JPH052753B2 - - Google Patents
Info
- Publication number
- JPH052753B2 JPH052753B2 JP26306485A JP26306485A JPH052753B2 JP H052753 B2 JPH052753 B2 JP H052753B2 JP 26306485 A JP26306485 A JP 26306485A JP 26306485 A JP26306485 A JP 26306485A JP H052753 B2 JPH052753 B2 JP H052753B2
- Authority
- JP
- Japan
- Prior art keywords
- mol
- stainless steel
- coloring
- electrolysis
- colored
- 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 - Fee Related
Links
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 238000005868 electrolysis reaction Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- 239000010935 stainless steel Substances 0.000 claims description 16
- 229910001220 stainless steel Inorganic materials 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 5
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 239000005078 molybdenum compound Substances 0.000 claims description 3
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 3
- 150000001845 chromium compounds Chemical class 0.000 claims description 2
- 238000004040 coloring Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 7
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- -1 Molybdic acid compound Chemical class 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- NPURPEXKKDAKIH-UHFFFAOYSA-N iodoimino(oxo)methane Chemical compound IN=C=O NPURPEXKKDAKIH-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 235000015393 sodium molybdate Nutrition 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 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
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Chemical Treatment Of Metals (AREA)
Description
＜産業上の利用分野＞
本発明は、主要な用途が建材用である着色ステ
ンレス鋼材の製造方法に関するものである。
＜従来技術とその問題点＞
ステンレス鋼板に着色する方法として、主に硫
酸＋クロム酸混合液を用いたいわゆるINCO法が
知られている。（特公昭52−32621号、同52−
25817号、同53−31817号）。
このINCO法では「着色処理」と「硬膜処理」
の２液２工程をとる。この煩雑さを克服するため
鋭意努力を重ねた結果、本出願人は、一液中で
「交番電流電解」をする方法を発明して出願して
いる（特願昭59−247542号）（特公昭63−8198
号）。これは一液中で陽極電解と陰極電解を交互
に繰り返し行なうものである。
しかし、着色電解液として６価クロムを用いな
い着色液として硫酸＋過マンガン酸塩に浸漬着色
する方法が知られている（特公昭51−40861号）。
これは硫酸水溶液に過マンガン酸塩を添加し酸素
ガスの発生が止むまで反応させた溶液にステンレ
ス鋼を90〜110℃の温度範囲で浸漬し、ブロンズ、
黒褐色、黒色等の着色皮膜を形成せしめる方法で
ある。
硫酸と過マンガン酸塩の混合水溶液で浸漬着色
する場合90〜110℃という非常に高温で行なうた
め、溶液の蒸発による濃度変化が大きいので溶液
の管理が難しい。また蒸気がでるので作業者の安
全衛生上問題があり、大規模な排気処理設備を施
す必要が生じ、これがコストを上昇させる要因と
なる。
また、着色ステンレス鋼材の主要な用途は建材
用であることから、ステンレス鋼の基本的性質と
しての耐食性の他に特に耐摩耗性が求められる。
＜発明の目的＞
本発明の目的は、従来技術の問題点を解消し、
この交番電流電解法をモリブデン酸塩の水溶液を
用いて耐摩耗性に優れた着色ステンレス鋼材の製
造方法を提供しようとするにある。
＜発明の構成＞
すなわち、本発明は、６価モリブデンとして
0.5〜2mol／のモリブデン化合物と、１〜
5mol／の硫酸と、６価クロムとして0.5〜
2mol／のクロム化合物とを含む混合水溶液中
において、陽極電流密度0.01〜0.5A／ｄm2、陰極
電流密度0.01〜0.5A／ｄm2、繰返し数10Hz以下の
交番電流電解を行なうことを特徴とする着色ステ
ンレス鋼材の製造方法を提供するものである。
以下に本発明を更に詳細に説明する。
ここでいうステンレス鋼材とは、線材、管材、
板材、塊、異形断面材、粉粒材などの任意の形状
でよいが、以下の説明は代表的に鋼板について行
なう。
本発明はステンレス鋼板を６価のモリブデンを
含む化合物と、６価のクロムを含む化合物と、硫
酸とを含む着色電解液中において、陽極電解、陰
極電解を交互に行ない、陽・陰極電解の電流密度
と電解時間を適宜に組み合せ、所定の回数上記電
解液中で交番電解を行なうことを特徴とするもの
である。
６価モリブデンを含む化合物としては、モリブ
デン酸、モリブデン酸ナトリウム等の水溶性化合
物を代表的にあげることができる。
着色電解液の組成を上記に限定した理由を説明
する。
(1) モリブデン酸化合物
６価モリブデンとして0.5mol／未満では、
酸化能力が低く着色に長時間を要することおよ
び十分な耐摩耗成をもたせられないこととな
り、2.0mol／を超えると効果が飽和状態と
なる。
(2) クロム酸化合物
６価クロムとして0.5mol／未満では、酸
化能力が低く着色に長時間を要することおよび
十分な耐摩耗性をもたせられないこととなり、
2.0mol／を超えること効果が飽和状態とな
る。
(3) 硫酸
1mol／未満では、着色処理で長時間を要
することとなり、5mol／を超えると均一に
着色せず硬膜も十分に行なわれず良好な耐摩耗
性が得られないこととなる。
交番連電解の条件を上記に限定した理由を説明
する。
(1) 陽極電流密度
0.01A／ｄm2未満では着色せず、0.5A／ｄm2
を超えると色ムラのない均一な皮膜が得られな
いので、陽極電流密度は0.01〜0.5A／ｄm2の範
囲とする。
(2) 陰極電流密度
0.01A／ｄm2未満では被膜が非常にもろく、
0.5A／ｄm2を超えると着色皮膜が得られない
ので、陰極電流密度は0.01〜0.5A／ｄm2の範囲
とする。
(3) 繰り返し数
10Hzを超えると着色しないので、10Hz以下と
する。
(4) 温度
40℃未満では着色に要する時間が長くなり過
ぎ、80℃を超えると色ムラが発生しやすく、良
好な着色被膜を得ることが困難となるため40〜
80℃で交番電流電解を行なうことが好ましい。
交番電流電解を行なう際対極はステンレス鋼
板、または他の適当な金属（合金）例えばＣ、
Pt、Pb、Ti等を用いることができる。
＜実施例＞
次に本発明を実施例を挙げて具体的に説明す
る。
実施例 １
モリブデン酸ナトリウム 1mol／
硫 酸 3mol／
無水クロム酸 0.5mol／
水 残部
上記の水溶液中にSUS304BA材（光輝焼鈍材）
（70×70mm平板）を浸漬し、第１表に示す条件で、
交番電流電解を行なつた。
その後荷重500ｇの条件で耐摩耗試験機を用い
て、着色皮膜表面を酸化クロム研磨紙で擦ること
により耐摩耗性試験を行なつた。耐摩耗性の評価
は、着色皮膜が完全に除去されるまでの酸化クロ
ム研磨紙による摩耗回数で行ない、この回数が多
くなる程耐摩耗性が優れていると判定した。
比較として従来法によるもの、即ち、自然浸漬
にて→硬膜処理したものを用いた。この際、着色
溶液は、実施例１と同様の溶液を用い、硬膜処理
は40℃、2.5ｇ／の硫酸と250ｇ／の無水クロ
ム酸からなる溶液を用いた。これらについては、
特公昭52−32621号に記載されている。
第１表に、詳細な電解条件と耐摩耗試験結果を
本発明および比較としての比較例とともにまとめ
て示す。
比較例での摩耗回数は、高々120回程度である
のに比べて、本発明に係る交番電流電解法の場
合、その摩耗回数は、610〜670回という約５倍の
値であつた。これらのデータより、本発明による
交番電流電解法で製造した着色ステンレス鋼板の
耐摩耗性は、従来法によるものより著しく優れて
いることは明白である。
<Industrial Application Field> The present invention relates to a method for manufacturing colored stainless steel materials whose main use is as building materials. <Prior art and its problems> The so-called INCO method, which mainly uses a mixture of sulfuric acid and chromic acid, is known as a method for coloring stainless steel sheets. (Special Publication No. 52-32621, 52-
No. 25817, No. 53-31817). In this INCO method, "coloring treatment" and "during treatment"
It takes two liquids and two steps. As a result of repeated efforts to overcome this complexity, the present applicant has invented and applied for a method of performing "alternating current electrolysis" in one liquid (Japanese Patent Application No. 59-247542). Kosho 63-8198
issue). This involves repeating alternating anodic electrolysis and cathodic electrolysis in one solution. However, a method of coloring by immersion in sulfuric acid + permanganate as a coloring solution that does not use hexavalent chromium as a coloring electrolyte is known (Japanese Patent Publication No. 40861/1983).
This is done by immersing stainless steel in a solution in which permanganate is added to an aqueous sulfuric acid solution and allowed to react until the generation of oxygen gas stops, at a temperature range of 90 to 110°C.
This is a method of forming a colored film such as blackish brown or black. When coloring by dipping with a mixed aqueous solution of sulfuric acid and permanganate, it is carried out at a very high temperature of 90 to 110°C, so it is difficult to control the solution because the concentration changes greatly due to evaporation of the solution. In addition, steam is emitted, which poses health and safety problems for workers, and requires large-scale exhaust treatment equipment, which increases costs. Furthermore, since the main use of colored stainless steel materials is for building materials, wear resistance is particularly required in addition to corrosion resistance, which is a basic property of stainless steel. <Object of the invention> The object of the invention is to solve the problems of the prior art,
The object of the present invention is to provide a method for producing a colored stainless steel material having excellent wear resistance using this alternating current electrolysis method using an aqueous solution of molybdate. <Structure of the invention> That is, the present invention provides
0.5~2mol/molybdenum compound and 1~2mol/molybdenum compound
5mol/sulfuric acid and 0.5~ as hexavalent chromium
It is characterized by carrying out alternating current electrolysis at an anode current density of 0.01 to 0.5 A/dm 2 , a cathode current density of 0.01 to 0.5 A/dm 2 , and a repetition rate of 10 Hz or less in a mixed aqueous solution containing 2 mol/of a chromium compound. The present invention provides a method for manufacturing colored stainless steel materials. The present invention will be explained in more detail below. Stainless steel materials here include wire rods, pipe materials,
Although any shape may be used, such as a plate material, a block, a modified cross-section material, or a powder material, the following description will be made with reference to a steel plate as a representative example. In the present invention, a stainless steel plate is alternately subjected to anodic electrolysis and cathodic electrolysis in a colored electrolytic solution containing a compound containing hexavalent molybdenum, a compound containing hexavalent chromium, and sulfuric acid. The method is characterized in that alternating electrolysis is carried out in the electrolytic solution a predetermined number of times by appropriately combining density and electrolysis time. Typical examples of compounds containing hexavalent molybdenum include water-soluble compounds such as molybdic acid and sodium molybdate. The reason why the composition of the colored electrolyte was limited to the above will be explained. (1) Molybdic acid compound Less than 0.5 mol/hexavalent molybdenum,
The oxidizing ability is low and it takes a long time for coloring and it is not possible to provide sufficient wear resistance, and when it exceeds 2.0 mol/L, the effect becomes saturated. (2) Chromic acid compound If the amount is less than 0.5 mol/hexavalent chromium, the oxidation ability will be low and it will take a long time for coloring and sufficient wear resistance will not be provided.
The effect reaches saturation when it exceeds 2.0 mol/. (3) If the amount of sulfuric acid is less than 1 mol, the coloring process will take a long time, and if it exceeds 5 mol, the coloring will not be uniform and hardening will not be sufficient, resulting in failure to obtain good wear resistance. The reason why the conditions for alternating electrolysis were limited to the above will be explained. (1) Anode current density less than 0.01A/dm 2 will not cause coloring, and 0.5A/dm 2
If it exceeds this, a uniform film without color unevenness cannot be obtained, so the anode current density is set in the range of 0.01 to 0.5 A/dm 2 . (2) If the cathode current density is less than 0.01A/ dm2 , the coating will be very brittle.
If the current density exceeds 0.5 A/dm 2 , a colored film cannot be obtained, so the cathode current density is set in the range of 0.01 to 0.5 A/dm 2 . (3) Number of repetitions If the repetition rate exceeds 10Hz, coloring will not occur, so the number of repetitions should be 10Hz or less. (4) If the temperature is less than 40°C, the time required for coloring will be too long, and if it exceeds 80°C, color unevenness will easily occur and it will be difficult to obtain a good colored film.
Preferably, alternating current electrolysis is carried out at 80°C. When performing alternating current electrolysis, the counter electrode is a stainless steel plate or other suitable metal (alloy) such as C,
Pt, Pb, Ti, etc. can be used. <Example> Next, the present invention will be specifically described with reference to Examples. Example 1 Sodium molybdate 1 mol / Sulfuric acid 3 mol / Chromic anhydride 0.5 mol / Water balance SUS304BA material (bright annealing material) in the above aqueous solution
(70 x 70 mm flat plate) under the conditions shown in Table 1.
Alternating current electrolysis was performed. Thereafter, an abrasion resistance test was carried out by rubbing the surface of the colored film with chromium oxide abrasive paper using an abrasion resistance tester under the condition of a load of 500 g. Abrasion resistance was evaluated based on the number of abrasions with chromium oxide abrasive paper until the colored film was completely removed, and it was determined that the greater the number of abrasions, the better the abrasion resistance. For comparison, we used a conventional method, that is, a material that was subjected to natural immersion → hardening treatment. At this time, the same coloring solution as in Example 1 was used, and the hardening treatment was performed at 40° C. using a solution consisting of 2.5 g/2.5 g of sulfuric acid and 250 g/of chromic anhydride. Regarding these,
It is described in Special Publication No. 52-32621. Table 1 shows detailed electrolytic conditions and abrasion test results together with the present invention and a comparative example. The number of times of wear in the comparative example was about 120 times at most, whereas in the case of the alternating current electrolysis method according to the present invention, the number of times of wear was 610 to 670 times, about five times as much. From these data, it is clear that the wear resistance of the colored stainless steel sheet produced by the alternating current electrolysis method according to the present invention is significantly superior to that produced by the conventional method.
【表】
＜発明の効果＞
本発明の交番電流電解による着色ステンレス鋼
材の製造方法は、モリブデン酸塩を含む着色電解
液を用いて、１液・１工程で耐摩耗性に優れた着
色ステンレス鋼材を製造するものであり、連続的
に着色ステンレス鋼材を生産する方法に適用でき
る。
本発明の方法により製造された着色ステンレス
鋼材の耐摩耗性は従来の製法のものに比べて著し
く向上している。[Table] <Effects of the Invention> The method for producing colored stainless steel materials by alternating current electrolysis of the present invention uses a colored electrolyte containing molybdate to produce colored stainless steel materials with excellent wear resistance in one liquid and one step. This method can be applied to the continuous production of colored stainless steel materials. The wear resistance of the colored stainless steel materials produced by the method of the present invention is significantly improved compared to those produced by conventional methods.
Claims (1)
ブデン化合物と、１〜5mol／の硫酸と、６価
クロムとして0.5〜2mol／のクロム化合物とを
含む混合水溶液中において、陽極電流密度0.01〜
0.5A／ｄm2、陰極電流密度0.01〜0.5A／ｄm2、繰
返し数10Hz以下の交番電流電解を行なうことを特
徴とする着色ステンレス鋼材の製造方法。1. In a mixed aqueous solution containing 0.5 to 2 mol/molybdenum compound as hexavalent molybdenum, 1 to 5 mol/sulfuric acid, and 0.5 to 2 mol/chromium compound as hexavalent chromium, the anode current density is 0.01 to 1.
A method for producing a colored stainless steel material, characterized by carrying out alternating current electrolysis at 0.5 A/dm 2 , cathode current density 0.01 to 0.5 A/dm 2 , and repetition rate 10 Hz or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26306485A JPS62124295A (en) | 1985-11-22 | 1985-11-22 | Production of colored stainless steel material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26306485A JPS62124295A (en) | 1985-11-22 | 1985-11-22 | Production of colored stainless steel material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62124295A JPS62124295A (en) | 1987-06-05 |
| JPH052753B2 true JPH052753B2 (en) | 1993-01-13 |
Family
ID=17384342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26306485A Granted JPS62124295A (en) | 1985-11-22 | 1985-11-22 | Production of colored stainless steel material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62124295A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101173367B (en) | 2006-10-31 | 2010-09-22 | 佛山市顺德区汉达精密电子科技有限公司 | A stainless steel electrochemical coloring process |
-
1985
- 1985-11-22 JP JP26306485A patent/JPS62124295A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62124295A (en) | 1987-06-05 |
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