US3337333A - Aluminum alloys and galvanic anodes made therefrom - Google Patents

Aluminum alloys and galvanic anodes made therefrom Download PDF

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Publication number
US3337333A
US3337333A US384795A US38479564A US3337333A US 3337333 A US3337333 A US 3337333A US 384795 A US384795 A US 384795A US 38479564 A US38479564 A US 38479564A US 3337333 A US3337333 A US 3337333A
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US
United States
Prior art keywords
aluminum
weight percent
oxidation potential
galvanic
alloy
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
Application number
US384795A
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English (en)
Inventor
John T Reding
Iii John J Newport
James R Minderhout
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
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Dow Chemical Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Priority to US384795A priority Critical patent/US3337333A/en
Priority to SE9022/65A priority patent/SE307675B/xx
Priority to FR25236A priority patent/FR1440519A/fr
Priority to DEP1268A priority patent/DE1268852B/de
Priority to GB31182/65A priority patent/GB1066723A/en
Priority to ES0315699A priority patent/ES315699A1/es
Priority to BE667339A priority patent/BE667339A/xx
Priority to DK380865AA priority patent/DK113536B/da
Priority to NL656509584A priority patent/NL146540B/xx
Application granted granted Critical
Publication of US3337333A publication Critical patent/US3337333A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C22C21/003—Alloys based on aluminium containing at least 2.6% of one or more of the elements: tin, lead, antimony, bismuth, cadmium, and titanium
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This invention relates to sacrificial galvanic anodes and more particularly is concerned with a novel aluminum based alloy exhibiting high oxidation potential and a useful high electrical output per unit mass of metal; i.e. a high electrochemical equivalent which is suitable for use in such galvanic anodes.
  • aluminum should be expected to perform satisfactorily as a galvanic anode because the element aluminum fulfills the two primary requirements for anodes: (l) a high theoretical oxidation potential (1.80 volts versus calomel reference) and (2) a high theoretical electrical output per unit mass of metal consumed (2.98 amp-hours per gram). In actual practice, however, aluminum has not proved to be satisfactory for use in such applications since it does not exhibit these favorable theoretical properties when used as a sacrificial galvanic anode.
  • the presence of the normally passive oxide surface film on the aluminum apparently presents a barrier to the oxidation of the aluminum metal thereby reducing the effective oxidation potential to about 0.7 volt (as measured in closed circuit at either 250 to 1000 milliamperes/ square foot in a synthetic seawater electrolyte with a standard saturated KCl calomel cell as reference).
  • the effective oxidation potential to about 0.7 volt (as measured in closed circuit at either 250 to 1000 milliamperes/ square foot in a synthetic seawater electrolyte with a standard saturated KCl calomel cell as reference).
  • no cathodic protection is given to ferrous based structures, for example; therefore the anode exhibits no useful electrical output.
  • the actual working potential of magnesium is about 1.5 volt and of zinc is about 1 volt.
  • the present invention comprises a novel aluminum based alloy composition containing small amounts of gallium, bismuth and lead.
  • the present composition comprises aluminum and from about 0.003 to about 0.2 weight percent gallium, from about 0.02 to about 2 weight percent bismuth and from about 0.02 to about 2 weight percent lead.
  • the alloy comprises aluminum having alloyed therewith from about 0.005 to about 0.03 Weight percent gallium, from about 0.03 to about 0.5 Weight 3,337,333 Patented Aug. 22, 1967 percent bismuth and from about 0.03 to about 0.5 weight percent lead. All weight percents are based on the total composition weight.
  • the alloy is further characterized in that the bismuth/ lead weight ratio preferably ranges from about 0.5 to about 2.
  • the present novel composition when employed as sacrificial galvanic anodes exhibits a satisfactory corrosion pattern, a high operating oxidation potential and a high electrical output per unit mass of metal consumed.
  • Galvanic anodes can be prepared from the novel compositions by use of alloying and casting or fabricating techniques ordinarily employed in the aluminum art. No special metal handling or fabricating operations are required.
  • Aluminum for use in preparing the present novel alloy compositions should preferably be commercial high purity metal (99.99% Al) but can be of a grade having a purity of about 99.93% aluminum. Conveniently, commercial grade (99.9%) metal having normal production introduced impurities associated therewith can be blended with high purity (99.99% Al) to provide the aluminum matrix.
  • the alloying elements also can be of high purity or of commercial grade. With aluminum of lower purity than specified, detrimental reduction in electropotential may be realized.
  • the resulting alloy product is not detrimentally degraded by storage in normal atmospheres through air oxiation.
  • Example-A number of anodes of the present invention were prepared by melting in a graphite crucible positioned within an electric furnace, a mixture of commercial 99.9% and 99.99% purity aluminum ingots to provide an aluminum matrix of about 99.97% purity or 99.99% purity aluminum ingots alone. Requisite amounts of gallium, bismuth and lead were introduced into the molten aluminum and the resulting mixture stirred to elfect dispersion of the alloying ingredients throughout the melt. The resulting alloy was cast in a graphite mold into cylindrical specimens about 5 /2 inches long and about /8 inch in diameter. The cooling and solidification rate of the castings were controlled such that these simulated the cooling rate experienced in production of commercial, field-sized cast anodes.
  • the performance of the alloys was evaluated by positioning each cast cylindrical specimen. (as anode) in a schedule 40 steel can 3 inches in diameter and 6- inches tall (as cathode). Synthetic sea water was used as an electrolyte with about 4 inches of each specimen being immersed. The cells were complete with respect to electrical circuitry, a rectifier being employed to maintain a constant current through a group of cells connected in series.
  • alloys all exhibit a high oxidation potential and electrical output and are suitable for use as sacrificial anodes for applications such as galvanic pigments in paint films, galvanic anode materials for primary batteries, sacrificial galvanic coatings for sheet steel and other metals cathodic to aluminum and sacrificial anodes for cathodic protection. Additionally these compositions find utility as an active ingredient in flares, for use in chemical reductions and in the preparation of aluminum alkyls.
  • An aluminum based sacrificial galvanic anode havmg a high useful oxidation potential and a high electrical equivalent which comprises;
  • An aluminum based sacrificial galvanic anode having a high useful oxidation potential and a high electrical equivalent which comprises;

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Prevention Of Electric Corrosion (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Electrolytic Production Of Metals (AREA)
US384795A 1964-07-23 1964-07-23 Aluminum alloys and galvanic anodes made therefrom Expired - Lifetime US3337333A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US384795A US3337333A (en) 1964-07-23 1964-07-23 Aluminum alloys and galvanic anodes made therefrom
SE9022/65A SE307675B (da) 1964-07-23 1965-07-08
FR25236A FR1440519A (fr) 1964-07-23 1965-07-20 Alliage à base d'aluminium, plus particulièrement pour anode galvanique
DEP1268A DE1268852B (de) 1964-07-23 1965-07-21 Aluminiumlegierung und deren Verwendung fuer galvanische Opferanoden
GB31182/65A GB1066723A (en) 1964-07-23 1965-07-22 Aluminum alloy particularly for galvanic anodes
ES0315699A ES315699A1 (es) 1964-07-23 1965-07-22 Un procedimiento para fabricar anodos consumibles.
BE667339A BE667339A (da) 1964-07-23 1965-07-23
DK380865AA DK113536B (da) 1964-07-23 1965-07-23 Aluminiumlegering fortrinsvis til brug ved fremstilling af offeranode til katodisk korrosionsbeskyttelse.
NL656509584A NL146540B (nl) 1964-07-23 1965-07-23 Werkwijze voor het bereiden van aluminiumlegeringen, die geschikt zijn voor de vervaardiging van verbruikbare anoden, en uit aldus bereide aluminiumlegeringen vervaardigde anoden.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US384795A US3337333A (en) 1964-07-23 1964-07-23 Aluminum alloys and galvanic anodes made therefrom

Publications (1)

Publication Number Publication Date
US3337333A true US3337333A (en) 1967-08-22

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US384795A Expired - Lifetime US3337333A (en) 1964-07-23 1964-07-23 Aluminum alloys and galvanic anodes made therefrom

Country Status (8)

Country Link
US (1) US3337333A (da)
BE (1) BE667339A (da)
DE (1) DE1268852B (da)
DK (1) DK113536B (da)
ES (1) ES315699A1 (da)
GB (1) GB1066723A (da)
NL (1) NL146540B (da)
SE (1) SE307675B (da)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5547560A (en) * 1993-10-29 1996-08-20 Etat Francais Represented By The Delegue General Pour L'armement Consumable anode for cathodic protection, made of aluminum-based alloy
US5728275A (en) * 1996-09-13 1998-03-17 Alumax Extrusions, Inc. Sacrificial anode and method of making same
CN112725809A (zh) * 2020-12-24 2021-04-30 中国科学院海洋研究所 一种AgBiS2敏化TiO2复合膜材料的应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1771805B1 (de) * 1968-07-12 1971-08-26 Guldager Electrolyse Verfahren zur erzeugung von korrosionsschutzschichten in rohrleitungen und armaturen

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1997165A (en) * 1933-10-20 1935-04-09 Aluminum Co Of America Duplex metal article
US2565544A (en) * 1946-08-28 1951-08-28 Aluminum Co Of America Cathodic protection and underground metallic structure embodying the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1997165A (en) * 1933-10-20 1935-04-09 Aluminum Co Of America Duplex metal article
US2565544A (en) * 1946-08-28 1951-08-28 Aluminum Co Of America Cathodic protection and underground metallic structure embodying the same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5547560A (en) * 1993-10-29 1996-08-20 Etat Francais Represented By The Delegue General Pour L'armement Consumable anode for cathodic protection, made of aluminum-based alloy
US5728275A (en) * 1996-09-13 1998-03-17 Alumax Extrusions, Inc. Sacrificial anode and method of making same
US5853553A (en) * 1996-09-13 1998-12-29 Alumax Extrusions, Inc. Sacrificial anode and method of making same
CN112725809A (zh) * 2020-12-24 2021-04-30 中国科学院海洋研究所 一种AgBiS2敏化TiO2复合膜材料的应用

Also Published As

Publication number Publication date
BE667339A (da) 1966-01-24
ES315699A1 (es) 1966-03-01
GB1066723A (en) 1967-04-26
SE307675B (da) 1969-01-13
DK113536B (da) 1969-03-31
NL6509584A (da) 1966-01-24
DE1268852B (de) 1968-05-22
NL146540B (nl) 1975-07-15

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