JP4539199B2 - Zinc alloy galvanic anode and method for galvanic protection of equipment placed in a high temperature environment using the zinc alloy galvanic anode - Google Patents
Zinc alloy galvanic anode and method for galvanic protection of equipment placed in a high temperature environment using the zinc alloy galvanic anode Download PDFInfo
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- JP4539199B2 JP4539199B2 JP2004197631A JP2004197631A JP4539199B2 JP 4539199 B2 JP4539199 B2 JP 4539199B2 JP 2004197631 A JP2004197631 A JP 2004197631A JP 2004197631 A JP2004197631 A JP 2004197631A JP 4539199 B2 JP4539199 B2 JP 4539199B2
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- 229910001297 Zn alloy Inorganic materials 0.000 title claims description 36
- 238000000034 method Methods 0.000 title claims description 6
- 238000005260 corrosion Methods 0.000 claims description 7
- 230000007797 corrosion Effects 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 230000005611 electricity Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- 239000013535 sea water Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Prevention Of Electric Corrosion (AREA)
Description
この発明は、亜鉛合金流電陽極およびその亜鉛合金流電陽極を用いて高温環境、特に５０℃以上の高温海水環境に置かれた設備を流電防食する方法に関するものである。 The present invention relates to a zinc alloy galvanic anode and a method for galvanic protection of equipment placed in a high temperature environment, particularly a high temperature seawater environment of 50 ° C. or higher, using the zinc alloy galvanic anode.
一般に、常温海水環境下で流電防食する時に使用される亜鉛合金流電陽極としてＭＩＬ規格（ＵＳ Ｍｉｌ Ｓｐｅｃ．Ａ１８００１Ｊ）やＡＳＴＭ規格（ＡＳＴＭＢ４１８−８８ Ｔｙｐｅ Ｉ）が推奨され用いられていた。この亜鉛合金流電陽極は流電陽極として優れた性能を有しているが、この亜鉛合金流電陽極は有害物質であると考えられているＣｄ：０．０２５〜０．０７質量％を含有するために、近年、Ｃｄを含まない亜鉛合金流電陽極が求められるようになってきた。かかるＣｄを含まない亜鉛合金流電陽極の一例として、Ａｌ：０．０１〜０．４質量％、Ｓｎ：０．０２〜０．２質量％未満を含有し、残部がＺｎおよび０．０１質量％以下の不可避不純物からなる組成を有する亜鉛合金流電陽極が知られている（特許文献１参照）。
前記従来のＣｄを含まない亜鉛合金流電陽極は常温において優れた流電防食作用を奏するものであるが、５０℃以上の高温環境、特に５０℃以上の海水中において粒界腐食を起こし、有効電気量が早期に低下するという問題点があった。 The conventional zinc alloy galvanic anode containing no Cd exhibits excellent galvanic anticorrosive action at room temperature, but causes intergranular corrosion in a high temperature environment of 50 ° C. or higher, particularly in seawater of 50 ° C. or higher. There was a problem that the amount of electricity was reduced early.
そこで、本発明者らは、これらの課題を解決すべく研究を行った結果、前記従来のＣｄを含まない亜鉛合金流電陽極において、Ｓｎ含有量を低減させてＳｎ含有量を０．０００５〜０．０２質量％未満に限定した亜鉛合金流電陽極は、５０℃以上の高温環境、特に５０℃以上の海水中において粒界腐食を起こし難くなり、有効電気量が早期に低下することはない、という研究結果が得られたのである。 Therefore, as a result of researches to solve these problems, the present inventors have reduced the Sn content in the conventional zinc alloy galvanic anode not containing Cd and reduced the Sn content to 0.0005 to 0.05. The zinc alloy galvanic anode limited to less than 0.02% by mass is less likely to cause intergranular corrosion in a high temperature environment of 50 ° C. or higher, particularly in seawater of 50 ° C. or higher, and the effective amount of electricity does not decrease early. The research result was obtained.
この発明は、かかる研究結果に基づいてなされたものであって、
（１）Ａｌ：０．０３〜０．５質量％、Ｓｎ：０．０００５〜０．０２質量％未満を含有し、残部がＺｎおよび不可避不純物からなる組成を有する亜鉛合金流電陽極、
（２）亜鉛合金流電陽極を用いて５０℃以上の高温環境下に置かれた設備を電気防食する方法において、亜鉛合金流電陽極としてＡｌ：０．０３〜０．５質量％、Ｓｎ：０．０００５〜０．０２質量％未満を含有し、残部がＺｎおよび不可避不純物からなる組成を有する亜鉛合金流電陽極を用いる高温環境下に置かれた設備の流電防食方法、に特徴を有するものである。
The present invention has been made based on the results of such research,
(1) Al: 0.03 to 0.5% by mass, Sn: 0.0005 to less than 0.02% by mass, a zinc alloy galvanic anode having a composition consisting of Zn and inevitable impurities,
(2) In a method of using a zinc alloy fluid anode to catalyze equipment placed in a high temperature environment of 50 ° C. or higher, Al: 0.03 to 0.5 mass% as a zinc alloy fluid anode, Sn: Featuring a galvanic anticorrosion method for equipment placed in a high temperature environment using a zinc alloy galvanic anode containing 0.0005 to less than 0.02% by mass and the balance being composed of Zn and inevitable impurities Is.
この発明の亜鉛合金流電陽極の成分組成を前述の如く限定した理由を説明する。Ａｌ：
Ａｌは高純度亜鉛地金に合金化させることで、流電陽極性能（陽極電位、有効電気量、溶解状態）を向上させる作用があり、さらに不可避不純物として含まれるＦｅの悪影響を抑制し、腐食生成物を軟化させる作用があるが、その含有量が０．０３質量％未満では十分な効果が得られず、一方、０．５質量％を越えて添加すると、有効電気量の低下が顕著になるので好ましくない。したがって、この発明の亜鉛合金流電陽極に含まれるＡｌの含有量を０．０３〜０．５質量％に定めた。一般的な製造設備で生産し、かつ安定した高性能品を得るにはＡｌ：０．１〜０．３質量％の範囲内にあることが好ましいので、一層好ましい範囲はＡｌ：０．１〜０．３質量％に定めた。
The reason why the component composition of the zinc alloy galvanic anode of this invention is limited as described above will be described. Al:
Al alloyed with high-purity zinc ingots has the effect of improving the galvanic anode performance (anode potential, effective amount of electricity, dissolved state), further suppressing the adverse effects of Fe contained as inevitable impurities, and corrosive Although there is an effect of softening the product, if the content is less than 0.03% by mass, a sufficient effect cannot be obtained. On the other hand, when the content exceeds 0.5% by mass, the reduction in the effective electricity amount is remarkable. This is not preferable. Therefore, the content of Al contained in the zinc alloy galvanic anode of this invention is set to 0.03 to 0.5% by mass. In order to obtain a stable high-performance product that is produced by general manufacturing equipment, it is preferable that Al is in the range of 0.1 to 0.3% by mass, so a more preferable range is Al: 0.1 to 0.1% by mass. It was set to 0.3% by mass.
Ｓｎ：
Ｓｎは不純物が低濃度である高純度亜鉛およびＺｎ−Ａｌ合金に対して、極微量の添加で流電陽極性能（陽極電位、有効電気量）を向上させる作用があるが、その含有量が０．０００５質量％未満では所望の効果が得られないので好ましくなく、一方、０．０２質量％以上添加すると、高温環境下において粒界腐食が進行し、短期間で有効電気量が低下するので好ましくない。したがって、この発明の亜鉛合金流電陽極に含まれるＳｎの含有量を０．０００５〜０．０２質量％未満に定めた。一層好ましい範囲は、０．００１〜０．０１質量％である。
Sn:
Sn has the effect of improving the galvanic anode performance (anode potential, effective electric quantity) by adding a trace amount to high-purity zinc and Zn-Al alloys with low impurity concentration, but its content is 0 If less than .0005 mass%, the desired effect cannot be obtained, which is not preferable. On the other hand, when 0.02 mass% or more is added, intergranular corrosion proceeds in a high-temperature environment, and the effective amount of electricity decreases in a short period. Absent. Therefore, the content of Sn contained in the zinc alloy galvanic anode of the present invention is set to 0.0005 to less than 0.02% by mass. A more preferable range is 0.001 to 0.01% by mass.
この発明の亜鉛合金流電陽極は、高温環境、特に５０℃以上の高温海水環境に置かれた設備を流電防食する際に、粒界腐食速度が小さいところから、長期間有効電気量が低下することがないと言う優れた効果を奏するものである。 The zinc alloy galvanic anode of the present invention has a low long-term effective electricity amount due to its low intergranular corrosion rate when galvanically preventing equipment placed in a high temperature environment, particularly in a high temperature seawater environment of 50 ° C. or higher. There is an excellent effect that there is nothing to do.
ＪＩＳ Ｈ ２１０７に規定される高純度亜鉛地金を黒鉛ルツボにて溶解し、これに所定量のＡｌおよびＳｎを添加して表１に示す成分組成の亜鉛合金溶湯を作製し、これら亜鉛合金溶湯を鋳造して直径：１５ｍｍの丸棒テストピースからなる本発明亜鉛合金流電陽極１〜１３、比較亜鉛合金流電陽極１〜３および従来亜鉛合金流電陽極１を作製した。これら本発明亜鉛合金流電陽極１〜１３、比較亜鉛合金流電陽極１〜３および従来亜鉛合金流電陽極１を８０℃および５０℃の人工海水中にそれぞれ浸漬し、陽極電流密度：１ｍＡ／ｃｍ２の通電条件で３０日間流電陽極試験を行い、陽極電位と有効電気量を求め、その結果を表１に示した。 A high-purity zinc ingot specified in JIS H 2107 is melted with a graphite crucible, and a predetermined amount of Al and Sn are added thereto to produce molten zinc alloys having the composition shown in Table 1, and these molten zinc alloys The zinc alloy current flowing anodes 1 to 13, the comparative zinc alloy current flowing anodes 1 to 3, and the conventional zinc alloy current flowing anode 1 comprising round bar test pieces having a diameter of 15 mm were produced. These zinc alloy galvanic anodes 1 to 13, comparative zinc alloy galvanic anodes 1 to 3 and conventional zinc alloy galvanic anode 1 were immersed in artificial seawater at 80 ° C. and 50 ° C., respectively, and an anode current density of 1 mA / A galvanic anode test was conducted for 30 days under a current-carrying condition of cm 2 , and the anode potential and effective amount of electricity were determined. The results are shown in Table 1.
表１に示される結果から、本発明亜鉛合金流電陽極１〜１３を使用して流電防食を行うと、３０日経過しても有効電気量がいずれも８００A・ｈ／ｋｇ以上有するに対し、従来亜鉛合金流電陽極１を使用して３０日間流電防食を行うと有効電気量がいずれも８００A・ｈ／ｋｇ未満となり、有効電気量が低下することが分かる。また、この発明の条件から外れた組成を有する比較亜鉛合金流電陽極１〜３も８００A・ｈ／ｋｇ未満となり、有効電気量が低下することが分かる。 From the results shown in Table 1, when galvanic corrosion protection is performed using the zinc alloy galvanic anodes 1 to 13 of the present invention, the effective electricity amount is 800 A · h / kg or more even after 30 days. It can be seen that when the conventional zinc alloy galvanic anode 1 is used for 30 days to prevent galvanic corrosion, the effective electricity amount is less than 800 A · h / kg, and the effective electricity amount is reduced. Further, it can be seen that the comparative zinc alloy galvanic anodes 1 to 3 having a composition deviating from the conditions of the present invention are also less than 800 A · h / kg, and the effective electricity amount is reduced.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53100125A (en) * | 1977-02-14 | 1978-09-01 | Nippon Boshoku Kogyo Kk | Zinc alloy for galvanic anode |
| JP2001519478A (en) * | 1997-10-02 | 2001-10-23 | フルー・コーポレイシヨン | Cathodic protection method and apparatus |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53100125A (en) * | 1977-02-14 | 1978-09-01 | Nippon Boshoku Kogyo Kk | Zinc alloy for galvanic anode |
| JP2001519478A (en) * | 1997-10-02 | 2001-10-23 | フルー・コーポレイシヨン | Cathodic protection method and apparatus |
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