JP7464717B2 - 耐食性とスポット溶接性に優れた亜鉛系めっき鋼材 - Google Patents
耐食性とスポット溶接性に優れた亜鉛系めっき鋼材 Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims description 123
- 239000010959 steel Substances 0.000 title claims description 123
- 230000007797 corrosion Effects 0.000 title description 36
- 238000005260 corrosion Methods 0.000 title description 36
- 239000010410 layer Substances 0.000 claims description 217
- 238000007747 plating Methods 0.000 claims description 140
- 239000011701 zinc Substances 0.000 claims description 89
- 229910052725 zinc Inorganic materials 0.000 claims description 82
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 81
- 239000000463 material Substances 0.000 claims description 62
- 239000011248 coating agent Substances 0.000 claims description 45
- 238000000576 coating method Methods 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 31
- 238000005240 physical vapour deposition Methods 0.000 claims description 26
- 239000011247 coating layer Substances 0.000 claims description 20
- 229910045601 alloy Inorganic materials 0.000 claims description 13
- 239000000956 alloy Substances 0.000 claims description 13
- 229910052749 magnesium Inorganic materials 0.000 claims description 13
- 229910001566 austenite Inorganic materials 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910009369 Zn Mg Inorganic materials 0.000 claims description 6
- 229910007573 Zn-Mg Inorganic materials 0.000 claims description 6
- 230000000717 retained effect Effects 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 229910000734 martensite Inorganic materials 0.000 claims description 2
- 239000010953 base metal Substances 0.000 claims 1
- 239000011777 magnesium Substances 0.000 description 55
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- 238000003466 welding Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 18
- 229910052742 iron Inorganic materials 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 238000002844 melting Methods 0.000 description 11
- 238000001771 vacuum deposition Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 238000000151 deposition Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000008021 deposition Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000005764 inhibitory process Effects 0.000 description 6
- 229910001335 Galvanized steel Inorganic materials 0.000 description 5
- 239000008397 galvanized steel Substances 0.000 description 5
- 229910001338 liquidmetal Inorganic materials 0.000 description 5
- 229910001297 Zn alloy Inorganic materials 0.000 description 4
- 238000005275 alloying Methods 0.000 description 4
- 239000010960 cold rolled steel Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005137 deposition process Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 230000005672 electromagnetic field Effects 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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
- C23C28/023—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 only coatings of metal elements only
- C23C28/025—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 only coatings of metal elements only with at least one zinc-based layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
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- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
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Description
[関係式1][C]+[Mn]/20+[Si]/30+2[P]+4[S]≧0.3
(ここで、[C]、[Mn]、[Si]、[P]及び[S]のそれぞれは、当該元素の含量(重量%)を意味する)
重量%で、C:0.18%、Si:1.5%、Mn:3.5%、Al:0.01%、P:0.006%、S:0.003%、残部Fe及び不可避不純物を含む厚さ1.4mmの自動車用の高強度冷延鋼鈑を用意し、図4の装置(真空度3.2×10-3mbar)を用いて、下記表1のような条件の多層めっき層を有する多層亜鉛系めっき鋼材を製造した。すべての例において、各層のめっき層は、別途の真空チャンバーで別途の工程を経て得られており、各層のめっき層の形成の際、一対の電磁気コイルに印加される電流は1.2kA、一対の電磁気コイルに印加される周波数は、蒸着物質2kgを基準として60kHz、加熱したコーティング物質の温度は1000℃、蒸気分配ボックスの温度は900℃と、一定にした。また、各層のめっき層の蒸着前後の素地鉄の温度は60℃と一定にした。
1.優秀:片面付着量60g/m2の亜鉛めっき鋼板(GI鋼板)に対して赤錆発生時間が2倍以上長い場合
2.普通:片面付着量60g/m2の亜鉛めっき鋼板(GI鋼板)に対して赤錆発生時間が同等レベル又は2倍未満長い場合
3.不良:片面付着量60g/m2の亜鉛めっき鋼板(GI鋼板)に対して赤錆発生時間が短い場合
1.極めて優秀:すべての試験片でType Bクラックが発生しなかった場合
2.優秀:一部或いはすべての試験片でType Bクラックが発生し、Type Bクラックの平均長さが素地鉄(冷延鋼鈑)の厚さの0.1倍以下である場合
3.普通:一部或いはすべての試験片でType Bクラックが発生し、Type Bクラックの平均長さが素地鉄(冷延鋼鈑)の厚さの0.1倍超え0.2倍以下である場合
4.不良:一部或いはすべての試験片でType Bクラックが発生し、Type Bクラックの平均長さが素地鉄(冷延鋼鈑)の厚さの0.2倍を超える場合
1.優秀:摩擦係数が0.3を超えるまでの摩擦回転数が80回以上
2.普通:摩擦係数が0.3を超えるまでの摩擦回転数が60回以上、80回未満
3.不良:摩擦係数が0.3を超えるまでの摩擦回転数が60回未満
1.優秀:剥離幅が6.0mm以下である場合
2.普通:剥離幅が6.0mm超え8.0mm以下である場合
3.不良:剥離幅が8.0mmを超える場合
1.良好:リン酸塩被膜が均一に形成
2.不良:リン酸塩被膜が不均一に形成
1.良好:△E≦3
2.普通:3<△E≦5
3.不良:△E>5
Claims (13)
- 素地鉄;及び
2以上の区別されるめっき層からなる多層の亜鉛系めっき層を含み、
前記多層の亜鉛系めっき層は、
0.12~0.64重量%のMgを含み、
全体付着量が15~35g/m2であり、
素地鉄との界面から順次第1めっき層、第2めっき層及び第3めっき層を含み、
前記第2めっき層が、Mgを0.4~0.9重量%を含み、前記第2めっき層の付着量は、9~15g/m 2 である、
亜鉛系めっき鋼材。 - 前記第1めっき層及び第3めっき層は、それぞれ0.1重量%以下(0重量%を含む)のMgを含むZn層である、請求項1に記載の亜鉛系めっき鋼材。
- 前記第1めっき層及び第3めっき層の付着量は、それぞれ3~10g/m2である、請求項2に記載の亜鉛系めっき鋼材。
- 前記素地鉄は、C:0.10~1.0%、Si:0.5~3%、Mn:1.0~25%、Al:0.01~10%、P:0.1%以下(0%を除く)、S:0.01%以下(0%を除く)、残部Fe及び不可避不純物を含む、請求項1に記載の亜鉛系めっき鋼材。
- 前記素地鉄に含まれるC、Si、Mn、P及びSの含量は、下記関係式1を満たす、請求項4に記載の亜鉛系めっき鋼材。
[関係式1][C]+[Mn]/20+[Si]/30+2[P]+4[S]≧0.3
(ここで、[C]、[Mn]、[Si]、[P]及び[S]のそれぞれは、当該元素の含量(重量%)を意味する) - 前記素地鉄は、微細組織として、オーステナイト、残留オーステナイト及びマルテンサイトの中から選択される1種又は2種以上を含む、請求項1に記載の亜鉛系めっき鋼材。
- SEP 1220-2規格に沿ってスポット溶接を施したとき、Type-Bクラックの平均長さが素地鉄厚さの0.1倍以下である、請求項1~請求項6のいずれか一項に記載の亜鉛系めっき鋼材。
- 前記多層の亜鉛系めっき層をなす2以上の区別されるめっき層のうち少なくとも一つのめっき層は、物理的気相蒸着(PVD)法によって形成される、請求項1~請求項6のいずれか一項に記載の亜鉛系めっき鋼材。
- 前記物理的気相蒸着(PVD)法によって形成されるめっき層は、Mgを0.4~0.9重量%含むZn-Mg合金層である、請求項8に記載の亜鉛系めっき鋼材。
- 素地鉄を用意する段階;
前記素地鉄上に2以上の区別されるめっき層からなる多層の亜鉛系めっき層を順次形成する段階を含み、
前記多層の亜鉛系めっき層は、
0.12~0.64重量%のMgを含み、
全体付着量が15~35g/m2であり、
素地鉄との界面から順次第1めっき層、第2めっき層及び第3めっき層を含み、
前記第2めっき層が、Mgを0.4~0.9重量%を含み、前記第2めっき層の付着量は、9~15g/m 2 である、
亜鉛系めっき鋼材の製造方法。 - 前記多層の亜鉛系めっき層を順次形成する段階は、
第1めっき層を形成する段階;
Mgを0.4~0.9重量%を含むZn-Mg合金層からなる第2めっき層を形成する段階;及び
第3めっき層を形成する段階を順次含む、
請求項10に記載の亜鉛系めっき鋼材の製造方法。 - 前記第1めっき層及び第3めっき層は、それぞれ0.1重量%以下(0重量%を含む)のMgを含むZn層である、請求項11に記載の亜鉛系めっき鋼材の製造方法。
- 前記多層の亜鉛系めっき層のうち一つ以上又はそれ以上のめっき層は、物理的気相蒸着(PVD)法によって形成される、請求項10~請求項12のいずれか一項に記載の亜鉛系めっき鋼材の製造方法。
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