JPH0570719B2 - - Google Patents
Info
- Publication number
- JPH0570719B2 JPH0570719B2 JP11823886A JP11823886A JPH0570719B2 JP H0570719 B2 JPH0570719 B2 JP H0570719B2 JP 11823886 A JP11823886 A JP 11823886A JP 11823886 A JP11823886 A JP 11823886A JP H0570719 B2 JPH0570719 B2 JP H0570719B2
- Authority
- JP
- Japan
- Prior art keywords
- stainless steel
- colored
- amorphous
- steel material
- oxide
- 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
- 229910001220 stainless steel Inorganic materials 0.000 claims description 20
- 239000010935 stainless steel Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 18
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 239000011651 chromium Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 2
- 238000002441 X-ray diffraction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 description 11
- 238000004040 coloring Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000004566 building material Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000005300 metallic glass Substances 0.000 description 3
- 239000000203 mixture 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
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-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
- 235000019646 color tone Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- NPURPEXKKDAKIH-UHFFFAOYSA-N iodoimino(oxo)methane Chemical compound IN=C=O NPURPEXKKDAKIH-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000243 solution 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
- 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
- 238000000576 coating method Methods 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
- 238000002050 diffraction method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution 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
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
＜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。
＜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INCO法が知られている（特公昭52−31817
号、特公昭52−25817号、特公昭53−31817号）。
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、表面に
生成する酸化物は、FeおよびCr主体の結晶質の
Cr、Feスピネル酸化物が主体であることが知ら
れている。
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。
ところが、耐候性に関して従来の着色ステンレ
ス鋼は必ずしも十分なものとは言えない。すなわ
ち、長期間の使用により、ほ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。
＜発明の目的＞
本発明の目的は、着色ステンレス鋼材における
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。
＜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
おける問題点を克服すべく種々の実験を行つた結
果、ステンレス鋼表面に着色層を形成する酸化皮
膜を、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。
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。
以下に本発明を詳細に説明する。
本発明者等は、すでに開示した特願昭59−
247542号（特公昭63−8198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、異つ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。
その結果
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上にすること。
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以上とすること、を知見し
た。
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チヤートとした結果、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以上である場合に良好な耐候性の得ら
れることを見出した。
すなわちHL研磨した厚み1.5mmのSUS304ステ
ンレス鋼を、特願昭59−247542号（特公昭63−
8198号）の方法を用い、種々の条件で着色した。
また従来法によつて着色したサンプルも作成し
た。これらのサンプルを、120minサイクル、う
ち18分降雨、残り照射（46℃）の条件でサンシヤ
インウエザオメーターで4000時間試験（促進耐候
性試験）したのち、目視観察により変色の程度を
調べた。また、上記着色処理により表面に形成さ
れた酸化物皮膜につき、薄膜Ｘ線回折法により、
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。
試験の結果を第１表に示す。
第１表の結果から、前記、非晶質酸化物ピーク
面積とCr、Feスピネル酸化物ピークの面積の比
が５以上であると、サンシヤインウエザオメータ
ー試験による変色が著しく押えられることが明ら
かであつた。
なお、非晶質酸化物は結晶質酸化物同様、主と
してCrおよびFe酸化物よりなることを確認した。
本発明の非晶質金属酸化物を表面に形成させる
着色ステンレス鋼材の製造方法の電解液組成とし
ては、２モル以上の６価クロムと2.5モル以上の
硫酸を含む混合溶液を用い、陽極電流密度として
は0.01〜3.0A／ｄm2、また陰極電流密度としては
0.03〜5.0A／ｄm2、さらに交番周波数としては
100Hz以下とする。電解処理温度40℃〜85℃が良
い。
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。
＜実施例＞
以下に実施例により本発明を具体的に説明す
る。
被着色物の形状、寸法は以下の３種を用いた。
通常工程で製造された厚さ0.5mmのSUS304ス
テンレス冷延板、
通常の工程で製造された厚さ50μのSUS304
ステンレス箔、
通常の工程で製造された外径35mm、肉厚0.8
mmのSUS304ステンレス溶接管
（実施例）
上記３種の被着色物を60℃、300ｇ／三酸化
クロムと450ｇ／硫酸の混合液中で陽極電流密
度；0.12A／ｄm2、陽極電解時間；７秒、陰極電
流密度；0.08A／ｄm2、陰極電解時間；５秒、で
110回繰返し電解を行い、ブロンズ色の表面酸化
物被膜を得た。
（比較例）
同様に上記３種の被着色物を用い、比較として
従来行なわれているINCO法により着色処理を行
なつた。実施例と同じ組成の溶液中で８分、85℃
で浸漬し、その後40℃で、250ｇ／の三酸化ク
ロムと５ｇ／のリン酸との混合溶液中で、陰極
処理として0.3A／ｄm2、５分行ない、ブロンズ
色にした。
実施例と比較例の表面生成被膜を薄膜用Ｘ線回
折装置にて分析し、非晶質酸化物と結晶質酸化物
のピーク面積の比（第１図で説明したＢ／Ａ＋
A′）を求めると同時に、3000時間のサンシヤイ
ンウエザオメーター試験後の変色の程度を目視観
察した。
結果を第２表に示す。
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。
<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. <Prior art and its problems> The so-called INCO method, which mainly uses a mixed solution of sulfuric acid and chromic acid, is known as a method for imparting various color tones to stainless steel materials (Japanese Patent Publication No. 52-31817).
No., Special Publication No. 52-25817, Special Publication No. 53-31817). 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 generated on the surface are Crystalline mainly composed of Fe and Cr
It is known that Cr and Fe spinel oxides are the main components. The main use of colored stainless steel is for building materials, and it is important to have uniform color tone, that is, no color unevenness,
In addition to good abrasion resistance, it is also required to have good weather resistance, especially when used for exterior purposes. However, conventional colored stainless steel cannot necessarily be said to have sufficient weather resistance. That is, when used for a long period of time, there are disadvantages such as stains due to adhesion of dust etc. that are difficult to remove or discoloration occurs. <Object of the Invention> An object of the present invention is to solve the problems associated with colored stainless steel materials and to provide colored stainless steel materials with less uneven coloring and good weather resistance. <Structure of the Invention> As a result of various experiments conducted by the present inventors in order to overcome the problems in the weather resistance of colored stainless steel materials, the present inventors have succeeded in making the oxide film that forms a colored layer on the surface of stainless steel amorphous. We have found that this problem can be solved by doing this. That is, the present invention provides a colored stainless steel material characterized by forming an amorphous metal oxide on its surface. The present invention will be explained in detail below. The present inventors have already disclosed the patent application filed in 1983-
Applying the alternating current electrolysis method according to No. 247542 (Special Publication No. 63-8198), we varied the coloring treatment conditions on stainless steel materials to form oxide films with different crystal states, and investigated the properties of the formed oxides. , the relationship between weather resistance was investigated in detail. Result 1: Increase the amorphous portion of the Cr and Fe oxides formed on the surface to a specified amount or more. 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 or more. As shown in Figure 1, the crystalline state of the surface oxide was measured by thin film X-ray diffraction method, and 2θ [deg]
As a result of cps chart, the area of the broad peak due to amorphous oxide (Fig. 1 B) and the (220) (Fig. 1 A) and (311) (Fig. 1
A') Ratio of total area of peaks (A+A'), B/A
It has been found that good weather resistance can be obtained when +A' is 5 or more. In other words, HL-polished SUS304 stainless steel with a thickness of 1.5 mm was manufactured using Japanese Patent Application No. 59-247542 (Special Publication No.
8198) under various conditions.
We also prepared colored samples using conventional methods. These samples were tested for 4,000 hours (accelerated weather resistance test) using a Sunshine Weather-Ometer under the conditions of a 120-minute cycle, including 18 minutes of rain and remaining irradiation (46℃), and then the degree of discoloration was examined by visual observation. . In addition, the oxide film formed on the surface by the above coloring treatment was analyzed by thin film X-ray diffraction method.
For broad peak area (B) due to amorphous oxide
The ratio (B/A+A') of the total area (A+A') of the (220) and (311) peaks of Cr and Fe spinel oxides was determined. The test results are shown in Table 1. From the results in Table 1, it can be seen that when the ratio of the amorphous oxide peak area to the Cr, Fe spinel oxide peak area is 5 or more, discoloration by the Sunshine Weather-Ometer test can be significantly suppressed. It was obvious. It was confirmed that the amorphous oxide is mainly composed of Cr and Fe oxides, similar to the crystalline oxide. The electrolytic solution composition of the method for manufacturing colored stainless steel materials in which amorphous metal oxides are formed on the surface of the present invention uses a mixed solution containing 2 moles or more of hexavalent chromium and 2.5 moles or more of sulfuric acid, and the anode current density 0.01~3.0A/dm 2 , and cathode current density
0.03 to 5.0A/dm 2 , and as an alternating frequency
It should be 100Hz or less. The electrolytic treatment temperature is preferably 40°C to 85°C. 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. <Example> The present invention will be specifically described below with reference to Examples. The following three types of shapes and dimensions of the objects to be colored were used. SUS304 cold-rolled stainless steel plate with a thickness of 0.5mm manufactured by a normal process, SUS304 with a thickness of 50μ manufactured by a normal process
Stainless steel foil, outer diameter 35mm, wall thickness 0.8mm manufactured using normal process
mm SUS304 stainless steel welded pipe (Example) The above three types of objects to be colored were heated at 60°C in a mixed solution of 300g/chromium trioxide and 450g/sulfuric acid, anode current density: 0.12A/dm 2 , anodic electrolysis time: 7 seconds, cathode current density: 0.08A/dm 2 , cathode electrolysis time: 5 seconds,
Electrolysis was repeated 110 times to obtain a bronze-colored surface oxide film. (Comparative Example) For comparison, coloring treatment was carried out using the above three types of colored objects using the conventional INCO method. 8 minutes at 85°C in a solution with the same composition as in the example.
After that, cathodic treatment was carried out at 0.3 A/dm 2 for 5 minutes in a mixed solution of 250 g of chromium trioxide and 5 g of phosphoric acid at 40° C. to give it a bronze color. The surface-generated coatings of Examples and Comparative Examples were analyzed using a thin film X-ray diffractometer, and the ratio of peak areas of amorphous oxide and crystalline oxide (B/A+ explained in Fig. 1)
At the same time as determining A′), the degree of discoloration after 3000 hours of Sunshine Weather-Ometer test was visually observed. The results are shown in Table 2. From the results in Table 2, it is clear that the steel materials of the present invention have excellent weather resistance.
【表】
時間試験
[Table] Time test
【表】
＜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、色ムラが少なく、耐
候性が優れている。
特に、建材用等の外装材分野に広く利用しう
る。[Table] <Effects of the Invention> The colored stainless steel material formed on the surface of the amorphous metal oxide of the present invention has little color unevenness and is excellent in weather resistance. In particular, it can be widely used in the field of exterior materials such as building materials.
第１図は、鋼材表面のCr、Fe非晶質酸化物と
晶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チヤートである。
Figure 1 shows the method for calculating the area ratio of Cr and Fe amorphous oxides to crystalline oxides on the steel surface.
This is a CPS chart using the line diffraction method.
Claims (1)
酸を含む混合溶液中において、陽極電流密度0.01
〜3.0A／ｄm2、陰極電流密度0.03〜5.0A／ｄm2、
繰返し数100Hz以下の交番電流電解を行つて得ら
れる着色ステンレス鋼材において、表面における
非晶質と結晶質とのＸ線回折におけるピーク面積
が、５以上であるCr、Feの酸化物皮膜を、該ス
テンレス鋼材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。1 In a mixed solution containing 2 moles or more of hexavalent chromium and 2.5 moles or more of sulfuric acid, an anode current density of 0.01
~3.0A/ dm2 , cathode current density 0.03~5.0A/ dm2 ,
In a colored stainless steel material obtained by performing alternating current electrolysis at a repetition rate of 100 Hz or less, a Cr, Fe oxide film having a peak area of 5 or more in X-ray diffraction between amorphous and crystalline on the surface is applied. A colored stainless steel material characterized by being formed on the surface of a stainless steel material.
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 JPS62274096A (en) | 1987-11-28 |
| JPH0570719B2 true 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 |
|---|---|---|---|---|
| DE102007051894B4 (en) * | 2006-10-30 | 2015-06-18 | Aida Engineering, Ltd. | Release mechanism and provided with this straightening device |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02130327U (en) * | 1989-04-03 | 1990-10-26 |
-
1986
- 1986-05-22 JP JP11823886A patent/JPS62274096A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007051894B4 (en) * | 2006-10-30 | 2015-06-18 | Aida Engineering, Ltd. | Release mechanism and provided with this straightening device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62274096A (en) | 1987-11-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |