JPS6345478B2 - - Google Patents
Info
- Publication number
- JPS6345478B2 JPS6345478B2 JP1891985A JP1891985A JPS6345478B2 JP S6345478 B2 JPS6345478 B2 JP S6345478B2 JP 1891985 A JP1891985 A JP 1891985A JP 1891985 A JP1891985 A JP 1891985A JP S6345478 B2 JPS6345478 B2 JP S6345478B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- nitride film
- film
- amine salt
- titanium alloy
- 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 34
- 239000010936 titanium Substances 0.000 claims description 34
- 229910052719 titanium Inorganic materials 0.000 claims description 34
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 29
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 150000001412 amines Chemical class 0.000 claims description 13
- 239000012266 salt solution Substances 0.000 claims description 11
- 239000008151 electrolyte solution Substances 0.000 claims description 10
- 238000004381 surface treatment Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 5
- -1 amine salt Chemical class 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 238000005121 nitriding Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910000960 colored gold Inorganic materials 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 238000011866 long-term treatment Methods 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003510 tertiary aliphatic amines Chemical class 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Description
【発明の詳細な説明】
［産業上の利用分野］
この発明は、チタンやチタン合金の表面に皮膜
を形成して、これらの表面を着色するチタンおよ
びチタン合金の表面処理方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for surface treatment of titanium and titanium alloys, in which a film is formed on the surfaces of titanium and titanium alloys to color the surfaces thereof.
［従来技術とその問題点］
従来、チタンやチタン合金の表面に皮膜を形成
してこれらの表面を着色する方法としては、一般
に陽極酸化法と呼ばれる方法が用いられている。
この方法は、硫酸や燐酸等を電解質溶液として用
い、この電解質溶液中において、表面処理を施す
チタンやチタン合金を陽極とし、陰極として白
金、チタン、ステンレス、鉛等を用い、これらに
直流電流を流して陽極のチタンまたはチタン合金
の表面に酸化皮膜を形成し、この酸化皮膜による
光の干渉によつて、これらの表面を発色させるよ
うになつている。しかし、このように形成された
酸化皮膜は、摩擦に弱く簡単に剥がれてしまい、
充分な着色を行なうことができないという問題が
あつた。また、このような酸化皮膜による着色
は、光の干渉によるものであるため、その皮膜の
表面に油膜や指紋が付くと色調が変化するという
問題があつた。さらに、このような酸化皮膜によ
る着色においては、皮膜の膜厚によつて色彩が変
化するため、同一の色彩に着色するには、その膜
厚を一定化させる必要があり、同一色彩のものを
量産することが非常に困難であつた。[Prior Art and its Problems] Conventionally, a method called anodic oxidation is generally used as a method for forming a film on the surface of titanium or a titanium alloy to color the surface.
This method uses sulfuric acid, phosphoric acid, etc. as an electrolyte solution, and in this electrolyte solution, titanium or titanium alloy to be surface treated is used as an anode, platinum, titanium, stainless steel, lead, etc. is used as a cathode, and a direct current is applied to these. This causes an oxide film to be formed on the surface of the titanium or titanium alloy of the anode, and the interference of light caused by this oxide film causes the surface to develop color. However, the oxide film formed in this way is weak against friction and easily peels off.
There was a problem that sufficient coloring could not be achieved. Further, since the coloring caused by such an oxide film is caused by light interference, there is a problem in that the color tone changes when an oil film or a fingerprint is attached to the surface of the film. Furthermore, when coloring with such an oxide film, the color changes depending on the thickness of the film, so in order to color the same color, it is necessary to keep the film thickness constant. It was extremely difficult to mass produce.
また、チタンやチタン合金の表面に着色を行な
う他の方法としては、一般に窒化法と呼ばれる方
法が存在しており、これはチタンやチタン合金を
窒素ガス雰囲気中で750℃以上に加熱し、これら
の表面に窒化チタンの皮膜を形成して黄金色に着
色するようになつている。このようにして得られ
た窒化チタンの皮膜は、上記の酸化皮膜に比べ耐
摩擦性が高く、色彩も一定化するのであるが、こ
の方法では、チタンやチタン合金を高温に加熱す
る必要があり、ランニングコストが高くなると共
に大量生産が行なえないという問題があつた。加
えて、窒化チタンの皮膜を厚くするため、高温で
長時間処理するとその表面に皺がよる等の欠点も
あつた。 Another method for coloring the surface of titanium and titanium alloys is the nitriding method, which involves heating titanium and titanium alloys to 750°C or higher in a nitrogen gas atmosphere. A titanium nitride film is formed on the surface, giving it a golden yellow color. The titanium nitride film obtained in this way has higher abrasion resistance than the oxide film described above and has a uniform color, but this method requires heating the titanium or titanium alloy to high temperatures. However, there were problems in that running costs were high and mass production was not possible. In addition, in order to thicken the titanium nitride film, there were other drawbacks, such as wrinkles on the surface of the film if it was treated at high temperatures for a long period of time.
［問題点を解決するための手段］
この発明は、上記のような従来の陽極酸化法や
窒化法における問題を解決せんとしてなされたも
のであり、以下に述べる方法によつてチタンおよ
びチタン合金の表面処理を行なうものである。[Means for Solving the Problems] This invention was made to solve the problems in the conventional anodic oxidation and nitriding methods as described above, and it is possible to solve the problems of titanium and titanium alloys by the method described below. It performs surface treatment.
この発明においては、表面処理を行なうチタン
またはチタン合金を陽極に用い、アミン塩溶液か
らなる電解液中において、これに直流電流を流
し、その表面に窒化チタンの皮膜を形成し、この
皮膜によつて表面を黄金色に着色するようにした
のである。 In this invention, titanium or a titanium alloy to be surface-treated is used as an anode, and a direct current is passed through it in an electrolytic solution consisting of an amine salt solution to form a titanium nitride film on the surface. The surface was colored gold.
ここで、電解液に用いるアミン塩は、可溶性で
あり、それに含まれる窒素がチタンと反応して窒
化チタンの皮膜をその表面に形成しうるものであ
ればよく、トリエチルアミン、ジエチルメチルア
ミン等の第一乃至第三脂肪族アミン、アリルアミ
ン等の脂肪族不飽和アミン、シクロヘキシルアミ
ン等の脂肪環式アミン、アニリン、トルイジン、
ベンジジン、アミノフエノール、１−および２−
ナフチルアミン等の芳香族アミンの他、ジメチル
ホルムアミド、エタノールアミン、エチレンジア
ミン、ヘキサメチレンテトラミン、ペンタエチレ
ンヘキサミン、エチレンイミン、ヒドラミド等の
各種アミン塩を用いることができる。また、この
ようなアミン塩溶液を用いる場合、その濃度が
0.01ppm以下では充分な厚みをもつ窒化チタンの
皮膜を形成することが困難であるため、通常は
0.01ppm以上の濃度で使用することが望ましく、
また、このようなアミン塩溶液は、チタンと反応
する窒素の解離が酸性下においては困難であるた
め、使用にあたつてはPH7.0〜12.0の範囲に調整
して行なうことが望ましい。 Here, the amine salt used in the electrolytic solution may be one that is soluble and the nitrogen contained in it can react with titanium to form a titanium nitride film on its surface. Mono- to tertiary aliphatic amines, aliphatic unsaturated amines such as allylamine, alicyclic amines such as cyclohexylamine, aniline, toluidine,
Benzidine, aminophenol, 1- and 2-
In addition to aromatic amines such as naphthylamine, various amine salts such as dimethylformamide, ethanolamine, ethylenediamine, hexamethylenetetramine, pentaethylenehexamine, ethyleneimine, and hydramide can be used. In addition, when using such an amine salt solution, its concentration is
It is difficult to form a titanium nitride film with sufficient thickness at 0.01ppm or less, so it is usually
It is desirable to use it at a concentration of 0.01ppm or higher,
Furthermore, since it is difficult for such an amine salt solution to dissociate nitrogen that reacts with titanium under acidic conditions, it is desirable to adjust the pH to a range of 7.0 to 12.0 before use.
次に、直流電流を流して陽極のチタンまたはチ
タン合金の表面に窒化チタンの皮膜を形成する場
合、その電圧が5V以下では窒化チタン皮膜の形
成が困難であり、また、300V以上では陽極のチ
タンまたはチタン合金の表面においてガスが発生
するため、一般に５〜300Vの範囲の電圧で行な
うことが望ましい。 Next, when applying a direct current to form a titanium nitride film on the surface of the titanium or titanium alloy anode, it is difficult to form a titanium nitride film if the voltage is less than 5V, and if the voltage is 300V or more, the titanium nitride film is Alternatively, since gas is generated on the surface of the titanium alloy, it is generally desirable to perform the test at a voltage in the range of 5 to 300V.
［作用］
この発明においては、電解液としてアミン塩溶
液を用い、この電解液中において陽極にチタンま
たはチタン合金を用い、これに直流電流を流し、
アミン塩溶液中の窒素とチタンとを反応させてそ
の表面に窒化チタンの皮膜を形成し、この窒化チ
タン皮膜によつてその表面を黄金色に着色するの
である。[Function] In this invention, an amine salt solution is used as an electrolyte, titanium or a titanium alloy is used as an anode in this electrolyte, and a direct current is passed through it.
Nitrogen in the amine salt solution reacts with titanium to form a titanium nitride film on the surface, and this titanium nitride film colors the surface golden yellow.
［実施例］ 以下、この発明の実施例について詳述する。[Example] Examples of the present invention will be described in detail below.
チタンまたはチタン合金の表面処理を行なうに
あたつては、まず、チタンまたはチタン合金の表
面に前処理を行なう。ここで行なう前処理として
は、その表面を脱脂するだけのもの、脱脂に加え
酸エツチングまで行なうもの、酸エツチングに加
えさらに化学研磨や電気研磨まで行なうもの等が
あり、どのような前処理を行なうかは、表面処理
の結果どのような表面状態の製品を得るかによつ
て適宜選択して行なうのである。例えば、表面を
ぼかした状態の製品を得る場合には、脱脂するだ
けの前処理を、また表面が鏡面のようになつた製
品を得る場合には、化学研磨や電気研磨までの前
処理を行なうのである。 When performing surface treatment on titanium or titanium alloy, first, the surface of titanium or titanium alloy is pretreated. The pretreatments performed here include those that simply degrease the surface, those that include acid etching in addition to degreasing, and those that perform chemical polishing and electropolishing in addition to acid etching.What kind of pretreatment is used? The method is selected depending on the surface condition of the product to be obtained as a result of the surface treatment. For example, if you want to obtain a product with a blurred surface, pretreatment is just degreasing, and if you want to obtain a product with a mirror-like surface, pretreatment including chemical polishing or electric polishing is performed. It is.
そして、このような前処理が施されたチタンま
たはチタン合金を陽極に用いると共に陰極には白
金、チタン、ステンレス、鉛、アルミニウム等を
用い、アミン塩溶液からなる電解液中において、
電圧が５〜300Vの直流電流を流してアミン塩溶
液中の窒素をチタンと反応させ、陽極のチタンま
たはチタン合金の表面に窒化チタンの皮膜を形成
し、この窒化チタンの皮膜によつてこれらの表面
を黄金色に着色するのである。 Then, titanium or titanium alloy subjected to such pretreatment is used for the anode, and platinum, titanium, stainless steel, lead, aluminum, etc. are used for the cathode, and in an electrolytic solution consisting of an amine salt solution,
A direct current with a voltage of 5 to 300 V is applied to cause the nitrogen in the amine salt solution to react with titanium, forming a titanium nitride film on the surface of the titanium or titanium alloy of the anode. The surface is colored golden.
このように、これらの表面を窒化チタンの皮膜
によつて黄金色に着色した後は、その表面に塗装
を行ない、これを焼付けて窒化チタンの皮膜を保
護するのである。 After these surfaces have been colored gold with the titanium nitride film, the surfaces are painted and baked to protect the titanium nitride film.
次に、この発明による表面処理方法によつてチ
タンまたはチタン合金の表面に窒化チタンの皮膜
を形成してその表面を着色した例を示す。前処理
を施したチタンまたはチタン合金を陽極に用い、
アルミニウムを陰極とし、40ppmのトリエチルア
ミン水溶液中において、これらに約150Vの直流
電流を１分間通電した。これにより、チタンまた
はチタン合金の表面に窒化チタンの皮膜が形成さ
れ、その表面が美しい黄金色に着色された。 Next, an example will be shown in which a titanium nitride film is formed on the surface of titanium or a titanium alloy and the surface is colored by the surface treatment method according to the present invention. Using pretreated titanium or titanium alloy for the anode,
Using aluminum as a cathode, a DC current of approximately 150 V was applied to these for 1 minute in a 40 ppm triethylamine aqueous solution. As a result, a titanium nitride film was formed on the surface of the titanium or titanium alloy, and the surface was colored a beautiful golden yellow.
なお、ここでは単に一例を示しただけである
が、電解液に用いるアミン塩溶液の種類等を変え
て行なつた場合も略同様の結果が得られた。 Although only one example is shown here, substantially the same results were obtained when the type of amine salt solution used in the electrolytic solution was changed.
［発明の効果］
以上詳述したように、この発明に係るチタンま
たはチタン合金の表面処理方法は、アミン塩溶液
からなる電解液中において、チタンまたはチタン
合金を陽極に用い、これに直流電流を流してこれ
らの表面に窒化チタンの皮膜を形成し、この皮膜
によつてこれらの表面を黄金色に着色するように
なつている。この結果、これらの表面は、従来の
酸化皮膜より耐摩擦性の高い窒化チタン皮膜によ
つて被装され、また、この皮膜によつて着色され
る表面の色彩も略一定の黄金色となるため、同一
色彩のものを量産することも容易に行なえるよう
になるのである。[Effects of the Invention] As detailed above, the method for surface treatment of titanium or titanium alloy according to the present invention uses titanium or titanium alloy as an anode in an electrolytic solution consisting of an amine salt solution, and applies a direct current to the anode. This process forms a film of titanium nitride on these surfaces, which gives them a golden yellow color. As a result, these surfaces are coated with a titanium nitride film that has higher abrasion resistance than conventional oxide films, and the color of the surfaces colored by this film also becomes a nearly constant golden yellow. This also makes it easier to mass-produce products of the same color.
また、この発明に係る方法は、従来の窒化法の
ようにチタンやチタン合金を高温に加熱する必要
がなく、ランニングコストが少なくてすむと共
に、量産も容易に行なえるようになるのである。
さらに、この発明においては、電解液として用い
るアミン溶液の濃度や通電する直流電流の電圧や
時間を変更させて窒化チタン皮膜の膜厚を自由に
調整することができ、皮膜を厚くする場合におい
ても、従来の窒化法のように高温で長時間処理す
る必要がなく、その表面に皺がよるという問題も
解消されるのである。 Further, the method according to the present invention does not require heating titanium or titanium alloy to a high temperature as in the conventional nitriding method, resulting in low running costs and easy mass production.
Furthermore, in this invention, the thickness of the titanium nitride film can be freely adjusted by changing the concentration of the amine solution used as the electrolytic solution and the voltage and time of the DC current applied. Unlike conventional nitriding methods, there is no need for long-term treatment at high temperatures, and the problem of wrinkles on the surface is also eliminated.
Claims (1)
ン塩溶液からなる電解液中において直流電流を流
し、上記チタンまたはチタン合金の表面に窒化チ
タンの皮膜を形成することを特徴とするチタンお
よびチタン合金の表面処理方法。 ２ 前記電解液として用いるアミン塩溶液の濃度
を0.01ppm以上とし、PH7.0〜12.0の範囲で使用す
ることを特徴とする特許請求の範囲第１項記載の
チタンおよびチタン合金の表面処理方法。 ３ チタンまたはチタン合金に流す直流電流の電
圧を５〜300Vにしたことを特徴とする特許請求
の範囲第１項または第２項記載のチタンおよびチ
タン合金の表面処理方法。[Claims] 1. A titanium or titanium alloy is used as an anode, and a direct current is passed through an electrolytic solution consisting of an amine salt solution to form a titanium nitride film on the surface of the titanium or titanium alloy. Surface treatment method for titanium and titanium alloys. 2. The method for surface treatment of titanium and titanium alloys according to claim 1, characterized in that the concentration of the amine salt solution used as the electrolytic solution is 0.01 ppm or more, and the pH is in the range of 7.0 to 12.0. 3. The method for surface treatment of titanium and titanium alloys according to claim 1 or 2, characterized in that the voltage of the direct current flowing through the titanium or titanium alloy is 5 to 300V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1891985A JPS61177397A (en) | 1985-02-01 | 1985-02-01 | Surface treatment of titanium and titanium alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1891985A JPS61177397A (en) | 1985-02-01 | 1985-02-01 | Surface treatment of titanium and titanium alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61177397A JPS61177397A (en) | 1986-08-09 |
| JPS6345478B2 true JPS6345478B2 (en) | 1988-09-09 |
Family
ID=11985019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1891985A Granted JPS61177397A (en) | 1985-02-01 | 1985-02-01 | Surface treatment of titanium and titanium alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61177397A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02118062A (en) * | 1988-10-26 | 1990-05-02 | Kawasaki Steel Corp | Manufacture of colored ceramic coated steel sheet |
| CN110607544B (en) * | 2019-08-27 | 2021-09-07 | 广东工业大学 | Aqueous electroplating solution for preparing titanium nitride coating film and preparation method and application thereof |
-
1985
- 1985-02-01 JP JP1891985A patent/JPS61177397A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61177397A (en) | 1986-08-09 |
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