CN115369343A - 金属镀覆钢带 - Google Patents
金属镀覆钢带 Download PDFInfo
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- CN115369343A CN115369343A CN202210715988.4A CN202210715988A CN115369343A CN 115369343 A CN115369343 A CN 115369343A CN 202210715988 A CN202210715988 A CN 202210715988A CN 115369343 A CN115369343 A CN 115369343A
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 45
- 239000010959 steel Substances 0.000 title claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 title description 9
- 239000002184 metal Substances 0.000 title description 9
- 238000000576 coating method Methods 0.000 claims abstract description 64
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 62
- 239000000956 alloy Substances 0.000 claims abstract description 62
- 239000011248 coating agent Substances 0.000 claims abstract description 59
- 229910007981 Si-Mg Inorganic materials 0.000 claims abstract description 54
- 229910008316 Si—Mg Inorganic materials 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 51
- 229910019064 Mg-Si Inorganic materials 0.000 claims abstract description 10
- 229910019406 Mg—Si Inorganic materials 0.000 claims abstract description 10
- 239000011247 coating layer Substances 0.000 claims abstract 2
- 239000010410 layer Substances 0.000 claims abstract 2
- 238000007747 plating Methods 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 18
- 229910052749 magnesium Inorganic materials 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 2
- 230000007547 defect Effects 0.000 description 30
- 239000011777 magnesium Substances 0.000 description 25
- 239000011701 zinc Substances 0.000 description 20
- 238000012360 testing method Methods 0.000 description 8
- 239000002023 wood Substances 0.000 description 5
- 239000008199 coating composition Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910018137 Al-Zn Inorganic materials 0.000 description 2
- 229910018573 Al—Zn Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005094 computer simulation Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical group [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 210000004894 snout Anatomy 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D5/00—Bending sheet metal along straight lines, e.g. to form simple curves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D53/00—Making other particular articles
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/10—Alloys based on aluminium with zinc 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
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
- C23C2/0222—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating in a reactive atmosphere, e.g. oxidising or reducing atmosphere
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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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/024—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by cleaning or etching
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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
- 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
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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
- 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
- C23C2/12—Aluminium or alloys based thereon
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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
- 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
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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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
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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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/50—Controlling or regulating the coating processes
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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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/50—Controlling or regulating the coating processes
- C23C2/52—Controlling or regulating the coating processes with means for measuring or sensing
- C23C2/521—Composition of the bath
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
- E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
- E04C2/02—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials
- E04C2/08—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of metal, e.g. sheet metal
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D3/00—Roof covering by making use of flat or curved slabs or stiff sheets
- E04D3/02—Roof covering by making use of flat or curved slabs or stiff sheets of plane slabs, slates, or sheets, or in which the cross-section is unimportant
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- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F13/00—Coverings or linings, e.g. for walls or ceilings
- E04F13/002—Coverings or linings, e.g. for walls or ceilings made of webs, e.g. of fabrics, or wallpaper, used as coverings or linings
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Abstract
在钢带上形成Al‑Zn‑Si‑Mg合金镀层的方法,所述方法包括将钢带浸入到熔融Al‑Zn‑Si‑Mg合金浴中,并在暴露的钢带表面形成合金镀层。所述方法还包括对镀覆浴的下游和熔融镀覆浴中的条件进行控制,从而使得在钢带上形成的镀层表面具有均一的Al/Zn比。Al‑Zn‑Mg‑Si镀覆钢带在Al‑Zn‑Si‑Mg合金镀层的最外层1‑2μm或表面上具有均一的Al/Zn比。
Description
本申请是申请日为2014年3月6日、发明名称为“金属镀覆钢带”的申请号为201480025117.3的专利申请的分案申请。
技术领域
本发明涉及金属带材、特别是钢带的生产,其具有耐腐蚀金属合金镀层,该镀层含有铝、锌、硅和镁作为合金中的主要元素,在此基础上,下面称之为“Al-Zn-Si-Mg合金”。
特别地,本发明涉及在带材上形成Al-Zn-Si-Mg合金镀层的热浸镀金属镀覆方法,该方法包含将未镀覆的带材浸入到熔融Al-Zn-Si-Mg合金浴中,并在带材上形成合金镀层。
通常而言,本发明所述Al-Zn-Si-Mg合金包含以下wt%范围的Al、Zn、Si和Mg元素:
更通常而言,本发明所述Al-Zn-Si-Mg合金包含以下wt%范围的Al、Zn、Si和Mg元素:
所述Al-Zn-Si-Mg合金镀层可包含其它元素作为有意加入的合金添加元素或作为不可避免的杂质。因此在本文中,短语“Al-Zn-Si-Mg合金”理解为涵盖了下述合金,该合金包含此类其它元素作为有意加入的合金添加元素或作为不可避免的杂质。所述其它元素可包括例如Ca、Ti、Fe、Sr、Cr和V中的任何一种或多种。
根据最终用途,可以在带材的一个或两个表面上,例如使用聚合物涂料对金属镀覆钢带进行涂覆。在这方面,金属镀覆带材本身可以作为最终产品出售,或者可以具有施用到一个或两个表面上的涂层产并作为涂覆的最终产品出售。
具体而言(但并不唯一),本发明涉及镀覆有上述Al-Zn-Si-Mg合金的钢带,该钢带可任选涂覆有涂层,随后进行冷成型(例如通过轧制成型)得到最终产品、例如建筑产品(例如型材壁或屋面板(profiled wall and roofing sheet))。
背景技术
在澳大利亚和其它地区广泛应用于建筑产品(特别是型材壁和屋面板)的一种耐腐蚀金属镀层组合物为55wt%Al-Zn镀层组合物,该组合物还包含Si。应当注意的是,除非另有说明,所有对百分数的引用均指重量百分数。
通常,通过将涂覆的金属合金镀覆带材冷成型来制造型材板。通常,通过将涂覆带材轧制成型来制造型材板。
在型材板上,镀层组合物的镀层微观结构通常包括富Al枝晶和富Zn枝晶间通道。
在专利文献中,数年来已经提出向55%Al-Zn-Si镀层组合物的这种已知组成中添加Mg,参见例如以新日本制铁株式会社(Nippon Steel Corporation)名义申请的美国专利6,635,359,但是钢带上的Al-Zn-Si-Mg镀层在澳大利亚不是市售的。
已经确定的是,当在55%Al-Zn-Si镀层组合物中包含Mg时,Mg对产品性能带来一定的有益效果,例如改善了割边防护(cut-edge protection)。
关于带材(例如包括工厂试验的钢带)上的Al-Zn-Si-Mg合金镀层,申请人进行了广泛的研发工作。本发明是此研发工作的一部分成果。
在工厂试验的过程中,申请人注意到Al-Zn-Si-Mg合金镀覆钢带表面上具有缺陷。使用具有以下组成的Al-Zn-Si-Mg合金(以wt%计)进行工厂试验:53Al-43Zn-2Mg-1.5Si-0.45Fe和不可避免的杂质。申请人惊异于该缺陷的发生。申请人并没有在Al-Zn-Si-Mg合金镀层的大量实验室工作中发现缺陷。此外,自从注意到在工厂试验中存在缺陷,申请人一直未能在实验室中重现该缺陷。申请人没有观察到在标准的55%Al-Zn合金镀覆钢带上的缺陷,该钢带已在澳大利亚和其它地区市售多年。
申请人已经发现该缺陷有许多不同的形式,包括条纹(streaks)、斑块(patches)和木纹图案(wood grain pattern)。申请人在内部将该缺陷描述为“灰”迹。
图1中示出了缺陷严重的实例,该实例为在室外观察条件-低角度阳光直射进行拍摄的情况下,来自工厂试验的Al-Zn-Si-Mg合金镀覆钢带的部分表面的照片。在图1中,缺陷本身显示为具有多种形状的较暗区域。在此实例中,灰迹缺陷表现为(a)斑块(一律比周围区域更暗的清楚界定的区域)、(b)条纹(沿带材长度方向延伸的窄的区域,该区域比周围区域更暗)和(c)在“最佳”光照下以低视角观察时在镀覆钢带表面上的木纹图案(沿带材长度方向延伸的区域,该区域在较暗线之间具有清楚的较暗线和较亮线,即类似于木纹)。申请人发现,随着视角向垂直方向增加,缺陷的视觉差别迅速减小直到无法看到,在表面没有明显的镀层伪迹(artefacts),例如金属点、浮渣或闪光(spangle)变化。
申请人发现该缺陷并不局限于图1所示的形态,可以是较暗区域的其它构造。
申请人从镀覆带材美观的立场关注了该缺陷的应用。这在商业上是非常重要的问题。
上面的说明不应视为承认在澳大利亚或其它地区中的公知常识。
发明内容
申请人已经发现,上述灰迹缺陷是因为在Al-Zn-Si-Mg合金镀层表面上的Al/Zn比的变化,具体而言是在缺陷区域内的表面Al/Zn比的降低,而该Al/Zn比的降低是由于在镀层表面上的富Zn枝晶间通道平均宽度的增加。
申请人已观察到,与缺陷相关的Al/Zn比的变化处于镀层横截面的最外层1-2μm中,但并不限于此。
申请人还发现,通过使用电子探针显微分析仪对缺陷边界进行元素映射(elemental mapping)最容易检测到该缺陷。
本发明提供了在基材、例如但不限于钢带上形成Al-Zn-Si-Mg系合金镀层的方法,该方法的特征在于通过控制(a)包含用于对基材进行镀覆的Al-Zn-Si-Mg系合金浴中的条件和(b)熔融镀覆浴的下游中的条件,从而使得在基材上形成的镀层表面上具有均一的Al/Zn比。
在本文中,术语“均一的”在Al/Zn比的上下文中理解为在任何两个或多个独立的1mm×1mm区域之间,通过X-射线能量分散谱(EDS)测定的Al/Zn比变化通常小于0.1。尽管上述Al/Zn比变化受到限定,该镀层在商业用途方面的适用性和由此的词语“均一的”其含义由在最佳光照条件下的视觉表面外观所定义。
本发明提供了在钢带上形成Al-Zn-Si-Mg合金镀层以形成上述Al-Zn-Mg-Si镀覆钢带的方法,该方法包括将钢带浸入到熔融Al-Zn-Si-Mg合金浴中,并在暴露的钢带表面上形成合金镀层;该方法包括对镀覆浴的下游和熔融镀覆浴中的条件进行控制,从而使得在钢带上形成的镀层表面具有均一的Al/Zn比。
虽然不希望受限于以下论述,申请人认为该缺陷可能是由于镀层微观结构中的Mg2Si的非均一表面/亚表面分布造成的。申请人已观察到在缺陷区域中镀层横截面的下半部之内,Mg2Si的成核速率增加。
本方法可以包括在镀覆浴的下游和熔融镀覆浴中控制任何适合的条件。
举例来说,本方法可以包括:控制熔融镀覆浴的任何一种或多种组成;以及在镀覆钢带离开熔融镀覆浴之后,控制镀覆钢带的冷却速率。
通常,本方法包括控制熔融镀覆浴的Ca浓度。
通常,由行业中通用的标准实践对熔融镀覆浴的Ca浓度进行测定,即取镀覆浴样品并通过多种已知的分析选项(例如XRF和ICP)的任何一种对样品进行分析,测量误差通常为正/负10ppm。
本方法可以包括将Ca浓度控制为至少100ppm。
本方法可以包括将Ca浓度控制为至少120ppm。
本方法可以包括将Ca浓度控制为小于200ppm。
本方法可以包括将Ca浓度控制为小于180ppm。
Ca浓度可以为任何其它适合的浓度范围。
通常,本方法包括控制熔融镀覆浴的Mg浓度。
通常,由行业中通用的标准实践对熔融镀覆浴的Mg浓度进行测定,即取镀覆浴样品并通过多种已知的分析选项(例如XRF和ICP)的任何一种对样品进行分析,测量误差通常为正/负10ppm。
本方法可以包括将Mg浓度控制为至少0.3%。
本方法可以包括将Mg浓度控制为至少1.8%。
本方法可以包括将Mg浓度控制为至少1.9%。
本方法可以包括将Mg浓度控制为至少2%。
本方法可以包括将Mg浓度控制为至少2.1%。
Mg浓度可以为任何其它适合的浓度范围。
本方法可包括使镀覆带材温度处于400℃-510℃的温度范围内的同时,将经历镀覆浴之后的冷却速率控制为小于40℃/s。
申请人已经发现,400℃-510℃的镀覆温度范围对于已测试的镀层合金组成是重要的,而且由于在此范围内的快速冷却将Al/Zn比的变化加剧到了使得差异变得明显可见(作为灰迹缺陷)的程度,因此是不期望的。在此温度范围内,基于使Al/Zn比的加剧变化的程度最小化,将冷却速率选择为小于40℃/s。
申请人已发现,低于400℃的镀覆温度对于镀层表面的Al/Zn比没有显著的影响。
申请人已发现,高于510℃的温度对于Al/Zn比的均一性没有显著的影响。
需要强调的是,在任何给定的情况下,对显著温度范围的限度将取决于镀层合金组成,本发明不必限定于400℃-510℃的镀覆温度范围。
本方法可以包括使镀覆带材温度处于400℃-510℃的温度范围内的同时,将经历镀覆浴之后的冷却速率控制为小于35℃/s。
本方法可以包括在400℃-510℃的温度范围内,将经历镀覆浴之后的冷却速率控制为大于10℃/s。
本方法可以包括在400℃-510℃的温度范围内,将经历镀覆浴之后的冷却速率控制为大于15℃/s。
通常,镀覆带材的冷却速率是通过计算机模型控制的。
申请人认为,对Ca浓度、Mg浓度和经历镀覆浴之后的冷却速率中的任何一个或多个条件而言,其选择不依赖于镀层质量。
概括地说,本发明似乎不依赖于镀层质量。
通常,镀层质量是50-200g/m2。
Al-Zn-Si-Mg合金可以包含大于1.8wt%的Mg。
Al-Zn-Si-Mg合金可以包含大于1.9%的Mg。
Al-Zn-Si-Mg合金可以包含大于2%的Mg。
Al-Zn-Si-Mg合金可以包含大于2.1%的Mg。
Al-Zn-Si-Mg合金可以包含小于3%的Mg。
Al-Zn-Si-Mg合金可以包含小于2.5%的Mg。
Al-Zn-Si-Mg合金可以包含大于1.2%的Si。
Al-Zn-Si-Mg合金可以包含小于2.5%的Si。
Al-Zn-Si-Mg合金可以包含以下wt%范围内的Al、Zn、Si和Mg元素:
特别地,Al-Zn-Si-Mg合金可以包含以下wt%范围内的Al、Zn、Si和Mg元素:
所述钢可以是低碳钢。
本发明还提供了由上述方法生产的Al-Zn-Mg-Si镀覆钢带。
本发明还提供了Al-Zn-Mg-Si镀覆钢带,该钢带在Al-Zn-Si-Mg合金镀层表面上具有均一的Al/Zn比。
本发明还提供了Al-Zn-Mg-Si镀覆钢带,该钢带在Al-Zn-Si-Mg合金镀层的最外层1-2μm或表面上具有均一的Al/Zn比。
本发明提供了由上述Al-Zn-Mg-Si镀覆钢带轧制成型或压制成型或以其它方式成型的型材壁和屋面板。
附图说明
下面参照附图对本发明作进一步举例说明:
图1是在理想观察条件进行拍摄的情况下,来自工厂试验的Al-Zn-Si-Mg合金镀覆钢带的部分表面的照片;以及
图2是依据本发明的方法生产Al-Zn-Si-Mg合金镀覆钢带的连续生产线的一个实施方式的示意图。
具体实施方式
参考图2,在使用中,在开卷工段1中将冷轧低碳钢带卷开卷,并通过焊接机2将连续开卷长度的带材头尾焊接,形成连续长度的带材。
然后将该带材依次通过累积器3(accumulator)、带材清洁段4和炉组件5。炉组件5包括预热装置、预热还原炉和还原炉。
在炉组件5中,通过小心控制过程变量来对带材进行热处理,所述过程变量包括:(i)炉中的温度曲线;(ii)炉中的还原气体浓度;(iii)通过该炉的气体流量;以及(iv)带材在炉中的停留时间(即线速度)。
控制炉组件5中的过程变量,使得从带材表面清除氧化铁残余物并且从带材表面清除残余的油和铁屑。
然后,使经过热处理的带材向下通过出口炉嘴,通入并且穿过处于镀覆锅6中的包含Al-Zn-Si-Mg合金的熔融浴(具有100-200ppm范围的Ca浓度),使带材镀覆Al-Zn-Si-Mg合金。使用加热感应器(未示出),在595-610℃范围内选定的温度下使Al-Zn-Si-Mg合金在镀覆锅中保持熔融。在浴内,带材围绕着浸入导辊穿过浴,并且从浴中向上穿出。对线速度进行选择以提供带材在镀覆浴中选定的浸没时间,从而生产出在带材的两个表面具有50-200g/m2镀层重量的镀层。
在离开镀覆浴6之后,带材垂直通过气刮工段(未示出),其镀覆表面在该处受到刮擦气体的喷射,以控制镀层的厚度。
然后,将镀覆带材通过冷却段7,在使镀覆带材的温度处于400℃-510℃的同时,在大于10℃/s但小于40℃/s的选定冷却速率下对其进行强制冷却。在小于400℃或大于510℃的镀覆带材温度下,冷却速率可以是任何合适的冷却速率。
然后,使经冷却的镀覆带材通过轧制段8,用来精整镀覆带材的表面。
然后在卷绕工段10将镀覆带材卷绕。
如上所述,申请人进行了与钢带上的Al-Zn-Si-Mg合金镀层有关的广泛的研发工作,其包括工厂试验;而且在工厂试验过程中,申请人注意到了Al-Zn-Si-Mg合金镀覆钢带表面上的缺陷。使用Al-Zn-Si-Mg合金进行了工厂试验,该Al-Zn-Si-Mg合金以wt%计具有以下组成:53Al-43Zn-2Mg-1.5Si-0.45Fe和不可避免的杂质。申请人惊异于该缺陷的发生。申请人并没有在Al-Zn-Si-Mg合金镀层的大量实验室工作中发现该缺陷。此外,自从注意到在工厂试验中存在缺陷,申请人一直未能在实验室中重现该缺陷。申请人在标准的55%Al-Zn合金镀覆钢带上没有观察到缺陷,该钢带已在澳大利亚和其它地区市售多年。此外,如上所述,申请人已经发现该缺陷具有许多不同的形式,包括条纹、斑块和木纹图案;图1中示出了这些形式的缺陷各自的严重实例。
如上所述,申请人已经发现上述缺陷是由于Al-Zn-Si-Mg合金镀层表面上Al/Zn比的变化,也可能是由于镀层微观结构中的Mg2Si的不均一分布;本发明包括对镀覆浴下游和熔融镀覆浴中的条件进行控制,从而使得在钢带上形成的镀层表面具有均一的Al/Zn比。
本发明的方法包括对镀覆浴下游和熔融镀覆浴中任何合适的条件进行控制,从而使得在钢带上形成的镀层表面(即,在镀层表面上或镀层横截面最外层1-2μm之内)具有均一的Al/Zn比(依据第5页的定义)。
如上述图2中所描述,举例来说,所描述的与图2相关的本发明所述方法的实施方式包括控制以下条件:(a)熔融镀覆浴的Ca浓度;(b)熔融镀覆浴的Mg浓度;以及(c)在镀覆钢带离开熔融镀覆浴之后,镀覆钢带的冷却速率。
应当注意的是,本发明并不局限于对此种条件组合的控制。
在不脱离本发明的精神和范围的情况下,可以对上述本发明作出许多变型。
Claims (18)
1.一种在钢带上形成Al-Zn-Si-Mg合金镀层以形成上述Al-Zn-Mg-Si镀覆钢带的方法,所述方法包括将钢带浸入到熔融Al-Zn-Si-Mg合金浴中,并在暴露的钢带表面上形成合金镀层;所述方法还包括对镀覆浴的下游和熔融镀覆浴中的条件进行控制,从而使得在所述钢带上形成的镀层表面具有均一的Al/Zn比。
2.如权利要求1所定义的方法,所述方法包括:控制所述熔融镀覆浴的任何一种或多种组成;以及在所述镀覆钢带离开所述熔融镀覆浴之后,控制所述镀覆钢带的冷却速率。
3.如权利要求1或权利要求2所定义的方法,所述方法包括控制所述熔融镀覆浴的Ca浓度。
4.如上述权利要求中任一项所定义的方法,所述方法包括将所述熔融镀覆浴的Ca浓度控制为至少100ppm。
5.如上述权利要求中任一项所定义的方法,所述方法包括将所述熔融镀覆浴的Ca浓度控制为小于200ppm。
6.如上述权利要求中任一项所定义的方法,所述方法包括将所述熔融镀覆浴的Mg浓度控制为至少1.8%。
7.如上述权利要求中任一项所定义的方法,所述方法包括使所述镀覆钢带的温度处于400℃-510℃的同时,将经历镀覆浴之后的冷却速率控制为小于40℃/s。
8.如上述权利要求中任一项所定义的方法,所述方法包括使所述镀覆钢带的温度处于400℃-510℃的同时,将经历镀覆浴之后的冷却速率控制为大于10℃/s。
9.如上述权利要求中任一项所定义的方法,其中,所述Al-Zn-Si-Mg合金包含大于1.8wt%的Mg。
10.如上述权利要求中任一项所定义的方法,其中,所述Al-Zn-Si-Mg合金包含小于3wt%的Mg。
11.如上述权利要求中任一项所定义的方法,其中,所述Al-Zn-Si-Mg合金包含小于2.5wt%的Mg。
12.如上述权利要求中任一项所定义的方法,其中,所述Al-Zn-Si-Mg合金包含大于1.2wt%的Si。
13.如上述权利要求中任一项所定义的方法,其中,所述Al-Zn-Si-Mg合金包含小于2.5wt%的Si。
16.通过上述权利要求中任一项所定义的方法生产的Al-Zn-Mg-Si镀覆钢带。
17.一种Al-Zn-Mg-Si镀覆钢带,所述Al-Zn-Mg-Si镀覆钢带在Al-Zn-Si-Mg合金镀层的最外层1-2μm或表面上具有均一的Al/Zn比。
18.一种型材壁和屋面板,所述型材壁和屋面板由权利要求16或权利要求17所定义的Al-Zn-Mg-Si镀覆钢带轧制成型或压制成型或以其它方式成型。
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CN1369020A (zh) * | 1999-08-09 | 2002-09-11 | 新日本制铁株式会社 | 耐腐蚀性优异的Zn-Al-Mg-Si合金镀覆钢材及其制造方法 |
CN101535521A (zh) * | 2006-08-29 | 2009-09-16 | 蓝野钢铁有限公司 | 镀覆有金属的钢带 |
CN101910446A (zh) * | 2008-03-13 | 2010-12-08 | 蓝野钢铁有限公司 | 金属镀覆钢带 |
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