JPH06207295A - Zr-alloy plating method on ceramic - Google Patents
Zr-alloy plating method on ceramicInfo
- Publication number
- JPH06207295A JPH06207295A JP33941192A JP33941192A JPH06207295A JP H06207295 A JPH06207295 A JP H06207295A JP 33941192 A JP33941192 A JP 33941192A JP 33941192 A JP33941192 A JP 33941192A JP H06207295 A JPH06207295 A JP H06207295A
- Authority
- JP
- Japan
- Prior art keywords
- ceramic
- plating
- metal
- alloy
- electrode
- 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.)
- Granted
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 30
- 238000007747 plating Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims description 11
- 229910001093 Zr alloy Inorganic materials 0.000 title abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- 238000005868 electrolysis reaction Methods 0.000 abstract 2
- 239000000203 mixture Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005219 brazing Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910013618 LiCl—KCl Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical group [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
【発明の詳細な説明】
［０００１］
［産業上の利用分野］本発明は、電気めっき法によりセ
ラミック上にＺｒまたはＺｒ合金めっきする方法に関す
る。
［０００２］
［従来の技術とその問題点］セラミック上をＺｒまたは
Ｚｒ合金で被覆した複合材料は、優れた耐食性と耐熱性
を有し、また熱中性子吸収断面積が小さいことから、そ
の開発が期待されている。従来一般に、セラミックをＺ
ｒまたはＺｒ合金で被覆する方法としては、真空蒸着
法、ＣＶＤ法、ろう付け法によるものがある。真空蒸着
法、ＣＶＤ法は、Ｚｒの沸点が高いために装置構成が複
雑化し、大量生産規模で実用化されたものはない。ろう
付け法もまた、Ｚｒの沸点が高いために装置構成が複雑
化し、密着性、平滑性、均一性に乏しい。このため比較
的安価に大量生産でき、密着性、平滑性、均一性にすぐ
れた被覆法が要望されていた。
［０００３］
［問題を解決するための手段］この発明は、Ｚｒイオン
を含有したＬｉＣｌ−ＫＣｌ系の溶融塩のめっき浴に
て、金属にセラミックを接触させているセラミック付き
金属電極の金属部にＺｒを電解析出させ、同時にセラミ
ック上にＺｒまたはＺｒ合金めっきさせることにより、
セラミック上ヘＺｒおよびＺｒ合金を被覆できるように
した。これらの被膜の成長は、金属とセラミックの接触
部分からセラミック上ヘ二次元的に成長していく。セラ
ミック付き金属電極の金属部にＺｒ，Ｔｉ，Ｆｅ，Ｎｉ
を用いた場合、セラミック上にＺｒ被膜が形成され、金
属部にＡｌを用いた場合、セラミック上にＺｒ−Ａｌ合
金被膜が形成される。このＺｒ−Ａｌ合金の組成はめっ
き条件によって変化する。めっき条件としては、めっき
浴のＺｒイオン濃度を１．５×１０−２ｍｏｌ／ｄｍ２
にし、Ｚｒイオン濃度のバランスを保つために陽極に金
属Ｚｒを用い、Ｚｒの陽極溶解を行った。また浴温を５
００〜５６０℃にして、直流電流またパルス電流により
電流密度０．４〜１．５Ａ／ｄｍ２でめっきする。さら
に均一なめっきを行うために浴を撹拌することが望まし
い。浴温を５００〜５６０℃の範囲にするのは、Ｚｒイ
オンが４５０〜５６０℃の範囲において、２価、４価の
原子価を取り、温度によってその存在比が変化し、４５
０℃付近では４価，５５０℃付近では２価で安定に存在
するという性質を持つため、４５０℃ではＺｒの析出が
Ｚｒ（ＩＶ）→Ｚｒ（ＩＩ）→Ｚｒのような２段階反応
となり、安定してＺｒを析出できない。つまり安定して
Ｚｒを析出させるためには低原子価のイオンが必要とな
るため、５００℃以下でのめっきは困難である。またＺ
ｒＣｌ４は４５０℃付近において、かなり揮発性が高
く、浴中のＺｒイオン濃度が減少するために、均一なめ
っきが得られない。逆に５６０℃より高くなると、浴の
分解が起こるという欠点を持つ。次に電流密度に関して
は、電流密度が０．４Ａ／ｄｍ２より低いと、金属部へ
のＺｒの析出は起こるがセラミック上へのめっきが困難
となる、また１．５Ａ／ｄｍ２より高いと、密着性の良
い均一なめっきは得られず、粉末状または樹枝状に析出
する。
［０００４］
［実施例］
［０００５］実施例１
Ａｌ２Ｏ３を主成分とするセラミックの板状試験片（２
ｍｍ厚×２０ｍｍ長×１０ｍｍ巾）をめっき母材に用
い、表面をアセトン脱脂し、１０％硝酸で酸洗および水
洗処理し、乾燥させた後、陰極となる電極（素材Ｚｒ，
Ｔｉ，Ｆｅ，Ｎｉ２ｍｍ厚×９ｍｍ長×１０ｍｍ巾）と
接するように取り付けた。次にこのセラミック付き電極
を乾燥させた後、乾燥Ａｒ雰囲気にした溶融塩めっき浴
を使用して下記の条件で電気めっきを施した。その結
果、どの素材の電極においても、めっき表面が灰色を呈
し、均一で密着性の良いＺｒめっきが形成された。
［０００６］実施例２
実施例１と同じセラミックの板状試験片に、陰極となる
電極（素材Ａｌ ２ｍｍ厚×９ｍｍ長×１０ｍｍ巾）と
接するように取り付け、実施例１と同様にして、電気め
っきを施した。その結果、めっき表面が銀白色を呈し、
均一で密着性の良いＺｒ−Ａｌ合金めっきが形成され
た。組成分析をした結果、被膜の組成はＺｒ４５．１ａ
ｔ％，Ａｌ５４．９ａｔ％であった。
［０００７］
［めっき条件］
浴組成： ＬｉＣｌ：ＫＣｌ＝５８．５ｍｏｌ％：４
１．５ｍｏｌ％
浴 温： ５４０℃
添加物： Ｚｒイオン １．５×１０−２ｍｏｌ／ｄ
ｍ２
電流密度：０．４〜０．９Ａ／ｄｍ２
陽 極： Ｚｒ
時 間： ３時間Description: [0001] The present invention relates to a method for plating Zr or Zr alloy on a ceramic by an electroplating method. [0002] [Prior art and its problems] A composite material in which a ceramic is coated with Zr or a Zr alloy has excellent corrosion resistance and heat resistance, and has a small thermal neutron absorption cross section. Is expected. Conventionally, Z
As a method of coating with r or Zr alloy, there are a vacuum deposition method, a CVD method, and a brazing method. The vacuum vapor deposition method and the CVD method have complicated apparatus configurations because of the high boiling point of Zr, and none have been put to practical use on a mass production scale. The brazing method also has a complicated apparatus configuration due to the high boiling point of Zr and is poor in adhesion, smoothness and uniformity. Therefore, there has been a demand for a coating method which can be mass-produced relatively inexpensively and has excellent adhesion, smoothness, and uniformity. [0003] [Means for Solving the Problem] The present invention relates to a metal part of a metal electrode with a ceramic in which a ceramic is brought into contact with a metal in a LiCl-KCl-based molten salt plating bath containing Zr ions. By electrolytically depositing Zr and simultaneously plating Zr or a Zr alloy on the ceramic,
It was made possible to coat Zr and Zr alloys on ceramics. The growth of these coatings is two-dimensionally grown on the ceramic from the metal / ceramic contact area. Zr, Ti, Fe, Ni on the metal part of the metal electrode with ceramic
When the alloy is used, a Zr coating film is formed on the ceramic, and when Al is used for the metal part, a Zr—Al alloy coating film is formed on the ceramic. The composition of this Zr-Al alloy changes depending on the plating conditions. As the plating conditions, the Zr ion concentration of the plating bath is 1.5 × 10 −2 mol / dm 2
Then, in order to keep the balance of Zr ion concentration, metal Zr was used for the anode, and anodic dissolution of Zr was performed. The bath temperature is 5
The temperature is set to 00 to 560 ° C., and plating is performed at a current density of 0.4 to 1.5 A / dm 2 with a direct current or a pulse current. It is desirable to stir the bath to achieve more uniform plating. The bath temperature is set in the range of 500 to 560 ° C. The Zr ion takes a divalent or tetravalent valence in the range of 450 to 560 ° C., and its abundance ratio changes depending on the temperature.
Since it has a property of being tetravalent near 0 ° C. and stable at around 550 ° C. and divalent, at 450 ° C., precipitation of Zr becomes a two-step reaction such as Zr (IV) → Zr (II) → Zr, Zr cannot be stably deposited. That is, low valence ions are required to stably deposit Zr, and thus plating at 500 ° C. or lower is difficult. Also Z
At around 450 ° C., rCl 4 is considerably volatile and the concentration of Zr ions in the bath decreases, so that uniform plating cannot be obtained. On the contrary, when the temperature is higher than 560 ° C, it has a drawback that decomposition of the bath occurs. Next, regarding the current density, if the current density is lower than 0.4 A / dm 2 , Zr will be deposited on the metal part, but plating on the ceramic will be difficult, and if it is higher than 1.5 A / dm 2. However, uniform plating with good adhesiveness cannot be obtained, and it deposits in powder or dendritic form. [0004] [Example] [0005] Example 1 A ceramic plate-shaped test piece (2 containing Al 2 O 3 as a main component).
(mm thickness × 20 mm length × 10 mm width) is used as a plating base material, the surface is degreased with acetone, pickled with 10% nitric acid and washed with water, and dried, and then an electrode (material Zr,
Ti, Fe, and Ni were attached so as to be in contact with 2 mm thick × 9 mm long × 10 mm width). Next, this electrode with ceramics was dried and then electroplated under the following conditions using a molten salt plating bath in a dry Ar atmosphere. As a result, the surface of the plating was gray in any of the electrodes, and uniform Zr plating with good adhesion was formed. [0006] Example 2 The same ceramic plate-shaped test piece as in Example 1 was attached so as to be in contact with an electrode (material Al 2 mm thickness x 9 mm length x 10 mm width) serving as a cathode, and the same procedure as in Example 1 was performed. It was plated. As a result, the plating surface is silver white,
A uniform Zr-Al alloy plating with good adhesion was formed. As a result of composition analysis, the composition of the film was Zr45.1a.
It was t% and Al54.9at%. [0007] [Plating conditions] Bath composition: LiCl: KCl = 58.5 mol%: 4
1.5 mol% bath temperature: 540 ° C. additive: Zr ion 1.5 × 10 −2 mol / d
m 2 current density: 0.4 to 0.9 A / dm 2 positive electrode: Zr time: 3 hours
Claims (1)
て、金属にセラミックを接触させた電極を用い、金属部
にＺｒを電解析出させ、同時にセラミック上にＺｒめっ
きすることを特徴とするセラミック上ヘのＺｒめっき方
法。 ［請求項２］ Ｚｒイオンを含んだ溶融塩のめっき浴に
て、金属にセラミックを接触させた電極を用い、Ａｌ部
分にＺｒを電解析出させ、同時にセラミック上にＺｒ−
Ａｌ合金めっきすることを特徴とするセラミック上への
Ｚｒ−Ａｌ合金めっき方法。Claims: [Claim 1] In a plating bath of a molten salt containing Zr ions, Zr is electrolytically deposited on the metal portion by using an electrode in which the metal is in contact with the ceramic, and at the same time Zr is deposited on the ceramic. A method for plating Zr on a ceramic, which comprises plating. [Claim 2] In a plating bath of a molten salt containing Zr ions, Zr is electrolytically deposited on the Al portion by using an electrode in which the metal is in contact with the ceramic, and at the same time Zr-on the ceramic.
A Zr-Al alloy plating method on a ceramic, characterized by performing Al alloy plating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4339411A JP2829304B2 (en) | 1992-11-05 | 1992-11-05 | Zr alloy plating method on ceramic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4339411A JP2829304B2 (en) | 1992-11-05 | 1992-11-05 | Zr alloy plating method on ceramic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06207295A true JPH06207295A (en) | 1994-07-26 |
| JP2829304B2 JP2829304B2 (en) | 1998-11-25 |
Family
ID=18327223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4339411A Expired - Fee Related JP2829304B2 (en) | 1992-11-05 | 1992-11-05 | Zr alloy plating method on ceramic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2829304B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003511564A (en) * | 1999-10-11 | 2003-03-25 | サントル・ナショナル・ドゥ・ラ・ルシェルシュ・シャンティフィク | Electrochemical metallizing method for insulating substrate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0361304A (en) * | 1989-07-27 | 1991-03-18 | Nkk Corp | Composite material manufacturing method |
-
1992
- 1992-11-05 JP JP4339411A patent/JP2829304B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0361304A (en) * | 1989-07-27 | 1991-03-18 | Nkk Corp | Composite material manufacturing method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003511564A (en) * | 1999-10-11 | 2003-03-25 | サントル・ナショナル・ドゥ・ラ・ルシェルシュ・シャンティフィク | Electrochemical metallizing method for insulating substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2829304B2 (en) | 1998-11-25 |
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