JPH0515799B2 - - Google Patents
Info
- Publication number
- JPH0515799B2 JPH0515799B2 JP19920783A JP19920783A JPH0515799B2 JP H0515799 B2 JPH0515799 B2 JP H0515799B2 JP 19920783 A JP19920783 A JP 19920783A JP 19920783 A JP19920783 A JP 19920783A JP H0515799 B2 JPH0515799 B2 JP H0515799B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- electrolytic polishing
- sulfuric acid
- liquid composition
- fluorosulfuric
- 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
- 238000005498 polishing Methods 0.000 claims description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 20
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 229910052758 niobium Inorganic materials 0.000 claims description 17
- 239000010955 niobium Substances 0.000 claims description 17
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 43
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 24
- 229960002050 hydrofluoric acid Drugs 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 6
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010000372 Accident at work Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
Landscapes
- Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
- Electrolytic Production Of Metals (AREA)
Description
【発明の詳細な説明】
本発明はニオブ材を鏡面研磨する際に用いられ
る電解研磨液組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electropolishing liquid composition used for mirror polishing niobium materials.
ニオブ材の鏡面研磨は、例えばその超伝導性を
利用して加速空洞共鳴体に用いる場合、ニオブ材
表面に於ける高周波吸収を防止してエネルギー損
失を抑制する為に行われる。この様なニオブ材の
鏡面研磨は、他の金属材料の鏡面研磨の場合と同
じく電解研磨法によつて行われ、電解研磨液とし
ては濃硫酸にフツ酸および水を配合したものが従
来使用されている。 Mirror polishing of the niobium material is performed to prevent high frequency absorption on the surface of the niobium material and suppress energy loss, for example, when the material is used in an accelerating cavity resonator by utilizing its superconductivity. Mirror polishing of niobium materials like this is carried out by electrolytic polishing, the same as mirror polishing of other metal materials, and the electrolytic polishing solution traditionally used is a mixture of concentrated sulfuric acid, hydrofluoric acid, and water. ing.
然し乍ら、上記従来の電解研磨液を調製しよう
とすると、フツ酸の配合時にフツ酸中の水に起因
する硫酸の稀釈熱によつて液温が著しく上昇し、
HF（フツ化水素）の激しい蒸発を生じてしまう。
この為、調製後の電解研磨液に於けるHF濃度が
低下してしまい、また蒸発したHFによつて作業
場が汚染されるという問題があつた。電解研磨液
中に於いて、HFは硫酸の酸化作用によりニオブ
材表面に形成された酸化被膜を溶解除去する作用
を有するものであり、従つてHF濃度の低下は直
接的に電解研磨液の性能を劣化させることにな
る。また、HFは人体にとつて極めて有害である
から、HFによる汚染は労働災害防止の観点から
無視できない重大な問題である。 However, when attempting to prepare the above-mentioned conventional electrolytic polishing solution, the temperature of the solution increases significantly due to the heat of dilution of sulfuric acid caused by the water in the hydrofluoric acid when it is mixed with hydrofluoric acid.
This will cause intense evaporation of HF (hydrogen fluoride).
As a result, the HF concentration in the prepared electrolytic polishing solution decreases, and the evaporated HF contaminates the workplace. In the electrolytic polishing solution, HF has the effect of dissolving and removing the oxide film formed on the surface of the niobium material due to the oxidizing action of sulfuric acid. Therefore, a decrease in the HF concentration directly affects the performance of the electrolytic polishing solution. It will cause deterioration. Furthermore, since HF is extremely harmful to the human body, HF contamination is a serious problem that cannot be ignored from the perspective of preventing industrial accidents.
上述の問題を回避する為の一つの方法として、
フツ酸を添加配合した後、直ちに調合容器を密閉
することによりHF蒸気を外部に逃さない様にす
ることが考えられる。ところがフツ酸配合後直ち
に容器を密閉すると、容器、容器内の電解研磨
液、容器内空気の間に夫々熱膨張差があることか
ら、前記稀釈熱により容器の内圧が著しく上昇し
てしまう。この結果、通常はプラスチツク製の調
合容器に破損のおそれが生じることとなる為、実
際上この方法を採用することは出来ない。 One way to avoid the above problem is to
It is possible to prevent HF vapor from escaping to the outside by immediately sealing the mixing container after adding and blending fluoric acid. However, if the container is sealed immediately after blending the hydrofluoric acid, the internal pressure of the container will rise significantly due to the heat of dilution because there is a difference in thermal expansion between the container, the electrolytic polishing liquid in the container, and the air in the container. As a result, there is a risk of damage to the mixing container, which is usually made of plastic, so this method cannot be adopted in practice.
前記HFの蒸発による問題を回避する為のもう
一つの方法として、配合する硫酸およびフツ酸を
予め冷却しておくことにより調合直後に於ける電
解研磨液の温度を常温以下に維持し、容器解放状
態でもHFが余り蒸発しない様にする方法が考え
られる。しかし、例えば濃硫酸85容量部に対して
40％フツ酸10容量部を配合する場合、調合直後に
於ける電解研磨液の温度を常温以下に維持しよう
とすれば、濃硫酸およびフツ酸を−30℃近くまで
冷却することが必要となる。この様な低温では硫
酸は凍結してしまい、また硫酸やフツ酸の容器と
して耐低温性のものを用いることが要求されるこ
とになる為、現実的にはこの方法を採用するのは
不可能である。 Another method to avoid the problem caused by evaporation of HF is to cool the sulfuric acid and hydrofluoric acid to be mixed in advance to maintain the temperature of the electrolytic polishing solution below room temperature immediately after mixing, and to release the container. A method can be considered to prevent HF from evaporating too much even under such conditions. However, for example, for 85 parts by volume of concentrated sulfuric acid,
When blending 10 parts by volume of 40% hydrofluoric acid, it is necessary to cool the concentrated sulfuric acid and hydrofluoric acid to around -30°C in order to maintain the temperature of the electrolytic polishing solution below room temperature immediately after blending. . In reality, it is impossible to adopt this method because sulfuric acid freezes at such low temperatures, and a container for sulfuric acid or hydrofluoric acid must be resistant to low temperatures. It is.
本発明は上記事情に鑑みて為されたもので、
HFの蒸発を伴うことなく調製することができる
ニオブ材用電解研磨液組成物と、その調製方法を
提供するものである。 The present invention was made in view of the above circumstances, and
The present invention provides an electropolishing liquid composition for niobium materials that can be prepared without evaporation of HF, and a method for preparing the same.
即ち、本発明によるニオブ材用電解研磨液組成
物は、濃硫酸、フルオロ硫酸および水を配合して
成ることを特徴とするものである。 That is, the electropolishing liquid composition for niobium materials according to the present invention is characterized by containing concentrated sulfuric acid, fluorosulfuric acid, and water.
また本発明によるニオブ材用電解研磨液組成物
の調製方法は、濃硫酸に水を添加混合し、更に冷
却した後、これにフルオロ硫酸を添加配合するこ
とを特徴とするものである。 Further, the method for preparing an electrolytic polishing liquid composition for niobium materials according to the present invention is characterized by adding and mixing water to concentrated sulfuric acid, further cooling, and then adding and blending fluorosulfuric acid thereto.
本発明の電解研磨液組成物は、ニオブ材の電解
研磨液として必須の成分であるHFを、従来のよ
うにフツ酸としてではなく、フルオロ硫酸として
配合したことを要点とするもので、次の二つの事
実に基づいている。即ち、発明者等による種々の
研究の結果、濃硫酸中に配合されたHFは一部が
遊離のHFとして存在すると共に、残部はフルオ
ロ硫酸（HSO3F）として存在し、かつ両者は化
学平衡を保つて共存しているという事実が見出だ
された。そして、このフルオロ硫酸は濃硫酸と混
合しても余り発熱しない。この為、本発明の電解
研磨液組成物は従来の電解研磨液とは異なり、本
発明の調製方法を適用することによつてHFの蒸
発を伴うことなく調製することが出来る。従つ
て、HF濃度の低下を生じることなく高性能の電
解研磨液組成物を得ることが出来、また安全管理
上の問題を生じることも無い。 The main feature of the electrolytic polishing liquid composition of the present invention is that HF, which is an essential component of an electrolytic polishing liquid for niobium materials, is blended as fluorosulfuric acid instead of as conventional hydrofluoric acid. It is based on two facts. That is, as a result of various studies conducted by the inventors, it was found that part of HF mixed in concentrated sulfuric acid exists as free HF, and the remainder exists as fluorosulfuric acid (HSO 3 F), and both are in chemical equilibrium. It was discovered that they coexist while maintaining the same Even when mixed with concentrated sulfuric acid, this fluorosulfuric acid does not generate much heat. Therefore, unlike conventional electrolytic polishing liquids, the electropolishing liquid composition of the present invention can be prepared without evaporation of HF by applying the preparation method of the present invention. Therefore, a high-performance electrolytic polishing liquid composition can be obtained without causing a decrease in HF concentration, and no safety management problems will occur.
本発明の調製方法に於いては、三種類の配合原
料の内で濃硫酸と水とを先に添加混合し、その際
に発生した稀釈熱を冷却によつて放出させた後に
フルオロ硫酸を配合するから、調製直後に於ける
電解液組成物の液温上昇は極く僅かですむ。従つ
て、フルオロ硫酸配合の直後に容器を密封するこ
とが出来るから、調製時のHF蒸発を殆ど無くす
ることが可能である。 In the preparation method of the present invention, among the three types of raw materials, concentrated sulfuric acid and water are first added and mixed, and the heat of dilution generated at that time is released by cooling, and then fluorosulfuric acid is added. Therefore, the rise in temperature of the electrolytic solution composition immediately after preparation is extremely small. Therefore, since the container can be sealed immediately after mixing fluorosulfuric acid, it is possible to almost eliminate HF evaporation during preparation.
以下に本発明の一実施例を説明する。 An embodiment of the present invention will be described below.
実施例
下記の配合処方および手順に従つて、ニオブ材
用電解研磨液組成物を調製した。Example An electrolytic polishing liquid composition for niobium materials was prepared according to the following formulation and procedure.
配合処方
濃硫酸（濃度98％）： 749c.c.／
フルオロ硫酸： 134c.c.／
水： 117c.c.／
() 先ず、濃硫酸749c.c.／中に水117c.c.／を
添加混合したところ、稀釈熱により液温が約70
℃まで上昇した。Mixed recipe Concentrated sulfuric acid (concentration 98%): 749 c.c. / Fluorosulfuric acid: 134 c.c. / Water: 117 c.c. / () First, add 117 c.c. of water to 749 c.c. of concentrated sulfuric acid. When added and mixed, the temperature of the liquid rose to about 70℃ due to the heat of dilution.
The temperature rose to ℃.
しかし、この時点ではフルオロ硫酸が未だ配
合されていないから、温度が高くても何等不都
合は生じない。 However, since fluorosulfuric acid has not yet been blended at this point, no problem will occur even if the temperature is high.
() 次に、これを約20℃まで水冷した後、フル
オロ硫酸134c.c.を添加混合してニオブ材用電解
研磨液組成物を得た。その際、フルオロ硫酸は
空気中で発煙するので、フルオロ硫酸が空気に
触れない様に、フルオロ硫酸の注入口を前記硫
酸稀釈液中に浸漬して注入した。また、フルオ
ロ硫酸を添加した後、直ちに蓋をして調合容器
を密封した。この為、フルオロ硫酸添加直後の
液温上昇は測定しなかつたが、容器に手を触れ
た感触では温度の上昇は殆ど感じられず、その
後も密封状態で何等不都合は無かつた。() Next, after cooling this with water to about 20° C., 134 c.c. of fluorosulfuric acid was added and mixed to obtain an electrolytic polishing liquid composition for niobium materials. At this time, since fluorosulfuric acid emits fumes in the air, the fluorosulfuric acid injection port was immersed in the sulfuric acid diluted solution to prevent the fluorosulfuric acid from coming into contact with the air. Immediately after adding fluorosulfuric acid, the preparation container was sealed with a lid. For this reason, we did not measure the rise in temperature of the liquid immediately after adding fluorosulfuric acid, but when we touched the container with our hands, we could hardly feel any rise in temperature, and even after that, the container remained sealed without any inconvenience.
なお、配合されたフルオロ硫酸は先に添加され
ている水と速やかに反応し、下記式に示すように
遊離のHFと硫酸とを生成して化学的平衡状態に
達する。 The blended fluorosulfuric acid quickly reacts with the previously added water to generate free HF and sulfuric acid as shown in the formula below, reaching a chemical equilibrium state.
HSO3F＋H2O→HF＋H2SO4
また、調製時に蒸発して失われたHFの濃度を
測定したところ、フルオロ硫酸換算で１ｇ／、
即ち、配合量134ｇ／の１％以下であつた。因
みに、従来のニオブ材用電解研磨液を調製する際
に生じるHF蒸発量は10〜13％であることを考慮
すれば、上記実施例に於ける結果は著しく改善さ
れたものであることが理解される。 HSO 3 F + H 2 O → HF + H 2 SO 4 Also, when the concentration of HF lost by evaporation during preparation was measured, it was found to be 1 g/fluorosulfuric acid equivalent.
In other words, it was less than 1% of the blended amount of 134g/. Incidentally, considering that the amount of HF evaporated when preparing conventional electrolytic polishing liquid for niobium materials is 10 to 13%, it is understood that the results in the above example are a significant improvement. be done.
次に、上記実施例で得られたニオブ材用電解研
磨液組成物を用い、30℃、20Vの条件で４時間
（２分通電、２分休止を繰返す）ニオブ材の電解
研磨を行なつたところ、次表に示すように、従来
の電解研磨液で得られているのと同等の品質が得
られた。 Next, using the electrolytic polishing liquid composition for niobium materials obtained in the above example, niobium materials were electrolytically polished at 30° C. and 20 V for 4 hours (repeatedly energizing for 2 minutes and resting for 2 minutes). However, as shown in the following table, the same quality as that obtained with conventional electrolytic polishing liquids was obtained.
表（電解研磨品質）
［項目］ ［品質］
研磨面の外観： 光沢のある均一で滑らかな表
面
研磨面の表面粗さ：1.2μRZ（研磨前）→0.3μRZ
（研磨後）
研磨速度： 0.9μ／分（通電中の片面当
り）
以上詳述した様に、本発明によればHF濃度の
低下を伴わずに高品質のニオブ材用電解研磨液組
成物が得られ、またその調製に際してもHFによ
る環境汚染を防止できる等、顕著な効果が得られ
るものである。 Table (electrolytic polishing quality) [Item] [Quality] Appearance of polished surface: Shiny, uniform and smooth surface Surface roughness of polished surface: 1.2μRZ (before polishing) → 0.3μRZ
(After polishing) Polishing speed: 0.9μ/min (per side during current application) As detailed above, according to the present invention, a high-quality electrolytic polishing liquid composition for niobium materials can be produced without reducing the HF concentration. It is possible to obtain remarkable effects such as being able to prevent environmental pollution caused by HF during its preparation.
Claims (1)
ることを特徴とするニオブ材用電解研磨液組成
物。 ２ 濃硫酸に水を添加混合し、更に冷却した後、
これにフルオロ硫酸を添加配合することを特徴と
するニオブ材用電解研磨液組成物の調製方法。[Scope of Claims] 1. An electrolytic polishing liquid composition for niobium materials, characterized by containing concentrated sulfuric acid, fluorosulfuric acid, and water. 2 Add and mix water to concentrated sulfuric acid, and after further cooling,
A method for preparing an electrolytic polishing liquid composition for niobium materials, which comprises adding and blending fluorosulfuric acid thereto.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19920783A JPS6092500A (en) | 1983-10-26 | 1983-10-26 | Liquid composition for electropolishing niobium material and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19920783A JPS6092500A (en) | 1983-10-26 | 1983-10-26 | Liquid composition for electropolishing niobium material and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6092500A JPS6092500A (en) | 1985-05-24 |
| JPH0515799B2 true JPH0515799B2 (en) | 1993-03-02 |
Family
ID=16403915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19920783A Granted JPS6092500A (en) | 1983-10-26 | 1983-10-26 | Liquid composition for electropolishing niobium material and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6092500A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1014727C2 (en) * | 2000-03-23 | 2001-09-25 | Univ Eindhoven Tech | A method for electrolytically polishing a metal in the presence of an electrolyte composition, as well as a molded article obtained by such a method. |
| US20030230548A1 (en) * | 2002-06-18 | 2003-12-18 | Wolfgang Sievert | Acid etching mixture having reduced water content |
| KR101600428B1 (en) | 2014-07-15 | 2016-03-07 | 한국화학연구원 | Niobium etching methods of heavy ion cavity |
-
1983
- 1983-10-26 JP JP19920783A patent/JPS6092500A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6092500A (en) | 1985-05-24 |
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