JPH0322470B2 - - Google Patents
Info
- Publication number
- JPH0322470B2 JPH0322470B2 JP10184588A JP10184588A JPH0322470B2 JP H0322470 B2 JPH0322470 B2 JP H0322470B2 JP 10184588 A JP10184588 A JP 10184588A JP 10184588 A JP10184588 A JP 10184588A JP H0322470 B2 JPH0322470 B2 JP H0322470B2
- Authority
- JP
- Japan
- Prior art keywords
- plating
- plating solution
- iron
- solution
- 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.)
- Expired
Links
- 238000007747 plating Methods 0.000 claims description 76
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 150000002506 iron compounds Chemical class 0.000 claims description 10
- 150000002038 dysprosium compounds Chemical class 0.000 claims description 9
- 239000003880 polar aprotic solvent Substances 0.000 claims description 9
- 229910001279 Dy alloy Inorganic materials 0.000 claims description 6
- RDTHZIGZLQSTAG-UHFFFAOYSA-N dysprosium iron Chemical compound [Fe].[Dy] RDTHZIGZLQSTAG-UHFFFAOYSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 description 57
- 239000010408 film Substances 0.000 description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 229910021645 metal ion Inorganic materials 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 150000002910 rare earth metals Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 208000005156 Dehydration Diseases 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MAYVZUQEFSJDHA-UHFFFAOYSA-N 1,5-bis(methylsulfanyl)naphthalene Chemical compound C1=CC=C2C(SC)=CC=CC2=C1SC MAYVZUQEFSJDHA-UHFFFAOYSA-N 0.000 description 2
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical compound C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- ZEYKLMDPUOVUCR-UHFFFAOYSA-N 2-chloro-5-(trifluoromethyl)benzenesulfonyl chloride Chemical compound FC(F)(F)C1=CC=C(Cl)C(S(Cl)(=O)=O)=C1 ZEYKLMDPUOVUCR-UHFFFAOYSA-N 0.000 description 1
- YNVZDODIHZTHOZ-UHFFFAOYSA-K 2-hydroxypropanoate;iron(3+) Chemical compound [Fe+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O YNVZDODIHZTHOZ-UHFFFAOYSA-K 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- PLKYGPRDCKGEJH-UHFFFAOYSA-N azane;2-hydroxypropane-1,2,3-tricarboxylic acid;iron Chemical compound N.[Fe].OC(=O)CC(O)(C(O)=O)CC(O)=O PLKYGPRDCKGEJH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229910003440 dysprosium oxide Inorganic materials 0.000 description 1
- KACTUDRDWYCYMT-UHFFFAOYSA-H dysprosium(3+);oxalate Chemical compound [Dy+3].[Dy+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O KACTUDRDWYCYMT-UHFFFAOYSA-H 0.000 description 1
- QGXMZGYYAAPYRV-UHFFFAOYSA-H dysprosium(3+);tricarbonate Chemical compound [Dy+3].[Dy+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QGXMZGYYAAPYRV-UHFFFAOYSA-H 0.000 description 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000001017 electron-beam sputter deposition Methods 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- -1 etc. can be used Chemical compound 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000002909 rare earth metal compounds Chemical class 0.000 description 1
- 229910000982 rare earth metal group alloy Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910000687 transition metal group alloy Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- FWQVINSGEXZQHB-UHFFFAOYSA-K trifluorodysprosium Chemical compound F[Dy](F)F FWQVINSGEXZQHB-UHFFFAOYSA-K 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、鉄−ジスプロシウム合金めつき液に
関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an iron-dysprosium alloy plating solution.
従来の技術及びその問題点
希土類金属は、各種の特有な性質を示すもので
あり、例えば、希土類金属と遷移金属との合金
は、光磁気メモリー材料として優れた特性を有す
ることが知られている。現在この種の磁気薄膜
は、電子ビーム蒸着法やスパツタリング法により
製造されているが、生産性が低く、装置が高価で
あるために、製造コストが高いという欠点があ
る。Prior art and its problems Rare earth metals exhibit various unique properties. For example, alloys of rare earth metals and transition metals are known to have excellent properties as magneto-optical memory materials. . Currently, this type of magnetic thin film is manufactured by electron beam evaporation or sputtering, but it has the drawbacks of low productivity and high manufacturing costs due to expensive equipment.
電析法は、金属薄膜を安価に得る方法の一つと
してよく知られているが、希土類金属は酸化還元
電位がかなり卑であるために、水溶液からは、
H+の放電が優先的に生じて、希土類金属を含む
めつき皮膜を得ることはできない、電解液として
非水溶液を用いる場合には、希土類金属が電析す
る可能性はあるが、工業的に実用化できる希土類
金属合金めつき液は得られていない。 The electrodeposition method is well known as one of the methods for obtaining thin metal films at low cost, but since rare earth metals have a fairly base redox potential, they cannot be easily deposited from an aqueous solution.
H + discharge occurs preferentially, making it impossible to obtain a plating film containing rare earth metals.If a non-aqueous solution is used as the electrolyte, there is a possibility that rare earth metals will be deposited, but this is not possible industrially. A practical rare earth metal alloy plating solution has not yet been obtained.
問題点を解決するための手段
本発明者は、上記した如き現状に鑑みて、工業
的規模において実用化し得る希土類金属合金めつ
き液を得るべく鋭意研究を重ねてきた。その結
果、希土類金属の化合物としてジスプロシウム化
合物を用い、これを鉄化合物と共に、極性非プロ
トン性溶媒に溶解してなるめつき液からは、実用
上充分な電流効率で、素地上に密着性よく良好な
外観のFe−Dy合金皮膜を形成することができ、
しかもめつき液中の組成比や電流密度を調節する
ことによつて、析出皮膜の合金組成を広い範囲で
変えることが可能であることを見出し、ここに本
発明を完成するに至つた。Means for Solving the Problems In view of the current situation as described above, the present inventor has conducted extensive research in order to obtain a rare earth metal alloy plating solution that can be put to practical use on an industrial scale. As a result, a plating solution made by using a dysprosium compound as a rare earth metal compound and dissolving it together with an iron compound in a polar aprotic solvent has a practically sufficient current efficiency and good adhesion to the substrate. It is possible to form a Fe-Dy alloy film with a beautiful appearance.
Furthermore, the present inventors have discovered that by adjusting the composition ratio and current density in the plating solution, it is possible to change the alloy composition of the deposited film over a wide range, and have now completed the present invention.
即ち、本発明は、鉄化合物及びジスプロシウム
化合物を、極性非プロトン性溶媒に溶解してなる
鉄−ジスプロシウム合金めつき液に係る。 That is, the present invention relates to an iron-dysprosium alloy plating solution formed by dissolving an iron compound and a dysprosium compound in a polar aprotic solvent.
本発明めつき液で用いるジスプロシウム化合物
は、特に限定はなく、具体例として、塩化ジスプ
ロシウム、硝酸ジスプロシウム、酸化ジスプロシ
ウム、フツ化ジスプロシウム、炭酸ジスプロシウ
ム、シユウ酸ジスプロシウム等を挙げることがで
き、これらのうちで、塩化ジスプロシウム、硝酸
ジスプロシウム等が好ましく用いられる。 The dysprosium compound used in the plating solution of the present invention is not particularly limited, and specific examples include dysprosium chloride, dysprosium nitrate, dysprosium oxide, dysprosium fluoride, dysprosium carbonate, and dysprosium oxalate. , dysprosium chloride, dysprosium nitrate, and the like are preferably used.
鉄化合物としては、二価あるいは三価の鉄化合
物を使用すればよく、具体例としては、硫酸第一
鉄アンモニウム、臭化鉄（）、塩化鉄（）、乳
酸鉄（）、しゆう酸鉄（）、リン酸鉄（）、
硫酸第一鉄、硫化鉄（）、くえん酸鉄（）ア
ンモニウム、しゆう酸第二鉄アンモニウム、硫酸
鉄（）アンモニウム、臭化鉄（）、塩化第二
鉄、くえん酸鉄（）、硝酸鉄（）、リン酸鉄
（）、硫酸第二鉄等を挙げることができる。これ
らのうちで、塩化鉄（）、硫酸第一鉄、硫酸第
一鉄アンモニウム等が好ましく用いられる。 As the iron compound, divalent or trivalent iron compounds may be used, and specific examples include ferrous ammonium sulfate, iron bromide (), iron chloride (), iron lactate (), and iron oxalate. (), iron phosphate (),
Ferrous sulfate, iron sulfide (), ammonium iron citrate, ferric ammonium oxalate, ammonium iron sulfate (), iron bromide (), ferric chloride, iron citrate (), iron nitrate ( ), iron phosphate ( ), ferric sulfate, and the like. Among these, iron chloride (), ferrous sulfate, ferrous ammonium sulfate, etc. are preferably used.
本発明めつき液では、溶媒としては、極性非プ
ロトン性溶媒を用いる。極性非プロトン性溶媒
は、誘電率が高く、ジスプロシウム化合物及び鉄
化合物を均一に溶解できるものであり、しかも、
電析時に、プロトンや水素結合の関与する反応が
生じ難く、かなり卑な電位においても安定であ
る。そして、この極性非プロトン性溶媒の溶液か
らは、実用上充分な効率で良好な外観のFe−Dy
合金めつき皮膜を形成することができる。極性非
プロトン性溶媒としては、例えばジメチルホルム
アミド、ジメチルスルホキシド、プロピレンカー
ボネート、アセトニトリル等を用いることがで
き、ジメチルホルムアミドを特に好ましく用いる
ことができる。 In the plating solution of the present invention, a polar aprotic solvent is used as the solvent. The polar aprotic solvent has a high dielectric constant and can uniformly dissolve dysprosium compounds and iron compounds, and
During electrodeposition, reactions involving protons and hydrogen bonds are unlikely to occur, and it is stable even at fairly base potentials. From this polar aprotic solvent solution, Fe-Dy with good appearance and sufficient efficiency for practical use was obtained.
An alloy plating film can be formed. As the polar aprotic solvent, for example, dimethylformamide, dimethylsulfoxide, propylene carbonate, acetonitrile, etc. can be used, and dimethylformamide can be particularly preferably used.
本発明めつき液では、ジスプロシウム化合物及
び／又は鉄化合物として、結晶水を有する化合物
を用いることができ、これを極性非プロトン性溶
媒に溶解したものをそのままめつき液として使用
してもよいが、水素の発生を防止して、電流効率
を向上させるためには、ジスプロシウム化合物及
び鉄化合物として無水物を用いるか、あるいはめ
つき処理前に、予めめつき液を脱水処理すること
が好ましい。脱水処理方法は、特に限定はなく、
例えば、めつき液中にモレキユラーシーブ等の吸
着剤を添加して、吸着脱水する方法等を採用でき
る。 In the plating solution of the present invention, a compound having water of crystallization can be used as the dysprosium compound and/or iron compound, and a solution of this in a polar aprotic solvent may be used as it is as the plating solution. In order to prevent hydrogen generation and improve current efficiency, it is preferable to use anhydrides as the dysprosium compound and iron compound, or to dehydrate the plating solution in advance before plating. The dehydration treatment method is not particularly limited;
For example, a method can be adopted in which an adsorbent such as a molecular sieve is added to the plating solution to perform adsorption and dehydration.
本発明めつき液では、ジスプロシウム化合物及
び鉄化合物の添加量を、両者の合計量として0.01
〜0.6モル／ｄm3程度とする場合に、良好な合金
皮膜を形成することができ、特に0.05〜0.3モ
ル／ｄm3程度の場合に効率よくめつき皮膜を形成
することができる。 In the plating solution of the present invention, the amount of dysprosium compound and iron compound added is 0.01 as the total amount of both.
When the amount is about 0.6 mol/dm 3 , a good alloy film can be formed, and particularly when the amount is about 0.05 to 0.3 mol/dm 3 , a plated film can be formed efficiently.
めつき液中のジスプロシウム化合物と鉄化合物
の比率は、広い範囲で変更可能であり、Dy：Fe
（モル比）＝１：９〜９：１程度の範囲において、
合金めつき皮膜を形成できるが、特にDy：Fe（モ
ル比）＝２：８〜６：４程度の場合に、密着性、
外観ともに良好なめつき皮膜を得ることができ
る。また、Dy：Fe（モル比）＝２：８〜４：６程
度の場合に特に効率よくめつき皮膜を形成するこ
とができる。 The ratio of dysprosium compounds to iron compounds in the plating solution can be varied within a wide range, and Dy:Fe
(molar ratio) in the range of about 1:9 to 9:1,
An alloy plating film can be formed, but the adhesion and
A plated film with good appearance can be obtained. Furthermore, a plating film can be formed particularly efficiently when Dy:Fe (molar ratio) is about 2:8 to 4:6.
本発明めつき液は、液温０℃〜60℃程度で使用
することができ、15〜30℃程度で使用することが
好ましい。めつき時の陰極電流密度（Dk）は、
0.5〜20mA／cm2程度、好ましくは２〜10mA／cm2
程度とすればよい。特にDy：Fe（モル比）＝２：
８〜６：４程度のめつき液を用い、陰極電流密度
２〜8mA／cm2程度でめつきを行なう場合に、平
滑で光沢外観を有し、しかも密着性の優れためつ
き皮膜を得ることができる。 The plating solution of the present invention can be used at a liquid temperature of about 0°C to 60°C, preferably at a temperature of about 15 to 30°C. The cathode current density (Dk) during plating is
About 0.5-20mA/ cm2 , preferably 2-10mA/ cm2
It is sufficient to set the degree. Especially Dy:Fe (molar ratio) = 2:
To obtain a plating film with a smooth and glossy appearance and excellent adhesion when plating is performed using a plating solution with a ratio of about 8 to 6:4 and a cathode current density of about 2 to 8 mA/cm2. Can be done.
尚、めつき時には、常法に従つて、スターラー
やバブリングにより、めつき液の撹拌を行なうこ
とが好ましく、例えば溶存酵素の除去とめつき液
の撹拌を兼ねて、N2ガスによるバブリングを行
ないながらめつきを行なえばよい。 During plating, it is preferable to stir the plating solution using a stirrer or bubbling according to a conventional method. For example, to remove dissolved enzymes and stir the plating solution, bubbling with N 2 gas is performed. All you have to do is plating.
本発明めつき液では、被めつき物は、特に限定
はなく、銅、鉄、ニツケル、炭素等の通常の導電
性物質であればいずれもめつき可能である。 In the plating solution of the present invention, there is no particular limitation on the material to be plated, and any ordinary conductive material such as copper, iron, nickel, carbon, etc. can be plated.
本発明めつき液から形成されるめつき皮膜は、
Ｘ線回析によつて、Dy、Fe等の存在を示すピー
クを生じない。従つて析出物は、無定形又は非晶
質の物質であると推測される。 The plating film formed from the plating solution of the present invention is
X-ray diffraction shows no peaks indicating the presence of Dy, Fe, etc. Therefore, it is presumed that the precipitate is an amorphous or amorphous substance.
発明の効果
本発明のめつき液によれば、従来得られなかつ
た鉄−ジスプロシウム合金めつき皮膜を実用上充
分な電流効率で得ることができ、しかもめつき液
中の組成比や電流密度を調節することによつて析
出皮膜の合金組成を広い範囲で変えることができ
る。そして、形成されるめつき皮膜は、良好な外
観を有し、素地との密着性に優れたものとなる。Effects of the Invention According to the plating solution of the present invention, it is possible to obtain an iron-dysprosium alloy plating film, which could not be obtained conventionally, with practically sufficient current efficiency, and moreover, the composition ratio and current density in the plating solution can be changed. By adjustment, the alloy composition of the deposited film can be varied within a wide range. The formed plating film has a good appearance and has excellent adhesion to the substrate.
実施例
以下、実施例を示して本発明を更に詳細に説明
する。Examples Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例 １
めつき液の準備
ジメチルホルムアミドにモレキユラーシーブ
３Ａを加えて、４日間脱水処理した後、BaO
を加えて時々振り混ぜながら２日間放置した。
この上澄液をArガス雰囲気中10〜15mmHgの
減圧下で、約50℃で蒸留し、留分の中央部を集
めた。Example 1 Preparation of plating solution Molecular sieve 3A was added to dimethylformamide, dehydrated for 4 days, and then BaO
was added and left to stand for 2 days with occasional shaking.
This supernatant liquid was distilled at about 50° C. under a reduced pressure of 10 to 15 mmHg in an Ar gas atmosphere, and the central portion of the fraction was collected.
次いで得られたジメチルホルムアミドを用い
て、0.6モル／ｄm3DyCl3・6H2Oのジメチルホ
ルムアミド溶液を作成した。これにモレキユラ
ーシーブ３Ａを加えて、24時間脱水処理した
後、モレキユラーシーブ３Ａを除去して、0.6
モル／ｄm3DyCl3のジメチルホルムアミド溶液
を得た。また、同様に、0.6モル／ｄm3FeCl2・
4H2Oのジメチルホルムアミド溶液を作成し、
これをモレキユラーシーブ３Ａで脱水して、
0.6モル／ｄm3FeCl2のジメチルホルムアミド溶
液を得た。得られたDyCl3溶液及びFeCl2溶液
には、いずれも250〜500ppm程度の水が残存し
ていた。 Next, a dimethylformamide solution of 0.6 mol/dm 3 DyCl 3 .6H 2 O was prepared using the obtained dimethylformamide. Molecular sieve 3A was added to this, and after dehydration treatment for 24 hours, molecular sieve 3A was removed and 0.6
A solution of mol/dm 3 DyCl 3 in dimethylformamide was obtained. Similarly, 0.6 mol/dm 3 FeCl 2 .
Make a dimethylformamide solution of 4H2O ,
Dehydrate this with molecular sieve 3A,
A dimethylformamide solution of 0.6 mol/dm 3 FeCl 2 was obtained. Approximately 250 to 500 ppm of water remained in both the obtained DyCl 3 solution and FeCl 2 solution.
上記した方法で得られたDyCl3溶液及び
FeCl2溶液を用いて、以下の方法でめつき液を
調製し、めつき試験を行なつた。 DyCl 3 solution obtained by the above method and
A plating solution was prepared using the FeCl 2 solution in the following manner, and a plating test was conducted.
めつき試験
上記したDyCl3溶液及びFeCl2溶液を用いて、
Dy／（Dy＋Fe）＝20モル％、40モル％、60モ
ル％及び80モル％の各割合で、全金属イオン量
0.1モル／ｄm3のめつき液を調製した。被めつ
き物としては、10×25×0.2mmの銅板を用いた。
該銅板は、前処理として、あらかじめ2000番エ
メリーペーパーで研磨し、0.3μmアルミナでバ
フ研磨した後、水洗し、次いでアセトン中で20
分間超音波洗浄し、更に、蒸留水中で10分間超
音波洗浄を行なつた後、10％硫酸で酸洗した。 Plating test Using the above DyCl 3 solution and FeCl 2 solution,
Total metal ion amount at each ratio of Dy/(Dy + Fe) = 20 mol%, 40 mol%, 60 mol%, and 80 mol%
A plating solution of 0.1 mol/dm 3 was prepared. A 10 x 25 x 0.2 mm copper plate was used as the covering material.
As a pretreatment, the copper plate was polished with No. 2000 emery paper, buffed with 0.3 μm alumina, washed with water, and then polished in acetone for 20 minutes.
After ultrasonic cleaning for 1 minute, further ultrasonic cleaning in distilled water for 10 minutes, and pickling with 10% sulfuric acid.
上記した各めつき液について、第１図に示す
めつき装置を用いて、めつき試験を行なつた。
該めつき装置では、前処理後の銅板を陰極１と
し、20×30×１mmのグラシーカーボン板を陽極
２として、ガス入口３からN2ガスを導入して
バブリングによりめつき液を撹拌しつつ、めつ
きを行なつた。バブリング後のN2ガスは、ガ
ス排出口４から排出した。 A plating test was conducted on each of the above-mentioned plating solutions using the plating apparatus shown in FIG.
In this plating device, a pretreated copper plate is used as a cathode 1, a 20 x 30 x 1 mm glassy carbon plate is used as an anode 2, and N2 gas is introduced from a gas inlet 3 to stir the plating solution by bubbling. Then, I went to meet him. The N 2 gas after bubbling was exhausted from the gas outlet 4.
めつき時の液晶は、25℃として、0.5mA／
cm2、2mA／cm2、4mA／cm2、6mA／cm2、8mA／
cm2、10mA／cm2及び20mA／cm2の各電流密度で
通電量10クローンまでめつきを行なつた。 The liquid crystal during plating is 0.5mA/at 25℃.
cm 2 , 2mA/cm 2 , 4mA/cm 2 , 6mA/cm 2 , 8mA/cm 2
Plating was carried out at current densities of 10 mA/cm 2 , 10 mA/cm 2 and 20 mA/cm 2 up to 10 clones.
又、得られためつき皮膜の表面状態は光学顕
微鏡で観察した。電析後試料をジメチルホルム
アミドで洗浄し乾燥後、塩酸中にめつき皮膜を
溶解して、原子吸光分析法により、めつき皮膜
中のDy量及びFe量を測定した。 In addition, the surface condition of the obtained flecked film was observed using an optical microscope. After the electrodeposition sample was washed with dimethylformamide and dried, the plating film was dissolved in hydrochloric acid, and the amounts of Dy and Fe in the plating film were measured by atomic absorption spectrometry.
めつき試験の結果、Dy／（Dy＋Fe）＝20〜60
モル％のめつき液を用いた場合には、陰極電流密
度（Dk）＝２〜8mA／cm2の範囲内で、平滑で光
沢を有し、密着性の良好なめつき皮膜が得られた
が、0.5mA／cm2では、密着性の悪い白色外観のめ
つき皮膜が形成された。又、Dk＝10〜20mA／
cm2では、浴電圧が高くなり、密着性の悪い白色外
観のめつき皮膜が形成された。また、Dy／（Dy
＋Fe）＝80モル％のめつき液では、Dk＝0.5〜
20mA／cm2のすべての範囲で、浴電圧が高くな
り、密着性の悪い白色外観のめつき皮膜が形成さ
れた。 Result of plating test, Dy/(Dy+Fe)=20~60
When a mol% plating solution was used, a smooth, glossy, and well-adhered plating film was obtained within the range of cathode current density (Dk) = 2 to 8 mA/ cm2 . , 0.5 mA/cm 2 , a white-appearing plating film with poor adhesion was formed. Also, Dk=10~20mA/
cm 2 , the bath voltage was high and a white-appearing plating film with poor adhesion was formed. Also, Dy/(Dy
+Fe) = 80 mol% plating solution, Dk = 0.5 ~
In the entire range of 20 mA/cm 2 , the bath voltage increased and a white-appearing plating film with poor adhesion was formed.
各めつき液の電流密度と電流効率との関係を第
２図に、電流密度と析出物中のDy量との関係を
第３図に示す。各図において、〇はDy／（Dy＋
Fe）＝20モル％のめつき液、●はDy／（Dy＋Fe）
＝40モル％にめつき液、△はDy／（Dy＋Fe）＝
60モル％めつき液、▲はDy／（Dy＋Fe）＝80モ
ル％のめつき液についての結果を示す。第２図か
ら、Dy／（Dy＋Fe）＝20〜40モル％でDk＝４〜
6mA／cm2の場合に、最も電流効率がよくなるこ
とが判る。また第３図から、いずれのめつき液に
おいてもDkの増加に伴つて、析出物中のDy量が
増加する傾向にあり、Dk＝４〜6mA／cm2程度
で、めつき液中のDy割合と析出物中のDy割合と
が、ほぼ同程度となることが判る。 FIG. 2 shows the relationship between the current density and current efficiency of each plating solution, and FIG. 3 shows the relationship between the current density and the amount of Dy in the precipitate. In each figure, 〇 is Dy/(Dy+
Fe) = 20 mol% plating solution, ● is Dy/(Dy+Fe)
= 40 mol% plating solution, △ is Dy/(Dy + Fe) =
60 mol% plating solution, ▲ shows the results for Dy/(Dy + Fe) = 80 mol% plating solution. From Figure 2, Dy/(Dy+Fe) = 20 to 40 mol% and Dk = 4 to
It can be seen that the current efficiency is the best at 6 mA/cm 2 . Furthermore, from Fig. 3, the amount of Dy in the precipitate tends to increase as Dk increases in any plating solution. It can be seen that the proportion and the proportion of Dy in the precipitate are approximately the same.
実施例 ２
実施例１で調製したDyCl3溶液とFeCl2溶液を
用い、めつき液中のDy／（Dy＋Fe）を36モル％
とし、全金属イオン濃度を0.01〜0.6モル／ｄm3
の間で変化させてめつき液を調製し、実施例１と
同様の方法でめつき試験を行なつた。めつき液の
液温は25℃とし、電流密度5mA／cm2、通電量10
クローンとした。Example 2 Using the DyCl 3 solution and FeCl 2 solution prepared in Example 1, Dy/(Dy+Fe) in the plating solution was 36 mol%.
and the total metal ion concentration is 0.01 to 0.6 mol/dm 3
A plating solution was prepared by varying the concentration between 1 and 2, and a plating test was conducted in the same manner as in Example 1. The temperature of the plating solution was 25℃, the current density was 5mA/ cm2 , and the amount of current was 10.
It was cloned.
第４図にめつき液中の全金属イオン濃度と電流
効率との関係を、第５図にめつき液中の全金属イ
オン濃度と析出物中のDy量との関係を示す。第
４図から、全金属イオン濃度が0.1モル／ｄm3程
度のめつき液からは60％程度の電流効率でめつき
皮膜が析出し、0.1モル／ｄm3の場合をピークと
して、それより全金属イオン濃度が増加した場
合、減少した場合ともに、それに伴つて、電流効
率が低下することが判る。また、第５図から、め
つき液中の全金属イオン濃度0.05〜0.2モル／ｄ
m3程度の場合に、めつき液中のDyの割合と析出
物中のDy割合がほぼ同程度となり全金属イオン
濃度がこれを上回る場合、下回る場合ともに析出
物中のDyの割合が減少する傾向にあることがわ
かる。 FIG. 4 shows the relationship between the total metal ion concentration in the plating solution and the current efficiency, and FIG. 5 shows the relationship between the total metal ion concentration in the plating solution and the amount of Dy in the precipitate. From Figure 4, a plating film is deposited with a current efficiency of about 60% from a plating solution with a total metal ion concentration of about 0.1 mol/dm 3 , with a peak at 0.1 mol/dm 3 , and a plating film with a total metal ion concentration of about 0.1 mol/dm 3 . It can be seen that the current efficiency decreases as the metal ion concentration increases and decreases. Also, from Figure 5, the total metal ion concentration in the plating solution is 0.05 to 0.2 mol/d.
m3 , the percentage of Dy in the plating solution and the percentage of Dy in the precipitate are almost the same, and the percentage of Dy in the precipitate decreases when the total metal ion concentration exceeds or falls below this. It can be seen that there is a trend.
第１図はめつき装置の概略図、第２図は、電流
密度と電流効率との関係のグラフ、第３図は、電
流密度と析出物中のDy量との関係のグラフ、第
４図は、全金属イオン濃度と電流効率との関係の
グラフ、第５図は、全金属イオン濃度と析出物中
のDy量との関係のグラフである。
１……陰極、２……陽極、３……ガス入口、４
……ガス排出口。
Figure 1 is a schematic diagram of the plating device, Figure 2 is a graph of the relationship between current density and current efficiency, Figure 3 is a graph of the relationship between current density and the amount of Dy in the precipitate, and Figure 4 is a graph of the relationship between current density and the amount of Dy in the precipitate. , a graph of the relationship between the total metal ion concentration and the current efficiency, and FIG. 5 is a graph of the relationship between the total metal ion concentration and the amount of Dy in the precipitate. 1...Cathode, 2...Anode, 3...Gas inlet, 4
...Gas exhaust port.
Claims (1)
プロトン性溶媒に溶解してなる鉄−ジスプロシウ
ム合金めつき液。 ２ 極性非プロトン性溶媒がジメチルホルムアミ
ドである請求項１に記載の鉄−ジスプロシウム合
金めつき液。[Claims] 1. An iron-dysprosium alloy plating solution prepared by dissolving an iron compound and a dysprosium compound in a polar aprotic solvent. 2. The iron-dysprosium alloy plating solution according to claim 1, wherein the polar aprotic solvent is dimethylformamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10184588A JPH01272787A (en) | 1988-04-25 | 1988-04-25 | Iron-dysprosium alloy plating solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10184588A JPH01272787A (en) | 1988-04-25 | 1988-04-25 | Iron-dysprosium alloy plating solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01272787A JPH01272787A (en) | 1989-10-31 |
| JPH0322470B2 true JPH0322470B2 (en) | 1991-03-26 |
Family
ID=14311390
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10184588A Granted JPH01272787A (en) | 1988-04-25 | 1988-04-25 | Iron-dysprosium alloy plating solution |
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| Country | Link |
|---|---|
| JP (1) | JPH01272787A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001077418A1 (en) * | 2000-04-07 | 2001-10-18 | Hui Gao | The method for electrodepositing rare-earth and transition metal alloys |
| JP4802008B2 (en) * | 2006-02-16 | 2011-10-26 | ジュズ インターナショナル ピーティーイー エルティーディー | Electroless plating solution and plating method |
| JP4765747B2 (en) * | 2006-04-19 | 2011-09-07 | 日立金属株式会社 | Method for producing R-Fe-B rare earth sintered magnet |
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1988
- 1988-04-25 JP JP10184588A patent/JPH01272787A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01272787A (en) | 1989-10-31 |
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