JPH0328516B2 - - Google Patents
Info
- Publication number
- JPH0328516B2 JPH0328516B2 JP62060408A JP6040887A JPH0328516B2 JP H0328516 B2 JPH0328516 B2 JP H0328516B2 JP 62060408 A JP62060408 A JP 62060408A JP 6040887 A JP6040887 A JP 6040887A JP H0328516 B2 JPH0328516 B2 JP H0328516B2
- Authority
- JP
- Japan
- Prior art keywords
- reference electrode
- potential
- temperature
- copper
- zinc
- 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
- 239000013505 freshwater Substances 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 description 15
- 230000007797 corrosion Effects 0.000 description 13
- 239000002184 metal Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000004210 cathodic protection Methods 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical class [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 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」
この発明は、淡水用特に高温淡水用に適したパ
ーマネント型照合電極に関する。DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a permanent reference electrode suitable for fresh water use, particularly for high-temperature fresh water use.
「従来技術」
火力発電所、製鉄所、石油化学工場等の熱交換
器或いはホテル、学校、病院等で用いられている
貯湯槽や温水器の内面防食に電気防食法を採用す
るに際して、必要防食電流（直流）を供給して初
めて防食が達成される訳であるが、その必要防食
電流はその金属の完全防食電位値によつて決定さ
れる。``Prior art'' The necessary corrosion protection is required when applying the cathodic protection method to prevent internal corrosion of heat exchangers in thermal power plants, steel mills, petrochemical factories, etc., or internal corrosion protection of hot water tanks and water heaters used in hotels, schools, hospitals, etc. Corrosion protection is achieved only by supplying a current (direct current), and the required corrosion protection current is determined by the complete corrosion protection potential value of the metal.
例えば、鉄鋼を電気防食する場合、飽和甘汞照
合電極基準で淡水中に於ける鉄の自然電位が−
300〜−600ｍＶ（温度によつて変化）であるから、
完全防食電位の−770ｍＶ迄防食電流を供給し陰
分極させる必要がある。 For example, when cathodic protection is applied to steel, the natural potential of iron in fresh water is -
Since it is 300 to -600 mV (varies depending on temperature),
It is necessary to supply an anti-corrosion current up to the complete anti-corrosion potential of -770 mV to achieve cathodic polarization.
上記の完全防食電位の計測は上述の如く基準と
なる照合電極を用いて行なわれる。 The measurement of the complete corrosion protection potential is performed using the reference electrode as described above.
この場合、基準照合電極としては、飽和甘汞照
合電極（−770ｍＶ）、飽和硫酸銅照合電極（−
850ｍＶ）、海水塩化銀照合電極（−780ｍＶ）等
が鉄鋼との対応から周知である。〔（ ）内はいず
れも鉄鋼の防食電位で、以下同じ。〕
これ等は何れもガラス管やプラスチツク管内部
に緩衝液として電解質溶液を充填して態様で使わ
れている。 In this case, the reference reference electrodes are a saturated Amane reference electrode (-770 mV), a saturated copper sulfate reference electrode (-
850 mV), seawater silver chloride reference electrode (-780 mV), etc. are well known because of their correspondence with steel. [The numbers in parentheses are the corrosion protection potentials of steel, and the same applies below. ] All of these are used in the form of filling an electrolyte solution as a buffer inside a glass tube or plastic tube.
一方、かかる電解質溶液を充填する必要のない
剥き出しの金属照合電極として、鉄照合電極（約
−200〜−300ｍＶ）、亜鉛照合電極（約＋200〜＋
280ｍＶ）、鉛照合電極（約−50〜０ｍＶ）等があ
るが、鉄照合電極にあつては酸化被膜の形成で電
位が不安定となること、亜鉛照合電極にあつては
温度で電位不安定であり固有電位が卑なために腐
食を伴うという不都合があり、採用することはで
きない。 On the other hand, as bare metal reference electrodes that do not need to be filled with such an electrolyte solution, iron reference electrodes (approximately -200 to -300 mV) and zinc reference electrodes (approximately +200 to +
280 mV), lead reference electrodes (approximately -50 to 0 mV), etc. However, with iron reference electrodes, the potential becomes unstable due to the formation of an oxide film, and with zinc reference electrodes, the potential becomes unstable due to temperature. However, it cannot be used because it has the disadvantage of corrosion due to its low inherent potential.
「発明が解決しようとする問題点」
しかるに、上記の一般に認められている基準照
合電極は熱的、強度的に極めて脆弱であり、長期
に渡るプラント内部への設置が不可能である。``Problems to be Solved by the Invention'' However, the above-mentioned generally accepted reference reference electrode is extremely fragile in terms of heat and strength, and cannot be installed inside a plant for a long period of time.
そこで、従来は例えば貯湯槽の防食では実際の
電位を計測出来ないまま設計電流をそのまま通電
している。 Therefore, conventionally, for example, in corrosion protection of a hot water storage tank, the design current is passed without being able to measure the actual potential.
しかし、水質、温度、塗膜、ヒーターの有無等
に応じた適正電流量が供給され防食電位が維持さ
れないかぎり腐食に至る。すなわち、高温淡水用
パーマネント型照合電極が未開発であるばかり
に、適正な防食管理が出来ず、貯湯槽等では腐食
事故に至る事例が多く、電気防食への信頼を失い
兼ねない状態になつているのが実情である。 However, unless an appropriate amount of current is supplied depending on the water quality, temperature, coating film, presence or absence of a heater, etc. and the anticorrosion potential is maintained, corrosion will occur. In other words, as permanent reference electrodes for high-temperature freshwater have not yet been developed, proper corrosion protection cannot be managed, and there are many cases of corrosion accidents in hot water tanks, etc., and there is a risk of losing trust in cathodic protection. The reality is that there are.
「問題点を解決するための手段」、「作用」
本発明は上述の事情に鑑みなされたもので、そ
の要旨とするところは、銅50〜80％、亜鉛50％未
満、鉛12％以下、錫12％以下である銅−亜鉛合金
より成る常高温の淡水等の電解質中に在する各種
金属の電位を計測するに際して用いられる金属製
パーマネント型銅・亜鉛照合電極を提供すること
により、周知の概存照合電極電位と近似した値を
安定して有して、熱的、強度上の問題点を解消し
て設置条件を有利にすると共にその材質上腐食し
ないために電流の流出がない利点を奏し、電気防
食への信頼を回復するとした点にある。"Means for Solving Problems" and "Operation" The present invention was made in view of the above-mentioned circumstances, and its gist is that copper 50 to 80%, zinc 50% or less, lead 12% or less, By providing a metallic permanent copper-zinc reference electrode that is used to measure the potential of various metals present in an electrolyte such as room-temperature fresh water, which is made of a copper-zinc alloy containing 12% or less tin, we have achieved the well-known It stably has a value close to the general reference electrode potential, which eliminates thermal and strength problems and provides favorable installation conditions.The material also has the advantage of not corroding, so there is no current flow. The aim is to restore confidence in cathodic protection.
「実施例」 以下、これを詳細に説明する。"Example" This will be explained in detail below.
本発明者は既述の既存の照合電極がその構造か
ら熱的、強度上の問題点を有して設置不可である
ことから、あくまでも強度上心配のない金属製パ
ーマネント型の電極の開発を目指し、種々研究の
結果、銅−亜鉛合金に於いて、銅50〜80％、亜鉛
50％以下、鉛０〜12％以下、スズ０〜12％以下の
成分として、このものの対温安定性を調べると、
他の金属製パーマネント型の電極よりもすぐれて
いた。すなわち、第１図は本発明になる銅−亜鉛
合金（サンプルNo.１〜９）と他の金属（サンプル
No.10〜14）の金属組成を示したものであり、これ
らサンプルに対して飽和甘汞照合電極基準のもと
で、各温度における電位を測定した結果を第２図
に示す。 Since the existing reference electrodes mentioned above have thermal and strength problems due to their structure and cannot be installed, the inventor aims to develop a permanent metal electrode that does not have to worry about strength. As a result of various studies, copper-zinc alloy contains 50-80% copper and zinc.
Examining the temperature stability of this material as a component of 50% or less, lead 0-12% or less, and tin 0-12% or less, we find that:
It was superior to other permanent metal electrodes. That is, Figure 1 shows the copper-zinc alloys of the present invention (sample Nos. 1 to 9) and other metals (sample No. 9).
Fig. 2 shows the metal compositions of samples Nos. 10 to 14), and the results of measuring the potentials of these samples at various temperatures using a saturated Amane reference electrode standard are shown in Fig. 2.
又、第３図はサンプルNo.12（亜鉛）、13（鉛）及
び14（鉄SS41）を除く銅系金属の経時変化を対比
した結果である。第２図の結果を図表化すると第
３図の如くで、純胴サンプルNo.11は温度の上昇と
共に大きく自然電位(E)が貴化しているのが解る。
その他銅合金は温度の上昇で卑化する傾向である
が、特にサンプルNo.10は他の合金と異なり亜鉛と
鉛がなく、Ｐの成分が多いことによつてか卑化の
傾向が大きい。 Furthermore, Fig. 3 shows the results of comparing the changes over time of copper-based metals except for samples No. 12 (zinc), 13 (lead), and 14 (iron SS41). When the results in Figure 2 are graphed, Figure 3 shows that the natural potential (E) of pure shell sample No. 11 becomes more noble as the temperature rises.
Other copper alloys tend to become baser as the temperature rises, but Sample No. 10 in particular has a strong tendency to become baser because unlike other alloys, it does not contain zinc or lead and has a large P component.
照合電極は温度の影響を受けにくいことが望ま
しので、サンプルNo.１〜９はCu、Zn、Su、Pbの
合金で前者の合金に比較して余り大きな電位変化
を起こしていないゆえに最も望ましい。かくし
て、温度差50℃程度の温度変化のもとで、プラス
側でも、またマイナス側でも20ｍｖ以下程度の安
定した電位を呈する金属製パーマネント型照合電
極が開発された訳である。 It is desirable that the reference electrode be less affected by temperature, so samples No. 1 to 9 are alloys of Cu, Zn, Su, and Pb, which are most desirable because they do not cause a large potential change compared to the former alloy. . Thus, a permanent metal reference electrode was developed that exhibits a stable potential of about 20 mV or less on both the positive and negative sides under temperature changes of about 50°C.
なを、本発明による照合電極は高温淡水はもち
ろんのこと、常温淡水でも、常温淡水を加温して
いる過程においても使用することができる。 Furthermore, the reference electrode according to the present invention can be used not only for high-temperature fresh water, but also for room-temperature fresh water, or during the process of heating room-temperature fresh water.
上述の如く、本発明に係る照合電極は金属製で
あるので取り付けに際する強度は充分にあり、第
４図に示す如き要領にて貯湯槽等の熱交換器類に
組付けすることが可能である。 As mentioned above, since the reference electrode according to the present invention is made of metal, it has sufficient strength during installation, and can be assembled into a heat exchanger such as a hot water tank as shown in Fig. 4. It is.
すなわち、第４図は貯湯槽本体１に対する本発
明の高温淡水用パーマネント型照合電極２（電位
検知センサー）の組付構造を示す断面図で、該本
体１の穿孔に溶接着のソケツト３に電極ケースと
してのパイプ４を螺合着し、更に、前者照合電極
２に絶縁スリーブ５を捲着し、基部のリード線７
止着部を樹脂モールド６にて被覆したところの電
極２を挿着し、カツプリング本体１０に挿入され
たシール用パツキン８を介してカツプリング９止
めにて組付けしている。しかして本体１外側より
防食系内部の電解質中に電線配線を行なう必要な
く簡易に取り付け、並びに交換がなし得る。 That is, FIG. 4 is a sectional view showing the assembly structure of the permanent reference electrode 2 (potential detection sensor) for high-temperature freshwater according to the present invention to the main body 1 of the hot water storage tank. A pipe 4 as a case is screwed together, an insulating sleeve 5 is wrapped around the former reference electrode 2, and a lead wire 7 at the base is attached.
The electrode 2 whose fixing portion is covered with a resin mold 6 is inserted and assembled with a coupling 9 through a sealing packing 8 inserted into the coupling body 10. Therefore, it is possible to easily install and replace the main body 1 without having to run electric wires from the outside to the electrolyte inside the anticorrosive system.
「発明の効果」
以上の如く、本発明によるならば、熱的、強度
的問題を有せず既存の照合電極と近似した電位の
安定した金属製パーマネント型照合電極が提供さ
れるので、貯湯槽等での電気防食への信頼を確保
し得極めて有意義である。"Effects of the Invention" As described above, according to the present invention, a permanent metal reference electrode which does not have thermal or strength problems and has a stable potential similar to that of existing reference electrodes is provided. This is extremely meaningful as it can ensure trust in cathodic protection.
第１〜３図は本発明内容を示す各種結果の図
表、第４図は本発明品の貯湯槽に対する組付態様
図である。
１……貯湯槽本体、２……高温淡水用パーマネ
ント型照合電極、３……ソケツト、４……パイ
プ、５……絶縁スリーブ、６……樹脂モールド、
７……リード線、８……シール用パツキン、９…
…カツプリング、１０……カツプリング本体。
1 to 3 are charts showing various results showing the content of the present invention, and FIG. 4 is a diagram showing how the product of the present invention is assembled into a hot water storage tank. 1...Hot water tank body, 2...Permanent reference electrode for high temperature fresh water, 3...Socket, 4...Pipe, 5...Insulating sleeve, 6...Resin mold,
7...Lead wire, 8...Seal packing, 9...
...Cup ring, 10...Cup ring body.
Claims (1)
12％以下である銅−亜鉛合金より成る淡水用特に
高温淡水用に適したパーマネント型照合電極。1 50-80% copper, less than 50% zinc, less than 12% lead, tin
A permanent reference electrode made of a copper-zinc alloy with a content of 12% or less, suitable for freshwater applications, especially high-temperature freshwater applications.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62060408A JPS63227789A (en) | 1987-03-16 | 1987-03-16 | Permanent reference electrode for hot fresh water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62060408A JPS63227789A (en) | 1987-03-16 | 1987-03-16 | Permanent reference electrode for hot fresh water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63227789A JPS63227789A (en) | 1988-09-22 |
| JPH0328516B2 true JPH0328516B2 (en) | 1991-04-19 |
Family
ID=13141322
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62060408A Granted JPS63227789A (en) | 1987-03-16 | 1987-03-16 | Permanent reference electrode for hot fresh water |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63227789A (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59129873U (en) * | 1983-02-09 | 1984-08-31 | 株式会社東芝 | Reference electrode for cathodic protection |
-
1987
- 1987-03-16 JP JP62060408A patent/JPS63227789A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63227789A (en) | 1988-09-22 |
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