JPS6152389A - Method for carrying out direct bright plating of titanium or titanium alloy with noble metal - Google Patents
Method for carrying out direct bright plating of titanium or titanium alloy with noble metalInfo
- Publication number
- JPS6152389A JPS6152389A JP17407584A JP17407584A JPS6152389A JP S6152389 A JPS6152389 A JP S6152389A JP 17407584 A JP17407584 A JP 17407584A JP 17407584 A JP17407584 A JP 17407584A JP S6152389 A JPS6152389 A JP S6152389A
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- plating
- noble metal
- titanium alloy
- soluble
- 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.)
- Pending
Links
Landscapes
- Electroplating Methods And Accessories (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はチタンまたはチタン合金を素材とする金属製の
眼鏡フレーム、ペンダント、時計ケースおよびバンドな
どの装飾をかねそなえた製品において、上記素材に直接
貴金属メッキを施す方法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to decorative products such as metal eyeglass frames, pendants, watch cases, and bands made of titanium or titanium alloy. This relates to a method of directly applying precious metal plating.
チタン又はチタン合金そのものは軽量かつ耐食性の優れ
た材料であるが、チタン又はチタン合金の素材上に貴金
属メッキを施した場合、外観が損なわれるだけでなく貴
金属メッキの密着性が不完全であった。Titanium or titanium alloy itself is a material that is lightweight and has excellent corrosion resistance, but when precious metal plating is applied to titanium or titanium alloy material, not only the appearance is damaged but also the adhesion of the precious metal plating is incomplete. .
そこで従来は、チタン又はチタン合金の素材に直接では
なく、該素材にニッケルや銅などのメッキ可能な金属の
張シ材を作シ、チタン−ニッケル張υ材及びチタン−銅
張シ材（以下チタン張シ材という）を素材に、製品を加
工し貴金属メッキを施していた。Therefore, in the past, instead of directly applying cladding materials to titanium or titanium alloy materials, cladding materials of metals that can be plated, such as nickel or copper, were manufactured on titanium-nickel cladding materials and titanium-copper cladding materials (hereinafter referred to as titanium-copper cladding materials). Products were processed using titanium-clad material (known as titanium-clad material) and plated with precious metals.
〔発明が解決しようとする問題点０
以上述べたようにチタン又はチタン合金の素材に直接貴
金属メッキを施したものは、外観が損なわれ貴金属メッ
キの密着性も不完全なため、チタン又はチタン合金の素
材上に鏡面光沢を有し外観が優美で、密着性が完全な実
用性に富んだ貴金属メッキを施すことができなかった。[Problem to be solved by the invention 0 As mentioned above, when titanium or titanium alloy materials are directly plated with precious metals, the appearance is impaired and the adhesion of the precious metal plating is incomplete. It has not been possible to apply precious metal plating, which has a specular luster, an elegant appearance, and perfect adhesion and is rich in practicality, onto the material.
また素材にチタン張シ材を使用した場合は、チタン張シ
材そのものの製造に非常に高い加工コストが必要とされ
、さらに製造型状に整える加工段階で地金であるチタン
又はチタン合金の素材に張られたニッケルや銅が局部的
に摩耗などで消失してしまうという問題点もあった。In addition, when titanium clad material is used as a material, extremely high processing costs are required to manufacture the titanium clad material itself, and in addition, the raw material of titanium or titanium alloy is required at the processing stage to prepare the manufacturing mold. There was also a problem in that the nickel and copper covered in the material would disappear locally due to wear and other factors.
本発明はチタン又はチタン合金の素材に直接貴金属メッ
キを施しても外観が損なわれず、光沢を有する優美な貴
金属メッキ方法とすることを目的とするものでおる。The object of the present invention is to provide an elegant noble metal plating method that does not impair the appearance of titanium or titanium alloy materials even when the material is directly plated with noble metals and has a glossy appearance.
上述した目的を達成するため、本発明はチタン又はチタ
ン合金を素材とする製品に第１処理として、１００〜６
００℃の温度条件下の大気中又は酸化雰囲気中で５分間
以上の加熱処理を行う。In order to achieve the above-mentioned object, the present invention provides a first treatment for products made of titanium or titanium alloy.
Heat treatment is performed for 5 minutes or more in the air or in an oxidizing atmosphere at a temperature of 00°C.
次に第２処理として加熱処理された素材の表面を脱脂洗
浄し、水溶性還元剤とチタンの可溶解性塩を主成分とし
た処理液で、浸漬もしくは電気分解によシ活性化を行い
、続いて活性化された素材に貴金属メッキを施したこと
にある。Next, as a second treatment, the surface of the heat-treated material is degreased and cleaned, and activated by immersion or electrolysis in a treatment solution containing a water-soluble reducing agent and a soluble salt of titanium as the main components. Next, the activated material was plated with precious metals.
以下本発萌の第１〜第４の実施例を第１図及び第２図に
基づいて説明する。The first to fourth embodiments of this invention will be described below with reference to FIGS. 1 and 2.
第１図は外気と温度変化におけるメッキ層の密着状態を
示す図表、第２図は水溶性還元剤とチタンの可溶解性塩
の含有量の有無及び変化におけるメッキ層の密着状態を
示す図表である。Figure 1 is a diagram showing the state of adhesion of the plating layer in the outside air and temperature changes, and Figure 2 is a chart showing the state of adhesion of the plating layer in the presence or absence of and changes in the content of water-soluble reducing agent and soluble titanium salt. be.
第１の実施例は、チタン合金板（第１種、５０×１００
×１．０１ａｌｌ）を、第１処理として２００℃の温度
条件下の大気中で１０分間加熱処理を行う。The first example is a titanium alloy plate (first type, 50×100
×1.01all) is subjected to a heat treatment for 10 minutes in the atmosphere at a temperature of 200° C. as a first treatment.
次に第２処理として加熱処理されたチタン合金板の表面
を公知の方法で脱脂洗浄し、脱脂洗浄されたチタン合金
板をホルマリン１０ ｍｔ／ｌ 、酸性弗化アンモニウ
ム１０ ｔ／ｌ、及びグルコン酸す） ＩＪウム３ Ｑ
ｆｉｌの溶解液に室温で２５分間浸漬することによシ
活性化を行う。続いて活性化されたチタン合金板を水洗
後Ｐ（３ＣＮＨ５）ＩＩｃ１２２０ｙ／ｌ 、 ＮＨｕ
Ｃ７１００ｙ／ｌ 、 ＮｉＣ７２６Ｈ２Ｏ３０ｙ／Ｌ
及び光沢剤１０ｙ７ｔの溶解液でＮＨ４ＯＨがｐ）（８
，０に調整された公知のパラジウム合金メッキ浴を用い
、常法に従い温度が３０℃、２Ａ／ｄｍの条件下で１０
分間のメッキを行ったところ、外観に光沢を有する白色
優美なパラジウム合金メッキが得られた。又、パラジウ
ム合金メッキを行ったチタン合金板を９０°に折シ曲け
た結果密着性に異常は認められなかった。Next, as a second treatment, the surface of the heat-treated titanium alloy plate is degreased and cleaned by a known method, and the degreased titanium alloy plate is treated with 10 mt/l of formalin, 10 t/l of acidic ammonium fluoride, and gluconic acid. ) IJum 3 Q
Activation is performed by immersing in a solution of fil for 25 minutes at room temperature. Subsequently, after washing the activated titanium alloy plate with water, P(3CNH5)IIc1220y/l, NHu
C7100y/l, NiC726H2O30y/L
and a solution of brightener 10y7t with NH4OH p) (8
Using a known palladium alloy plating bath adjusted to
After plating for a few minutes, an elegant white palladium alloy plating with a glossy appearance was obtained. Further, when the titanium alloy plate plated with palladium alloy was bent at 90°, no abnormality was observed in adhesion.
第２の実施例は、チタンを素材とする眼鏡フレームを、
第１処理として２５０℃の温度条件下の大気中で２０分
間加熱処理を行う。次に第２処理として加熱処理された
チタン合金板の表面を公知の方法で脱脂洗浄した後、ヒ
ドラジン５ ｙ／ｌ、 弗化ナトリウム１０ ｆｉを及
びクエン酸ナトリウム５０？／１の溶解液を用いＩＡ／
ｄｊ′ｎの条件下で２分間電気分解をすることによシ活
性化を行う。続いて活性化されたチタンを素材とする眼
鏡フレームを第１の実施例と同様にパラジウム合金メッ
キ浴を用いてパラジウム合金メッキを行う。The second example is an eyeglass frame made of titanium.
As a first treatment, heat treatment is performed in the atmosphere at a temperature of 250° C. for 20 minutes. Next, as a second treatment, the surface of the heat-treated titanium alloy plate was degreased and cleaned by a known method, and then treated with 5 y/l of hydrazine, 10 y/l of sodium fluoride, and 50 y/l of sodium citrate. IA/ using the solution of /1
Activation is carried out by electrolysis for 2 minutes under the conditions of dj'n. Next, eyeglass frames made of activated titanium are plated with palladium alloy using a palladium alloy plating bath in the same manner as in the first embodiment.
さらにＫＡＬＩ（ＣＮ）２１０ ｆｉＡとクエン酸アン
モニウム１００ ｙ／ｌの溶解液をクエン酸でｐＨ４，
０に調整し、光沢剤０．５ｆ／ｌを添加した公知の金メ
ッキ液を用い、パラジウム合金メッキが成された眼鏡フ
レームを温度が６０℃、 ０ 、５１ｖ’ｄｍの条件下
で１５分間メッキを行ったところ、２年間経果した時点
でも光沢や密着性に異常は認められなかった。Furthermore, a solution of KALI (CN) 210 fiA and ammonium citrate 100 y/l was diluted with citric acid to pH 4.
Using a known gold plating solution adjusted to 0.0 and added with a brightener of 0.5 f/l, eyeglass frames plated with palladium alloy were plated for 15 minutes at a temperature of 60°C, 0, and 51 v'dm. When tested, no abnormalities in gloss or adhesion were observed even after 2 years.
第３の実施例は、第１の実施例と同じチタン合金板を用
いて、第１処理及び第２処理により第１の実施例と同様
に活性化を行う。続いて活性化されたチタン合金板を、
第２の実施例と同様の金メッキ液を用いて温度が６０℃
、 Ｑ 、 ５ Ａ／ｄｊ′ｒＬの条件下で２０分間メ
ッキを行ったところ、外観の優美な金メッキが得られた
と共に密着性も完全であった。In the third example, the same titanium alloy plate as in the first example is used, and activation is performed in the same manner as in the first example through the first treatment and the second treatment. Next, the activated titanium alloy plate was
Using the same gold plating solution as in the second example, the temperature was 60°C.
When plating was carried out for 20 minutes under conditions of , Q, 5 A/dj'rL, a gold plating with an elegant appearance was obtained and the adhesion was perfect.
第４の実施例は、第１の実施例と同じチタン合金板を用
い、第１図に示す各条件下で第１処理を行い、次に第２
処理として加熱処理されたチタン合金板を酸性弗化アン
モニウム１０ ｆｉｌ 、次亜リン酸ナトリウム１０
ｆｉを及びクエン酸ナトリウム３０ ｆｉｌの溶解液を
用いて、温度４０℃、０．５ｆｉ、／ｄｙｎ の条件下
で３分間陰極電気分解することによシ活性化を行う。続
いて活性化されたチタン合金板を第１の実施例と同様の
パラジウム合金メッキ浴を用い２Ａ／ｄｎＬの条件下で
２０分間メッキを行ったところ、第１図に示すように加
熱温度が５０゜の場合、加熱時間が２分間の場合及び無
酸化雰囲気中で加熱した場合についてはメッキ層の密着
性が不良であったが、他の条件下では密着性、外観共に
優れたパラジウム合金メッキが得られた。The fourth example uses the same titanium alloy plate as the first example, performs the first treatment under the conditions shown in Figure 1, and then performs the second treatment.
As a treatment, a heat-treated titanium alloy plate was treated with 10 fil of acidic ammonium fluoride and 10 fil of sodium hypophosphite.
Activation is performed by cathodic electrolysis using a solution of fi and 30 fil of sodium citrate at a temperature of 40° C. and 0.5 fi, /dyn for 3 minutes. Subsequently, the activated titanium alloy plate was plated for 20 minutes under the condition of 2 A/dnL using the same palladium alloy plating bath as in the first example, and as shown in FIG. In the case of ゜, the adhesion of the plating layer was poor when the heating time was 2 minutes or when it was heated in a non-oxidizing atmosphere, but under other conditions, the palladium alloy plating had excellent adhesion and appearance. Obtained.
上述した第１〜第４の実施例の中で第２条理に使用した
活性化液を、第２図に示す各条件で実施した。その結果
水溶性還元剤とチタンの可溶解性塩のいづれか一方が存
在しない活性化液を用いた場合は、チタンの活性効果が
失なわれることによシ、密着性が不完全となる結果を得
た。The activation liquid used in the second strip in the first to fourth examples described above was tested under the conditions shown in FIG. As a result, if an activation solution is used that does not contain either a water-soluble reducing agent or a soluble salt of titanium, the activation effect of titanium will be lost, resulting in incomplete adhesion. Obtained.
又水溶性還元剤としては無電解メッキなどに用いられて
いる次亜リン酸ナトリウムやホウ水素化ナトリウムなど
も利用でき、添加量は０．５Ｗ／ｌの微量でも効果が認
められるが電気分解または浸漬の処理時間がかがシ経済
的でなく、好ましくは５％以上が良い。In addition, sodium hypophosphite and sodium borohydride, which are used in electroless plating, can be used as water-soluble reducing agents, and although they are effective even when added in a small amount of 0.5 W/l, electrolysis or The immersion treatment time is too long, which is not economical, and is preferably 5% or more.
さらに可溶解性塩は弗化ナトリウム、酸性弗化アンモニ
ウムおよびホウ弗化ナトリウムなどが好ましく、添加量
は０ 、１ ｆ／ｌの微量でも効果があるが処理時間が
かがシ好ましくは１． 、 Ｏｔ／を以上が良い。又、
硫酸や塩酸などでも良好な結果が得られる条件があるが
、処理温度を高温にしなければならないと共に処理時間
も長時間かけなければチタンの酸化物が溶出しないため
あまシ好ましくない。Further, the soluble salts are preferably sodium fluoride, acidic ammonium fluoride, sodium borofluoride, etc., and even a small amount of 0.0 to 1 f/l is effective, but the treatment time is longer, so preferably 1.0 f/l is added. , Ot/ or more is better. or,
There are conditions under which good results can be obtained using sulfuric acid, hydrochloric acid, etc., but this is not preferable because the titanium oxide will not be eluted unless the treatment temperature is high and the treatment time is not long.
以上詳細に説明したように本発明はチタン又はチタン合
金を素材とする製品に１００〜６００℃の温度条件下の
大気中又は酸化雰囲気中で加熱処理を行うことによ多安
定な酸化皮膜をチタン又はチタン合金の表面につくり、
さらに水溶性還元剤を１．０ｆ／を以上含有すると共に
チタンの可溶解性塩を含有するｐＨ１０，０以下の処理
液で酸化皮膜を除去したことによシ密着性が完全になる
と共に光沢を有する貴金属メッキを行うことができる。As explained in detail above, the present invention applies a heat treatment to a product made of titanium or a titanium alloy in the air or in an oxidizing atmosphere at a temperature of 100 to 600°C to form a multistable oxide film on titanium. Or made on the surface of titanium alloy,
Furthermore, by removing the oxide film with a treatment solution containing 1.0 f/ or more of a water-soluble reducing agent and a soluble salt of titanium and having a pH of 10.0 or less, the adhesion is perfect and the gloss is improved. Noble metal plating can be performed.
又、チタン材の耐蝕性や軽量性を損うことなく、外観の
優美な光沢、色調及び電導性に優れた貴金属装飾製品を
安価に提供できるなどの効果が得られる。Further, it is possible to provide a noble metal decorative product with an elegant appearance, excellent gloss, color tone, and conductivity at a low cost without impairing the corrosion resistance and lightness of titanium materials.
Claims (1)
条件下の大気中又は酸化雰囲気中で加熱処理を行い、こ
の加熱処理された素材に水溶性還元剤とチタンの可溶解
性塩を主成分としｐＨが１０．０以下の処理液を用いて
浸漬または電気分解した後、チタン又はチタン合金の素
材に直接貴金属メッキすることを特徴とするチタン又は
チタン合金の直付け光沢貴金属メッキ方法。A titanium or titanium alloy material is heat-treated in the air or an oxidizing atmosphere at a temperature of 100 to 600°C, and the heat-treated material contains a water-soluble reducing agent and a soluble salt of titanium as the main components. A direct bright noble metal plating method for titanium or titanium alloy, characterized in that the noble metal is plated directly on the titanium or titanium alloy material after immersion or electrolysis using a treatment solution with a pH of 10.0 or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17407584A JPS6152389A (en) | 1984-08-23 | 1984-08-23 | Method for carrying out direct bright plating of titanium or titanium alloy with noble metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17407584A JPS6152389A (en) | 1984-08-23 | 1984-08-23 | Method for carrying out direct bright plating of titanium or titanium alloy with noble metal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6152389A true JPS6152389A (en) | 1986-03-15 |
Family
ID=15972199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17407584A Pending JPS6152389A (en) | 1984-08-23 | 1984-08-23 | Method for carrying out direct bright plating of titanium or titanium alloy with noble metal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6152389A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6279877U (en) * | 1985-11-06 | 1987-05-21 | ||
| JPS6396295A (en) * | 1986-10-13 | 1988-04-27 | Nippon Kagaku Sangyo Kk | Plating method on titanium and titanium alloy |
| JPH06116782A (en) * | 1992-10-02 | 1994-04-26 | Nippon Alum Co Ltd | Plating pretreatment of titanium material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51131426A (en) * | 1975-05-12 | 1976-11-15 | Oki Electric Ind Co Ltd | Plating method |
| JPS56166394A (en) * | 1980-04-16 | 1981-12-21 | Rolls Royce | Treatment prior to electroplating metal to titanium or titanium alloy |
-
1984
- 1984-08-23 JP JP17407584A patent/JPS6152389A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51131426A (en) * | 1975-05-12 | 1976-11-15 | Oki Electric Ind Co Ltd | Plating method |
| JPS56166394A (en) * | 1980-04-16 | 1981-12-21 | Rolls Royce | Treatment prior to electroplating metal to titanium or titanium alloy |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6279877U (en) * | 1985-11-06 | 1987-05-21 | ||
| JPS6396295A (en) * | 1986-10-13 | 1988-04-27 | Nippon Kagaku Sangyo Kk | Plating method on titanium and titanium alloy |
| JPH06116782A (en) * | 1992-10-02 | 1994-04-26 | Nippon Alum Co Ltd | Plating pretreatment of titanium material |
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