩擦和磨损。
根据基板的不同，有铁、锌或者锰的磷化处理法、电解液磷化处理法或铬化法、草酸化法和阳极化法。被证明能非常有效地防腐的是含铬的转化层。在铬化时，用酸性的、含有铬(VI)离子的溶液处理金属表面，其中，铬(VI)还原为铬(III)。通过处理在金属表面上形成防腐的、含铬的转化层。
然而，铬(VI)毒性极强并且致癌的。针对汽车制造和家用电器中的应用，欧盟已经禁止了用含有铬(VI)的物质钝化金属表面。出于这个原因，在现有技术中研发了无铬的转化层。例如由WO 97/40208-A和EP2532769A1中公知用于在锌制或铝制表面上制造无铬的转化层的方法。在WO2008/119675中还描述了用于制造无铬转化层的处理溶液，它们含有含氧阳离子和卤素配离子，这些成分使得转化层无色并且略微呈彩虹色。
白铁皮作为食品的包装材料具备出色的特性，几十年来就为此目的被生产和加工。然而，在白铁皮中作为防腐涂层的锡却由于全球资源的紧缺已经成为比较昂贵的材料。作为白铁皮的代替，在现有技术中尤其是公知将以电解的方式用铬涂层的钢片用作包装钢材，它被称为无锡的钢片(无锡镀层薄钢板“Tin Free Steel”，TFS)或者被称为“电解铬涂层薄钢板”(ECCS)。这些无锡的钢片的特征一方面在于对漆或者有机保护层有良好的附着能力(例如由PP或PET制成)，然而另一方面在实施涂层法时，却由于用于涂层的含有铬VI的材料有毒且有害健康的特性而具有显著缺点。
发明内容
因此，本发明的目的在于提供一种无铬的包装钢材，它适合用作无锡钢片(TFS或ECCS)的代替和白铁皮的代替，并且特别是不仅在抗腐蚀方面并且在对于漆或有机涂层的附着能力方面要与白铁皮或无锡钢片差不多。
该目的通过一种用于钝化带状黑铁皮的方法，具有以下步骤：通过将所述黑铁皮引导穿过电解液进行电化学处理来构造惰性的钢表面，冲洗所述黑铁皮，将水状的、无铬的处理溶液施加到黑铁皮的至少一个表面上来构造防腐的转换层和用于漆和有机涂层材料的附着层。根据这种方法，使用未涂层的带式黑铁皮，并且在第一方法步骤中通过电化学处理使其表面惰性化，紧接着用水或者另一种冲洗液冲洗，并且最后在进一步的步骤中涂上防腐蚀的转化涂层，为此在黑铁皮的至少一个表面上涂覆上无铬水状的处理溶液。
根据一种实施方式，在本发明的方法中，所述黑铁皮在所述电化学处理之前首先去除油脂，然后被冲洗、酸蚀并且再次被冲洗。
根据一种实施方式，在本发明的方法中，所述黑铁皮在施加所述处理溶液以后被干燥，从而在所述黑铁皮的所述表面上构造所述处理溶液的干燥涂覆面。
根据一种实施方式，在本发明的方法中，在接入作为阳极的所述黑铁皮情况下通过将所述黑铁皮引导穿过碱性电解液完成所述电化学处理。
根据一种实施方式，在本发明的方法中，所述转化层通过在免冲洗法中施加水状的所述处理溶液来涂覆。
根据一种实施方式，在本发明的方法中，水状的所述处理溶液要么在没有过剩的情况下利用旋转式喷洒器施加到所述黑铁皮上，要么在过剩的情况下利用辊涂机或者喷洒喷嘴施加到所述黑铁皮上，并且接着用挤压辊挤压出过剩的所述处理溶液。
根据一种实施方式，在本发明的方法中，所述干燥在50-250℃下进行。
根据一种实施方式，在本发明的方法中，在所述干燥过后利用DOS、ATBC、BSO或者聚二醇，特别是聚乙二醇(PEG)对所述处理溶液的所述干燥涂覆面进行再处理。
根据一种实施方式，在本发明的方法中，所述处理溶液的所述干燥涂覆面在1mg/m2到50mg/m2之间。
根据一种实施方式，在本发明的方法中，所述黑铁皮以至少200m/min的带速度移动。
根据一种实施方式，在本发明的方法中，所述黑铁皮是具有20-1000ppm的碳含量的、冷轧的、退火且精轧的、特别是铁氧体的或者多相的钢片。
根据一种实施方式，在本发明的方法中，在对所述黑铁皮进行所述电化学处理时，所述电解液的温度在20到50℃之间。
根据一种实施方式，在本发明的方法中，在对所述黑铁皮进行所述电化学处理时，电流密度在2到10A/dm2之间。
根据一种实施方式，在本发明的方法中，水状的所述处理溶液是无铬的，并且包含以下成分中的至少一种：金属成分：从Ti、Zr、Mn、Zn、P和它们的组合物中选择；有机成分：从聚丙烯酸酯、聚羧酸酯和它们的组合物中选择。
根据一种实施方式，在本发明的方法中，所述处理溶液包含至少一种用于漆或有机涂层材料的附着剂，其中，所述附着剂特别是具有马来酸、间苯二甲酸和环己烷二甲醇(CHDM)的成分或者具有它们的组合物。
本发明还涉及通过本发明的方法处理后的黑铁皮作为用于制造包装、特别是罐子的包装钢材的应用，所述处理后的黑铁皮在至少一个表面上具有无铬的转换层。
优选地使用具有20-1000ppm的碳含量的、非合金钢制成的、冷轧的、退火的并且精轧的或平整的钢带。以符合目的的方式，钢带(黑铁皮)具有以下特征：
·强度：300-1000Mpa
·断裂延伸率：1-40％
·厚度：0.05-0.49mm
·表面-粗糙度：0.1-1μm。
钢材例如可以是铁氧体钢或者也可以是具有多个拼接组成部分的多相钢，特别是铁氧体、马氏体、贝氏体和/或残留奥氏体。这种多相钢的特征在于在具备高于10％的良好的断裂延伸率的同时，还具有超过500Mpa的高强度。就预设的将根据本发明处理的黑铁皮用作包装钢材而言，优选地遵守在DIN EN 10202:2001：“冷轧包装金属片制品(电解镀锡和镀铬)”中定义的钢片的属性。在这项标准中，此外还定义了这种钢材的分析结果和机械特征值。属性特别是在TS230(软的罩式炉属性，屈服极限230MPa)到TH620(DO，620MPa)之间。
为了实施根据本发明的方法，以带状存在的黑铁皮以优选地大于200m/min到750m/min的带速度移动。首先完成的步骤是通过电化学处理在黑铁皮的表面上制造惰性层。为了准备电化学处理，首先在可能必要的预处理步骤中清洁移动的黑铁皮带，特别是为其去油脂，然后冲洗、酸蚀并且再冲洗。有可能需要的是，因为冷轧的和再结晶退火的黑铁皮通常在再结晶退火之后被精轧或被平整，其中，黑铁皮表面例如在利用水油悬浮液进行湿式精轧时或者也有可能在干式精轧时被油、铁屑、肥皂和其他的污染物所污染。这种污染通过(可选的)预处理步骤得以清除。
为此，将黑铁皮导入具有碱性的氢氧化钠或氢氧化钾溶液的清洁罐中。在池温在20到70℃时，碱性去油脂介质的浓度优选地在20到100g/l之间。根据目的，分成两个步骤为黑铁皮去油脂，其中，在第一个步骤中实施浸渗法，并且在第二个步骤中以2至30A/dm2的电流密度实施电解法。在去油脂以后，例如用三重级联冲洗法(Dreifachkaskadenspülen)冲洗黑铁皮带的每一侧，每重水量为10-30m3/h。在需要的情况下，可以通过在两个前后相继的浸渗流程中将黑铁皮带导入其他的、盐酸或硫酸蚀液浓度为例如10到120g/l的清洁罐中去除残余氧化物，然后在一个浸渗流程中进行浸洗。酸蚀溶液和冲洗水的温度通常在20到60℃之间。
在预处理之后，借助将黑铁皮带引导穿过电解液进行电化学处理制造出均质的、紧密的、惰性的钢制表面。这种电解液优选为碱性的。电化学处理(优选碱性处理)黑铁皮是为了在涂覆转化层之前惰性化钢带的表面属性，并且使其质地均匀。
在电化学处理的方法步骤中，以带速度引导黑铁皮带穿过电解池，并且在这里在电流密度优选为2-30A/dm2的情况下作为阳极接入。电解液例如是NaOH浓度优选为20-100g/l氢氧化钠溶液，特别是含有30％的NaOH溶液的氢氧化钠池。例如也可以使用苏打溶液，特别是5％的碳酸钠溶液(Na2CO3)作为电解液。其中，电解池的池温以符合目的的方式保持在20到80℃之间。
在电化学处理之后，用水冲洗黑铁皮。可以通过将带钢浸入水罐中完成冲洗，或者通过喷水完成冲洗。优选地为此使用温度为20-60℃的、全脱盐(VE)的去离子水、渗透水或蒸馏水。然而也可以使用未经处理的饮用水或者其他的冲洗液。在冲洗后对黑铁皮进行干燥。
最后在结束的步骤中，在黑铁皮的至少一个表面上涂覆上转化层，为此在黑铁皮的先前在电化学处理中被惰性化的表面上涂上无铬水状的处理溶液。
在这个过程中，根据目的在免冲洗法中涂覆上转化涂层，也就是在制造出转化层之后不进行冲洗。在此例如利用涂料装置在黑铁皮的表面上涂覆上构成转化涂层的水状的、无铬的处理溶液，该装置包括辊涂机、旋转式喷洒器或喷洒喷嘴。
优选地，为了涂上水状的处理溶液使用带有旋转式喷洒器的涂料装置。在涂上处理溶液之前，黑铁皮的需要涂覆上转化层的表面要尽可能的干净和干燥。因此，利用干燥装置(例如利用气刀)至少干燥黑铁皮的要用转化层涂覆的表面。利用气刀向运动着的带钢的这个表面上吹分层的热气流，从而将干扰性的异物颗粒从钢带表面上吹走并且使这个钢带表面干燥。
旋转式喷洒器具有多个横向朝向带钢运动方向并排布置的喷洒转子，这些喷洒转子被输送水状的处理溶液，并且被驱动件驱动旋转，从而借助离心力将水状的处理溶液以细密的喷洒束的形式喷洒到带钢的这个或者每个表面上，并且在那里构成水溶液的湿膜。在涂上水溶液的湿膜以后，借助黑铁皮的表面上被驱动的平滑辊使其均匀。在这里，平滑辊按照目的相对于黑铁皮表面如下地布置，即，使它们只能对水状的处理溶液的湿膜上施加很小的压力，并且不能或者顶多只能最少量地从表面上挤压走涂上的处理溶液。相应地，如下地调适利用旋转式喷洒器喷洒上去的处理溶液的量，即，使得黑铁皮表面上不存在过剩。由此可以不必像以前那样抛弃或者再处理处理溶液过剩的部分。在让喷上去的湿膜均匀以后使其干燥，从而在经处理的黑铁皮表面上留下处理物质的干燥涂覆面。按照目的，处理溶液的干燥覆盖物在干燥后达到1到50mg/m2，并且优选地在10至30mg/m2的范围内。按照目的使在每个时间单位内输送给旋转式喷洒器的喷洒转子的水状的处理溶液的量适应带速度。由此可以确保的是，只有刚好需要量的新鲜处理溶液以相应的浓度作为湿膜利用旋转式喷洒器喷到黑铁皮带上。于是例如可以在不考虑带速度的情况下将湿膜的恒定覆盖量设置在2ml/m2到8ml/m2的范围内，并且优选地带钢的每一侧大约5ml/m2。
在涂上处理溶液湿膜以后，为了干燥湿膜，引导带钢穿过带钢干燥器。在干燥以后，在黑铁皮每一侧的表面上留下2mg/m2到30mg/m2如此构成的转化层的干燥覆盖量。在这里可以利用在每个时间单位输送给旋转式喷洒器的处理溶液的量来调节转化层的理想的干燥覆盖量。
这样涂的优点在于，总是仅使用新鲜的处理溶液，并且它不可能会因为与钢带接触和再循环被脱落的铁屑所污染。此外已经显示的是，所述方法非常经济实惠，因为仅使用刚好需要的量，并且不需要过剩，由此不必再积累过剩的处理溶液。由此可以防止形成需要再处理的废水。
作为代替，也可以经由辊涂机通过辊涂覆上处理溶液，还是在先前已经干燥的黑铁皮表面上。优选地在带速度在较低速度范围内并且特别是在速度低于200m/min时使用辊涂机。作为代替，也可以通过喷上处理溶液或者通过将钢带浸入有处理溶液的池子涂上去。因为在这个过程中有过剩的处理溶液被带到黑铁皮上，为了实现转化层的预定的理想覆盖量，需要例如借助挤压辊挤压走过剩部分的湿膜，其中，这可以用“湿压湿”完成。然而，在这种方法中，不能在不考虑速度的情况下恒定不变地涂上溶液，并且此外处理溶液还可能被铁污染，然后必须更新并且在超过污染阈值时被抛弃。
利用所描述的涂覆法覆上的处理溶液的湿膜最终被干燥，形成干燥的转化层。这例如可以通过引导黑铁皮穿过干燥炉完成，在其中借助热气或者IR射线干燥湿膜。优选地在温度为50-250℃时完成干燥。最后用二辛基癸二酸酯(DOS)，乙酰柠檬酸三正丁酯(ATBC)，硬脂酸丁酯(BSO)或者聚二醇，特别是聚乙二醇(PEG，优选地具有6000g/mol的摩尔质量),或者用它们的组合物为干燥转化层的表面上油或者说对其进行再加工。按照目的，像在ECCS或白铁皮中一样利用常见的上油机用静电涂上DOS、ATBC、BSO或PEG，从而完成再处理。
用于转化涂层的水状的处理溶液优选地至少含有以下物质中的其中一种：
-金属成分：从Ti、Zr、Mn、Zn、P和它们的组合物中选择；
-有机成分：从聚丙烯酸酯、聚羧酸酯和它们的组合物中选择。
金属成分和有机成本又可以组合。
处理溶液还含有至少一种用于漆或有机涂层材料的附着介质，其中，附着介质特别是含有马来酸、间苯二甲酸和环己烷二甲醇(CHDM)的成分或者含有它们的组合物。被证明特别适合用作附着介质的组成物含有聚对苯二甲酸乙二醇酯树脂(PET)或者聚对苯二甲酸-1，4-环己烷二甲脂(PCT)，例如用乙二醇改性的聚对苯二甲酸乙二醇酯-1，4-环己烷二甲醇脂(PET-G，它含有低于大约30％的CHDM)或者PCTG(含有大于大约30％的CHDM)。
每种物质的覆盖量为1至50mg/m2。
下面展示了几种选择的、可购买的介质，它们适合用于利用根据本发明的方法制造转化涂层。
例如可以如下地组合成用于制造转化层的优选的处理溶液：
a)水溶液，含有Al：Zr：F的摩尔比为(0.15至0.67):1:(5至7)的氟锆酸铝，其中，AI+Zr+F的总浓度为0.1至2.0g/l，并且PH值被设置在5以下，优选地在3至5之间。
b)水溶液，主要含有：
-0.2至低于10g/l的锌离子，
-0.5至25g/l的锰离子以及
-2至300g/k的磷酸盐离子，算作P2O5，
其中锌：锰-磷酸盐溶液的比重比例保持在0.05:1至1:1的范围内。
c)含有锌和锰的水溶液，锌含量在0.05至5g/l的范围内，锰含量在0.075到5.2g/l的范围内，以及铜含量在0.008至0.05g/l的范围内，并且/或者总体上含有0.002至0.5g/l的、硼、铝、钛或/和锆的六氟化合物，算作F6。
d)含有至少一种成膜剂和至少一种颗粒形式的无机化合物的水溶液，成膜剂含有至少一种酸值在5至200范围内的、可溶于水或者可以在水中扩散的聚合物，无机化合物的平均颗粒直径经扫描电子显微镜测量在0.005至0.3μm的直径范围内，其中，这种聚合物从至少一种基于丙烯酸酯、乙烯、聚酯、聚氨酯、硅化聚酯、苯酚、苯乙烯、尿素-甲醛、它们的衍生物、共聚物、聚合物、混合物或/和混合聚合物的人工合成树脂中选出，并且颗粒形式的无机化合物从铝、硅、钛、锌或/和锆的至少一种化合物中选出。
e)含有以下成分的水溶液
i)至少一种有机成膜剂，它含有至少一种可溶于水或者可以在水中扩散的聚合物，这种聚合物是基于聚丙烯酸、聚丙烯酸酯或/和聚乙烯丙烯酸的人工合成树脂，或者是人工合成树脂混合产物或/和含有基于丙烯酸酯或聚丙烯酸酯的人工合成树脂的混合聚合物，以及
ii)相对于基础金属的含量，含量在0.2至30g/l范围内从钛、锆、硅、铝和硼中选择的阴离子和/或阴离子的六氟或四氟合成物。
根据本发明的方法可以在不增加安装耗费的情况下集成到现有的涂层设备中，例如集成到用于制造HCCS(或TFS)的带钢涂层设备中。在这类带钢涂层设备中，带速度通常为80到600m/min。
根据本发明的方法的优点在于在传统的黑铁皮上，特别是厚度在薄金属板和金属箔范围内的黑铁皮上实现无铬的并且因此环保的并且不危害健康的以及成本低廉的涂层。此外还通过所选择的用于涂覆转换层的涂覆法(免冲洗法)通过省去最后的冲洗有效地节约了成本和能量。特别是通过组合无机钝化和含聚合物的薄膜涂层还额外地实现了许多优点。利用根据本发明的方法处理的黑铁皮出色地适用于制造包装，特别是制造罐子，因此能够取代传统上用作包装钢材的白铁皮和无锡的钢片(TFS或ECCS)。这些黑铁皮就其抗腐蚀性而言与白铁皮差不多，对于漆和例如由PP或PET制成人工合成材料涂层具有类似于无锡的钢片(TFS或ECCS)的附着性能。
Claims (13)
1.一种用于钝化带状黑铁皮的方法，具有以下步骤：
-提供具有20-1000ppm的碳重量含量的冷轧的、退火的且精轧的钢带，并且使所述钢带以至少200m/min的带速移动，
-通过以所述带速引导所述钢带通过包含碱性的氢氧化钠或氢氧化钾溶液的清洁罐并且随后冲洗所述钢带将其清洁和去除油脂，
-通过以所述带速使作为阳极接入的所述钢带通过碱性电解液来对所述钢带进行电化学处理来构造惰性的钢表面，
-冲洗并且干燥所述钢带，
-将水状的处理溶液施加到所述钢带的至少一个表面上来构造防止所述钢带腐蚀和用作漆和有机涂层材料的附着层的转换层，其中所述处理溶液是无铬的并且包含钛和/或锆，
在电化学处理步骤中使用的电解液的温度在20℃至80℃之间。
2.根据权利要求1所述的方法，其中，所述钢带在所述清洁和去除油脂步骤之后进行酸蚀和冲洗。
3.根据权利要求1或2所述的方法，其中，所述钢带在施加所述处理溶液以后被干燥，从而在所述钢带的表面上构造所述处理溶液的干燥涂层面，其中干燥处理溶液的涂层面在1mg/m2至50mg/m2之间。
4.根据权利要求1所述的方法，其中，水状的所述处理溶液通过免冲洗法施加。
5.根据权利要求4所述的方法，其中，水状的所述处理溶液要么在没有过剩的情况下利用旋转式喷洒器施加到所述钢带上，要么在过剩的情况下利用辊涂机或者喷洒喷嘴施加到所述钢带上，并且接着用挤压辊挤压出过剩的所述处理溶液。
6.根据权利要求3所述的方法，其中，所述干燥在50-250℃下进行。
7.根据权利要求3所述的方法，其中，随后利用DOS、ATBC、BSO或者聚二醇对所述处理溶液的干燥涂覆面进行再处理。
8.根据权利要求1所述的方法，其中，所述钢带是由铁氧体的或者多相的钢片制成的。
9.根据权利要求1所述的方法，其中，在对所述钢带进行所述电化学处理时，所述电解液的温度在20到50℃之间。
10.根据权利要求1所述的方法，其中，在对所述钢带进行所述电化学处理时，电流密度在2到10A/dm2之间。
11.根据权利要求1所述的方法，其中，水状的所述处理溶液包含以下成分中的至少一种：
金属成分：从Ti、Zr、Mn、Zn、P和它们的组合物中选择；
有机成分：从聚丙烯酸酯、聚羧酸酯和它们的组合物中选择。
12.根据权利要求1所述的方法，其中，所述处理溶液包含至少一种用于漆或有机涂层材料的附着剂，所述附着剂包含马来酸、间苯二甲酸和环己烷二甲醇的成分或者具有它们的组合物。
13.一种按照根据前述任一 权利要求所述的方法处理后的钢带用于制造包装的应用，其中所述钢带在所述钢带的至少一个表面上具有包含钛和/或锆的无铬的转换层。
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| EP1978131B2 (de) | 2007-03-29 | 2019-03-06 | ATOTECH Deutschland GmbH | Mittel zur Herstellung von Korrosionsschutzschichten auf Metalloberflächen |
| US8673091B2 (en) * | 2007-08-03 | 2014-03-18 | Ppg Industries Ohio, Inc | Pretreatment compositions and methods for coating a metal substrate |
| JP5215043B2 (ja) * | 2008-06-02 | 2013-06-19 | 日本パーカライジング株式会社 | 金属の表面処理用処理液及び表面処理方法 |
| JP5380033B2 (ja) * | 2008-10-09 | 2014-01-08 | Ｊｆｅ建材株式会社 | 耐食性と塗料密着性に優れた塗装金属材 |
| EP2532769A1 (en) | 2011-06-10 | 2012-12-12 | Amcor Flexibles Kreuzlingen Ltd. | Method of producing a chromium-free conversion coating on a surface of an aluminium or aluminium alloy strip |
-
2013
- 2013-07-16 DE DE201310107506 patent/DE102013107506A1/de not_active Ceased
-
2014
- 2014-06-26 JP JP2014131073A patent/JP2015028210A/ja active Pending
- 2014-07-03 CA CA2855673A patent/CA2855673C/en active Active
- 2014-07-03 RS RS20170926A patent/RS56351B1/sr unknown
- 2014-07-03 EP EP14175621.3A patent/EP2826569B1/de active Active
- 2014-07-03 ES ES14175621.3T patent/ES2634870T3/es active Active
- 2014-07-10 RU RU2014128191A patent/RU2663232C2/ru not_active IP Right Cessation
- 2014-07-15 BR BR102014017368-4A patent/BR102014017368B1/pt not_active IP Right Cessation
- 2014-07-15 CN CN201410337358.3A patent/CN104294348B/zh active Active
- 2014-07-16 US US14/332,490 patent/US20150024222A1/en not_active Abandoned
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1291918A (zh) * | 1998-03-02 | 2001-04-18 | 克里斯英国有限公司 | 层压的金属带 |
| CN102575357A (zh) * | 2009-07-02 | 2012-07-11 | 日本帕卡濑精株式会社 | 不含铬和氟的金属表面用化学转化处理液、金属表面处理方法及金属表面涂装方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2855673C (en) | 2016-09-27 |
| CA2855673A1 (en) | 2015-01-16 |
| RU2663232C2 (ru) | 2018-08-02 |
| DE102013107506A1 (de) | 2015-01-22 |
| CN104294348A (zh) | 2015-01-21 |
| BR102014017368A2 (pt) | 2015-10-06 |
| RU2014128191A (ru) | 2016-01-27 |
| JP2015028210A (ja) | 2015-02-12 |
| BR102014017368B1 (pt) | 2021-06-29 |
| US20150024222A1 (en) | 2015-01-22 |
| ES2634870T3 (es) | 2017-09-29 |
| EP2826569A1 (de) | 2015-01-21 |
| EP2826569B1 (de) | 2017-06-21 |
| RS56351B1 (sr) | 2017-12-29 |
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