EP2276866B1 - Cadmium-free zinc-based alloy, its use as a sacrificial anode, a sacrificial anode, and a method for cathodic protection of corrosion-threatened constructions in aggressive environment - Google Patents

Cadmium-free zinc-based alloy, its use as a sacrificial anode, a sacrificial anode, and a method for cathodic protection of corrosion-threatened constructions in aggressive environment Download PDF

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Publication number
EP2276866B1
EP2276866B1 EP09724942A EP09724942A EP2276866B1 EP 2276866 B1 EP2276866 B1 EP 2276866B1 EP 09724942 A EP09724942 A EP 09724942A EP 09724942 A EP09724942 A EP 09724942A EP 2276866 B1 EP2276866 B1 EP 2276866B1
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EP
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Prior art keywords
weight
maximum
sacrificial anode
cadmium
zinc
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EP09724942A
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German (de)
French (fr)
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EP2276866A1 (en
Inventor
John Jensen
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BAC CORROSION CONTROL AS
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BAC CORROSION CONTROL AS
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C22C18/04—Alloys based on zinc with aluminium as the next major constituent
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Prevention Of Electric Corrosion (AREA)

Abstract

A cadmium-free, zinc-based alloy suitable as a sacrificial anode substantially consists of 0.4-0.6% by weight of aluminum, 0.02-0.03% by weight of indium, max. 0.001% by weight of cadmium, maximum 0.005% by weight of copper, maximum 0.006% by weight of lead, maximum 0.0005% by weight of tin, maximum 0.10% by weight of other metals, in particular nickel and thallium, and balance zinc having a purity of about 99.995% The alloy shows advantageous properties with respect to resistance to cracking and breaking during post machining of the casting, especially when producing sacrificial anodes having relatively small dimensions.

Description

    TECHNICAL FIELD
  • This invention relates to a new zinc-based alloy; the said alloy for use as the active part of a sacrificial anode; the use of the alloy as the active part of such an anode; a sacrificial anode, the active part of which is an alloy according to the invention; as well as a method for cathodic protection of corrosion-threatened constructions in aggressive environment.
    • BACKGROUND ART
  • Know alloys, such as e.g. known from WO 00/26426 , can be used for casting anodes of a relatively large size, the order of magnitude of the smallest dimension being several centimeters. However, when smaller anodes are needed, the inventors have realised that a tendency of breaking or crack development is observed, especially in connection with machining, e.g. threading or boring, after casting of the anodes. Another feature indicated to be essential in this document is that the sacrificial anodes should be free from cadmium, which poses a substantial risk factor with respect to loading and contamination of the environment.
    • DISCLOSURE OF THE INVENTION
  • Based on this prior art it is the object of the present invention to provide new zinc-based cadmium-free alloys, which are suitable as sacrificial anode alloys and which can be cast in relatively small dimensions, such as a smallest dimensioning in the order of 5-10 mm or less. Surprisingly, experiments made by the inventors have revealed that an alloy comprising 0 4-0.6% by weight of aluminum, 0.02 - 0.03% by weight of indium, maximum 0.001% by weight of cadmium, maximum 0.005% by weight of iron, maximum 0.005% by weight of copper, maximum 0.006% by weight of lead, maximum 0.0005% of tin, maximum 0.10% by weight of other metals, in particular nickel and thallium, and balance zinc having a purity of about 99.995 %, makes it possible to cast small sacrificial anodes with a smallest dimension in the order to 5-10 mm or less without the tendency of breaking or crack development in connection with post-machining of the castings. Furthermore, experiments by the inventors have shown that a possible change of the content of aluminum to a percentage above 0.6% by weight will induce problems when casting due to a higher viscosity of the molten metal. It will be possible to change this viscosity by raising the temperature, which would, however, increase the time necessary for casting and increase the risk of dimensional changes during solidification and cooling of the finished casting. Furthermore, such a higher temperature would increase the cost of heating up the molten metal.
  • Correspondingly, a change of the percentage of aluminum to a value below 0.4% by weight would make the alloy brittle and make the casting difficult to perform and possible post-machining of the casting will be difficult due to tendency of breaking of the material which will become brittle.
    • DESCRIPTION OF PREFERRED EMBODIMENTS
  • An alloy according to the invention, which is preferred on account of its particular advantages regarding casting of small anodes, consists substantially of 0.4 - 0.6% by weight of aluminum, 0.02 - 0.03% by weight of indium, maximum 0.001% by weight of cadmium, maximum 0.005% by weight of iron, maximum 0.005% by weight of copper, maximum 0.006% by weight of lead, maximum 0.0005% of tin, maximum 0.10% by weight of other metals, in particular nickel and thallium, and balance zinc having a purity of about 99.995 %.
  • A particularly preferred alloy according to the invention, which with a suitable margin avoids the problems mentioned above, when the aluminum content is less than 0.4% by weight or more than 0.6% by weight, consists substantially of 0.45 - 0.55% by weight of aluminum, 0.02 - 0.03% by weight of indium, maximum 0.001% by weight of cadmium, maximum 0.005% by weight of iron, maximum 0.005% by weight of copper, maximum 0.006% by weight of lead maximum 0.0005% of tin, maximum 0.10% by weight of other metals, in particular nickel and thallium, and balance zinc having a purity of about 99.995 %.
  • The high price of indium makes it advantageous to have a narrower indication of the amount of indium in the alloy and accordingly a more preferred alloy according to the invention consists substantially of 0.4 - 0.6% by weight of aluminum, 0.024 - 0.026% by weight of indium, maximum 0.001% by weight of cadmium, maximum 0..005% by weight of iron, maximum 0.005% by weight of copper, maximum 0.006% by weight of lead, maximum 0.0005% of tin, maximum 0.10% by weight of other metals, in particular nickel and thallium, and balance zinc having a purity of about 99.995 %.
  • WO 00/26426 suggests an alloy having a content of aluminum between 0.1 and 1% by weight, but only one of the specific embodiments shown in the table of this document, namely specimen No. 7, has an aluminum content in the narrower range in accordance with the present invention. However, this specimen No. 7 has an indium content of 500 ppm, which is outside the range provided for the alloy in accordance with the present invention, and furthermore the result of this specimen is indicated to be an anode with a coarse grained surface, which would not be acceptable for a relatively small anode in accordance with the present invention. Furthermore, this relatively coarse grained surface indicates a tendency of crack development, as indicated above.
  • This invention also relates to a zinc-based alloy as described above for use as the active part of a sacrificial anode, and the invention also relates to the use of an alloy of the present type as the active part of a sacrificial anode.
  • Finally, the invention relates to a sacrificial anode, the active part of which is a zinc-based alloy of the present type, as well as a method for the cathodic protection of corrosion-threatened constructions in aggressive environment, in particular smaller components, and this method is characterized in that the constructions are protected by using a sacrificial anode according to the invention.
  • The invention is further illustrated by means of the following test results obtained with alloys according to the invention, the test having been carried out according to the directions in the 'Det Norske Veritas' Offshore-standard RP B.401; the potentials have been measured vs. Ag/AgCl/seawater.
    • Alloy in accordance with the present invention:
  • Al: 0.4 - 0.6%
    In: 0.02 - 0.03%
    Cd: Max. 0.001%
    Fe: Max. 0.005%
    Cu: Max. 0.005%
    Pb: Max. 0.006%
    Sn: Max. 0.0005%
    Other metals: Max. 0.10%
    and balance zinc having a purity of about 99.995%.
    • Performance data:
  • Capacity: 780 Ah/kg
    Consumption rate: 1.,2 kg/A year
    Closed circuit potential: -1.03 V vs. Ag/AgCl/seawater
  • Using this alloy it has been possible to cast anodes of different sizes, including relatively small sizes, said anodes being resistant to breakage or crack development and relatively easy post machining of the castings without tendency to breakage or crack development.
    • Alloy having lower content of aluminum:
  • Al 0.1-0.4%
  • Other components as in the above alloy in accordance with the invention.
  • The performance data were substantially identical to the performance data for the alloy in accordance with the invention, despite the change of content of aluminum. However, with a content of aluminum of 0.4% and 0.1%, the casting becomes brittle and has a tendency to breakage or crack development, especially when post machining the castings. Furthermore, a tendency to crack development during solidification of the casting has been observed.
    • Aluminum content higher than in accordance with the present invention:
  • Al 0.6-1.0%
  • Other components as in accordance with the present invention.
  • Again it can be seen that the performance data are substantially unchanged despite the change of content of aluminum.
  • With this higher content of aluminum, between 0.6 and 1.0%, the alloy becomes thick and has a tendency not to fill the corners of the casting cavity. This may be changed by using a higher temperature of the casting metal, which however makes the casting more difficult due to higher temperature of the mould and results in longer time for cooling after casting. Additionally, a higher temperature will inevitably involve higher shrinkage, i.e. reduction of the size of the casting, during solidification, compared to the normally used temperature results. Furthermore, higher production costs can be envisaged when using a higher casting temperature.
  • It will be seen that the tested alloys according to the invention substantially meet the requirements according to U.S. Mill-A-1800 K1 and for a substantial part show even more advantageous values, and furthermore the test results show that small electrodes having a smallest dimensioning in the order of 5-10 mm or less can be cast with said alloy.

Claims (7)

  1. A zinc-based alloy, characterized in that it consists of
    0.4 - 0.6% by weight of aluminum,
    0.02 - 0.03% by weight of indium,
    maximum 0.001% by weight of cadmium,
    maximum 0.005% by weight of iron,
    maximum 0.005% by weight of copper,
    maximum 0.006% by weight of lead
    maximum 0.0005% of tin,
    maximum 0.10% by weight of other metals, in particular nickel and thallium, and balance zinc having a purity of about 99.995 %.
  2. An alloy according to claim 1, characterized in that it consists of
    0.45 - 0.55% by weight of aluminum
    0.02 - 0.03% by weight of indium,
    maximum 0.001% by weight of cadmium,
    maximum 0.005% by weight of iron,
    maximum 0.005% by weight of copper,
    maximum 0.006% by weight of lead
    maximum 0.0005% of tin,
    maximum 0.10% by weight of other metals, in particular nickel and thallium, and balance zinc having a purity of about 99.995 %.
  3. An alloy according to claim 1, characterized in that it consists of
    0.4 - 0.6% by weight of alminum,
    0.024 - 0.026% by weight of indium,
    maximum 0.001% by weight of cadmium,
    maximum 0.005% by weight of iron,
    maximum 0.005% by weight of copper,
    maximum 0.006% by weight of lead
    maximum 0.0005% of tin.
    maximum 0.10% by weight of other metals, in particular nickel and thallium, and balance zinc having a purity of about 99.995 %.
  4. A zinc-based alloy according to any of the claims 1-3 for use as the active part of a sacrificial anode.
  5. The use of an alloy according to any of the claims 1-3 as the active part of a sacrificial anode.
  6. A sacrificial anode, characterized in that its active part is a zinc-based alloy according to any of the claim 1-3.
  7. A method for the cathodic protection of corrosion-threatened constructions in aggressive environment, characterized in that the constructions are protected by using a sacrificial anode according to claim 6.
EP09724942A 2008-03-28 2009-03-25 Cadmium-free zinc-based alloy, its use as a sacrificial anode, a sacrificial anode, and a method for cathodic protection of corrosion-threatened constructions in aggressive environment Active EP2276866B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DKPA200800453 2008-03-28
US4201308P 2008-04-03 2008-04-03
PCT/IB2009/051239 WO2009118693A1 (en) 2008-03-28 2009-03-25 Cadmium-free zinc-based alloy, its use as a sacrificial anode, a sacrificial anode, and a method for cathodic protection of corrosion-threatened constructions in aggressive environment

Publications (2)

Publication Number Publication Date
EP2276866A1 EP2276866A1 (en) 2011-01-26
EP2276866B1 true EP2276866B1 (en) 2011-09-07

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US (1) US20110089047A1 (en)
EP (1) EP2276866B1 (en)
AT (1) ATE523609T1 (en)
ES (1) ES2373024T3 (en)
WO (1) WO2009118693A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2989386A1 (en) * 2012-04-12 2013-10-18 A M P E R E Ind Zinc-based alloy, useful for manufacturing a sacrificial anode used for the protection of boat hulls, comprises aluminum, gallium, and zinc

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101928944B (en) * 2010-03-12 2012-04-18 邹积强 Alloy sacrificial anode film preventing stress corrosion cracking and preparation method thereof
CN103243238A (en) * 2013-05-23 2013-08-14 南通鑫祥锌业有限公司 Zinc composite material for alloy zinc belt
US11634822B2 (en) * 2017-09-15 2023-04-25 Onesubsea Ip Uk Limited Systems and methods for providing monitored and controlled cathodic protection potential
EP3647465A1 (en) * 2018-11-05 2020-05-06 BAC Corrosion Control A/S Zink-based sacrificial anode alloy, use of a zink-based alloy, and a sacrificial anode
CN112853359A (en) * 2021-01-05 2021-05-28 中国石油天然气股份有限公司 Sacrificial anode material and preparation method and application thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6152337A (en) * 1984-08-20 1986-03-15 Nippon Mining Co Ltd Zinc alloy for hot dip galvanizing
RU1788064C (en) * 1991-04-22 1993-01-15 Государственный научно-исследовательский, проектный и конструкторский институт сплавов и обработки цветных металлов "Гипроцветметобработка" Alloy on the basis of zinc for anodes, and a method of its working
DK173514B1 (en) * 1998-11-03 2001-01-22 Bac Corrosion Control As Zinc-based alloy, its use as a sacrificial anode, sacrificial anode and cathodic protection method
ES2200827T3 (en) * 1999-02-09 2004-03-16 Umicore ZINC ALLOY POWDER ATOMIZED BY CENTRIFUGATION FOR ALKAL BATTERIES.

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2989386A1 (en) * 2012-04-12 2013-10-18 A M P E R E Ind Zinc-based alloy, useful for manufacturing a sacrificial anode used for the protection of boat hulls, comprises aluminum, gallium, and zinc

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WO2009118693A1 (en) 2009-10-01
ATE523609T1 (en) 2011-09-15
ES2373024T3 (en) 2012-01-30
US20110089047A1 (en) 2011-04-21
EP2276866A1 (en) 2011-01-26

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