JPH0468392B2 - - Google Patents
Info
- Publication number
- JPH0468392B2 JPH0468392B2 JP60079967A JP7996785A JPH0468392B2 JP H0468392 B2 JPH0468392 B2 JP H0468392B2 JP 60079967 A JP60079967 A JP 60079967A JP 7996785 A JP7996785 A JP 7996785A JP H0468392 B2 JPH0468392 B2 JP H0468392B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc alloy
- steel sheet
- acid
- colored
- content
- 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 - Lifetime
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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/53—Treatment of zinc or alloys based thereon
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Chemical Treatment Of Metals (AREA)
Description
［産業上の利用分野］
本発明は着色亜鉛合金めつき鋼板の製造方法に
関し、さらに詳しくは、表面を黒色に着色させた
亜鉛合金めつき鋼板の製造方法に関する。
［従来技術］
従来から装飾性、光吸収性、吸熱性および光の
反射防止等を向上させるために、亜鉛表面に黒色
着色を施すことが行なわれてきている。
そして、このような黒色着色を施す方法として
次に示すような方法がある。
(1) 黒色塗料を塗布する方法。
(2) 塩素酸塩浸漬方法。
(3) モリブデン酸塩浸漬方法。
(4) 無水クロム酸浸漬方法。
(5) 硫化物溶液浸漬方法。
(6) 硫酸銅溶液浸漬方法。
(7) 加熱方法。
(8) 電解方法。
しかしながら、(1)の方法は塗装費用が高く、(2)
〜(6)の方法は処理液の管理が困難で、かつ、廃液
処理上の問題があり、さらに、短時間処理で安定
した黒色皮膜を得ることは困難であり、また、(7)
(8)の方法は設備費用が高く、特に、(8)の方法では
液管理および電解条件の制御が困難である。
［発明が解決しようとする問題点］
本発明は上記に説明したような亜鉛表面に対す
る黒色着色を行なう方法における種々の問題点を
解消すべくなされたものであり、本発明者の鋭意
研究の結果、基本的には亜鉛めつき自体をコバル
ト、ニツケル、モリブデンを含有する亜鉛合金め
つきとして施した鋼板を酸化剤を含む酸溶液で処
理することにより、亜鉛合金めつき表面を酸溶解
すると同時に酸化することによつて、極めて簡単
に亜鉛合金めつき層表面を黒色化させることがで
きることを見出し、着色亜鉛合金めつき鋼板の製
造方法を開発したのである。
［問題点を解決するための手段］
本発明に係る着色亜鉛合金めつき鋼板の製造方
法の特徴とするところは、
Co0.5〜30wt％、Ni0.5〜30wt％、Mo0.5〜
10wt％
のうちから選んだ１種または２種以上を含有し、
残部Znよりなる亜鉛合金めつきを施した鋼板を、
塩酸、硫酸、有機酸（カルボン酸）
の１種または２種以上を合計で0.1〜20wt％を含
有し、かつ、
過酸化水素水0.1〜20wt％
を含有する混合水溶液中で処理することにある。
本発明に係る着色亜鉛合金めつき鋼板の製造方
法について以下詳細に説明する。
即ち、Co，Ni、またはMoのうちから選んだ１
種または２種以上を含有し、残部Znよりなる亜
鉛合金めつき鋼板を酸と酸化剤との混合水溶液中
で処理すると、亜鉛合金めつき層表面に存在する
Znが優先的に溶解するが、それに比してCo，Ni
またはMoは少量の溶解であり、亜鉛合金めつき
層表面は亜鉛合金めつき母体よりCo，Niおよび
Moが富化した状態の層となり、同時に、酸化剤
の作用によつてCo，NiおよびMoが酸化されて黒
色系を呈する表面となる。
次に、本発明に係る着色亜鉛合金めつき鋼板の
製造方法において施される亜鉛合金めつきの含有
成分および成分割合と亜鉛合金めつき鋼板の処理
液について説明する。
亜鉛合金めつきについて。
Co，Niは含有量が0.5wt％未満では着色し難
く、また、30wt％を越えると亜鉛合金めつき層
の密着性が悪化する。よつて、Co含有量は0.5〜
30wt％、Ni含有量は0.5〜30wt％とする。
Moは含有量が0.5wt％未満では着色し難く、
また、10wt％を越えると亜鉛合金めつき層の密
着性が悪化する。よつて、Mo含有量は0.5〜
10wt％とする。
処理液について。
酸と酸化剤との混合処理液。
酸としては、塩酸、硫酸、有機酸（カルボン
酸）等が使用でき、これらの酸は含有量が0.1wt
％未満では着色反応が遅く、かつ、均一な着色皮
膜が得られず、また、20wt％を越えると着色反
応と溶解反応が激しくなり、着色を制御すること
ができなくなる。よつて、酸濃度は0.1〜20wt％
とする。なお、有機酸のカルボン酸は弱酸であ
り、上記の濃度範囲も広くなるが、高濃度で使用
しても害はない。なお、この有機カルボン酸とし
て、モノカルボン酸、ジカルボン酸、トリカルボ
ン酸、鎖式カルボン酸、芳香族カルボン酸、飽和
カルボン酸、不飽和カルボン酸等を含む。
酸化剤としては、過酸化水素水を使用すること
ができ、含有量が0.1wt％未満では酸化反応が遅
く、均一な着色が不可能となり、また、20wt％
を越えると酸との組合せにより鋼板の亜鉛合金め
つき層の溶解反応が著しく、着色を制御すること
ができない。よつて、酸化剤濃度は0.1〜20wt％
とする。
そして、本発明に係る亜鉛合金めつき鋼板の製
造方法においては、処理液は酸と酸化剤が単独で
は上記に説明した現象は起らず、必ず、酸と酸化
剤とが同時に存在することが大切である。
［実施例］
本発明に係る着色亜鉛合金めつき鋼板の製造方
法について実施例を説明する。
実施例 １
Ni0.5〜30wt％含有のZn−Nu合金めつき鋼板
を使用し、硫酸5wt％および過酸化水素水2wt％
混合溶液中で10秒間の浸漬処理を行なつた鋼板の
Ｌ値と皮膜中のNi含有量との関係を第１図に示
す。
本発明に係る着色亜鉛合金めつき鋼板の製造方
法による鋼板は茶黒色ないし青黒色を呈した。
なお、Ｌ値とは、色差計により測定して黒色化
度を表わす数値である。
実施例 ２
Co0.5〜30wt％含有のZn−Co合金めつき鋼板
を、硫酸5wt％、過酸化水素水2wt％混合溶液中
で５秒間浸漬処理を行なつた。その鋼板のＬ値と
皮膜中のCo含有量との関係を第２図に示す。
本発明に係る着色亜鉛合金めつき鋼板の製造方
法により得られた鋼板は黒色を呈した。
実施例 ３
Mo0.5〜10wt％含有のZn−Mo合金めつき鋼板
を硫酸5wt％、過酸化水素水2wt％混合溶液中で
２秒間浸漬処理を行なつた。その鋼板のＬ値と
Mo含有量との関係を第３図に示す。
実施例 ４〜９
Zn−Ni合金めつき、Mo−Co合金めつき、Zn
−Mo合金めつきを施した鋼板を酸および酸化剤
の混合溶液中で浸漬処理を行なうことにより黒色
化した鋼板について、比較例と共に第１表に示
す。
[Industrial Application Field] The present invention relates to a method for manufacturing a colored zinc alloy coated steel sheet, and more particularly, to a method for manufacturing a zinc alloy coated steel sheet whose surface is colored black. [Prior Art] In order to improve decorative properties, light absorption, heat absorption, light reflection prevention, etc., zinc surfaces have been colored black. The following methods are available for applying such black coloring. (1) Method of applying black paint. (2) Chlorate immersion method. (3) Molybdate dipping method. (4) Chromic anhydride immersion method. (5) Sulfide solution immersion method. (6) Copper sulfate solution immersion method. (7) Heating method. (8) Electrolysis method. However, method (1) requires high painting costs, and method (2)
Methods (6) to (6) are difficult to manage the treatment liquid and have problems in waste liquid treatment.Furthermore, it is difficult to obtain a stable black film in a short treatment time, and (7)
Method (8) requires high equipment costs, and in particular, method (8) makes it difficult to control liquid management and electrolytic conditions. [Problems to be Solved by the Invention] The present invention has been made in order to solve various problems in the method of blacking the zinc surface as explained above, and is the result of intensive research by the inventor. Basically, the galvanized steel sheet is treated with a zinc alloy plating containing cobalt, nickel, and molybdenum, and is treated with an acid solution containing an oxidizing agent. They discovered that the surface of the zinc alloy plating layer could be blackened very easily by doing this, and developed a method for producing colored zinc alloy plated steel sheets. [Means for Solving the Problems] The method for producing a colored zinc alloy coated steel sheet according to the present invention is characterized by: Co0.5-30wt%, Ni0.5-30wt%, Mo0.5-30wt%
Contains one or more selected from 10wt%,
A zinc alloy plated steel sheet with the remainder being Zn, containing a total of 0.1 to 20 wt% of one or more of hydrochloric acid, sulfuric acid, and organic acid (carboxylic acid), and hydrogen peroxide solution of 0.1 to 20 wt% The method consists of processing in a mixed aqueous solution containing 20wt%. The method for manufacturing a colored zinc alloy plated steel sheet according to the present invention will be described in detail below. That is, one selected from Co, Ni, or Mo
When a zinc alloy coated steel sheet containing one or more Zn and the remainder being Zn is treated in a mixed aqueous solution of an acid and an oxidizing agent, Zn is present on the surface of the zinc alloy coated layer.
Zn dissolves preferentially, but Co, Ni
Or, a small amount of Mo is dissolved, and the surface of the zinc alloy plating layer has more Co, Ni and
The layer becomes enriched with Mo, and at the same time, Co, Ni, and Mo are oxidized by the action of the oxidizing agent, resulting in a black surface. Next, the components and proportions of the zinc alloy plating applied in the method for producing a colored zinc alloy coated steel sheet according to the present invention and the treatment solution for the zinc alloy coated steel sheet will be explained. Regarding zinc alloy plating. If the content of Co and Ni is less than 0.5 wt%, it will be difficult to color, and if the content exceeds 30 wt%, the adhesion of the zinc alloy plating layer will deteriorate. Therefore, the Co content is 0.5~
30wt%, and the Ni content is 0.5 to 30wt%. When Mo content is less than 0.5wt%, it is difficult to color.
Moreover, if it exceeds 10 wt%, the adhesion of the zinc alloy plating layer will deteriorate. Therefore, the Mo content is 0.5~
The content shall be 10wt%. Regarding the processing liquid. Mixed treatment liquid containing acid and oxidizing agent. As acids, hydrochloric acid, sulfuric acid, organic acids (carboxylic acids), etc. can be used, and these acids have a content of 0.1wt.
If it is less than 20 wt %, the coloring reaction will be slow and a uniform colored film will not be obtained, and if it exceeds 20 wt %, the coloring reaction and dissolution reaction will become intense, making it impossible to control the coloring. Therefore, the acid concentration is 0.1-20wt%
shall be. Note that the organic acid carboxylic acid is a weak acid, and the above concentration range is wide, but there is no harm in using it at a high concentration. The organic carboxylic acids include monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, chain carboxylic acids, aromatic carboxylic acids, saturated carboxylic acids, unsaturated carboxylic acids, and the like. As an oxidizing agent, hydrogen peroxide can be used; if the content is less than 0.1wt%, the oxidation reaction will be slow and uniform coloring will be impossible;
If the amount exceeds this amount, the dissolution reaction of the zinc alloy plating layer of the steel sheet will be significant due to the combination with acid, and coloration cannot be controlled. Therefore, the oxidizing agent concentration is 0.1-20wt%
shall be. In the method for producing zinc alloy coated steel sheets according to the present invention, the above-described phenomenon will not occur if the acid and oxidizing agent are present alone in the treatment solution, but the acid and oxidizing agent must be present at the same time. It's important. [Example] Examples of the method for manufacturing a colored zinc alloy plated steel sheet according to the present invention will be described. Example 1 Using a Zn-Nu alloy plated steel sheet containing 0.5 to 30 wt% Ni, 5 wt% sulfuric acid and 2 wt% hydrogen peroxide solution.
Figure 1 shows the relationship between the L value and the Ni content in the film of a steel plate that was immersed in a mixed solution for 10 seconds. The steel sheet obtained by the method for producing a colored zinc alloy coated steel sheet according to the present invention exhibited a brownish-black to blue-black color. Note that the L value is a numerical value representing the degree of blackening measured with a color difference meter. Example 2 A Zn--Co alloy plated steel sheet containing 0.5 to 30 wt% Co was immersed for 5 seconds in a mixed solution of 5 wt% sulfuric acid and 2 wt% hydrogen peroxide. Figure 2 shows the relationship between the L value of the steel plate and the Co content in the film. The steel sheet obtained by the method for producing a colored zinc alloy coated steel sheet according to the present invention exhibited a black color. Example 3 A Zn-Mo alloy coated steel sheet containing 0.5 to 10 wt% Mo was immersed for 2 seconds in a mixed solution of 5 wt% sulfuric acid and 2 wt% hydrogen peroxide. The L value of the steel plate
The relationship with Mo content is shown in Figure 3. Examples 4 to 9 Zn-Ni alloy plating, Mo-Co alloy plating, Zn
Table 1 shows steel plates coated with -Mo alloy which were blackened by immersion treatment in a mixed solution of an acid and an oxidizing agent, together with comparative examples.
【表】
［発明の効果］
以上説明したように、本発明に係る着色亜鉛合
金めつき鋼板の製造方法は上記の構成を有してい
るものであるから、処理時間が短かく、均一な着
色を行なうことができ、色調おいて安定し、か
つ、生産性に優れ、廃液処理も簡単であり、コス
トも低いという優れた効果を有するものである。[Table] [Effects of the Invention] As explained above, since the method for manufacturing a colored zinc alloy coated steel sheet according to the present invention has the above configuration, the processing time is short and uniform coloring can be achieved. It has excellent effects such as stable color tone, excellent productivity, easy waste liquid treatment, and low cost.
第１図、第２図および第３図は本発明に係る着
色亜鉛合金めつき鋼板の製造方法において、Ni，
CoおよびMoの含有量とＬ値との関係を示す図で
ある。
FIGS. 1, 2, and 3 show a method for manufacturing a colored zinc alloy coated steel sheet according to the present invention.
FIG. 3 is a diagram showing the relationship between the contents of Co and Mo and the L value.
Claims (1)
10wt％ のうちから選んだ１種または２種以上を含有し、
残部Znよりなる亜鉛合金めつきを施した鋼板を、 塩酸、硫酸、有機酸（カルボン酸） の１種または２種以上を合計で0.1〜20wt％を含
有し、かつ、 過酸化水素水0.1〜20wt％ を含有する混合水溶液中で処理することを特徴と
する着色亜鉛合金めつき鋼板の製造方法。[Claims] 1 Co0.5-30wt%, Ni0.5-30wt%, Mo0.5-30wt%
Contains one or more selected from 10wt%,
A zinc alloy plated steel sheet with the remainder being Zn, containing a total of 0.1 to 20 wt% of one or more of hydrochloric acid, sulfuric acid, and organic acid (carboxylic acid), and hydrogen peroxide solution of 0.1 to 20 wt% A method for producing a colored zinc alloy coated steel sheet, characterized by processing in a mixed aqueous solution containing 20 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7996785A JPS61238979A (en) | 1985-04-15 | 1985-04-15 | Production of colored zinc alloy plated steel plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7996785A JPS61238979A (en) | 1985-04-15 | 1985-04-15 | Production of colored zinc alloy plated steel plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61238979A JPS61238979A (en) | 1986-10-24 |
| JPH0468392B2 true JPH0468392B2 (en) | 1992-11-02 |
Family
ID=13705085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7996785A Granted JPS61238979A (en) | 1985-04-15 | 1985-04-15 | Production of colored zinc alloy plated steel plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61238979A (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5472524A (en) * | 1990-05-17 | 1995-12-05 | The Boeing Company | Non-chromated cobalt conversion coating method and coated articles |
| US5411606A (en) * | 1990-05-17 | 1995-05-02 | The Boeing Company | Non-chromated oxide coating for aluminum substrates |
| US5551994A (en) * | 1990-05-17 | 1996-09-03 | The Boeing Company | Non-chromated oxide coating for aluminum substrates |
| US5298092A (en) * | 1990-05-17 | 1994-03-29 | The Boeing Company | Non-chromated oxide coating for aluminum substrates |
| US5468307A (en) * | 1990-05-17 | 1995-11-21 | Schriever; Matthias P. | Non-chromated oxide coating for aluminum substrates |
| CA2087473C (en) * | 1990-05-17 | 2001-10-16 | Matthias P. Schriever | Non-chromated oxide coating for aluminum substrates |
| JPH09137290A (en) * | 1995-11-13 | 1997-05-27 | Sumitomo Metal Ind Ltd | Black zinc-based electroplated steel sheet |
| US5873953A (en) * | 1996-12-26 | 1999-02-23 | The Boeing Company | Non-chromated oxide coating for aluminum substrates |
| WO2001012877A1 (en) * | 1998-08-18 | 2001-02-22 | Walter Hillebrand Gmbh & Co. Galvanotechnik | Passivation method for zinc-nickel layers |
| DE19905134A1 (en) * | 1999-02-09 | 2000-09-28 | Hillebrand Walter Gmbh & Co Kg | Passivation process |
| US6432225B1 (en) | 1999-11-02 | 2002-08-13 | The Boeing Company | Non-chromated oxide coating for aluminum substrates |
| ATE530680T1 (en) * | 2009-03-20 | 2011-11-15 | Universo Sa | GALVANIC COATING PROCESS FOR APPLYING AN ANTHRACITE-COLORED COATING AND METAL PARTS PROVIDED WITH THIS COATING |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60121275A (en) * | 1983-12-05 | 1985-06-28 | Sumitomo Metal Ind Ltd | Blackened steel sheet and its production |
-
1985
- 1985-04-15 JP JP7996785A patent/JPS61238979A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61238979A (en) | 1986-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3964936A (en) | Coating solution for metal surfaces | |
| JPH0468392B2 (en) | ||
| RU2135637C1 (en) | Method of formation of coating from oxide of conversion cobalt, product, chemical solution for application of coating from conversion cobalt and coated article | |
| ATE154401T1 (en) | CHROMATE FREE COBALT CONVERSION COATING | |
| JPH07504942A (en) | Method for treating metal surfaces of articles and treatment solutions used in this method | |
| DE1421985A1 (en) | Process for chrome plating aluminum and other base metals | |
| US1965269A (en) | Method of coloring aluminum | |
| JPH0230795A (en) | Production of black steel sheet | |
| JP2006342376A (en) | Surface treatment liquid and method for depositing chemical conversion film | |
| JPH0129873B2 (en) | ||
| JPS5916994A (en) | Formation of colored protective film on surface of aluminum material | |
| JPS60190588A (en) | Method for blackening zinc or zinc alloy plated steel sheet | |
| US2522474A (en) | Treatment of zinc surfaces | |
| Alliott et al. | Producing a thin coloured film on stainless steels–a review. Part 1: electrochemical processes | |
| JPH0564237B2 (en) | ||
| WO2005014890A1 (en) | An electrolyte solution | |
| JPS60200996A (en) | Blackened rustproof steel sheet and its manufacture | |
| JPS5928638B2 (en) | Method of forming a colored protective film on the surface of magnesium material | |
| JPS5916997A (en) | Formation of colored protective film on surface of magnesium material | |
| JP3943100B2 (en) | Stainless steel coloring method and stainless steel coloring treatment solution | |
| JPS61183496A (en) | Coloring method by low current density electrolysis of stainless steel or metallic titanium | |
| KR100239506B1 (en) | Oxidation coloring method for stainless steel product | |
| JPS6137997A (en) | Surface treatment of aluminum or aluminum alloy | |
| JPS5948879B2 (en) | Aluminum electrolytic coloring method | |
| JPS61253381A (en) | Manufacture of blackened and surface treated steel sheet having superior weldability and corrosion resistance |