JP7400766B2 - Zinc-based electroplated steel sheet and its manufacturing method - Google Patents
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- 239000011701 zinc Substances 0.000 title claims description 75
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 66
- 229910052725 zinc Inorganic materials 0.000 title claims description 66
- 229910000831 Steel Inorganic materials 0.000 title claims description 55
- 239000010959 steel Substances 0.000 title claims description 55
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 238000007747 plating Methods 0.000 claims description 93
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 13
- 238000011282 treatment Methods 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 9
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 description 41
- 230000007797 corrosion Effects 0.000 description 41
- 229910002651 NO3 Inorganic materials 0.000 description 10
- -1 nitrate ions Chemical class 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- 229940007718 zinc hydroxide Drugs 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910006367 Si—P Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910021549 Vanadium(II) chloride Inorganic materials 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- RBFRVUKIVGOWND-UHFFFAOYSA-L oxygen(2-);vanadium(4+);sulfate Chemical compound [O-2].[V+4].[O-]S([O-])(=O)=O RBFRVUKIVGOWND-UHFFFAOYSA-L 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 description 1
- ITAKKORXEUJTBC-UHFFFAOYSA-L vanadium(ii) chloride Chemical compound Cl[V]Cl ITAKKORXEUJTBC-UHFFFAOYSA-L 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Description
本発明は、高い耐食性を有する亜鉛系電気めっき鋼板およびその製造方法に関するものである。 The present invention relates to a zinc-based electroplated steel sheet having high corrosion resistance and a method for manufacturing the same.
亜鉛系電気めっき鋼板は、高い耐食性、皮膜の均一性および外観に優れていることから、家電製品、自動車、建材などの広範な用途で使用されている。しかし、亜鉛は枯渇性資源の一つであり、今後の価格高騰も予想されることから、亜鉛めっき付着量の低減や亜鉛めっきに替わる表面処理皮膜の開発が要求されている。 Zinc-based electroplated steel sheets have high corrosion resistance, uniform coating, and excellent appearance, so they are used in a wide range of applications such as home appliances, automobiles, and building materials. However, since zinc is one of the exhaustible resources and the price is expected to rise in the future, there is a need to reduce the amount of zinc plating deposited and to develop a surface treatment film to replace zinc plating.
ここで、亜鉛系めっき鋼板とは、亜鉛を主体として、亜鉛以外の金属成分や酸化物等の非金属成分を含有するめっき鋼板の総称である。 Here, the zinc-based plated steel sheet is a general term for plated steel sheets containing zinc as a main ingredient and metal components other than zinc and non-metallic components such as oxides.
亜鉛めっき付着量低減の手法の一つとして、めっき層の耐食性を向上させる技術が挙げられる。めっき層の耐食性が向上すれば、めっき層を薄くすることができ、亜鉛付着量の低減につながる。 One method for reducing the amount of zinc plating deposited is a technique that improves the corrosion resistance of the plating layer. If the corrosion resistance of the plating layer is improved, the plating layer can be made thinner, leading to a reduction in the amount of zinc deposited.
亜鉛めっきの耐食性を向上させる試みは古くからなされており、Ｎｉ、 Ｃｏ， Ｆｅ等亜鉛よりも電気化学的に貴な金属との合金化が検討されてきた。しかしそれらの合金めっきは初期段階では高い耐食性を示すものが多いが、一旦腐食が始まると、亜鉛及び素材鋼板の腐食が促進され、早期に穴あき腐食が発生するという問題があった。それらの問題を解決するため、ＳｉＯ２、 ＴｉＯ２、 Ａｌ２Ｏ３等の酸化物や、ＡｌやＶなど卑な活性金属を含む電気めっきの検討がなされてきた。 Attempts to improve the corrosion resistance of zinc plating have been made for a long time, and alloying with metals electrochemically more noble than zinc, such as Ni, Co, and Fe, has been considered. However, although many of these alloy platings exhibit high corrosion resistance in the initial stage, once corrosion begins, corrosion of the zinc and raw steel sheets is accelerated, leading to early pitting corrosion. In order to solve these problems, studies have been made on electroplating containing oxides such as SiO 2 , TiO 2 , Al 2 O 3 and base active metals such as Al and V.
特許文献１には、亜鉛めっき層中に２～１５質量％のＳｉＯ２を含む分散めっきで、耐食性が向上することが記載されている。 Patent Document 1 describes that corrosion resistance is improved by dispersion plating containing 2 to 15% by mass of SiO 2 in the galvanized layer.
特許文献２には、Ｚｎ－Ｓｉ－Ｐ複合めっき鋼板が亜鉛めっき鋼板に比べて耐摩損性、耐応力腐食割れ性およびクロメート処理後の耐食性が向上することが記載されている。 Patent Document 2 describes that a Zn-Si-P composite plated steel sheet has improved abrasion resistance, stress corrosion cracking resistance, and corrosion resistance after chromate treatment compared to a galvanized steel sheet.
特許文献３には、Ｚｎイオンと、Ａｌ、 Ｓｃ、 Ｙ、 Ｌａ、 Ｃｅ、 Ｎｄ、 Ｚｒ及びＶの１種以上の金属イオンと硝酸イオンを含有し、鋼板との相対流速０．６ｍ／ｓ以上で電解を行うことにより、優れた耐食性、外観均一性をもつ亜鉛系複合電気亜鉛めっき鋼板を製造できることが記載されている。 Patent Document 3 discloses that the material contains Zn ions, one or more metal ions of Al, Sc, Y, La, Ce, Nd, Zr, and V, and nitrate ions, and has a relative flow velocity of 0.6 m/s or more with respect to the steel plate. It is stated that a zinc-based composite electrogalvanized steel sheet with excellent corrosion resistance and uniform appearance can be produced by electrolyzing with.
特許文献４には、亜鉛めっき浴中に硝酸イオンを含有することで、効率よくＳｉＯ２粒子をめっき層中に共析できることが記載されている。 Patent Document 4 describes that SiO 2 particles can be efficiently eutectoided into a plating layer by containing nitrate ions in a zinc plating bath.
特許文献５には、ＳｉＯ２、ＴｉＯ２、ＺｒＯ２などの酸化物粒子にＮｉ２＋, Ｃｏ２＋, Ｆｅ２＋を一定量以上吸着させて正に帯電化させ、亜鉛めっき浴中に安定に分散させて複合めっき浴を作成することで、効率よく共析できることが記載されている。 Patent Document 5 discloses that oxide particles such as SiO 2 , TiO 2 , and ZrO 2 are adsorbed with a certain amount or more of Ni 2+ , Co 2+ , and Fe 2+ to be positively charged, and then stably dispersed in a galvanizing bath. It is stated that efficient eutectoid deposition can be achieved by creating a composite plating bath.
特許文献１、２、３に開示されているように、亜鉛に酸化物を分散共析することによって耐食性が向上する場合がある。しかし、特許文献１、２、３の技術では、酸化物をめっき層中に均一に分散共析させることは容易ではない。そこで、効率良く酸化物を分散させる手法が検討されてきた。 As disclosed in Patent Documents 1, 2, and 3, corrosion resistance may be improved by dispersing and eutectoiding an oxide to zinc. However, with the techniques disclosed in Patent Documents 1, 2, and 3, it is not easy to uniformly disperse and eutectoid the oxide in the plating layer. Therefore, methods for efficiently dispersing oxides have been studied.
特許文献４の技術では、硝酸イオンを添加することでＳｉＯ２の共析量は増加するが、硝酸イオン濃度変化に伴うＳｉＯ２の共析量変化が大きく、めっき浴中の硝酸イオン濃度を一定に保つことが困難であるため、ＳｉＯ２の共析量の安定した制御が難しい。 In the technique of Patent Document 4, the amount of SiO 2 eutectoid increases by adding nitrate ions, but the amount of SiO 2 eutectoid changes greatly as the nitrate ion concentration changes, and it is difficult to keep the nitrate ion concentration in the plating bath constant. Therefore, it is difficult to stably control the amount of eutectoid SiO 2 .
特許文献５の技術でも、亜鉛と亜鉛よりも電気化学的に貴なＮｉ, Ｃｏ, Ｆｅとの合金めっきがベースとなるため、めっき進行に伴うＮｉ２＋, Ｃｏ２＋, Ｆｅ２＋濃度変化によるＳｉＯ２、ＴｉＯ２、ＺｒＯ２などの酸化物共析量の変化が大きく、共析量の制御が困難である。 The technology disclosed in Patent Document 5 is also based on alloy plating of zinc and Ni, Co, and Fe, which are electrochemically more noble than zinc, so SiO 2 changes due to changes in Ni 2+ , Co 2+ , and Fe 2+ concentrations as plating progresses. , TiO 2 , ZrO 2 , etc. The amount of eutectoid oxides changes greatly, making it difficult to control the amount of eutectoid.
本発明の目的は、亜鉛めっき鋼板に共析させて耐食性を向上させる酸化物としてＳｉＯ２に着目し、亜鉛めっき層中に安定して一定のＳｉＯ２共析量を有する亜鉛系電気めっき鋼板およびその製造方法を提供することである。 The purpose of the present invention is to focus on SiO 2 as an oxide that improves corrosion resistance by eutectoiding a galvanized steel sheet, and to provide a zinc-based electroplated steel sheet and a zinc-based electroplated steel sheet having a stable and constant amount of SiO 2 eutectoid in the galvanized layer. An object of the present invention is to provide a manufacturing method thereof.
本発明者らは、前記課題を解決すべく、亜鉛めっき層中に一定のＳｉＯ２共析量を有する亜鉛系めっきを安定して得られる方法について鋭意研究を重ねた。特許文献４には、亜鉛めっき層中に浴中のＳｉＯ２を分散析出させる方法として、硝酸イオンを添加する方法が開示されている。これは、硝酸イオンを添加することにより、硝酸イオンの酸化作用で鋼板界面のｐＨが上昇し、水酸化亜鉛の生成が促進され、水酸化亜鉛とＳｉＯ２が共析し、亜鉛めっき層中にＳｉＯ２が多く含まれるものと考えられている。 In order to solve the above problems, the present inventors have conducted extensive research on a method for stably obtaining zinc-based plating having a constant amount of SiO 2 eutectoid in the galvanized layer. Patent Document 4 discloses a method of adding nitrate ions as a method of dispersing and precipitating SiO 2 in a bath into a galvanized layer. This is because by adding nitrate ions, the pH at the steel plate interface increases due to the oxidizing effect of nitrate ions, promoting the production of zinc hydroxide, and zinc hydroxide and SiO2 eutectoid, forming the zinc plating layer. It is thought that a large amount of SiO 2 is contained.
しかし、硝酸イオンでは、ｐＨを上昇させる作用が大きいため、鋼板界面のｐＨが急激に上昇し、皮膜中のＳｉＯ２含有量の制御が困難であった。また、硝酸イオンを用いた場合、界面のｐＨが急激に上昇するため、亜鉛が局所的に水酸化物や酸化物の形で残存しやすく、めっき密着性が低下する課題があった。 However, since nitrate ions have a large pH-increasing effect, the pH at the steel plate interface rapidly increases, making it difficult to control the SiO 2 content in the film. Furthermore, when nitrate ions are used, the pH at the interface rapidly increases, so zinc tends to remain locally in the form of hydroxides or oxides, resulting in a decrease in plating adhesion.
ところで、Ｖの分散めっきにおいては、Ｚｎ２＋より低いｐＨで加水分解するＶＯ２＋をめっき液に添加し、陰極電解処理をすることで、亜鉛めっき皮膜中にＶが酸化物の形で共析することが知られている。ＶＯ２＋をめっき液に添加し陰極電解処理した場合、鋼板界面のｐＨが上昇すると考えられるが、ＶＯ２＋の酸化作用は硝酸イオンよりも弱いため、鋼板界面のｐＨ上昇は硝酸イオン添加の場合に比べて少なく、鋼板界面のｐＨ上昇を制御しやすいのではないかと考えた。その技術思想に基づき、ＳｉＯ２を分散させ、Ｖイオンを含有するめっき浴を用いて陰極電解処理を行った結果、亜鉛めっき層中に安定して一定のＳｉＯ２共析量を得ることが可能であることを見出し、高い耐食性を持つ亜鉛系めっきが得られることが明らかになった。 By the way, in dispersion plating of V, by adding VO 2+ , which hydrolyzes at a lower pH than Zn 2+ , to the plating solution and performing cathodic electrolysis treatment, V is eutectoid in the form of oxide in the zinc plating film. It is known. When VO 2+ is added to the plating solution and cathodic electrolytic treatment is performed, the pH at the steel plate interface is thought to increase, but since the oxidizing effect of VO 2+ is weaker than nitrate ions, the pH increase at the steel plate interface is caused by the addition of nitrate ions. We thought that it would be easier to control the pH increase at the steel plate interface. Based on this technical idea, by dispersing SiO 2 and performing cathodic electrolytic treatment using a plating bath containing V ions, it is possible to stably obtain a constant amount of SiO 2 eutectoid in the galvanized layer. It was found that zinc-based plating with high corrosion resistance can be obtained.
更に、ＶＯ２＋をめっき液に添加し陰極電解処理した場合、めっき皮膜中にＶ酸化物が析出し、ＳｉＯ２のみを含有する場合よりも耐食性が向上することを見出した。 Furthermore, it has been found that when VO 2+ is added to the plating solution and cathodic electrolysis treatment is performed, V oxide is precipitated in the plating film, and the corrosion resistance is improved compared to the case where only SiO 2 is contained.
なお、Ｖイオンとしては、めっき浴中でＶＯ２＋となることが必要であり、使用するめっき浴のめっき条件（ｐＨ、温度、他のイオンの存在量等）下でＶＯ２＋となるＶ化合物をめっき浴に添加することが可能である。 It should be noted that the V ion needs to become VO 2+ in the plating bath, and the V compound that becomes VO 2+ under the plating conditions (pH, temperature, amount of other ions, etc.) of the plating bath used is It can be added to the plating bath.
本発明はこのような知見に基づきなされたもので、その要旨は以下の通りである。
［１］鋼板の少なくとも片面に亜鉛系めっき皮膜を備え、
前記亜鉛系めっき皮膜は、亜鉛を主体とし、Ｖを０．５～１０．０質量％、ＳｉＯ２を０．１～１５．０質量％含有することを特徴とする亜鉛系電気めっき鋼板
［２］亜鉛イオンを含有するめっき浴中で、鋼板を陰極として電解し、前記鋼板の少なくとも片面面に亜鉛系電気めっき皮膜を形成する亜鉛系電気めっき鋼板の製造方法であって、
前記めっき浴は、ＶＯ２＋を０．１０ｍｏｌ／Ｌ以上、ＳｉＯ２を０．０５ｍｏｌ／Ｌ以上含有し、ｐＨが１．０以上であって、陰極電解処理の電流密度が２０Ａ／ｄｍ２以上であることを特徴とする、亜鉛系電気めっき鋼板の製造方法。
［３］［２］に記載の亜鉛系電気めっき鋼板の製造方法であって、
前記めっき浴は、Ｚｎイオンを０．１０ｍｏｌ／Ｌ以上含有し、ｐＨが２．５以下であることを特徴とする、亜鉛系電気めっき鋼板の製造方法。
［４］［２］または［３］に記載の亜鉛系電気めっき鋼板の製造方法であって、
前記めっき浴の相対流速が２ｍ／ｓ以上であって、陰極電解処理の電流密度が１５０Ａ／ｄｍ２以下であることを特徴とする、亜鉛系電気めっき鋼板の製造方法。
ここで、亜鉛系めっき皮膜が亜鉛を主体とするとは、めっき皮膜が亜鉛を５０質量％以上含有し、残部が亜鉛以外の元素からなることを意味する。亜鉛系めっき皮膜は、亜鉛を主体とし、Ｖを０．５～１０．０質量％、ＳｉＯ２を０．１～１５．０質量％含有するが、めっき皮膜が亜鉛を５０質量％以上含有し、上記範囲のＶとＳｉＯ２を含有し、残部が本発明の作用効果を阻害しない成分と不可避的不純物からなることを意味する。亜鉛系めっき皮膜が亜鉛と上記範囲のＶとＳｉＯ２を含有し、残部不可避的不純物からなる場合も当然本発明に含まれる。
The present invention was made based on such knowledge, and the gist thereof is as follows.
[1] A zinc-based plating film is provided on at least one side of the steel plate,
The zinc-based electroplated steel sheet [2] is characterized in that the zinc-based plating film is mainly composed of zinc and contains 0.5 to 10.0% by mass of V and 0.1 to 15.0% by mass of SiO 2 . ] A method for producing a zinc-based electroplated steel sheet, comprising electrolyzing the steel sheet as a cathode in a plating bath containing zinc ions to form a zinc-based electroplated film on at least one side of the steel sheet,
The plating bath contains VO 2+ of 0.10 mol/L or more, SiO 2 of 0.05 mol/L or more, has a pH of 1.0 or more, and has a cathodic electrolytic treatment current density of 20 A/dm 2 or more. A method for producing a zinc-based electroplated steel sheet.
[3] A method for producing a zinc-based electroplated steel sheet according to [2],
A method for producing a zinc-based electroplated steel sheet, wherein the plating bath contains Zn ions in an amount of 0.10 mol/L or more and has a pH of 2.5 or less.
[4] A method for producing a zinc-based electroplated steel sheet according to [2] or [3],
A method for manufacturing a zinc-based electroplated steel sheet, characterized in that the relative flow velocity of the plating bath is 2 m/s or more, and the current density of the cathodic electrolytic treatment is 150 A/dm 2 or less.
Here, the expression that the zinc-based plating film is mainly composed of zinc means that the plating film contains 50% by mass or more of zinc, and the remainder consists of elements other than zinc. The zinc-based plating film mainly contains zinc, 0.5 to 10.0% by mass of V, and 0.1 to 15.0% by mass of SiO2 , but the plating film contains 50% by mass or more of zinc. , means that it contains V and SiO 2 in the above range, and the remainder consists of components that do not inhibit the effects of the present invention and unavoidable impurities. Naturally, the present invention also includes a case where the zinc-based plating film contains zinc, V and SiO 2 in the above range, and the remainder consists of unavoidable impurities.
本発明により、電気亜鉛めっき層中に安定して一定のＳｉＯ２含有量とＶ酸化物を含有する亜鉛系めっき鋼板の製造が可能となり、耐食性の良好な亜鉛系電気めっき鋼板を得ることができる。 According to the present invention, it is possible to manufacture a zinc-based electroplated steel sheet containing a stable and constant SiO 2 content and V oxide in the electrogalvanized layer, and it is possible to obtain a zinc-based electroplated steel sheet with good corrosion resistance. .
めっき浴中にＺｎイオンが存在する状態で、鋼板を陰極電解し、その後水洗を行う。なお、必要に応じて、その後、乾燥を行ってもよい。なお、水洗、乾燥の方法は特に限定されず、一般的な方法を採用可能である。 The steel plate is subjected to cathodic electrolysis in the presence of Zn ions in the plating bath, and then washed with water. Note that, if necessary, drying may be performed after that. Note that the washing and drying methods are not particularly limited, and general methods can be used.
亜鉛めっきが施される鋼板の種類は特に限定されるものではなく、低炭素鋼、極低炭素鋼、ＩＦ鋼、各種合金元素を添加した高張力鋼板等の種々の鋼板を用いることができる。また、前記鋼板は、熱延鋼板、冷延鋼板のいずれも用いることができる。鋼板の厚さは特に限定されないが、家電、自動車車体、建材等の用途に用いる観点から、０．４～５．０ｍｍが好ましい。 The type of steel plate to which galvanization is applied is not particularly limited, and various steel plates such as low carbon steel, ultra-low carbon steel, IF steel, and high-strength steel plates to which various alloying elements are added can be used. Moreover, either a hot-rolled steel plate or a cold-rolled steel plate can be used as the steel plate. The thickness of the steel plate is not particularly limited, but is preferably 0.4 to 5.0 mm from the viewpoint of use in home appliances, automobile bodies, building materials, etc.
亜鉛系めっき皮膜のＶ含有率は０．５質量％以上１０．０質量％以下とする必要がある。Ｖが０．５質量％未満では皮膜中のＳｉＯ２含有量が０．１質量％以上でも良好な耐食性が得られない。また、Ｖが１０．０質量％より多いと結晶の凹凸が大きくなり、鋼板との密着性が低下し、加工後の耐食性が低下する。 The V content of the zinc-based plating film needs to be 0.5% by mass or more and 10.0% by mass or less. If V is less than 0.5% by mass, good corrosion resistance cannot be obtained even if the SiO 2 content in the film is 0.1% by mass or more. Moreover, when V is more than 10.0% by mass, the unevenness of the crystals becomes large, the adhesion with the steel plate decreases, and the corrosion resistance after processing decreases.
亜鉛系めっき皮膜のＳｉＯ２含有率は０．１質量％以上１５．０質量％以下とする必要がある。ＳｉＯ２が０．１質量％未満では良好な耐食性が得られない。また、ＳｉＯ２含有率１５．０質量％を超えるめっきを安定して製造することは困難である。 The SiO 2 content of the zinc-based plating film needs to be 0.1% by mass or more and 15.0% by mass or less. If SiO 2 is less than 0.1% by mass, good corrosion resistance cannot be obtained. Furthermore, it is difficult to stably produce plating with an SiO 2 content of more than 15.0% by mass.
めっき付着量は５～４０ｇ／ｍ２が好ましい。めっき付着量が５ｇ／ｍ２以上であるとより高い耐食性が発揮される。４０ｇ／ｍ２を超えるとコストが増加してしまう。 The amount of plating deposited is preferably 5 to 40 g/m 2 . Higher corrosion resistance is exhibited when the coating weight is 5 g/m 2 or more. If it exceeds 40 g/m 2 , the cost will increase.
亜鉛系めっき皮膜へは、性能向上を目的に、Ｆｅ、Ｍｎ、Ｃｏ、Ｃｒなどの合金元素を合計２０質量％以下含有してもよく、合計１５質量％以下であることがより好ましい。 The zinc-based plating film may contain alloying elements such as Fe, Mn, Co, and Cr in a total amount of 20% by mass or less, more preferably a total of 15% by mass or less, for the purpose of improving performance.
めっき浴中のＺｎイオンは０．１０ｍｏｌ／Ｌ以上が好ましい。０．１０ｍｏｌ／Ｌ未満では、亜鉛の供給が不足し、均一なめっき皮膜が形成できないため、めっき密着性が低下する場合がある。また、Ｚｎイオンは１．００ｍｏｌ／Ｌ以下が好ましい。１．００ｍｏｌ／Ｌを超えると、コストが増加する。 The amount of Zn ions in the plating bath is preferably 0.10 mol/L or more. If it is less than 0.10 mol/L, the supply of zinc is insufficient and a uniform plating film cannot be formed, so that plating adhesion may deteriorate. Moreover, the Zn ion content is preferably 1.00 mol/L or less. If it exceeds 1.00 mol/L, the cost will increase.
亜鉛めっき浴としては、鋼板界面のｐＨ上昇が起こり得る酸性のめっき浴であれば特に限定は無く、硫酸浴、塩化物浴等が適用可能である。工業生産には、薬液コストがより安価で、製造設備の制約が少なく、高電流密度でのめっきが可能な硫酸浴が好ましい。 The zinc plating bath is not particularly limited as long as it is an acidic plating bath that can cause an increase in the pH of the steel sheet interface, and sulfuric acid baths, chloride baths, etc. are applicable. For industrial production, a sulfuric acid bath is preferred because it has lower chemical costs, fewer restrictions on production equipment, and allows plating at high current densities.
めっき浴中のＶＯ２＋は、０．１０ｍｏｌ／Ｌ以上とする必要がある。０．１０ｍｏｌ／Ｌ未満では、めっき皮膜中のＶ濃度が低く、かつＳｉＯ２を共析させる効果が得られない。また、ＶＯ２＋は０．５０ｍｏｌ／Ｌ以下が好ましい。０．５０ｍｏｌ／Ｌを超えると、皮膜中のＶの割合が増加してしまい、めっき密着性が低下する。 VO 2+ in the plating bath needs to be 0.10 mol/L or more. If it is less than 0.10 mol/L, the V concentration in the plating film will be low and the effect of eutectoiding SiO 2 will not be obtained. Further, VO 2+ is preferably 0.50 mol/L or less. If it exceeds 0.50 mol/L, the proportion of V in the film will increase and the plating adhesion will decrease.
めっき浴中のＶＯ２＋添加は、使用するめっき浴中でＶＯ２＋となるＶ化合物の添加で行うことが可能である。そのような化合物としては、酸化硫酸バナジウム、二塩化酸化バナジウム等を例示できる。 Addition of VO 2+ to the plating bath can be carried out by adding a V compound that becomes VO 2+ in the plating bath used. Examples of such compounds include vanadium sulfate oxide and vanadium dichloride oxide.
めっき浴に含有させるＳｉＯ２は、０．０５ｍｏｌ／Ｌ以上とする必要がある。０．０５ｍｏｌ／Ｌ未満では、皮膜中のＳｉＯ２量が少なく、耐食性を向上させる効果が得られない。また、ＳｉＯ２は０．５０ｍｏｌ／Ｌ未満が好ましい。０．５０ｍｏｌ／Ｌを超えても、皮膜中のＳｉＯ２量は増加せず、コストが増加する。めっき浴に添加するＳｉＯ２としては、コロイダルシリカ、ＳｉＯ２ナノ粒子分散液等が使用できる。中でもコロイダルシリカが浴の安定性、コストの理由で好適である。 The amount of SiO 2 contained in the plating bath must be 0.05 mol/L or more. If it is less than 0.05 mol/L, the amount of SiO 2 in the film is small and the effect of improving corrosion resistance cannot be obtained. Moreover, SiO 2 is preferably less than 0.50 mol/L. Even if it exceeds 0.50 mol/L, the amount of SiO 2 in the film does not increase and the cost increases. As SiO 2 added to the plating bath, colloidal silica, SiO 2 nanoparticle dispersion, etc. can be used. Among them, colloidal silica is preferred for reasons of bath stability and cost.
めっき浴のｐＨは１．０以上とする必要がある。ｐ１．０未満では、電解でのｐＨ上昇が不十分となり、皮膜中にＶおよびＳｉＯ２が共析されない。また、ｐＨは２．５以下が好ましい。ｐＨが２．５を超えると、局所的にｐＨが上がりすぎ、めっきの密着性が低下する場合がある。 The pH of the plating bath needs to be 1.0 or higher. If p is less than 1.0, the pH increase in electrolysis will be insufficient, and V and SiO 2 will not be eutectoid in the film. Further, the pH is preferably 2.5 or less. When the pH exceeds 2.5, the pH locally increases too much and the adhesion of the plating may decrease.
めっき浴の浴温は特に限定されないが、３０～６０℃が好ましい。３０℃未満では浴電導度が低く電気代ロスが大きく、６０℃を超えると液の蒸発が課題となる。 The temperature of the plating bath is not particularly limited, but is preferably 30 to 60°C. If the temperature is below 30°C, the bath conductivity will be low and the electricity cost loss will be large, and if it exceeds 60°C, evaporation of the liquid will become a problem.
めっき浴へは、浴電導度向上を目的に、硫酸ナトリウムなど電導度補助剤を添加したり、Ｆｅ、Ｍｎ、Ｃｏ、Ｃｒなどの他の金属イオンを含有させてもよい。 A conductivity aid such as sodium sulfate may be added to the plating bath for the purpose of improving bath conductivity, or other metal ions such as Fe, Mn, Co, and Cr may be contained.
鋼板とめっき浴の相対流速は２ｍ／ｓ以上が好ましい。流速が２ｍ／ｓ未満の場合には、陰極電解により局所的に界面ｐＨが上昇する場合があり、より安定して外観良好なめっきを得るためには２ｍ／ｓ以上が好ましい。上限は限定されないが、６ｍ／ｓを超えても品質への効果は見られないので、製造コストの観点からは６ｍ／ｓ以下が好ましい。 The relative flow velocity between the steel plate and the plating bath is preferably 2 m/s or more. If the flow rate is less than 2 m/s, the interfacial pH may locally increase due to cathodic electrolysis, and in order to obtain more stable plating with good appearance, the flow rate is preferably 2 m/s or more. Although the upper limit is not limited, no effect on quality is observed even if the speed exceeds 6 m/s, so 6 m/s or less is preferable from the viewpoint of manufacturing cost.
陰極電解の電流密度は、２０Ａ／ｄｍ２以上とする。２０Ａ／ｄｍ２未満では、界面ｐＨの上昇が不十分となり、皮膜中にＶおよびＳｉＯ２が共析されない。上限は１５０Ａ／ｄｍ２以下が好ましい。１５０Ａ／ｄｍ２を超えると局所的にｐＨが上がる場合があり、より安定して外観良好なめっきを得るためには１５０Ａ／ｄｍ２以下が好ましい。 The current density of cathode electrolysis is 20 A/dm 2 or more. If it is less than 20 A/dm 2 , the interface pH will not increase sufficiently, and V and SiO 2 will not be eutectoid in the film. The upper limit is preferably 150 A/dm 2 or less. If it exceeds 150 A/dm 2 , the pH may locally increase, and in order to obtain more stable plating with good appearance, it is preferably 150 A/dm 2 or less.
電気めっき処理後、必要により、耐食性、耐疵付き性、加工性等の各種性能の更なる向上を目的として、クロメート又はクロメートフリー型の各種化成処理皮膜（塗布型、反応型、電解型）、更にはその上に樹脂被覆処理等を実施することができる。なお、これらの処理を施した鋼板についても、本発明の効果は得られる。 After electroplating, if necessary, various chromate or chromate-free chemical conversion coatings (spray type, reaction type, electrolytic type), Furthermore, resin coating treatment or the like can be performed thereon. Note that the effects of the present invention can also be obtained with steel plates subjected to these treatments.
本発明を実施例により説明する。なお、本発明は以下の実施例に限定されない。 The present invention will be explained by examples. Note that the present invention is not limited to the following examples.
素材鋼板として、板厚０．７ｍｍの冷延鋼板を使用し、これをアルカリで電解脱脂、水洗および酸洗処理（硫酸濃度：７０ｇ／Ｌ、液温：２５～４０℃、５秒浸漬）を施した。次いで、表１に示す条件により亜鉛系電気めっき鋼板を製造した。 A cold-rolled steel plate with a thickness of 0.7 mm was used as the material steel plate, which was electrolytically degreased with alkali, washed with water, and pickled (sulfuric acid concentration: 70 g/L, liquid temperature: 25-40°C, immersed for 5 seconds). provided. Next, a zinc-based electroplated steel sheet was manufactured under the conditions shown in Table 1.
亜鉛めっき浴は硫酸亜鉛浴を用いた。 A zinc sulfate bath was used as the galvanizing bath.
ＶＯ２＋は酸化硫酸バナジウムとして添加した。また、ＳｉＯ２はコロイダルシリカ（日産化学製スノーテックスＯ）として添加した。 VO 2+ was added as vanadium oxide sulfate. Further, SiO 2 was added as colloidal silica (Snowtex O manufactured by Nissan Chemical).
めっき付着量、めっき皮膜中のＳｉＯ２、Ｖはめっきを酸で剥離し、ＩＣＰを用いて定量分析した。 The amount of plating deposited, SiO 2 and V in the plating film were determined by peeling off the plating with acid and quantitatively analyzing it using ICP.
以上のようにして得られた試験片について、以下の評価を行った。得られた結果を、表１に示す。 The test pieces obtained as described above were evaluated as follows. The results obtained are shown in Table 1.
（１）平板部耐食性
めっき鋼板から５０ｍｍ×１５０ｍｍの試験片を切り出し、せん断端面をシール後、ＪＩＳＺ２３７１の塩水噴霧試験を実施し、５％赤錆発生時間により平板部の耐食性を評価した。
◎および〇の場合を耐食性良好と判定した。
(1) Corrosion resistance of flat plate part A test piece of 50 mm x 150 mm was cut out from a plated steel plate, and after sealing the sheared end surface, a salt spray test according to JIS Z2371 was conducted, and the corrosion resistance of the flat plate part was evaluated based on the 5% red rust generation time.
Cases of ◎ and ○ were judged to have good corrosion resistance.
◎：赤錆発生時間＞４８時間
○：４８時間≧赤錆発生時間＞２４時間
×：赤錆発生時間≦２４時間
（２）加工部耐食性
めっき鋼板から５０ｍｍ×１５０ｍｍの試験片を切り出し、エリクセン７ｍｍ押し出し加工を行い、せん断端面をシール後、ＪＩＳＺ２３７１の塩水噴霧試験を実施し、５％赤錆発生時間により加工部の耐食性を評価した。
◎および〇の場合を耐食性良好と判定した。
◎: Red rust occurrence time > 48 hours ○: 48 hours ≧ Red rust occurrence time > 24 hours ×: Red rust occurrence time ≦ 24 hours (2) Corrosion resistance of processed parts A test piece of 50 mm x 150 mm was cut out from a plated steel plate and subjected to Erichsen 7 mm extrusion processing. After sealing the sheared end face, a JIS Z2371 salt water spray test was carried out, and the corrosion resistance of the processed part was evaluated based on the 5% red rust generation time.
Cases of ◎ and ○ were judged to have good corrosion resistance.
◎：赤錆発生時間＞４８時間
○：４８時間≧赤錆発生時間＞２４時間
×：赤錆発生時間≦２４時間
（３）めっき密着性
３０ｍｍ×１００ｍｍに切り出した試験片の評価面を外側に向け、先端が２．０Ｒで９０°の金型を用いて曲げ加工を加えた後にセロハンテープ（登録商標）を評価面全面に貼り付けて引き離した後、テープに付着しためっき付着量を測定し、密着性を評価した。
◎および〇の場合を耐食性良好と判定した。
◎: Red rust generation time > 48 hours ○: 48 hours ≧ Red rust generation time > 24 hours ×: Red rust generation time ≦ 24 hours (3) Plating adhesion A test piece cut into a size of 30 mm x 100 mm was cut out, with the evaluation side facing outward, and the tip After bending using a 90° mold with 2.0R, apply cellophane tape (registered trademark) to the entire evaluation surface and pull it apart.The amount of plating adhered to the tape was measured, and the adhesion was evaluated. was evaluated.
Cases of ◎ and ○ were judged to have good corrosion resistance.
◎：めっき残存率≧初期の９０％
○：初期の９０％＞めっき残存率≧初期の８０％
×：めっき残存率＜初期の８０％
表1において、Ｎｏ．１はＶＯ２＋を添加し、ＳｉＯ２を添加しない場合の比較例である。めっき皮膜中にＶは本発明技術範囲で含有しているがＳｉＯ２は含有しておらず、平板部耐食性と加工部耐食性が劣っている。Ｎｏ．２はＳｉＯ２を必要量添加し、ＶＯ２＋を添加しない場合の比較例である。めっき皮膜中にＶもＳｉＯ２も含有しておらず、平板部耐食性と加工部耐食性が劣っている。
◎: Plating residual rate ≧ initial 90%
○: Initial 90% > Plating residual rate ≧ Initial 80%
×: Plating residual rate <80% of initial value
In Table 1, No. 1 is a comparative example in which VO 2+ was added and SiO 2 was not added. Although the plating film contains V within the technical scope of the present invention, it does not contain SiO 2 , and the corrosion resistance of the flat plate portion and the processed portion are poor. No. 2 is a comparative example in which a required amount of SiO 2 is added and VO 2+ is not added. Neither V nor SiO 2 is contained in the plating film, and the corrosion resistance of the flat plate part and the processed part are poor.
Ｎｏ．３はＳｉＯ２を必要量添加し、ＶＯ２＋添加量が０．０５ｍｏｌ／Ｌと必要量よりも少ない場合である。めっき皮膜中にＳｉＯ２を含有しておらず、Ｖ含有量が本発明技術範囲外で少ないため、平板部耐食性と加工部耐食性は劣っている。 No. 3 is a case where the required amount of SiO 2 is added and the amount of VO 2+ added is 0.05 mol/L, which is smaller than the required amount. Since the plating film does not contain SiO 2 and the V content is low and outside the technical range of the present invention, the corrosion resistance of the flat plate part and the processed part are poor.
Ｎｏ．４はＶＯ２＋添加量が１．００ｍｏｌ／Ｌと、本発明技術範囲より多すぎる場合であるが、平板部耐食性は良好となるものの、加工部耐食性とめっき密着性は不良である。 No. In No. 4, the amount of VO 2+ added is 1.00 mol/L, which is too much than the technical range of the present invention, and although the corrosion resistance of the flat plate part is good, the corrosion resistance of the processed part and the plating adhesion are poor.
Ｎｏ．５はめっき浴ｐＨが０．８と低い場合であるが、めっき皮膜中にＶもＳｉＯ２も含有しておらず、平板部耐食性と加工部耐食性が劣っている。 No. No. 5 is a case where the plating bath pH is as low as 0.8, but the plating film contains neither V nor SiO 2 and the corrosion resistance of the flat plate part and the processed part are poor.
Ｎｏ．６は電流密度が低い場合であるが、めっき皮膜中にＳｉＯ２を含有しておらず、平板部耐食性と加工部耐食性が劣っている。 No. No. 6 is a case where the current density is low, but the plating film does not contain SiO 2 and the corrosion resistance of the flat plate part and the processed part are poor.
Ｎｏ．７～１０は本件発明例であり、平板部耐食性と加工部耐食性とめっき密着性のいずれもが〇であるが、めっき浴ｐＨ、Ｚｎ濃度、相対流速、電流密度のいずれかが好適範囲を外れており、めっき浴ｐＨ、Ｚｎ濃度、相対流速、電流密度がすべて好適範囲内でありめっき密着性がすべて◎で、平板部耐食性と加工部耐食性の多くも◎であるＮｏ．１１～２２に比較して、性能は劣っている。 No. 7 to 10 are examples of the present invention, and the corrosion resistance of the flat plate part, the corrosion resistance of the processed part, and the plating adhesion are all ○, but any of the plating bath pH, Zn concentration, relative flow rate, and current density is outside the preferred range. The plating bath pH, Zn concentration, relative flow rate, and current density are all within suitable ranges, the plating adhesion is all ◎, and the corrosion resistance of the flat plate part and the processed part are also ◎. Performance is inferior compared to 11-22.
本発明の亜鉛系電気めっき鋼板は、亜鉛めっき層中に安定して必要量のＳｉＯ２を含有し、更にはＶ酸化物を含有することにより、高い耐食性と密着性を有し、家電製品、自動車、建材などの広範な用途で好適に使用することが可能である。 The zinc-based electroplated steel sheet of the present invention stably contains a necessary amount of SiO 2 in the galvanized layer and further contains V oxide, so it has high corrosion resistance and adhesion, and can be used for home appliances, It can be suitably used in a wide range of applications such as automobiles and building materials.
Claims (4)
前記亜鉛系めっき皮膜は、亜鉛を主体とし、Ｖを０．５～１０．０質量％、ＳｉＯ２を０．１～１５．０質量％含有することを特徴とする亜鉛系電気めっき鋼板。 A zinc-based plating film is provided on at least one side of the steel plate,
The zinc-based electroplated steel sheet is characterized in that the zinc-based plating film is mainly composed of zinc and contains 0.5 to 10.0% by mass of V and 0.1 to 15.0% by mass of SiO 2 .
前記めっき浴は、Ｚｎイオンを０．１０ｍｏｌ／Ｌ以上含有し、ｐＨが２．５以下であることを特徴とする亜鉛系電気めっき鋼板の製造方法。 A method for manufacturing a zinc-based electroplated steel sheet according to claim 2, comprising:
A method for producing a zinc-based electroplated steel sheet, wherein the plating bath contains Zn ions in an amount of 0.10 mol/L or more and has a pH of 2.5 or less.
前記めっき浴の相対流速が２ｍ／ｓ以上であって、陰極電解処理の電流密度が１５０Ａ／ｄｍ２以下であることを特徴とする亜鉛系電気めっき鋼板の製造方法。 A method for manufacturing a zinc-based electroplated steel sheet according to claim 2 or 3, comprising:
A method for producing a zinc-based electroplated steel sheet, characterized in that the relative flow velocity of the plating bath is 2 m/s or more, and the current density of the cathodic electrolytic treatment is 150 A/dm 2 or less.
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| JP2004263252A (en) | 2003-03-03 | 2004-09-24 | Jfe Steel Kk | Chromium-free chemically treated steel sheet excellent in resistance to white rust |
| JP2010095746A (en) | 2008-10-15 | 2010-04-30 | Nippon Steel Corp | Surface-treated metal material having excellent corrosion resistance, conductivity and heat resistance, and method for manufacturing the same |
| JP2011236471A (en) | 2010-05-11 | 2011-11-24 | Nippon Steel Corp | Composite electrogalvanized steel sheet, and method for producing the same |
| JP2013108183A (en) | 2011-03-29 | 2013-06-06 | Nippon Steel & Sumitomo Metal Corp | Method for manufacturing surface-treated steel sheet |
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| JP2004263252A (en) | 2003-03-03 | 2004-09-24 | Jfe Steel Kk | Chromium-free chemically treated steel sheet excellent in resistance to white rust |
| JP2010095746A (en) | 2008-10-15 | 2010-04-30 | Nippon Steel Corp | Surface-treated metal material having excellent corrosion resistance, conductivity and heat resistance, and method for manufacturing the same |
| JP2011236471A (en) | 2010-05-11 | 2011-11-24 | Nippon Steel Corp | Composite electrogalvanized steel sheet, and method for producing the same |
| JP2013108183A (en) | 2011-03-29 | 2013-06-06 | Nippon Steel & Sumitomo Metal Corp | Method for manufacturing surface-treated steel sheet |
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