JP2002241986A - Ni-W-P ALLOY PLATING SOLUTION AND CONTINUOUS PLATING METHOD THEREWITH - Google Patents
Ni-W-P ALLOY PLATING SOLUTION AND CONTINUOUS PLATING METHOD THEREWITHInfo
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- JP2002241986A JP2002241986A JP2001043156A JP2001043156A JP2002241986A JP 2002241986 A JP2002241986 A JP 2002241986A JP 2001043156 A JP2001043156 A JP 2001043156A JP 2001043156 A JP2001043156 A JP 2001043156A JP 2002241986 A JP2002241986 A JP 2002241986A
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- plating
- alloy
- plating solution
- salt
- sodium
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は電気めっき法による
Ｎｉ−Ｗ−Ｐ合金めっき液及びその連続めっき方法に関
するものであり、耐食性、硬さを必要とする各種ロー
ル、金型、装飾用仕上げめっきとしてのクロムめっきの
代替めっき技術として利用されるものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a Ni-WP alloy plating solution by electroplating and a continuous plating method therefor, and various kinds of rolls, dies, decorative finish plating requiring corrosion resistance and hardness. It is used as an alternative plating technology for chrome plating.
【０００２】[0002]
【従来の技術】従来、各種ロール、金型、装飾用仕上げ
めっきとして６価クロムを主成分とするめっき液を用い
て得られるクロムめっきが広く用いられている。クロム
めっきは耐食性、硬さ、光沢等の点で優れた特性を有し
ているが、６価クロムが有害物質であることから、Ｎｉ
−Ｐ、Ｎｉ−Ｗ、Ｎｉ−Ｂ、Ｎｉ−Ｓｎなどの合金めっ
きが代替技術として用いられ始めている。Ｎｉ−Ｗ、Ｎ
ｉ−Ｐ、Ｎｉ−Ｂはめっき時の硬さがＨｖ５００〜７０
０であり、加熱処理によりＨｖ８００以上になるが、Ｃ
ＡＳＳ試験により腐食・変色する。Ｎｉ−ＳｎはＨｖ８
００以上の硬さを得られない。いずれも硬さ、あるいは
色調等においてクロムめっきに匹敵あるいは凌駕する優
れた特性を示す場合があるものの、耐食性においてはク
ロムめっきに比べて未だ十分なものはない。めっき時の
硬さを大きくするため、Ｎｉ−ＷめっきにＢを共析させ
る、あるいは酸化クロム、ＳｉＣ、ＢＮなどの炭化物、
窒化物を共析させる例があるが、ＣＡＳＳ試験による耐
食性向上を目指したものではない。2. Description of the Related Art Conventionally, chrome plating obtained by using a plating solution containing hexavalent chromium as a main component has been widely used as a finish plating for various rolls, dies, and decorations. Chromium plating has excellent properties in terms of corrosion resistance, hardness, gloss, etc., but hexavalent chromium is a harmful substance.
Alloy plating such as -P, Ni-W, Ni-B, Ni-Sn has begun to be used as an alternative technique. Ni-W, N
iP and Ni-B have a hardness at plating of Hv 500 to 70.
0, and Hv 800 or more due to heat treatment.
Corrosion and discoloration due to ASS test. Ni-Sn is Hv8
A hardness of 00 or more cannot be obtained. Although each of them may show excellent properties comparable or superior to chromium plating in hardness, color tone, etc., there is still no sufficient corrosion resistance compared to chromium plating. In order to increase the hardness at the time of plating, B is codeposited on Ni-W plating, or carbide such as chromium oxide, SiC, BN,
Although there is an example of eutectoid nitride, it is not aimed at improving corrosion resistance by a CASS test.
【０００３】めっき時の硬度が比較的高く、耐食性の良
いニッケル系合金めっき皮膜としてＮｉ−Ｗ−Ｐ合金め
っきがあるが、次亜リン酸を還元剤とする無電解めっき
法である。この方法では、還元剤は酸化されて亜リン酸
イオンになり、めっき液内に蓄積するとともに、Ｗおよ
びＰがめっき皮膜内に析出する際に水素イオンを発生し
て浴ｐＨが低下し、浴組成を一定に維持できない。ま
た、めっき速度を維持するため硫酸ニッケル、タングス
テン酸ナトリウムなどの金属塩および次亜リン酸を補給
するとともにＮａＯＨ溶液の添加によりｐＨ調整の必要
がある。このため、めっき液中には亜リン酸、硫酸ナト
リウムなどの補給薬品に起因する塩が蓄積し、良好なめ
っきが得られなくなり、定期的に廃棄されるなどの問題
がある。[0003] There is Ni-WP alloy plating as a nickel-based alloy plating film having a relatively high hardness at the time of plating and good corrosion resistance, but it is an electroless plating method using hypophosphorous acid as a reducing agent. In this method, the reducing agent is oxidized to phosphite ions and accumulates in the plating solution, and when W and P are precipitated in the plating film, hydrogen ions are generated to lower the pH of the bath. The composition cannot be kept constant. In addition, in order to maintain the plating rate, it is necessary to replenish metal salts such as nickel sulfate and sodium tungstate and hypophosphorous acid and adjust the pH by adding a NaOH solution. For this reason, there is a problem that salts resulting from replenishing chemicals such as phosphorous acid and sodium sulfate accumulate in the plating solution, so that good plating cannot be obtained and the plating solution is periodically discarded.
【０００４】[0004]
【発明が解決しようとする課題】本発明は電気めっき法
により硬度が大きく耐食性良好なＮｉ−Ｗ−Ｐ合金めっ
き皮膜を得られるめっき液の組成を提案することを課題
とする。また、めっき液中に亜リン酸イオン、硫酸イオ
ン、ナトリウムイオン等が蓄積されず、めっき液の廃棄
を少なくできる連続めっき方法を提供することを課題と
する。SUMMARY OF THE INVENTION An object of the present invention is to propose a composition of a plating solution capable of obtaining a Ni—WP alloy plating film having high hardness and good corrosion resistance by electroplating. It is another object of the present invention to provide a continuous plating method in which phosphite ions, sulfate ions, sodium ions, and the like are not accumulated in a plating solution and the plating solution can be discarded less.
【０００５】[0005]
【課題を解決するための手段】１９５０年代に米国のＢ
ｒｅｎｎｅｒ、Ｈｏｌｔｚらがクエン酸塩、ニッケル塩
およびタングステン酸塩を基本成分とするＮｉ−Ｗ合金
めっき液を提案して以来、種々検討が進められ、ｐＨ９
〜１０のアルカリ浴、およびｐＨ６〜７の中性浴が用い
られている。中性浴の場合、ニッケルイオン、タングス
テン酸イオンおよびクエン酸の比率を１：１：２程度に
選んだ場合、Ｎｉ−Ｗ合金めっきのＷ含有率は３０〜４
０ｗｔ％となる。電気めっき法によるＮｉ−Ｐ合金めっ
きは、硫酸ニッケルと亜リン酸を基本浴成分とし、ｐＨ
３以下の条件でめっきされている。それ以上のｐＨでは
不溶性の亜リン酸ニッケルを沈殿するなどの問題を生じ
る。[MEANS FOR SOLVING THE PROBLEMS] In the 1950s, US B
Since Renner, Holtz et al. have proposed a Ni-W alloy plating solution containing citrate, nickel salt and tungstate as basic components, various studies have been conducted, and pH 9
Alkaline baths of 10 to 10 and neutral baths of pH 6 to 7 are used. In the case of a neutral bath, when the ratio of nickel ion, tungstate ion and citric acid is selected to be about 1: 1: 2, the W content of the Ni-W alloy plating is 30 to 4%.
0 wt%. Ni-P alloy plating by the electroplating method uses nickel sulfate and phosphorous acid as basic bath components,
Plated under conditions of 3 or less. At a higher pH, problems such as precipitation of insoluble nickel phosphite occur.
【０００６】ここでは、これらの知見を基礎に、クエン
酸塩、ニッケル塩、タングステン酸塩をめっき液の基本
構成成分として、さらにＰ源として亜リン酸を加え、適
切なｐＨ領域でめっきをした場合、Ｗ含有率は減少する
もののＰを共析させることができ、Ｎｉ−Ｗ−Ｐ合金め
っき皮膜を得ることができることがわかった。Ｐ含有
率、Ｗ含有率の亜リン酸濃度および浴ｐＨによる変化を
図１に示す。電流密度は一定とした。Here, based on these findings, citrate, nickel salt, and tungstate were used as basic components of the plating solution, and further, phosphorous acid was added as a P source to perform plating in an appropriate pH range. In this case, it was found that although the W content was reduced, P could be eutectoid, and a Ni—WP alloy plating film could be obtained. FIG. 1 shows changes in the P content and the W content depending on the phosphorous acid concentration and the bath pH. The current density was constant.
【０００７】浴ｐＨが７以上になるとＰは析出せず、ｐ
Ｈ６以下ではｐＨが下がるとともにＰ含有率は高くな
る。ｐＨ３に達するとめっき液は、液中にタングステン
酸の沈殿を生じて分解し、めっきに不具合を生じる。ク
エン酸濃度を増加させるとめっき液は、より低いｐＨ領
域でも安定化し、Ｐ含有率も大きくなるが、析出電流効
率が低下する。クエン酸濃度を低下させると析出電流効
率は大きくなるものの浴は不安定化する。図２に析出電
流効率に与えるクエン酸濃度の影響の一例を示す。When the bath pH is 7 or more, P does not precipitate,
Below H6, the pH decreases and the P content increases. When the pH reaches 3, the plating solution precipitates and decomposes tungstic acid in the solution, causing plating problems. Increasing the concentration of citric acid stabilizes the plating solution even in a lower pH range and increases the P content, but decreases the deposition current efficiency. When the concentration of citric acid is reduced, the deposition current efficiency increases, but the bath becomes unstable. FIG. 2 shows an example of the effect of citric acid concentration on the deposition current efficiency.
【０００８】めっき皮膜中のＰ含有率は、めっき電流密
度の影響を受ける。その例を図３に示す。析出電流効率
３０％以上を維持してＰ含有率１ｗｔ％以上のめっきを
できる最適領域はｐＨ４〜５で、クエン酸濃度は金属イ
オン量の総和に対するモル比；クエン酸／（Ｎｉ＋Ｗ）
が０．７〜１．２程度である。この比率が０．７未満で
はタングステンが析出し、１．２を超えると電流効率が
下がる。このｐＨ条件で得られたＮｉ−Ｗ−Ｐ合金めっ
きは、１Ａ／ｄｍ2 以下の低電流密度から１０Ａ／ｄｍ
2 程度の高電流密度まで良好な光沢を示す。こうして得
られた少量のＰを含有するＮｉ−Ｗ合金めっき膜は、め
っきの耐食性試験で多用される塩水噴霧試験で良好な耐
食性を示すばかりでなく、クロムめっきの耐食性試験に
用いられているＣＡＳＳ試験でも優れた耐食性を示し
た。[0008] The P content in the plating film is affected by the plating current density. An example is shown in FIG. The optimal region where plating with a P content of 1 wt% or more can be performed while maintaining the deposition current efficiency of 30% or more is pH 4 to 5, and the citric acid concentration is a molar ratio to the total amount of metal ions; citric acid / (Ni + W)
Is about 0.7 to 1.2. If this ratio is less than 0.7, tungsten will precipitate, and if it exceeds 1.2, the current efficiency will decrease. The Ni-WP alloy plating obtained under these pH conditions has a low current density of 1 A / dm < 2 >
It shows good gloss up to a high current density of about 2 . The thus obtained Ni-W alloy plating film containing a small amount of P not only shows good corrosion resistance in a salt spray test frequently used in a corrosion resistance test of plating, but also has CASS used in a corrosion resistance test of chromium plating. The test also showed excellent corrosion resistance.
【０００９】[0009]
【発明の実施の形態】図４に本発明の実施に好適なめっ
き装置の構造を示す。１はめっき室、２は陽極室であ
り、陽極室２とめっき室１との間に設けた孔３にはカチ
オン交換膜４を配してある。５は不溶性陽極であり、白
金チタン電極、鉛、白金、貴金属酸化電極などが利用で
きる。６は金属ニッケル陽極であり、金属板あるいはチ
ップが用いられる。なお、ニッケルがチップである場合
は、一般のチタンバスケットに収納し陽極とする。金属
ニッケル陽極６の位置は、めっき室１あるいは陽極室２
のいずれにも設置できる。７は金属タングステン陽極
で、金属板、金属チップなどが利用できる。金属チップ
の場合には、一般のチタンバスケットに収納し陽極とす
る。８はめっき品である。９，１０，１１は電流計であ
り、各陽極５，６，７に流れる直流電流を計測し、計算
量の電流になるように１２，１３，１４の直流電源を制
御する。各陽極５，６，７に流れる直流電流の制御は分
配器ならびに抵抗を用いると、電源の数を減じることが
できる。FIG. 4 shows the structure of a plating apparatus suitable for carrying out the present invention. 1 is a plating chamber, 2 is an anode chamber, and a cation exchange membrane 4 is disposed in a hole 3 provided between the anode chamber 2 and the plating chamber 1. Reference numeral 5 denotes an insoluble anode, and a platinum titanium electrode, lead, platinum, a noble metal oxide electrode, or the like can be used. Reference numeral 6 denotes a metal nickel anode, which is a metal plate or a chip. When nickel is used as a chip, it is housed in a general titanium basket and used as an anode. The position of the metal nickel anode 6 is in the plating chamber 1 or the anode chamber 2
Can be installed in any of. Reference numeral 7 denotes a metal tungsten anode, which can be a metal plate, a metal chip, or the like. In the case of a metal chip, it is stored in a general titanium basket and used as an anode. 8 is a plated product. Reference numerals 9, 10, and 11 denote ammeters that measure the DC current flowing through each of the anodes 5, 6, and 7, and control the DC power supplies 12, 13, and 14 so that the calculated current is obtained. The control of the direct current flowing through each of the anodes 5, 6, and 7 can reduce the number of power supplies by using a distributor and a resistor.
【００１０】めっき室１における溶液成分としては、亜
リン酸あるいは亜リン酸ナトリウム、亜リン酸アンモニ
ウム、亜リン酸カリウムなどの塩およびタングステン酸
ナトリウム、タングステン酸アンモニウム、タングステ
ン酸カリウムなどの塩および硫酸ニッケルあるいはニッ
ケル塩およびクエン酸あるいはクエン酸ナトリウム、ク
エン酸アンモニウム、クエン酸カリウムなどの塩を含む
めっき液がｐＨ３〜７の範囲で用いられる。陽極室２に
おける溶液成分としては、硫酸などが用いられる。The solution components in the plating chamber 1 include salts such as phosphorous acid or sodium phosphite, ammonium phosphite, potassium phosphite, salts such as sodium tungstate, ammonium tungstate, potassium tungstate, and sulfuric acid. A plating solution containing nickel or a nickel salt and a salt such as citric acid or sodium citrate, ammonium citrate or potassium citrate is used in a pH range of 3 to 7. Sulfuric acid or the like is used as a solution component in the anode chamber 2.
【００１１】カチオン交換膜によって不溶性陽極がある
陽極室とめっき室とを分離すると、クエン酸などの有機
錯化剤のアニオンはカチオン交換膜を透過できない。一
方、水素イオンなどのカチオンは、カチオン交換膜を容
易に透過することができ、隔膜による大きな電気抵抗は
生じない。カチオン交換膜を用いることにより、不溶性
陽極とめっき液の直接的接触が妨げられるとともに、め
っき液のアニオンの陽極室への移動は起こらない。この
ため、連続めっきしてもめっき液の有効成分である有機
錯化剤の陽極上での酸化分解は完全に阻止することがで
きる。When the anode compartment where the insoluble anode is located and the plating compartment are separated by a cation exchange membrane, anions of an organic complexing agent such as citric acid cannot pass through the cation exchange membrane. On the other hand, cations such as hydrogen ions can easily permeate the cation exchange membrane, and no large electrical resistance is generated by the diaphragm. By using the cation exchange membrane, direct contact between the insoluble anode and the plating solution is prevented, and the migration of anions of the plating solution to the anode chamber does not occur. Therefore, even when continuous plating is performed, the oxidative decomposition of the organic complexing agent, which is an effective component of the plating solution, on the anode can be completely prevented.
【００１２】連続めっきする場合には、めっき室では電
析反応により、めっき液中のニッケルイオンは減少す
る。これを補給するために、金属ニッケル陽極が用いら
れる。ニッケル陽極の溶解状態はカチオンであるため、
この金属ニッケル極の配置は、めっき室あるいは陽極室
のいずれの槽内に配置しても良い。同様に、タングステ
ン成分もめっき皮膜への取り込みによりめっき液中の濃
度が減少する。めっき液へのタングステン酸の補給法と
しては、タングステン酸のナトリウム塩やアンモニウム
塩などを補給する方法がある。しかし、前述したよう
に、これらの塩をめっき液に連続して補給するとナトリ
ウム、アンモニウムイオンがめっき液に蓄積する。これ
を防止するには、金属タングステンを陽極に用い、タン
グステン成分をめっき液に溶解させて補給する。さら
に、合金成分であるリンを連続的に補給するために、亜
リン酸を適宜の電解時間毎にめっき液に添加する。な
お、めっき槽からポンプ等で別槽にめっき液を汲み出
し、そこで金属ニッケル陽極ならびに金属タングステン
陽極を電解して金属イオン成分を補給して元のめっき槽
に戻すようにしてもよい。In the case of continuous plating, nickel ions in the plating solution are reduced in the plating chamber due to an electrodeposition reaction. To replenish this, a metallic nickel anode is used. Since the dissolution state of the nickel anode is cationic,
The metal nickel electrode may be arranged in either the plating chamber or the anode chamber. Similarly, the concentration of the tungsten component in the plating solution is reduced by incorporation into the plating film. As a method of replenishing the plating solution with tungstic acid, there is a method of replenishing a sodium salt or an ammonium salt of tungstic acid. However, as described above, when these salts are continuously supplied to the plating solution, sodium and ammonium ions accumulate in the plating solution. To prevent this, metal tungsten is used for the anode, and the tungsten component is dissolved in the plating solution and supplied. Further, phosphorous acid is added to the plating solution every suitable electrolysis time in order to continuously supply phosphorus as an alloy component. The plating solution may be pumped out of the plating tank to a separate tank, where the metal nickel anode and the metal tungsten anode are electrolyzed to supply metal ion components and return to the original plating tank.
【００１３】[0013]
【実施例】以下、本発明を実施例によって具体的に説明
する。 実施例１ ハルセル外観に及ぼす亜リン酸濃度の影響 めっき液組成を硫酸ニッケル０．２Ｍ、タングステン酸
ナトリウム０．２Ｍ、クエン酸アンモニウム０．４Ｍお
よびギ酸ナトリウム０．２Ｍの基本浴組成に亜リン酸を
０．０５〜０．３Ｍの範囲で添加し、アンモニア水、硫
酸によりｐＨを４．０〜５．５の範囲で調整して変化さ
せてハルセル試験（全電流３Ａ、５分）を行った。陽極
にはＳＵＳ３０４を用い、カチオン交換膜は用いなかっ
た。代わりに、クエン酸の陽極での分解を防ぐためにめ
っき液にギ酸ナトリウムを添加したが、めっきの外観に
は影響を与えなかった。The present invention will be specifically described below with reference to examples. Example 1 Influence of Phosphorous Acid Concentration on Hull Cell Appearance Phosphorous acid was added to the basic bath composition of nickel sulfate 0.2M, sodium tungstate 0.2M, ammonium citrate 0.4M and sodium formate 0.2M. Was added in the range of 0.05 to 0.3 M, and the pH was adjusted and changed with ammonia water and sulfuric acid in the range of 4.0 to 5.5 to perform a Hull cell test (total current 3 A, 5 minutes). . SUS304 was used for the anode, and no cation exchange membrane was used. Instead, sodium formate was added to the plating solution to prevent decomposition of the citric acid at the anode, but did not affect the appearance of the plating.
【００１４】亜リン酸０．０５ＭではｐＨ４およびｐＨ
４．５で全電流密度領域で光沢外観が得られたが、それ
以上のｐＨでは低電流密度領域で曇りが認められた。亜
リン酸濃度が高くなると光沢外観が得られるｐＨ領域は
広がり、０．１ＭではｐＨ５．０まで全電流密度領域で
光沢外観となった。０．１５ＭではｐＨ５．５で全域光
沢外観にはならなかったが、光沢領域は広がった。０．
３Ｍを超えるとピットが発生し、高電流密度で曇りが発
生する。図５にハルセルパターンを示す。At 0.05M phosphorous acid, pH 4 and pH
At 4.5, a glossy appearance was obtained in the entire current density region, but at a pH higher than that, cloudiness was observed in the low current density region. As the phosphorous acid concentration was increased, the pH range in which a glossy appearance was obtained widened, and at 0.1 M, the glossy appearance was obtained in the entire current density range up to pH 5.0. At 0.15 M, the entire area did not have a gloss appearance at pH 5.5, but the gloss area was widened. 0.
If it exceeds 3M, pits are generated and fogging occurs at a high current density. FIG. 5 shows a Hull cell pattern.
【００１５】実施例２ Ｎｉ−Ｗ−Ｐ合金めっき皮膜の
耐食性 容量１．２リットルのアクリル製矩形電解槽をカチオン
交換膜（デュポン製ナフィオン膜）で２室に分けて、陽
極室（２００ｍｌ）に硫酸（０．１モル／ｌ）を、めっ
き室にＮｉ−Ｗ−Ｐ合金めっき液を満たした。陽極には
Ｐｔ板（５ｃｍ×５ｃｍ）を用い、めっき試験片は、あ
らかじめ厚さ１０μｍの光沢ニッケルめっきを施した軟
鋼板（５ｃｍ×１０ｃｍ×０．５ｍｍ）とし、これに厚
さ１μｍ、３μｍおよび５μｍのＮｉ−Ｗ−Ｐ合金めっ
きを、めっき電流密度５Ａ／ｄｍ 2 で行った。めっき液
組成およびめっき条件を表１に示す。Example 2 Ni—WP alloy plating film
Corrosion resistance Cathode of 1.2 liter acrylic rectangular electrolytic cell
Separate into two chambers with an exchange membrane (Dupont Nafion membrane)
Sulfuric acid (0.1 mol / l) was added to the electrode room (200 ml).
The chamber was filled with a Ni-WP alloy plating solution. On the anode
Using a Pt plate (5 cm x 5 cm),
Soft 10 mm thick bright nickel plated
Steel plate (5cm × 10cm × 0.5mm)
1 μm, 3 μm and 5 μm Ni-WP alloy
The plating current density is 5 A / dm TwoI went in. Plating solution
Table 1 shows the composition and plating conditions.
【００１６】[0016]
【表１】 [Table 1]
【表２】 [Table 2]
【００１７】Ｎｉ−Ｗ−Ｐめっきした試験片はいずれも
鏡面光沢を示し、これをＣＡＳＳ試験に供し、８時間
後、１６時間後および４８時間後の外観を観察した。結
果を表２に示す。表２にはめっき皮膜の組成を合わせて
示した。Ｎｉ−Ｗ−Ｐ合金めっきの厚さが１μｍの場
合、８時間でほぼ全面に干渉色を示したが、３μｍおよ
び５μｍのものでは１６時間後では外観の変化は認めら
れず、４８時間でわずかな干渉色が認められた。Each of the Ni-WP plated test pieces showed a specular gloss, which was subjected to a CASS test, and the appearance was observed after 8, 16 and 48 hours. Table 2 shows the results. Table 2 also shows the composition of the plating film. When the thickness of the Ni—WP alloy plating was 1 μm, an interference color was shown on almost the entire surface in 8 hours, but in the cases of 3 μm and 5 μm, no change in appearance was observed after 16 hours, and a slight change was observed after 48 hours. Interference color was observed.
【００１８】比較例１ Ｎｉ−Ｗ合金めっき皮膜の耐食
性 めっき槽、試験片は実施例２と同様のものを用いた。Ｎ
ｉ−Ｗ合金めっき液の組成、めっき条件は表３に示し
た。Comparative Example 1 Corrosion Resistance of Ni-W Alloy Plating Film The same plating bath and test piece as in Example 2 were used. N
Table 3 shows the composition of the iW alloy plating solution and the plating conditions.
【表３】 めっき皮膜厚さは２μｍ、５μｍとし、これをＣＡＳＳ
試験に供した。Ｎｉ−Ｗ合金めっきでは、いずれも４時
間で全面にわずかな干渉色を示し、８時間で全面が黒変
色を示した。[Table 3] The thickness of the plating film is 2 μm and 5 μm, and this is
Tested. In the case of Ni-W alloy plating, a slight interference color was exhibited on the entire surface in 4 hours, and black discoloration was observed on the entire surface in 8 hours.
【００１９】比較例２ Ｎｉ−Ｐ合金めっき皮膜の耐食
性 めっき槽、試験片は実施例２と同様のものを用いた。Ｎ
ｉ−Ｐ合金めっき液の組成、めっき条件は表４に示し
た。Comparative Example 2 Corrosion Resistance of Ni-P Alloy Plating Film The same plating bath and test pieces as in Example 2 were used. N
Table 4 shows the composition of the iP alloy plating solution and the plating conditions.
【表４】 めっき皮膜厚さは５μｍとし、これをＣＡＳＳ試験に供
した。Ｎｉ−Ｐ合金めっきでは、２４時間で黒変色を示
した。[Table 4] The thickness of the plating film was 5 μm, which was subjected to a CASS test. Ni-P alloy plating showed black discoloration in 24 hours.
【００２０】[0020]
【発明の効果】請求項１ないし３のめっき液を用いれ
ば、電気めっき法により硬度が大きく耐食性良好なＮｉ
−Ｗ−Ｐ合金めっき皮膜を得ることができる。また、請
求項４ないし６の連続めっき方法によれば、めっき液中
に亜リン酸イオン、硫酸イオン、ナトリウムイオン等が
蓄積されず、めっき液の廃棄を少なくできる効果があ
る。According to the present invention, the use of the plating solution according to any one of claims 1 to 3 allows the Ni to have high hardness and good corrosion resistance by electroplating.
A -WP alloy plating film can be obtained. Further, according to the continuous plating method of claims 4 to 6, phosphite ions, sulfate ions, sodium ions, and the like are not accumulated in the plating solution, and there is an effect that disposal of the plating solution can be reduced.
【図１】Ｐ含有率、Ｗ含有率の亜リン酸濃度および浴ｐ
Ｈによる変化を示す図である。FIG. 1: Phosphorous acid concentration of P content, W content and bath p
It is a figure showing change by H.
【図２】析出電流効率に及ぼすクエン酸濃度の影響を示
す図である。FIG. 2 is a graph showing the effect of citric acid concentration on deposition current efficiency.
【図３】Ｐ含有率に及ぼすめっき電流密度の影響を示す
図である。FIG. 3 is a diagram showing the effect of plating current density on the P content.
【図４】本発明の実施に適しためっき装置の概略構成図
である。FIG. 4 is a schematic configuration diagram of a plating apparatus suitable for implementing the present invention.
【図５】Ｎｉ−Ｗ−Ｐ合金めっきのハルセルパターンを
示す図である。FIG. 5 is a view showing a Hull cell pattern of Ni-WP alloy plating.
１ めっき室 ２ 陽極室 ３ 孔 ４ カチオン交換膜 ５ 不溶性陽極 ６ ニッケル陽極 ７ タングステン陽極 ８ めっき品 ９〜１１ 電流計 １２〜１４ 直流電源 DESCRIPTION OF SYMBOLS 1 Plating chamber 2 Anode chamber 3 Hole 4 Cation exchange membrane 5 Insoluble anode 6 Nickel anode 7 Tungsten anode 8 Plating product 9-11 Ammeter 12-14 DC power supply
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ２５Ｄ 21/14 Ｃ２５Ｄ 21/14 Ｂ (71)出願人 397055252 国光鍍金工業株式会社 大阪市生野区巽北１丁目24番23号 (71)出願人 399120419 有限会社 ウイング 大阪府豊中市長興寺北１丁目５番37号 (71)出願人 397018361 大阪府鍍金工業組合 大阪府大阪市東成区中道３丁目１番14号 (72)発明者 中出 卓男 大阪府和泉市あゆみ野２丁目７番１号 大 阪府立産業技術総合研究所内 (72)発明者 左藤 眞市 大阪府和泉市あゆみ野２丁目７番１号 大 阪府立産業技術総合研究所内 (72)発明者 森河 務 大阪府和泉市あゆみ野２丁目７番１号 大 阪府立産業技術総合研究所内 (72)発明者 横井 昌幸 大阪府和泉市あゆみ野２丁目７番１号 大 阪府立産業技術総合研究所内 (72)発明者 石田 幸平 大阪府大阪市西淀川区姫島５丁目12番20号 株式会社野村鍍金内 (72)発明者 野中 康裕 大阪府大阪市城東区今福東３丁目１番40号 オテック株式会社内 (72)発明者 寺内 攻二 大阪府大阪市生野区巽北１丁目24番23号 国光鍍金工業株式会社内 (72)発明者 湯屋 進 大阪府豊中市長興寺北１丁目５番37号 有 限会社ウイング内 (72)発明者 山本 貴則 大阪府大阪市東成区中道３丁目１番14号 大阪府鍍金工業組合内 Ｆターム(参考） 4K023 AB21 BA06 BA08 BA16 BA19 CA09 CB05 DA02 DA06 4K024 AA03 AA14 AB02 BB06 BB07 BB20 CA01 CB06 CB07 CB08 CB24 GA04 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C25D 21/14 C25D 21/14 B (71) Applicant 397055252 Kenko Kogane Kogyo Co., Ltd. 1-chome Tatsumikita, Ikuno-ku, Osaka-shi 24-23 (71) Applicant 399120419 Wing Co., Ltd. 1-5-37, Chokoji-Kita, Toyonaka-shi, Osaka (71) Applicant 397018361 Osaka Prefecture Plating Industry Association 3-1-1 Nakamichi, Higashinari-ku, Osaka-shi, Osaka No. (72) Inventor Takuo Nakade 2-7-1, Ayumino, Izumi, Osaka Prefecture Inside the Osaka Prefectural Institute of Advanced Industrial Science and Technology (72) Inventor Makoto Sato 2-7-1, Ayumino, Izumi, Osaka, Osaka Within the Prefectural Institute of Advanced Industrial Science and Technology (72) Inventor Tsutomu Morikawa 2-7-1, Ayumino, Izumi City, Osaka Prefecture Within the Osaka Prefectural Institute of Advanced Industrial Science and Technology (72) Inventor Masayuki Yokoi 2-7-1, Ayumino, Izumi City, Osaka Prefecture, Osaka Prefecture, National Institute of Advanced Industrial Science and Technology (72) Kohei Ishida 5-12-20 Himeshima, Nishiyodogawa-ku, Osaka-shi, Osaka Nomura Plating Co., Ltd. (72) Inventor Nonaka Yasuhiro 3-140 Imafuku-Higashi 3-chome, Joto-ku, Osaka-shi, Japan Otec Co., Ltd. Person Susumu Yuya 1-5-37, Chokoji-Kita, Toyonaka-shi, Osaka Limited company Wing (72) Inventor Takanori Yamamoto 3-1-1, Nakamichi, Higashinari-ku, Osaka-shi, Osaka F-term in the Osaka Plating Industry Association (Reference) 4K023 AB21 BA06 BA08 BA16 BA19 CA09 CB05 DA02 DA06 4K024 AA03 AA14 AB02 BB06 BB07 BB20 CA01 CB06 CB07 CB08 CB24 GA04
Claims (6)
のめっき液であって、亜リン酸あるいは亜リン酸ナトリ
ウム、亜リン酸アンモニウム、亜リン酸カリウムなどの
塩およびタングステン酸ナトリウム、タングステン酸ア
ンモニウム、タングステン酸カリウムなどの塩および硫
酸ニッケルあるいはニッケル塩およびクエン酸あるいは
クエン酸ナトリウム、クエン酸アンモニウム、クエン酸
カリウムなどの塩を含み、浴ｐＨが３〜７であることを
特徴とするＮｉ−Ｗ−Ｐ合金めっき液。1. A plating solution for a Ni-WP alloy by an electroplating method, comprising a phosphorous acid or a salt such as sodium phosphite, ammonium phosphite, potassium phosphite, sodium tungstate, and tungstic acid. Ni- containing a salt such as ammonium and potassium tungstate and a salt such as nickel sulfate or nickel salt and citric acid or sodium citrate, ammonium citrate and potassium citrate, and having a bath pH of 3 to 7. WP alloy plating solution.
るクエン酸イオンのモル比が０．７〜１．２であること
を特徴とする請求項１記載のＮｉ−Ｗ−Ｐ合金めっき
液。2. The Ni-WP alloy plating solution according to claim 1, wherein the molar ratio of citrate ions to the total amount of metal ions of Ni and W is 0.7 to 1.2.
あることを特徴とする請求項１記載のＮｉ−Ｗ−Ｐ合金
めっき液。3. The Ni-WP alloy plating solution according to claim 1, wherein the phosphorous acid concentration is 0.05 to 0.3 M.
−Ｐ合金の電気めっきにおいて、めっき液の成分である
合金金属成分の補給に、亜リン酸を適宜の電解時間毎に
めっき液に添加することを特徴とするＮｉ−Ｗ−Ｐ合金
の連続めっき方法。4. Ni-W using the plating solution of claim 1.
Continuous plating of Ni-WP alloy characterized by adding phosphorous acid to the plating solution at an appropriate electrolysis time for replenishment of the alloy metal component which is a component of the plating solution in electroplating of -P alloy Method.
−Ｐ合金の電気めっきにおいて、めっき液の成分である
合金金属成分の補給に、金属タングステンあるいはその
合金、もしくはニッケルあるいはその合金からなる陽極
を用いることを特徴とするＮｉ−Ｗ−Ｐ合金の連続めっ
き方法。5. Ni-W using the plating solution of claim 1.
A continuous Ni-WP alloy characterized by using metal tungsten or an alloy thereof or an anode made of nickel or an alloy thereof to supply an alloy metal component which is a component of a plating solution in electroplating of a -P alloy. Plating method.
−Ｐ合金の電気めっきにおいて、カチオン交換膜を介し
てめっき液から分離された不溶性陽極を用いることを特
徴とするＮｉ−Ｗ−Ｐ合金の連続めっき方法。6. Ni-W using the plating solution of claim 1.
A method for continuously plating a Ni-WP alloy, comprising using an insoluble anode separated from a plating solution via a cation exchange membrane in electroplating of a -P alloy.
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| JP2001043156A JP3458843B2 (en) | 2001-02-20 | 2001-02-20 | Continuous plating method for Ni-WP alloy |
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|---|---|---|---|
| JP2001043156A JP3458843B2 (en) | 2001-02-20 | 2001-02-20 | Continuous plating method for Ni-WP alloy |
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