JPH0466694A - Production of highly corrosion resistant pb-sn alloy-plated cr-containing steel sheet excellent in coating property and adhesive strength - Google Patents
Production of highly corrosion resistant pb-sn alloy-plated cr-containing steel sheet excellent in coating property and adhesive strengthInfo
- Publication number
- JPH0466694A JPH0466694A JP17782590A JP17782590A JPH0466694A JP H0466694 A JPH0466694 A JP H0466694A JP 17782590 A JP17782590 A JP 17782590A JP 17782590 A JP17782590 A JP 17782590A JP H0466694 A JPH0466694 A JP H0466694A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- aqueous solution
- plating
- sulfuric acid
- containing steel
- 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 47
- 239000010959 steel Substances 0.000 title claims abstract description 47
- 230000007797 corrosion Effects 0.000 title claims abstract description 26
- 238000005260 corrosion Methods 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000011248 coating agent Substances 0.000 title abstract description 10
- 238000000576 coating method Methods 0.000 title abstract description 10
- 239000000853 adhesive Substances 0.000 title abstract 2
- 230000001070 adhesive effect Effects 0.000 title abstract 2
- 238000007747 plating Methods 0.000 claims abstract description 79
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 51
- 239000000956 alloy Substances 0.000 claims abstract description 51
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000007864 aqueous solution Substances 0.000 claims abstract description 25
- 239000011247 coating layer Substances 0.000 claims abstract description 22
- 238000005554 pickling Methods 0.000 claims abstract description 22
- 229910020220 Pb—Sn Inorganic materials 0.000 claims abstract description 14
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 9
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910017709 Ni Co Inorganic materials 0.000 claims abstract description 6
- 229910003267 Ni-Co Inorganic materials 0.000 claims abstract description 6
- 229910003262 Ni‐Co Inorganic materials 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229940104869 fluorosilicate Drugs 0.000 claims abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 7
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 5
- 150000002823 nitrates Chemical class 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 5
- 239000010410 layer Substances 0.000 abstract description 36
- -1 sulfuric acid ion Chemical class 0.000 abstract description 5
- 229910002651 NO3 Inorganic materials 0.000 abstract description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005238 degreasing Methods 0.000 abstract description 2
- 238000011156 evaluation Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 10
- 238000000137 annealing Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229910019043 CoSn Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 101150071746 Pbsn gene Proteins 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
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007716 flux method Methods 0.000 description 1
- 239000002828 fuel tank Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 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
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Electroplating Methods And Accessories (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、被覆性と密着性に優れた高耐食性Ｐｂ−Ｓｎ
合金めっきＣｒ含有鋼板の製造法に関するものである。Detailed Description of the Invention (Industrial Field of Application) The present invention is a highly corrosion-resistant Pb-Sn film with excellent coverage and adhesion.
The present invention relates to a method for manufacturing an alloy-plated Cr-containing steel sheet.
（従来の技術）
従来からＰｂ−Ｓｎ合金めっき鋼板は、湿潤環境で優れ
た高耐食性を示し、加工性、溶接性、ハンダ付は性にも
優れていることから、ガソリンタンク、家庭用電気製品
など広く使用されている。(Prior art) Pb-Sn alloy plated steel sheets have traditionally shown excellent corrosion resistance in humid environments, and have excellent workability, weldability, and soldering properties, so they have been used in gasoline tanks and household electrical appliances. etc. are widely used.
そのＰｂ−Ｓｎ合金めっき鋼板は、その製造過程や各種
の製品形状に成形加工する際に発生したピンホールや擦
り疵によって起こる耐食性の劣化を防止するため、例え
ば特公昭５５−５１４２６号公報のごときｒＳｎと反応
し易いＮｉやＣｏの下地めっき層を施したＰｂ−Ｓｎ合
金めっき鋼板」、特開昭６３−１８３１９１号公報のよ
うに「上下にｐｂ −Ｓｎ合金の二層めっきを施した鋼
板」など各種の鋼板が開発されている。さらに優れた耐
食性の要求に対応して、特開昭Ｂｌ −１１９６７８号
公報のようなｒＣｒ含有鋼板にＮｉやＣｏの下地めっき
層を施した後、高温度で拡散処理し、続いてＰｂ−Ｓｎ
合金めっきを施したＰｂ−Ｓｎ合金めっきＣｒ含有鋼板
」も製造されている。The Pb-Sn alloy plated steel sheet is used in order to prevent deterioration in corrosion resistance caused by pinholes and scratches that occur during the manufacturing process and when forming into various product shapes. ``Pb-Sn alloy plated steel sheet with a Ni or Co undercoating layer that easily reacts with rSn'', and ``Steel plate with two layers of pb-Sn alloy plating on top and bottom'' as in JP-A-63-183191. Various types of steel plates have been developed. In response to the demand for even better corrosion resistance, an underplating layer of Ni or Co is applied to an rCr-containing steel sheet as disclosed in Japanese Patent Application Laid-Open No. 119678, followed by diffusion treatment at high temperature, followed by Pb-Sn.
"Pb-Sn alloy plated Cr-containing steel sheet with alloy plating" is also manufactured.
しかしながら、その中でも、鋼表面に安定で強固な酸化
Ｈ（不動態化皮膜）が生成されたＣｒ含有鋼板のＰｂ−
Ｓｎ合金めつき鋼板は、必ずしも良好なめっき性能（均
一被覆性、めっき密着性、耐食性）が得られない問題が
しばしば見られた。However, among these, Pb-
Sn alloy plated steel sheets often have the problem of not necessarily providing good plating performance (uniform coverage, plating adhesion, corrosion resistance).
（発明が解決すべき課題）
上記のように、Ｐｂ−Ｓｎ合金めっきＣｒ含含銅鋼板製
造法は、工業的生産として確立されておらず、製造面あ
るいは性能面における不めっき、ピンホールの発生、下
地めっき層の剥離など未解決な問題が残されていた。(Problems to be Solved by the Invention) As mentioned above, the method for producing Pb-Sn alloy plated Cr-containing copper-containing steel sheets has not been established for industrial production, and unplatedness and pinholes occur in terms of production and performance. However, there remained unresolved problems such as peeling of the underlying plating layer.
本発明者らは、Ｃｒ含有鋼板を対象にこれらの問題を解
決した被覆性と密着性に優れた高耐食性Ｐｂ−Ｓｎ合金
めっき鋼板の製造法を提供することを目的とする。The present inventors aim to provide a method for manufacturing a highly corrosion-resistant Pb-Sn alloy plated steel sheet with excellent coverage and adhesion that solves these problems for Cr-containing steel sheets.
（課題を解決するための手段）
本発明者らは、上記目的を達成するために多くの探索実
験を試みた中から、次のようなことを知見した。(Means for Solving the Problems) The inventors of the present invention have conducted many exploration experiments to achieve the above object, and have discovered the following.
すなわち、Ｃｒ含有鋼板を、例えば仕上表面の美麗な鋼
板か短時間で得られる電解処理法とじて開発された特公
昭８３−４５４８０号公％ｉ記載の酸洗法で処理しても
、不めっきやピンホールの発生は避けられなかった。こ
の原因は、一般に冷間圧延されたＣｒ含有鋼板は、焼鈍
されて酸洗されめっきに供されるが、その際焼鈍過程で
生成されたＣｒ酸化膜の内側直下に難還元性で難溶解性
のＳ＋酸化膜を生成して、不めっきなどの諸問題を引き
起こす。図は、酸化膜の深さ方向のグロー放電分光分析
装置による成分分析結果を示す。すなわち、「ステンレ
ス鋼便覧、昭和５０年１２月２０日発行２日刊工業新聞
、第１２４９頁１表３．８」で示されるように、一般に
Ｃｒ含有鋼板には、Ｃｒの他に１％以下の８１が含有さ
れている点に問題があった。That is, even if a Cr-containing steel plate is treated with the pickling method described in Japanese Patent Publication No. 83-45480, which was developed as an electrolytic treatment method that can obtain a steel plate with a beautiful finished surface in a short time, it will not be plated. The occurrence of cracks and pinholes was unavoidable. The reason for this is that cold-rolled Cr-containing steel sheets are generally annealed, pickled, and plated, but at that time, the Cr oxide film that is generated during the annealing process has a hard-to-reducible and hard-to-dissolve Cr oxide film that is hard to reduce and hard to dissolve. This produces an S+ oxide film, causing various problems such as non-plating. The figure shows the results of component analysis in the depth direction of the oxide film using a glow discharge spectrometer. In other words, as shown in "Stainless Steel Handbook, December 20, 1975, Issue 2, Nikkan Kogyo Shimbun, Page 1249, Table 3.8," Cr-containing steel sheets generally contain 1% or less of Cr in addition to Cr. There was a problem in that it contained 81.
これまでＳｔ酸化膜は、耐食性向上の点から残存させた
方が好ましいとされているが、めっき原板として用いる
場合密着性やピンホールが発生し、さらに最悪の場合は
全面にわたって不めっきを発生する問題があった。Until now, it has been said that it is preferable to leave the St oxide film in view of improving corrosion resistance, but when used as a plating base plate, adhesion and pinholes occur, and in the worst case, non-plating occurs over the entire surface. There was a problem.
本発明は、このような知見を基に構成したものであって
、その要旨とするところは、焼鈍したＳ １；＜ ｏ、
ｔ％、Ｃｒ；＜２５％のＣｒ含有鋼板を、２０〜４００
ｇ／ｌＩの硫酸水溶液にフルオロケイ酸塩もしくはフル
オロホウ酸塩を添加し、さらに硝酸塩、硫酸塩の１種ま
たは２種を混合した酸洗水溶液中で電解酸洗し、脱脂し
、遊離硫酸が７５〜３５０ｇ ／ Ｉ）の水溶液中、あ
るいはＮｉ２″″またはｃｏ２″″あるいはその両者を
（金属イオン濃度）／（全硫酸イオン濃度）≦１１５の
硫酸水溶液中で、電流密度が７．５〜３５Ａ／ｄ１１２
、処理時間が１〜１５秒の陰極電解処理を行い、続いて
ｐＨ； ＜ ３以下のめっき洛中で厚さ０．Ｏ１〜１μ
ｓのＮｉ、ＣｏあるいはＮｉ−Ｃｏ合金の被覆層を施し
た後、Ｓｎを３〜３０％含有するＰｂ−Ｓｎ合金の被覆
層を施す被覆性と密着性に優れた高耐食性Ｐｂ−Ｓｎ合
金めっきＣｒ含有鋼板の製造法である。The present invention was constructed based on such knowledge, and its gist is that annealed S1;
t%, Cr; <25% Cr-containing steel plate, 20 to 400
A fluorosilicate or fluoroborate is added to a sulfuric acid aqueous solution of g/lI, and then electrolytically pickled and degreased in a pickling aqueous solution containing one or both of nitrates and sulfates, and the free sulfuric acid is reduced to 75 g/lI. ~350g/I) or in a sulfuric acid aqueous solution of (metal ion concentration)/(total sulfate ion concentration)≦115 Ni2'''' or co2'''' or both at a current density of 7.5 to 35 A/I). d112
, a cathodic electrolytic treatment with a treatment time of 1 to 15 seconds is performed, followed by a plating film with a thickness of 0.0. O1~1μ
High corrosion-resistant Pb-Sn alloy plating with excellent coverage and adhesion, in which a coating layer of Pb-Sn alloy containing 3 to 30% Sn is applied after applying a coating layer of Ni, Co or Ni-Co alloy of s. This is a method for manufacturing a Cr-containing steel plate.
以下、本発明について詳細に説明をする。The present invention will be explained in detail below.
本発明の対象とする鋼板は、転炉、電気炉等の溶解炉で
溶製された溶鋼を連続鋳造法あるいは造塊・分塊法を経
て製造されたスラブを熱間圧延、酸洗、冷間圧延、焼鈍
する通常の薄鋼板製造工程を経て製造したＳｊ；＜０．
１％、Ｃｒ；＜２５％のＣｒ含有鋼の焼鈍板である。The steel sheet that is the object of the present invention is a slab manufactured by continuous casting or ingot making/blowing of molten steel in a melting furnace such as a converter or electric furnace, then hot rolling, pickling, and cooling. Sj manufactured through the normal thin steel plate manufacturing process of rolling and annealing; <0.
It is an annealed plate of steel containing 1% Cr; <25% Cr.
含有成分のうちＳｉは、電解酸洗に溶解し難い強固なＳ
ｉ酸化膜を形成して、前記したように、めっき鋼板の被
覆性と密着性を劣化せしめる有害成分であるため、その
含有量を０．１％以下に抑制する必要がある。鋼中の含
有量を０．１％以下にすることによって、厚いＳｔ酸化
膜の形成を防止しまた該酸化膜を除去するまでの電解酸
洗時間を短縮し、延いては酸洗溶液の使用寿命を延長す
る効果を奏する。Among the contained components, Si is a strong S that is difficult to dissolve in electrolytic pickling.
Since it is a harmful component that forms an oxide film and deteriorates the coverage and adhesion of the plated steel sheet as described above, it is necessary to suppress its content to 0.1% or less. By reducing the content of St in the steel to 0.1% or less, the formation of a thick St oxide film can be prevented, the electrolytic pickling time required to remove the oxide film can be shortened, and the use of a pickling solution can be reduced. It has the effect of extending the lifespan.
Ｃｒは、鋼表面にＣｒの不動態化皮膜を形成し、鋼の耐
食性を向上する有効な成分として２５％以下を添加する
。このようなＣｒの作用効果は含有量と共に増加するた
め、その含有量の下限を限定するものではない。しかし
ながら、どんなに細心の注意を払ってもＰｂ−５ｎ合金
めっき作業時に生成する微量のピンホールや各種の形状
の成形加工時に発生する疵の問題は避けられず、またｐ
ｂ −５ｎ合金めっき鋼板が不純物を多量に含有する粗
悪ガソリン燃料タンクや建材などのように特に長期耐食
性が要求される用途に対しては２．５％以上、好ましく
は５％以上添加をするとよい。Cr is added in an amount of 25% or less as an effective component that forms a Cr passivation film on the steel surface and improves the corrosion resistance of the steel. Since the effects of Cr increase with the content, the lower limit of the content is not limited. However, no matter how careful you are, you cannot avoid problems such as minute pinholes generated during Pb-5n alloy plating work and scratches that occur during molding into various shapes.
b - For applications where long-term corrosion resistance is particularly required, such as inferior gasoline fuel tanks and building materials that contain large amounts of impurities, it is recommended to add 2.5% or more, preferably 5% or more. .
このようにして製造されたＣｒ含有鋼板の焼鈍板は、続
いて、２０〜４００ｇ／ｌ以上の硫酸水溶液中にフルオ
ロケイ酸塩、硝酸塩などを添加した酸洗溶液中で陰極酸
洗または陽極酸洗あるいは陰極酸洗後陽極酸洗するなど
を選択して電解処理する。The annealed Cr-containing steel sheet produced in this way is then cathodic pickled or anodic pickled in a pickling solution in which fluorosilicate, nitrate, etc. are added to a sulfuric acid aqueous solution of 20 to 400 g/l or more. Electrolytic treatment is performed by selecting washing or cathodic pickling followed by anodic pickling.
本発明において使用する硫酸水溶液は、酸化膜の溶解作
用や通電性向上から主剤に使用するものであって、２０
ｇ／１未満の薄い濃度では酸化膜の溶解作用を減じて酸
洗効率を低下する。また４００ｇ ／ （ｌを越える濃
い濃度では、酸化膜の溶解作用も飽和域に達して素地が
溶解され、過酸洗が促進され、酸洗水溶液の性能劣化を
早める。さらに、硫酸水溶液中に選択的に添加されるフ
ルオロケイ酸ソーダ、フルオロケイ酸カリウムの如きフ
ルオロケイ酸塩もしくはフルオロホウ酸ソーダ、フルオ
ロホウ酸カリウムの如きフルオロホウ酸塩は、酸化膜の
溶解速度を大幅に助長させる有効な添加剤で、焼鈍板の
鋼成分や酸化膜厚みなどによってその程度は異なるか、
０．５ｇ／ｌ以上の添加が好ましい。さらにまた選択的
に添加される硝酸塩、硫酸塩の１種または２種は、Ｃｒ
酸化膜を溶解させて素地の過酸洗を抑制する効果がある
。中でも硝酸塩では硝酸ソーダが最も一般的であるが、
硝酸カリウムや硝酸アンモニウムなどあらゆる塩が使用
される。また硫酸塩では、硫酸ナトリウムか最もよい。The sulfuric acid aqueous solution used in the present invention is used as a main agent for dissolving oxide films and improving conductivity, and is
If the concentration is less than 1 g/1, the dissolving action of the oxide film will be reduced and the pickling efficiency will be lowered. In addition, at a high concentration exceeding 400 g/l, the dissolving action of the oxide film also reaches the saturation range and the substrate is dissolved, promoting overpickling and hastening the deterioration of the performance of the pickling aqueous solution. Fluorosilicates such as sodium fluorosilicate and potassium fluorosilicate, or fluoroborates such as sodium fluoroborate and potassium fluoroborate, which are added as additives, are effective additives that greatly accelerate the dissolution rate of the oxide film. , does the degree of damage vary depending on the steel composition of the annealed plate, the thickness of the oxide film, etc.?
It is preferable to add 0.5 g/l or more. Furthermore, one or both of the nitrates and sulfates that are selectively added are Cr
It has the effect of dissolving the oxide film and suppressing overpickling of the substrate. Among the nitrates, sodium nitrate is the most common, but
Any salt can be used, including potassium nitrate and ammonium nitrate. Among sulfates, sodium sulfate is the best.
このようにして電解酸洗された焼鈍板は、オルソケイ酸
ソーダあるいはリン酸ソーダなどに界面活性を添加した
水溶液中で浸漬処理あるいは電解処理された後、遊離硫
酸が７５〜３５０ｇ／Ｎの水溶液中、またはＮｉ２″″
、Ｃｏ”″のそれぞれあるいはその両者を（金属イオン
濃度）／（全硫酸イオン濃度）≦１１５の硫酸水溶液中
で、電流密度が７．５〜３５Ａ／ｄｍ２、処理時間が１
〜１５秒の陰極電解処理をする。この処理は、前記の電
解酸洗処理後大気中の運搬過程または放置過程において
生成したＣｒの不動態酸化膜をめっき直前に溶解除去す
ることを目的としたものである。従って、遊離硫酸の濃
度はその酸化膜の溶解性から規定したものであって、７
５ｇ／ｌＩ未満の、薄い濃度では鋼板の表面に生成され
たＣｒの不動態酸化膜を均一に溶解除去して表面を活性
化することが困難となる。The annealed plate electrolytically pickled in this way is immersed or electrolytically treated in an aqueous solution containing surfactants such as sodium orthosilicate or sodium phosphate, and then immersed in an aqueous solution containing 75 to 350 g/N of free sulfuric acid. , or Ni2″″
, Co"" or both in a sulfuric acid aqueous solution with (metal ion concentration)/(total sulfate ion concentration)≦115 at a current density of 7.5 to 35 A/dm2 and a treatment time of 1.
Perform cathodic electrolysis treatment for ~15 seconds. The purpose of this treatment is to dissolve and remove the passive oxide film of Cr, which was generated during the transport process in the atmosphere or during the storage process after the electrolytic pickling process, just before plating. Therefore, the concentration of free sulfuric acid is determined based on the solubility of the oxide film, and is 7
At a thin concentration of less than 5 g/lI, it becomes difficult to uniformly dissolve and remove the passive Cr oxide film formed on the surface of the steel sheet and activate the surface.
また３５０ｇ／ｌ）を越える過剰な濃度は、Ｃｒ不動態
酸化膜の溶解除去が過飽和域に達すると共に、洛中にミ
ストを発生し、処理装置の損耗を著しく早めるなど多く
の問題かある。In addition, an excessive concentration exceeding 350 g/l) causes many problems such as dissolution and removal of the Cr passive oxide film reaching the supersaturation range, generation of mist in the air, and extremely accelerated wear and tear on the processing equipment.
また硫酸水溶液中にＮｉ２＋またはＣｏ２“あるいはそ
の両者を（金属イオン濃度）／（全硫酸イオン濃度）≦
１１５の添加量で含有させることにより、焼鈍板の酸化
膜を効率的に除去しながら、めっき密着性を向上させる
Ｎｉ、Ｃｏの微量を同時析出する。しかし硫酸水溶液中
の金属イオン濃度が１１５を越える場合、酸化膜の溶解
除去能が低下して活性化されない焼鈍板の表面にめっき
層の生成あるいはこれら金属の水酸化物や酸化物を析出
し、均一な被覆性やめっき外観を損なう問題がある。In addition, Ni2+ or Co2" or both in the sulfuric acid aqueous solution (metal ion concentration) / (total sulfate ion concentration) ≦
By adding Ni in an amount of 115, trace amounts of Ni and Co, which improve plating adhesion, are simultaneously precipitated while efficiently removing the oxide film of the annealed plate. However, if the metal ion concentration in the sulfuric acid aqueous solution exceeds 115, the ability to dissolve and remove the oxide film decreases, and a plating layer is formed on the surface of the annealed plate that is not activated, or hydroxides and oxides of these metals are deposited. There is a problem that uniform coverage and plating appearance are impaired.
この陰極電解処理は、酸化膜の溶解除去と金属の同時析
出から得られる範囲から規定したものであって、電流密
度は７．５Ａ／ｄｍ２以上、また処理時間は１〜１５秒
で行う。この場合電流密度が７．５Ａ／ｄｍ２未満では
その効果が得られない。その反対に電流密度が３５Ａ／
ｄｉ２を越えると、焼鈍板のもつ高い比抵抗からコンダ
クタ−ロールと処理浴との間で発生する高温度によって
、焼鈍板が酸化される問題がある。また処理時間が１秒
未満の短時間ではその効果が得られず、１５秒を越える
長時間ではその効果が飽和すると共に、Ｎｉ等の金属イ
オンの析出部に更に重畳して金属イオンが析出し、部分
的に厚さの異なる金属めっき層か生成され、次いで行な
われる金属めっきの厚さも不均一になる。従って、本発
明の処理時間は１〜１５秒間、好ましくは１．５〜７．
５秒間である。This cathodic electrolytic treatment is specified based on the range obtained by dissolving and removing the oxide film and co-precipitating the metal, and is performed at a current density of 7.5 A/dm2 or more and a treatment time of 1 to 15 seconds. In this case, the effect cannot be obtained if the current density is less than 7.5 A/dm2. On the other hand, the current density is 35A/
When di2 is exceeded, there is a problem that the annealed plate is oxidized due to the high temperature generated between the conductor roll and the treatment bath due to the high specific resistance of the annealed plate. In addition, if the treatment time is short, less than 1 second, the effect cannot be obtained, and if the treatment time is longer than 15 seconds, the effect is saturated, and the metal ions are further superimposed on the precipitated area of metal ions such as Ni. , a metal plating layer having a partially different thickness is generated, and the thickness of the subsequent metal plating also becomes non-uniform. Therefore, the treatment time of the present invention is 1 to 15 seconds, preferably 1.5 to 7 seconds.
It is 5 seconds.
次いで、水洗した後、Ｎｉめっき、Ｃｏめっき、あるい
はＮｉ−Ｃｏめっき処理を施す。このめっき層は、Ｐｂ
−８ｎ合金めっきの下地処理層としてピンホールか少な
く、密着性に優れていることが必要である。そのために
は、金属イオンのＮｉ” Ｃｏ２° Ｎ ｉ ”＋Ｃ
ｏ”を含有するめっき浴を用いて下地めっき層を施す。Next, after washing with water, Ni plating, Co plating, or Ni-Co plating treatment is performed. This plating layer is Pb
As a base treatment layer for -8n alloy plating, it is necessary to have few pinholes and excellent adhesion. For that purpose, the metal ion Ni"Co2°N i "+C
A base plating layer is applied using a plating bath containing "o".
この下地被覆層の厚さが０．０１−未満てはＰｂ−３ｎ
合金めつき浴中のＳｎと下地被覆層との均一緻密な合金
層か生成され難く、均一被覆性とめつき層の密着性が得
られず、耐食性に優れた合金めっき鋼板が得られない。If the thickness of this base coating layer is less than 0.01, Pb-3n
It is difficult to form a uniform and dense alloy layer of Sn in the alloy plating bath and the underlying coating layer, and uniform coating and adhesion of the plating layer cannot be obtained, making it impossible to obtain an alloy-plated steel sheet with excellent corrosion resistance.
また、下地被覆層の厚さが１ｔｌｒａを越える場合は、
Ｓｎとの反応で生成されるＮｉ−５ｎ。In addition, if the thickness of the base coating layer exceeds 1 tlra,
Ni-5n produced by reaction with Sn.
Ｃｏ−８ｎあるいはＮｉ −Ｃｏ −５ｎ合金層が硬
くて脆いため、成形加工時にこの合金層にクラックを発
生し、めっき層を剥離し、耐食性か著しく劣化する。従
って、本発明ではこの下地被覆層の厚さは０．０１〜１
即とする。その好ましくは０．０３〜０．５顔である。Since the Co-8n or Ni-Co-5n alloy layer is hard and brittle, cracks occur in this alloy layer during molding, the plating layer peels off, and the corrosion resistance deteriorates significantly. Therefore, in the present invention, the thickness of this base coating layer is 0.01 to 1
Immediately. The preferred range is 0.03 to 0.5.
また、本発明においては、この下地めっき浴にｐＨが３
．０以下の浴を使用する。すなわち、めっき浴のｐＨか
３．０以下では、下地被覆層処理後めっき工程までの間
のＮｉ等の析出物表面の酸化あるいはこれら析出物のピ
ンホール部での原板の再酸化による酸化膜を除去する効
果が大きい。その結果、より一層の均一被覆性に優れ、
ピンホールか少なく、密着性に優れたＮｉ等の下地被覆
が得られる。In addition, in the present invention, this base plating bath has a pH of 3.
．． Use a bath with a temperature below 0. In other words, if the pH of the plating bath is below 3.0, an oxide film may be formed due to oxidation of the surface of precipitates such as Ni or re-oxidation of the original plate at the pinholes of these precipitates during the period between the base coating layer treatment and the plating process. It has a great removal effect. As a result, it has excellent even coverage,
A base coating made of Ni or the like with few pinholes and excellent adhesion can be obtained.
特にｐＨ２，５以下が好ましい。In particular, a pH of 2.5 or less is preferred.
次に、この下地めっき層を施した後、水洗し、あるいは
希塩酸等の水溶液でその表面を活性化した後、７．ｎＣ
１２を主成分とするフラックス処理をし、Ｐｂ−５ｎ合
金めっきを行なう。このＰｂ−５ｎ合金めっき浴にはＳ
ｎを３〜３０％含有するめっき浴を使用する。Ｓｎ含有
量が３％未満では、良好な下地被覆層が十分に形成され
てもＳｎとの反応により形成される下地被覆層との合金
層の生成が不十分で、均一緻密な合金層が生成され難い
ためＰｂ−３ｎ合金めっき層の均一な被覆性、耐食性等
が得られない。また、Ｓｎ含有量が３０％を越えると下
地被覆層とＳｎとの合金層生成量が多くなり、成形加工
時に合金層がクラック発生源となって、加工後の耐食性
と成形加工性を劣化する等の欠点を生じる。従って、Ｐ
ｂ−５ｎ合金めっき浴のＳｎ含有量は３〜３０％、好ま
しくは５〜２５％である。尚、前記のＮｆ、Ｃｏ等の下
地被覆処理あるいはＰｂ−３ｎ合金めつきにおいて、各
々不可避的に含有される数％の不純物、例えば下地被覆
処理にＳ、ＦｃあるいはＰｂ−５ｎ合金めっきにＳｂ、
Ｃｕ等が含有されても本発明の目的に支障とならない。Next, after applying this base plating layer, after rinsing with water or activating the surface with an aqueous solution such as dilute hydrochloric acid, 7. nC
A flux treatment containing 12 as the main component is performed, and Pb-5n alloy plating is performed. This Pb-5n alloy plating bath contains S
A plating bath containing 3 to 30% n is used. If the Sn content is less than 3%, even if a good base coating layer is sufficiently formed, the formation of an alloy layer with the base coating layer formed by reaction with Sn is insufficient, and a uniform and dense alloy layer is formed. Therefore, it is difficult to obtain uniform coverage, corrosion resistance, etc. of the Pb-3n alloy plating layer. Furthermore, if the Sn content exceeds 30%, the amount of alloy layer formed between the base coating layer and Sn increases, and the alloy layer becomes a source of cracks during forming, deteriorating the corrosion resistance and formability after forming. This results in disadvantages such as: Therefore, P
The Sn content of the b-5n alloy plating bath is 3 to 30%, preferably 5 to 25%. In addition, in the base coating treatment of Nf, Co, etc. or Pb-3n alloy plating, several percent of impurities are unavoidably contained, for example, S in the base coating treatment, Sb in Fc or Pb-5n alloy plating,
Even if Cu or the like is contained, it does not impede the purpose of the present invention.
本発明は、前記したように溶融Ｐｂ−８ｎ合金めっきに
適用される場合、めっき浴中のＳｎと反応して合金層の
形成を緻密化し、Ｐｂ−３ｎ合金めっきの性能向上に有
効であり、また電気ｐｂＳｎ合金めっきに適用しても構
わない。この場合においても、めっき原板の表面性状が
劣り、活性化処理が不十分な場合は溶融めっきの場合と
同様に電気Ｐｂ−３ｎ合金めつき層の均一被覆性が劣り
、ピンホールが多くなり、めっき層の密着性が劣る。こ
の欠点を、本発明によってＮｉ系の良好な下地被覆層を
施して電気Ｐｂ−５ｎ合金めっき層を設けることによっ
て防止することができる。As described above, when applied to hot-dip Pb-8n alloy plating, the present invention reacts with Sn in the plating bath to densify the formation of the alloy layer, and is effective in improving the performance of Pb-3n alloy plating. It may also be applied to electric pbSn alloy plating. Even in this case, if the surface quality of the plating original plate is poor and the activation treatment is insufficient, the uniform coverage of the electrolytic Pb-3n alloy plating layer will be poor and there will be many pinholes, as in the case of hot-dip plating. The adhesion of the plating layer is poor. This drawback can be prevented according to the present invention by applying a good Ni-based undercoating layer and providing an electrolytic Pb-5n alloy plating layer.
さらに、このＰｂ−３ｎ合金中のＳｎとの濡れ性の良好
なＮｉ系の下地被覆層が存在することにより、製品が溶
接あるいは半田接合される場合、その熱影響部に均一緻
密な合金層が生成される効果か得られる。すなわち、Ｎ
ｉ系の下地被覆層を形成させずに直接Ｐｂ−３ｎ合金め
っき層を設けた場合、上記のような熱影響部で溶融Ｐｂ
−５ｎが凝固する時にピンホールを発生し易く、耐食性
劣化の原因となる。Ｎｉ系下地被覆層が存在する場合は
Ｎｉ−３ｎ、Ｃｏ−５ｎ、Ｎｉ −ＣｏＳｎ系合金層の
形成によりピンホールの生成を抑制する効果が得られ、
耐食性の劣化を防止する。Furthermore, due to the presence of the Ni-based base coating layer that has good wettability with Sn in this Pb-3n alloy, when the product is welded or soldered, a uniform and dense alloy layer is formed in the heat affected zone. You can get the effect generated. That is, N
When a Pb-3n alloy plating layer is directly provided without forming an i-based base coating layer, molten Pb
-5n tends to generate pinholes when it solidifies, causing deterioration in corrosion resistance. When a Ni-based base coating layer is present, the formation of a Ni-3n, Co-5n, or Ni-CoSn-based alloy layer has the effect of suppressing the formation of pinholes.
Prevents deterioration of corrosion resistance.
以上のように本発明によれば焼鈍中に生成する強固な酸
化膜を比較的短時間で除去し、酸洗処理後に大気中で生
成する安定な不働態膜もめっき直前に除去でき、均一被
覆性、耐食性あるいはめっき層の密着性に優れたＰｂ−
３ｎ合金めっき鋼板を製造することができる。As described above, according to the present invention, the strong oxide film that is generated during annealing can be removed in a relatively short time, and the stable passive film that is generated in the atmosphere after pickling treatment can also be removed just before plating, resulting in uniform coverage. Pb-, which has excellent corrosion resistance, corrosion resistance, and adhesion of the plating layer.
3N alloy plated steel sheet can be manufactured.
尚、本発明のＰｂ−５ｎ合金めっき鋼板の表面に、更に
一層の耐食性向上あるいは塗装性能の向上を目的として
、リン酸あるいはクロム酸等を主成分とする水溶液を用
いて化成処理を施してもよい。In addition, the surface of the Pb-5n alloy plated steel sheet of the present invention may be subjected to chemical conversion treatment using an aqueous solution containing phosphoric acid or chromic acid as a main component for the purpose of further improving corrosion resistance or coating performance. good.
（実 施 例）
０．８ｍまて冷間圧延された後、焼鈍された第１表に示
す鋼成分の素材をめっき原板として、第２表及び以下に
示す処理法を適用してＰｂ−５ｎ合金めっき鋼板を製造
した。(Example) Using the steel material shown in Table 1 that was cold rolled to 0.8 m and then annealed as a plating base plate, Pb-5n was prepared by applying the treatment method shown in Table 2 and below. Alloy plated steel sheets were manufactured.
（酸洗処理）
焼鈍処理により鋼板上に生成した酸化膜を、ｌｏｎｇ／
ｉｔ Ｈ２Ｓ ０４ １００ ｇ／ｌ−Ｎ ａ Ｎ Ｏ
３１００ｇ ／ １） Ｎ ａ ２ Ｓ ０４ １０
ｇ ／ （ＩＮ２ａＳ ｉ Ｆ６−ＡＯｇ／ｌＩ Ｎａ
ＢＦ４系酸洗浴中で陽極電解処理により剥離した。処理
浴の温度、電解電流密度、電解酸洗時間を第２表に示し
た。(Pickling treatment) The oxide film generated on the steel plate by the annealing treatment is
it H2S 04 100 g/l-N a N O
3100g / 1) N a 2 S 04 10
g / (IN2aS i F6-AOg/lI Na
It was peeled off by anodic electrolysis in a BF4 pickling bath. Table 2 shows the temperature of the treatment bath, electrolytic current density, and electrolytic pickling time.
（脱脂処理）
６０℃に保った４％オルソケイ酸ソーダ水溶液中におい
て、電流密度ｌＯＡ／ｄＩ１１２、電解時間４秒の陰極
電解処理を行った。(Degreasing Treatment) Cathodic electrolysis treatment was performed in a 4% sodium orthosilicate aqueous solution maintained at 60° C. at a current density of lOA/dI of 112 and an electrolysis time of 4 seconds.
（陰極酸洗処理）
５０℃に保っｔ： １５０ｇ／ｌＩＨ２ＳＯ４４０ｆ／
ｌ Ｎ ｉ ＳＯ４・７Ｈ２０２０ｆ／ｌ） Ｃｏ ５
０４７Ｈ２０水溶液中において、電流密度２０Ａ／ｄｏ
＋２電解時間４秒の陰極電解処理を行った。(Cathode pickling treatment) Maintained at 50℃: 150g/lIH2SO440f/
l N i SO4・7H2020f/l) Co 5
In 047H20 aqueous solution, current density 20A/do
+2 Cathode electrolysis treatment was performed for an electrolysis time of 4 seconds.
（下地被覆層処理）
以下に示す組成を有するめっき浴で電気めっきすること
により下地被覆層を形成させた。ＮｊとＣｏの合金の組
成はＮ ｊ Ｓ Ｏ４” ７Ｈ２０ＣｏＳＯ４・７Ｈ２
０−ＮｉＣｊＪ２−２Ｈ２０−ＣｏＣｊＪ２・２Ｈ２０
の含有量を調整することにより変えた。めっき浴の温度
は５０℃、電解電流密度はＩＯＡ／ｄｍ２であった。形
成させた下地被覆処理層の合金組成、被覆量及びめっき
浴のｐ）Ｉは第２表に掲げた。(Base coating layer treatment) A base coating layer was formed by electroplating with a plating bath having the composition shown below. The composition of the alloy of Nj and Co is N j S O4” 7H20CoSO4・7H2
0-NiCjJ2-2H20-CoCjJ2・2H20
This was changed by adjusting the content of The temperature of the plating bath was 50°C, and the electrolytic current density was IOA/dm2. The alloy composition, coating amount, and p)I of the plating bath of the formed base coating layer are listed in Table 2.
ＮｉＳＯ４・７Ｈ２０＋
ＣｏＳＯ４”７Ｈ２０２”ｇ／ｌＩ
Ｎ ｉ Ｃｉ） ２ ・７Ｈ２０＋
ＣｏＣＮ２・２Ｈ２０４５ｇ／ｇ
ホ ウ 酸 ３
０ｇ＃ｐＨ１〜４
（硫酸で調整）
（Ｐｂ−３關合金めっき処理）
Ｐｂ−８關合金めっき処理は溶融めっき法あるいは電気
めっき法により行った。その処理条件を以下に示す。NiSO4・7H20+ CoSO4”7H202”g/lI Ni Ci) 2 ・7H20+ CoCN2・2H2045g/g Boric acid 3
0 g #pH 1 to 4 (adjusted with sulfuric acid) (Pb-3 alloy plating treatment) Pb-8 alloy plating treatment was performed by hot-dip plating or electroplating. The processing conditions are shown below.
溶融めっき処理の場合
下地被覆層処理して水洗後、２％ＨＣｇ溶液中に７０℃
で４秒間浸漬して、ＺｎＣｊｌ）２系フラツクスを用い
た湿式フラックス法により片面当り５０ｇ／ｒｄのＰｂ
−８％Ｓｎ溶融合金めっきを行った。In the case of hot-dip plating, after treating the base coating layer and washing with water, place the plate in a 2% HCg solution at 70°C.
50g/rd of Pb per side by wet flux method using ZnCjl)2 system flux.
-8% Sn molten alloy plating was performed.
・ 電気めっきの場合
下地被覆層処理して水洗後、片面当り５０ｇ／ｄのＰｂ
−１０％Ｓｎ電気合金めっきを行った。その処理条件は
以下に示した。- In the case of electroplating, after treating the base coating layer and washing with water, 50 g/d of Pb per side.
-10%Sn electroalloy plating was performed. The processing conditions are shown below.
Ｐｂ（Ｂ Ｆ４） ２ ３４０ｇ／ＦＳｎ（
Ｂ Ｆ４ ） ２ ５０ｔ／ｌＨＢＦ４Ｌ
ＯＯ１ｒ／ｆ）
ヒドロキノン ５ ｇ ／ ｉ）浴温
度 ５０℃
電流密度 ３０Ａ／ｄＩＩ１２（評価試験
方法及び評価規１）
■、めっき被覆層の均一被覆性
溶融めっき材の場合は以下の評価規準で評価して、その
均一被覆性を検討した。Pb(B F4) 2 340g/FSn(
B F4) 2 50t/lHBF4L
OO1r/f) Hydroquinone 5 g/i) Bath temperature 50°C Current density 30A/dII12 (Evaluation test method and evaluation criteria 1) ■. Uniform coverage of the plating layer In the case of hot-dip plated materials, the following evaluation criteria were used to evaluate: We investigated its uniform coverage.
◎・・・めっき浴の濡れ性極めて良好で、めっき外観極
めて良好
Ｏ・・・めっき浴の濡れ性比較的良好で、１０ｄＩＩ１
２の評価面に対して流れ模様（めっき厚さの部分的に厚
い部分）が２点以下発生
△・・・めっき浴の濡れ性若干劣るため、１０ｄｍ２の
評価面にざらつき状の点状欠陥部（微小不めっきが１０
数点群発）が発生
×・・・めっき浴の濡れ性著しく劣るため、１Ｏｄａ＋
２の評価面にざらつき状の点状欠陥部が多量に発生
２、めっき層の密着性
曲率半径０．８關て衝撃曲げ加工を行い、セロテープ（
登録商標）を貼付、剥離して、めっき層の剥離状況を調
査した。なお、評価規準は以下の通りである。◎...The wettability of the plating bath is extremely good, and the appearance of the plating is very good.O...The wettability of the plating bath is relatively good, 10dII1
2 or less flow patterns (partially thick parts of the plating thickness) occurred on the evaluation surface of 2.△...Due to slightly poor wettability of the plating bath, there were rough dot-like defects on the evaluation surface of 10 dm2. (Minute non-plating is 10
1 Oda+ due to extremely poor wettability of the plating bath.
A large number of rough point-like defects occurred on the evaluation surface of 2.2, the plating layer was subjected to impact bending with a radius of curvature of 0.8, and cellophane tape (
(registered trademark) was applied and peeled off, and the peeling status of the plating layer was investigated. The evaluation criteria are as follows.
◎・・・めっき層の剥離なく、セロテープ（登録商標）
への剥離物の付着なし
○・・・めっき層の表面部が若干剥離、セロテープ（登
録商標）に極軽微な剥離物が付着
△・・・めっき層の鋼板界面からの部分的剥離が発生、
セロテープ（登録商標）への剥離物の付着が明瞭に認め
られる
Ｘ・・・めっき層全面剥離
３、耐食性能
（１）評価法Ａ
Ａｌ２０Ｘ１２ｏサイズの鋼板について、塩水噴霧試験
２４０時間実施後、端部のシール部を除いた１００Ｘ１
００＋ａｍの評価面を１×１龍サイズのます目１００個
に区分して、赤錆の発生したまず目の数を測定して、そ
の耐食性を評価した。◎・・・No peeling of plating layer, Sellotape (registered trademark)
No peeling material adhered to ○... The surface of the plating layer peeled off slightly, very slight peeling material adhered to Sellotape (registered trademark) △... Partial peeling of the plating layer from the steel plate interface occurred,
Adhesion of peeled substances to Sellotape (registered trademark) is clearly observed 100X1 excluding the seal part
The evaluation surface of 00+am was divided into 100 squares of 1×1 dragon size, and the number of squares where red rust occurred was measured to evaluate its corrosion resistance.
◎・・・赤錆発生個数５個以下
Ｏ・・・赤組発生個数６〜１０個
△・・・赤錆発生個数１１〜３０個
×・・・赤錆発生個数３１個以上
（２）評価法Ｂ
ブランクサイズ径１５０ｍｍの鋼板を用いて、しわ押え
圧力２０００ ｋｇで円筒成形加工を行なって、径７５
１１１Ｘ高さ４０ｍｍの円筒型容器を作成して評価材と
した。この評価材にガソリン７部と、１９４１度のＮａ
Ｃ４）を含有する水溶液３部とからなる腐食試験液を充
填して耐ガソリン性を対象とした評価試験を実施した。◎...Number of red rust occurrences 5 or less O...Number of red rust occurrences 6 to 10 △...Number of red rust occurrence 11 to 30 ×...Number of red rust occurrence 31 or more (2) Evaluation method B Blank Using a steel plate with a size diameter of 150 mm, cylindrical molding was performed with a wrinkle pressing pressure of 2000 kg, and the diameter was 75 mm.
A cylindrical container measuring 111×40 mm in height was prepared and used as an evaluation material. 7 parts of gasoline and 1941 degree Na
An evaluation test for gasoline resistance was conducted by filling a corrosion test liquid consisting of 3 parts of an aqueous solution containing C4).
６箇月間室温に放置した後、その赤錆発生状況を調査し
、以下の評価基準で評価した。After being left at room temperature for 6 months, the occurrence of red rust was investigated and evaluated using the following evaluation criteria.
◎・・・赤錆発生状況３個以下
○・・・赤錆発生個数４〜ｌＯ個以下
△・・・赤錆発生個数１１〜２０個以下×・・・赤組発
生個数２１個以上
（発明の効果）
以上説明したように本発明法により、成分を調整した鋼
板を使用し、焼鈍時に生成した強固な酸化皮膜を短時間
で除去し、またその後生成した不働態膜もめっき前に除
去して活性表面とすることかでき、均一な被覆性、密着
性を有し、しかも耐食性の優れたＰｂ−５部合金めっき
鋼板を得ることができる。◎...Situation of occurrence of red rust 3 or less ○...Number of red rust occurrence 4 to 10 or less △...Number of red rust occurrence 11 to 20 or less ×...Number of red rust occurrence 21 or more (effect of the invention) As explained above, by using the method of the present invention, the strong oxide film generated during annealing is removed in a short time by using a steel plate with adjusted composition, and the passive film that is subsequently formed is also removed before plating to surface the active surface. As a result, it is possible to obtain a Pb-5-part alloy plated steel sheet having uniform coverage and adhesion and excellent corrosion resistance.
第１図は１１％Ｃｒ及び０，４％Ｓｉが含有され、８５
０℃で２分間焼鈍された鋼板をグロー放電分光分析装置
を用いて酸化膜深さ方向分析したものを示す。
第１図
復代理人Figure 1 contains 11% Cr and 0.4% Si, 85
This figure shows an oxide film depth direction analysis of a steel plate annealed at 0° C. for 2 minutes using a glow discharge spectrometer. Figure 1 Sub-agent
Claims (2)
ｒ含有鋼板を、２０〜４００ｇ／ｌの硫酸水溶液にフル
オロケイ酸塩もしくはフルオロホウ酸塩を添加し、さら
に硝酸塩、硫酸塩の１種または２種を混合した酸洗水溶
液中で電解酸洗し、脱脂し、遊離硫酸が７５〜３５０ｇ
／ｌの水溶液中で電流密度が７．５〜３５Ａ／ｄｍ＾２
、処理時間が１〜１５秒の陰極電解処理を行い、続いて
ｐＨ；＜３以下のめっき浴中で厚さ０．０１〜１μｍの
Ｎｉ、ＣｏあるいはＮｉ−Ｃｏ合金の被覆層を施した後
、Ｓｎを３〜３０％含有するＰｂ−Ｓｎ合金めっきを施
すことを特徴とする被覆性と密着性に優れた高耐食性Ｐ
ｂ−Ｓｎ合金めっきＣｒ含有鋼板の製造法。(1) Annealed Si; <0.1%, Cr; <25% C
The R-containing steel plate is electrolytically pickled in an aqueous pickling solution in which a fluorosilicate or fluoroborate is added to an aqueous solution of 20 to 400 g/l of sulfuric acid, and one or two of nitrates and sulfates are mixed. Defatted, free sulfuric acid 75-350g
/l aqueous solution with a current density of 7.5 to 35 A/dm^2
, after performing cathodic electrolysis treatment with a treatment time of 1 to 15 seconds, followed by applying a coating layer of Ni, Co or Ni-Co alloy with a thickness of 0.01 to 1 μm in a plating bath with a pH of <3 or less. , high corrosion resistance P with excellent coverage and adhesion, characterized by applying Pb-Sn alloy plating containing 3 to 30% Sn.
b-Method for producing Sn alloy plated Cr-containing steel sheet.
ｒ含有鋼板を、２０〜４００ｇ／ｌの硫酸水溶液にフル
オロケイ酸塩もしくはフルオロホウ酸塩を添加し、さら
に硝酸塩、硫酸塩の１種または２種を混合した酸洗水溶
液中で電解酸洗し、脱脂し、Ｎｉ＾２＾＋またはＣｏ＾
２＾＋あるいはその両者を（金属イオン濃度）／（全硫
酸イオン濃度）≦１／５の硫酸水溶液中で電流密度が７
．５〜３５Ａ／ｄｍ＾２、処理時間が１〜１５秒の陰極
電解処理を行い、続いてｐＨ；＜３以下のめっき浴中で
厚さ０．０１〜１μｍのＮｉ、ＣｏあるいはＮｉ−Ｃｏ
合金の被覆層を施した後、Ｓｎを３〜３０％含有するＰ
ｂ−Ｓｎ合金めっきを施すことを特徴とする被覆性と密
着性に優れた高耐食性Ｐｂ−Ｓｎ合金めっきＣｒ含有鋼
板の製造法。(2) Annealed Si; <0.1%, Cr; <25% C
The R-containing steel plate is electrolytically pickled in an aqueous pickling solution in which a fluorosilicate or fluoroborate is added to an aqueous solution of 20 to 400 g/l of sulfuric acid, and one or two of nitrates and sulfates are mixed. Degrease and coat with Ni^2^+ or Co^
2^+ or both at a current density of 7 in a sulfuric acid aqueous solution with (metal ion concentration)/(total sulfate ion concentration) ≦ 1/5.
．． 5 to 35 A/dm^2 and a treatment time of 1 to 15 seconds, followed by Ni, Co, or Ni-Co with a thickness of 0.01 to 1 μm in a plating bath with a pH of <3 or less.
After applying the alloy coating layer, P containing 3 to 30% Sn
A method for producing a highly corrosion-resistant Pb-Sn alloy-plated Cr-containing steel sheet with excellent coverage and adhesion, characterized by applying b-Sn alloy plating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2177825A JP2726144B2 (en) | 1990-07-05 | 1990-07-05 | Manufacturing method of high corrosion resistance Pb-Sn alloy plated Cr-containing steel sheet with excellent coverage and adhesion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2177825A JP2726144B2 (en) | 1990-07-05 | 1990-07-05 | Manufacturing method of high corrosion resistance Pb-Sn alloy plated Cr-containing steel sheet with excellent coverage and adhesion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0466694A true JPH0466694A (en) | 1992-03-03 |
| JP2726144B2 JP2726144B2 (en) | 1998-03-11 |
Family
ID=16037763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2177825A Expired - Fee Related JP2726144B2 (en) | 1990-07-05 | 1990-07-05 | Manufacturing method of high corrosion resistance Pb-Sn alloy plated Cr-containing steel sheet with excellent coverage and adhesion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2726144B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007254848A (en) * | 2006-03-24 | 2007-10-04 | Nippon Steel Corp | METHOD FOR MANUFACTURING MULTILAYER Ni-DIFFUSION PLATED STEEL SHEET |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61266596A (en) * | 1985-05-20 | 1986-11-26 | Nippon Steel Corp | Steel sheet for fuel container |
| JPH02153095A (en) * | 1988-12-05 | 1990-06-12 | Nippon Steel Corp | Production of pb-sn alloy plated steel sheet having high corrosion resistance, uniform covering property and superior adhesion of coating layer |
-
1990
- 1990-07-05 JP JP2177825A patent/JP2726144B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61266596A (en) * | 1985-05-20 | 1986-11-26 | Nippon Steel Corp | Steel sheet for fuel container |
| JPH02153095A (en) * | 1988-12-05 | 1990-06-12 | Nippon Steel Corp | Production of pb-sn alloy plated steel sheet having high corrosion resistance, uniform covering property and superior adhesion of coating layer |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007254848A (en) * | 2006-03-24 | 2007-10-04 | Nippon Steel Corp | METHOD FOR MANUFACTURING MULTILAYER Ni-DIFFUSION PLATED STEEL SHEET |
| JP4612573B2 (en) * | 2006-03-24 | 2011-01-12 | 新日本製鐵株式会社 | Method for producing multilayer Ni diffusion plated steel sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2726144B2 (en) | 1998-03-11 |
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