JPS5817254B2 - Method for improving corrosion resistance of galvanized steel - Google Patents
Method for improving corrosion resistance of galvanized steelInfo
- Publication number
- JPS5817254B2 JPS5817254B2 JP56071983A JP7198381A JPS5817254B2 JP S5817254 B2 JPS5817254 B2 JP S5817254B2 JP 56071983 A JP56071983 A JP 56071983A JP 7198381 A JP7198381 A JP 7198381A JP S5817254 B2 JPS5817254 B2 JP S5817254B2
- Authority
- JP
- Japan
- Prior art keywords
- tin
- zinc
- zinc plating
- corrosion resistance
- plating
- 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.)
- Expired
Links
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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
- Electroplating Methods And Accessories (AREA)
Description
【発明の詳細な説明】
本発明は亜鉛めっきの耐食性を改良する方法に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for improving the corrosion resistance of zinc plating.
鉄鋼の耐食性向上のためにその表面に亜鉛めっきを施す
ことは知られている。It is known that zinc plating is applied to the surface of steel to improve its corrosion resistance.
しかしながら、この亜鉛めっきは、耐食性が不十分なも
のであるため、亜鉛めっきに代えて、すず−亜鉛合金を
用いる電解めっきが検討されている。However, since this zinc plating has insufficient corrosion resistance, electrolytic plating using a tin-zinc alloy is being considered in place of the zinc plating.
しかし、このすず−亜鉛合金めっきの場合、すず含量が
６０係以上のものを用いないと耐食性が向上しないとい
う欠点がある上、合金めっきであるため浴管理が難しく
、しかも亜鉛より高価なすすを亜鉛より多くの世相いる
ため、亜鉛めっきの場合よりも高価になるという欠点が
ある。However, in the case of this tin-zinc alloy plating, corrosion resistance cannot be improved unless a tin content of 60 parts or more is used, and since it is an alloy plating, bath management is difficult, and moreover, soot is more expensive than zinc. Since it is more common than zinc, it has the disadvantage that it is more expensive than zinc plating.
本発明は、これらの欠点を克服したもので、亜鉛めっき
の耐食性を改良するにあたり、該亜鉛めっきの表面を塩
化アンモニウム水溶液で処理した後、すず置換処理し、
必要に応じ、クロメート処理することを特徴とする亜鉛
めっきの耐食性改良方法が提供される。The present invention overcomes these drawbacks and improves the corrosion resistance of zinc plating by treating the surface of the zinc plating with an aqueous ammonium chloride solution and then subjecting it to tin substitution treatment.
Provided is a method for improving the corrosion resistance of zinc plating, which is characterized by subjecting it to chromate treatment, if necessary.
本発明における亜鉛めっきは、従来公知の電解めっき法
で得られたものであり、例えば、硫酸亜鉛、ヒアン化亜
鉛、ＺｎＯ−Ｎａ０Ｉ−（を含む亜鉛めっき浴中から、
鉄又は鉄鋼表面に亜鉛めっきを形成することができる。The zinc plating in the present invention is obtained by a conventionally known electrolytic plating method, for example, from a zinc plating bath containing zinc sulfate, zinc hyanide, ZnO-Na0I-(
Galvanization can be formed on iron or steel surfaces.
本発明においては、亜鉛めっきの耐食性を改良するには
、先ず、亜鉛めっきの表面を塩化アンモニウム（ＮＨ２
Ｃ１）水溶液で処理することが重要である。In the present invention, in order to improve the corrosion resistance of zinc plating, first, the surface of the zinc plating is coated with ammonium chloride (NH2).
C1) It is important to treat with an aqueous solution.
この処理によって、後続のすず置換処理を容易かつ確実
なものにする。This process makes the subsequent tin replacement process easy and reliable.
この塩化アンモニウム水溶液を用いる処理は、濃度１〜
２０重量係重量ましくは２〜１０重量係重量化アンモニ
ウム水溶液中に亜鉛めっきを浸漬することによって実施
される。The treatment using this ammonium chloride aqueous solution has a concentration of 1 to
This is carried out by immersing the zinc plating in an aqueous ammonium solution weighing 20% by weight or 2-10% by weight.
処理温度は１０〜３０°Ｃであり、処理時間は２〜１０
分間で十分である。The processing temperature is 10-30°C, and the processing time is 2-10°C.
A minute is enough.
この塩化アンモニウム水溶液で処理した後の亜鉛めっき
は、水洗して表面に付着する塩化アンモニウムを除去し
た後、すず置換処理を行う。The zinc plating treated with this ammonium chloride aqueous solution is washed with water to remove ammonium chloride adhering to the surface, and then subjected to tin substitution treatment.
このすず置換処理は、前記塩化アンモニウムで表面処理
された亜鉛めっきを、塩化すず又は硫酸すずなどのすず
塩の水溶液中に浸漬することによって実施される。This tin substitution treatment is carried out by immersing the zinc plating surface-treated with ammonium chloride in an aqueous solution of a tin salt such as tin chloride or tin sulfate.
水溶液中のすず濃度は、水溶液ｌｌ中、０．５〜５０Ｊ
１好ましくは１．０〜２Ｍである。The tin concentration in the aqueous solution is 0.5 to 50 J in 1 liter of the aqueous solution.
1, preferably 1.0 to 2M.
処理温度は１０〜３０°Ｃの温度であるが、一般には常
温が採用される。The treatment temperature is 10 to 30°C, but room temperature is generally employed.
処理時間は５〜３０分である。Processing time is 5-30 minutes.
また、このすず水溶液のｐＨは、１．５以下に保持する
。Further, the pH of this tin aqueous solution is maintained at 1.5 or less.
このすず置換処理により、次の反応式に従って亜鉛めっ
きの表面部がすすにより置換される。Through this tin substitution treatment, the surface portion of the galvanized layer is substituted with soot according to the following reaction formula.
この場合、すずによる置換量は、全亜鉛中０．５〜１０
重量係重量味しくは、１〜５重量重量ある。In this case, the amount of tin replacement is 0.5 to 10% of the total zinc.
In terms of weight, it weighs between 1 and 5.
なお、すず皮膜を厚くするために１０〜１００ｍＡ７ｄ
ｍ２の直流電解を上記めっき浴を用いて行うとよい。In addition, in order to thicken the tin film, 10 to 100mA7d
It is preferable to perform direct current electrolysis of m2 using the above plating bath.
Ｚｎ２Ｓｎ２＋−”Ｚｎ２＋Ｓｎ
前記のようにしてすず置換処理された亜鉛めっきは、必
要に応じて、慣用のクロメート処理を施すことができる
。Zn2Sn2+-"Zn2+Sn The zinc plating that has been subjected to the tin substitution treatment as described above can be subjected to a conventional chromate treatment, if necessary.
この場合、クロメート液としては、無水クロム酸５〜３
０９／１１を含む水溶液が用いられる。In this case, the chromate solution is chromic anhydride 5 to 3
An aqueous solution containing 09/11 is used.
本発明によるめっきは、従来の亜鉛めっきはもちろん、
亜鉛−すず合金めつきを施したものよりもその面１食性
は著しく改良されたものであり、しかもその亜鉛−すず
合金めつきの場合よりも処理操作が簡単かつ安価である
。The plating according to the present invention can be applied not only to conventional zinc plating, but also to
Its surface monocorrosion properties are significantly improved over those plated with zinc-tin alloy, and the processing operation is simpler and cheaper than that with zinc-tin alloy plating.
次に本発明を実施例によりさらに詳細に説明する０
実施例
第１表に示す亜鉛めっき条件により、サンプルとしての
鉄鋼片（寸法： ９０ｍｍＸ ３０ｍｍＸ １ ｍｍ
）上に、厚さ１０μｍの亜鉛めっきを施した。Next, the present invention will be explained in more detail with reference to examples.0 Example A steel piece as a sample (dimensions: 90 mm x 30 mm x 1 mm) was prepared under the galvanizing conditions shown in Table 1.
), zinc plating was applied to a thickness of 10 μm.
第１表 （亜鉛めっき条件）
浴組成
硫酸亜鉛 ４１０ ｇ／ｌ
塩化アルミニウム ３０ 〃
硫酸ナトリウム ７５ 〃
浴温 ２５°Ｃ
ｐＨ３，５
電流密度 ２Ａ／ｄｍ”次に、この
亜鉛めっきサンプルを塩化アンモニウムの５係水溶液中
に、室温で１０分間浸漬した後、サンプル表面を水洗し
た。Table 1 (Zinc plating conditions) Bath composition Zinc sulfate 410 g/l Aluminum chloride 30 Sodium sulfate 75 Bath temperature 25°C pH 3,5 Current density 2 A/dm After being immersed in the aqueous solution at room temperature for 10 minutes, the surface of the sample was washed with water.
このサンプルを１、塩化すず２ｇ／／ｊを含む水溶液（
ｐＨ１，５）中に、室温で２０分間浸漬した後、サンプ
ル表面を水洗した。This sample was mixed with an aqueous solution containing 1 g//j of tin chloride (
The sample surface was washed with water after being immersed in the sample (pH 1, 5) for 20 minutes at room temperature.
このようにして得た製品についてその腐食試験を行った
。The product thus obtained was subjected to a corrosion test.
この場合の腐食試験は、ＪＩＳ Ｈ８１６０（電気亜鉛
めっき）の付属書３の条件による塩水噴霧試験を２〜２
４時間行い、試験結果は、腐食減少量により評価した。In this case, the corrosion test is a salt spray test conducted under the conditions of Appendix 3 of JIS H8160 (electrogalvanizing) for 2 to 2 days.
The test was conducted for 4 hours, and the test results were evaluated based on the amount of corrosion reduction.
その結果を次に示す。な。お、使用したサンプルは次の
通りである。The results are shown below. Na. The samples used are as follows.
Ｓ−１・・・・・・亜鉛めっき
Ｓ−２・・・・・・亜鉛めっき十ＮＨ，ＣＩ処理＋すず
置換Ｓ−３・・・・・・亜鉛めつき＋すず置換Ｓ−４・
・・・・・亜鉛めつき＋すず置換＋熱処理（１８０°Ｃ
）（なお、熱処理は亜鉛に対しすすを合金化するための
もので、シリコンオイル中で１８０℃に加熱することに
より行った。S-1...Zinc plating S-2...Zinc plating 1NH, CI treatment + tin substitution S-3...Zinc plating + tin substitution S-4...
...Zinc plating + tin substitution + heat treatment (180°C
) (Note that the heat treatment was for alloying soot with zinc, and was performed by heating to 180° C. in silicone oil.
）前記衣から明らかなように、本発明による亜鉛めっき
処理の後、ＮＨ４Ｃｌ処理及びすず置換処理を施すこと
によって、亜鉛めっきの耐食性は最も大きく改善される
ことがわかる。) As is clear from the above coating, it can be seen that the corrosion resistance of the zinc plating is improved most significantly by performing the NH4Cl treatment and the tin substitution treatment after the zinc plating treatment according to the present invention.
また、本発明法においては、すず置換後に、下記組成の
クロメート処理条件を用いて、クロメート処理を施した
場合でも、塩水噴霧試験により、良質のクロメート皮膜
が形成されることが確認された。In addition, in the method of the present invention, even when chromate treatment was performed using the chromate treatment conditions of the following composition after tin substitution, it was confirmed by a salt spray test that a high quality chromate film was formed.
第３表 （クロメート処理条件） 処理浴 無水クロム酸 １０ｇ／ｌ 硫酸 ０．５ｍ／ｌ 浸漬時間 ２０秒間 空中放置（自然乾燥） ２分間Table 3 (Chromate treatment conditions) treatment bath Chromic anhydride 10g/l Sulfuric acid 0.5m/l Soaking time 20 seconds Leave in air (natural drying) for 2 minutes
Claims (1)
っきの表面を塩化アンモニウム水溶液で処理した後、す
ず置換処理することを特徴とする亜鉛めっきの耐食性改
良方法。1. A method for improving the corrosion resistance of zinc plating, which comprises treating the surface of the zinc plating with an aqueous ammonium chloride solution and then subjecting it to tin substitution treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56071983A JPS5817254B2 (en) | 1981-05-13 | 1981-05-13 | Method for improving corrosion resistance of galvanized steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56071983A JPS5817254B2 (en) | 1981-05-13 | 1981-05-13 | Method for improving corrosion resistance of galvanized steel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57188663A JPS57188663A (en) | 1982-11-19 |
| JPS5817254B2 true JPS5817254B2 (en) | 1983-04-06 |
Family
ID=13476199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56071983A Expired JPS5817254B2 (en) | 1981-05-13 | 1981-05-13 | Method for improving corrosion resistance of galvanized steel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5817254B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59501621A (en) * | 1982-09-30 | 1984-09-13 | フオ−ド モ−タ− カンパニ− | seat belt positioning device |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007021364A1 (en) * | 2007-05-04 | 2008-11-06 | Henkel Ag & Co. Kgaa | Metallizing pretreatment of zinc surfaces |
| US9574093B2 (en) | 2007-09-28 | 2017-02-21 | Ppg Industries Ohio, Inc. | Methods for coating a metal substrate and related coated metal substrates |
| JP6986826B2 (en) * | 2015-12-04 | 2021-12-22 | 日東精工株式会社 | Manufacturing method of fasteners |
-
1981
- 1981-05-13 JP JP56071983A patent/JPS5817254B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59501621A (en) * | 1982-09-30 | 1984-09-13 | フオ−ド モ−タ− カンパニ− | seat belt positioning device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57188663A (en) | 1982-11-19 |
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