JP2016040413A - 耐黒変性及び密着力に優れたＺｎ‐Ｍｇ合金コーティング鋼板及びその製造方法 - Google Patents
耐黒変性及び密着力に優れたＺｎ‐Ｍｇ合金コーティング鋼板及びその製造方法 Download PDFInfo
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- JP2016040413A JP2016040413A JP2015214095A JP2015214095A JP2016040413A JP 2016040413 A JP2016040413 A JP 2016040413A JP 2015214095 A JP2015214095 A JP 2015214095A JP 2015214095 A JP2015214095 A JP 2015214095A JP 2016040413 A JP2016040413 A JP 2016040413A
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- alloy
- steel sheet
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- coated steel
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- 229910009369 Zn Mg Inorganic materials 0.000 title claims abstract description 94
- 229910007573 Zn-Mg Inorganic materials 0.000 title claims abstract description 94
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 62
- 239000010959 steel Substances 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000011247 coating layer Substances 0.000 claims abstract description 51
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 32
- 239000000956 alloy Substances 0.000 claims abstract description 32
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 27
- 239000010410 layer Substances 0.000 claims abstract description 22
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 12
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 30
- 238000005229 chemical vapour deposition Methods 0.000 claims description 29
- 238000005240 physical vapour deposition Methods 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 23
- 239000011248 coating agent Substances 0.000 abstract description 22
- 239000010408 film Substances 0.000 description 34
- 239000011701 zinc Substances 0.000 description 22
- 239000000463 material Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000005674 electromagnetic induction Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000005596 ionic collisions Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 201000009240 nasopharyngitis Diseases 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005019 vapor deposition process Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
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
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- 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
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Abstract
【課題】本発明は、黒変現象に対する抵抗性に優れ、コーティング密着力に優れたＺｎ‐Ｍｇ合金コーティング鋼板とこれを製造する方法を提供する。
【解決手段】素地鋼板と、上記素地鋼板上に形成されたＺｎ‐Ｆｅ金属間化合物層と、上記Ｚｎ‐Ｆｅ金属間化合物層上に形成され、Ｚｎの含量が９５重量％以上のＺｎ‐Ｍｇ金属間化合物を含む第１のＺｎ‐Ｍｇコーティング層と、上記第１のＺｎ‐Ｍｇコーティング層上に形成され、Ｚｎの含量が８０〜９５重量％のＺｎ‐Ｍｇ金属間化合物を含む第２のＺｎ‐Ｍｇコーティング層と、上記第２のＺｎ‐Ｍｇコーティング層上に形成され、金属酸化物を含む酸化皮膜とを含む耐黒変性及び密着力に優れたＺｎ‐Ｍｇ合金コーティング鋼板、およびその製造方法を提供する。
【選択図】図１
【解決手段】素地鋼板と、上記素地鋼板上に形成されたＺｎ‐Ｆｅ金属間化合物層と、上記Ｚｎ‐Ｆｅ金属間化合物層上に形成され、Ｚｎの含量が９５重量％以上のＺｎ‐Ｍｇ金属間化合物を含む第１のＺｎ‐Ｍｇコーティング層と、上記第１のＺｎ‐Ｍｇコーティング層上に形成され、Ｚｎの含量が８０〜９５重量％のＺｎ‐Ｍｇ金属間化合物を含む第２のＺｎ‐Ｍｇコーティング層と、上記第２のＺｎ‐Ｍｇコーティング層上に形成され、金属酸化物を含む酸化皮膜とを含む耐黒変性及び密着力に優れたＺｎ‐Ｍｇ合金コーティング鋼板、およびその製造方法を提供する。
【選択図】図１
Description
本発明は、自動車、家電、建材等の産業全般の基礎素材として用いられるＺｎ‐Ｍｇ合金コーティング鋼板に関し、より詳細には、耐黒変性及び密着力に優れたＺｎ‐Ｍｇ合金コーティング鋼板に関する。
一般の鋼板製品の表面には、耐食性及び耐久性の向上のために電気メッキや溶融メッキ等の方式で亜鉛メッキが施される。このような亜鉛メッキ処理製品は、何の処理もされていない鋼板製品に比べ、亜鉛の犠牲方式機能により高い耐食性を示すため、自動車、家電、建材等に広く用いられている。
しかしながら、最近、関連産業分野では、耐久性により優れ、且つ軽く、経済性に優れたメッキ製品への要求が大きくなっている。
一方、地球上の亜鉛埋蔵量の限界のために、亜鉛が枯渇する恐れがあり、埋蔵亜鉛の資源兵器化が加速している。また、既存の電気メッキ及び溶融メッキ工程で消耗される大量のエネルギー及び排出される汚染物質への規制が強化されている。
よって、最近では、真空蒸着方式によるＺｎ‐Ｍｇ合金コーティング鋼板が注目を浴びている。上記真空蒸着方式によるＺｎ‐Ｍｇ合金コーティング鋼板の場合、真空中でコーティング工程が行われるため汚染物質がほぼ排出されず、コーティングのためのコーティング物質を蒸発させる技術の開発によって既存のメッキ工程に比べて高い生産速度の発現が可能である。また、耐食性の高いＺｎ‐Ｍｇコーティング製品であることから、既存の製品より薄い薄膜によって物性の実現が可能であり、経済性にも非常に優れた未来型鋼板製品として脚光を浴びている。
しかしながら、このような製造工程上の長所及び優れた製品特性にもかかわらず、Ｚｎ‐Ｍｇコーティングは、亜鉛コーティングと比べて破損しやすい特性を有するため、密着力の確保が困難である。
また、Ｍｇの活性が非常に高いことから、湿った雰囲気で製品の表面が水分と反応して黒く変わる黒変現象が発生するため、製品の品質を低下させる。
このような黒変現象の問題を解決するための技術として、特許文献１の技術がある。上記特許文献１では、Ｚｎ‐Ｍｇコーティング製品を０．０１〜３０％のリン酸塩溶液で処理し、表面からのＭｇの溶出による表面のＭｇ濃度を１重量％以下にして黒変現象を防止しようとした。しかしながら、上記特許文献１は、実際にはＭｇの溶出が均一に起こらないことからムラが発生したり、コーティング表面にＭｇが含まれたリン酸塩が形成されることからリン酸塩処理後に表面の色相が殆ど黒色に変わったりするという問題がある。
本発明の目的は、黒変現象に対する抵抗性に優れ、コーティング密着力に優れたＺｎ‐Ｍｇ合金コーティング鋼板とこれを製造する方法を提供することである。
本発明は、素地鋼板と、上記素地鋼板上に形成されたＺｎ‐Ｆｅ金属間化合物層と、上記Ｚｎ‐Ｆｅ金属間化合物層上に形成され、Ｚｎの含量が９５重量％以上のＺｎ‐Ｍｇ金属間化合物を含む第１のＺｎ‐Ｍｇコーティング層と、上記第１のＺｎ‐Ｍｇコーティング層上に形成され、Ｚｎの含量が８０〜９５重量％のＺｎ‐Ｍｇ金属間化合物を含む第２のＺｎ‐Ｍｇコーティング層と、上記第２のＺｎ‐Ｍｇコーティング層上に形成され、金属酸化物を含む酸化皮膜とを含む、耐黒変性及び密着力に優れたＺｎ‐Ｍｇ合金コーティング鋼板を提供する。
また、本発明は、素地鋼板上にＺｎ‐Ｍｇコーティング層を形成する段階と、燃焼化学気相蒸着（ＣＣＶＤ）処理を施して酸化皮膜を形成する段階とを含む、耐黒変性及び密着力に優れたＺｎ‐Ｍｇ合金コーティング鋼板の製造方法を提供する。
本発明によれば、ＣＣＶＤ処理により表面に酸化皮膜が形成されたＺｎ‐Ｍｇコーティング鋼板素材は、既存の素材の短所である密着力低下と湿気による黒変を防止することにより自動車、家電、建材等の産業において経済的な価格で用いることができる産業基盤素材であるため、高耐性高級表面処理鋼板素材への商業化が可能であり、それ自体で非常に大きな素材市場を確保することができる。
本発明に用いられる技術である燃焼化学気相蒸着（Ｃｏｍｂｕｓｔｉｏｎ Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ、ＣＣＶＤ）処理法は、真空中で行われる既存の物理的（ＰＶＤ：Ｐｈｙｓｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ）又は化学的（ＣＶＤ：Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ）蒸着工程とは異なり、大気圧下で燃焼反応の原料となる炭化水素（例えば、プロパン）と空気との混合気体に前駆体（例えば、ＨＭＤＳＯ、原料ガス分子）を投入し、上記混合気体の燃焼熱をエネルギー源として、上記前駆体を気化、分解し、化学反応を起こすことにより、基材の表面にコーティング層を形成する技術である。
本発明では、ＣＣＶＤによってコーティング層を形成するにあたり、前駆体として有機シラン（Ｏｒｇａｎｉｃ Ｓｉｌａｎｅ）を用いることにより、大気中の酸素との結合によって架橋された形の金属酸化物、好ましくは、シリコンオキサイド蒸着塗膜を金属表面に形成する。
以下、本発明について詳細に説明する。
本発明者らは、物理的気相蒸着（Ｐｈｙｓｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ、ＰＶＤ）で製造されたＺｎ‐Ｍｇ合金コーティング鋼板は、コーティング層にＺｎ‐Ｍｇ、Ｚｎ、Ｍｇの結晶領域が不均一に分布されており、特に、素地鋼板との界面に微細な自然酸化膜が存在するためコーティング層から分離されやすく、水分との反応により水和物形態が表面に形成されて黒変が発生することを見出した。
よって、本発明者らは、Ｚｎ‐Ｍｇ合金コーティング鋼板の表面に燃焼化学気相蒸着（Ｃｏｍｃｕｓｔｉｏｎ Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ、ＣＣＶＤ）技術を用いることにより、高温のフレーム（ｆｌａｍｅ）がＺｎ‐Ｍｇ合金コーティング鋼板の表面に作用してコーティング層を均質化し、これによるメッキ層の密着性増大及び酸化皮膜による黒変現象防止がなされることを見出し、本発明に至った。
上記燃焼化学気相蒸着（ＣＣＶＤ）法は、大気圧下で炭化水素（プロパン）と原料ガス分子（前駆体）が飽和されている空気との混合気体の燃焼熱をエネルギー源として上記原料ガス分子が気化、分解、酸化されて架橋された形の酸化皮膜を形成する技術である。
まず、本発明のＺｎ‐Ｍｇ合金コーティング鋼板について詳細に説明する。
本発明のＺｎ‐Ｍｇ合金コーティング鋼板は、素地鋼板と、上記素地鋼板上に形成されたＺｎ‐Ｆｅ金属間化合物層と、上記Ｚｎ‐Ｆｅ金属間化合物層上に形成され、Ｚｎの含量が９５重量％以上のＺｎ‐Ｍｇ金属間化合物を含む第１のＺｎ‐Ｍｇコーティング層と、上記第１のＺｎ‐Ｍｇコーティング層上に形成され、Ｚｎの含量が８０〜９５重量％のＺｎ‐Ｍｇ金属間化合物を含む第２のＺｎ‐Ｍｇコーティング層と、上記第２のＺｎ‐Ｍｇコーティング層上に形成され、金属酸化物を含む酸化皮膜とを含む。
上記素地鋼板の種類は特に限定されず、熱延鋼板、冷延鋼板等のすべての種類の鋼板の素材及び金属材質が使用可能である。
上記素地鋼板上にＺｎ‐Ｆｅ金属間化合物層を含む。上記Ｚｎ‐Ｆｅ金属間化合物層は、後述するＣＣＶＤ処理により素地鋼板とＺｎ‐Ｍｇコーティング層との間に存在していた微小酸化皮膜をコーティング層中に分散させて形成されたもので、これにより、素地鋼板とＺｎ‐Ｍｇコーティング層の密着力を向上させる役割をする。
上記Ｚｎ‐Ｆｅ金属間化合物層上に形成され、Ｚｎの含量が９５重量％以上のＺｎ‐Ｍｇ金属間化合物を含む第１のＺｎ‐Ｍｇコーティング層を含む。上記第１のＺｎ‐Ｍｇコーティング層は、Ｚｎが豊富（Ｒｉｃｈ）で柔らかい領域である。したがって、コーティング層の付着力を向上させる役割をする。
上記Ｚｎの含量が９５重量％未満の場合は、Ｚｎ‐Ｍｇ合金の影響でコーティング層が破損しやすい特性が現れるため、密着力増大の効果が弱くなる。上記Ｚｎの含量が多いほど良いが、Ｚｎ‐Ｍｇの金属間化合物を形成するためには上記Ｚｎの含量が１００重量％未満であることが好ましい。
上記第１のＺｎ‐Ｍｇコーティング層上に形成され、Ｚｎの含量が８０〜９５重量％のＺｎ‐Ｍｇ金属間化合物を含む第２のＺｎ‐Ｍｇコーティング層を含む。上記第２のＺｎ‐Ｍｇコーティング層は、Ｚｎ‐Ｍｇ合金特性により、一般の亜鉛コーティングよりも優れた耐食性を発現する。
上記Ｚｎ‐Ｍｇの金属間化合物は、Ｚｎの含量が８０〜９５重量％であることが好ましい。上記含量が８０重量％未満の場合は、異なる結晶状のＺｎ‐Ｍｇ合金コーティング層の影響で耐食性が再度低下する現象が現れる。
上記第２のＺｎ‐Ｍｇコーティング層上に形成された酸化皮膜を含む。上記酸化皮膜は、金属酸化物を含む。上記酸化皮膜は、水分がコーティング塗膜の内部に浸透することを妨害することにより黒変性を改善する役割をする。
上記酸化皮膜は金属酸化物を含み、上記金属酸化物はＣＣＶＤ処理による金属酸化物（例えば、シリコン酸化物（ＳｉＯ２））であり、ＣＣＶＤ処理中に高温の雰囲気下で大気中の酸素と結合して自然酸化皮膜を形成するＭｇＯが上記酸化皮膜層に一部形成されて混在している。
一方、上記酸化皮膜の厚さは１０〜４０ｎｍであることが好ましい。上記酸化皮膜の厚さが１０ｎｍ未満の場合は、湿気が塗膜の内部に浸入することを十分に遮断することができないため、十分な耐黒変性を期待するのが困難であり、４０ｎｍを超える場合は、上記酸化皮膜の酸化物粒子、即ち、ＳｉＯ２粒子が巨大になるため、この巨大粒子の形成によって、却って、バリア（Ｂａｒｒｉｅｒ）塗膜としての役割を阻害させる。
以下、本発明の製造方法について詳細に説明する。
まず、素地鋼板にＺｎ‐Ｍｇコーティング層を形成する。この際、Ｚｎ‐Ｍｇコーティング層は、前述した第１及び第２のＺｎ‐Ｍｇコーティング層とは区別されるもので、最終Ｚｎ‐Ｍｇコーティング層ではなく、後続するＣＣＶＤ処理前に形成されたものである。
上記Ｚｎ‐Ｍｇコーティング層を物理的気相蒸着（ＰＶＤ）方法により形成することが好ましい。上記ＰＶＤ工程を用いたＺｎ‐Ｍｇコーティング層の形成は、本発明の属する技術分野で行われる通常の方法による。
好ましい一例としては、熱ＰＶＤ法又はスパッタリング法でコーティングされる物質であるＺｎ‐Ｍｇ又はＺｎ、Ｍｇのコーティング原料を真空中で熱エネルギー又はイオンの衝突エネルギーにより高速で大量蒸気化させ、これをロールツーロール（Ｒｏｌｌ‐ｔｏ‐Ｒｏｌｌ）の方式で連続して真空中に投入される鋼板又は金属板の表面に誘導して、表面にＺｎ‐Ｍｇ合金コーティングを形成する工程技術を用いる。特に、熱ＰＶＤ法のうち電磁誘導現象を用いたＥＭＬ‐ＰＶＤ（Ｅｌｅｃｔｒｏ Ｍａｇｎｅｔｉｃ ＰＶＤ）は、電磁誘導現象によってＺｎ‐Ｍｇ合金コーティング物質を真空中で浮揚加熱して高速で大量の蒸気を発生させてコーティングする技術であり、高い生産性による経済性の確保が可能であるため、Ｚｎ‐Ｍｇコーティング製品に多く用いられる。
上記Ｚｎ‐Ｍｇコーティング層が形成された素地鋼板に燃焼化学気相蒸着法（ＣＣＶＤ）を用いて酸化皮膜を形成する。上記ＣＣＶＤ処理により、前述した素地鋼板上に形成されたＺｎ‐Ｆｅ金属間化合物層と、上記Ｚｎ‐Ｆｅ金属間化合物層上に形成され、Ｚｎの含量が９５重量％以上のＺｎ‐Ｍｇ金属間化合物を含む第１のＺｎ‐Ｍｇコーティング層と、上記第１のＺｎ‐Ｍｇコーティング層上に形成され、Ｚｎの含量が８０〜９５重量％のＺｎ‐Ｍｇ金属間化合物を含む第２のＺｎ‐Ｍｇコーティング層と、上記第２のＺｎ‐Ｍｇコーティング層上に形成され、金属酸化物を含む酸化皮膜とを含む、本発明のＺｎ‐Ｍｇ合金コーティング鋼板が製造される。
上記ＣＣＶＤ処理は、素地鋼板とＣＣＶＤ装備のバーナー（ｂｕｒｎｅｒ）との距離が１０ｍｍ以下であることが好ましい。また、ＣＣＶＤ処理時、空気供給量に対する前駆体蒸気の投入比が前駆体流量：空気供給量＝０．８：２１０〜２．１：２１０Ｌ／分のとき、最も優れた特性の金属酸化物の蒸着塗膜が得られる。
上記投入比が０．８：２１０Ｌ／分未満の場合は、空気に対して塗膜を形成する粒子が少なくなり、塗膜が薄膜又は微細化されるため、十分なバリア役割を行うことができず、２．１：２１０Ｌ／分を超える場合は、上記前駆体の凝集（粒子巨大化）現象によって緻密でないコーティングが形成されるため、バリア役割を行うことができないという問題がある。
上記ＣＣＶＤ処理時の鋼板温度は３３０〜４５０℃であることが好ましい。上記温度が３３０℃未満の場合は、コーティング層内に原子の拡散に必要なエネルギーが十分にないため、ＣＣＶＤ工程中にコーティング層が均質化するのが困難であり、４５０℃を超える場合は、素地鋼板と第１のＺｎ‐Ｍｇコーティング層の間でＺｎ‐Ｆｅ合金化反応が非常に活発に起こり、過度なＺｎ‐Ｆｅ合金層が形成されるため、却って、密着力に悪影響を及ぼす可能性がある。
以下、本発明の実施例について詳細に説明する。但し、下記実施例は、本発明の理解のためのものであって、本発明を限定するものではない。
酸化皮膜の厚さと鋼板の加熱温度による耐黒変性と密着力を調べるために、下記のような実験を行った。
一般の冷延鋼板を連続的なストリップコイル（Ｓｔｒｉｐ Ｃｏｉｌ）状にして用意し、熱ＰＶＤの一種である電磁誘導現象を用いたＥＭＬ‐ＰＶＤ（Ｅｌｅｃｔｒｏ Ｍａｇｎｅｔｉｃ ＰＶＤ）、即ち、電磁誘導現象によってＺｎ‐Ｍｇ合金コーティング物質を真空中で浮揚加熱して高速で大量の蒸気を発生させ、これをロールツーロール（Ｒｏｌｌ‐ｔｏ‐Ｒｏｌｌ）の方式で連続して真空中に投入される鋼板素材の表面に誘導して、表面にＺｎ‐Ｍｇコーティング層を形成した。
上記Ｚｎ‐Ｍｇコーティング鋼板に有機シランを用いてシリコン酸化皮膜を形成するためにＣＣＶＤ処理を施して、表面に酸化皮膜が形成されたＺｎ‐Ｍｇ合金コーティング鋼板を製造した。上記ＣＣＶＤ処理時には、下記表１に記載されているように酸化皮膜の厚さ（処理サイクル数）と試験片の温度を変化させて行った。
なお、下記表１のうち比較例７〜１０は、ＣＣＶＤ処理時の鋼板の温度による密着力をテストするためのものであって、酸化皮膜を形成せずに鋼板（試験片）の温度のみを変化させてテストしたものである。
上記のように製造されたＺｎ‐Ｍｇ合金コーティング鋼板の耐黒変性と密着力を測定し、その結果を表１に示した。上記密着力については、試験片にテープ（ｔａｐｅ）を張って屈曲させた後に剥離してコーティング塗膜の脱落の有無を観察して良と不良とを判断し、耐黒変性については、試験片を熱湯に５分間浸漬した後に色相変化の有無を観察して良と不良とを判断した。
本発明の条件を満たす発明例は、優れた耐黒変性と密着力を確保している。これは、図１（ａ）の従来例と図１（ｂ）の発明例の構造から分かる。即ち、図１（ａ）の従来例は、素地上にＺｎ‐Ｍｇ合金メッキ層が混合層として形成されているのに対し、図１（ｂ）の発明例は、素地上に金属間化合物層、Ｚｎ豊富層、Ｚｎ‐Ｍｇ合金層が形成され、最表面に酸化皮膜が形成されている。したがって、本発明による発明例は、優れた耐黒変性のみならず、優れた密着力も確保している。
比較例１及び６は、本発明の酸化皮膜の厚さの範囲から外れたもので、優れた耐黒変性を期待するのが困難であり、比較例２〜５は、酸化皮膜の厚さが本発明の範囲を満たしているが試験片の温度が本発明の範囲を満たしておらず、耐黒変性には優れるが密着力が低い。
比較例８及び９は、試験片の温度が本発明の範囲を満たしており、優れた密着力を確保しているが、酸化皮膜が形成されていないため、耐黒変性が劣る。また、比較例７及び１０は、本発明の試験片の温度を外れており、優れた密着力を確保するのが困難である。
図２の（ａ）及び（ｂ）はそれぞれ発明例と従来例の沸騰水処理前後を観察した写真である。図２の（ａ）及び（ｂ）から分かるように、発明例は、色相変化がないため、優れた耐黒変性を有するのに対し、従来例は、全面黒変が発生した。
図３の（ａ）及び（ｂ）はそれぞれ発明例と従来例のテープテスト結果を示すものである。図３の（ａ）及び（ｂ）から分かるように、発明例は、従来例に比べて優れた密着力を有する。
Claims (7)
- 素地鋼板上にＺｎ‐Ｍｇコーティング層を形成する段階と、
燃焼化学気相蒸着（ＣＣＶＤ）処理を施して酸化皮膜を形成する段階
とを含む、耐黒変性及び密着力に優れたＺｎ‐Ｍｇ合金コーティング鋼板の製造方法。 - 前記Ｚｎ‐Ｍｇコーティング層を形成する段階は、ＰＶＤ法で行われる、請求項１に記載の耐黒変性及び密着力に優れたＺｎ‐Ｍｇ合金コーティング鋼板の製造方法。
- 前記ＣＣＶＤ処理時、空気供給量に対する前駆体蒸気の投入比は前駆体流量：空気供給量＝０．８：２１０〜２．１：２１０Ｌ／分である、請求項１に記載の耐黒変性及び密着力に優れたＺｎ‐Ｍｇ合金コーティング鋼板の製造方法。
- 前記ＣＣＶＤ処理時、素地鋼板の温度は３３０〜４５０℃である、請求項１に記載の耐黒変性及び密着力に優れたＺｎ‐Ｍｇ合金コーティング鋼板の製造方法。
- 前記Ｚｎ‐Ｍｇ合金コーティング鋼板は、
素地鋼板と、
前記素地鋼板上に形成されたＺｎ‐Ｆｅ金属間化合物層と、
前記Ｚｎ‐Ｆｅ金属間化合物層上に形成され、Ｚｎの含量が９５重量％以上のＺｎ‐Ｍｇ金属間化合物を含む第１のＺｎ‐Ｍｇコーティング層と、
前記第１のＺｎ‐Ｍｇコーティング層上に形成され、Ｚｎの含量が８０〜９５重量％のＺｎ‐Ｍｇ金属間化合物を含む第２のＺｎ‐Ｍｇコーティング層と、
前記第２のＺｎ‐Ｍｇコーティング層上に形成され、金属酸化物を含む酸化皮膜
とを含む、請求項１に記載の耐黒変性及び密着力に優れたＺｎ‐Ｍｇ合金コーティング鋼板の製造方法。 - 前記酸化皮膜は、金属酸化物を含み、前記金属酸化物は、シリコン酸化物（ＳｉＯ２）を含み、ＭｇＯを一部含む、請求項１に記載の耐黒変性及び密着力に優れたＺｎ‐Ｍｇ合金コーティング鋼板の製造方法。
- 前記酸化皮膜の厚さは１１〜４０ｎｍである、請求項１に記載の耐黒変性及び密着力に優れたＺｎ‐Ｍｇ合金コーティング鋼板の製造方法。
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| WO2018124630A1 (ko) * | 2016-12-26 | 2018-07-05 | 주식회사 포스코 | 점용접성 및 내식성이 우수한 단층 아연합금도금강재 및 그 제조방법 |
| US11203802B2 (en) | 2016-12-26 | 2021-12-21 | Posco | Single layer zinc alloy plated steel material exhibiting excellent spot weldability and corrosion resistance, and fabrication method therefor |
| KR20220076773A (ko) * | 2020-12-01 | 2022-06-08 | 주식회사 포스코 | 다층구조 도금강판 및 그 제조방법, 이를 이용한 용접 구조체 |
| KR102443926B1 (ko) | 2020-12-01 | 2022-09-19 | 주식회사 포스코 | 다층구조 도금강판 및 그 제조방법, 이를 이용한 용접 구조체 |
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| Publication number | Publication date |
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| US20160355926A1 (en) | 2016-12-08 |
| CN104024468B (zh) | 2017-04-12 |
| JP2015510033A (ja) | 2015-04-02 |
| EP2799591B1 (en) | 2017-08-30 |
| US20150030875A1 (en) | 2015-01-29 |
| WO2013100616A1 (ko) | 2013-07-04 |
| KR101359259B1 (ko) | 2014-02-06 |
| US9441302B2 (en) | 2016-09-13 |
| CN104024468A (zh) | 2014-09-03 |
| KR20130075501A (ko) | 2013-07-05 |
| EP2799591A1 (en) | 2014-11-05 |
| US9982342B2 (en) | 2018-05-29 |
| EP2799591A4 (en) | 2015-10-07 |
| JP6099722B2 (ja) | 2017-03-22 |
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