JP7027526B2 - 被覆金属基材 - Google Patents
被覆金属基材 Download PDFInfo
- Publication number
- JP7027526B2 JP7027526B2 JP2020512541A JP2020512541A JP7027526B2 JP 7027526 B2 JP7027526 B2 JP 7027526B2 JP 2020512541 A JP2020512541 A JP 2020512541A JP 2020512541 A JP2020512541 A JP 2020512541A JP 7027526 B2 JP7027526 B2 JP 7027526B2
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- JP
- Japan
- Prior art keywords
- coating
- steel substrate
- coated steel
- thickness
- deposition
- 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.)
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- 229910052751 metal Inorganic materials 0.000 title claims description 49
- 239000002184 metal Substances 0.000 title claims description 49
- 239000000758 substrate Substances 0.000 title claims description 47
- 238000000576 coating method Methods 0.000 claims description 79
- 239000011248 coating agent Substances 0.000 claims description 72
- 229910000831 Steel Inorganic materials 0.000 claims description 38
- 239000010959 steel Substances 0.000 claims description 38
- 239000011701 zinc Substances 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 26
- 229910052725 zinc Inorganic materials 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 238000000151 deposition Methods 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000011651 chromium Substances 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 12
- 238000001771 vacuum deposition Methods 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 238000007740 vapor deposition Methods 0.000 claims description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 238000010894 electron beam technology Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 238000004070 electrodeposition Methods 0.000 claims description 3
- 238000001912 gas jet deposition Methods 0.000 claims description 3
- 238000001540 jet deposition Methods 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005422 blasting Methods 0.000 claims description 2
- 238000000313 electron-beam-induced deposition Methods 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000005339 levitation Methods 0.000 claims description 2
- 238000005289 physical deposition Methods 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 238000005488 sandblasting Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 description 22
- 230000007797 corrosion Effects 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 13
- 239000010410 layer Substances 0.000 description 13
- 230000004888 barrier function Effects 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 3
- 229910001338 liquidmetal Inorganic materials 0.000 description 3
- 229910001092 metal group alloy Inorganic materials 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 229910000619 316 stainless steel Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000036316 preload Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Images
Classifications
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- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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- 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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- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
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- B32B15/017—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of aluminium or an aluminium alloy, another layer being formed of an alloy based on a non ferrous metal other than aluminium
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- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
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Description
本発明は、被覆金属基材及びこの被覆金属基材の製造方法に関する。本発明は、自動車産業での使用に特に適している。
車両の重量を節約するという観点から、良好な耐腐食性や良好なりん酸亜鉛処理性などの特性を有する金属被覆を付加することにより、鋼板又は鋼製パネルの厚さが減少することが知られている。加えて、厚さが薄いと溶接性が向上することになる。
亜鉛系被覆は、バリア防食効果及びカソード防食効果の働きで腐食から保護できるため、一般に使用されている。このバリア効果は、鋼表面に金属被覆を施すことにより得られる。その結果、この金属被覆は鋼と腐食性大気との接触を防止する。一方、犠牲カソード防食は、亜鉛が鋼よりも腐食しやすい金属であるという事実に基づいている。したがって、腐食が発生すると、亜鉛が鋼よりも優先的に消耗することになる。カソード防食効果は、周囲の亜鉛が鋼よりも先に消耗する切り口のように、鋼が腐食性大気に直接曝露される範囲では不可欠である。
亜鉛被覆には犠牲防食効果があるが、バリア効果が十分ではないため、腐食に対する防食効果は十分に高くはない。
その上、かかる亜鉛被覆鋼板で加熱工程、たとえばプレス硬化又は溶接が実行されると、鋼の被覆に割れが広がるのが観察されている。実際、加熱工程後に被覆鋼板に割れが生じるため、金属の機械的性質が低下することもある。これらの割れは、以下の条件、すなわち、高温であること、応力に加えて低融点の液体金属（亜鉛など）と接触することや、基材粒塊及び基材境界を有する溶融金属が不均一に拡散することで出現する。かかる現象が持つ名称は液体金属脆化（ＬＭＥ）であり、液体金属助長割れ（ＬＭＡＣ）とも呼ばれている。
したがって、可能な限り最小の厚さ、すなわち、良好な溶接性を実現するような薄い厚さを有する、十分に防食効果のある被覆金属基材を提供する必要がある。
そのため、本発明の目的は、腐食に対する強化された防食、すなわち、バリア防食に加えて犠牲カソード防食を有し、ＬＭＥの問題を引き起こすことのない最薄の被覆金属基材を提供することである。その目的においては、かかる被覆金属基材を得るために、特に実施が容易な方法を利用できるようにすることを目指している。
腐食に対する犠牲防食に関しては、電気化学電位を金属基材の電位よりも少なくとも５０ｍＶ負側としなければならない。たとえば、鋼基材の場合、飽和カロメル電極（ＳＣＥ）に対する最大電位を－０．７８Ｖとすることが必要である。－１．４Ｖ／ＳＣＥ、さらには－１．２５Ｖ／ＳＣＥの値でさえも電位を低下させないことが望ましく、こうした低下によって消耗が早まり、最終的に鋼の防食期間を短縮してしまうことになる。
この目的は、請求項１に記載の被覆金属基材を提供することにより達成される。本被覆金属基材は、請求項２～１０のいずれかの特徴をさらに含み得る。
別の目的は、請求項１１に記載の製造方法を提供することにより達成される。本方法は、請求項１２～１４のいずれかの特徴をさらに含み得る。
さらに、この目的は、請求項１５に記載の被覆金属基材の使用を実現することにより達成される。
最後に、この目的は、請求項２０に記載の移動中の金属基材上に被覆を連続真空蒸着するための設備を提供することにより達成される。本設備は、請求項１６～１９のいずれかの特徴をさらに含み得る。
本発明の他の特徴及び利点は、本発明の以下の詳細な説明から明らかになるであろう。
本発明を説明するために、具体的に以下の図を参照しながら、非限定的な例の様々な実施形態及び試行について記載する。
すべての図において、示している層の厚さは専ら説明を目的としており、これを異なる縮尺の層を表すと見なすことはできない。
次の用語を定義する。
－「ｗｔ．％」は重量パーセントを意味する。
－「ｗｔ．％」は重量パーセントを意味する。
本発明は、アルミニウムからなる少なくとも第１の被覆を備える被覆金属基材に関し、かかる第１の被覆は厚さが１．０～４．５μｍであり、及び亜鉛をベースとする第２の被覆によって直接上面が覆われており、かかる第２の被覆の厚さは１．５～９．０μｍであり、並びに第２の被覆に対する第１の被覆の厚さ比は０．２～１．２である。この第１の被覆はアルミニウムからなり、これはすなわち、第１の被覆のアルミニウム量が９９．０重量％を超えていることを意味する。
いかなる理論にも束縛されるものではないが、上記の被覆金属基材は、可能な限り薄い厚さで腐食に対する高い防食効果を実現すると考えられる。実際、上記の特定の厚さ及び厚さ比を有する第１及び第２の被覆を組み合わせることにより、高いバリア効果及び高い犠牲防食効果をもたらすと思われる。
アルミニウムからなる第１の被覆の厚さは１．０～４．５μｍであり、これにより高い耐腐食性、特に高いバリア効果が得られると思われる。亜鉛をベースとする第２の被覆の厚さは３．０～９．０μｍであり、これにより高い耐腐食性、特に、高い犠牲防食効果が得られる。さらに、高い耐腐食性を有する最薄の被覆金属基材を得るために、第２の被覆に対する第１の被覆の厚さ比を０．２～１．２としなければならないことが分かった。この厚さ比が０．２未満である場合、耐腐食性が十分でないリスクがあると考えられる。この厚さ比が１．２を超えている場合、最高のバリア効果、最高の犠牲防食効果及び良好な溶接挙動を有する被覆金属基材において、最薄の厚さが得られないリスクがある。
最後に、第１及び第２の層を有する本被覆金属基材は、主として上記の特定の厚さを有するアルミニウムが存在することにより、ＬＭＥに対する高い耐性を有する。その結果、本発明による特定の被覆金属基材を用いると、ＬＭＥに対する耐性に加えて、高いバリア効果、すなわち、高い犠牲防食効果及び高いバリア効果を有する最薄の被覆金属基材を得ることができる。
好ましくは、第２の被覆は０．５重量％未満のマグネシウムを含む。
有利には、第２の被覆は、Ｓｉ及びＭｇから選択される少なくとも１つの元素を含む。
別の好ましい実施形態では、第２の被覆は、次のマグネシウム、アルミニウム、銅及びシリコンのうちの少なくとも１つの元素を含まない。実際、いかなる理論にも束縛されるものではないが、第２の被覆にマグネシウムが存在することにより、酸化マグネシウムが形成されて表面欠陥が発生する可能性があり、アルミニウムが存在することにより、犠牲防食効果を低下させる可能性があり、また、シリコンが存在することによっても、犠牲防食効果を低下させる可能性があると思われる。
有利には、第２の被覆は亜鉛からなり、これはすなわち、第１の被覆の亜鉛量が９９．０重量％を超えていることを意味する。
好ましくは、第１の被覆の厚さは２～４μｍである。
有利には、第２の被覆の厚さは１．５～８．５μｍである。たとえば、第２の被覆の厚さは１．５μｍ～４．５μｍ又は４．５μｍ～８．５μｍである。
好ましくは、第２の被覆に対する第１の被覆の比は０．２～０．８、より好ましくは０．３～０．７である。
好ましくは、金属基材と第１の被覆との間に中間層を設けており、かかる中間層は鉄、ニッケル、クロム及び任意にチタンを含む。いかなる理論にも束縛されるものではないが、この中間被覆層は、金属基材上における第１の被覆の接着性をさらに改良するものと思われる。
１つの好ましい実施形態では、この中間層はニッケルを少なくとも８重量％、また、クロムを少なくとも１０重量％含み、残部は鉄である。たとえば、この金属被覆層は、Ｃｒを１６～１８重量％、Ｎｉを１０～１４重量％含み、残部がＦｅである、３１６ステンレス鋼である。
別の好ましい実施形態では、この中間層はＦｅ、Ｎｉ、Ｃｒ及びＴｉを含み、Ｔｉ量は５重量％以上であり、次の式、すなわち、８重量％＜Ｃｒ＋Ｔｉ＜４０重量％が満たされ、残部はＦｅ及びＮｉであり、かかる中間被覆層は、防食金属被覆である被覆層によって直接上面が覆われている。
本金属基材は、アルミニウム基材、鋼基材、ステンレス鋼基材、銅基材、鉄基材、銅合金基材、チタン基材、コバルト基材又はニッケル基材の中から選択されることができる。
本発明はまた、本発明による被覆金属基材の製造方法に関し、以下の工程、
Ａ．金属基材を設ける工程、
Ｂ．任意に金属基材の表面処理を行う工程、
Ｃ．アルミニウムからなる第１の被覆を堆積させる工程であって、かかる第１の被覆の厚さが１．０～４．５μｍである、工程並びに
Ｄ．亜鉛をベースとする第２の被覆を堆積させる工程であって、かかる第２の被覆の厚さが１．５～９．０μｍであり、及び第２の被覆に対する第１の被覆の厚さ比が０．２～１．２である、工程を含む。
Ａ．金属基材を設ける工程、
Ｂ．任意に金属基材の表面処理を行う工程、
Ｃ．アルミニウムからなる第１の被覆を堆積させる工程であって、かかる第１の被覆の厚さが１．０～４．５μｍである、工程並びに
Ｄ．亜鉛をベースとする第２の被覆を堆積させる工程であって、かかる第２の被覆の厚さが１．５～９．０μｍであり、及び第２の被覆に対する第１の被覆の厚さ比が０．２～１．２である、工程を含む。
好ましくは、工程Ｂ）が実行されるとき、表面処理は、ショットブラスト、酸洗、エッチング、研磨、サンドブラスト、研削、並びに鉄、ニッケル、クロム及び任意にチタンを含む中間層の堆積から選択される。好ましくは、この表面処理は、金属基材上に中間層を堆積させることからなる。さらに、この中間層は、金属基材上に自然に存在している酸化物層の除去を回避することができる。
好ましくは、工程Ｃ）及び工程Ｄ）において、第１及び第２の被覆を堆積させる工程は、互いに独立して、溶融めっき、電着法又は真空蒸着により実行される。たとえば、第１の被覆を溶融めっきによって堆積させ、第２の被覆を真空蒸着によって堆積させる。別の実施例では、第１及び第２の被覆を真空蒸着によって堆積させる。
工程Ｃ）及び工程Ｄ）において、真空蒸着が実行されるとき、第１及び第２の被覆を互いに独立して、マグネトロンカソード粉砕法、ジェット蒸着法、電磁浮上蒸着法又は電子ビーム物理蒸着法により蒸着される。たとえば、第１の被覆をマグネトロンカソード粉砕法によって蒸着され、第２の被覆をジェット蒸着法によって蒸着される。
本発明はまた、自動車両の部品製造のための、本発明による被覆金属基材の使用に関する。
最後に、本発明は、本発明による被覆金属基材の本発明による製造方法を用いる、走行中の金属基材上に被覆を連続真空蒸着するための設備に関し、以下の順序で
Ａ．任意に、マグネトロンカソード粉砕装置を含む中間部分、
Ｂ．電子ビーム蒸着装置を含む第１の部分及び
Ｃ．ジェット蒸着装置を含む第２の部分、
を備える。
Ａ．任意に、マグネトロンカソード粉砕装置を含む中間部分、
Ｂ．電子ビーム蒸着装置を含む第１の部分及び
Ｃ．ジェット蒸着装置を含む第２の部分、
を備える。
好ましくは、中間部分を設けている場合、マグネトロンカソード粉砕装置は、鉄、クロム、ニッケル及び任意にチタンからなる１つのターゲットを含む真空蒸着チャンバ、及び鉄、ニッケル、クロム及び任意にチタンを含む中間層を本金属基材上に蒸着させるプラズマ源を備える。
この場合、１０－５～１０－９ｍバールの圧力の真空蒸着チャンバに不活性ガスを注入する。このプラズマ源は、ガスを帯電させるプラズマを生成している。このターゲットの表面原子は、プラズマで生成されるエネルギー粒子（イオン）の衝撃によって物理的に放出される。放出された原子は、金属基材上に蒸着する。
好ましくは、第１の部分において、電子ビーム蒸着装置は、アルミニウムからなる金属を含む蒸発るつぼを備える真空蒸着チャンバ、加熱装置及び厚さが１．０～４．５μｍである第１の被覆を蒸着する電子銃を備える。
好ましくは、第２の部分において、ジェット蒸着装置は、少なくとも蒸発るつぼを含む真空蒸着チャンバ、蒸気ジェットコーター及び亜鉛をベースとする蒸気をこの蒸気ジェットコーターに供給するのに適した、少なくとも１つの蒸発るつぼを備える。
好ましくは、この蒸気ジェットコーターは超音波蒸気ジェットコーターであり、蒸発るつぼは誘導加熱炉を含む。
有利には、蒸発るつぼの下に再充填炉を配置し、これを大気圧に維持されるように適合させている。より好ましくは、この再充填炉を金属インゴット供給手段に接続している。
真空蒸着チャンバにおいては、被覆する必要のある金属基材表面のそばに、蒸気ジェットコーターを設けている。このコーターは、亜鉛をベースとする金属合金蒸気を移動中の基材に噴霧するのに適している。
亜鉛をベースとする蒸気を蒸気ジェットコーターに供給するのに適した蒸発るつぼに、この蒸気ジェットコーターを取り付けている。１つの好ましい実施形態では、１つの蒸発るつぼは、基材上に蒸着する蒸気を生成する亜鉛を含む金属浴を収容するのに適している。別の好ましい実施形態では、２つの蒸発るつぼを使用し、一方の蒸発るつぼは別の金属を収容しており、もう一方の蒸発るつぼは亜鉛を収容しており、ここで両方の金属からなる蒸気の混合物を基材上に蒸着している。好ましくは、少なくとも蒸発るつぼを蒸着チャンバ内に配置している。
この蒸発るつぼに加熱手段を設けて、金属合金蒸気を形成し、また、これを蒸気ジェットコーターに供給するようにすることができる。有利には、この蒸発るつぼには、攪拌及び金属合金浴の組成均質化を容易にするという利点を有する、誘導加熱炉を設けている。
蒸発るつぼ内の圧力は、浴温及び金属浴の組成に依存する。通常、１０－３～１０－１バールの間で圧力が変化している。したがって、蒸着チャンバ２内の圧力は蒸発るつぼ内の圧力よりも高く保たれている。
亜鉛及び／又は別の金属を蒸発るつぼに供給するのに適した再充填炉に、少なくとも蒸発るつぼを接続することができる。好ましくは、該再充填炉は、真空蒸着チャンバの外側に位置している。好ましくは、蒸発るつぼの下に該再充填炉を配置し、これを大気圧に維持されるように適合させている。蒸発るつぼと再充填炉との間の高さ、及びそれらの間に生じる圧力差により、金属浴が蒸発するにつれて、気圧効果により溶融主元素が蒸発るつぼ内で上昇することになる。これにより、蒸発るつぼへの連続供給が確実に行われ、また、ライン速度に関係なく、蒸発るつぼ内の液位を一定に保つことができる。
本発明について、ここで情報提供のみを目的として行われた試験において説明する。これらの試験によって本発明を限定するものではない。
すべてのサンプルにおいて、使用している鋼板の組成は、Ｃ０．２重量％、Ｓｉ１．５重量％、Ｍｎ２重量％、Ａｌ０．０４重量％であり、残部は鉄である。
試験体１の場合、Ｚｎの被覆を電着によって鋼板上に蒸着した。
試験体２～試験体４では、Ｃｒを１６～１８重量％、Ｎｉを１０～１４重量％含み、残部がＦｅである、３１６ステンレス鋼である中間層を、マグネトロンカソード粉砕によって蒸着しており、その際、アルミニウムからなる第１の被覆を電子ビーム蒸着によって蒸着し、さらに、亜鉛からなる第２の被覆をＪＶＤによって蒸着した。
試験体５では、鋼板上に被覆を何ら蒸着しなかった。
［実施例１］
ＬＭＥ試験
ＬＭＥ感度を測定するために、スポット溶接条件に可能な限り近似している条件で高温引張試験を実施した。
ＬＭＥ試験
ＬＭＥ感度を測定するために、スポット溶接条件に可能な限り近似している条件で高温引張試験を実施した。
引張試験体を図１に示す。ヘッドの２つの孔にピンを挿入するために、これらを機械加工しているため、これによって試験中にスライドすることが確実にないようにしている。
次いで、１ｋＮの予荷重を各試験体に加える。これらの試験体を約１０００℃／ｓの加熱速度で加熱して、７５０～９５０℃の温度に到達させる。当該温度に到達すると、完全に破断するまで、試験体に変位が加えられる。本試験中、３ｍｍ／ｓのひずみ速度を使用した。
応力－ひずみ曲線を求め、これらを分析する。この応力－ひずみ曲線の導出を計算して、これを描画する。ひずみの微分値が最小のときの鋼の延性は、試験体破断に対応する。この破断がＬＭＥ現象に起因する場合、すなわち、割れが液体亜鉛によるものである場合、この延性を「ＬＭＥ限界延性値」として定義する。この破断が延性破断である場合、この延性を「限界延性値」として定義する。その後この値を、引張試験の温度の関数としてプロットする。
結果を以下の表１に示しているが、０の場合は良好、つまり、割れが液体亜鉛によるものではない、すなわち、その破断が延性的であることを意味し、１の場合は不良、つまり、ＬＭＥ割れに相当する割れが液体亜鉛によるものであることを意味する。
本発明による試験体２～試験体４では、無被覆鋼と同レベル、すなわち、試験体５で見られたような、ＬＭＥに対する優れた耐性を示した。
［実施例２］
電気化学的挙動試験
試験体１、試験体３及び試験体４を作成し、電気化学電位試験を行った。
電気化学的挙動試験
試験体１、試験体３及び試験体４を作成し、電気化学電位試験を行った。
被覆された鋼表面板の電気化学電位を測定することからなる試験を実施した。鋼板と被覆とを分離し、ｐＨ７の塩化ナトリウムを５重量％含む溶液に浸漬した。飽和カロメル電極（ＳＣＥ）もこの溶液に浸漬した。当該表面の結合電位を経時的に測定した。結果を以下の表２に示す。
本発明による試験体３及び試験体４は、試験体１と比較してより高い犠牲防食効果を有する。試験体３及び試験体４における結合電位を、必要に応じて－０．７８Ｖ／ＳＣＥ未満、すなわち、腐食に対する犠牲防食効果が得られる最小の電気化学電位としている。
Claims (16)
- アルミニウムからなる少なくとも第１の被覆を備える被覆鋼基材であって、かかる第１の被覆は厚さが１．０～４．５μｍであり、及び亜鉛をベースとする第２の被覆によって直接上面が覆われており、かかる第２の被覆の厚さは１．５～９．０μｍであり、並びに第２の被覆に対する第１の被覆の厚さ比は０．２～１．２であり、
鋼基材と第１の被覆との間に中間層を設けており、かかる中間層が鉄、ニッケル、クロム及び任意にチタンを含む、被覆鋼基材。 - 第２の被覆が、Ｓｉ及びＭｇから選択される少なくとも１つの元素を含む、請求項１に記載の被覆鋼基材。
- 第２の被覆が、０．５重量％未満のマグネシウムを含む、請求項１又は２に記載の被覆鋼基材。
- 第２の被覆が、次のマグネシウム、アルミニウム、銅及びシリコンのうちの少なくとも１つの元素を含まない、請求項１～３のいずれか一項に記載の被覆鋼基材。
- 第２の被覆が亜鉛からなる、請求項１～４のいずれか一項に記載の被覆鋼基材。
- 第１の被覆の厚さが２～４μｍである、請求項１～５のいずれか一項に記載の被覆鋼基材。
- 第２の被覆の厚さが１．５～８．５μｍである、請求項１～６のいずれか一項に記載の被覆鋼基材。
- 第２の被覆に対する第１の被覆の厚さ比が、０．２～０．８である、請求項１～７のいずれか一項に記載の被覆鋼基材。
- 請求項１～８のいずれか一項に記載の被覆鋼基材の製造方法であって、以下の工程、
Ａ．鋼基材を設ける工程、
Ｂ．任意に前記鋼基材の表面処理を行う工程、
Ｃ．アルミニウムからなる第１の被覆を堆積させる工程であって、かかる第１の被覆の厚さが１．０～４．５μｍである、工程並びに
Ｄ．亜鉛をベースとする第２の被覆を堆積させる工程であって、かかる第２の被覆の厚さが１．５～９．０μｍであり、及び前記第２の被覆に対する前記第１の被覆の厚さ比が０．２～１．２である、工程
を含む、方法。 - 工程Ｂ）が実行されるとき、表面処理は、ショットブラスト、酸洗、エッチング、研磨、サンドブラスト、研削、並びに鉄、ニッケル、クロム及び任意にチタンを含む中間層の堆積から選択される、請求項９に記載の方法。
- 工程Ｃ）及び工程Ｄ）において、第１及び第２の被覆を堆積させる工程は、互いに独立して、溶融めっき、電着法又は真空蒸着により実行される、請求項９又は１０に記載の方法。
- 工程Ｃ）及び工程Ｄ）において、真空蒸着が実行されるとき、第１及び第２の被覆は、互いに独立して、マグネトロンカソード粉砕法、ジェット蒸着法、電磁浮上蒸着法又は電子ビーム物理蒸着法により蒸着される、請求項１１に記載の方法。
- 自動車両の部品の製造のための、請求項１～９のいずれか一項に記載の被覆鋼基材の使用。
- 請求項１～８のいずれか一項に記載の被覆鋼基材を得るための、請求項９～１２のいずれか一項に記載の方法を用いる、走行中の鋼基材上に被覆を連続真空蒸着するための設備であって、以下の順序で
Ａ．任意に、マグネトロンカソード粉砕装置を含む中間部分、
Ｂ．電子ビーム蒸着装置を含む第１の部分及び
Ｃ．ジェット蒸着装置を含む第２の部分、
を備え、
中間部分を設けている場合、マグネトロンカソード粉砕装置が、鉄、クロム、ニッケル及び任意にチタンからなる１つのターゲットを含む真空蒸着チャンバ、並びに鉄、ニッケル、クロム及び任意にチタンを含む中間層を鋼基材上に蒸着させるプラズマ源を備える、
設備。 - 第１の部分において、電子ビーム蒸着装置が、アルミニウムからなる金属を含む蒸発るつぼを備える真空蒸着チャンバ、加熱装置及び電子銃を備える、請求項１３又は１４に記載の設備。
- 第２の部分において、ジェット蒸着装置が、少なくとも蒸発るつぼを含む真空蒸着チャンバ、蒸気ジェットコーター及び亜鉛をベースとする蒸気を前記蒸気ジェットコーターに供給するのに適した、少なくとも１つの蒸発るつぼを備える、請求項１３～１５のいずれか一項に記載の設備。
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| PCT/IB2017/001048 WO2019043424A1 (en) | 2017-08-30 | 2017-08-30 | COATED METALLIC SUBSTRATE |
| IBPCT/IB2017/001048 | 2017-08-30 | ||
| PCT/IB2018/055408 WO2019043473A1 (en) | 2017-08-30 | 2018-07-20 | COATED METALLIC SUBSTRATE |
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| RU2020111277A (ru) | 2021-09-20 |
| KR20200024904A (ko) | 2020-03-09 |
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| CN111032901A (zh) | 2020-04-17 |
| PL3676413T3 (pl) | 2022-03-28 |
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| CN111032901B (zh) | 2022-12-09 |
| BR112020001905B1 (pt) | 2022-12-06 |
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| HUE056855T2 (hu) | 2022-03-28 |
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