CN104364411B - 用于生产具有Zn‑Al‑Mg涂层的预涂漆金属板的方法及相应的金属板 - Google Patents
用于生产具有Zn‑Al‑Mg涂层的预涂漆金属板的方法及相应的金属板 Download PDFInfo
- Publication number
- CN104364411B CN104364411B CN201380028894.9A CN201380028894A CN104364411B CN 104364411 B CN104364411 B CN 104364411B CN 201380028894 A CN201380028894 A CN 201380028894A CN 104364411 B CN104364411 B CN 104364411B
- Authority
- CN
- China
- Prior art keywords
- metal coating
- weight
- coating
- magnesium
- metallic plate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
- C23C2/16—Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives
- C23C2/18—Removing excess of molten coatings from elongated material
- C23C2/20—Strips; Plates
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
- C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
- C23C2/29—Cooling or quenching
-
- 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
-
- 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
- C23C22/78—Pretreatment of the material to be coated
-
- 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
- C23C22/82—After-treatment
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
-
- 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
- C23G1/10—Other heavy metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2252/00—Sheets
- B05D2252/10—Applying the material on both sides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2350/00—Pretreatment of the substrate
- B05D2350/60—Adding a layer before coating
- B05D2350/65—Adding a layer before coating metal layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12542—More than one such component
Abstract
本发明的方法包括以下步骤:提供具有通过使钢基材(3)在浴中淬火而涂覆的两个面(5)的钢基材(3),通过施用酸溶液、任选地pH为1至2的转化溶液和/或机械应力来改变金属涂层(7)的外表面(15)上形成的氢氧化镁或氧化镁层,以及对金属涂层(7)的外表面(15)进行涂漆。
Description
本发明涉及包含钢基材的金属板,所述钢基材具有两个面,每个面涂覆有包含锌、镁和铝的金属涂层以及漆膜。
这样的金属板通常被称作“预涂漆(pre-lacquered)金属板”,并且例如用于家用电器领域或建筑业。
用于生产这种金属板的整个方法由炼钢工人执行,减少了成本以及与使用者涂漆相关的约束条件。
基本上包含小比例(通常约0.1重量%)锌和铝的金属涂层传统上被用于良好的腐蚀保护。这些金属涂层目前面临特别是包含锌、镁和铝的涂层的竞争。
这样的金属涂层在下文中统一称作锌-铝-镁涂层或Zn-Al-Mg涂层。
镁的添加显著增加了这些涂层的耐腐蚀性,从而使得可减少其厚度或增加随时间推移腐蚀保护的保证。
本发明的一个目的是提出一种可生产具有Zn-Al-Mg涂层的预涂漆金属板的方法,这些金属板具有更进一步提高的耐腐蚀性。
为此目的,本发明首先涉及根据权利要求1、9和13所述的方法。
所述方法还可包括单独或组合考虑的权利要求8、10至12和14至22的特征。
本发明还涉及根据权利要求23所述的金属板。
现在将通过提供信息但并非限制性的实施例,并且参照附图说明本发明,其中:
-图1是说明使用根据本发明的方法获得的金属板的结构的示意性截面视图,以及
-图2和3示出了金属板外表面的XPS光谱分析的结果。
图1的金属板1包括钢基材3,在其两面5的每个面上由金属涂层7所覆盖。涂层7分别由上漆膜9和下漆膜11所覆盖。
应注意,为了便于说明,图1中没有遵照基材3和覆盖其的不同层的相对厚度。
两个面5上存在的涂层7是相似的,仅一个将在下面详细描述。
涂层7的厚度一般小于或等于25μm,并且通常其目的是保护基材3免受腐蚀。
涂层7包含锌、铝和镁。特别优选的是,涂层7包含0.1重量%至10重量%的镁和0.1重量%至20重量%的铝。
同样优选地,涂层7包含多于0.3重量%的镁或甚至0.3重量%至4重量%的镁和/或0.5重量%至11重量%或甚至0.7重量%至6重量%的铝。
优选地,涂层7中镁与铝的Mg/Al重量比小于或等于1,或者甚至严格地小于1,或者甚至严格地小于0.9。
漆膜9和11是例如基于聚合物的。优选地,其包含至少一种选自以下的聚合物:三聚氰胺交联的聚酯、异氰酸酯交联的聚酯、聚氨酯和乙烯基聚合物的卤化衍生物,不包括阳离子电泳漆。
漆膜9和11的厚度通常为1μm至200μm。
为了生产金属板1,可例如使用以下方法。
所使用装置可包括单线或者例如两条不同线来分别执行金属涂覆和涂漆。如果使用两条不同线,则其可位于相同位置或不同位置。在本说明书的其余部分中,一个替代方案将被认为是使用两条不同线的一个实例。
在用于生产金属涂层7的第一条线中,使用例如通过热轧然后冷轧获得的基材3。基材3是带的形式,使得其穿过浴以通过热浸镀使涂层7沉积。
所述浴是包含镁和铝的熔融锌浴。所述浴还可包含各自多达0.3重量%的任选的添加元素,例如Si、Sb、Pb、Ti、Ca、Mn、Sn、La、Ce、Cr、Ni、Zr或Bi。
这些不同元素尤其可改善基材3上涂层7的延性或粘附性。本领域技术人员知道它们对涂层7的特征的作用,会知道如何根据所寻求的额外目标来使用它们。最后一点,所述浴可包含来自供应锭或由基材3通过浴所得到的残余元素,例如含量多达5重量%并且一般为2重量%至4重量%的铁。
在使涂层7沉积之后,例如,使用喷嘴将气体发射在基材3的任一侧上使基材3旋干。
然后,使涂层7以受控方式冷却。
由此处理的带可接着经历所谓的光整冷轧(skin-pass)步骤,使得可对其进行冷加工,从而消除弹性平台、设定机械特征并给予其适于冲压操作的粗糙度和期望获得的涂漆表面品质。用于调整光整冷轧操作的方式是延伸率水平,其必须足以实现目标并且足够小以保持后续变形能力。延伸率水平通常为0.3重量%至3重量%,并且优选为0.3重量%至2.2重量%。
所述带在传送至预涂漆线之前可任选地进行缠绕。
使涂层7的外表面15经受以下步骤,其中:
-脱脂,例如通过施用碱性溶液进行,然后
-漂洗并干燥,然后
-表面处理以增加漆的粘附性和耐腐蚀性,然后
-漂洗并任选地干燥,然后
-涂漆。
脱脂步骤的目的是清洁外表面15并因此去除有机污渍、金属颗粒和灰尘的痕迹。
优选地,除了改变任何氧化铝/氢氧化铝表面层之外,该步骤不会改变外表面15的化学性质。因此,用于该脱脂步骤的溶液是非氧化性的。因此,在脱脂步骤期间并且更通常地在涂漆步骤之前,外表面15上没有形成氧化镁或氢氧化镁。
表面处理步骤包括将转化溶液施用在外表面15上,其与外表面15发生化学反应并因此可在外表面15上形成转化层(未示出)。优选地,转化溶液不包含铬。因此,其可以是基于六氟钛酸或六氟锆酸的溶液。
涂漆可例如通过使两个连续漆层(即底漆层和顶涂层)沉积(一般是生产上膜9的情况)或者通过使单个漆层沉积(一般是生产下膜11的情况)来进行。在某些替代方案中可使用其他数量的层。
例如,使用辊式涂布机(roller coaters)使漆层沉积。
通常在漆层每次沉积之后在炉中进行焙烧。
由此获得的金属板1在进行切割之前可由使用者再次进行卷绕,任选地成形或者与其他金属板1或其他元件进行组装。
本发明人已表明,使用用于改变每个涂层7的外表面15上存在的氧化镁或氢氧化镁的步骤使得可改善金属板1的耐腐蚀性,并且特别地当金属板1经受腐蚀环境时限制漆膜9和11的起泡现象。
氧化镁或氢氧化镁层在本文中是指可包含MgxOy型化合物或Mgx(OH)y型化合物或这两种类型化合物的混合物的层。
事实上,涂层7外表面15的XPS(X射线光电子发射光谱)光谱分析表明了涂漆前,甚至当涂层7具有相似的铝和镁含量水平时,氧化镁或氢氧化镁以优势量存在。
然而,在基本上包含小比例的锌和铝的典型涂层中,金属涂层的外表面由氧化铝层所覆盖,但是铝含量水平非常低。因此,对于相似含量水平的镁和铝而言,预计存在优势量的氧化铝。
还使用XPS光谱来测量涂漆前的外表面15上存在的氧化镁或氢氧化镁层的厚度。显示这些层的厚度为几纳米。
应注意,这些XPS光谱分析在未经受腐蚀环境的金属板1的试样上进行。因此,氧化镁或氢氧化镁层的形成与涂层7的沉积相关。
图2和图3分别说明了XPS光谱分析期间元素关于能级的谱图:C1s(曲线17)、O1s(曲线19)、Mg1s(曲线21)、Al2p(曲线23)和Zn2p3(曲线25)。对应的原子百分比示于y轴且分析深度示于x轴。
图2中所分析的样品对应于包含3.7重量%铝和3重量%镁的涂层7并经受延伸率为0.5%的常规光整冷轧步骤;而图3的试样未经受这个步骤。
在这两种试样上,根据XPS光谱分析,可估计出氧化镁或氢氧化镁层的厚度为约5nm。
由此看来,通过常规光整冷轧步骤或通过常规碱法脱脂和常规表面处理没有移除这些氧化镁或氢氧化镁层。
根据本发明,生产金属板1的方法包括在涂漆前改变涂层7的外表面15上存在的氧化镁或氢氧化镁层的步骤。
这种改变步骤可在表面处理步骤之前或期间发生。其可例如在涂层7的生产线或预涂漆线上发生。
在第一实施方案中,改变步骤包括在外表面15上施用酸溶液,例如pH为1至4、优选1至3.5并且甚至更优选1至3的酸溶液。例如,所述溶液可包括盐酸、硫酸或磷酸。
根据酸溶液的pH、以及其施用的时间和方式,所述溶液的施用持续时间可为0.2秒至30秒,优选0.2秒至15秒,并且更优选0.5秒至15秒。
所述溶液可通过浸渍、喷洒或任何其他系统施用。例如,所述溶液的温度可以为环境温度或任何其他温度。
在第一实施方案中,施用酸溶液的步骤在脱脂之后的漂洗和干燥步骤之后发生。施用酸溶液之后是外表面15的漂洗和任选地干燥步骤,然后是转化溶液的施用步骤。
在第二实施方案中,用于施用转化溶液的步骤构成了涂层7的外表面15上氧化镁或氢氧化镁层的改变步骤。
在这种情况下,所使用的转化溶液的pH为1至2。
施用时间与第一实施方案的施用时间相似。
在第三实施方案中,改变步骤包括在金属涂层7的外表面15上施加机械力,和任选地施用酸溶液。
这种机械力可通过辊式矫直机(roller leveler)、刷涂装置、喷丸清理装置(shotblasting devices)等来施加。
这些机械力由于其单独作用可用来改变氧化镁或氢氧化镁层。因此,刷涂装置和喷丸清理装置可移除全部或部分的这些层。
同样地,可对特征在于通过在辊之间的弯曲施加塑性变形的辊式矫直机进行调整,以使穿过其的金属板变形到足以在氧化镁或氢氧化镁层中产生裂纹。
如果将施加机械力与施用酸溶液组合,则优选在酸溶液之前或者当外表面15上存在酸溶液时施加机械力,以有利于酸溶液作用。
在这种情况中,机械力可能较不强烈。
然后可在辊式矫直机中施用酸性溶液。
当酸溶液与机械力施加组合使用时,酸溶液的pH可较高,并且特别地大于3。
在该第三实施方案中,改变步骤在脱脂步骤之前发生。
如果第三实施方案的改变步骤包括施用酸溶液,则其之后是对金属涂层7的外表面15的漂洗或任选地干燥步骤。
使利用根据发明的方法(即具有用于改变金属涂层上存在的氧化镁或氢氧化镁层的步骤)获得的金属板1以及常规获得的金属板的试样经受耐腐蚀测试。显示了使用根据本发明的方法获得的金属板1具有较好的耐腐蚀性。
Claims (16)
1.一种用于生产金属板(1)的方法,所述方法包括以下一系列步骤:
-提供钢基材(3),所述钢基材(3)具有两个面(5),每个面(5)涂覆有通过将所述基材(3)浸渍在浴中并冷却而获得的金属涂层(7),每个金属涂层(7)包含锌、0.1重量%至20重量%的铝和0.1重量%至10重量%的镁,使由此涂覆的所述基材(3)经受光整冷轧步骤,
-使所述金属涂层(7)的外表面(15)脱脂,
-漂洗并干燥所述金属涂层(7)的所述外表面(15),
-改变所述金属涂层(7)的所述外表面(15)上形成的氧化镁或氢氧化镁层,所述改变步骤包括将pH为1至4的酸溶液施用在所述金属涂层(7)的所述外表面(15)上,
-漂洗并任选地干燥所述金属涂层(7)的所述外表面(15),
-将转化溶液施用在所述金属涂层(7)的所述外表面(15)上,由此所述转化溶液与所述外表面发生化学反应以在所述外表面(15)上形成转化层,
-干燥所述金属涂层(7)的所述外表面(15),
-对所述金属涂层(7)的所述外表面(15)进行涂漆以用漆膜(9、11)对每一个所述外表面(15)进行覆盖,所述漆膜(9、11)包含选自以下的至少一种聚合物:三聚氰胺交联的聚酯、异氰酸酯交联的聚酯、聚氨酯、和乙烯基聚合物的卤化衍生物,不包括阳离子电泳漆。
2.根据权利要求1所述的方法,所述脱脂步骤包括将碱性溶液施用在所述金属涂层(7)的所述外表面(15)上。
3.根据权利要求1所述的方法,其中将所述酸溶液在0.2秒至30秒的持续时间期间施用在所述金属涂层(7)的所述外表面(15)上。
4.一种用于生产金属板(1)的方法,所述方法包括以下一系列步骤:
-提供钢基材(3),所述钢基材(3)具有两个面(5),每个面(5)涂覆有通过将所述基材(3)浸渍在浴中并冷却而获得的金属涂层(7),每个金属涂层(7)包含锌、0.1重量%至20重量%的铝和0.1重量%至10重量%的镁,使由此涂覆的所述基材(3)经受光整冷轧步骤,
-使所述金属涂层(7)的外表面(15)脱脂,
-漂洗并干燥所述金属涂层(7)的所述外表面(15),
-将不包含铬的酸转化溶液施加在所述金属涂层(7)的所述外表面(15)上,由此所述转化溶液与所述外表面发生化学反应以在所述外表面(15)上形成转化层,所述转化溶液的pH为1至2,
-干燥所述金属涂层(7)的所述外表面(15),
-对所述金属涂层(7)的所述外表面(15)进行涂漆以用漆膜(9、11)对每一个所述外表面(15)进行覆盖,所述漆膜(9、11)包含选自以下的至少一种聚合物:三聚氰胺交联的聚酯、异氰酸酯交联的聚酯、聚氨酯、和乙烯基聚合物的卤化衍生物,不包括阳离子电泳漆。
5.根据权利要求4所述的方法,其中将所述酸转化溶液在0.2秒至30秒的持续时间期间施用在所述金属涂层(7)的所述外表面(15)上。
6.一种用于生产金属板(1)的方法,所述方法包括以下一系列步骤:
-提供钢基材(3),所述钢基材(3)具有两个面(5),每个面(5)涂覆有通过使所述基材(3)浸渍在浴中并冷却而获得的金属涂层(7),每个金属涂层(7)包含锌、0.1重量%至20重量%的铝和0.1重量%至10重量%的镁,使由此涂覆的所述基材(3)经受光整冷轧步骤,
-改变所述金属涂层(7)的外表面(15)上形成的氧化镁或氢氧化镁层,所述改变步骤包括使用辊式矫直机、刷涂装置或喷丸清理装置将机械力施加在所述金属涂层(7)的所述外表面(15)上,并且任选地将酸溶液施用在所述金属涂层(7)的所述外表面(15)上,
-如果所述改变步骤包括施用酸溶液,则漂洗并任选地干燥所述金属涂层(7)的所述外表面(15),
-将所述金属涂层(7)的所述外表面(15)进行非氧化脱脂,
-漂洗并干燥所述金属涂层(7)的所述外表面(15),
-将转化溶液施用在所述金属涂层(7)的所述外表面(15)上,由此所述转化溶液与所述外表面发生化学反应以在所述外表面(15)上形成转化层,
-干燥所述金属涂层(7)的所述外表面(15),
-对所述金属涂层(7)的所述外表面(15)进行涂漆以用漆膜(9、11)对每一个所述外表面(15)进行覆盖,所述漆膜(9、11)包含选自以下的至少一种聚合物:三聚氰胺交联的聚酯、异氰酸酯交联的聚酯、聚氨酯、和乙烯基聚合物的卤化衍生物,不包括阳离子电泳漆。
7.根据权利要求6所述的方法,其中在施用所述酸溶液之前或当所述外表面(15)上存在所述酸溶液时,将所述机械力施加在所述金属涂层(7)的所述外表面(15)上。
8.根据权利要求7所述的方法,其中所述机械力借助于通过辊式矫直机来施加。
9.根据权利要求6所述的方法,其中所述机械力使所述氧化镁或氢氧化镁层破裂。
10.根据权利要求1至9中任一项所述的方法,其中所述金属涂层(7)包含0.3重量%至10重量%的镁。
11.根据权利要求10所述的方法,其中所述金属涂层(7)包含0.3重量%至4重量%的镁。
12.根据权利要求1至9中任一项所述的方法,其中所述金属涂层(7)包含0.5重量%至11重量%的铝。
13.根据权利要求12所述的方法,其中所述金属涂层(7)包含0.7重量%至6重量%的铝。
14.根据权利要求13所述的方法,其中所述金属涂层(7)包含1重量%至6重量%的铝。
15.根据权利要求1至9中任一项所述的方法,其中所述金属涂层(7)中所述镁与所述铝的重量比小于或等于1。
16.一种金属板(1),所述金属板(1)具有两个面(5),每个面(5)涂覆有包含锌、铝和镁的金属涂层(7)以及漆膜(9、11),所述漆膜(9、11)包含选自以下的至少一种聚合物:三聚氰胺交联的聚酯、异氰酸酯交联的聚酯、聚氨酯、和乙烯基聚合物的卤化衍生物,不包括阳离子电泳漆,所述金属板能够通过根据权利要求1至15中任一项所述的方法获得。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FRPCT/FR2012/050910 | 2012-04-25 | ||
PCT/FR2012/050910 WO2013160567A1 (fr) | 2012-04-25 | 2012-04-25 | Procédé de réalisation d'une tôle prélaquée à revêtements znalmg et tôle correspondante. |
PCT/IB2013/053279 WO2013160866A1 (fr) | 2012-04-25 | 2013-04-25 | PROCÉDÉS DE RÉALISATION D'UNE TÔLE PRÉLAQUÉE À REVÊTEMENTS ZnAlMg ET TÔLE CORRESPONDANTE |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104364411A CN104364411A (zh) | 2015-02-18 |
CN104364411B true CN104364411B (zh) | 2017-11-21 |
Family
ID=48577184
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201380028894.9A Active CN104364411B (zh) | 2012-04-25 | 2013-04-25 | 用于生产具有Zn‑Al‑Mg涂层的预涂漆金属板的方法及相应的金属板 |
Country Status (13)
Country | Link |
---|---|
US (2) | US20150329952A1 (zh) |
EP (1) | EP2841613B1 (zh) |
JP (1) | JP6348107B2 (zh) |
CN (1) | CN104364411B (zh) |
BR (1) | BR112014026680B1 (zh) |
CA (1) | CA2871561C (zh) |
ES (1) | ES2716302T3 (zh) |
IN (1) | IN2014DN09952A (zh) |
PL (1) | PL2841613T3 (zh) |
RU (1) | RU2625927C2 (zh) |
TR (1) | TR201903632T4 (zh) |
WO (2) | WO2013160567A1 (zh) |
ZA (1) | ZA201407671B (zh) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102018216317A1 (de) * | 2018-09-25 | 2020-03-26 | Thyssenkrupp Ag | Verfahren zur Modifikation von feuerverzinkten Oberflächen |
EP3858495A1 (en) | 2020-02-03 | 2021-08-04 | Public Joint-Stock Company NOVOLIPETSK STEEL | Method for production of corrosion-resistant steel strip |
RU2727391C1 (ru) * | 2020-02-03 | 2020-07-21 | Публичное Акционерное Общество "Новолипецкий металлургический комбинат" | Способ производства коррозионностойкого окрашенного стального проката с цинк-алюминий-магниевым покрытием |
CN114645232A (zh) * | 2020-12-18 | 2022-06-21 | 广东美的制冷设备有限公司 | 一种涂层板和家用电器 |
EP4148163A1 (de) | 2021-09-13 | 2023-03-15 | Henkel AG & Co. KGaA | Verfahren zur reinigung und/oder korrosionsschützenden vorbehandlung einer vielzahl von bauteilen umfassend verzinktem (zm) stahl |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1199376A1 (en) * | 1999-05-24 | 2002-04-24 | Nippon Steel Corporation | Plated steel product, plated steel sheet and precoated steel sheet having excellent resistance to corrosion |
CN1612947A (zh) * | 2002-01-09 | 2005-05-04 | 新日本制铁株式会社 | 涂装后的耐蚀性与涂装鲜映性优异的镀锌钢板 |
Family Cites Families (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1081058A (en) * | 1976-11-05 | 1980-07-08 | Robert F. Hunter | Pretreatment of portion of ferrous metal strip with phosphoric acid solution to prevent subsequent galvanization thereon |
EP0500015B1 (en) * | 1991-02-18 | 1998-09-16 | Sumitomo Metal Industries, Ltd. | Use of plated aluminum sheet having improved spot weldability |
US6794060B2 (en) * | 1992-03-27 | 2004-09-21 | The Louis Berkman Company | Corrosion-resistant coated metal and method for making the same |
DE19923084A1 (de) | 1999-05-20 | 2000-11-23 | Henkel Kgaa | Chromfreies Korrosionsschutzmittel und Korrosionsschutzverfahren |
AUPQ633200A0 (en) * | 2000-03-20 | 2000-04-15 | Commonwealth Scientific And Industrial Research Organisation | Process and solution for providing a conversion coating on a metallic surface I |
JP2001348678A (ja) * | 2000-04-03 | 2001-12-18 | Nisshin Steel Co Ltd | 耐久性の良好な塗装鋼板 |
JP3690962B2 (ja) * | 2000-04-26 | 2005-08-31 | 三井金属鉱業株式会社 | キャリア箔付電解銅箔及びそのキャリア箔付電解銅箔の製造方法並びに銅張積層板 |
US20020114884A1 (en) | 2000-09-01 | 2002-08-22 | Friedersdorf Fritz J. | Process for applying a coating to a continuous steel sheet and a coated steel sheet product therefrom |
JP2002241962A (ja) | 2001-02-13 | 2002-08-28 | Sumitomo Metal Ind Ltd | 溶融Zn−Al−Mg合金めっき鋼板とその製造方法 |
JP2002317257A (ja) * | 2001-04-19 | 2002-10-31 | Sumitomo Metal Ind Ltd | 合金化溶融亜鉛めっき鋼板およびその製造方法 |
US20030000846A1 (en) * | 2001-05-25 | 2003-01-02 | Shipley Company, L.L.C. | Plating method |
JP3600804B2 (ja) * | 2001-06-27 | 2004-12-15 | 新日本製鐵株式会社 | 成形性に優れた溶融亜鉛めっき鋼板 |
TWI290177B (en) * | 2001-08-24 | 2007-11-21 | Nippon Steel Corp | A steel sheet excellent in workability and method for producing the same |
WO2003035922A1 (fr) * | 2001-10-23 | 2003-05-01 | Sumitomo Metal Industries, Ltd. | Procede de travail a la presse, produit en acier plaque destine a ce procede et procede de production de ce produit en acier |
AU2003265019B2 (en) | 2002-09-09 | 2008-08-14 | Keronite International Limited | Surface treatment of magnesium and its alloys |
JP2005023422A (ja) * | 2003-06-09 | 2005-01-27 | Nippon Paint Co Ltd | 金属表面処理方法及び表面処理金属 |
US8785000B2 (en) * | 2004-06-29 | 2014-07-22 | Tata Steel Ijmuiden B.V. | Steel sheet with hot dip galvanized zinc alloy coating and process to produce it |
JP4374289B2 (ja) | 2004-07-07 | 2009-12-02 | 新日本製鐵株式会社 | 加工部耐食性に優れた表面処理鋼板 |
JP2006062214A (ja) | 2004-08-27 | 2006-03-09 | Kunio Nakamura | 鉱石積層体及びその製造方法 |
JP4969831B2 (ja) * | 2004-10-26 | 2012-07-04 | 日本パーカライジング株式会社 | 金属表面処理剤、金属材料の表面処理方法及び表面処理金属材料 |
KR101082122B1 (ko) * | 2004-12-08 | 2011-11-10 | 신닛뽄세이테쯔 카부시키카이샤 | 프리코트 금속판 및 프리코트 금속판의 제조 방법 |
DE102005005858A1 (de) | 2005-02-08 | 2006-08-17 | Henkel Kgaa | Verfahren zur Beschichtung von Metallblech, insbesondere Zinkblech |
DE102005027633A1 (de) * | 2005-06-14 | 2006-12-21 | Basf Ag | Verfahren zum Herstellen von lackierten, flächenförmigen, metallischen Formkörpern |
JP4800682B2 (ja) | 2005-06-22 | 2011-10-26 | 矢崎総業株式会社 | 吊下ユニット及び吊下具 |
JP4757608B2 (ja) * | 2005-11-09 | 2011-08-24 | 新日本製鐵株式会社 | Zn系合金めっき鋼材 |
RU2417273C2 (ru) * | 2006-03-20 | 2011-04-27 | Ниппон Стил Корпорейшн | Стальной материал с высокой коррозионной стойкостью, получаемый с помощью горячего цинкования методом погружения |
JP4411326B2 (ja) * | 2007-01-29 | 2010-02-10 | 株式会社神戸製鋼所 | リン酸塩処理性に優れた高強度合金化溶融亜鉛めっき鋼板 |
DE102007021364A1 (de) | 2007-05-04 | 2008-11-06 | Henkel Ag & Co. Kgaa | Metallisierende Vorbehandlung von Zinkoberflächen |
WO2009116484A1 (ja) * | 2008-03-17 | 2009-09-24 | 大成プラス株式会社 | 亜鉛系鍍金鋼板と被着材の接合体及びその製造方法 |
JP2011206646A (ja) | 2010-03-29 | 2011-10-20 | Nisshin Steel Co Ltd | 塗装鋼板およびその製造方法 |
-
2012
- 2012-04-25 WO PCT/FR2012/050910 patent/WO2013160567A1/fr active Application Filing
-
2013
- 2013-04-25 EP EP13727379.3A patent/EP2841613B1/fr active Active
- 2013-04-25 CA CA2871561A patent/CA2871561C/fr active Active
- 2013-04-25 WO PCT/IB2013/053279 patent/WO2013160866A1/fr active Application Filing
- 2013-04-25 CN CN201380028894.9A patent/CN104364411B/zh active Active
- 2013-04-25 JP JP2015507653A patent/JP6348107B2/ja active Active
- 2013-04-25 RU RU2014147322A patent/RU2625927C2/ru active
- 2013-04-25 TR TR2019/03632T patent/TR201903632T4/tr unknown
- 2013-04-25 ES ES13727379T patent/ES2716302T3/es active Active
- 2013-04-25 IN IN9952DEN2014 patent/IN2014DN09952A/en unknown
- 2013-04-25 US US14/397,093 patent/US20150329952A1/en not_active Abandoned
- 2013-04-25 BR BR112014026680-8A patent/BR112014026680B1/pt active IP Right Grant
- 2013-04-25 PL PL13727379T patent/PL2841613T3/pl unknown
-
2014
- 2014-10-22 ZA ZA2014/07671A patent/ZA201407671B/en unknown
-
2016
- 2016-02-24 US US15/052,365 patent/US10612118B2/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1199376A1 (en) * | 1999-05-24 | 2002-04-24 | Nippon Steel Corporation | Plated steel product, plated steel sheet and precoated steel sheet having excellent resistance to corrosion |
CN1612947A (zh) * | 2002-01-09 | 2005-05-04 | 新日本制铁株式会社 | 涂装后的耐蚀性与涂装鲜映性优异的镀锌钢板 |
Also Published As
Publication number | Publication date |
---|---|
IN2014DN09952A (zh) | 2015-08-14 |
ZA201407671B (en) | 2015-11-25 |
EP2841613A1 (fr) | 2015-03-04 |
RU2014147322A (ru) | 2016-06-10 |
WO2013160567A1 (fr) | 2013-10-31 |
WO2013160866A1 (fr) | 2013-10-31 |
EP2841613B1 (fr) | 2018-12-19 |
US20150329952A1 (en) | 2015-11-19 |
ES2716302T3 (es) | 2019-06-11 |
US10612118B2 (en) | 2020-04-07 |
CA2871561C (fr) | 2016-11-15 |
JP6348107B2 (ja) | 2018-06-27 |
JP2015515379A (ja) | 2015-05-28 |
BR112014026680A2 (pt) | 2017-06-27 |
TR201903632T4 (tr) | 2019-04-22 |
PL2841613T3 (pl) | 2019-05-31 |
RU2625927C2 (ru) | 2017-07-19 |
CA2871561A1 (fr) | 2013-10-31 |
BR112014026680B1 (pt) | 2020-10-20 |
US20160168683A1 (en) | 2016-06-16 |
CN104364411A (zh) | 2015-02-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104334764B (zh) | 用于生产具有涂油Zn‑Al‑Mg涂层的金属板的方法和对应的金属板 | |
CN104364411B (zh) | 用于生产具有Zn‑Al‑Mg涂层的预涂漆金属板的方法及相应的金属板 | |
CN104364412B (zh) | 包括施用酸溶液和粘合剂的用于生产具有Zn‑Al‑Mg涂层的金属板的方法和对应的金属板及组合件 | |
JP4757608B2 (ja) | Zn系合金めっき鋼材 | |
GB2566832A (en) | A method for manufacturing a metal sheet with a ZnAl coating and with optimised drying, corresponding metal sheet, part and vehicle | |
CN105829568B (zh) | 具有改善的挠性的ZnAlMg涂覆的金属板及相应的制造方法 | |
CN106029933B (zh) | 用于生产具有最佳擦拭的ZnAlMg涂覆的金属板材的方法和相应的金属板材 | |
JP2005169765A (ja) | 耐食性に優れた塗装Zn−Al系合金めっき鋼板 | |
JP2004323932A (ja) | 塗装鋼板、及びその母材めっき鋼板、並びにそれらの製造方法 | |
JP2013204054A (ja) | 化成処理Zn系めっき鋼板の製造方法、それによって得られる化成処理Zn系めっき鋼板、および塗装Zn系めっき鋼板 | |
JP2020019152A (ja) | 塗装金属板 | |
JP3572944B2 (ja) | 耐クラック性及び耐食性に優れた溶融Al−Zn系合金めっき鋼板の製造方法 | |
JP2003277903A (ja) | 加工性及び加工部耐食性に優れた塗装めっき鋼板 | |
JP6203924B2 (ja) | 前処理Zn系めっき鋼板、および塗装Zn系めっき鋼板 | |
JP3329272B2 (ja) | 耐クラック性及び耐食性に優れた溶融Al−Zn系合金めっき鋼板 | |
JPH02122056A (ja) | 合金化溶融亜鉛めっき鋼板 | |
JPH11343551A (ja) | 耐食性に優れた溶融Al−Zn系合金めっき鋼板 | |
JP2005022105A (ja) | 塗装鋼板 | |
JPH0734262A (ja) | 自動車用表面処理鋼板の製造方法 | |
JPH07278776A (ja) | 合金化処理亜鉛めっき鋼板およびその製造方法 | |
JPH11343553A (ja) | 耐食性に優れた溶融Al−Zn系合金めっき鋼板 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |