JPS644593B2 - - Google Patents
Info
- Publication number
- JPS644593B2 JPS644593B2 JP10441686A JP10441686A JPS644593B2 JP S644593 B2 JPS644593 B2 JP S644593B2 JP 10441686 A JP10441686 A JP 10441686A JP 10441686 A JP10441686 A JP 10441686A JP S644593 B2 JPS644593 B2 JP S644593B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- sulfuric acid
- immersed
- black
- hydrofluoric acid
- 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
Links
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 32
- 239000010936 titanium Substances 0.000 claims description 32
- 229910052719 titanium Inorganic materials 0.000 claims description 32
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 238000007654 immersion Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 235000019646 color tone Nutrition 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000004566 building material Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C23C22/34—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 containing fluorides or complex fluorides
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)
- Chemical Treatment Of Metals (AREA)
Description
〔産業上の利用分野〕
本発明は化成処理法による黒色チタン材の製造
方法に係る。
〔従来の技術〕
近年、着色チタンは腐食環境の厳しい地域での
建築材料としてだけでなく、意匠性及び美感を重
視するインテリアやパネル部材として、また高級
性及びフアツシヨン性を重視するアクセサリーや
ネクタイピン等の装飾品として注目されている。
特に、黒色チタン材の工業的製造法は確立され
ていないが、そのアクセント材としての潜在的な
需要ニーズは非常に高い。
従来のチタンの着色法としては陽極酸化法及び
大気酸化法があり、多種類の色調を得ることが可
能で実用化も検討されているが、黒色皮膜を得る
ことは前記の方法では不可能である。
そこで、チタン表面に黒色皮膜を生成する方法
として、極めてまれではあるが、酸性溶液に可溶
性の銅化合物と過マンガン酸カリウム及び二酸化
マンガンを含む硫酸水溶液にチタンを浸漬し、酸
化銅としてチタン表面を黒色に被着せしめる方法
がある。
また、チタンを1wt％以下の弗酸水溶液中に浸
漬し、黒色皮膜を生成する表面処理法がある。
〔発明が解決しようとする問題点〕
しかし、上記の方法の内、前者については金属
チタンの表面に異種金属の黒色化合物皮膜を被着
せしめたという問題点があり、後者については明
度が高く（Ｌ＝20〜25）、着色前処理により表面
を非常に清浄化したチタンを使用する必要があ
り、また着色班が発生しやすいという問題があ
る。
そこで、本発明は上記のような欠点がなく、密
着性、加工性、耐摩耗性、耐指紋性、更には耐候
性及び耐食性にも優れた黒色チタン材を得ること
が可能な化成処理法による黒色チタン材の製造方
法を提供することを目的として創作された。
〔問題点を解決するための手段〕
本発明は、チタンまたはチタン合金を硫酸水溶
液中に下記(A)の条件で浸漬する第一次処理工程
と、該第一次処理工程を経たチタンまたはチタン
合金を下記(B)の条件で弗酸水溶液に浸漬する第二
次処理工程からなる化成処理法による黒色チタン
材の製造方法に係る。
条件(A)
硫酸濃度（wt％）≧10
溶液温度（℃） ≧50
浸漬時間（min）≧10
条件(B)
２≦弗酸濃度（wt％）＜10
溶液温度（℃）≦35
１≦浸漬時間（sec）≦1000
〔作用〕
本発明は上記のように二つの処理工程からなる
が、チタンまたはチタン合金に該二工程を施すこ
とにより、金属表面に安定した黒色皮膜を得るこ
とができる。
以下、各処理工程における浸漬条件を限定した
理由について説明する。
第一次処理工程の浸漬条件(A)について：硫酸濃
度が10wt％未満ではチタンとの反応が遅く、第
二次処理を行なつても黒色皮膜が生成され難い。
この硫酸濃度に上限はないが、98wt％以上は入
手が困難である。従つて、硫酸濃度（wt％）≧10
としたが、経済性も考慮すると、30〜50wt％の
濃度範囲を採用することが好ましい。
溶液温度については、50℃未満では硫酸とチタ
ンが反応せず、このことから溶液温度（℃）≧50
としたが、90℃以上になるとミストの発生が著し
いため、80〜90℃の範囲が好ましいといえる。
浸漬時間については、10分間未満では第二次処
理工程を経たチタン材の明度が高く、灰色ないし
灰黒色に見える。この浸漬時間は長くなつてもチ
タンの黒色化度は変化しないため、浸漬時間
（min）≧10としたが、好ましくは30〜60分間の範
囲である。
第二次処理工程の浸漬条件(B)について：
弗酸濃度が2wt％未満では反応速度が遅く、黒
色皮膜を生成するために長時間を要し、工業的生
産に向かない。一方、10wt％以上とすると生成
した黒色皮膜が弗酸に溶解するため明度が高くな
る。従つて、黒色化度と生産性を考慮して２≦弗
酸濃度（wt％）＜10としたが、好ましくは３〜
8wt％の範囲である。
溶液温度については、35℃を越えると黒色皮膜
が弗酸と激しく反応して無色となる。下限温度に
ついては別段規定する必要はないが、温度が低い
ほど反応に長時間を要する上、０℃以下では溶液
として存在しない。従つて、溶液温度（℃）≦35
としたが、好ましくは10〜25℃の範囲である。
浸漬時間は１秒未満では潜伏時間に相当するた
め反応が見かけ上発生せず、一方1000秒以上では
生成した皮膜が弗酸に溶解されて消失することに
なる。従つて、１≦浸漬時間（sec）≦1000とした
が、一般に反応時間が短か過ぎれば反応が充分で
ないため明度が高く、逆に長過ぎると皮膜が溶解
する傾向を生じることになり、この明度の問題と
経済性をも考慮して、好ましくは20〜100秒の範
囲である。
以上に本発明の第一及び第二の処理工程の浸漬
条件について説明したが、本発明の方法において
は、金属表面に生成する黒色皮膜の明度は各処理
条件、即ち試薬濃度、溶液温度、及び浸漬時間に
よつて変化させることができるため、これを制御
することにより黒色化度を調整できる。また、本
発明による発色法は陽極酸化法に比較して着色班
の発生が生じ難く、ハンドリングが簡単である。
〔実施例〕
実施例 １
純チタン冷延板（3001×300W×0.6t、単位：mm）
を第１表に示す条件で硫酸水溶液中に浸漬した
後、更に室温にて5wt％の弗酸水溶液中に浸漬し
たところ、同表に示される明度及び色調の着色チ
タン板が得られた。
同表から明らかなように、本発明の方法に係る
浸漬条件の範囲での黒色化度は明度及び色調とも
要望に応えるものであつた。
実施例 ２
純チタン板（701×150W×0.3t、単位：mm）を80
℃の37wt％の硫酸溶液中に30分間浸漬した後、
表面を流水中で洗浄し、更に第２表に示す条件下
で該金属板を弗酸水溶液中に浸漬したところ、同
表に示される明度及び色調の着色チタン板が得ら
れた。
同表から明らかなように、本発明の方法に係る
浸漬条件の範囲での黒色化度は明度及び色調とも
要望に応えるものであつた。
実施例 ３
純チタン板（701×150W×0.5t、単位：mm）を80
℃の37wt％の硫酸溶液中に60分間浸漬した後、
室温にて5wt％の弗酸水溶液に浸漬したところ表
面が黒色に変化した。
そのサンプルを、色差計により色彩を測定した
結果を第３表に示す。更に、サンシヤインウエザ
ーメーター試験機を使用した耐候性の評価結果、
及び塩水噴霧試験装置を用いた試験結果を同表に
併記したが、何れの試験においても変色はほとん
ど見られない。
更に、密着性、加工性、耐摩耗性、及び耐指紋
性の評価結果が第４表に示されるが、何れの性能
においても使用上問題がないと判断される。
実施例 ４
チタン合金板（Ti―2Mo、50f×150W×1.0t単
位：mm）を85℃の40wt％の硫酸溶液中に60分間
浸漬した後、室温にて5wt％の弗酸水溶液に浸漬
したところ、表面が黒色に変化した。そして、前
記と同様の色彩測定を行なつたところ、Ｌ＝
17.0、ａ＝0.3、ｂ＝3.0であつた。従つて、純チ
タンだけでなく、チタン合金においても同様に黒
色チタン材を製造することができる。
〔発明の効果〕
以上のように、本発明はチタンまたはチタン合
金に密着性、加工性、耐摩耗性、耐指紋性、更に
は耐候性及び耐食性にも優れ、且つ美感を有する
黒色皮膜を生成させることにより、耐腐食性を要
する建築材のような用途としてだけでなく、チタ
ン材の用途を装飾品の領域へ大きく拡大するもの
である。
[Industrial Application Field] The present invention relates to a method for producing a black titanium material using a chemical conversion treatment method. [Conventional technology] In recent years, colored titanium has been used not only as a building material in areas with severe corrosive environments, but also as interior and panel components that emphasize design and aesthetics, and for accessories and tie pins that emphasize luxury and fashion. It is attracting attention as a decorative item. In particular, although an industrial manufacturing method for black titanium material has not been established, there is a very high potential demand for it as an accent material. Conventional methods for coloring titanium include anodic oxidation and atmospheric oxidation, which make it possible to obtain a wide variety of color tones, and are being considered for practical use; however, it is impossible to obtain a black film using the methods described above. be. Therefore, as a method to generate a black film on the titanium surface, although it is extremely rare, titanium is immersed in an aqueous sulfuric acid solution containing a copper compound soluble in an acidic solution, potassium permanganate, and manganese dioxide, and the titanium surface is coated as copper oxide. There is a way to coat it in black. There is also a surface treatment method in which titanium is immersed in a hydrofluoric acid aqueous solution of 1 wt% or less to form a black film. [Problems to be solved by the invention] However, among the above methods, the former has a problem in that a black compound film of a different metal is deposited on the surface of titanium metal, and the latter has a high brightness ( L=20-25), it is necessary to use titanium whose surface has been extremely cleaned by pre-coloring treatment, and there is also the problem that colored spots are likely to occur. Therefore, the present invention uses a chemical conversion treatment method that does not have the above-mentioned drawbacks and can obtain a black titanium material that has excellent adhesion, workability, abrasion resistance, fingerprint resistance, and further has excellent weather resistance and corrosion resistance. It was created with the purpose of providing a method for manufacturing black titanium material. [Means for Solving the Problems] The present invention includes a first treatment step in which titanium or a titanium alloy is immersed in an aqueous sulfuric acid solution under the following conditions (A), and a titanium or titanium alloy that has undergone the first treatment step. The present invention relates to a method for producing a black titanium material using a chemical conversion treatment method, which includes a secondary treatment step of immersing an alloy in a hydrofluoric acid aqueous solution under the conditions (B) below. Condition (A) Sulfuric acid concentration (wt%) ≧10 Solution temperature (℃) ≧50 Immersion time (min) ≧10 Condition (B) 2≦Hydrofluoric acid concentration (wt%) ＜10 Solution temperature (℃)≦35 1≦ Immersion time (sec)≦1000 [Operation] The present invention consists of two treatment steps as described above, and by performing these two steps on titanium or titanium alloy, a stable black film can be obtained on the metal surface. . The reasons for limiting the immersion conditions in each treatment step will be explained below. Regarding the immersion conditions (A) in the first treatment step: If the sulfuric acid concentration is less than 10 wt%, the reaction with titanium is slow and a black film is difficult to form even in the second treatment.
Although there is no upper limit to this sulfuric acid concentration, it is difficult to obtain a concentration of 98 wt% or more. Therefore, sulfuric acid concentration (wt%) ≧10
However, considering economic efficiency, it is preferable to adopt a concentration range of 30 to 50 wt%. Regarding the solution temperature, sulfuric acid and titanium do not react at temperatures below 50°C, so solution temperature (°C) ≧50
However, if the temperature exceeds 90°C, the generation of mist will be significant, so it can be said that the range of 80 to 90°C is preferable. Regarding the immersion time, if the immersion time is less than 10 minutes, the titanium material that has undergone the secondary treatment process will have a high brightness and appear gray or gray-black. Since the degree of blackening of titanium does not change even if the immersion time becomes longer, the immersion time (min) was set to ≧10, but is preferably in the range of 30 to 60 minutes. Regarding the immersion conditions (B) in the second treatment step: If the hydrofluoric acid concentration is less than 2 wt%, the reaction rate is slow and it takes a long time to form a black film, making it unsuitable for industrial production. On the other hand, when the content is 10 wt% or more, the black film produced dissolves in hydrofluoric acid, resulting in increased brightness. Therefore, considering the degree of blackening and productivity, the concentration of hydrofluoric acid (wt%) was set to 2≦hydrofluoric acid concentration (wt%)<10, but preferably 3 to 10.
It is in the range of 8wt%. Regarding the solution temperature, if it exceeds 35°C, the black film will react violently with hydrofluoric acid and become colorless. There is no need to specify the lower limit temperature, but the lower the temperature, the longer the reaction takes, and at 0° C. or lower, the reaction does not exist as a solution. Therefore, solution temperature (°C) ≦35
However, the temperature is preferably in the range of 10 to 25°C. If the immersion time is less than 1 second, the reaction does not appear to occur because it corresponds to the incubation time, whereas if the immersion time is 1000 seconds or more, the formed film will be dissolved in the hydrofluoric acid and disappear. Therefore, we set 1≦immersion time (sec)≦1000, but in general, if the reaction time is too short, the reaction will not be sufficient and the brightness will be high, whereas if it is too long, the film will tend to dissolve. Considering brightness issues and economic efficiency, the time is preferably in the range of 20 to 100 seconds. The immersion conditions of the first and second treatment steps of the present invention have been explained above, but in the method of the present invention, the brightness of the black film formed on the metal surface depends on each treatment condition, that is, the concentration of the reagent, the temperature of the solution, and Since it can be changed depending on the immersion time, the degree of blackening can be adjusted by controlling this. Furthermore, the coloring method according to the present invention is less likely to produce colored spots than the anodic oxidation method, and is easier to handle. [Example] Example 1 Pure titanium cold-rolled plate (300 1 × 300 W × 0.6 t , unit: mm)
was immersed in a sulfuric acid aqueous solution under the conditions shown in Table 1, and then further immersed in a 5 wt % hydrofluoric acid aqueous solution at room temperature.A colored titanium plate having the brightness and color tone shown in the table was obtained. As is clear from the same table, the degree of blackening within the range of dipping conditions according to the method of the present invention met the requirements in terms of both brightness and color tone. Example 2 80 pure titanium plates (70 1 × 150 W × 0.3 t , unit: mm)
After 30 min immersion in 37wt% sulfuric acid solution at °C.
When the surface was washed in running water and the metal plate was further immersed in an aqueous hydrofluoric acid solution under the conditions shown in Table 2, a colored titanium plate having the brightness and color tone shown in Table 2 was obtained. As is clear from the same table, the degree of blackening within the range of dipping conditions according to the method of the present invention met the requirements in terms of both brightness and color tone. Example 3 80 pure titanium plates (70 1 × 150 W × 0.5 t , unit: mm)
After 60 min immersion in 37wt% sulfuric acid solution at °C.
When immersed in a 5wt% hydrofluoric acid aqueous solution at room temperature, the surface turned black. The color of the sample was measured using a color difference meter and the results are shown in Table 3. Furthermore, the weather resistance evaluation results using Sunshine Weather Meter tester,
The test results using a salt spray test device and a salt spray test device are also listed in the same table, and almost no discoloration was observed in any of the tests. Furthermore, the evaluation results of adhesion, processability, abrasion resistance, and fingerprint resistance are shown in Table 4, and it is judged that there is no problem in use in any of the performances. Example 4 A titanium alloy plate (Ti-2Mo, 50 f × 150 W × 1.0 t unit: mm) was immersed in a 40 wt% sulfuric acid solution at 85°C for 60 minutes, and then immersed in a 5 wt% hydrofluoric acid aqueous solution at room temperature. When immersed, the surface turned black. Then, when the same color measurement as above was performed, L=
17.0, a=0.3, b=3.0. Therefore, black titanium material can be produced not only from pure titanium but also from titanium alloys. [Effects of the Invention] As described above, the present invention produces a black film on titanium or titanium alloy that has excellent adhesion, workability, abrasion resistance, fingerprint resistance, as well as weather resistance and corrosion resistance, and has an aesthetic appearance. This greatly expands the use of titanium materials, not only as building materials that require corrosion resistance, but also as decorative items.
【表】【table】
【表】
の実施例
Example of [Table]
【表】
発明の実施例
[Table] Examples of the invention
【表】【table】
Claims (1)
記(A)の条件で浸漬する第一次処理工程と、該第一
次処理工程を経たチタンまたはチタン合金を下記
(B)の条件で弗酸水溶液に浸漬する第二次処理工程
からなる化成処理法による黒色チタン材の製造方
法。 条件(A) 硫酸濃度（wt％）≧10 溶液温度（℃） ≧50 浸漬時間（min）≧10 条件(B) ２≦弗酸濃度（wt％）＜10 溶液温度（℃）≦35 １≦浸漬時間（sec）≦1000[Claims] 1. A first treatment step in which titanium or a titanium alloy is immersed in an aqueous sulfuric acid solution under the following conditions (A), and a titanium or titanium alloy that has undergone the first treatment step is immersed in a sulfuric acid aqueous solution under the following conditions (A).
A method for producing black titanium material by a chemical conversion treatment method comprising a secondary treatment step of immersing it in a hydrofluoric acid aqueous solution under the conditions of (B). Condition (A) Sulfuric acid concentration (wt%) ≧10 Solution temperature (℃) ≧50 Immersion time (min) ≧10 Condition (B) 2≦Hydrofluoric acid concentration (wt%) ＜10 Solution temperature (℃)≦35 1≦ Immersion time (sec)≦1000
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10441686A JPS62260070A (en) | 1986-05-06 | 1986-05-06 | Production of black titanium material by chemical conversion treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10441686A JPS62260070A (en) | 1986-05-06 | 1986-05-06 | Production of black titanium material by chemical conversion treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62260070A JPS62260070A (en) | 1987-11-12 |
| JPS644593B2 true JPS644593B2 (en) | 1989-01-26 |
Family
ID=14380086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10441686A Granted JPS62260070A (en) | 1986-05-06 | 1986-05-06 | Production of black titanium material by chemical conversion treatment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62260070A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103215579B (en) * | 2013-04-18 | 2015-05-20 | 沈阳理工大学 | Chemical blackening method for surface of titanium alloy |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56123382A (en) * | 1980-02-29 | 1981-09-28 | Pentel Kk | Treatment for metal surface |
| JPH0245710B2 (en) * | 1982-02-25 | 1990-10-11 | Tanaka Precious Metal Ind | CHITANOYOBICHITANGOKINNOMAESHORYOKU |
-
1986
- 1986-05-06 JP JP10441686A patent/JPS62260070A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62260070A (en) | 1987-11-12 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |