JPS62230999A - Dispersion-plated steel sheet having high corrosion resistance - Google Patents
Dispersion-plated steel sheet having high corrosion resistanceInfo
- Publication number
- JPS62230999A JPS62230999A JP7484086A JP7484086A JPS62230999A JP S62230999 A JPS62230999 A JP S62230999A JP 7484086 A JP7484086 A JP 7484086A JP 7484086 A JP7484086 A JP 7484086A JP S62230999 A JPS62230999 A JP S62230999A
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- layer
- corrosion resistance
- plated steel
- dispersion
- 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.)
- Granted
Links
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 51
- 239000010959 steel Substances 0.000 title claims abstract description 51
- 230000007797 corrosion Effects 0.000 title claims abstract description 37
- 238000005260 corrosion Methods 0.000 title claims abstract description 37
- 239000010419 fine particle Substances 0.000 claims abstract description 20
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 150000004767 nitrides Chemical class 0.000 claims abstract description 5
- 150000001247 metal acetylides Chemical class 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 150000003568 thioethers Chemical class 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 229910052684 Cerium Inorganic materials 0.000 claims abstract 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract 2
- 239000010410 layer Substances 0.000 claims description 34
- 239000011247 coating layer Substances 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 238000007747 plating Methods 0.000 abstract description 20
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229910052804 chromium Inorganic materials 0.000 abstract description 2
- 229910052748 manganese Inorganic materials 0.000 abstract description 2
- 229910052796 boron Inorganic materials 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 229910052716 thallium Inorganic materials 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 13
- 238000011282 treatment Methods 0.000 description 11
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 10
- 238000007789 sealing Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910007567 Zn-Ni Inorganic materials 0.000 description 2
- 229910007614 Zn—Ni Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000203 mixture Substances 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
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000655 Killed steel Inorganic materials 0.000 description 1
- -1 MoE+ are suitable Chemical compound 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010349 cathodic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- 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
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は高耐食性分散めっき鋼板に係わり、更に詳しく
は優れた耐食性を有し、種々の用途、例えば自動車、硅
材、家電等に適用できる高耐食性分散めっき鋼板に関す
るものである。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a highly corrosion-resistant dispersion-plated steel sheet, and more specifically, it has excellent corrosion resistance and can be applied to various uses, such as automobiles, silicon materials, home appliances, etc. This relates to highly corrosion resistant dispersion plated steel sheets.
一般に表面処理鋼板は、腐食環境下での耐食性として裸
耐食性のみならず、塗装後の耐食性、すなわち塗膜偏部
の塗膜密着性、耐孔あき性や耐赤錆性等が要求される。In general, surface-treated steel sheets are required to have not only bare corrosion resistance in a corrosive environment, but also corrosion resistance after painting, that is, paint film adhesion of uneven parts of the paint film, porosity resistance, red rust resistance, etc.
また、耐食性のみでなく、加工性や溶接性にも優れるこ
とが重要である。従来この分野に於いてはＺｎ系を中心
に各種めつき鋼板が使用されている。また、それらの改
良も種々試みられている。In addition, it is important to have excellent not only corrosion resistance but also workability and weldability. Conventionally, various types of plated steel sheets, mainly Zn-based ones, have been used in this field. In addition, various attempts have been made to improve them.
しかしながら、例えば特開昭５６−１３３４８８号公報
に見られるＺｎ −Ｆｅ ２層めっき鋼板や、特公昭５
０−２９８２１号公報に見られるＺｎ −Ｎｉ めっ
き鋼板といえども現在の厳しい要求水準から見て必ずし
も満足すべき性質を有していない。However, for example, the Zn-Fe double-layer plated steel sheet seen in Japanese Patent Application Laid-Open No. 56-133488,
Even the Zn-Ni plated steel sheet disclosed in Japanese Patent No. 0-29821 does not necessarily have properties that are satisfactory in view of the current strict requirements.
また、特公昭５６−４９９９９号、特公昭５７−１７９
６０号、特開昭５６−１２３３９５号、特開昭５２−１
０９４３９号、特公昭４６−３７８８２号各公報には各
種の複合めっき方法あるいは複合めっき鋼板が提案され
ているが、これらに関しても現在の要求水準を満足する
性能を有しているとは言い難い。Also, Special Publication No. 56-49999, Special Publication No. 57-179
No. 60, JP-A-56-123395, JP-A-52-1
Although various composite plating methods or composite plated steel sheets have been proposed in Japanese Patent Publication No. 09439 and Japanese Patent Publication No. 46-37882, it is difficult to say that these have the performance that satisfies the current required level.
そこで、本発明者らは上記実情に鑑み、種々の実験を重
ねた結果、鋼板の片面あるいは両面に下層としてＺｎ単
独もしくはＺｎ合金めっき層を有し、上層として平均粒
径５μ以下の非金属微粒子を単独あるいは複合で０．０
１〜３０ｗｔ％含有する２０単独もしくはＺｎ合金めっ
き層を有するようなＺｎ系複合めっき鋼板が耐食性、加
工性共に優れた性能を有することを見い出し、すでに特
願昭５９−１８５３００号として出願済である。この複
合めっき鋼板は棟材の耐赤錆性、塗装耐食性に優れてい
るが、さらに近年では一段と苛酷な加工の施される例え
ば自動車ヘム部等に対する適用も要求され、これに対応
するための一層の改良が望まれている。Therefore, in view of the above circumstances, the present inventors conducted various experiments and found that a steel plate has a Zn alone or Zn alloy plating layer as a lower layer on one or both sides of the steel plate, and non-metal fine particles with an average particle size of 5 μm or less as an upper layer. 0.0 alone or in combination
It has been discovered that a Zn-based composite plated steel sheet containing 1 to 30 wt% of 20 alone or having a Zn alloy plating layer has excellent performance in both corrosion resistance and workability, and has already filed a patent application as Japanese Patent Application No. 185300/1983. . This composite plated steel sheet has excellent red rust resistance and paint corrosion resistance as a ridge material, but in recent years it has also been required to be applied to areas that undergo even more severe processing, such as automobile hems, and further efforts have been made to meet this demand. Improvements are desired.
本発明は、以上の如き問題点を解決すべくなされたもの
であって、加工部の封孔あき性に浸れ、しかも自動車等
の用途において極めて優れた耐食性を発揮する高耐食性
分散めっき銅板を提供することを目的とするものである
。The present invention has been made to solve the above-mentioned problems, and provides a highly corrosion-resistant dispersion-plated copper plate that has excellent sealing properties in processed parts and exhibits extremely excellent corrosion resistance in applications such as automobiles. The purpose is to
即ち、本発明の要旨とする所は、Ｓｉ 、 Ａｌ 。 That is, the gist of the present invention is Si, Al.
Ｆｅ 、 Ｔｉ 、 Ｍｏ 、 Ｏｕ 、 Ｚｎ 、
Ｎｉ 、 Ｃｏ 、 Ｌａ 、 Ｏｅ。Fe, Ti, Mo, Ou, Zn,
Ni, Co, La, Oe.
Ｂの１種以上の酸化物、炭化物、窒化物、硼化物、燐化
物、硫化物の単独あるいは複合で平均粒径５μ以下の微
粒子含有量係で３０％超、９５優以下含有するＺｎもし
くはＺｎ合金被覆層を上層とし、ＺｎあるいはＺｎｎ合
金被覆層下層とする２層′ｊｆｔＩ覆層を鋼板の片面あ
るいは両面に設けたことを特徴とする高耐食性分散めっ
き鋼板であり、このような構成とすることによって複合
めっき銅板に要求される各枠耐食性のうち、背に自動車
のヘム部等の加工された部分での封孔あき性に極めて優
れたものが得られる。Zn or Zn containing one or more of B's oxides, carbides, nitrides, borides, phosphides, and sulfides alone or in combination with a fine particle content of more than 30% and less than 95% with an average particle size of 5μ or less A highly corrosion-resistant dispersion plated steel sheet characterized by having a two-layer 'jftI coating layer on one or both sides of the steel plate, with an alloy coating layer as an upper layer and a Zn or Znn alloy coating layer as a lower layer, and having such a structure. As a result, among the various frame corrosion resistances required for composite plated copper plates, it is possible to obtain extremely excellent sealing properties at processed parts such as the hem of an automobile on the back.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
まず、本発明において微粒子の種類を８ｉ、Ａｌ。 First, in the present invention, the types of fine particles are 8i and Al.
Ｉｒｅ 、 Ｔｉ 、 Ｍｏ 、 Ｑｕ 、 Ｚｎ 、
Ｎｉ 、 Ｃｏ 、 Ｌａ 、 Ｏｅ 。Ire, Ti, Mo, Qu, Zn,
Ni, Co, La, Oe.
Ｂの１種以上の酸化物、炭化物、窒化物、硼化物、燐化
物、硫化物の単独あるいは複合と定めたのは、微粒子を
含有しないＺｎ若しくはＺｎ合金被覆層。B is defined as one or more oxides, carbides, nitrides, borides, phosphides, and sulfides alone or in combination, which is a Zn or Zn alloy coating layer that does not contain fine particles.
又は、上記以外の微粒子を含有するＺｎ若しくはＺｎ合
金層に比較して、耐食性のうち、特に加工部の封孔あき
性に優れることが判明したためである。酸化物としては
８１０２、Ａｌ２Ｏ３、Ｆｅ２Ｏ３、ＴｉＯ２、Ｍｏ
Ｏｓ、ｃｕｏ 、ＺｎＯ、ＮＩＯ、Ｌａ２Ｏ３、ＣｅＯ
２゜炭化物としてはＥｐｉｃ 、 Ｔｉ０％窒化物とし
てはＢＮ。Alternatively, this is because it has been found to be superior in corrosion resistance, particularly in sealing properties of processed parts, compared to Zn or Zn alloy layers containing fine particles other than those mentioned above. Oxides include 8102, Al2O3, Fe2O3, TiO2, Mo
Os, cuo, ZnO, NIO, La2O3, CeO
Epic is the 2° carbide, and BN is the Ti0% nitride.
ＳＩ３Ｎ４、硼化物としてはＴｉＢ 、燐化物としては
ＣｊｕＰ 、硫化物としてはＭｏＥ＋等が好適であって
、これらの粒子は他の粒子に比較して腐食反応のうちカ
ソード反応である０２還元反応を抑制し易い。これが、
封孔あき性向上の１つの理由と考えられる。SI3N4, boride such as TiB, phosphide such as CjuP, and sulfide such as MoE+ are suitable, and these particles suppress the 02 reduction reaction, which is a cathodic reaction among corrosion reactions, compared to other particles. Easy to do. This is,
This is considered to be one of the reasons for the improvement in sealing performance.
また、′ここでいうＺｎ合金被覆層とは、 ｕｉ 。Furthermore, the Zn alloy coating layer referred to here is ui.
Ｃｏ 、 Ｃｒ 、 Ｆ′ｅ 、 Ｍｎ 、 ＴＩ、
Ｏｅを単独あるいは複合で含有するＺｎ被覆層を指す。Co, Cr, F'e, Mn, TI,
Refers to a Zn coating layer containing Oe alone or in combination.
なお、合金成分金属の含有量は約０．３〜８０％の場
合に塗膜密着性、加工部の封孔あき性が特に良好となる
。Note that when the content of the alloying component metal is about 0.3 to 80%, the coating film adhesion and the sealing property of the processed part are particularly good.
次に、本発明において微粒子の平均粒径は５μ以下であ
ることが必要である。５μ以下に保つことによって厳し
い加工を受けた場合の耐パウダリング性が良好になる。Next, in the present invention, it is necessary that the average particle size of the fine particles is 5 μm or less. By keeping the thickness below 5μ, powdering resistance when subjected to severe processing becomes better.
なお、ここで言う平均粒径とは、全粒子のうち最も分布
量が大である粒径を意味する。Note that the average particle size as used herein means the particle size that has the largest distribution among all particles.
次に、本発明において微粒子の含有量の下限を３０％超
と定めたのは、３０％超添加で特に加工部の耐食性が良
好になる事が、ヘムモデルを作製しよシ実際の腐食環境
に近似した腐食サイクルテス） （ＣＯＴ）で評価した
結果判明したためである。Next, in the present invention, the lower limit of the content of fine particles was set at more than 30% because the addition of more than 30% improves corrosion resistance, especially in processed parts. This is because it was found as a result of evaluation using the approximate corrosion cycle test (COT).
さらに１本発明において微粒子含有量の上限を９５％と
定めたのは、 Ｚｎ系合金の犠牲防果の及ぶ範囲を考慮
したためである。微粒子含有量が９５％ｆ超えると Ｚ
ｎ系合金の含有量はそれだけ下るので、その犠牲防食作
用が薄れる。そのため、特に犠牲防食作用が要求される
ような環境下では９５％を超えない事が耐食性にとって
不可欠である。Furthermore, the reason why the upper limit of the fine particle content is set at 95% in the present invention is to take into consideration the range of sacrificial protection of the Zn-based alloy. When the fine particle content exceeds 95%f, Z
Since the content of the n-based alloy decreases accordingly, its sacrificial anticorrosion effect weakens. Therefore, it is essential for corrosion resistance that the corrosion resistance does not exceed 95%, especially in environments where sacrificial corrosion protection is required.
また、本発明において微粒子含有層を上層とし。Further, in the present invention, the fine particle-containing layer is an upper layer.
ＺｎまたはＺｎ合金被覆層を下層として設けたのは、上
層との組み合わせによシ相乗作用が発揮され、加工部の
耐食性及び加工性が飛躍的に良好となるためである。The reason why the Zn or Zn alloy coating layer is provided as the lower layer is that when combined with the upper layer, a synergistic effect is exhibited, and the corrosion resistance and workability of the processed part are dramatically improved.
下層の組成は特に定めないが、Ｚｎ合金としてはＮｉ
、 Ｃｏ 、 Ｏｒ 、 Ｍｏ 、 Ｆｅ 等を単独
又は複合で含有するものが有効である。The composition of the lower layer is not particularly determined, but as a Zn alloy, Ni
, Co, Or, Mo, Fe, etc. alone or in combination are effective.
また、２層構造である本発明分散めっき鋼板は、単層の
分散めっき層を有する鋼板に比較して加工部の耐孔あき
性、加工性が大幅に優れている。ここで言う加工性とは
めつき鋼板特有の耐、ｏラダリング性である。ここでノ
ぞラダリングとは、加工によるめっき層の一部の剥離挙
動を指す。Furthermore, the dispersion-plated steel sheet of the present invention having a two-layer structure has significantly better hole resistance and workability in the processed portion than a steel sheet having a single-layer dispersion plating layer. The term "workability" referred to here refers to the resistance and laddering properties peculiar to a fitted steel sheet. Here, "noso laddering" refers to the peeling behavior of a part of the plating layer due to processing.
２層めっき鋼板の加工性は単層分散めっき鋼板のみなら
ず、単層のＺｎ系めっき鋼板よりも良好となる。この原
因は明らかではないが、上層と下層とが相乗作用を有し
、お互いに一種の潤滑作用を及ぼすのではないかと推定
される。加工部の耐食性に関しても同様であり、上層と
下層との相乗作用が認められる。The workability of the double-layer plated steel sheet is better than not only the single-layer dispersion-plated steel sheet but also the single-layer Zn-based plated steel sheet. Although the cause of this is not clear, it is presumed that the upper layer and the lower layer have a synergistic effect and exert a kind of lubricating effect on each other. The same applies to the corrosion resistance of the processed part, and a synergistic effect between the upper layer and the lower layer is recognized.
以上の如き構放の本発明分散めっき鋼板が、特に自動車
のヘム部等のような苛酷な加工を受けた部分の耐孔あき
性が向上する理由は明らかではないが、めっき層中の微
粒子が一種のバリヤーとなり、腐食反応のうち酸素還元
反応を抑制し、またＺｎ及びＺｎ合金めつき層の犠牲防
食作用により耐食性が優れるものと思われる。It is not clear why the dispersion-coated steel sheet of the present invention, as described above, has improved perforation resistance, especially in areas that have undergone severe processing, such as the hem of automobiles, but the reason is that the fine particles in the coating layer It is thought that it acts as a kind of barrier, suppresses the oxygen reduction reaction among corrosion reactions, and has excellent corrosion resistance due to the sacrificial anticorrosive action of the Zn and Zn alloy plated layer.
なお、微粒子の電析メカニズムについては、従来より静
電的引力による共析説、機械的なめつき中への共析説等
種々あるが、現時点では不明である。Regarding the mechanism of electrodeposition of fine particles, there have been various theories such as eutectoid theory due to electrostatic attraction and eutectoid theory during mechanical plating, but it is unclear at present.
次に、本発明の分散めっき鋼板の製造手段について述べ
ると、本発明鋼板は電気めっき法或いは蒸着めっき法で
製造可能であるつ最も好ましいル造手段は電気めっき法
である。例えば ｐＨｌ〜３の硫酸塩浴又は塩化物浴を
用いて電流密度１〜２００ Ａ／ｄｍ 、 クイ／スピ
ード１−２５０ ｍ／ｍｉｎのめつき条件下で炸裂でき
る。また、Ｚｎ″！たはＺｎ合金層を有する下層の製造
手段としては、電気′めつきのみでなく溶融めっき、蒸
着めっき等も適用できる。下地鋼板としては普通鋼、
Ａｌキルド鋼、高張力鋼板等種々のものが適用できる。Next, the method for manufacturing the dispersion-plated steel sheet of the present invention will be described. The steel sheet of the present invention can be manufactured by electroplating or vapor deposition plating, and the most preferred method for forming is electroplating. For example, it can be exploded under plating conditions using a sulfate or chloride bath with a pH of 1 to 3 and a current density of 1 to 200 A/dm and a speed of 1 to 250 m/min. In addition, as a manufacturing method for the lower layer having the Zn''! or Zn alloy layer, not only electroplating but also hot-dip plating, vapor deposition plating, etc. can be applied.As the base steel plate, ordinary steel,
Various materials such as Al-killed steel and high-tensile steel plates can be used.
このように本発明分散めっき鋼板Ｆｉ特に加工部の耐食
性に優れているので、鋼板を製造するに際しては必ずし
も銅板両面を全面にわたって被覆しなくても、加工を予
定される部分のみあらかじめ片面或いは部分的にのみ被
覆することも有効であることは云うまでもない。In this way, the dispersion-plated steel sheet Fi of the present invention has excellent corrosion resistance, especially in the processed parts, so when manufacturing a steel plate, it is not necessary to coat both sides of the copper plate over the entire surface, but only the part that is planned to be processed can be coated on one side or partially. Needless to say, it is also effective to coat only the surface of the surface.
また、本発明の如く分散めっき層を片面に形成させる場
合、他の面はＦｅ面あるいＦｉＺｎめっき、Ｚｎ合金め
つきを施すこともできる。即ち、少なくとも片面が本発
明の要件を澗たす２層被覆層であれば、他面は本発明以
外のめつき面であっても良い。Further, when the dispersion plating layer is formed on one side as in the present invention, the other side may be plated with Fe, FiZn, or Zn alloy. That is, as long as at least one side is a two-layer coating that satisfies the requirements of the present invention, the other side may be a plated surface other than that of the present invention.
なお、本発明鋼板は自動車用などの用途に供せられるの
で、当然のことながら最終的には塗装されて使用される
ものであるが、この場合、分散めっき終了後、鋼板の少
なくとも片面にシランカップリング処理或いは化成処理
のいずれかによる後処理皮膜金形放させれば、その後の
塗装に際し塗膜−次密着性が良好となる。なお、ここで
言うシランカップリング処理とは、ビニルトリクロルシ
ラン、ビニルトリメトキシシラン等のカップリング剤を
塗布する処理、化成処理とはリン酸塩処理。Since the steel sheet of the present invention is used for applications such as automobiles, it will naturally be coated before use. In this case, at least one side of the steel sheet is coated with silane after dispersion plating is completed. If the mold is released from the post-treated film by either coupling treatment or chemical conversion treatment, good adhesion between the coating film and subsequent coating will be achieved during subsequent painting. Note that the silane coupling treatment referred to here refers to a treatment in which a coupling agent such as vinyltrichlorosilane or vinyltrimethoxysilane is applied, and the chemical conversion treatment refers to a phosphate treatment.
クロメート処理等を指す。Refers to chromate treatment, etc.
以下、実施例をもって本発明の効果をさらに具体的に説
明する。Hereinafter, the effects of the present invention will be explained in more detail with reference to Examples.
本発明鋼板のうち、片面めっき鋼板の代表的なもののめ
つき層組収及び耐食性試験、加工性試験、溶接性試験結
果を第１表にまとめて示す。Among the steel sheets of the present invention, the results of the plating layer aggregation, corrosion resistance test, workability test, and weldability test of typical single-sided plated steel sheets are summarized in Table 1.
試料扁１−１３．１５〜１９．２２〜２４．２６〜６９
．７６．７７が本発明鋼板であり、他は比較材（ス印）
である。めっき層組成は化学分析で調べた。Sample flat 1-13.15~19.22~24.26~69
．． 76.77 is the steel plate of the present invention, the others are comparative materials (marked with a cross)
It is. The composition of the plating layer was investigated by chemical analysis.
耐食性試験用のサンプルには化成処理として通常のリン
酸Ｚｎ系ディップ型のものを施し、さらにカチオンＥＤ
塗装（２０μｍ）ｆｊｒ−施した。耐食性試験としては
、冷熱サイクル腐食試験（ＯＣＴ）を行なった。ＯＣＴ
は、塩水噴霧試験に乾燥、湿潤、冷却試験を組み合わせ
たものを行なった。なお、加工部封孔あき性試験用のサ
ンプルとしてはヘム型の合わせ材を使用した。Samples for corrosion resistance tests were subjected to a normal Zn phosphate dip type chemical conversion treatment, and were further treated with cationic ED.
Painting (20 μm) fjr-applied. As a corrosion resistance test, a thermal cycle corrosion test (OCT) was conducted. OCT
conducted a salt spray test combined with dry, wet, and cool tests. Note that a hem-shaped laminated material was used as a sample for the processing part sealing test.
一方、加工性は深絞り成形後、／−１’ウダリング性全
テープテストによす調べた。On the other hand, workability was investigated by performing a /-1' undulating total tape test after deep drawing.
さらに、溶接性は２枚のめつき鋼板をめっき面を上側に
して重ね合わせ、スポット溶接を行ない、適正な溶接電
流範囲を調べた。Furthermore, weldability was determined by spot welding two plated steel plates placed one on top of the other with the plated surfaces facing upward, and examining the appropriate welding current range.
各試験の評価基準は次の通りである。The evaluation criteria for each test are as follows.
（耐食性）
加工部封孔あき性・・・（ＩＣＴ４週後最大孔あき深さ
０．１ｖｚ未満 ◎］
０．１ ｍｓ以上０．２Ｕ未満 ００．２＋−３以
上０．３Ｕ未満 Δ０．３ｕを超える場合
×
耐外面錆性・・・クロスカット部耐赤錆性（８ＥＩＴ１
０００時間）
赤錆発生なし ◎
極一部点錆発生 〇
一部赤錆発生 Δ
赤錆全面発生 ×
偏部の塗膜密着性・・・Ｃ！ｃＴ４週後クロスカりト部
最大ふくれ幅
２ｕ未満 ◎
２ｕ以上３ｕ未満 ０
３ｕ以上５ｕ未満 Δ
５ｕ以上 ×
（加工性〕
パウダリング性・・・深絞シ収形後テープテスト黒化度
の目視判定
剥離なし ◎
一部剥離 ○
半分剥離 Δ
全面剥離 ×
（溶接性）
適正溶接電流範囲
５ＫＡ以上５．５ＫＡ未満 ◎
５．５ＫＡ以上６ＫＡ未満 ０
６ＫＡ以上６．５ Ｋ Ａ未満 Δ
６．５ Ｋ Ａ以上７ＫＡ未満 ×
（総合評価）
最愛 ◎
優 ○
良 Δ
劣 Ｘ
本発明鋼板は、微粒子を含有していないＺｎ −Ｆｅ
２層めっき鋼板（Ａ７４）、Ｚｎ−Ｎｉめつき鋼板（／
に７５）及び本発明以外の分散めっき鋼板（扁７０〜７
３〕よりも優れた耐食性を示す。(Corrosion resistance) Processed part sealing property...(Maximum perforation depth less than 0.1vz after 4 weeks of ICT ◎) 0.1 ms or more and less than 0.2U 00.2+-3 or more and less than 0.3U Δ0.3u If it exceeds
× External rust resistance... Cross-cut area red rust resistance (8EIT1
000 hours) No red rust occurred ◎ Rust occurred in only a few spots 〇 Red rust occurred in some areas Δ Red rust occurred all over × Paint film adhesion in uneven areas...C! Maximum bulge width of cross-cut part less than 2u after cT 4 weeks ◎ 2u or more and less than 3u 0 3u and less than 5u Δ 5u or more × (Workability) Powderability: Visual judgment of degree of blackening in tape test after deep drawing No peeling ◎ Partial peeling ○ Half peeling Δ Full peeling × (Weldability) Appropriate welding current range 5 KA or more and less than 5.5 KA ◎ 5.5 KA or more and less than 6 KA 0 6 KA or more and less than 6.5 KA Δ 6.5 KA or more Less than 7KA × (Overall evaluation) Favorite ◎ Excellent ○ Good Δ Poor
Double-layer plated steel plate (A74), Zn-Ni plated steel plate (/
75) and dispersion-plated steel sheets other than the present invention (70 to 7
3] shows superior corrosion resistance.
Ａ１〜３，１４〜２１は微粒子含有量を変化させた場合
である。微粒子含有量が本発明の範囲内にある場合に特
に加工部の耐孔あき性が極めて良好である。微粒子含有
量が３０％以下の場合（／１ｌｈ１４）には、耐食性の
うち加工部の耐孔あき性がやや劣る。また、Ａ２０，２
１の如く９５％ヲ超えると加工部の耐孔あき性のみでな
く耐赤錆性、溶接性も劣化する。A1-3 and 14-21 are cases where the fine particle content was changed. Especially when the fine particle content is within the range of the present invention, the hole resistance of the processed part is extremely good. When the fine particle content is 30% or less (/1lh14), the corrosion resistance of the processed portion is slightly inferior. Also, A20,2
If it exceeds 95% as in No. 1, not only the hole resistance of the processed portion but also the red rust resistance and weldability deteriorate.
さらに、ＪｋＬ２２〜２５は微粒子の平均粒径を変化さ
せた場合である。平均粒径が５μ以下の場合（ム２２〜
２４）の方が加工性が良好である。５／１を超えると加
工性が劣化するＣｔＫ２５）、、ノｌａ ７６に示した
通シ、部分めっきした場合にも本分散めっき層は優れた
効果を有する。なお、試料としては、鋼板上に縞状に部
分めっきしためつき鋼板（被覆率５０％）を用いた。ま
た、ＪＦ１７７に示した通シ、シランカップリング処理
等の後処理を行なうことにより、本発明鋼板はさらに優
れた性能″ｆｒ：発揮する。Furthermore, JkL22 to JkL25 are cases where the average particle diameter of the fine particles was changed. When the average particle size is 5μ or less (Mu22~
24) has better workability. If the ratio exceeds 5/1, the workability deteriorates (CtK25), Nola76, and the present dispersion plating layer has excellent effects even when it is partially plated. The sample used was a plated steel plate (coverage rate 50%) in which stripes were partially plated on the steel plate. Further, by performing post-treatments such as through-hole treatment and silane coupling treatment as shown in JF177, the steel sheet of the present invention exhibits even more excellent performance.
なお、以上の結果は全て片面めっきに関するものである
が１両面めっきについても同等な性能を有することを本
発明者らは確認している。Although the above results are all related to single-sided plating, the present inventors have confirmed that single-sided plating also has equivalent performance.
〔発明の効果〕
以上述べた如く、本発明の高耐食性分散めっき鋼板は耐
食性のみならず加工性、溶接性にも優れた高性能のめつ
き鋼板であり、その実用的価値は誠に大きい。[Effects of the Invention] As described above, the highly corrosion-resistant dispersion-plated steel sheet of the present invention is a high-performance plated steel sheet that has excellent not only corrosion resistance but also workability and weldability, and its practical value is truly great.
代理人 弁理士 秋 沢 政 光 他１名Agent Patent Attorney Masaaki Aki Sawa 1 other person
Claims (1)
ｉ、Ｃｏ、Ｌａ、Ｃｅ、Ｂ１種以上の酸化物、炭化物、
窒化物、硼化物、燐化物、硫化物の単独あるいは複合で
平均粒径５μ以下の微粒子を重量％で３０％超、９５％
以下含有するＺｎもしくはＺｎ合金被覆層を上層とし、
ＺｎあるいはＺｎ合金被覆層を下層とする２層被覆層を
鋼板の片面あるいは両面に設けたことを特徴とする高耐
食性分散めつき鋼板。(1) Si, Al, Fe, Ti, Mo, Cu, Zn, N
i, Co, La, Ce, B1 or more oxides, carbides,
More than 30% to 95% by weight of fine particles of nitrides, borides, phosphides, and sulfides, singly or in combination, with an average particle size of 5μ or less
A Zn or Zn alloy coating layer containing the following is used as an upper layer,
A highly corrosion-resistant dispersion plated steel sheet, characterized in that a two-layer coating layer with a Zn or Zn alloy coating layer as the lower layer is provided on one or both sides of the steel plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7484086A JPS62230999A (en) | 1986-04-01 | 1986-04-01 | Dispersion-plated steel sheet having high corrosion resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7484086A JPS62230999A (en) | 1986-04-01 | 1986-04-01 | Dispersion-plated steel sheet having high corrosion resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62230999A true JPS62230999A (en) | 1987-10-09 |
| JPH0248638B2 JPH0248638B2 (en) | 1990-10-25 |
Family
ID=13558929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7484086A Granted JPS62230999A (en) | 1986-04-01 | 1986-04-01 | Dispersion-plated steel sheet having high corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62230999A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005120441A1 (en) * | 2004-05-03 | 2005-12-22 | Dgtec | Compound for a cosmetic product |
| US20140048181A1 (en) * | 2011-03-08 | 2014-02-20 | Thyssenkrupp Steel Europe Ag | Flat Steel Product and Method for Producing a Flat Steel Product |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58157995A (en) * | 1982-03-16 | 1983-09-20 | Nippon Steel Corp | Weldable painted steel plate having excellent corrosion resistance |
| JPS59123796A (en) * | 1982-12-28 | 1984-07-17 | Kawasaki Steel Corp | Production of electrogalvanized steel sheet having high corrosion resistance |
| JPS60211096A (en) * | 1984-04-03 | 1985-10-23 | Kawasaki Steel Corp | Surface treated steel sheet having high corrosion resistance |
-
1986
- 1986-04-01 JP JP7484086A patent/JPS62230999A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58157995A (en) * | 1982-03-16 | 1983-09-20 | Nippon Steel Corp | Weldable painted steel plate having excellent corrosion resistance |
| JPS59123796A (en) * | 1982-12-28 | 1984-07-17 | Kawasaki Steel Corp | Production of electrogalvanized steel sheet having high corrosion resistance |
| JPS60211096A (en) * | 1984-04-03 | 1985-10-23 | Kawasaki Steel Corp | Surface treated steel sheet having high corrosion resistance |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005120441A1 (en) * | 2004-05-03 | 2005-12-22 | Dgtec | Compound for a cosmetic product |
| US20140048181A1 (en) * | 2011-03-08 | 2014-02-20 | Thyssenkrupp Steel Europe Ag | Flat Steel Product and Method for Producing a Flat Steel Product |
| US20140057130A1 (en) * | 2011-03-08 | 2014-02-27 | Thyssenkrupp Steel Europe Ag | Flat Steel Product, Method for Production of a Flat Steel Product and Method for Production of a Component |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0248638B2 (en) | 1990-10-25 |
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| EXPY | Cancellation because of completion of term |