JPH0297691A - Molybdenum electroplating bath and plating method by bath thereof - Google Patents
Molybdenum electroplating bath and plating method by bath thereofInfo
- Publication number
- JPH0297691A JPH0297691A JP24704488A JP24704488A JPH0297691A JP H0297691 A JPH0297691 A JP H0297691A JP 24704488 A JP24704488 A JP 24704488A JP 24704488 A JP24704488 A JP 24704488A JP H0297691 A JPH0297691 A JP H0297691A
- Authority
- JP
- Japan
- Prior art keywords
- molybdenum
- halide
- bath
- plating
- plating bath
- 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 54
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 47
- 239000011733 molybdenum Substances 0.000 title claims abstract description 47
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims description 30
- 238000000034 method Methods 0.000 title claims description 8
- 238000009713 electroplating Methods 0.000 title abstract description 6
- 150000004820 halides Chemical class 0.000 claims abstract description 24
- -1 molybdenum halide Chemical class 0.000 claims abstract description 23
- 238000002844 melting Methods 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 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 5
- 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
- 125000005843 halogen group Chemical group 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 4
- 229910000831 Steel Inorganic materials 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 239000010959 steel Substances 0.000 abstract description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 4
- 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
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 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
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- PQMFVUNERGGBPG-UHFFFAOYSA-N (6-bromopyridin-2-yl)hydrazine Chemical compound NNC1=CC=CC(Br)=N1 PQMFVUNERGGBPG-UHFFFAOYSA-N 0.000 description 1
- POKOASTYJWUQJG-UHFFFAOYSA-M 1-butylpyridin-1-ium;chloride Chemical compound [Cl-].CCCC[N+]1=CC=CC=C1 POKOASTYJWUQJG-UHFFFAOYSA-M 0.000 description 1
- 102100027194 CDP-diacylglycerol-inositol 3-phosphatidyltransferase Human genes 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 101000914522 Homo sapiens CDP-diacylglycerol-inositol 3-phosphatidyltransferase Proteins 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 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
- 230000006866 deterioration Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- JBJYTZXCZDNOJW-JLHYYAGUSA-N ic261 Chemical compound COC1=CC(OC)=CC(OC)=C1\C=C\1C2=CC=CC=C2NC/1=O JBJYTZXCZDNOJW-JLHYYAGUSA-N 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 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
- 150000005324 oxide salts Chemical class 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 208000008918 voyeurism Diseases 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、高融点金属であるモリブデンを低温でｍ密に
高純度めっきできる電気モリブデ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 (Field of Industrial Application) The present invention relates to an electrolytic molybdenum plating bath capable of high-purity plating of molybdenum, which is a high-melting point metal, at low temperatures and m-density, and a plating method using the bath.
（従来技術）
モリブデンは、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) Molybdenum is a high-melting point metal and also has excellent high-temperature corrosion resistance, so its plating material is suitable for nuclear reactor members, high-temperature reactor materials, and the like.
このモリブデンのめっきには、ＣＶＤ法、電気めっさ法
などがあるが、電気めっき法の場合は、モリブデンと酸
素との親和力が非常に強く、水溶液系めっ！１浴で行う
ことは困難であることがら、非水溶Ｘｌ系のめっき浴、
例えば、ｎ２［Ｐ（ＭＯ３０１ｏ）＜］−ｎＣＯＮ Ｉ
Ｉ□−Ｃ，＋ｎ０？（クエン酸）−ｎ２０２−Ｎｎ．Ｃ
Ｉ系などの有機溶媒系やＮｏ酸化物塩十ＫＦ＋ホウ酸系
などの溶融塩系のめっき浴で行なわれていた。Molybdenum plating methods include CVD and electroplating methods, but in the case of electroplating, the affinity between molybdenum and oxygen is very strong, and aqueous solution plating is used! Since it is difficult to perform plating in one bath, a non-aqueous Xl-based plating bath,
For example, n2[P(MO301o)<]-nCON I
I□-C, +n0? (citric acid)-n202-Nn. C
Plating baths have been carried out using organic solvent systems such as I-based plating baths or molten salt-based plating baths such as No oxide salt 10KF+boric acid system.
（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
きした場合にめっきされるものは、モリブデンとモリブ
デン酸化物の混合物で、高純度のモリブデンをめっきす
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８００℃以上と高温であるため、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 an organic solvent-based plating bath as described above, what is plated is a mixture of molybdenum and molybdenum oxide, and it is difficult to plate high-purity molybdenum. It was difficult. In addition, in the case of a molten salt plating bath, the plating temperature is as high as 800° C. or higher, so the workability is poor and the plated surface is not dense.
そこで、本発明は、このような問題を解決した電気モリ
ブデンめっき浴およびその浴によるめっき方法を提供す
るものである。Therefore, the present invention provides an electrolytic molybdenum plating bath that solves these problems and a plating method using the bath.
（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モリブデン
めっき浴を開発すべく、種々検討した結果、比較的低温
でめっきできるモリブデンハロゲン化物と第四級アンモ
ニウム塩、すなわち、Ｎ−置換アルキルピリジニウムハ
ロゲン化物またはＮ−置換アルキルピリジニウムハロゲ
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 electrolytic molybdenum plating bath that does not have the above-mentioned problems, the present inventors have conducted various studies and found that molybdenum halides and quaternary molybdenum halides, which can be plated at relatively low temperatures, We have successfully developed molten salt baths with ammonium salts, namely N-substituted alkylpyridinium halides or N-substituted alkylpyridinium halides.
すなわち、本発明は、モリブデンハロゲン化物（ＭｏＸ
ｎ、Ｘはハロゲン原子、ｎは２−６ ）２０−８０モル
％とＮ−アルキルピリジニウムハロゲン化物（Ｃ６ＩＩ
、Ｎ−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
−ノ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％とを溶融
してなるめっき浴が、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−ジアルキルイミグ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モリブデンを比較的低温
で電気めっきできるようにした。That is, the present invention provides molybdenum halide (MoX
n, X are halogen atoms, n is 2-6) 20-80 mol% and N-alkylpyridinium halide (C6II
, N-RX, where R is an alkyl group having 1 to 5 carbon atoms,
is a halogen atom), or 1-alkyl or 1.3
- a plating bath formed by melting 20 to 80 mol% of a noalkylimidazolium halide (however, the number of carbon atoms in the alkyl group is 1 to 12), or an N-alkylpyridinium halide or 1-alkyl Or 1,3-dialkyl imigzolium halide
to 79 mol %, and high purity molybdenum can be electroplated at a relatively low temperature using a plating bath to which 1 to 79 mol % of an alkali metal, alkaline earth metal, or aluminum halide is added.
本発明のめっき浴は、モリブデンハロゲン化物と第四級
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−ジアルキルピリ
ジ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、ハロゲン化モリブデンの７
ニオンと、フルキルピリジニウムカチオンまたはイミグ
ゾリウムカチオンとにイオン解離するので、電気めっき
によりモリブデンをめっきすることができる。The plating bath of the present invention can be used even at room temperature if the mixing ratio of molybdenum halide and quaternary ammonium salt N-alkylpyridinium halide or 1-alkyl or 1,3-dialkylpyridinium halide is within the above range. 7 of molybdenum halide becomes liquid
Molybdenum can be plated by electroplating because the molybdenum is ionically dissociated into ions and furkylpyridinium cations or imigzolium cations.
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、モリブデンハロゲン化物と混合し
た場合、常温で液体になりにくくなるためである。二〇
Ｎ−フルキルピリノ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 carbon numbers of 6 or more, and it is difficult to synthesize them with molybdenum halides. This is because when mixed, it becomes difficult to become a liquid at room temperature. As the 20N-furkylpyrinonium 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
ルジアルキルクロリドが好ましい。In the case of this imiguzole derivative, 1-methyl-3-ethyldialkyl chloride is preferred.
浴中のモリブデンハロゲン化物は、２０〜８０モル％に
する。これは、２０％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１土イミダゾリウム力チオン濃度が高くなり、モリブ
デンが電析する際、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 molybdenum halide in the bath should be 20 to 80 mol%. If it is less than 20%, it becomes difficult to dissolve at room temperature, and the concentration of alkylpyridinium cations and imidazolium cations becomes high, and when molybdenum is electrodeposited, reduction of the cations proceeds at the same time. This is because this results in 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？１着性が劣
る。かがる場合には、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、ＬｉＣ１
、Ｌｉ１）ｒ、 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, which is a common plating bath for electroplating. When plating a plated object, is it uniform? First-placeability is poor. In the case of sintering, halides of alkali metals, alkaline earth metals or aluminum, such as LiCl
, Li1)r, LiF.
ＮａＣｌ、 ＣａＣｌ２、＾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, CaCl2, 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、酸化還元電位がモ
リブデンより卑であるので、電解の際、モリブデンが電
析する際析出することはない。These halides dissociate into metal ions and halogen ions in the bath, but since the metal ions have a less oxidation-reduction potential than molybdenum, they do not precipitate when molybdenum is deposited during electrolysis.
一方、ハロゲンイオンは、モリブデンの錯イオンを形成
する。On the other hand, halogen ions form molybdenum complex ions.
この融点低下用のハロゲン化物添加量は、モリブデンハ
ロゲン化物を２０〜８０モル％に維持した状態でＮ−フ
ルキルピリノ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％、融点低下用のハロゲン化物を１〜７
９モル％の割合にする。The amount of halide added to lower the melting point is such that while maintaining molybdenum halide at 20 to 80 mol%, N-furkylpyrinonium halide or 1-alkyl or 1,3-dialkylimidazolium halide is added to ~79 mol%, 1 to 7 halides to lower the melting point
The proportion is 9 mol%.
低温でめり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、キンレン、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、モリブデンイオン濃度が低くなりす
ぎる。A method for reducing the viscosity of the bath when performing metallization at low temperatures may be to add an organic solvent. In this case, the organic solvent may be an aromatic hydrocarbon such as toluene, quinolene, benzene, etc. are preferred, and one or two of them are added in an amount of 10 to 75 vol%. 10
At less than vol%, the addition effect is not observed much, and at 75v
If it exceeds ol%, the molybdenum 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、モリ
ブデン錯イオンの酸化防止のため、乾燥無酸素雰囲気中
（乾ｅ！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０．１〜５０八／ｄＩｎ２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＾／ｄｒｂ２より高くすると、有
機物カチオンの還元が起こり、めっ！＆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 molybdenum complex ions, it is preferable to conduct the plating in a dry oxygen-free atmosphere (dry e!N2 or medium). The bath temperature is 0 to 30% by direct current or pulsed current.
When carried out at 0° C. and a current density of 0.1 to 508/dIn2, the 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^/drb2, reduction of organic cations will occur, resulting in plating! & As the layer turns gray, the current efficiency also decreases.
ストリップなどを均一に連続めっきする場合、めっｂ浴
にモリブデンイオンを補給して、浴中のモリブデンイオ
ン濃度を一定の範囲に保つ必要があるが、この場合、陽
極をモリブデン製可溶性陽極にすると、通電量に応じて
モリブデンイオンが自動補給され、モリブデンハロゲン
化物の補給によらなくてもモリブデ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 molybdenum ions to maintain the molybdenum ion concentration within a certain range.In this case, if the anode is a soluble molybdenum anode, Molybdenum ions are automatically replenished according to the amount of current applied, and the molybdenum ion concentration can be maintained within a certain range without replenishment of molybdenum halide.
（実施例）
板ＦＪ０．５■の冷ｌＩＲ板に常法により溶剤蒸気洗浄
、ア）レカリ覗脂および酸洗などを施した後、乾燥して
、直ちに予めＮ２雰囲気に保っておいたｍ１表に示すめ
っき浴に浸漬し、冷延鋼板を陰極、モリブデン板（純度
９９．９％、板厚１ｍｍ）を陽極にして、直流によりモ
リブデンめっきを行なった。ＰＩＳ１表にめグき浴組成
、電解条件と得られたモリブデンめっき鋼板の関係を示
す。(Example) A cold lIR plate of plate FJ0.5■ was subjected to solvent vapor cleaning by a conventional method, a) Recali peeping oil and pickling, etc., and then dried and immediately kept in an N2 atmosphere in advance. Molybdenum plating was performed by immersing the steel plate in the plating bath shown in Figure 2 and using a cold rolled steel plate as a cathode and a molybdenum plate (purity 99.9%, plate thickness 1 mm) as an anode using direct current. Table PIS1 shows the relationship between the plating bath composition, electrolytic conditions, and the obtained molybdenum-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、高純度のモ
リブデンめっきを行うことができ、また、浴温を従来の
溶融塩系めっ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 molybdenum plating can be performed, and the bath temperature can be lower than that of conventional molten salt plating baths. This makes it possible to achieve excellent workability and to make the plating surface denser.
Claims (6)
ゲン原子、ｎは２〜６）２０〜８０モル％およびＮ−ア
ルキルピリジニウムハロゲン化物（Ｃ＿５Ｈ＿５Ｎ−Ｒ
Ｘ）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
る電気モリブデンめっき浴。(1) Molybdenum halide (MoX_n, X is a halogen atom, n is 2-6) 20-80 mol% and N-alkylpyridinium halide (C_5H_5N-R
X) However, R is an alkyl group having 1 to 5 carbon atoms; An electrolytic molybdenum plating bath made by mixing and melting 80 mol% of molybdenum.
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％添加した電気モリブデ
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 molybdenum plating bath containing 1 to 79 mol% of
添加した電気モリブデンめっき浴。(3) An electrolytic molybdenum plating bath obtained by adding an organic solvent to the plating bath according to claim 1 or 2.
に記載の電気モリブデンめっき浴。(4) Claim 3 in which 10 to 75 vol% of an organic solvent is added.
Electrolytic molybdenum 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モリブデンめっき方法。(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^
An electrolytic molybdenum plating method that performs plating under the electrolytic conditions of 2.
５に記載の電気モリブデンめっき方法。(6) The electrolytic molybdenum plating method according to claim 5, wherein the anode is a molybdenum anode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24704488A JPH0297691A (en) | 1988-09-30 | 1988-09-30 | Molybdenum electroplating bath and plating method by bath thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24704488A JPH0297691A (en) | 1988-09-30 | 1988-09-30 | Molybdenum electroplating bath and plating method by bath thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0297691A true JPH0297691A (en) | 1990-04-10 |
Family
ID=17157578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24704488A Pending JPH0297691A (en) | 1988-09-30 | 1988-09-30 | Molybdenum electroplating bath and plating method by bath thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0297691A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007029663A1 (en) * | 2005-09-07 | 2007-03-15 | Kyoto University | Method for electrodepositing metal |
-
1988
- 1988-09-30 JP JP24704488A patent/JPH0297691A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007029663A1 (en) * | 2005-09-07 | 2007-03-15 | Kyoto University | Method for electrodepositing metal |
| JP2007070698A (en) * | 2005-09-07 | 2007-03-22 | Kyoto Univ | Method for electrodepositing metal |
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