JP4655788B2 - 合金化溶融亜鉛めっき鋼板の製造方法および合金化溶融亜鉛めっき鋼板 - Google Patents
合金化溶融亜鉛めっき鋼板の製造方法および合金化溶融亜鉛めっき鋼板 Download PDFInfo
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- JP4655788B2 JP4655788B2 JP2005197492A JP2005197492A JP4655788B2 JP 4655788 B2 JP4655788 B2 JP 4655788B2 JP 2005197492 A JP2005197492 A JP 2005197492A JP 2005197492 A JP2005197492 A JP 2005197492A JP 4655788 B2 JP4655788 B2 JP 4655788B2
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- 229910001335 Galvanized steel Inorganic materials 0.000 title claims description 26
- 239000008397 galvanized steel Substances 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 229910000831 Steel Inorganic materials 0.000 claims description 47
- 239000010959 steel Substances 0.000 claims description 47
- 238000005406 washing Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000010410 layer Substances 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 27
- 239000003929 acidic solution Substances 0.000 claims description 23
- 238000005096 rolling process Methods 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 7
- 159000000000 sodium salts Chemical class 0.000 claims description 7
- 239000002344 surface layer Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005246 galvanizing Methods 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 238000005238 degreasing Methods 0.000 description 33
- 239000007788 liquid Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 19
- 238000007747 plating Methods 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 239000011324 bead Substances 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000011701 zinc Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 239000003921 oil Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 238000005275 alloying Methods 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000003449 preventive effect Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
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- 239000001632 sodium acetate Substances 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- 229910001297 Zn alloy Inorganic materials 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
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- 238000007865 diluting Methods 0.000 description 3
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- 101000993059 Homo sapiens Hereditary hemochromatosis protein Proteins 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
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- 239000000460 chlorine Substances 0.000 description 2
- -1 chlorine ions Chemical class 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
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- 238000000227 grinding Methods 0.000 description 2
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- 229910002651 NO3 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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- 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
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- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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- C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
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- 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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
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- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
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- 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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
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- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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Description
[1]鋼板に溶融亜鉛めっきを施し、さらに加熱処理により合金化し、調質圧延を施した後、酸性溶液に接触させ、接触終了後1〜30秒放置した後、水洗を行うことにより、亜鉛めっき鋼板表面に10nm以上のZn系酸化物層を形成する合金化溶融亜鉛めっき鋼板の製造方法において、前記水洗を、酢酸、クエン酸、ホウ酸、炭酸、フタル酸、酒石酸、乳酸から選ばれる1種以上のナトリウム塩またはカリウム塩を含有する水溶液により行うことを特徴とする合金化溶融亜鉛めっき鋼板の製造方法。
[2]前記[1]において、前記ナトリウム塩または前記カリウム塩の濃度が0.001〜1.0mol/lであることを特徴とする合金化溶融亜鉛めっき鋼板の製造方法。
[3]前記[1]または[2]において、前記水洗時の水溶液のpHが7.0〜12.0の範囲であることを特徴とする合金化溶融亜鉛めっき鋼板の製造方法。
[4]前記[1]〜[3]のいずれかに記載の合金化溶融亜鉛めっき鋼板の製造方法により生産されるめっき鋼板であり、該めっき鋼板の平坦部表層におけるZnおよびAlを必須成分として含む酸化物層が10nm以上であることを特徴とする合金化溶融亜鉛めっき鋼板。
板厚0.8mmの冷延鋼板上に、常法の合金化溶融亜鉛めっき皮膜を形成し、更に調質圧延を行った。引き続き、図1に示す構成の処理設備を用いて酸化物層を形成した。
(1)プレス成形性評価試験(摩擦係数測定試験)
プレス成形性を評価するために、各供試材の摩擦係数を以下のようにして測定した。
[条件1]
図3に示すビードを用い、押し付け荷重N:400kgf、試料の引き抜き速度(スライドテーブル13の水平移動速度):100cm/minとした。
[条件2]
図4に示すビードを用い、押し付け荷重N:400kgf、試料の引き抜き速度(スライドテーブル13の水平移動速度):20cm/minとした。
供試材とビードとの間の摩擦係数μは、式:μ=F/Nで算出した。
(2)化成処理前アルカリ脱脂性評価
各供試体に、防錆油を塗油し、垂直に24時間保持することで塗油量を約2g/m2と一定にした後、化成処理前のアルカリ脱脂液(日本パーカライジング製FC-L4460)に45℃で2分間浸漬した後、スプレー圧:1kg/cm2で30秒間水洗を実施した。その後、供試体を垂直に30秒間保持し、その際の水濡れ率(供試体全面積に対する水ハジキが発生していない面積の割合)を目視で判定した。ここで、完全に脱脂が完了した場合の水濡れ率は100%であり、脱脂不良が生じるに伴い水濡れ率は低下する。
(1)No.1は酸性溶液による処理を行っていないため、平坦部に摺動性を向上させるのに十分な酸化膜が形成されず、摩擦係数が高い。
(2)No.2は、酸化物形成処理を行ったが水洗槽5での洗浄は水洗のみを行った比較例であり、No1と比較すると摩擦係数が低くなっており摺動性は向上しているが、アルカリ脱脂後の水濡れ率が非常に低く、アルカリ脱脂性は劣る。
(3) No.3〜5は強アルカリ性の水酸化ナトリウムの希釈液であるが、希釈によりpHは弱アルカリ領域にあるにもかかわらず水濡れ性はよくない。これは,水酸化ナトリウムのような強アルカリを希釈した液の場合、わずかな酸との反応によりpHが急激に低下するためであり,鋼板表面を弱アルカリ状態に保ちにくいためであると考えられる。
(4)No.6〜14は、弱アルカリ水溶液である酢酸ナトリウム水溶液での洗浄を行った例であり、溶液の濃度、pHが本発明で規定した範囲内にある場合(No7〜11、14)は摺動性の向上が見られるとともに、アルカリ脱脂後の水濡れ率が全て100%であり、特に良好なアルカリ脱脂性を示している。一方、溶液の濃度が低濃度側にはずれる場合(No.6)、および溶液のpHが低pH側にはずれる場合(No.13)は、水濡れ率は100%までは改善されていないものの比較材よりも良好であり、アルカリ脱脂液が劣化していない状態では、実用的には充分な水濡れ性を示すと考えられる。また、溶液のpHが高pH側にはずれる場合(No.12)は、水濡れ率は100%であるものの、酸化膜厚が減少しており、摺動性の向上が不十分である。
2 酸性溶液槽
3 絞りロール
4 シャワー水洗装置
5 水洗槽
6 洗浄槽
7 湯洗槽
8 ドライヤ
S 鋼板
11 摩擦係数測定用試料
12 試料台
13 スライドテーブル
14 ローラ
15 スライドテーブル支持台
16 ビード
17 第1ロードセル
18 第2ロードセル
19 レール
N 押付荷重
F 摺動抵抗力
Claims (4)
- 鋼板に溶融亜鉛めっきを施し、さらに加熱処理により合金化し、調質圧延を施した後、酸性溶液に接触させ、接触終了後1〜30秒放置した後、水洗を行うことにより、亜鉛めっき鋼板表面に10nm以上のZn系酸化物層を形成する合金化溶融亜鉛めっき鋼板の製造方法において、前記水洗を、酢酸、クエン酸、ホウ酸、炭酸、フタル酸、酒石酸、乳酸から選ばれる1種以上のナトリウム塩またはカリウム塩を含有する水溶液により行うことを特徴とする合金化溶融亜鉛めっき鋼板の製造方法。
- 前記ナトリウム塩または前記カリウム塩の濃度が0.001〜1.0mol/lであることを特徴とする請求項1に記載の合金化溶融亜鉛めっき鋼板の製造方法。
- 前記水洗時の水溶液のpHが7.0〜12.0の範囲であることを特徴とする請求項1または2に記載の合金化溶融亜鉛めっき鋼板の製造方法。
- 請求項1〜3のいずれかに記載の合金化溶融亜鉛めっき鋼板の製造方法により生産されるめっき鋼板であり、該めっき鋼板の平坦部表層におけるZnおよびAlを必須成分として含む酸化物層が10nm以上であることを特徴とする合金化溶融亜鉛めっき鋼板。
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