JP2508520B2 - Electrolyte for Zr and Zr alloy electrolytic polishing - Google Patents
Electrolyte for Zr and Zr alloy electrolytic polishingInfo
- Publication number
- JP2508520B2 JP2508520B2 JP62027694A JP2769487A JP2508520B2 JP 2508520 B2 JP2508520 B2 JP 2508520B2 JP 62027694 A JP62027694 A JP 62027694A JP 2769487 A JP2769487 A JP 2769487A JP 2508520 B2 JP2508520 B2 JP 2508520B2
- Authority
- JP
- Japan
- Prior art keywords
- polished
- fluoride
- polishing
- acid
- electrolytic
- 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 - Lifetime
Links
Landscapes
- ing And Chemical Polishing (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 この発明は、Zr（ジルコニウム）およびZr合金の電解
研摩に使用される電解液に関するものである。TECHNICAL FIELD The present invention relates to an electrolytic solution used for electrolytic polishing of Zr (zirconium) and a Zr alloy.
従来、ZrまたはZr合金からなる種々の部材の表面を電
解研摩で研磨する場合に使用される電解液として、過塩
素酸:10％−酢酸:90％からなる電解液のような過塩素酸
−酢酸系電解液、弗酸:4.3％−硝酸:8.7％−グリセリ
ン:87％からなる電解液のような弗酸−硝酸系電解液
（以上、容量％）、および特公昭32-10561号に記載され
ている、希薄弗酸水溶液または弗化物水溶液に燐酸と水
溶性有機溶媒を配合してなる電解液のような弗酸（弗化
物）−燐酸系電解液が知られている。Conventionally, as an electrolytic solution used when polishing the surface of various members made of Zr or Zr alloy by electrolytic polishing, perchloric acid: 10% -acetic acid: perchloric acid such as 90%- Acetic acid-based electrolytic solution, hydrofluoric acid-4.3% -nitric acid: 8.7% -glycerin: 87% -like hydrofluoric acid-nitric acid-based electrolytic solution (above,% by volume), and Japanese Patent Publication No. 32-10561 There is known a hydrofluoric acid (fluoride) -phosphoric acid-based electrolytic solution such as an electrolytic solution prepared by mixing phosphoric acid and a water-soluble organic solvent in a dilute aqueous solution of hydrofluoric acid or an aqueous solution of fluoride.
しかしながら、上記の過塩素酸−酢酸系の電解液は、
その取扱いに中に爆発を起こす危険性がある上に、研摩
面にピッティングを生じやすいという欠点があり、また
硝酸−弗酸系および弗酸（弗化物）−燐酸系の電解液
は、激しい電解研摩作用のために光沢のある研摩面が得
にくく、またその電解液に被研摩部材を単に浸しただけ
でも腐食反応が進行してしまうため、その被研摩部材の
形状が複雑である場合には、電解研摩終了後、水洗する
までの間に腐食反応が進んでしまうという問題があっ
た。However, the perchloric acid-acetic acid-based electrolyte solution is
In addition to the danger of exploding during handling, there is the drawback that pitting is likely to occur on the polished surface, and nitric acid-fluoric acid-based and hydrofluoric acid (fluoride) -phosphoric-acid-based electrolytes are violent. Due to the electrolytic polishing action, it is difficult to obtain a glossy polished surface, and even if the member to be polished is simply immersed in the electrolytic solution, the corrosion reaction proceeds, so if the shape of the member to be polished is complicated. Had a problem that the corrosion reaction proceeds after the electrolytic polishing and before washing with water.
そこで、本発明者等は、このような状況に鑑みて種々
研究を重ねた結果、 （ａ）適度の濃度、すなわち0.2〜5mol/lの弗化物を含
む水溶液からなる電解液では、ZrおよびZr合金の研摩が
程好く進行して比較的平滑な研摩面が得られること。Therefore, the present inventors have conducted various studies in view of such circumstances, and as a result, (a) Zr and Zr are contained in an electrolytic solution containing an aqueous solution containing fluoride at an appropriate concentration, that is, 0.2 to 5 mol / l. Polishing of the alloy progresses reasonably to obtain a relatively smooth polished surface.
（ｂ）この弗化物だけでは、被研摩部材表面に被膜が形
成されて金属色の表面光沢を有する研摩面が得られない
が、前記弗化物を含む電解液に、グルコン酸および／ま
たはグルコン酸塩を加えると、研摩面の表面光沢が改善
され、ピッティングを生ずることもなく適度な電解研摩
速度が得られること。(B) With this fluoride alone, a film is formed on the surface of the member to be polished and a polished surface having a metallic color surface gloss cannot be obtained, but gluconic acid and / or gluconic acid is added to the electrolyte solution containing the fluoride. Addition of salt should improve the surface gloss of the polished surface and should allow moderate electrolytic polishing speed without pitting.
（ｃ）さらにこのような電解液は単純な自然浸漬条件下
においてZrおよびZr合金に対する腐食作用が小さく、酸
化作用の激しい不安定な過塩素酸を含まないので、取扱
上爆発を起こすおそれがないこと。(C) Further, such an electrolytic solution has a small corrosive effect on Zr and a Zr alloy under a simple natural immersion condition and does not contain unstable perchloric acid having a strong oxidizing effect, so that there is no possibility of causing an explosion in handling. thing.
以上（ａ）〜（ｃ）に示される研究結果を得たのであ
る。The research results shown in (a) to (c) above were obtained.
この発明は、上記の研究結果に基づいてなされたもの
で、取扱いが容易で、単純な自然浸漬条件下で激しい腐
食作用を示さず、しかも表面光沢が改善され、かつ平滑
でピッティングを生じない研摩面を形成できるZrおよび
Zr合金の電解研摩用電解液を提供するもので、この電解
液が、溶媒としての水に、 弗化物:0.2〜5mol/l、 グルコン酸および／またはグルコン酸塩:0.01〜3mol/
l、 を含有させた水溶液からなることを特徴とするものであ
る。The present invention has been made based on the above-mentioned research results, is easy to handle, does not exhibit severe corrosive action under simple natural immersion conditions, has improved surface gloss, and is smooth and free from pitting. Zr and capable of forming a polished surface
It provides an electrolytic solution for electropolishing of Zr alloy, and this electrolytic solution is added to water as a solvent, fluoride: 0.2-5 mol / l, gluconic acid and / or gluconate: 0.01-3 mol / l.
It is characterized by comprising an aqueous solution containing l ,.
さらに、この発明の電解液について説明する。 Further, the electrolytic solution of the present invention will be described.
（１）弗化物 弗化物は、ZrおよびZr合金部材表面における電解研摩
を進めて、その表面を平滑に仕上げる作用を有し、例え
ば、種々の水溶性金属塩またはこれに相当する弗化物、
好ましくはこれらのアルカリ金属塩およびアンモニウム
塩、特に弗化ナトリウム、弗化カリウムおよび弗化アン
モニウムとして、この発明の電解液中に含有されるが、
それの分解液中に含まれる濃度が0.2mol/l未満である
と、研摩作用が弱く、所望の研摩量を得るのに長時間を
要し、一方それが5mol/lを越えると研摩面に凹凸を生
じ、平滑な研摩面が得られ難くなることから、弗化物の
濃度を0.2〜5mol/lと定めた。(1) Fluoride Fluoride has the function of promoting electrolytic polishing on the surfaces of Zr and Zr alloy members to finish the surface smooth, and for example, various water-soluble metal salts or fluorides corresponding thereto,
Preferably, these alkali metal salts and ammonium salts, especially sodium fluoride, potassium fluoride and ammonium fluoride, are contained in the electrolytic solution of the present invention.
When the concentration contained in the decomposed solution is less than 0.2 mol / l, the polishing action is weak and it takes a long time to obtain a desired polishing amount, while when it exceeds 5 mol / l, the polishing surface is The concentration of fluoride was determined to be 0.2 to 5 mol / l because unevenness occurs and it becomes difficult to obtain a smooth polished surface.
（２）グルコン酸およびグルコン酸塩 グルコン酸およびグルコン酸塩は、研摩面に光沢を与
えるために電解液中に添加されるが、これらの成分の電
解液中における濃度が0.01〜3mol/l、特に0.02〜1.5mol
/lであると、研摩面は特に平滑性にすぐれ金属色の光沢
を呈するようになる。したがってその濃度が0.01mol/l
未満でも、また3mol/lを越えても前記の平滑性にすぐれ
た金属色光沢の研摩面は得られない。(2) Gluconic Acid and Gluconate Gluconic acid and gluconate are added to the electrolytic solution to give gloss to the polished surface, but the concentration of these components in the electrolytic solution is 0.01 to 3 mol / l. Especially 0.02-1.5mol
When it is / l, the polished surface is particularly smooth and has a metallic luster. Therefore, its concentration is 0.01 mol / l
When the amount is less than 3 mol / l or more than 3 mol / l, the polished surface having a metallic luster excellent in smoothness cannot be obtained.
ついで、この発明の電解液を実施例により説明する。 Next, the electrolytic solution of the present invention will be described with reference to Examples.
被研摩部材として、いずれも幅:20mm×長さ:50mm×厚
さ:5mmの寸法を有するジルカロイ−４（Sn:1.5％‐Fe:
0.2％‐Cr:0.1％‐O:0.1％‐Zr:残り）、ジルカロイ−
２（Sn:1.5％‐Fe:0.15％‐Cr:0.1％‐Ni:0.05％‐O:0.
1％‐Zr:残り）（以上重量％）、および純Zr製の板材を
用意した。As a member to be polished, Zircaloy-4 (Sn: 1.5% -Fe: Fe: W: 20 mm × L: 50 mm × T: 5 mm)
0.2% -Cr: 0.1% -O: 0.1% -Zr: remaining), Zircaloy-
2 (Sn: 1.5% -Fe: 0.15% -Cr: 0.1% -Ni: 0.05% -O: 0.
A plate material made of 1% -Zr: the rest) (above weight%) and pure Zr was prepared.
ついで、溶媒としての脱イオン水に種々の弗化物と、
グルコン酸および／またはグルコン酸塩を溶解して、第
１表に示される組成を有する本発明電解液１〜５、およ
び前記構成成分のうちのいずれかの含有割合がこの発明
の範囲から外れた組成を有する比較電解液１〜５を調製
した。Next, various fluorides were added to deionized water as a solvent,
Gluconic acid and / or gluconate was dissolved, and the content ratio of any one of the electrolytic solutions 1 to 5 of the present invention having the composition shown in Table 1 and the above-mentioned components was out of the range of the present invention. Comparative electrolytic solutions 1 to 5 having compositions were prepared.
つぎに、この結果得られた各種の電解液中に、上記の
被研摩部材を浸漬し、いずれも液温:20℃、電流密度:20
A/dm2（ただし、比較電解液１および３においては、電
解液中に弗化物が含まれていないことから、被研摩物表
面に抵抗性の不動態化被膜が瞬時に形成され、このため
電流が殆ど流れず、したがって電流密度は０である）、
および研摩時間:5分の条件下で、前記各被研摩部材を電
解研摩し、それによって得られた研摩量（μｍ）をマイ
クロメータによって測定するとともに、上記被研摩部材
の研摩面を観察して、その研摩面が非常に平滑で金属光
沢があり、かつピッティングを生じていない場合を◎、
平滑で光沢を有し、か つピッティングを生じていないものを○、平滑に研摩さ
れていても、被膜に被われて光沢がないか、あるいは光
沢はあっても凹凸を生じて平滑でないものを△、そして
研摩作用自体を受けていないものを×として評価し、こ
れらの結果を合わせて第１表と第２表に示した。Next, in the various electrolytic solutions obtained as a result of the above, the above-mentioned member to be polished was immersed, and the liquid temperature was 20 ° C. and the current density was 20
A / dm 2 (However, in Comparative Electrolytes 1 and 3, since the electrolyte does not contain fluoride, a resistive passivation film is instantaneously formed on the surface of the object to be polished. Little current flows, so the current density is 0),
And polishing time: each of the members to be polished is electrolytically polished under the condition of 5 minutes, and the amount of polishing (μm) thus obtained is measured by a micrometer, and the polished surface of the member to be polished is observed. , When the polished surface is very smooth and has metallic luster and no pitting occurs, ◎,
Smooth and glossy One that does not cause pitting is ○, even if it is polished smoothly, it is covered by the coating and is not glossy, or even if it is glossy, it is uneven and has unevenness △, and the polishing action itself Those that did not receive were evaluated as x, and these results are shown together in Tables 1 and 2.
第１表および第２表中に示される結果から、本発明電解
液１〜５においては、いずれも、平滑で表面光沢にすぐ
れ、かつピッティングを生じていない研摩面が得られた
のに対し、比較電解液2,4,5においては研摩面に凹凸が
生じたか、あるいは表面光沢がなく、また比較電解液１
および３では、電解液中に弗化物が含まれていないとこ
ろから、電流が殆ど流れず、その結果研摩が全く進行し
なかったことが明らかである。From the results shown in Tables 1 and 2, in the case of the electrolytic solutions 1 to 5 of the present invention, in all cases, a polished surface which was smooth and had excellent surface gloss and which was free from pitting was obtained. In Comparative Electrolytes 2, 4 and 5, there was unevenness on the polished surface or there was no surface gloss.
In Nos. 3 and 3, it is clear that almost no current flows because the electrolyte solution contains no fluoride, and as a result, polishing does not proceed at all.
以上述べた説明から明らかなように、この発明の電解
液によれば、ZrおよびZr合金の電解研摩において、平滑
で表面光沢にすぐれ、かつピッティングを生じない研摩
面を形成することができるのである。As is clear from the above description, according to the electrolytic solution of the present invention, in electrolytic polishing of Zr and Zr alloy, it is possible to form a polished surface that is smooth and has excellent surface gloss, and does not cause pitting. is there.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭63−195300（ＪＰ，Ａ) 特公 昭32−10561（ＪＰ，Ｂ２) 特公 昭58−35280（ＪＰ，Ｂ２) 特公 昭60−56797（ＪＰ，Ｂ２) ─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-63-195300 (JP, A) JP-B 32-10561 (JP, B2) JP-B 58-35280 (JP, B2) JP-B 60- 56797 (JP, B2)
Claims (1)
l、 を含有させた水溶液からなることを特徴とするZrおよび
Zr合金電解研摩用電解液。1. In water as a solvent, fluoride: 0.2-5 mol / l, gluconic acid and / or gluconate: 0.01-3 mol / l
Zr and an aqueous solution containing l,
Zr alloy electrolytic polishing electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62027694A JP2508520B2 (en) | 1987-02-09 | 1987-02-09 | Electrolyte for Zr and Zr alloy electrolytic polishing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62027694A JP2508520B2 (en) | 1987-02-09 | 1987-02-09 | Electrolyte for Zr and Zr alloy electrolytic polishing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63195299A JPS63195299A (en) | 1988-08-12 |
| JP2508520B2 true JP2508520B2 (en) | 1996-06-19 |
Family
ID=12228080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62027694A Expired - Lifetime JP2508520B2 (en) | 1987-02-09 | 1987-02-09 | Electrolyte for Zr and Zr alloy electrolytic polishing |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2508520B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2701489B2 (en) * | 1989-11-28 | 1998-01-21 | 株式会社島津製作所 | Turbo molecular pump |
| WO2011063353A2 (en) * | 2009-11-23 | 2011-05-26 | Metcon, Llc | Electrolyte solution and electropolishing methods |
| CN114689411A (en) * | 2020-12-29 | 2022-07-01 | 中核北方核燃料元件有限公司 | Preparation method of Zr-4 alloy welding metallographic sample |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5835280A (en) * | 1982-05-20 | 1983-03-01 | Honda Motor Co Ltd | Oil pump driving device by engine |
-
1987
- 1987-02-09 JP JP62027694A patent/JP2508520B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63195299A (en) | 1988-08-12 |
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