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WO2000026426A1 - 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

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
WO2000026426A1
WO2000026426A1 PCT/DK1999/000586 DK9900586W WO0026426A1 WO 2000026426 A1 WO2000026426 A1 WO 2000026426A1 DK 9900586 W DK9900586 W DK 9900586W WO 0026426 A1 WO0026426 A1 WO 0026426A1
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Prior art keywords
per cent
weight
zinc
max
sacrificial anode
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Ceased
Application number
PCT/DK1999/000586
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French (fr)
Inventor
Jan Søren Brøgger ARENTOFT
Per Schantz
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BAC CORROSION CONTROL AS
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BAC CORROSION CONTROL AS
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Priority to AU63269/99A priority Critical patent/AU6326999A/en
Publication of WO2000026426A1 publication Critical patent/WO2000026426A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C22C18/02—Alloys based on zinc with copper as the next major constituent
    • 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

Definitions

  • 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 ag- gressive environment.
  • the majority of the sacrificial anodes presently being produced and used for the cathodic protection of constructions in aggressive environment comprises zinc- based or aluminum-based alloys as the active part.
  • the presently used zinc-based alloys meet the requirements of US Military Standard (U.S.-Mill-A-1800 1 K) which ir> ter alia prescribes the addition of cadmium;
  • U.S.-Mill-A-1800 1 K comprises the following data:
  • this invention relates to a zinc-based alloy which is characterized in that it consists substantially of 0J - 1.0 per cent by weight of aluminum,
  • An alloy according to the invention which is preferred on account of its particularly advantageous potential, capacity and effectivity, cf. the following test results, consists substantially of 0J - 1.0 per cent by weight of aluminum,
  • a preferred indium-free alloy or alloy having a very low indium content is according to the invention characterized in that it consists substantially of 0.1 - 0.2 per cent by weight of aluminum, 0.05 - 0J 0 per cent by weight of tin, 0 - 50 ppm of indium, max. 0.0030 per cent by weight of lead, iron and/or copper, and max.
  • 2,982,705 there is also known a zinc alloy for cathodic protection contai- ning at least one element selected from indium, thallium, cadmium and tin in an amount of 0.01 - 3%; this alloy may consist of zinc and indium, only, or of zinc and tin, only.
  • This invention also relates to a zinc-based alloy as defined 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.
  • 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 offshore constructions, hulls, tanks, cooling containers, pipes and the like, 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 tests having been carried out according to the directions in Det Norske Veritas' Offshore-standard RP.B.401; the potentials have been measured vs. Cu/CuSO 4 . Zn-based alloys (Zn-purity 99.995%)
  • test alloys according to the invention substantially meet the requirements according to U.S.-MHI-A-1800 K 1 and for a substantial part show even more advantageous values.

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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 0.1-1.0 per cent by weight of aluminum, 0.005-1.0 per cent by weight of tin, 0-0.5 per cent by weight of indium, max. 0.0030 per cent by weight of lead, iron and/or copper, and max. 0.0050 per cent by weight of lead, iron and/or copper as well as other metals, in particular nickel, thallium and cadmium, and balance zinc having a purity of about 99.995 per cent. The alloy shows advantageous properties with respect to potential, capacity and effectivity and can with good results be used for cathodic protection of corrosion-threatened constructions in aggressive environment, in particular offshore constructions, hulls, tanks, cooling containers, pipes and the like.

Description

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.
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 ag- gressive environment.
BACKGROUND ART
The majority of the sacrificial anodes presently being produced and used for the cathodic protection of constructions in aggressive environment comprises zinc- based or aluminum-based alloys as the active part. The presently used zinc-based alloys meet the requirements of US Military Standard (U.S.-Mill-A-1800 1 K) which ir> ter alia prescribes the addition of cadmium; U.S.-Mill-A-1800 1 K comprises the following data:
Composition of alloy Potential Capacity Effectivitv
Al: 0.10 - 0.50% -1 100 mV 780 Ah/kg 95%
Cd: 0.025 - 0.07%
Fe: max. 0.005% Cu: max. 0.005%
Pb: max. 0.006%
Other metals: max. 0.10%
Balance: Zn - purity min. 99.314%
(the potential is measured vs. a Cu/CuSO4 reference electrode). Although zinc alloys of the above type have proved to be well suited as sacrificial anodes, they suffer from the serious drawback that they contain in particular the heavy metal cadmium which poses a substantial risk factor with respect to loading and contamination of the environment. It is therefore to be expected that alloys of this type will in the near future be subjected to restrictions going beyond the present ones. Thus, there is a pressing need for providing non-cadmium containing, more environmentally acceptable zinc-based alloys which are at least or substantially as effective for cathodic protection as the known alloys of the above mentioned type.
DISCLOSURE OF THE INVENTION
Thus, it is the object of this invention to provide new zinc-based alloys which are suitable as sacrificial anode alloys and which to the highest possible extent are free of environment-loading heavy metals such as cadmium, and which are furthermore extremely effective for cathodic protection, in particular of offshore constructions, hulls, tanks, cooling containers, pipes, sheet pilings and the like.
It has surprisingly been found that a zinc-based alloy having specific contents of aluminum, tin and, if desired, indium substantially fully meets the requirements of U.S.-MNI-A-1800 1 K with respect to potential, capacity and effectivity and for certain alloy compositions shows even more advantageous properties of the said type, and to this comes that the alloy is cadmium-free and when used for cathodic protection gives rise to a uniform corrosion pattern and no pit corrosion, and the object of the invention is thus achieved with such an alloy.
Accordingly, this invention relates to a zinc-based alloy which is characterized in that it consists substantially of 0J - 1.0 per cent by weight of aluminum,
0.005 - 1.0 per cent by weight of tin,
0 - 0.5 per cent by weight of indium, max. 0.0030 per cent by weight of lead, iron and/or copper, and max. 0.0050 per cent by weight of lead, iron and/or copper as well as other metals, in particular nickel, thallium and cadmium, and balance zinc having a purity of about 99.995 per cent. DESCRIPTION OF PREFERRED EMBODIMENTS
An alloy according to the invention which is preferred on account of its particularly advantageous potential, capacity and effectivity, cf. the following test results, consists substantially of 0J - 1.0 per cent by weight of aluminum,
0.01 - 0J per cent by weight of tin,
0 - 0J per cent by weight of indium, max. 0.0030 per cent by weight of lead, iron and/or copper, and max 0.0050 per cent by weight of lead, iron and/or copper as well as other metals, in particular nickel, thallium and cadmium, and balance zinc having a purity of about 99.995 per cent, and this is in particular true for an alloy, which consists substantially of 0.1 - 0.2 per cent by weight of aluminum, 0.01 - 0.03 per cent by weight of tin, 100 - 300 ppm of indium, max. 0.0030 per cent by weight of lead, iron and/or copper, and max. 0.0050 per cent by weight of lead, iron and/or copper as well as other metals, in particular nickel, thallium and cadmium, and balance zink having a purity of about 99.995 per cent.
In practice it will often be preferred to use an alloy which does not contain indium or only contains a very small amount of indium. Hereby there is obtained a substantial economic advantage due to the high price of indium, and at the same time there are obtained properties almost as good as with the above, preferred alloy, cf. the following test results. A preferred indium-free alloy or alloy having a very low indium content is according to the invention characterized in that it consists substantially of 0.1 - 0.2 per cent by weight of aluminum, 0.05 - 0J 0 per cent by weight of tin, 0 - 50 ppm of indium, max. 0.0030 per cent by weight of lead, iron and/or copper, and max. 0.0050 per cent by weight of lead, iron and/or copper as well as other metals, in particular nickel, thallium and cadmium, and balance zinc having a purity of about 99.995 per cent. From DE Offenlegungsschrift No. 2,41 1 ,608 there is known a zinc-indium- alloy for cathodic protection without contamination of the environment. This alloy contains 0.005 - 0.02% indium, and the balance is high purity zinc. From US Patent Specification No. 2,982,705 there is also known a zinc alloy for cathodic protection contai- ning at least one element selected from indium, thallium, cadmium and tin in an amount of 0.01 - 3%; this alloy may consist of zinc and indium, only, or of zinc and tin, only.
In the above publications there is no disclosure of including aluminum in the alloys, whereas this is the case in the alloy according to the present invention. It has been found that including 0J - 1.0 per cent by weight of aluminum in the alloy has a favourable impact on the structure in the cast anode alloy, which has the advantage that under normal circumstances the anode will be consumed more uniformly, thereby avoiding pit corrosion which can lead to pieces falling off the anode which thereby cannot be used optimally. Furthermore, the aluminum content provides better casting pro- perties, because the anodes, which must often be after-worked, do not break by threading and other mechanical working, whereas zinc without the addition of aluminum is very coarse-cristalline and therefore brittle and easily breaking.
This invention also relates to a zinc-based alloy as defined 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 offshore constructions, hulls, tanks, cooling containers, pipes and the like, 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 tests having been carried out according to the directions in Det Norske Veritas' Offshore-standard RP.B.401; the potentials have been measured vs. Cu/CuSO4. Zn-based alloys (Zn-purity 99.995%)
Figure imgf000007_0001
It will be seen that the tested alloys according to the invention substantially meet the requirements according to U.S.-MHI-A-1800 K 1 and for a substantial part show even more advantageous values.

Claims

CLAIMS:
1. A zinc-based alloy, characterized in that it substantially consists of 0J - 1.0 per cent by weight of aluminum, 0.005 - 1.0 per cent by weight of tin, 0 - 0.5 per cent by weight of indium, max. 0.0030 per cent by weight of lead, iron and/or copper, and max. 0.0050 per cent by weight of lead, iron and/or copper as well as other metals, in particular nickel, thallium and cadmium, and balance zinc having a purity of about 99.995 per cent.
2. An alloy according to claim 1 , characterized in that it substantially consists of
0J - 1.0 per cent by weight of aluminum, 0.01 - 0J per cent by weight of tin,
0 - 0J per cent by weight of indium, max. 0.0030 per cent by weight of lead, iron and/or copper, and max 0.0050 per cent by weight of lead, iron and/or copper as well as other metals, in particular nickel, thallium and cadmium, and balance zinc having a purity of about 99.995 per cent.
3. An alloy according to claim 1 , characterized in that it substantially consists of
0.1 - 0.2 per cent by weight of aluminum,
0.01 - 0.03 per cent by weight of tin,
100 - 300 ppm of indium, max. 0.0030 per cent by weight of lead, iron and/or copper, and max. 0.0050 per cent by weight of lead, iron and/or copper as well as other metals, in particular nickel, thallium and cadmium, and balance zink having a purity of about 99.995 per cent.
4. An alloy according to claim 1 , characterized in that it substantially consists of
0.1 - 0.2 per cent by weight of aluminum, 0.05 - 0.10 per cent by weight of tin,
0 - 50 ppm of indium, max. 0.0030 per cent by weight of lead, iron and/or copper, and max. 0.0050 per cent by weight of lead, iron and/or copper as well as other metals, in particular nickel, thallium and cadmium, and balance zinc having a purity of about 99.995 per cent.
5. A zinc-based alloy according to any of claims 1-4 for use as the active part of a sacrificial anode.
6. The use of an alloy according to any of claims 1-4 as the active part of a sacrificial anode.
7. A sacrificial anode, characterized in that its active part is a zinc-based alloy according to any of clalims 1-4.
8. A method for the cathodic protection of corrosion-threatened constructions in aggressive environment, in particular offshore constructions, hulls, tanks, cooling containers, pipes and the like, characterized in that the constructions are protected by using a sacrificial anode according to claim 7.
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-
ABSTRACT OF THE INVENTION
A cadmium-free, zinc-based alloy suitable as a sacrificial anode substantially consists of
0J - 1.0 per cent by weight of aluminum, 0.005 - 1.0 per cent by weight of tin, 0 - 0.5 per cent by weight of indium, max. 0.0030 per cent by weight of lead, iron and/or copper, and max. 0.0050 per cent by weight of lead, iron and/or copper as well as other metals, in particular nickel, thallium and cadmium, and balance zinc having a purity of about 99.995 per cent. The alloy shows advantageous properties with respect to potential, capacity and effectivity and can with good results be used for cathodic protection of corrosion- threatened constructions in aggressive environment, in particular offshore constructions, hulls, tanks, cooling containers, pipes and the like.
PCT/DK1999/000586 1998-11-03 1999-10-28 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 Ceased WO2000026426A1 (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009118693A1 (en) * 2008-03-28 2009-10-01 Bac Corrosion Control A/S 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
CN101928944A (en) * 2010-03-12 2010-12-29 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
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
CN113046755A (en) * 2021-03-10 2021-06-29 青岛双瑞海洋环境工程股份有限公司 High-temperature-resistant zinc alloy sacrificial anode and preparation method thereof
CN117210719A (en) * 2023-08-10 2023-12-12 深圳市中金岭南有色金属股份有限公司韶关冶炼厂 Zn-Al-Sn-Li eutectic alloy sacrificial anode and preparation method and application thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005087961A1 (en) * 2004-03-12 2005-09-22 Zab Danmark A/S A metal alloy and the use of the metal alloys as a weight

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009118693A1 (en) * 2008-03-28 2009-10-01 Bac Corrosion Control A/S 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
CN101928944A (en) * 2010-03-12 2010-12-29 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
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
CN113046755A (en) * 2021-03-10 2021-06-29 青岛双瑞海洋环境工程股份有限公司 High-temperature-resistant zinc alloy sacrificial anode and preparation method thereof
CN117210719A (en) * 2023-08-10 2023-12-12 深圳市中金岭南有色金属股份有限公司韶关冶炼厂 Zn-Al-Sn-Li eutectic alloy sacrificial anode and preparation method and application thereof

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DK199801415A (en) 2000-05-04
AU6326999A (en) 2000-05-22

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