JPH0613757B2 - Cathodic protection of stainless steel - Google Patents
Cathodic protection of stainless steelInfo
- Publication number
- JPH0613757B2 JPH0613757B2 JP63214337A JP21433788A JPH0613757B2 JP H0613757 B2 JPH0613757 B2 JP H0613757B2 JP 63214337 A JP63214337 A JP 63214337A JP 21433788 A JP21433788 A JP 21433788A JP H0613757 B2 JPH0613757 B2 JP H0613757B2
- Authority
- JP
- Japan
- Prior art keywords
- stainless steel
- corrosion
- amorphous alloy
- cathodic protection
- potential
- 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 - Fee Related
Links
- 239000010935 stainless steel Substances 0.000 title claims description 41
- 229910001220 stainless steel Inorganic materials 0.000 title claims description 41
- 238000004210 cathodic protection Methods 0.000 title claims description 14
- 238000005260 corrosion Methods 0.000 claims description 39
- 230000007797 corrosion Effects 0.000 claims description 38
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 25
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 12
- 229910017604 nitric acid Inorganic materials 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 11
- 239000000956 alloy Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 3
- 229910018137 Al-Zn Inorganic materials 0.000 description 2
- 229910018573 Al—Zn Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000003758 nuclear fuel Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
Landscapes
- Prevention Of Electric Corrosion (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明はステンレス鋼のカソード防食法に係り、特にア
モルファス合金を利用したカソード防食法に関する。TECHNICAL FIELD The present invention relates to a cathodic protection method for stainless steel, and more particularly to a cathodic protection method using an amorphous alloy.
［従来の技術］ ステンレス鋼はＦｅを基とし１３％以上のＣｒを含む合
金鋼で、優れた耐食性を備える。しかしながら、高温濃
硝酸等の苛酷な腐食環境下では、耐硝酸ステンレス鋼で
も粒界腐食や全面腐食を受ける。[Prior Art] Stainless steel is an alloy steel containing 13% or more of Cr based on Fe and has excellent corrosion resistance. However, in a severe corrosive environment such as high temperature concentrated nitric acid, even nitric acid resistant stainless steel undergoes intergranular corrosion and general corrosion.
Ｆｅ基合金の腐食防止方法としては、下記又はの方
法が知られている。The following methods are known as methods for preventing corrosion of Fe-based alloys.
カソード分極によつてＦｅの安定域に持ち込む。It is brought into the stable region of Fe by cathode polarization.
アノード分極によって不動態域に持ち込む。It is brought into the passive region by anodic polarization.
はカソード防食法（cathodic protection）、はア
ノード防食法（anodic protection）と称され、これら
は電気化学的防食法、略して電気防食法と称される。こ
れらのうち、カソード防食法は港湾施設、建築物基礎、
化学装置、ボイラなどに広く用いられて効果があげい
る。Is referred to as cathodic protection, and is referred to as anodic protection, and these are referred to as electrochemical corrosion protection, or electrocorrosion protection for short. Of these, the cathodic protection method is for port facilities, building foundations,
It is widely used in chemical equipment, boilers, etc., and is effective.
カソード防食法の方式は、目的物をカソード分極するた
めの電源を、外部の直流電源に求めるか、あるいはより
低電位な他金属との組合せによる電池に求めるかによっ
て、二つの方式に分類される。前者は外部電源方式ある
いは通電方式（impressed current method）、また後者
を流電アノード方式（galvanic anode method）または
犠牲アノード方式（sacrificial anode method）とよ
ぶ。これらのうち、流電アノード法は、 施工が簡単で、ある期間管理が不要である。Cathodic protection methods are classified into two methods depending on whether an external DC power supply or a battery in combination with another metal having a lower electric potential is used as a power supply for cathodic polarization of a target object. . The former is called an external power supply method or an energized current method, and the latter is called a galvanic anode method or a sacrificial anode method. Among these, the galvanic anode method is easy to install and does not require management for a certain period.
電源が得られない場所や小形のものなどに適用して経
済的である。It is economical to apply to places where power cannot be obtained or small things.
などの利点を有する。It has advantages such as
ところで、流電アノード方式において、目的の環境中で
保護すべき金属より低電位で、かつ防食に必要なだけの
分極を与えることのできる金属として、Ｆｅ基合金に対
してはＭｇ，Ｚｎ及びＡｌが使われる。これらのアノー
ドとしてはその保護性が十分に長期間一定に保たれるこ
とが必要で、このため特別なアノード用合金がつくられ
ている。例えば、Ｆｅに対してはＭｇ−Ａｌ−Ｚｎ合
金、Ａｌ−Ｚｎ合金（Ｉｎ，Ｓｎなどの少量添加）、Ｚ
ｎ−Ａｌ合金（Ｃｄ，Ｈｇ，Ｉｎなどの少量添加）又は
高純度Ｚｎなどがある。こらのうち、Ｍｇ合金はＦｅと
の電位差が大きいので、地中や淡水中などの回路抵抗の
高いときにはよいが、自己腐食量が多いので長持ちしな
い。そこで海水中などではＺｎ又はＡｌのほうが適して
いる。By the way, in the galvanic anode method, Mg, Zn and Al are used for Fe-based alloys as metals capable of imparting polarization necessary for corrosion protection at a lower potential than the metal to be protected in the target environment. Is used. It is necessary for these anodes to have their protective properties kept constant for a sufficiently long period of time, and for this reason special anode alloys have been made. For example, for Fe, a Mg-Al-Zn alloy, an Al-Zn alloy (a small amount of In, Sn, etc. added), Z
There are n-Al alloys (a small amount of Cd, Hg, In, etc. added) or high-purity Zn. Of these, the Mg alloy has a large potential difference from Fe, so it is preferable when the circuit resistance is high in the ground or in fresh water, but it does not last long because it has a large amount of self-corrosion. Therefore, Zn or Al is more suitable for seawater.
［発明が解決しようとする課題］ 流電アノード方式では 環境とアノード配置が適正でないと防食不十分となる
ことがある。[Problems to be Solved by the Invention] In the galvanic anode method, corrosion protection may be insufficient unless the environment and the anode arrangement are proper.
十分長期間防食作用を一定に保つことは困難で、数年
程度で取換えが必要になる。It is difficult to keep the anticorrosion effect constant for a sufficiently long period of time, and replacement is necessary within a few years.
等の問題があり、適当なアノード用合金の改善が強く望
まれている。特に、高温濃硝酸のような過酷な環境下に
おいて、ステンレス鋼を十分に防食することができるア
ノード用合金が要望されている。Therefore, there is a strong demand for improvement of suitable anode alloys. In particular, there is a demand for an alloy for an anode that can sufficiently prevent corrosion of stainless steel under a severe environment such as high temperature concentrated nitric acid.
本発明は上記従来の問題点を解決し、高温濃硝酸のよう
な苛酷な腐食環境下においても、ステンレス鋼の腐食を
有効に防止し得るカソード防食法を提供するものであ
る。The present invention solves the above-mentioned conventional problems and provides a cathodic protection method capable of effectively preventing corrosion of stainless steel even under a severe corrosive environment such as high temperature concentrated nitric acid.
［課題を解決するための手段］ 本発明のステンレス鋼のカソード防食法は、ステンレス
鋼に、該ステンレス鋼よりも腐食電位の引くアモルファ
ス合金を導通させることを特徴とする。[Means for Solving the Problem] The method of cathodic protection for stainless steel of the present invention is characterized in that an amorphous alloy having a corrosion potential lower than that of the stainless steel is conducted to the stainless steel.
即ち、本発明の方法は、ステンレス鋼の一部に、ステン
レス鋼よりも腐食電位が低く、かつ耐食性に優れたアモ
ルファス合金を取り付けるなどの方法で導通させること
により、全体の腐食電位（混成電位）を下げ、ステンレ
ス鋼のアトード溶解反応を抑制し、ステンレス鋼をカソ
ード防食するものである。That is, the method of the present invention, the corrosion potential is lower than stainless steel in a part of stainless steel, and by conducting by a method such as attaching an amorphous alloy having excellent corrosion resistance, the entire corrosion potential (mixed potential) To lower the stainless steel's atode dissolution reaction and prevent the stainless steel from cathodic protection.
なお、本発明において、防食対象となるステンレス鋼は
硝酸系溶液中において、アモルファス合金と導通させた
場合、腐食電位がアモルファス合金の腐食電位よりも高
くなるものである。In the present invention, the stainless steel to be protected against corrosion has a corrosion potential higher than that of the amorphous alloy when brought into conduction with the amorphous alloy in a nitric acid-based solution.
また、アモルファス合金としても防食対象とするステン
レス鋼よりも腐食電位の低いものであれば良く、合金と
しては各種のものを用い得る。例えば、ＳＵＳ ３１０
系ステンレス鋼の硝酸系溶液中での防食には、６０〜３
６Ｆｅ−１６〜１０Ｃｒ−７〜４Ｎｉ−１７〜５０Ｔａ
（原子％）アモルファス合金が好適である。Further, any amorphous alloy may be used as long as it has a lower corrosion potential than the stainless steel to be protected against corrosion, and various alloys can be used. For example, SUS 310
For corrosion protection of nitric acid-based stainless steel in nitric acid-based solution, 60 to 3
6Fe-16-10Cr-7-4Ni-17-50Ta
Amorphous alloys (at%) are preferred.
このようなアモルファス合金をステンレス鋼に導通させ
る方法としては、例えば、次の〜の方法が挙げられ
る。Examples of the method of conducting such an amorphous alloy to stainless steel include the following methods (1) to (3).
ステンレス鋼１とアモルファス合金２とをリード線３
で結線する（第１図（ａ））。この場合、アモルファス
合金２はブロック状のものであっても良く、薄片状など
その他の形状のものであっても良い。Lead wire 3 with stainless steel 1 and amorphous alloy 2
To connect (Fig. 1 (a)). In this case, the amorphous alloy 2 may have a block shape or may have another shape such as a flaky shape.
ステンレス鋼１とアモルファス合金２とを機械的に接
触させる（第１図（ｂ））。この場合の、アモルファス
合金の形状は任意である。The stainless steel 1 and the amorphous alloy 2 are mechanically contacted (Fig. 1 (b)). The shape of the amorphous alloy in this case is arbitrary.
ステンレス鋼１の防食対象領域１ａ以外に、アモルフ
ァス合金のコーティング膜２ａを形成する。この場合、
アモルファス合金のコーティング膜の形成方法として
は、従来より公知のスパッタリング法が採用される。膜
厚は１０〜４０μｍ程度とするのが好ましい。A coating film 2a of an amorphous alloy is formed on the stainless steel 1 in addition to the corrosion protection target area 1a. in this case,
As a method of forming the amorphous alloy coating film, a conventionally known sputtering method is adopted. The film thickness is preferably about 10 to 40 μm.
なお、アモルファス合金に対するステンレス鋼の面積比
が小さい程防食効果が高いことから、本発明において
は、腐食環境の程度によっても異なるが、上記面積比を
１以下、特に、０．５以下、とりわけ０．２以下とする
のが好ましい。The smaller the area ratio of the stainless steel to the amorphous alloy, the higher the anticorrosion effect. Therefore, in the present invention, the above area ratio is 1 or less, particularly 0.5 or less, and particularly 0, although it depends on the degree of corrosive environment. It is preferably not more than 0.2.
本発明の方法は、例えば原子力燃料容器の高温高濃度硝
酸のような腐食性の高い腐食液にさらされるステンレス
鋼のカソード防食等に極めて有効である。The method of the present invention is extremely effective for cathodic protection of stainless steel exposed to a highly corrosive corrosive liquid such as high temperature and high concentration nitric acid in a nuclear fuel container.
［作用］ 第２図に、高温濃硝酸（沸点、４〜１１規定ＨＮＯ３水
溶液）中でステンレス鋼（ＳＵＳ３１０Ｎｂ）とアモル
ファス合金（Ｔａ系）の腐食電位の関係を模式的に示
す。ステンレス鋼の腐食電位をＥ（ｓｕｓ）、アモルフ
ァス合金の腐食電位をＥ（Ａｍ）とすると、それぞれが
単独で浸漬されている場合は、それぞれｉ（ｓｕｓ）、
ｉ（Ａｍ）の腐食電流で腐食反応が進行することにな
る。[Operation] FIG. 2 schematically shows the relationship between the corrosion potentials of stainless steel (SUS310Nb) and amorphous alloys (Ta series) in high temperature concentrated nitric acid (boiling point, 4-11N HNO 3 aqueous solution). Assuming that the corrosion potential of stainless steel is E (sus) and the corrosion potential of amorphous alloy is E (Am), if each is immersed alone, i (sus),
Corrosion reaction proceeds at a corrosion current of i (Am).
一方、これらの材料を接触させると、そのときの混成電
位はＥ（ｓｕｓ）とＥ（Ａｍ）の間の値Ｅ（ｍｉｘ）と
なり、ステンレス鋼がカソード、アモルファス合金がア
ノードとなる。即ち、ステンレス鋼はカソードに分極さ
れる。On the other hand, when these materials are brought into contact with each other, the mixed potential at that time becomes a value E (mix) between E (sus) and E (Am), and the stainless steel serves as the cathode and the amorphous alloy serves as the anode. That is, stainless steel is polarized into the cathode.
ステンレス鋼についてみると、Ｅ（ｓｕｓ）ではアノー
ド反応（溶解反応）とカソード反応がｉ（ｓｕｓ）でつ
り合っているが、アモルファス合金と接することで、ア
ノード反応はｉ（ｓｕｓ）からｉＡへと減少する（カソ
ード反応はｉＢ）。すなわち、ステンレス鋼の溶解反応
はｉ（ｓｕｓ）からｉＡへと減少し、カソード防食され
ることになる。As for stainless steel, in E (sus), the anode reaction (dissolution reaction) and the cathode reaction are balanced by i (sus), but by contact with the amorphous alloy, the anode reaction changes from i (sus) to iA. Decrease (cathode reaction is iB). That is, the dissolution reaction of stainless steel is reduced from i (sus) to iA, and cathodic protection is performed.
一方、アモルファス合金についてみると、アノード反応
はｉ（Ａｍ）からｉＣへと増加し、アノード反応が促進
される方向に分極される。しかしながら、アモルファス
合金は、周知のように、原子配列に規則性のない非晶質
構造の金属であり、結晶質金属にはみられない物理的特
性、化学的特性を有し、その耐食性も著しく高いもので
あるため、アノード分極されても腐食が促進しないこと
から、腐食は殆ど増加しないことになる。On the other hand, regarding the amorphous alloy, the anodic reaction increases from i (Am) to iC and is polarized in a direction in which the anodic reaction is promoted. However, as is well known, an amorphous alloy is a metal having an amorphous structure with no regular atomic arrangement, has physical properties and chemical properties not found in crystalline metals, and its corrosion resistance is remarkably high. Since it is high, the corrosion does not accelerate even when it is anodically polarized, so that the corrosion hardly increases.
従って、本発明の方法によれば、ステンレス鋼をアモル
ファス合金により効果的にカソード防食することがで
き、しかも防食に用いるアモルファス合金も殆ど腐食を
受けることがなく、防食効果を長期間維持することがで
きる。Therefore, according to the method of the present invention, the stainless steel can be effectively cathodic protected by the amorphous alloy, and the amorphous alloy used for the corrosion is hardly corroded, and the anticorrosion effect can be maintained for a long time. it can.
［実施例］ 以下に実施例を挙げて本発明により具体的に説明する。[Examples] The present invention will be specifically described below with reference to Examples.
実施例１ ステンレス鋼及びアモルファス合金として、下記組成の
もの用い、アモルファス合金に対するステンレス鋼の面
積比を１、０．２、０．１と変えて、両者をリード線に
て接触させて下記試験液Ａ及びＢに対するガルバニック
腐食を調べた。なお、比較のため、各々単独で試験液Ａ
及びＢに浸漬した場合の腐食結果についても調べた。Example 1 A stainless steel and an amorphous alloy having the following compositions were used. The area ratio of stainless steel to the amorphous alloy was changed to 1, 0.2 and 0.1, and both were contacted with a lead wire to make the following test solution. The galvanic corrosion on A and B was investigated. For comparison, test liquid A was used alone.
The results of corrosion when immersed in B and B were also examined.
ステンレス鋼組成（重量％） Ｃｒ：２５ Ｎｉ：２０ Ｎｂ：０．２〜０．３ Ｆｅ：残部 アモルファス合金組成（原子％） Ｆｅ：６０〜３６ Ｃｒ：１６〜１０ Ｎｉ： ７〜 ４ Ｔａ：１７〜５０ 試験液 Ａ液：５価バナジウムイオン３ｇ／を含む４Ｎ硝酸 Ｂ液：１１Ｎ硝酸 なお、上記の試験液中における各材料の腐食電位は下記
の通りであり、ステンレス鋼に対してアモルファス合金
は常に低い電位であるため、ステンレス鋼はアモルファ
ス合金と接触するとカソード防食されることになる。Stainless steel composition (% by weight) Cr: 25 Ni: 20 Nb: 0.2 to 0.3 Fe: balance Amorphous alloy composition (atomic%) Fe: 60 to 36 Cr: 16 to 10 Ni: 7 to 4 Ta: 17 ˜50 Test liquid A liquid: 4N nitric acid containing pentavalent vanadium ions 3 g / B liquid: 11N nitric acid The corrosion potential of each material in the above test liquid is as follows. Because of the low potential at all times, stainless steel will be cathodic protected when in contact with amorphous alloys.
ステンレス鋼：７６０〜８６０ｍＶ アモルファス合金：７００〜７２０ｍＶ 試験結果を第３図に示す。Stainless steel: 760-860 mV Amorphous alloy: 700-720 mV The test results are shown in FIG.
第３図より、次のことが明らかである。即ち、Ａ液中で
は、面積比が１ではステンレス鋼の腐食量はアモルファ
ス合金と接触していない場合と大差はないが、面積比が
０．２になると腐食量は約1/2に、０．１では約1/3に減
少する。Ｂ液においては、面積比が１でも腐食量は約1/
2となり、優れた防食効果が得られている。The following is clear from FIG. That is, in liquid A, when the area ratio is 1, the corrosion amount of stainless steel is not much different from that when it is not in contact with the amorphous alloy, but when the area ratio is 0.2, the corrosion amount is about 1/2, 0 It decreases to about 1/3 at 1. In liquid B, even if the area ratio is 1, the amount of corrosion is about 1 /
2, which is an excellent anticorrosion effect.
［発明の効果］ 以上詳述した通り、本発明のステンレス鋼のカソード防
食法によれば、従来困難とされていた、高温濃硝酸等の
苛酷な環境下におけるステンレス鋼の腐食を効果的に防
止することができる。しかも、カソード防食の陽極とし
ても用いる材料自体が耐食性に優れたアモルファス合金
であるため、全体としても腐食量は低減され、防食効果
の持続性にも極めて優れる。[Effects of the Invention] As described in detail above, according to the method for cathodic protection of stainless steel of the present invention, it is possible to effectively prevent the corrosion of stainless steel in a harsh environment such as high temperature concentrated nitric acid, which has been conventionally difficult. can do. Moreover, since the material itself used also as the cathode for cathodic protection is an amorphous alloy having excellent corrosion resistance, the amount of corrosion is reduced as a whole and the anticorrosion effect is extremely excellent in sustainability.
第１図（ａ）〜（ｃ）は各々本発明の一実施例を示す概
略図、第２図は材料の腐食電位を示すグラフ、第３図は
実施例１の結果を示す図である。 １……ステンレス鋼、 ２……アモルファス合金、 ３……リード線。1 (a) to 1 (c) are schematic views showing one embodiment of the present invention, FIG. 2 is a graph showing the corrosion potential of a material, and FIG. 3 is a view showing the results of the first embodiment. 1 ... Stainless steel, 2 ... Amorphous alloy, 3 ... Lead wire.
Claims (1)
食電位の低いアモルファス合金を導通させることを特徴
とするステンレス鋼のカソード防食法。1. A method of cathodic protection for stainless steel, characterized in that an amorphous alloy having a lower corrosion potential than that of the stainless steel is conducted to the stainless steel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63214337A JPH0613757B2 (en) | 1988-08-29 | 1988-08-29 | Cathodic protection of stainless steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63214337A JPH0613757B2 (en) | 1988-08-29 | 1988-08-29 | Cathodic protection of stainless steel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0261080A JPH0261080A (en) | 1990-03-01 |
| JPH0613757B2 true JPH0613757B2 (en) | 1994-02-23 |
Family
ID=16654091
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63214337A Expired - Fee Related JPH0613757B2 (en) | 1988-08-29 | 1988-08-29 | Cathodic protection of stainless steel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0613757B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007095318A (en) * | 2005-09-27 | 2007-04-12 | Daido Steel Co Ltd | Corrosion-resistant member, fuel cell separator and fuel cell |
| CA2706215C (en) | 2010-05-31 | 2017-07-04 | Corrosion Service Company Limited | Method and apparatus for providing electrochemical corrosion protection |
-
1988
- 1988-08-29 JP JP63214337A patent/JPH0613757B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0261080A (en) | 1990-03-01 |
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