JPH0280589A - Tungsten electroplating bath and plating method using the bath - Google Patents
Tungsten electroplating bath and plating method using the bathInfo
- Publication number
- JPH0280589A JPH0280589A JP23319188A JP23319188A JPH0280589A JP H0280589 A JPH0280589 A JP H0280589A JP 23319188 A JP23319188 A JP 23319188A JP 23319188 A JP23319188 A JP 23319188A JP H0280589 A JPH0280589 A JP H0280589A
- Authority
- JP
- Japan
- Prior art keywords
- tungsten
- plating
- bath
- halide
- mol
- 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
- 238000007747 plating Methods 0.000 title claims abstract description 53
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 38
- 239000010937 tungsten Substances 0.000 title claims abstract description 38
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims description 9
- 238000009713 electroplating Methods 0.000 title abstract description 6
- 150000004820 halides Chemical class 0.000 claims abstract description 25
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims abstract description 7
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 239000003960 organic solvent Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 abstract description 8
- 230000008018 melting Effects 0.000 abstract description 7
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 229910003091 WCl6 Inorganic materials 0.000 abstract 1
- -1 aluminum halide Chemical class 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 5
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- POKOASTYJWUQJG-UHFFFAOYSA-M 1-butylpyridin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1=CC=CC=C1 POKOASTYJWUQJG-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003657 tungsten Chemical class 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、高融点金属であるタングステンを低温でＩＩ
ｋ密に亮純度めっきできる電気タングステンめっき浴と
その浴によるめっき方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention is a method for processing tungsten, which is a high melting point metal, at a low temperature.
The present invention relates to an electrolytic tungsten plating bath that can perform k-density plating with high purity, and a plating method using the bath.
（従来技術）
タングステンは、高融点金属であるとともに、高温耐食
性にも優れているので、そのめっき材は、原子炉部材、
高温炉材などに適している。(Prior art) Tungsten is a high-melting point metal and has excellent high-temperature corrosion resistance, so its plating material is used for nuclear reactor parts,
Suitable for high-temperature furnace materials, etc.
このタングステンのめっきには、ＣＶＤ法、電気めっき
法などがあるが、電気めっき法の場合は、タングステン
と酸素との親和力が非常に強く、水溶液系めっき浴で行
うことは困難であることがら、非水溶液系のめっき浴、
特に有機溶媒系や溶融塩系のめっき浴で行なわなければ
ならない０例えば、１１３［Ｐ（Ｗ、０１．）、１−Ｈ
ＣＯＮＨｚ−Ｈ，ＢＯ，−）１２０２− ＮＨ４Ｃｌ系
の有機溶媒系めっき浴やＬｉＣｌ−ＫＣｌ−に２冒０．
−に２ＣＯ。This tungsten plating method includes CVD and electroplating methods, but in the case of electroplating, the affinity between tungsten and oxygen is very strong, and it is difficult to perform it in an aqueous plating bath. Non-aqueous plating bath,
For example, 113 [P(W, 01.), 1-H
CONHz-H,BO,-)1202- NH4Cl-based organic solvent plating bath or LiCl-KCl-.
-2CO.
系の溶融塩系めっき浴で行わなければならない。must be performed in a molten salt plating bath.
（発明が解決しようとする問題点）
しかしながら、上記のような有機溶媒系めっき浴でめっ
きした場合めっきされるのは、タングステンと酸化タン
グステンの混合物で、高純度のタングステンをめっきす
ることは困難であった。また、溶融塩系めっき浴の場合
は、めっき温度が５５０〜７００℃と高温であるため、
作業性が劣り、しかも、めっき面が緻密にならないもの
であった。(Problems to be Solved by the Invention) However, when plating is performed using the above-mentioned organic solvent-based plating bath, what is plated is a mixture of tungsten and tungsten oxide, and it is difficult to plate high-purity tungsten. there were. In addition, in the case of a molten salt plating bath, the plating temperature is as high as 550 to 700°C, so
Workability was poor, and the plated surface was not dense.
そこで、本発明は、このような問題を解決した電気タン
グステンめっ！浴およびその俗によるめっき方法を提供
するものである。Therefore, the present invention is an electric tungsten metal plate that solves these problems! The present invention provides a bath and a conventional plating method thereof.
（問題点を解決するための手段）
本発明者らは、上記のような問題のない電気タングステ
ンめっき浴を開発すべく、種々検討した結果、比較的低
温でめっきできる大塩化タングステンと第四級アンモニ
ウム塩、すなわち、Ｎ−ｆｉ換アルキルピリツニウムハ
ロゲン化物またはＮ−置換アルキルイミグゾリウムハロ
ゲン化物との溶融塩浴の開発に成功した。(Means for Solving the Problems) In order to develop an electric tungsten plating bath that does not have the above-mentioned problems, the present inventors have conducted various studies and found that large tungsten chloride and quaternary tungsten chloride, which can be plated at relatively low temperatures, have been developed. We have successfully developed molten salt baths with ammonium salts, namely N-fi-substituted alkylpyritunium halides or N-substituted alkylimigzolium halides.
すなわち、本発明は、六塩化タングステン（ＷＣｌ、）
２０〜８０モル％とＮ−アルキルピリジニウムカチオン
化物（Ｃ５Ｈ５Ｎ−ＲＸ、 ｍ Ｌ、Ｒは炭素数１−５
のアルキル基、Ｘはハロゲン原子）、または１−アルキ
ルもしくは１．３−ジアルキルイミダゾリウムハロゲン
化物（但し、アルキル基の炭素数は１〜１２）２０〜８
０モル％とを溶融してなるめっき浴か、またはこのめっ
き浴のＮ−アルキルピリジニウムハロゲン化物または１
−アルキルもしくは１．３−ジアルキルイミダゾリウム
ハロゲン化物を１〜７９モル％にして、アルカリ金属、
アルカリ土類金属またはアルミニウムのハロゲン化物を
１〜７９モル％添加しためっき浴により高純度のタング
ステンを比較的低温で電気めっきできるようにした。That is, the present invention provides tungsten hexachloride (WCl)
20 to 80 mol% and N-alkylpyridinium cationized product (C5H5N-RX, m L, R is carbon number 1-5
alkyl group, X is a halogen atom), or 1-alkyl or 1,3-dialkylimidazolium halide (however, the number of carbon atoms in the alkyl group is 1 to 12) 20 to 8
A plating bath formed by melting 0 mol% of N-alkylpyridinium halide or 1 of this plating bath.
- 1 to 79 mol% of alkyl or 1,3-dialkylimidazolium halide, an alkali metal,
High purity tungsten can be electroplated at a relatively low temperature using a plating bath to which 1 to 79 mol% of an alkaline earth metal or aluminum halide is added.
本発明のめっき浴は、大塩化タングステンと第四級アン
モニウム塩のＮ−アルキルピリジニウムハロゲン化物ま
たは１−アルキルもしくは１，３−ノアルキルビリノニ
ウムハロゲン化物との混合割合が上記範囲にあると、常
温付近でも液体になり、ハロゲン化タングステンの７ニ
オンと、アルキルピリジニウムカチオンまたはイミダゾ
リウムカチオンとにイオン解離するので、電気めっきに
よりタングステンをめっきすることができる。In the plating bath of the present invention, when the mixing ratio of large tungsten chloride and the quaternary ammonium salt N-alkylpyridinium halide or 1-alkyl or 1,3-noalkylvinonium halide is within the above range, Since it becomes a liquid even at around room temperature and ionically dissociates into tungsten halide 7 ions and alkylpyridinium cations or imidazolium cations, tungsten can be plated by electroplating.
Ｎ−アルキルピリジニウムハロゲン化物としては、アル
キル基の炭素数が１〜５のものを使用する。As the N-alkylpyridinium halide, one having an alkyl group of 1 to 5 carbon atoms is used.
これは、Ｎ−アルキルピリジニウムハロゲン化物の場合
、需要がないため、市販されておらず、使用にあたって
は合成しなければならないが、炭素数が６以上のものの
合成は難しく、また、大塩化タングステンのような塩化
物と混合した場合、常温で液体になりにくくなるためで
ある。このＮ−アルキルピリジニウムハロゲン化物とし
ては、ブチルピリジニウムクロリドが好ましい。In the case of N-alkylpyridinium halides, they are not commercially available because there is no demand for them, and they must be synthesized before they can be used. However, it is difficult to synthesize those with 6 or more carbon atoms, and large tungsten chloride is difficult to synthesize. This is because when mixed with such chlorides, it becomes difficult to become liquid at room temperature. As the N-alkylpyridinium halide, butylpyridinium chloride is preferred.
１−アルキルもしくは１，３−ジアルキルイミグゾリウ
ムハロゲン化物の場合も上記同様の理由からアルキル基
の炭素数が１〜１２のものを使用する。In the case of 1-alkyl or 1,3-dialkyl imigzolium halides, those in which the alkyl group has 1 to 12 carbon atoms are used for the same reason as above.
このイミグゾール誘導体の場合、１−メチル−３−エチ
ルノアルキルのものの方が好ましい。In the case of this imiguzole derivative, 1-methyl-3-ethylnoalkyl is preferred.
洛中の大塩化タングステンは、２０〜８０モル％にする
。これは、２０モル％未満であると、常温で溶解しにく
くなるとともに、アルキルピリジニウムカチオンまたは
イミダゾリウムカチオン濃度が高くなり、タングステン
が電析する際、そのカチオンの還元が同時に進行して、
浴の劣化、電流効率の低下およびめっき層の表面外観不
良を招くからである。一方、８０モル％を越えると、浴
の導電率が低下し、めっきしにくくなる。The amount of large tungsten chloride in Rakuchu should be 20 to 80 mol%. If it is less than 20 mol%, it becomes difficult to dissolve at room temperature and the concentration of alkylpyridinium cations or imidazolium cations becomes high, and when tungsten is electrodeposited, the reduction of the cations proceeds at the same time.
This is because it causes deterioration of the bath, reduction in current efficiency, and poor surface appearance of the plating layer. On the other hand, if it exceeds 80 mol%, the conductivity of the bath decreases and plating becomes difficult.
しかし、このめっき浴は、融点が従来の溶融塩浴より低
いが、電気めっきの一般的なめっき浴である水溶液系に
比べると、粘性が高い。このため、導電率が低く、凹凸
のある被めっき物をめっきする場合、均一電着性が劣る
。かかる場合には、アルカリ金属、アルカリ土類金属ま
たはアルミニウムのハロゲン化物、例えば、ＬｉＣｌ、
Ｌｉａｒ、 ＬｉＦ。However, although this plating bath has a lower melting point than a conventional molten salt bath, it has a higher viscosity than an aqueous solution type plating bath, which is a common plating bath for electroplating. For this reason, when plating an object with low electrical conductivity and irregularities, uniform electrodeposition is poor. In such cases, halides of alkali metals, alkaline earth metals or aluminum, such as LiCl,
Liar, LiF.
ＮａＣｌ、ＣａＣＩ ａ、＾ＩＣ１，などを添加すると
、融点が低下して浴の粘性が低下し、導電率を高くでき
る。When NaCl, CaCI a, ^IC1, etc. are added, the melting point is lowered, the viscosity of the bath is lowered, and the conductivity can be increased.
これらのハロゲン化物は、浴中で金属イオンとハロゲン
イオンに解離するが、金属イオンは、酸化還元電位がタ
ングステンより卑であるので、電解の際、タングステン
が電析する際析出することはない６一方、ハロゲンイオ
ンは、タングステンの錯イオンを形成する。These halides dissociate into metal ions and halogen ions in the bath, but since metal ions have a less oxidation-reduction potential than tungsten, they do not precipitate when tungsten is deposited during electrolysis6. On the other hand, halogen ions form tungsten complex ions.
この融、α低下用のハロゲン化物添加量は、六塩化タン
グステンを２０〜８０モル％に維持した状態でＮ−アル
キルビリノニウムハロゲン化物またはｌ−アルキルもし
くは１，３−ノアルキルイミグゾリウムハロゲン化物を
１〜７９モル％、融息低下用のハロゲン化物を１〜７９
モル％の割合にする。The amount of halide added to reduce the melting point and α is N-alkylvinonium halide, l-alkyl or 1,3-noalkylimigzolium, while maintaining tungsten hexachloride at 20 to 80 mol%. 1 to 79 mol% of halide, 1 to 79 mol% of halide for reducing melting temperature
Make it a ratio of mole %.
低温でめっきする場合の浴の粘性を低下させる方法とし
ては、有機溶媒を添加する方法によってもよい、この場
合、有機溶媒としては、トルエン、キシレン、ベンゼン
などのような芳香族炭化水素のものが好ましく、それら
の１種または２種を１０〜７５ｖｏｌ％添加する。１０
ｖｏｌ％未満では添加効果があまり認められず、７５ｖ
ｏｌ％を越えると、タングステンイオン濃度が低くなり
すぎる。When plating at low temperatures, the viscosity of the bath may be reduced by adding an organic solvent. In this case, the organic solvent may be an aromatic hydrocarbon such as toluene, xylene, benzene, etc. Preferably, 10 to 75 vol% of one or two of them is added. 10
At less than vol%, the addition effect is not observed much, and at 75v
If it exceeds ol%, the tungsten ion concentration becomes too low.
以上のアルカリ金属、アルカリ土類金属またはアルミニ
ウムのハロゲン化物添加と有機溶媒の添加は、併用して
もよい。The above addition of an alkali metal, alkaline earth metal or aluminum halide and addition of an organic solvent may be used in combination.
めっき浴は、酸素や空気に触れても安全であるが、タン
グステン錯イオンの酸化防止のため、乾燥無酸素雰囲気
中（乾燥Ｎ２や＾「中）で行うのが好ましい。また、電
解条件は、直流もしくはパルス電流により浴温０〜３０
０℃、電流密度０．１〜５０＾／ｄＩ６２で行うと、電
流効率がよく、均一にめっきすることができる。浴温が
０℃より低いと、均一にめっきできず、３００℃より高
くして電流密度を５０＾／ｄｍ２より高くすると、有機
物カチオンの還元が起こり、めっき層が灰色になるとと
もに、電流効率も低下する。The plating bath is safe even when exposed to oxygen or air, but to prevent oxidation of tungsten complex ions, it is preferable to conduct the plating in a dry oxygen-free atmosphere (dry N2 or inside).The electrolytic conditions are as follows: Bath temperature 0-30 by direct current or pulse current
When carried out at 0° C. and a current density of 0.1 to 50^/dI62, current efficiency is good and uniform plating can be achieved. If the bath temperature is lower than 0℃, uniform plating will not be possible, and if the bath temperature is higher than 300℃ and the current density is higher than 50^/dm2, organic cations will be reduced, the plating layer will turn gray, and the current efficiency will decrease. descend.
ストリップなどを均一に連続めっきする場合、めっき浴
にタングステンイオンを補給して、浴中のタングステン
イオン濃度を一定の範囲に保つ必要があるが、この場合
、陽極をタングステン製可溶性陽極にすると、通電量に
応じてタングステンイオンが自動補給され、六塩化タン
グステンの補給によらなくてもタングステンイオン濃度
を一定の範囲に保つことができる。When uniformly and continuously plating strips, etc., it is necessary to replenish the plating bath with tungsten ions to maintain the tungsten ion concentration in the bath within a certain range. Tungsten ions are automatically replenished according to the amount, and the tungsten ion concentration can be maintained within a certain range without replenishing tungsten hexachloride.
（実施例）
板厚０．５ｍｍの冷延鋼板に常法により溶剤蒸気洗浄、
アルカリ脱脂および酸洗などを施した後、乾燥しで、直
ちに予めＮ２雰囲気に保っておいた第１表に示すめっ８
浴に浸漬し、冷延鋼板を陰極、タングステン板（純度９
９％、板厚１１）を陽極にして、直流によりタングステ
ンめっきを行なった。第１表にめっき浴組成、電解条件
と得られたタングステンめっき鋼板の関係を示す。(Example) A cold-rolled steel plate with a thickness of 0.5 mm was cleaned with solvent vapor using a conventional method.
After performing alkaline degreasing and pickling, etc., the plate 8 shown in Table 1 was immediately dried and kept in an N2 atmosphere in advance.
Immerse the cold-rolled steel plate in the bath and use the tungsten plate (purity 9) as the cathode.
Tungsten plating was performed by direct current using a plate having a thickness of 9% and a thickness of 11) as an anode. Table 1 shows the relationship between the plating bath composition, electrolytic conditions, and the obtained tungsten-plated steel sheets.
（発明の効果）
以上のように、本発明のめっき浴によれば、高純度のタ
ングステンめっきを行うことができ、また、浴温を従来
の溶融塩系めつさ浴より低温にすることができるので、
作業性に優れ、めっき面も緻密にすることができる。(Effects of the Invention) As described above, according to the plating bath of the present invention, high-purity tungsten plating can be performed, and the bath temperature can be lower than that of conventional molten salt baths. Because you can
It has excellent workability and allows the plating surface to be made dense.
Claims (6)
ル％およびＮ−アルキルピリジニウムハロゲン化物（Ｃ
＿５Ｈ＿５Ｎ−ＲＸ、但し、Ｒは炭素数１〜５のアルキ
ル基、Ｘはハロゲン原子）、または１−アルキルもしく
は１，３−ジアルキルイミダゾリウムハロゲン化物（但
し、アルキル基の炭素数は１〜１２）２０〜８０モル％
を混合溶融してなる電気タングステンめっき浴。(1) 20 to 80 mol% of tungsten hexachloride (WCl_6) and N-alkylpyridinium halide (C
_5H_5N-RX, where R is an alkyl group having 1 to 5 carbon atoms, X is a halogen atom), or 1-alkyl or 1,3-dialkylimidazolium halide (however, the alkyl group has 1 to 12 carbon atoms) 20-80 mol%
Mix and melt the tungsten into an electric tungsten plating bath.
ゲン化物または１−アルキルもしくは１，３−ジアルキ
ルイミダゾリウムハロゲン化物を１〜７９モル％にして
、アルカリ金属、アルカリ土類金属またはアルミニウム
のハロゲン化物を１〜７９モル％添加した電気タングス
テンめっき浴。(2) A halide of an alkali metal, an alkaline earth metal, or aluminum, containing 1 to 79 mol% of the N-alkylpyridinium halide or the 1-alkyl or 1,3-dialkylimidazolium halide according to claim 1. An electrolytic tungsten plating bath containing 1 to 79 mol% of
添加した電気タングステンめっき裕。(3) An electrolytic tungsten plating method comprising adding an organic solvent to the plating bath according to claim 1 or 2.
に記載の電気タングステンめっき浴。(4) Claim 3 in which 10 to 75 vol% of an organic solvent is added.
Electric tungsten plating bath described in.
て、乾燥無酸素雰囲気中で直流もしくはパルス電流によ
り浴温０〜３００℃、電流密度０．１〜５０Ａ／ｄｍ＾
２の電解条件でめっきする電気タングステンめっき方法
。(5) Using the plating bath according to any one of claims 1 to 4, plating with direct current or pulse current in a dry oxygen-free atmosphere at a bath temperature of 0 to 300°C and a current density of 0.1 to 50 A/dm^
Electrolytic tungsten plating method that performs plating under the electrolytic conditions of 2.
項５に記載の電気タングステンめっき方法。(6) The electric tungsten plating method according to claim 5, wherein the anode is a tungsten anode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23319188A JPH0280589A (en) | 1988-09-17 | 1988-09-17 | Tungsten electroplating bath and plating method using the bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23319188A JPH0280589A (en) | 1988-09-17 | 1988-09-17 | Tungsten electroplating bath and plating method using the bath |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0280589A true JPH0280589A (en) | 1990-03-20 |
Family
ID=16951171
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23319188A Pending JPH0280589A (en) | 1988-09-17 | 1988-09-17 | Tungsten electroplating bath and plating method using the bath |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0280589A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009235462A (en) * | 2008-03-26 | 2009-10-15 | Sumitomo Electric Ind Ltd | Molten salt bath, method for producing molten salt bath, and tungsten deposit |
| JP2011014917A (en) * | 2010-08-20 | 2011-01-20 | Sumitomo Electric Ind Ltd | Metal laminate structure |
| CN102002743A (en) * | 2010-12-01 | 2011-04-06 | 北京科技大学 | Preparation method for electroplating thick tungsten coating on pure copper or copper alloy substrate with molten salt |
| WO2011102059A1 (en) * | 2010-02-19 | 2011-08-25 | 住友電気工業株式会社 | Metal laminate structure and production method for same |
| US9199433B2 (en) | 2009-06-30 | 2015-12-01 | Sumitomo Electric Industries, Ltd. | Metal laminated structure and method for producing the metal laminated structure |
-
1988
- 1988-09-17 JP JP23319188A patent/JPH0280589A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009235462A (en) * | 2008-03-26 | 2009-10-15 | Sumitomo Electric Ind Ltd | Molten salt bath, method for producing molten salt bath, and tungsten deposit |
| US9199433B2 (en) | 2009-06-30 | 2015-12-01 | Sumitomo Electric Industries, Ltd. | Metal laminated structure and method for producing the metal laminated structure |
| WO2011102059A1 (en) * | 2010-02-19 | 2011-08-25 | 住友電気工業株式会社 | Metal laminate structure and production method for same |
| JP2011171564A (en) * | 2010-02-19 | 2011-09-01 | Sumitomo Electric Ind Ltd | Metal laminate structure and method of manufacturing metal laminate structure |
| US8993121B2 (en) | 2010-02-19 | 2015-03-31 | Sumitomo Electric Industries, Ltd. | Metal laminated structure and method for producing the same |
| JP2011014917A (en) * | 2010-08-20 | 2011-01-20 | Sumitomo Electric Ind Ltd | Metal laminate structure |
| CN102002743A (en) * | 2010-12-01 | 2011-04-06 | 北京科技大学 | Preparation method for electroplating thick tungsten coating on pure copper or copper alloy substrate with molten salt |
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