JPH0511259B2 - - Google Patents
Info
- Publication number
- JPH0511259B2 JPH0511259B2 JP22802884A JP22802884A JPH0511259B2 JP H0511259 B2 JPH0511259 B2 JP H0511259B2 JP 22802884 A JP22802884 A JP 22802884A JP 22802884 A JP22802884 A JP 22802884A JP H0511259 B2 JPH0511259 B2 JP H0511259B2
- Authority
- JP
- Japan
- Prior art keywords
- oxide film
- metal
- sample piece
- metal sample
- constant current
- 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
- 239000002184 metal Substances 0.000 claims description 76
- 229910052751 metal Inorganic materials 0.000 claims description 76
- 239000008151 electrolyte solution Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000007654 immersion Methods 0.000 description 5
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000009825 accumulation Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000941 radioactive substance Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000012857 radioactive material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Testing Resistance To Weather, Investigating Materials By Mechanical Methods (AREA)
Description
【発明の詳細な説明】
〔発明の技術分野〕
この発明は腐食酸化皮膜の剥離別装置に係り、
特に、沸騰水型原子炉の一次冷却系構造物の表面
に生成された腐食酸化皮膜、あるいはこの一次冷
却系を模擬した試験装置において試料表面に生成
した腐食酸化皮膜をそれぞれ剥離させる腐食酸化
皮膜の剥離装置に関する。[Detailed Description of the Invention] [Technical Field of the Invention] This invention relates to a peeling device for a corroded oxide film,
In particular, the corrosion oxide film formed on the surface of the primary cooling system structure of a boiling water nuclear reactor, or the corrosion oxide film formed on the sample surface in a test device simulating this primary cooling system, is removed. This invention relates to a peeling device.
一般に、沸騰水型原子炉の一次冷却系構造物に
はステンレス鋼が使用され、原子炉の運転ととも
に、このテスンレス鋼表面に鉄、クロムおよびニ
ツケル等を主成分とする腐食酸化皮膜が経時的に
生成される。この腐食酸化皮膜の成長過程におい
て、冷却材たる水中に溶解されたイン状の放射性
物質が取り込まれる。したがつて、一次冷却系構
造物に蓄積される放射性物質は、腐食酸化皮膜の
成長とともに、増加し、放射能汚染を高めるもの
と考えられる。そこで、腐食酸化皮膜量を測定
し、この腐食酸化皮膜の成長過程を認識すること
が、原子炉一次冷却系構造物における放射性物質
の蓄積挙動および放射能蓄積に関する将来予測に
とつて非常に重要なものとなる。
Generally, stainless steel is used for the primary cooling system structure of boiling water nuclear reactors, and as the reactor operates, a corrosive oxide film consisting mainly of iron, chromium, and nickel forms on the surface of this stainless steel over time. generated. During the growth process of this corrosive oxide film, radioactive substances dissolved in the coolant water are taken in. Therefore, it is thought that the radioactive substances accumulated in the primary cooling system structure increase as the corroded oxide film grows, increasing radioactive contamination. Therefore, measuring the amount of corroded oxide film and recognizing the growth process of this corroded oxide film is extremely important for future predictions of radioactive material accumulation behavior and radioactivity accumulation in reactor primary cooling system structures. Become something.
従来、この腐食酸化皮膜の定量は、まず実際の
原子炉一次冷却系配管を数cm角に切断して金属試
料片とすることから始める。次に、この金属試料
片を0.1wt％程度のシユウ酸等の弱酸溶液中に浸
漬させて、金属試料片に生成された腐食酸化皮膜
を電気化学的に溶解させ、その溶解液を原子吸光
光度計等で分析する。その後、再び金属試料片を
溶解液に浸漬させ、溶解液を同様に分析する。そ
して金属試料片に金属光沢が現われるまで上記操
作を繰返す。このようにして、腐食酸化皮膜量の
測定が行なわれているが、この測定工程は非常に
複雑であり、多大な時間を要する。そのため、こ
の測定操作においては測定作業員に高度な伎倆お
よび熟練が要求されることになる。
Conventionally, the quantitative determination of this corroded oxide film begins by cutting the actual reactor primary cooling system piping into pieces of several centimeters square to obtain metal sample pieces. Next, this metal sample piece is immersed in a weak acid solution such as oxalic acid of about 0.1 wt% to electrochemically dissolve the corrosive oxide film formed on the metal sample piece. Analyze by total. Thereafter, the metal sample piece is immersed in the solution again, and the solution is analyzed in the same manner. The above operation is then repeated until a metallic luster appears on the metal sample piece. In this way, the amount of corroded oxide film is measured, but this measurement process is very complicated and takes a lot of time. Therefore, this measurement operation requires a high degree of skill and skill from the measuring operator.
この発明は上記事実を考慮してなされたもので
あり、金属表面に生成した腐食酸化皮膜を簡単か
つ迅速に剥離させることができる腐食酸化皮膜の
剥離装置を提供することを目的とする。
The present invention has been made in consideration of the above facts, and an object of the present invention is to provide a corrosive oxide film stripping device that can easily and quickly peel off a corrosive oxide film formed on a metal surface.
上記目的を達成するために、この発明に係る腐
食酸化皮膜の剥離装置は、陽極端子および陰極端
子を有し、この陽陰極端子間に定電流を発生せし
める定電流発生装置と、上記陽陰極端子に電気的
に接続され表面部に腐食酸化皮膜が形成された金
属試料片と、上記陰極端子に電気的に接続され上
記金属試料片を覆うように所定間隔をおいて配設
された金属ネツトと、上記金属試料片および金属
ネツトを浸漬可能とする電解液を貯留した電解槽
とから成るものであり、電解液中に浸漬した金属
試料片および金属ネツトに通電させることにより
金属試料片の表面部分の地金を電気的に溶解せし
め、この金属試料片の表面に生成された腐食酸化
皮膜を迅速に地金部分から剥離させるものであ
る。
In order to achieve the above object, a corrosive oxide film peeling device according to the present invention includes a constant current generating device that has an anode terminal and a cathode terminal and generates a constant current between the anode and cathode terminals, and a constant current generator that generates a constant current between the anode and cathode terminals. a metal sample piece electrically connected to the cathode terminal and having a corroded oxide film formed on its surface; and a metal net electrically connected to the cathode terminal and disposed at a predetermined interval so as to cover the metal sample piece. , and an electrolytic tank storing an electrolytic solution in which the metal specimen and the metal net can be immersed, and the surface portion of the metal specimen is This method electrically melts the base metal, and quickly peels off the corrosive oxide film formed on the surface of the metal specimen from the base metal.
ここで上記定電流発生装置としては、任意の直
流電流を発生することにより酸化皮膜の剥離とい
う目的は達成することが可能であるため、必ずし
も定電流である必要はないが、以下に述べる剥離
条件を最適に調整するために、一定の範囲におい
て電流値および電圧値が可変であり、各剥離操作
時において一定の電流値を与える汎用の定電流定
電圧発生装置（直流電源）を使用する。 Here, the above-mentioned constant current generator does not necessarily have to be a constant current because the purpose of peeling off the oxide film can be achieved by generating any DC current, but it does not necessarily have to be a constant current, but the peeling conditions described below can be used. In order to optimally adjust the current and voltage values, a general-purpose constant current and constant voltage generator (DC power supply) is used that has variable current and voltage values within a certain range and provides a constant current value during each stripping operation.
すなわち本願の剥離装置を使用して腐食酸化皮
膜を剥離する際に、酸化皮膜が電解液中に溶解し
てしまうと、回収できる固形状の酸化皮膜量が減
少してしまい、酸化皮膜量を過少評価するおそれ
がある。 In other words, when removing a corroded oxide film using the peeling device of the present application, if the oxide film dissolves in the electrolytic solution, the amount of solid oxide film that can be recovered will decrease, and the amount of oxide film may be reduced. There is a risk of evaluation.
特に主たる測定対象である原子炉機器の構成材
であるステンレス鋼を金属試料片として使用する
場合には、ステンレス鋼の酸化皮膜の構成金属
は、やや組成比は異なるものの、地金としてのス
テンレス鋼（Fe−Cr−Ni）に近い組成となるた
め、電解液中に含まれる金属量を測定し、その測
定値から溶解した酸化皮膜量を補正することは困
難である。そのため剥離操作時における酸化皮膜
の溶解を極力抑制するように電流などの最適な剥
離条件を設定する必要がある。 Particularly when using stainless steel, which is a constituent material of nuclear reactor equipment, which is the main object of measurement, as a metal specimen, the constituent metals of the stainless steel oxide film are similar to the base metal stainless steel, although the composition ratio is slightly different. Since the composition is close to (Fe-Cr-Ni), it is difficult to measure the amount of metal contained in the electrolytic solution and correct the amount of dissolved oxide film from the measured value. Therefore, it is necessary to set optimal stripping conditions such as electric current so as to suppress dissolution of the oxide film as much as possible during the stripping operation.
上記の最適な剥離条件は金属試料片の形状やそ
の履歴等によつて変化するため、一律に決定する
ことは困難であり、試行錯誤法によつて決定され
る。具体的には、一定電流を一時間（例えば１分
程度）流して金属試料片を電解槽から取り出し、
超音波洗浄を実施した後にその表面の剥離状況を
観察する。もし剥離していない場合には、さらに
定電流発生装置の電流値を上昇させて同様に剥離
状況を観察する。このように徐々に電流値を上昇
させると、ある電流値以下で酸化皮膜の剥離が起
き、この場合は、酸化皮膜の溶解は殆ど起こら
ず、固形分として電解液中に分散される。 The above-mentioned optimal peeling conditions vary depending on the shape of the metal sample piece, its history, etc., and therefore are difficult to uniformly determine, and are determined by a trial-and-error method. Specifically, a constant current is passed for one hour (for example, about one minute), and the metal sample piece is removed from the electrolytic bath.
After performing ultrasonic cleaning, the state of peeling on the surface is observed. If no peeling occurs, the current value of the constant current generator is further increased and the peeling status is observed in the same manner. When the current value is gradually increased in this way, the oxide film peels off below a certain current value, and in this case, the oxide film hardly dissolves and is dispersed in the electrolytic solution as a solid component.
一方、電流値を最適な剥離条件より高く設定し
た場合には、一瞬にして酸化皮膜が剥離すると同
時に酸化皮膜が粉々に砕けて、その一部は明らか
に電解液中に溶解するため、濾別して得られる酸
化皮膜量が減少し測定精度が低下してしまう。す
なわち最適な剥離条件とは最も低い電流値で剥離
が発生する条件を意味し、この条件を調整選択し
ながら剥離装置を実施することになる。したがっ
て電解用電源としては電流値が可変であり、各操
作時において一定の電流値を与える汎用の定電流
発生装置を使用するとよい。 On the other hand, if the current value is set higher than the optimal stripping conditions, the oxide film will be peeled off instantly and at the same time it will be broken into pieces, and some of it will obviously dissolve in the electrolyte, so it must be filtered out. The amount of oxide film obtained decreases, and measurement accuracy decreases. In other words, the optimum peeling condition means a condition under which peeling occurs at the lowest current value, and the peeling apparatus is operated while adjusting and selecting these conditions. Therefore, as a power source for electrolysis, it is preferable to use a general-purpose constant current generator whose current value is variable and which provides a constant current value during each operation.
第１図はこの発明に係る腐食酸化皮膜の剥離装
置の一実施例を部分的に破断して示す概略側断面
図である。
FIG. 1 is a partially cutaway side sectional view showing an embodiment of a corrosive oxide film peeling apparatus according to the present invention.
電解槽１には、表面に腐食酸化皮膜３が生成さ
れた金属試料片５が収容される。この金属試料片
５は、実際の沸騰水型原子炉における一次冷却系
配管の一部を数cm角に切断した金属試料片である
か、またはこの原子炉一次冷却系を模擬した試料
装置において、表面に腐食酸化皮膜を生成させた
金属試料片である。 The electrolytic bath 1 accommodates a metal sample piece 5 with a corroded oxide film 3 formed on its surface. This metal sample piece 5 is either a metal sample piece obtained by cutting a part of the primary cooling system piping in an actual boiling water reactor into several cm square pieces, or a sample device that simulates this reactor primary cooling system. This is a metal specimen with a corroded oxide film formed on its surface.
また、金属試料片５はリード線７を介して、定
電流を発生可能とする定電流発生装置９の陽極端
子９ａに接続される。したがつて、この金属試料
片５は電解槽１内において陽極として機能する。
一方、定電流発生装置の陽極端子９ｂにはリード
線１１を介し、陽極として機能する金属ネツト１
３が接続される。この金属ネツト１３は例えば白
金ネツトであり、金属試料片５を内部に収容する
大きさに形成される。さらに、金属ネツト１３は
フレキシブルに構成され、陽極としての金属試料
片５の形状に対応して自在に曲げ可能に設けられ
る。 Further, the metal sample piece 5 is connected via a lead wire 7 to an anode terminal 9a of a constant current generator 9 capable of generating a constant current. Therefore, this metal sample piece 5 functions as an anode within the electrolytic cell 1.
On the other hand, a metal net 1 which functions as an anode is connected to the anode terminal 9b of the constant current generator through a lead wire 11.
3 is connected. This metal net 13 is, for example, a platinum net, and is formed in a size that accommodates the metal sample piece 5 therein. Furthermore, the metal net 13 is constructed to be flexible and can be freely bent in accordance with the shape of the metal sample piece 5 serving as an anode.
また、電解槽１内には電解液１５が満たされ、
この電解液１５により金属試料片５および金属ネ
ツト１３が浸漬可能とされる。この電解液１５と
しては、腐食酸化皮膜３を溶解させない程度の低
濃度の強酸あるいは弱酸が用いられる。 Further, the electrolytic cell 1 is filled with an electrolytic solution 15,
The metal sample piece 5 and the metal net 13 can be immersed in this electrolytic solution 15. As this electrolytic solution 15, a strong acid or a weak acid with a low concentration that does not dissolve the corrosive oxide film 3 is used.
次に作用を説明する。 Next, the effect will be explained.
まず、電解槽１に電解液１５を満たす。次に、
リード線７を接続した金属試料片５を金属ネツト
１３内に配置させ、これら金属試料片５および金
属ネツト１３を定電流発生装置９の陽極端子、陰
極端子にそれぞれリード線７，１１を介して電気
的に接続させる。その後、金属試料片５および金
属ネツト１３を電解液１５中に浸漬させ、これら
金属試料片５および金属ネツト１３に通電する。
通電後約１分間程すると金属試料片５の地金表層
部が電気分解作用を受けて、電解液１５中に溶解
し、その結果、金属試料片５の表面に生成された
腐食酸化皮膜３が迅速に剥離する。 First, the electrolytic cell 1 is filled with an electrolytic solution 15. next,
The metal sample piece 5 to which the lead wire 7 is connected is placed in the metal net 13, and the metal sample piece 5 and the metal net 13 are connected to the anode terminal and cathode terminal of the constant current generator 9 via the lead wires 7 and 11, respectively. Connect electrically. Thereafter, the metal sample piece 5 and the metal net 13 are immersed in the electrolytic solution 15, and electricity is applied to the metal sample piece 5 and the metal net 13.
Approximately 1 minute after energization, the surface layer of the bare metal of the metal specimen 5 undergoes electrolysis and dissolves in the electrolyte 15, and as a result, the corrosive oxide film 3 formed on the surface of the metal specimen 5 is Peel quickly.
このように、腐食酸化皮膜３の剥離を短時間か
つ簡単に行なうことができる。したがつて、この
剥離した腐食酸化皮膜を捕獲し、その重量を測定
することにより、金属試料片５の表面に生成され
た腐食酸化皮膜量を測定することができる。 In this way, the corrosion oxide film 3 can be easily peeled off in a short time. Therefore, by capturing this peeled off corrosive oxide film and measuring its weight, the amount of the corrosive oxide film generated on the surface of the metal sample piece 5 can be measured.
上記腐食酸化皮膜３の捕獲および定量は、従来
の液体中の固形分の一般的な定量分析法に準拠し
て次のような操作手順で実施される。 The capture and quantitative determination of the corroded oxide film 3 is carried out in accordance with the conventional general quantitative analysis method for solid content in a liquid, using the following operating procedure.
すなわち、剥離した腐食酸化皮膜３は電解液５
１５中に浮遊するので、これを予め重量を測定し
ておいたフイルタ（濾紙等）を使用して濾過操作
によつてフイルタ上に濾別回収する。次にフイル
タ全体を乾燥後、重量を再度測定し、フイルタ自
体の乾物重量を差引き、その重量増加分としての
腐食酸化皮膜３の重量を算出する。そして上記重
量増加分と金属試料片５の表面積とから単位面積
当りの酸化皮膜量（mg／cm2）が算出される。なお
上記のような重量法によつて定量できない程、酸
化皮膜量が少ない場合には、蛍光Ｘ線分析法によ
つて酸化皮膜領域の金属量を定量し、測定値に酸
化物換算係数を掛けて、酸化皮膜量を決定するこ
ともできる。 That is, the peeled off corrosion oxide film 3 is removed from the electrolyte 5.
15, so it is separated and collected on a filter by a filtration operation using a filter (filter paper, etc.) whose weight has been measured in advance. Next, after drying the entire filter, the weight is measured again, and the dry weight of the filter itself is subtracted to calculate the weight of the corroded oxide film 3 as the weight increase. Then, the amount of oxide film per unit area (mg/cm 2 ) is calculated from the weight increase and the surface area of the metal sample piece 5. In addition, if the amount of oxide film is so small that it cannot be determined by the gravimetric method as described above, quantify the amount of metal in the oxide film area by fluorescent X-ray analysis, and multiply the measured value by the oxide conversion factor. The amount of oxide film can also be determined by
また、原子炉一次冷却系の冷却材たる水または
試験装置の試験水への接液時間が異なり、その結
果、腐食酸化皮膜量が異なる多数の金属試料片に
ついて各試料片毎にその皮膜量を測定すれば、腐
食酸化皮膜量と接液時間との関係、すなわち腐食
酸化皮膜の生成速度が判明する。例えば金属試験
片を液体中に浸漬した場合、金属試験片表面に生
成される酸化皮膜量は浸漬時間（接液時間）に対
して一般に放射線則や対数則に近似した相関をも
つて増加する。具体的には、浸漬時間ｔにける酸
化皮膜量をＭ(t)とすると、下記(1)，(2)式に示すよ
うな関係式が成立する。 In addition, the amount of coating on each sample piece was calculated for a large number of metal specimens with different amounts of corroded oxide film due to different contact times with the water that is the coolant in the reactor primary cooling system or the test water of the test equipment. By measuring, the relationship between the amount of corrosive oxide film and the time of contact with liquid, that is, the rate of formation of corrosive oxide film can be determined. For example, when a metal test piece is immersed in a liquid, the amount of oxide film generated on the surface of the metal test piece generally increases with a correlation similar to the radial law or logarithmic law with respect to the immersion time (liquid contact time). Specifically, if the amount of oxide film during the immersion time t is M(t), the following relational expressions (1) and (2) hold true.
Ｍ(t)＝K1t1/2 ……(1)
Ｍ(t)＝K2ｎ（at＋１） ……(2)
ここで、K1，K2，ａは定数であり、金属試験
片の組成，種類、および液体の腐食性、温度等に
よつて一定の値を持つ。すなわち酸化皮膜の生成
速度は一定ではなく、初期に腐食が早く進行し、
次第に進行が緩速化するのが一般的な傾向であ
る。この原因としては生成した酸化皮膜が防食的
に機能するからである。一般的に浸漬時間が比較
的に短い場合には(1)式で示すような放物線則に近
似した相関が得られる一方、長期に亘る場合には
(2)式に示す対数則に近似した相関が得られる。し
たがつて浸浸時間が異なる数個の金属試料片の腐
食酸化皮膜量Ｍ(t)を実測し、そのデータを(1)，(2)
式によつて回帰し、各定数を求めることにより、
任意の時間ｔにおける腐食酸化皮膜量Ｍ(t)を高い
精度で推定することができる。それ故、この腐食
酸化皮膜の生成速度からその皮膜に取り込まれる
放射能の蓄積速度や機構が容易に把握でき、原子
炉一次冷却系構造物における放射能の蓄積挙動お
よびその予測が可能となる。 M(t)=K 1 t 1/2 ...(1) M(t)=K 2 n(at+1) ...(2) Here, K 1 , K 2 , a are constants, and the metal test piece It has a certain value depending on the composition, type, corrosivity of the liquid, temperature, etc. In other words, the rate of formation of an oxide film is not constant, and corrosion progresses quickly in the initial stage.
The general trend is for progress to gradually slow down. This is because the formed oxide film functions as anti-corrosion. In general, if the immersion time is relatively short, a correlation similar to the parabolic law as shown in equation (1) can be obtained; however, if the immersion time is long,
A correlation approximated by the logarithmic law shown in equation (2) can be obtained. Therefore, we actually measured the amount of corrosion oxide film M(t) on several metal specimens with different immersion times, and used the data as (1) and (2).
By regressing according to the formula and finding each constant,
The amount of corroded oxide film M(t) at any time t can be estimated with high accuracy. Therefore, from the formation rate of this corrosive oxide film, it is easy to understand the accumulation rate and mechanism of radioactivity taken into the film, and it becomes possible to predict the accumulation behavior of radioactivity in the reactor primary cooling system structure.
また、この実施例では、金属ネツト１３がフレ
キシブルに構成され、金属試料片５の形状に対応
して曲げられることから、金属試料片５が複雑形
状を有する場合であつても金属試料片５の各表面
部に作用する電場が均一となり、金属試料片５の
表面から腐食酸化皮膜３をむらなく均一に剥離さ
せることができる。 In addition, in this embodiment, the metal net 13 is configured to be flexible and can be bent in accordance with the shape of the metal sample piece 5, so even when the metal sample piece 5 has a complicated shape, the metal net 13 is The electric field acting on each surface portion becomes uniform, and the corroded oxide film 3 can be evenly and uniformly peeled off from the surface of the metal sample piece 5.
なお、この実施例では金属ネツト１３が白金製
の場合につき述べたが、金属試料片を構成する元
素を含まず導電性を有する金または銀またはカー
ボンフアイバーであつてもよい。 In this embodiment, the case has been described in which the metal net 13 is made of platinum, but it may also be made of gold, silver, or carbon fiber, which does not contain the elements constituting the metal sample piece and has conductivity.
また、この実施例では、電解槽１内における陽
極としての金属試料片５がステンレス製であるも
のにつき述べたが、炭素鋼の場合２ついても同様
に適用することができる。 Further, in this embodiment, the case where the metal sample piece 5 as an anode in the electrolytic cell 1 is made of stainless steel has been described, but the same applies to the case where the metal sample piece 5 is made of carbon steel.
さらに、上記実施例では、陽極側に金属試料片
５を接続した場合につき説明したが、この陽極側
に原子炉一次冷却系の機器等を接続することもで
きる。この場合には、原子炉一次冷却系の機器か
ら腐食酸化皮膜を剥離させて、これらの機器等の
除染を効率的に行なうことができる。 Further, in the above embodiment, the case where the metal sample piece 5 is connected to the anode side has been described, but it is also possible to connect equipment of the reactor primary cooling system, etc. to the anode side. In this case, the corroded oxide film can be peeled off from the equipment of the reactor primary cooling system, and these equipment etc. can be efficiently decontaminated.
以上のように、この発明に係る腐食酸化皮膜の
剥離装置によれば、腐食酸化皮膜が形成された金
属試料片を電解液中に浸漬し、かつこの試料片を
定電流発生装置の陽極端子に接続する一方、上記
金属試料片を覆うように配設した金属ネツトを同
じ電解液中に浸漬し、かつこの金属ネツトを定電
流発生装置の陰極端子に接続されることから、電
解液に浸漬された金属試料片および金属ネツトに
通電することにより、金属試料片表面に生成され
た腐食酸化皮膜を簡単かつ迅速に剥離させること
ができるという効果を奏する。
As described above, according to the corrosive oxide film peeling apparatus of the present invention, a metal sample piece on which a corrosive oxide film is formed is immersed in an electrolytic solution, and the sample piece is connected to the anode terminal of a constant current generator. On the other hand, a metal net arranged to cover the metal sample piece is immersed in the same electrolytic solution, and this metal net is connected to the cathode terminal of a constant current generator, so that it is not immersed in the electrolytic solution. By energizing the metal sample piece and the metal net, the corrosion oxide film formed on the surface of the metal sample piece can be easily and quickly removed.
第１図は本発明に係る腐食酸化皮膜の剥離装置
の一実施例を部分的に破断して示す概略側断面図
である。
１……電解槽、３……腐食酸化皮膜、５……金
属試料片、７……リード線、９……定電流発生装
置、９ａ……陽極端子、９ｂ……陰極端子、１１
……リード線、１３……金属ネツト、１５……電
解液。
FIG. 1 is a partially cutaway side sectional view showing an embodiment of a corrosive oxide film peeling apparatus according to the present invention. DESCRIPTION OF SYMBOLS 1... Electrolytic cell, 3... Corrosion oxide film, 5... Metal sample piece, 7... Lead wire, 9... Constant current generator, 9a... Anode terminal, 9b... Cathode terminal, 11
... Lead wire, 13 ... Metal net, 15 ... Electrolyte.
Claims (1)
端子間に定電流を発生せしめる定電量流発生装置
と、上記陽極端子に電気的に接続され表面部に腐
食酸化皮膜が形成された金属試料片と、上記陰極
端子に電気的に接続され上記金属試料片を覆うよ
うに所定間隔をおいて配設された金属ネツトと、
上記金属試料片および金属ネツトを浸漬可能とす
る電解液を貯留した電解槽とから成ることを特徴
とする腐食酸化皮膜の剥離装置。 ２ 電解液は腐食酸化皮膜を溶解させない溶液に
より構成された特許請求の範囲第１項記載の腐食
酸化皮膜の剥離装置。 ３ 金属ネツトは、その形状が金属試料片の形状
に対応して曲げ得るようフレキシブルに構成され
た特許請求の範囲第１項記載の腐食酸化皮膜の剥
離装置。[Claims] 1. A constant current flow generator having an anode terminal and a cathode terminal and generating a constant current between the anode terminal and the cathode terminal, and a constant current flow generator electrically connected to the anode terminal and having a corroded oxide film on the surface. a formed metal sample piece; a metal net electrically connected to the cathode terminal and disposed at a predetermined interval so as to cover the metal sample piece;
A device for removing a corrosive oxide film, comprising an electrolytic bath storing an electrolytic solution in which the metal sample piece and the metal net can be immersed. 2. The corrosive oxide film stripping apparatus according to claim 1, wherein the electrolytic solution is a solution that does not dissolve the corrosive oxide film. 3. The apparatus for removing a corroded oxide film according to claim 1, wherein the metal net is configured to be flexible so that its shape can be bent in accordance with the shape of the metal sample piece.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22802884A JPS61107151A (en) | 1984-10-31 | 1984-10-31 | Apparatus for releasing corrosive oxidation film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22802884A JPS61107151A (en) | 1984-10-31 | 1984-10-31 | Apparatus for releasing corrosive oxidation film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61107151A JPS61107151A (en) | 1986-05-26 |
| JPH0511259B2 true JPH0511259B2 (en) | 1993-02-15 |
Family
ID=16870063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22802884A Granted JPS61107151A (en) | 1984-10-31 | 1984-10-31 | Apparatus for releasing corrosive oxidation film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61107151A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104630874A (en) * | 2015-01-20 | 2015-05-20 | 北方工业大学 | Method for completely separating film from film composite material |
-
1984
- 1984-10-31 JP JP22802884A patent/JPS61107151A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61107151A (en) | 1986-05-26 |
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