EP0651075A1 - Selbstverzehrende Anode für den kathodischen Korrosionschutz aus einer Aluminiumlegierung - Google Patents

Selbstverzehrende Anode für den kathodischen Korrosionschutz aus einer Aluminiumlegierung Download PDF

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Publication number
EP0651075A1
EP0651075A1 EP94402419A EP94402419A EP0651075A1 EP 0651075 A1 EP0651075 A1 EP 0651075A1 EP 94402419 A EP94402419 A EP 94402419A EP 94402419 A EP94402419 A EP 94402419A EP 0651075 A1 EP0651075 A1 EP 0651075A1
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EP
European Patent Office
Prior art keywords
max
seawater
aluminum
cathodic protection
steels
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EP94402419A
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English (en)
French (fr)
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EP0651075B1 (de
Inventor
Hervé Le Guyader
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Direction General pour lArmement DGA
Etat Francais
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Direction General pour lArmement DGA
Etat Francais
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
    • C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
    • C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
    • C23F13/12—Electrodes characterised by the material
    • C23F13/14—Material for sacrificial anodes

Definitions

  • the present invention relates to a reactive or consumable anode made of an aluminum-based alloy for cathodic protection in sea water of iron, steels and alloys sensitive to corrosion and to embrittlement by hydrogen.
  • the performances and the electrochemical characteristics of such an anode which are mainly the electrochemical potential at zero flow, the current delivered per unit area at a given potential, the electrochemical yield, the mass energy or quantity of current delivered per unit mass of anode dissolved in Ampere-hours per kilogram, are determined by the alloy of which the reactive anode is made.
  • Patent FR 2 377 455 describes alloy compositions comprising weight percentages of aluminum or zinc of 8 to 40%, the rest being made of zinc or aluminum.
  • Aluminum-based alloys with an addition of zinc they have impurities of iron, silicon, copper and must have a purity at least equal to 99, 80%.
  • Electrode potential stabilizers, such as mercury, indium, manganese, titanium can be added.
  • Patent FR 2 449 730 discloses a protective alloy composition based on aluminum containing gallium in the proportions of 0.005 to 3.5% by weight and magnesium in the proportions of 0.1 to 1% by weight, and having good electrochemical properties.
  • a marine protection aluminum alloy containing 0.04% by weight of mercury and from 2 to 4.5% by weight of zinc, with impurities of iron, silicon, titanium, having a high specific energy of 2790 Ampere-hours per kilogram.
  • This alloy is effective at a potential below - 1045 mV / DHW, with a current density of 1.5 mA / cm2.
  • an aluminum alloy for marine protection comprising 0.02% by weight of indium and 5% by weight of zinc, with a lower mass energy than the previous one.
  • Patent FR 2 616 806 describes an aluminum-based alloy composition containing percentages by weight of indium from 0.005 to 0.05, of zinc from 0.05 to 8, of gallium of 0.003 to 0.05, manganese from 0.01 to 0.3, iron from 0.03 to 0.3 and magnesium from 0.02 to 2 and silicon from 0.03 to 0.4.
  • the aim of the invention is therefore to propose a reactive or consumable anode for cathodic protection, made from a certain alloy composition based on aluminum and capable of operating in a limited potential range of - 870 mV to - 700 mV by reference to the potential of a saturated calomel electrode, which corresponds to the field in which the hydrogen embrittlement of steels and alloys with high yield strength is low.
  • the reactive anodes according to the invention make it possible to correctly protect from generalized corrosion and from corrosion by galvanic coupling of moderately alloyed steels, in particular with the nickel element, in the field of cathodic potential included in the range from - 870 mV to - 700 mV / DHW, different from the usual range from - 850 mV to - 1100 mV / DHW. In this protection area, the kinetics of hydrogen evolution are significantly reduced.
  • the subject of the invention is therefore a reactive anode for the cathodic protection in seawater of steels and alloys against corrosion in seawater and hydrogen embrittlement, characterized in that it is made of an alloy based of aluminum cast on a steel fixing and electrical conduction support, the aluminum-based alloy comprising the following composition indicated in percentage by weight: Gallium or Cadmium 0.03 to 0.20% Manganese 0.15% max Iron 0.15% max Silicon 0.15% max Zinc 0.15% max Indium 0.007% max Mercury 0.007% max Magnesium 0.10% max Titanium 0.02% max Various 0.01% max Aluminum the rest, and operating in a range of electrochemical potential in seawater from - 870 mV to - 700 mV by reference to the potential of a saturated calomel electrode.
  • the percentage by weight of gallium is preferably equal to 0.1%.
  • the aluminum-based alloy composition comprises cadmium in a range of values from 0.03 to 0.20% by weight as a replacement for gallium.
  • the percentage by weight of cadmium is preferably equal to 0.1%.
  • the aluminum-based alloy composition comprises cadmium in a range of values from 0.03 to 0.20% by weight in addition to the alloy composition already comprising gallium in the range of 0.03 to 0.20% by weight.
  • the cathodic protection anode according to the invention can comprise at least one steel wedging strip for regulating the anode potential at low flow rate.
  • the cathode protection anode is characterized in that the surface area ratio between the aluminum-based alloy part and the lamella (s) is less than 5, preferably equal to 1.5.
  • Figure 1 is a sectional view of a reactive anode according to the invention.
  • the reactive cathode protection anode comprises a cylindrical part 2 of an aluminum-based alloy having the electrochemical properties targeted for protection, cast on a core 3 or support for fixing and electrical conduction and one or more lamellae 1 of wedging in steel.
  • the lamellae serve as anode potential regulators at low flow rates, since aluminum alloys have an unstable potential at low flow rates.
  • the aluminum alloy according to the invention has a gallium content which can vary from 0.03 to 0.20% by weight and preferably equal to 0.1%.
  • the contents of manganese, iron, zinc, silicon are at most 0.15% by weight, those of indium and mercury at most 0.007% by weight, that of magnesium at most 0.10% by weight, that of titanium up to 0.02% in weight.
  • the basic aluminum has a purity at least equal to 99.80% by weight.
  • This alloy is due to gallium, according to a mechanism of anodic dissolution of gallium in solid solution, then precipitation of the finely divided metal on the surface of aluminum.
  • Gallium while promoting the uniform activation of the anode surface, helps maintain a constant anode potential.
  • titanium in the form of Ti ⁇ makes it possible to control the particle size in the desired range.
  • Another alloy composition according to the invention comprises a content of 0.03% to 0.20% by weight of cadmium and preferably equal to 0.10%, replacing the gallium or in addition to the composition already comprising gallium.
  • the area ratio between the part 2 of aluminum alloy and the lamellae 1 or lamellae is less than 5, preferably equal to 1.5 for optimal protection.
  • An alloy cast in an anode according to the invention was tested, comprising the following weight percentages: Gallium 0.102% Iron 0.046% Silicon 0.035% Zinc 0.065% Titanium 0.02% max Manganese ⁇ 0.15% Other ⁇ 0.01% Aluminum the rest.
  • the resting potential in seawater is - 850 mV +/- 50 mV / DHW.
  • the anode potential measured with a current density of 30 mA / dm2 is - 800 mV / DHW.
  • the mass energy is 1937 Ah / kg.
  • Tests were carried out in accordance with a NACE (National Association Corrosion Engineer) specification involving 15 days of exposure to seawater of samples of diameter 38 mm, height 16.8 mm, active surface 0.4095 dm2 with a flow rate of 25.4 mA.
  • the average potential is - 804 mV / DHW and the electrochemical efficiency of 80%.
  • the corrosion rate is of the order of 1 to 10 micrometers / year at - 700 mV / DHW for steel with high elastic limit type Ni 5%; it is of the same order of magnitude at a potential of - 760 mV / DHW for structural steel type E28.
  • corrosion becomes significant at a potential greater than - 600 mV / DHW.
  • the hydrogen release kinetics are further reduced by a factor of 10 between - 800 mV and - 1020 mV and by a factor of 20 to - 1060 mV.
  • the resting potential in seawater is - 850 mV +/- 50 mV / DHW.
  • the anode potential measured at 2 mA / cm2 is - 730 mV / DHW.
  • the mass energy is 2384 Ah / kg and the electrochemical yield is 80%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Prevention Of Electric Corrosion (AREA)
EP94402419A 1993-10-29 1994-10-27 Selbstverzehrende Anode für den kathodischen Korrosionschutz aus einer Aluminiumlegierung Expired - Lifetime EP0651075B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9312916 1993-10-29
FR9312916A FR2713244B1 (fr) 1993-10-29 1993-10-29 Anode consommable de protection cathodique en alliage à base d'aluminium.

Publications (2)

Publication Number Publication Date
EP0651075A1 true EP0651075A1 (de) 1995-05-03
EP0651075B1 EP0651075B1 (de) 1999-06-02

Family

ID=9452341

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94402419A Expired - Lifetime EP0651075B1 (de) 1993-10-29 1994-10-27 Selbstverzehrende Anode für den kathodischen Korrosionschutz aus einer Aluminiumlegierung

Country Status (6)

Country Link
US (1) US5547560A (de)
EP (1) EP0651075B1 (de)
DE (1) DE69418817T2 (de)
ES (1) ES2131652T3 (de)
FR (1) FR2713244B1 (de)
NO (1) NO307661B1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104018164A (zh) * 2014-04-18 2014-09-03 天津恒仁石油设备有限公司 一种锌铝镉合金牺牲阳极
US11684893B2 (en) 2016-07-26 2023-06-27 Guangzhou Supbio Bio-Technology And Science Co., Ltd. Method for exosome separation and extraction by stacked centrifugal filtration

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10213289A1 (de) * 2001-03-30 2002-11-14 Yokohama Rubber Co Ltd Elastomer-und-Stahlkord-Verbundwerkstoff und Prozess zur Herstellung desselben
US9243150B2 (en) * 2005-04-21 2016-01-26 The United States Of America As Represented By The Secretary Of The Navy Oxide coated metal pigments and film-forming compositions
US9243333B2 (en) * 2012-09-27 2016-01-26 The United States Of America, As Represented By The Secretary Of The Navy Coated aluminum alloy pigments and corrosion-resistant coatings

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE667337A (de) * 1964-07-23 1966-01-24
DE2150102A1 (de) * 1970-10-07 1972-04-13 Mitsubishi Metal Mining Co Ltd Aluminiumlegierung fuer Anoden fuer galvanische Baeder
FR2301600A1 (fr) * 1975-02-20 1976-09-17 Inst Sciences Tech Acad Serb Alliage d'aluminium electrochimiquement actif, procede de sa preparation et son emploi
JPS56119785A (en) * 1980-02-26 1981-09-19 Sumitomo Metal Ind Ltd Corrosion prevention for steel structure in ocean environment

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2930568A (en) * 1954-01-11 1960-03-29 Clarence M Rader Hanger for electrolytic liquid treating device
NL288527A (de) * 1963-02-04
FR1399752A (fr) * 1964-04-04 1965-05-21 Soc Gen Magnesium Nouvel alliage à base d'aluminium et de mercure et son application à la réalisation d'anodes
US3240688A (en) * 1964-04-21 1966-03-15 Olin Mathieson Aluminum alloy electrode
US3379636A (en) * 1964-07-23 1968-04-23 Dow Chemical Co Indium-gallium-aluminum alloys and galvanic anodes made therefrom
US3337333A (en) * 1964-07-23 1967-08-22 Dow Chemical Co Aluminum alloys and galvanic anodes made therefrom
US3721618A (en) * 1971-03-11 1973-03-20 Dow Chemical Co Aluminum sacrifical anode
US3870615A (en) * 1971-12-30 1975-03-11 Standard Brass & Mfg Sacrificial anode
FR2377455A1 (en) * 1978-05-25 1978-08-11 Petrocokino Denis Sacrificial aluminium-zinc alloy anodes - for cathodic protection of metal structures in corrosive electrolytes
US4240829A (en) * 1979-01-25 1980-12-23 Dunaev Jury D Aluminum-base alloy used as material for galvanic protector
FR2449730A1 (fr) * 1979-02-23 1980-09-19 Inst Orch Kataliza Alliage a base d'aluminium, destine a la fabrication de protecteurs contre la corrosion d'articles en fer et en acier
NZ224999A (en) * 1987-06-16 1990-10-26 Comalco Alu Aluminium alloy suitable for sacrificial anodes
US5006214A (en) * 1990-02-05 1991-04-09 Burchnell Donald H Cathodic protection apparatus

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE667337A (de) * 1964-07-23 1966-01-24
DE2150102A1 (de) * 1970-10-07 1972-04-13 Mitsubishi Metal Mining Co Ltd Aluminiumlegierung fuer Anoden fuer galvanische Baeder
FR2301600A1 (fr) * 1975-02-20 1976-09-17 Inst Sciences Tech Acad Serb Alliage d'aluminium electrochimiquement actif, procede de sa preparation et son emploi
JPS56119785A (en) * 1980-02-26 1981-09-19 Sumitomo Metal Ind Ltd Corrosion prevention for steel structure in ocean environment

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 5, no. 195 (C - 083) 11 December 1981 (1981-12-11) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104018164A (zh) * 2014-04-18 2014-09-03 天津恒仁石油设备有限公司 一种锌铝镉合金牺牲阳极
US11684893B2 (en) 2016-07-26 2023-06-27 Guangzhou Supbio Bio-Technology And Science Co., Ltd. Method for exosome separation and extraction by stacked centrifugal filtration

Also Published As

Publication number Publication date
DE69418817D1 (de) 1999-07-08
NO944110L (no) 1995-05-02
NO307661B1 (no) 2000-05-08
ES2131652T3 (es) 1999-08-01
NO944110D0 (no) 1994-10-28
FR2713244B1 (fr) 1996-01-12
US5547560A (en) 1996-08-20
DE69418817T2 (de) 1999-11-11
EP0651075B1 (de) 1999-06-02
FR2713244A1 (fr) 1995-06-09

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