JPS62274096A - Colored stainless steel material - Google Patents
Colored stainless steel materialInfo
- Publication number
- JPS62274096A JPS62274096A JP11823886A JP11823886A JPS62274096A JP S62274096 A JPS62274096 A JP S62274096A JP 11823886 A JP11823886 A JP 11823886A JP 11823886 A JP11823886 A JP 11823886A JP S62274096 A JPS62274096 A JP S62274096A
- Authority
- JP
- Japan
- Prior art keywords
- stainless steel
- steel material
- oxide
- colored
- amorphous
- 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
- 239000000463 material Substances 0.000 title claims abstract description 23
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 22
- 239000010935 stainless steel Substances 0.000 title claims abstract description 22
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 239000005300 metallic glass Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011651 chromium Substances 0.000 abstract description 8
- 238000005868 electrolysis reaction Methods 0.000 abstract description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000423 chromium oxide Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000002845 discoloration Methods 0.000 description 6
- 238000004040 coloring Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000004566 building material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229940117975 chromium trioxide Drugs 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002050 diffraction method Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000002233 thin-film X-ray diffraction Methods 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 101100342332 Mus musculus Klf16 gene Proteins 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method 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
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
〈産業上の利用分野〉
本発明は、建材用を主要な用途とする、色ムラの少ない
耐候性の良い着色ステンレス鋼材に関する。Detailed Description of the Invention 3. Detailed Description of the Invention <Industrial Field of Application> The present invention relates to a colored stainless steel material that is mainly used as a building material and has good weather resistance with little color unevenness.
〈先行技術とその問題点）
ステンレス鋼材に多彩な色調を付与する方法として、主
に硫酸＋クロム酸の混合液を用いたいわゆるｌＮＣ０法
が知られている（特公昭５２−３１８１７号、特公昭５
２−２５８１７号、特公昭５３−３１８１７号）。(Prior art and its problems) The so-called lNC0 method, which mainly uses a mixture of sulfuric acid and chromic acid, is known as a method for imparting various colors to stainless steel materials (Japanese Patent Publication No. 52-31817, Japanese Patent Publication No. 31817, 5
2-25817, Special Publication No. 53-31817).
これらの方法は「着色」工程と「硬膜」工程の２液２工
程からなるもので、各々独立の溶液組成・処理条件・温
度で２液２工程を行い１表面に生成する酸化物は、Ｉ’
ｃおよびＣｒ上体の結晶質のＣｒ、 Ｆｅスピネル酸化
物が主体であることが知られている。These methods consist of two two-liquid steps, a "coloring" step and a "hardening" step.The two-liquid two steps are performed with independent solution compositions, processing conditions, and temperatures, and the oxides produced on the surface are as follows: I'
It is known that crystalline Cr and Fe spinel oxides with a superstructure of c and Cr are the main components.
着色ステンレス鋼の主要な用途は建材用であり、色調の
統一性すなわち、色ムラのないこと、耐摩耗性のよいこ
との他に、特に外装用として用いる場合には耐候性の良
いことが要求される。The main use of colored stainless steel is for building materials, and in addition to uniformity of color, that is, no color unevenness, and good abrasion resistance, it is also required to have good weather resistance, especially when used for exterior purposes. be done.
ところが、耐候性に関して従来の着色ステンレス鋼は必
ずしもト分なものとは言えない。すなわち、長期間の使
用により、はこりの付着等による汚れが落ちにくい、あ
るいは変色が起こるなどの欠点がある。However, conventional colored stainless steel cannot necessarily be said to be satisfactory in terms of weather resistance. That is, when used for a long period of time, there are drawbacks such as stains due to adhesion of lumps etc. being difficult to remove or discoloration occurring.
〈発明の目的〉
本発明の目的は、着色ステンレス索材における問題点を
解決し、色ムラの少ない耐候性の良い着色ステンレス鋼
材を提供することにある。<Objective of the Invention> An object of the present invention is to solve the problems associated with colored stainless steel rope materials and to provide a colored stainless steel material with less uneven coloring and good weather resistance.
〈発明の構成）
本発明者等は、着色ステンレス鋼材の耐候性における開
通点を克服すべく種々の実験を行った結果、ステンレス
鋼表面に着色層を形成する酸化皮■桑を、非晶質化する
ことにより、この問題が解決されることを見出した。(Structure of the Invention) The present inventors conducted various experiments in order to overcome the break-through point in the weather resistance of colored stainless steel materials. We have found that this problem can be solved by
すなわち、本発明は、非晶質金属酸化物を表面に形成さ
せてなることを特徴とする着色ステンレス鋼材を提供す
る。That is, the present invention provides a colored stainless steel material characterized by forming an amorphous metal oxide on its surface.
以Ｆに本発明の詳細な説明する。The present invention will be explained in detail below.
本発明者等は、すでに開示した特願昭５９−２４７５４
２号による交番電流電解法を適用して、ステンレス鋼材
への着色処理条件を種々に変え、異った結晶状態の酸化
物皮膜を形成させ、形成酸化物の性状と、耐候性の関係
を詳細に調べた。The present inventors have already disclosed the patent application No. 59-24754.
Applying the alternating current electrolysis method according to No. 2, we varied the coloring treatment conditions on stainless steel materials to form oxide films with different crystal states, and investigated the relationship between the properties of the formed oxides and weather resistance in detail. I looked into it.
その−結果。The result.
１、表面に形成されるＣｒ、 Ｆｅの酸化物中の非晶質
の部分を特定量以トにすること。1. The amorphous portion of the Cr and Fe oxides formed on the surface must be reduced to a specific amount.
２、この特定量とは、Ｃｒ、 Ｆｅの酸化物中の非晶質
：結晶質の比を５以七とすること、を知見した。2. It has been found that this specific amount means that the ratio of amorphous to crystalline in the oxides of Cr and Fe is 5 to 7.
第１図に示すように、表面酸化物の結晶状態を、薄膜Ｘ
線回折法により測定し、２θ［ｄｅｇ］−ｃｐｓチャー
トとした結果、非晶質酸化物によるブロードピーク（第
１図Ｂ）の面積とＦｅ、 Ｃｒスピネルの（２２０）（
第１図Ａ）および（３１１）（第１図Ａ’ ）ピークの
合計面積（Ａ＋Ａ’）の比、Ｂ／Ａ ＋ Ａ ’が５以
りである場合に良好な耐候性のｊ；ｔられることを見出
した。As shown in Figure 1, the crystalline state of the surface oxide is
As a result of measurement using a line diffraction method and a 2θ [deg]-cps chart, the area of the broad peak due to amorphous oxide (Figure 1 B) and the (220) (
When the ratio of the total area (A + A') of the peaks A) and (311) (A' in Figure 1), B/A + A', is 5 or more, good weather resistance is determined. I discovered that.
すなわちＨＬ研磨した厚み１．５ ｍｍの５ＵＳ３０４
ステンレス鋼を、特願昭５９−２４７５４２号の方法を
用い、種々の条件で着色した。また従来法によって着色
したサンプルも作成した。That is, 5US304 with a thickness of 1.5 mm after HL polishing.
Stainless steel was colored under various conditions using the method disclosed in Japanese Patent Application No. 59-247542. We also created colored samples using conventional methods.
これらのサンプルを、１２０ｍ１ｎサイクル、うち１８
分降１（４、残り照射（４６℃）の条件でサンシャイン
ウエザオメーターで４０００時間試験（促進耐較性試験
）したのち、Ｉ］視Ｉ＆察により変色の程度を調べた。These samples were subjected to 120 m1n cycles, of which 18
After 4,000 hours of testing (accelerated resistance test) using a Sunshine Weather-Ometer under the conditions of 1 minute precipitation and remaining irradiation (46° C.), the degree of discoloration was examined by visual inspection.
また、Ｌ配着色処理により表面に形成された酸化物皮１
漠につき、薄膜Ｘｉ！１１回折法により、非晶質酸化物
によるブロードピーク面積（Ｂ）に対しＣｒ％Ｆｅスピ
ネル酸化物の（２２０）、（３１１）ピークの合計面積
（Ａ＋Ａ’ ）の比（Ｂ／Ａ＋Ａ’ ）を求めた。In addition, the oxide skin 1 formed on the surface by the L coloring process
In the distance, thin film Xi! 11 Using the diffraction method, the ratio (B/A+A') of the total area (A+A') of the (220) and (311) peaks of the Cr%Fe spinel oxide to the broad peak area (B) of the amorphous oxide was calculated. I asked for it.
試験の結果を７ｊＳ１表に示す。The test results are shown in Table 7jS1.
第１表の結果から、ＩＴｉ′ｒ記、非晶質酸化物ピーク
面積とＣ「、Ｆｅスピネル酸化物ピークの面積の比が５
以トであると、サンシャインウェザオメーター試験によ
る変色か著しく押えられることが明らかであった。From the results in Table 1, it can be seen that the ratio of the area of the amorphous oxide peak to the area of the Fe spinel oxide peak is 5.
It was clear that under these conditions, the discoloration caused by the Sunshine Weather-Ometer test was significantly suppressed.
なお、非晶質酸化物は結晶質酸化物同様、ｔとしてＣｒ
およびＦｅ酸化物よりなることを確認した。Note that in amorphous oxides, as in crystalline oxides, t is Cr.
and Fe oxide.
本発明の非晶質金属酸化物を表面に形成させた着色ステ
ンレス鋼材の製造方法は、いかなる製造方法で−もよい
。例えば種々の溶液組成、処理条件、温度、による浸漬
処理、陽極処理、陰極処理および加熱処理等を適切に選
択して行ってもよい。好ましくは以下の条件による交番
電解法を用いる。 ゛
電解液組成としては、２モル以上の６価クロムと２．５
モル以−トの硫酸を含む混合溶液を用い、陽極型流密、
度としては０．０１〜：１．０−八／ｄば、また陰極電
流密度としては０．０３〜５．０ ＾／ｄゴ、さらに
交番周波数としては１００ｔｌｚ以下が好ましい。電解
処理温度は４０℃〜８５℃が良い。The colored stainless steel material having an amorphous metal oxide formed on its surface according to the present invention may be produced by any method. For example, immersion treatment, anodic treatment, cathodic treatment, heat treatment, etc. may be appropriately selected and carried out using various solution compositions, treatment conditions, and temperatures. Preferably, an alternating electrolysis method under the following conditions is used.゛The electrolyte composition includes 2 moles or more of hexavalent chromium and 2.5 moles of hexavalent chromium.
Using a mixed solution containing more than molar sulfuric acid, anode type flowtight,
Preferably, the frequency is 0.01 to 1.0-8/d, the cathode current density is 0.03 to 5.0/d, and the alternating frequency is preferably 100 tlz or less. The electrolytic treatment temperature is preferably 40°C to 85°C.
また、本発明の着色ステンレス鋼材の形状はいか、なる
ものでもよく、線材、管材、板材、箔、パイプ、塊、異
形断面材、粉粒体などを代表的に挙げることができる。Further, the colored stainless steel material of the present invention may have any shape, and representative examples thereof include wire rod, tube material, plate material, foil, pipe, lump, irregular cross-section material, and powder.
〈実施例〉 以ドに実施例により本発明を具体的に説明する。<Example> The present invention will be specifically explained below with reference to Examples.
被着色物の形状、寸法は以ドの３種を用いた。The following three types of shapes and dimensions of the objects to be colored were used.
■通常ｌ−程で製造された厚さ０．５ ｍｍの５ＵＳ３
０４ステンレス冷延板、
■通常のＩ程で製造された厚さ５０μの５ＵＳ３０４ス
テンレス箔、
■通常のＬ程で製造された外径３５ｍｍ、肉ノゾ０．８
ｎｍの５ＵＳ３０４ステンレス溶接管（実に例）
１−記３種の被着色物を６０℃、３００ｇ１ｌ三酸化ク
ロムと４５０ｇ／Ｉｌ硫酸の混合液中で陽極電流密度；
０．＋２＾／ｄば、陽極′１“ば解時間＝７秒、陰極
′１「流密度； Ｏ，Ｏａ八へｄｒｎ’、陰極電解時間
２５秒、で１１０回繰返し電解を行い、ブロンズ色の表
面酸化物皮膜を得た。■5US3 with a thickness of 0.5 mm, usually manufactured at about l-
04 stainless steel cold-rolled plate, ■ 5US304 stainless steel foil with a thickness of 50μ manufactured by the usual I degree, ■ Outer diameter 35 mm, meat thickness 0.8 manufactured by the usual L degree
nm 5US304 stainless steel welded pipe (actual example) 1- The three types of materials to be colored were heated at 60°C in a mixed solution of 300g/l chromium trioxide and 450g/Il sulfuric acid at anode current density;
0. +2^/d, anode '1' decomposition time = 7 seconds, cathode '1 'flow density; An oxide film was obtained.
（比較例）
同様に上記３種の被着色物を用い、比較として従来性な
われているｌＮＣ０法により着色処理を行なった。実施
例と同じ組成の溶液中で８分、８５℃で浸ｉｉ１ シ、
その後４０℃で、２５０ｇ／ｆｆｉの三酸化クロムと５
ｇ／ｆｉのリン酸との混合溶液中で、陰極処理として０
．３ 八／ｄｒｒｆ、５分行ない、ブロンズ色にした
。(Comparative Example) Similarly, using the above three types of colored objects, coloring treatment was carried out by the conventional lNC0 method for comparison. Immersion at 85°C for 8 minutes in a solution with the same composition as in Example iii1
Thereafter, at 40°C, 250 g/ffi of chromium trioxide and 5
g/fi in a mixed solution with phosphoric acid as cathodic treatment.
．． 3 8/drrf, 5 minutes, bronze color.
実施例と比較例の表面生成皮膜を薄膜用Ｘ線回折装置に
て分析し、非晶質酸化物と結晶質酸化物のピーク面ｈ１
の比（第１図で説明したＢ／Ａ＋Ａ’ ）を求めると同
時に、３０００時間のサンシャインウエザオフ−ター試
験後の変色の程度を目視観察した。The surface formed films of Examples and Comparative Examples were analyzed using a thin film X-ray diffraction device, and the peak plane h1 of amorphous oxide and crystalline oxide was
At the same time, the degree of discoloration after the 3000 hour sunshine weather off-ter test was visually observed.
結果を第２表に示す。The results are shown in Table 2.
第２表の結果から本発明鋼材の耐候性の優れていること
が明らかである。It is clear from the results in Table 2 that the steel materials of the present invention have excellent weather resistance.
第１表 表面酸化物皮ＩＩ！２中の非晶質酸化物の割
合と促進耐候性試験
における変色との関係
！）第１し１参照
２）サンシャインウェザオフ−ター４０００時間試験
第 ２ 表 表面酸化物皮膜中の非晶質酸化物の割合
と促進耐候性試験における変色との関係
１） 第１図参照
２）サンシャインウェザオフ−ター３０００時間試験〈
発明の効果〉
本発明の非晶質金属酸化物を表面に形成させてなる着色
ステンレス鋼材は、色ムラか少なく、耐候性が優れてい
る。Table 1 Surface oxide skin II! Relationship between the proportion of amorphous oxide in 2 and discoloration in accelerated weathering test! 2) Sunshine Weather Off-Tar 4000 Hour Test Table 2 Relationship between the proportion of amorphous oxide in the surface oxide film and discoloration in accelerated weathering test 1) See Figure 1 2) Sunshine weather off-ter 3000 hour test
Effects of the Invention> The colored stainless steel material formed on the surface of the amorphous metal oxide of the present invention has less uneven color and has excellent weather resistance.
特に、建材用等の外装材分野に広く利用しつる。In particular, it is widely used in the field of exterior materials such as building materials.
第１図は、鋼材表面のＣｒ、 Ｆｃ非晶質酸化物と品質
酸化物との面積比の計算方法を示す、薄膜Ｘ線回折法に
よるＣＰＳチャートである。FIG. 1 is a CPS chart based on a thin film X-ray diffraction method showing a method for calculating the area ratio between Cr and Fc amorphous oxides and quality oxides on the surface of steel materials.
Claims (1)
特徴とする着色ステンレス鋼材。(1) A colored stainless steel material characterized by forming an amorphous metal oxide on its surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11823886A JPS62274096A (en) | 1986-05-22 | 1986-05-22 | Colored stainless steel material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11823886A JPS62274096A (en) | 1986-05-22 | 1986-05-22 | Colored stainless steel material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62274096A true JPS62274096A (en) | 1987-11-28 |
| JPH0570719B2 JPH0570719B2 (en) | 1993-10-05 |
Family
ID=14731654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11823886A Granted JPS62274096A (en) | 1986-05-22 | 1986-05-22 | Colored stainless steel material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62274096A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02130327U (en) * | 1989-04-03 | 1990-10-26 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8250894B2 (en) * | 2006-10-30 | 2012-08-28 | Aida Engineering, Ltd. | Releasing mechanism and leveling apparatus |
-
1986
- 1986-05-22 JP JP11823886A patent/JPS62274096A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02130327U (en) * | 1989-04-03 | 1990-10-26 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0570719B2 (en) | 1993-10-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zuo et al. | Investigation of composition and structure for a novel Ti–Zr chemical conversion coating on 6063 aluminum alloy | |
| JP6806152B2 (en) | Sn-based alloy plated steel sheet | |
| JP5842988B2 (en) | Steel plate for containers | |
| US3714001A (en) | Method for forming anodic oxide coatings having improved adhesive properties | |
| JPS62274096A (en) | Colored stainless steel material | |
| JPS581093A (en) | Method for forming protective film on surface of magnesium material | |
| JPS5817278B2 (en) | Method of forming a protective film on the surface of aluminum materials | |
| JPS5928638B2 (en) | Method of forming a colored protective film on the surface of magnesium material | |
| US4579633A (en) | Method of producing tin-free steel sheets | |
| JPS5916997A (en) | Formation of colored protective film on surface of magnesium material | |
| JPH01208494A (en) | Formation of fluororesin coating film on surface of zinc, zinc alloy or galvanized material | |
| JPH089798B2 (en) | Surface treatment method for stainless steel | |
| RU2677388C1 (en) | Method of making protective coatings on valve metals and alloys thereof | |
| JPS589159B2 (en) | Dou Mataha Dougo Kinnochiyakushiyokuhouhou | |
| CA1223544A (en) | Method of producing tin-free steel sheets | |
| Junxi et al. | The growth mechanism of the coloured passive film formed on 304 stainless steel in sulfuric solution without Cr6+ ion by using AV passivation | |
| JPS605670B2 (en) | Chemical conversion treatment method for zinc and zinc alloys | |
| JPS6044772A (en) | Heat collecting plate for solar energy-powered hot water supplyer and its manufacture | |
| JPH04235300A (en) | Surface treatment of stainless steel | |
| JPS638198B2 (en) | ||
| JPS62156297A (en) | Production of surface treated steel products having high degree of blackening and excellent corrosion resistance and discoloration resistance | |
| JPS639038B2 (en) | ||
| JPS58177490A (en) | Production of tin-free steel plate | |
| JPS6260892A (en) | Method for coloring stainless steel material | |
| JPS58177489A (en) | Production of tin-free steel plate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |