JPH02107798A - Method for coloring stainless steel - Google Patents
Method for coloring stainless steelInfo
- Publication number
- JPH02107798A JPH02107798A JP26100788A JP26100788A JPH02107798A JP H02107798 A JPH02107798 A JP H02107798A JP 26100788 A JP26100788 A JP 26100788A JP 26100788 A JP26100788 A JP 26100788A JP H02107798 A JPH02107798 A JP H02107798A
- Authority
- JP
- Japan
- Prior art keywords
- stainless steel
- potential
- coloring
- time
- pulse
- 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
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 38
- 238000004040 coloring Methods 0.000 title claims abstract description 35
- 239000010935 stainless steel Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 229910000831 Steel Inorganic materials 0.000 abstract description 4
- 239000010959 steel Substances 0.000 abstract description 4
- 229940075397 calomel Drugs 0.000 abstract 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 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 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- -1 5CE (saturated calomel Chemical class 0.000 description 1
- 102100025837 JNK1/MAPK8-associated membrane protein Human genes 0.000 description 1
- 101710176060 JNK1/MAPK8-associated membrane protein Proteins 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000002354 daily effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KPVWDKBJLIDKEP-UHFFFAOYSA-L dihydroxy(dioxo)chromium;sulfuric acid Chemical compound OS(O)(=O)=O.O[Cr](O)(=O)=O KPVWDKBJLIDKEP-UHFFFAOYSA-L 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910001105 martensitic stainless steel Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ステンレス鋼の着色方法、特に電解水溶液に
浸漬させながらパルス電位を印加して行うステンレス鋼
の着色方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for coloring stainless steel, and particularly to a method for coloring stainless steel by applying a pulsed potential while immersing the stainless steel in an electrolytic aqueous solution.
（従来の技術）
近年、ステンレス鋼の用途は著しく拡大し、日常生活用
品にも多量に使用されるようになってきており、それに
要求される特性も多岐に亘っている。日常生活品にステ
ンレス鋼が汎用されるようになると、ステンレス鋼本来
の耐食性ばかりでなく今度は装飾的機能も求められるよ
うになり、そのために各種の着色法が開発され、そのう
ちのいくつかはすでに実用化されている。(Prior Art) In recent years, the uses of stainless steel have expanded significantly, and a large amount of stainless steel has come to be used in daily life products, and the properties required therefor are wide-ranging. As stainless steel became widely used in everyday life products, not only the inherent corrosion resistance of stainless steel but also decorative functions were required, and various coloring methods were developed for this purpose, some of which have already been applied. It has been put into practical use.
特に、安価なステンレス鋼としてのフェライト系ステン
レス鋼には汎用品としてその用途拡大が求められており
、そのための手段としての着色法についても多く検討さ
れている。したがって、本明細書においては、以下、ス
テンレス鋼として「フェライト系ステンレス鋼」を例に
とって説明する。In particular, ferritic stainless steel, which is an inexpensive stainless steel, is required to expand its use as a general-purpose product, and many studies are being conducted on coloring methods as a means for achieving this goal. Therefore, in this specification, "ferritic stainless steel" will be described as an example of stainless steel.
ところで、ステンレス鋼の着色技術としては、塗料を塗
布する場合はともがくとして、化学的着色法と電気化学
的着色法とに大別される。化学的着色法の代表例は硫酸
−クロム酸水溶液浸漬着色法であり、ｌＮＣ０着色法と
も呼ばれている。特公昭５２−３２６２１号参照。By the way, the coloring techniques for stainless steel are roughly divided into chemical coloring methods and electrochemical coloring methods, although there are difficulties in applying paint. A typical example of the chemical coloring method is the sulfuric acid-chromic acid aqueous solution immersion coloring method, which is also called the 1NC0 coloring method. See Special Publication No. 52-32621.
しかしながら、この方法は着色処理に長時間を要するば
かりでなくクロム酸溶液を使用するため廃液処理等が問
題であって高価な着色法といえる。However, this method not only requires a long time for the coloring process, but also has problems with waste liquid treatment because it uses a chromic acid solution, making it an expensive coloring method.
その他、米国特許第１，０８９，４９６号および特公昭
４９−１６１７８号に開示されているように酸性または
アルカリ性の水溶液中において電解、着色する電解着色
法、米国特許第６４１，０９１号および米国特許２．４
３１．９８６号に開示されているように溶融塩浴中に浸
漬して着色する熔融塩性などの方法もＩ！されているが
、まだ実用性ある方法とは言えない。In addition, as disclosed in U.S. Patent No. 1,089,496 and Japanese Patent Publication No. 49-16178, the electrolytic coloring method involves electrolyzing and coloring in an acidic or alkaline aqueous solution, U.S. Patent No. 641,091, and U.S. Pat. 2.4
As disclosed in No. 31.986, methods such as the molten salt method in which coloring is performed by immersing in a molten salt bath are also applicable to I! However, it cannot be said to be a practical method yet.
なお、特開昭６２−６０８９２号、同６２−１２４２９
４号、そして同６２−１５８８９８号等においてもステ
ンレス鋼の着色法が開示されているが、これらはいずれ
もＭｎ、Ｖ、Ｃｒ等の重金属の化合物を含有する電解液
を使用するとともに、交番電流電解を行うものであって
、排液処理の問題が依然残るとともに、撮作が煩雑にな
ることは避けられなかった。In addition, Japanese Patent Application Laid-open No. 62-60892 and No. 62-12429
4 and No. 62-158898, etc., methods for coloring stainless steel are disclosed, but all of these methods use electrolytes containing compounds of heavy metals such as Mn, V, and Cr, and use an alternating current. Since it involves electrolysis, there still remains the problem of wastewater treatment, and it is unavoidable that the photographic process becomes complicated.
（発明が解決しようとする課題）
ここに、本発明の目的は、無公害のステンレス鋼の着色
方法を提供することである。(Problems to be Solved by the Invention) An object of the present invention is to provide a pollution-free method for coloring stainless steel.
本発明の別の目的は、短時間で着色が可能であって、し
かも設定条件を変えるだけで各種色彩を発現できる簡便
なステンレス鋼の着色方法を提供することである。Another object of the present invention is to provide a simple method for coloring stainless steel that can be colored in a short time and can produce various colors simply by changing the setting conditions.
（課題を解決するための手段）
本発明者らは、そのような課題解決にあたって、電解着
色法に注目して検討を重ね、その結果、般には浸漬して
も着色することはできない硫酸水溶ン夜等の電解水溶液
を浸漬浴として使用し、印加電位としてパスル波電位を
使用したところ、その設定条件如何によっては各種の着
色が可能であることを知り、本発明を完成した。(Means for Solving the Problems) In order to solve such problems, the present inventors have repeatedly investigated the electrolytic coloring method, and as a result, they have found that a sulfuric acid aqueous solution, which cannot be colored even by immersion, By using an electrolytic aqueous solution such as Nihonyo as an immersion bath and using a pulse wave potential as the applied potential, it was discovered that various colors could be produced depending on the setting conditions, and the present invention was completed.
すなわち、ステンレス鋼の硫酸水溶液中での陽極酸化に
より不働態化電位領域で生成した表面不働態皮膜は厚さ
５０オングストローム以下の透明なものである。また過
不（ｉｔ［域で分極しても着色しない。つまり、クロム
酸を添加しない硫酸水溶液中において過不働！ぶ電位で
の陽極酸化を行ったところ、皮膜の着色は行われなかっ
た。そこで、その理由について検討したところ、クロム
の過不働態反応速度が速いため着色皮膜が得られなかっ
たものと考えられたため、今度は、同し条件下において
定電位パルス波を加えながら分極したところ着色皮膜が
形成され、しかも電解条件を変更することによりその色
彩を各種に変更できることが判明し、本発明に至った。That is, the surface passivation film produced in the passivation potential region by anodic oxidation of stainless steel in an aqueous sulfuric acid solution is transparent and has a thickness of 50 angstroms or less. In addition, no coloring occurs even when polarized in the nit region. In other words, when anodic oxidation was performed at a potential in a sulfuric acid aqueous solution to which chromic acid was not added, the film was not colored. When we investigated the reason for this, we found that a colored film could not be obtained due to the fast reaction rate of chromium in its hyperpassive state.We then conducted polarization under the same conditions while applying a constant potential pulse wave. It has been found that a colored film is formed and that the color can be varied by changing the electrolytic conditions, leading to the present invention.
したがって、本発明は、最も広義には、電解水溶液中に
ステンレス鋼片を浸漬して該ステンレス鋼片を一方の電
極としてパルス電位を印加することを特徴とするステン
レス鋼の着色方法である。Therefore, in the broadest sense, the present invention is a method for coloring stainless steel, which is characterized by immersing a piece of stainless steel in an electrolytic aqueous solution and applying a pulsed potential using the piece of stainless steel as one electrode.
より特定的には、本発明は、硫酸、硝酸、リン酸等の電
解水溶液中にステンレス鋼片を浸漬し、該ステンレス鋼
片を一方の電極として、陽極パルス電位、次いで陰極パ
ルス電位を交互に繰り返えし印加するとともに、そのと
きのパルス電位を−０゜２〜１．５Ｖ （ｖｓ、 ５Ｃ
Ｅ）、パルス時間を０．００１〜１．０秒間とするとと
もに印加時間を５０秒ないし３時間とすることを特徴と
するステンレス鋼の着色方法である。More specifically, the present invention involves immersing a piece of stainless steel in an electrolytic aqueous solution such as sulfuric acid, nitric acid, phosphoric acid, etc., using the piece of stainless steel as one electrode, and applying an anodic pulse potential and then a cathode pulse potential alternately. While applying it repeatedly, the pulse potential at that time was -0°2~1.5V (vs, 5C
E) is a method for coloring stainless steel, characterized in that the pulse time is 0.001 to 1.0 seconds and the application time is 50 seconds to 3 hours.
上記ステンレス鋼としては代表的にはフェライト系ステ
ンレス鋼であるが、クロムを含む材料であるかぎり、オ
ーステナイト系あるいはマルテンサイト系のいずれであ
っても同様の効果は当然期待され本発明により着色され
る。The above-mentioned stainless steel is typically ferritic stainless steel, but as long as it contains chromium, the same effect can naturally be expected with either austenitic or martensitic stainless steel, and it can be colored according to the present invention. .
また、上記電解水溶液としては、後述するように、本発
明の処理条件下でクロムの）容出が行われる限り特に制
限なく、例えば硫酸、硝酸、リン酸等の電解水溶液が包
含される。なお、本発明にあっては着色用にＭｎ、■な
どの重金属の化合物を電解水溶液に添加する必要はない
。Further, as described below, the electrolytic aqueous solution is not particularly limited as long as chromium is removed under the treatment conditions of the present invention, and includes, for example, electrolytic aqueous solutions of sulfuric acid, nitric acid, phosphoric acid, and the like. In addition, in the present invention, it is not necessary to add heavy metal compounds such as Mn and ■ to the electrolytic aqueous solution for coloring.
このように、本発明によれば、定電位パルス法により、
つまり陽極パルス電位での過不働態化溶解と陰極パルス
電位でのＣｒ酸化物の還元析出によりＣｒ含有着色皮膜
が生成するのであって、その場合、パルス電位、パルス
時間あるいは処理時間を変えることにより、青色、金色
、紫色、緑色、そして黒色と順次彩色を変更することが
できる。Thus, according to the present invention, by the constant potential pulse method,
In other words, a Cr-containing colored film is generated by overpassivation dissolution at the anodic pulse potential and reductive precipitation of Cr oxide at the cathode pulse potential.In this case, by changing the pulse potential, pulse time, or treatment time, You can change the coloring sequentially from , blue, gold, purple, green, and black.
（作用）
次に、本発明の着色法について着色条件を上述のように
限定した理由を次に説明する。(Function) Next, the reason why the coloring conditions for the coloring method of the present invention are limited as described above will be explained.
まず、添付図面にはパルス電位の波形概念を模式的に示
すが、５ＣＥ（飽和カロメル電極）を基準にした電位は
、ゼロから陽極パルス電位に到達してから所定時間経過
後、ステンレス鋼表面の不働態皮膜が安定になる電位（
Ｅｏ）を経て陰極パルス電位に切り換えられ、所定時間
経過後再び陽極パルス電位に切り換えられ、以後これを
繰り返す。このときの陽極パルス電位印加開始から次の
陽極パルス電位印加までの時間をパルス時間（ｔ）と称
する。First, the attached drawing schematically shows the waveform concept of the pulse potential.The potential based on 5CE (saturated calomel electrode) reaches the anode pulse potential from zero, and after a predetermined time elapses, the stainless steel surface The potential at which the passive film becomes stable (
Eo), the potential is switched to the cathode pulse potential, and after a predetermined period of time, it is switched again to the anode pulse potential, and this process is repeated thereafter. The time from the start of application of the anode pulse potential at this time to the application of the next anode pulse potential is referred to as pulse time (t).
浸漬浴としての電解水？８液についてであるが、これは
硫酸、硝酸、リン酸などの水溶液であるいわゆる電解水
溶液であれば特に制限されない。本発明の具体的態様に
よれば、この電解水溶液、例えば硫酸水溶液の液温度は
、０〜１００℃に限定するが、この範囲を越えた温度領
域では電解処理に際しての分極が迅速に進行しないこと
から、本発明の具体的態様にあっては液温度を上記範囲
に限定する。好ましくは２５〜８０℃である。Electrolyzed water as an immersion bath? Regarding the 8 liquid, there is no particular restriction as long as it is a so-called electrolytic aqueous solution, which is an aqueous solution of sulfuric acid, nitric acid, phosphoric acid, etc. According to a specific embodiment of the present invention, the temperature of this electrolytic aqueous solution, for example, a sulfuric acid aqueous solution, is limited to 0 to 100°C, but polarization does not proceed rapidly during electrolytic treatment in a temperature range exceeding this range. Therefore, in a specific embodiment of the present invention, the liquid temperature is limited to the above range. Preferably it is 25-80°C.
電解水溶液は、陽極電解に際しＣｒを溶出させる必要が
あり、その限りにおいてその濃度は制限されないが、実
用上の観点からはＣｒ’（９出を容易にさせるために硫
酸水溶液の場合０．１〜１８ ｋｍｏｌ／ｍ″の濃度の
硫酸水溶液を使用するのが良い。余り希薄であると溶出
は速度が遅くなる。−力筒濃度側ではそのような問題は
ないが、実際上余り高濃度の溶液は得られない。好まし
くは、０．５〜５ ｋｍｏｌ／ｍ’である。It is necessary for the electrolytic aqueous solution to elute Cr during anodic electrolysis, and as long as this is the case, the concentration is not limited, but from a practical point of view, in the case of a sulfuric acid aqueous solution, in order to facilitate the elution of Cr' (9), it is necessary to elute Cr. It is best to use a sulfuric acid aqueous solution with a concentration of 18 kmol/m''. If it is too dilute, the elution rate will be slow. - There is no such problem on the side of concentration, but in reality, solutions with too high concentration is not obtained. Preferably, it is 0.5 to 5 kmol/m'.
定電位パルス波の陰極パルス電位は、−０，２Ｖがら０
．５Ｖの範囲とするが、特に陰極電位をＯＶがら０．５
ｖに増加するにつれて皮膜の形成速度が減少する。パル
ス電位を０．４Ｖ （ｖｓ、 ５ＣＥ）を越えて高くす
ると、着色皮膜形成のための還元反応が起こらず、着色
皮膜が得られない。The cathode pulse potential of the constant potential pulse wave is -0.2V to 0.
．． The range is 5V, but especially the cathode potential is 0.5V from OV.
The rate of film formation decreases as v increases. When the pulse potential is increased to more than 0.4 V (vs. 5CE), the reduction reaction for forming a colored film does not occur, and a colored film cannot be obtained.
パルス時間は、０．００１〜１．０秒間とするが、この
ＬＮ囲より短時間側ではＣｒの溶出、析出が十分に行わ
れず、一方長時間側ではＣｒの溶出が過度に行われ、着
色皮膜は生成されない、好ましくは０．０１ ｓ〜０．
２ｓである。この範囲で特に光沢ある皮膜が得られる。The pulse time is set to 0.001 to 1.0 seconds. On the shorter side than this LN range, Cr elution and precipitation are not sufficiently performed, while on the longer side, Cr elution and precipitation occur excessively, resulting in discoloration. No film is formed, preferably between 0.01 s and 0.01 s.
It is 2s. Within this range, a particularly glossy film can be obtained.
処理時間は、５０分間ないし３時間であり、あまり長時
間の処理では皮膜が厚くなりすぎて母材との付着特性が
むしろ劣化する傾向がある。The treatment time is from 50 minutes to 3 hours; if the treatment is too long, the film becomes too thick and the adhesion properties to the base material tend to deteriorate.
ステンレス鋼中のクロム成分に関する反応式は下記のよ
うに表記される。これから０．５ｖ〜０．８５ Ｖから
プラスの方へ過小Ｉｔｌ１Ｍ化反応が、この電位からマ
イナスの方へ還元反応が起こるものと考えられる。The reaction formula regarding the chromium component in stainless steel is expressed as follows. From this, it is thought that an under-Itl1M conversion reaction occurs from 0.5 V to 0.85 V toward the positive side, and a reduction reaction occurs from this potential toward the negative side.
Ｃｒｙ（ｈ＋ ４Ｈｚ’０＝Ｃｒ２０７”−＋ ８１１
”＋６ｅ ・・・＋１１このような還元反応は表面皮
膜の生成反応であると考えられる。したがって、Ｃｒの
過不働態化反応電位域とクロム酸イオンの還元電位域が
見られるような条件では、ステンレス鋼のパルス電位域
を変化させることによって着色皮膜が得られる。Cry(h+ 4Hz'0=Cr207"-+ 811
”+6e ...+11 Such a reduction reaction is considered to be a surface film formation reaction. Therefore, under conditions where the overpassivation reaction potential range of Cr and the reduction potential range of chromate ions are observed, A colored film is obtained by changing the pulse potential range of stainless steel.
次に、実施例によって本発明の作用効果についてさらに
具体的に説明する。Next, the effects of the present invention will be explained in more detail with reference to Examples.
実施例１
供試材として５ＵＳ４３０鋼の焼鈍済みの棒材を使用し
た。かかる棒材がら試験片を切り出し、表面の研磨、脱
脂処理をおこなってから参照電極にＳＣＥ電極を使用し
、対極として白金線を使用し、硫酸水／８液に浸潤して
着色試験を行った。Example 1 An annealed 5US430 steel bar was used as a test material. A test piece was cut out from the bar material, the surface was polished and degreased, and then a coloring test was conducted by soaking it in sulfuric acid water/8 solution using an SCE electrode as a reference electrode and a platinum wire as a counter electrode. .
着色試験は、まず試験片を一方の′ＩＭ極とし、ボテン
ショスクノトで試験片電極の電位を一定に制ｉ１Ｌ、そ
こに定電位パルス波を加えた。In the coloring test, first, the test piece was used as one IM electrode, the potential of the test piece electrode was controlled to be constant with a potentiometer, and a constant potential pulse wave was applied thereto.
生成した着色皮膜はオージェ（口木電子＠製、ＪＡＭＰ
−１０５）分析に供した。The colored film produced is Auger (manufactured by Kuchiki Denshi@, JAMP
-105) Provided for analysis.
８０℃、５ ｋＩｌｏｔ／ｍ’の硫酸水溶液中で陽極パ
ルス電位０．９ｖの場合、時間とともに青色、金色、緑
色、黒色の着色皮膜が試験片表面に得られた。しかし、
ｔ ＝Ｏ，Ｓ秒以上となると、着色皮膜が得られテ「＜
なった。また、ｔが０．０１秒以下になると着色速度が
非常に遅くなることが分かった。When the anode pulse potential was 0.9 V in an aqueous sulfuric acid solution of 5 kIlot/m' at 80° C., colored films of blue, gold, green, and black were formed on the surface of the test piece over time. but,
When t = O, S seconds or more, a colored film is obtained.
became. It was also found that when t was 0.01 seconds or less, the coloring speed became extremely slow.
実施例２
本例では実施例１を繰り返したが、陽極パルス電位を０
．９ｖの一定値とし、陰極パルス電位を変えた。硫酸水
溶液の濃度は５ ｋｍｏｌ／ｍ３、／＆湯温度８０℃で
あった。陰極パルス電位が０．４Ｖ、 ０．３Ｌ ＯＶ
と変わると共に試験片表面では金属光沢（皮膜なし）、
薄灰色皮膜、黄色皮膜が形成された。各電流波形を比べ
てみると、陰極パルス電位が０．４Ｖの時、電流マイナ
ス波が非常に小さ（、陰極パルス電位が０．３Ｌ ＯＶ
になると共に電流マイナス波が大きくなる傾向にあった
。それと同時に着色皮膜が現れた。Example 2 In this example, Example 1 was repeated, but the anode pulse potential was changed to 0.
．． A constant value of 9V was used, and the cathode pulse potential was varied. The concentration of the sulfuric acid aqueous solution was 5 kmol/m3, and the hot water temperature was 80°C. Cathode pulse potential is 0.4V, 0.3L OV
At the same time, the surface of the test piece has a metallic luster (no film),
A light gray film and a yellow film were formed. Comparing each current waveform, when the cathode pulse potential is 0.4V, the negative current wave is very small (, when the cathode pulse potential is 0.3L OV
There was a tendency for the negative current wave to become larger as the temperature increased. At the same time, a colored film appeared.
これは生成したクロム酸イオンが還元されて表面皮膜に
なりやすいためと考えられる。また、着色皮膜の生成と
同時に皮膜表面のＣｒ含有率も高くなり、それにしたが
ってＣｒの過不働態化反応が生じやすくなるためにプラ
ス電流も上がるものと考えられる。This is thought to be because the generated chromate ions are easily reduced and form a surface film. Furthermore, it is thought that at the same time as the colored film is formed, the Cr content on the film surface also increases, and accordingly, the overpassivation reaction of Cr becomes more likely to occur, so that the positive current also increases.
（発明の効果）
以上詳述したように、本発明によれば、従来よりとかく
問題のあったステンレス冒の着色が硫酸水溶液などの電
解水溶液に浸潤して定電位パルス波を印加するだけで容
易に行うことができ、しかも着色の程度も処理条件に変
更するだけで種々変更できるのであって、その実用上の
意義は大きい。(Effects of the Invention) As detailed above, according to the present invention, coloring of stainless steel, which has been a problem in the past, can be easily done by simply soaking it in an electrolytic aqueous solution such as a sulfuric acid solution and applying a constant potential pulse wave. Furthermore, the degree of coloring can be varied simply by changing the processing conditions, which is of great practical significance.
添付図面はパルス電位の波形概念の模式的説明図である
。The attached drawing is a schematic explanatory diagram of the waveform concept of the pulse potential.
Claims (2)
ンレス鋼片を一方の電極としてパルス電位を印加するこ
とを特徴とするステンレス鋼の着色方法。(1) A method for coloring stainless steel, which comprises immersing a piece of stainless steel in an electrolytic aqueous solution and applying a pulsed potential using the piece of stainless steel as one electrode.
鋼片を浸漬し、該ステンレス鋼片を一方の電極として、
陽極パルス電位、次いで陰極パルス電位を交互に繰り返
えし印加するとともに、そのときのパルス電位を−０．
２〜１．５Ｖ（ｖｓ．ＳＣＥ）、パルス時間を０．００
１〜１．０秒間とするとともに印加時間を５０秒ないし
３時間とすることを特徴とするステンレス鋼の着色方法
。(2) Immerse a stainless steel piece in an aqueous solution of sulfuric acid, nitric acid, or phosphoric acid, and use the stainless steel piece as one electrode.
An anode pulse potential and then a cathode pulse potential are applied repeatedly, and the pulse potential at that time is set to -0.
2-1.5V (vs.SCE), pulse time 0.00
A method for coloring stainless steel, characterized in that the application time is 1 to 1.0 seconds and the application time is 50 seconds to 3 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26100788A JPH02107798A (en) | 1988-10-17 | 1988-10-17 | Method for coloring stainless steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26100788A JPH02107798A (en) | 1988-10-17 | 1988-10-17 | Method for coloring stainless steel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02107798A true JPH02107798A (en) | 1990-04-19 |
| JPH0518915B2 JPH0518915B2 (en) | 1993-03-15 |
Family
ID=17355760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26100788A Granted JPH02107798A (en) | 1988-10-17 | 1988-10-17 | Method for coloring stainless steel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02107798A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5858200A (en) * | 1996-05-30 | 1999-01-12 | Bridgestone Metalpha Corporation | Method of and apparatus for manufacturing metallic fiber and the twine of metallic fibers, and method of coloring metallic fiber and the twine of metallic fibers |
| JP2007205207A (en) * | 2006-01-31 | 2007-08-16 | Hitachi Ltd | Reciprocating compressor |
| CN114108049A (en) * | 2020-08-28 | 2022-03-01 | 马尼株式会社 | Black medical instrument and manufacturing method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6227597A (en) * | 1985-07-29 | 1987-02-05 | Kinki Yakuhin Kogyo Kk | Surface treatment of chromium alloy |
-
1988
- 1988-10-17 JP JP26100788A patent/JPH02107798A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6227597A (en) * | 1985-07-29 | 1987-02-05 | Kinki Yakuhin Kogyo Kk | Surface treatment of chromium alloy |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5858200A (en) * | 1996-05-30 | 1999-01-12 | Bridgestone Metalpha Corporation | Method of and apparatus for manufacturing metallic fiber and the twine of metallic fibers, and method of coloring metallic fiber and the twine of metallic fibers |
| US6270913B1 (en) | 1996-05-30 | 2001-08-07 | Bridgestone Metalpha Corporation | Apparatus for manufacturing metallic fibers, method of manufacturing twine of metallic fibers, twine of metallic fibers and method of coloring metallic fiber |
| US6338780B2 (en) | 1996-05-30 | 2002-01-15 | Bridgestone Metalpha Corporation | Apparatus for manufacturing metallic fibers and method of manufacturing colored metallic fiber |
| JP2007205207A (en) * | 2006-01-31 | 2007-08-16 | Hitachi Ltd | Reciprocating compressor |
| CN114108049A (en) * | 2020-08-28 | 2022-03-01 | 马尼株式会社 | Black medical instrument and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0518915B2 (en) | 1993-03-15 |
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