US3033775A - Anode for cathodic protection - Google Patents

Anode for cathodic protection Download PDF

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Publication number
US3033775A
US3033775A US830784A US83078459A US3033775A US 3033775 A US3033775 A US 3033775A US 830784 A US830784 A US 830784A US 83078459 A US83078459 A US 83078459A US 3033775 A US3033775 A US 3033775A
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United States
Prior art keywords
anode
titanium
cathodic protection
alloy
iron
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Expired - Lifetime
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US830784A
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Raymond A Chevigny
Richaud Henri
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Pechiney SA
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Pechiney SA
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    • 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
    • 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
    • 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
    • C23F2213/00—Aspects of inhibiting corrosion of metals by anodic or cathodic protection
    • C23F2213/30—Anodic or cathodic protection specially adapted for a specific object
    • C23F2213/31—Immersed structures, e.g. submarine structures

Definitions

  • cathodic protection wherein a sacrificial anode is used having a lower electrolytic potential than the material of which the object to be protected is made.
  • this protection is brought about by the formation of a galvanic action be tween the metal to be protected and the sacrificial anode; sometimes a direct current is connected between the auxiliary anode and the metal to be protected.
  • anodes made of steel, graphite, or platinum have been used, although most of these materials have drawbacks. For instance, steel anodes are rapidly destroyed.
  • Another object of this invention is the provision of an anode which has a fairly long life, which does not become brittle, and which is relatively inexpensive to manufacture.
  • the invention comprises the features hereinafter fully described and particularly pointed out in the claims, the following description and the annexed drawing setting forth in detail an illustrative embodiment of the invention, this being indicative, however, of but one of the various ways in which the principle of the invention may be employed.
  • the single figure is a schematic illustration of the method in which the anode of the invention may be applied to the protection of an iron ship.
  • a source 14 of direct electrical current is connected between the anode 10 and the ship 11, the positive poles of the source being connected to the anodes and the negative pole being connected to the ship.
  • the ship 11 is made of iron and, as is well known, would readily be attacked by the salt water if no means were provided for protecting it.
  • the anode 10 consists of an alloy containing a predominant proportion of titanium; the alloy is characterized as a composition of matter that contains 3,033,775 Patented May 8, 1962 at least one element which lowers the polarization voltage of titanium.
  • titanium alloys will be used which contain one or more members such as cobalt, nickel, manganese, zinc, tin, or the like which have the effect of lowering the polarization potential of titanium.
  • Such an alloy may also contain aluminum. It is particularly advantageous to use a titanium alloy in which the additional element amounts to .5 to 10% by weight of the elements.
  • the anode 10 is used without a coating of any sort, contrary to the usual practice of using pure titanium which has been platinum plated. Furthermore, the alloy of the anode 10 may have its polarization potential further lowered by a heat treatment such as annealing or quenching followed by a tempermg.
  • An iron plate was placed in sea water at room temperature with an anode formed of an alloy of titanium having 4% aluminum and 4% manganese.
  • the anode was connected to the positive pole of a generator of direct current electricity and the iron sheet was connected to the negative pole.
  • the test was carried on for 500 hours with a cathodic current of 150 milliamperes per square meter.
  • the voltage after two hours was three volts.
  • the voltage after 100 hours was 2.8 volts and the voltage after 500 hours was 3 volts.
  • the iron sheet showed no trace of corrosion after the test.
  • a second example of the use of the anode of the invention involved the comparison of an iron plate having an anode formed of pure titanium with a similar iron plate having an anode having titanium alloy with 4% manganese both being tested in sea Water.
  • the pure titanium anode when used with an anodic current density of 0.2 amp. per sq. decimeter (20 amps. per sq. meter), a voltage of at least 8.5 volts was necessary.
  • the titanium alloy having a 4% content of manganese it was only necessary to use 4.5 volts to maintain the same current.
  • the pure titanium anode required a voltage of 6.5 volts while the alloy anode required only 3 volts to maintain that current.
  • Apparatus for the cathodic protection of an iron device immersed in salt water comprising an anode, a source of direct current electricity connected to the device at its negative terminal and to the anode at its posi tive terminal, the anode consisting of an alloy of titanium and a metal selected from the class consisting of manganese, cobalt, nickel, zinc, and tin, the proportion of the total of the said metals being from 0.5% to 10% by weight, the total titanium being substantially or over by weight.

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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)

Description

May 8, 1962 R. A. CHEVIGNY ET ANODE FOR CATHODIC PROTECTION i ||'+a 3| l II Filed July 51, 1959 lll TITANIUM ALLOY INVENTORS Raymoncl llcheu'iqny yHenTi Richaud H nay United States Patent Filed July 31, 1959, Ser. N0. 830,784 Claims priority, application France g- 1953 2 Claims. (Cl. 204-196) This invention relates to an anode for cathodic protection and more particularly to a sacrificial anode for use in protecting iron objects immersed in sea water and the like.
When objects such as ships are immersed for long periods of time in salt water they are subjected to considerable corrosion due to electrolytic action. For that reason it is usual to use a so-called cathodic protection, wherein a sacrificial anode is used having a lower electrolytic potential than the material of which the object to be protected is made. Sometimes this protection is brought about by the formation of a galvanic action be tween the metal to be protected and the sacrificial anode; sometimes a direct current is connected between the auxiliary anode and the metal to be protected. In the past anodes made of steel, graphite, or platinum have been used, although most of these materials have drawbacks. For instance, steel anodes are rapidly destroyed. Those which are formed of graphite show a tendency to become very brittle, while platinum anodes are very expensive. At times the metal titanium has been proposed for use in the anode, but it suffers from the nature of a strong polarization so that the auxiliary source of electrical current must be of rather high voltage. These and other difficulties experienced with the prior art devices have been obviated in a novel manner by the present invention.
It is, therefore, an outstanding object of the present invention to provide a novel anode for cathodic protection and more particularly for the cathodic protection of metals using an auxiliary source of electrical current.
Another object of this invention is the provision of an anode which has a fairly long life, which does not become brittle, and which is relatively inexpensive to manufacture.
To the accomplishment of the foregoing and related ends, the invention, then, comprises the features hereinafter fully described and particularly pointed out in the claims, the following description and the annexed drawing setting forth in detail an illustrative embodiment of the invention, this being indicative, however, of but one of the various ways in which the principle of the invention may be employed.
In said annexed drawing:
The single figure is a schematic illustration of the method in which the anode of the invention may be applied to the protection of an iron ship.
Referring now to the drawing, the anode of the invention, indicated generally by the referencenumeral 10,
is shown in use as associated with an iron or steel ship 11 intended for use in a body 12 of sea water. As is evident in the drawing, the anode is separated electrically from the ship 11 by electrical insulation 13. A source 14 of direct electrical current is connected between the anode 10 and the ship 11, the positive poles of the source being connected to the anodes and the negative pole being connected to the ship.
The ship 11 is made of iron and, as is well known, would readily be attacked by the salt water if no means were provided for protecting it. The anode 10 consists of an alloy containing a predominant proportion of titanium; the alloy is characterized as a composition of matter that contains 3,033,775 Patented May 8, 1962 at least one element which lowers the polarization voltage of titanium. For instance, titanium alloys will be used which contain one or more members such as cobalt, nickel, manganese, zinc, tin, or the like which have the effect of lowering the polarization potential of titanium. Such an alloy may also contain aluminum. It is particularly advantageous to use a titanium alloy in which the additional element amounts to .5 to 10% by weight of the elements. It should be noted that the anode 10 is used without a coating of any sort, contrary to the usual practice of using pure titanium which has been platinum plated. Furthermore, the alloy of the anode 10 may have its polarization potential further lowered by a heat treatment such as annealing or quenching followed by a tempermg.
An example of the use of an anode made according to the invention is as follows:
An iron plate was placed in sea water at room temperature with an anode formed of an alloy of titanium having 4% aluminum and 4% manganese. The anode was connected to the positive pole of a generator of direct current electricity and the iron sheet was connected to the negative pole. The test was carried on for 500 hours with a cathodic current of 150 milliamperes per square meter. The voltage after two hours (approximately at the beginning of the test) was three volts. The voltage after 100 hours was 2.8 volts and the voltage after 500 hours was 3 volts. There was negligible loss of weight of the titanium electrode and there was a negligible loss of weight for the iron plate. The iron sheet showed no trace of corrosion after the test.
A second example of the use of the anode of the invention involved the comparison of an iron plate having an anode formed of pure titanium with a similar iron plate having an anode having titanium alloy with 4% manganese both being tested in sea Water. In the first case, when the pure titanium anode was used with an anodic current density of 0.2 amp. per sq. decimeter (20 amps. per sq. meter), a voltage of at least 8.5 volts was necessary. In the test with the titanium alloy having a 4% content of manganese, it was only necessary to use 4.5 volts to maintain the same current. When the current density was decreased to 0.0015 amp. per sq. decimeter (0.15 amp. per sq. meter) the pure titanium anode required a voltage of 6.5 volts while the alloy anode required only 3 volts to maintain that current.
Other modes of practicing the principle of the invention may be employed, changes being made as regards the details described, provided the features stated in the following claim, or equivalent of such, be employed.
The invention having been thus described, what is claimed as new and desired to secure by Letters Patent is as follows:
1. Apparatus for the cathodic protection of an iron device immersed in salt water, comprising an anode, a source of direct current electricity connected to the device at its negative terminal and to the anode at its posi tive terminal, the anode consisting of an alloy of titanium and a metal selected from the class consisting of manganese, cobalt, nickel, zinc, and tin, the proportion of the total of the said metals being from 0.5% to 10% by weight, the total titanium being substantially or over by weight.
2. Apparatus as recited in claim 1 wherein the said alloy includes aluminum.
References Cited in the file of this patent UNITED STATES PATENTS 2,636,856 Suggs et al Apr. 28, 1953 2,822,269 Long Feb. 4, 1958' 2,878,173 Obermann Mar. 17,1959

Claims (1)

1. APPARATUS FOR THE CATHODIC PROTECTION OF AN IRON DEVICE IMMERSED IN SALT WATER, COMPRISING AN ANODE, A SOURCE OF DIRECT CURRENT ELECTRICITY CONNECTED TO THE DEVICE AT ITS NEGATIVEE TERMINAL AND TO THE ANODE AT ITS POSITIVE TERMINAL, THE ANODE CONSISTING OF AN ALLOY OF TITANIUM AND A METAL SELECTEED FROM THE CLASS CONSISTING OF MANGANESE, COBALT, NICKEL, ZINC, AND TIN, THE PROPORTION OF THE TOTAL OF THE SAID METALS BEING FROM 0.5% TO 100% BY
US830784A 1958-08-07 1959-07-31 Anode for cathodic protection Expired - Lifetime US3033775A (en)

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DE (1) DE1135727B (en)
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GB (1) GB904553A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4080278A (en) * 1975-07-08 1978-03-21 Rhone-Poulenc Industries Cathode for electrolytic cell
US4663010A (en) * 1985-05-08 1987-05-05 Sigri Gmbh Anode for electrochemical process
US4997492A (en) * 1990-06-08 1991-03-05 Nippon Mining Co., Ltd. Method of producing anode materials for electrolytic uses
US5052962A (en) * 1990-05-21 1991-10-01 The United States Of America As Represented By The Secretary Of The Navy Naval electrochemical corrosion reducer
US5061358A (en) * 1990-06-08 1991-10-29 Nippon Mining Co., Ltd. Insoluble anodes for producing manganese dioxide consisting essentially of a titanium-nickel alloy
US10309019B2 (en) 2017-08-01 2019-06-04 Frank Seth Gaunce Corrosion protection methods for the protection of the national infrastructure of copper/iron, copper, lead/iron potable water distribution systems and the national iron-based infrastructure

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140262824A1 (en) * 2013-03-15 2014-09-18 Physical Sciences, Inc. Corrosion protection system for non-immersed equipment

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2636856A (en) * 1948-06-29 1953-04-28 Mallory & Co Inc P R Electrode for electrochemical oxidation
US2822269A (en) * 1953-06-22 1958-02-04 Roger A Long Alloys for bonding titanium base metals to metals
US2878173A (en) * 1957-06-04 1959-03-17 Obermann Walter Method for cathodic protection of ship hulls in sea water by electron concentration

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2636856A (en) * 1948-06-29 1953-04-28 Mallory & Co Inc P R Electrode for electrochemical oxidation
US2822269A (en) * 1953-06-22 1958-02-04 Roger A Long Alloys for bonding titanium base metals to metals
US2878173A (en) * 1957-06-04 1959-03-17 Obermann Walter Method for cathodic protection of ship hulls in sea water by electron concentration

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4080278A (en) * 1975-07-08 1978-03-21 Rhone-Poulenc Industries Cathode for electrolytic cell
US4663010A (en) * 1985-05-08 1987-05-05 Sigri Gmbh Anode for electrochemical process
US5052962A (en) * 1990-05-21 1991-10-01 The United States Of America As Represented By The Secretary Of The Navy Naval electrochemical corrosion reducer
US4997492A (en) * 1990-06-08 1991-03-05 Nippon Mining Co., Ltd. Method of producing anode materials for electrolytic uses
US5061358A (en) * 1990-06-08 1991-10-29 Nippon Mining Co., Ltd. Insoluble anodes for producing manganese dioxide consisting essentially of a titanium-nickel alloy
US10309019B2 (en) 2017-08-01 2019-06-04 Frank Seth Gaunce Corrosion protection methods for the protection of the national infrastructure of copper/iron, copper, lead/iron potable water distribution systems and the national iron-based infrastructure

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FR1205704A (en) 1960-02-04
GB904553A (en) 1962-08-29
DE1135727B (en) 1962-08-30

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