WO1992000400A1 - Reference electrodes and electrode assemblies for protection of submarine structures - Google Patents

Reference electrodes and electrode assemblies for protection of submarine structures Download PDF

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Publication number
WO1992000400A1
WO1992000400A1 PCT/GB1991/001002 GB9101002W WO9200400A1 WO 1992000400 A1 WO1992000400 A1 WO 1992000400A1 GB 9101002 W GB9101002 W GB 9101002W WO 9200400 A1 WO9200400 A1 WO 9200400A1
Authority
WO
WIPO (PCT)
Prior art keywords
reference electrode
chamber
assembly according
cup
sealing means
Prior art date
Application number
PCT/GB1991/001002
Other languages
French (fr)
Inventor
Richard Brian Hughes
Peter Woodland
Original Assignee
Corrintec/Uk Limited
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 Corrintec/Uk Limited filed Critical Corrintec/Uk Limited
Publication of WO1992000400A1 publication Critical patent/WO1992000400A1/en

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Classifications

    • 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
    • C23F13/04—Controlling or regulating desired parameters
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N17/00—Investigating resistance of materials to the weather, to corrosion, or to light
    • G01N17/02—Electrochemical measuring systems for weathering, corrosion or corrosion-protection measurement
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/301—Reference electrodes
    • 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

  • This invention relates to reference electrodes and also to assemblies of reference electrodes and associated components for use in the electrolytic protection against corrosion of submarine structures.
  • the invention is particularly intended for use in the protection of the hull of a submarine vessel but the invention is intended to have utility in the protection of other submarine structures, particularly those intended for use at great depth.
  • the purpose of the reference electrode is to provide a measure of the potential difference between the electrode and sea water. This measure of potential may be employed by a control system to control the current impressed on an anode which is likewise associated with the structure.
  • a reference electrode in the form of for example a sintered mixture of silver and silver choride within a cup or shallow retainer of the same metal and to provide at the rear of the cup a bundle of filaments of the reference metal.
  • the filaments may be sintered to the cup.
  • the purpose of the filaments is to provide by means of a tubular connector a connection of the reference electrode to an electrical cable which couples the electrode to the remainder of the control system.
  • the cup may be mounted in a conformingly shaped recess in a support body which may be of a suitable synthetic, insulating material such as a glass-reinforced plastic or an epoxy resin.
  • reference electrodes of this generally known construction operate satisfactorily, they are, when used at substantial depths of water, potentially susceptible to ingress of water between the electrode and its insulating support, particularly between the metal cup and the surrounding material. This ingress of water degrades the electrical performance of the cell because the potential measured by the reference electrode will then be that between the material of the connector and seawater rather than between the reference electrode and seawater.
  • the present invention is concerned with an improved construction of reference electrode and a correspondingly improved design for an electrode assembly.
  • the main object of the invention is to facilitate the exclusion of seawater from the region in which the silver/silver chloride reference electrode is connected to or is adapted to be connected to the electrical cable.
  • a further or alternative object of the invention is to provide an electrode or electrode assembly which is more convenient to manufacture and/or assemble.
  • the invention is based on a reference electrode for use in protection of submarine structures against corrosion comprising a body of a reference electrode material within an insulating support body and a rigid extension from the rear of the electrode through the body, the extension being adapted for connection at a terminal portion.
  • the purpose of the extension is to enable the electrode to be accommodated in an assembly which includes a seal around the rigid extension so that an additional barrier to the ingress of water may be provided and thereby ensure that the connection between the terminal portion and the cable can be made in a dry region.
  • the single figure illustrates a particular embodiment by way of example of a reference electrode assembly which is primarily though not exclusively intended for use in the protection from corrosion of a submarine vessel or other submarine structure intended to be used or disposed at a substantial depth in seawater.
  • the reference electrode itself is mainly constituted by a body or mass 1 of reference electrode material. This preferably consists of a sintered body of silver and silver chloride but other materials may be used.
  • the body of reference electrode material is disposed within a shallow cup 2 of silver.
  • the electrode itself is disposed in a facial recess 3 in an insulating body 4. This body may be formed by potting with epoxy resin in a container 5, which may be a shell in two parts 6 and 7.
  • the shell is filled, apart from the components which are thereby embedded, with the epoxy resin so as to secure the reference electrode and a hollow body 8, constituting an adaptor, which is generally cylindrical in form and which has a radial flange 9 disposed within the epoxy body or infill 3.
  • the front of the reference electrode is protected by means of a mat 1A which may be of woven glass and which is held in place between the epoxy resin infill 3 and the front portion 6 of the shell.
  • the adaptor 8 has rearwardly of the flange an external annular portion 10 which is of substantially the same diameter as the internal diameter of the central aperture 11 of the rear portion 7 of the shell.
  • the adaptor 8 has an internal chamber 12. Forward of the chamber is an internally threaded portion 13, a bevelled annular shoulder 14 constituting a seat and a front passageway 15. Rearwardly of the chamber is a wider, internally threaded portion 16.
  • a rod or spigot 17 From the rear of the reference electrode extends a rod or spigot 17.
  • the extension is substantially of the same material as the cup and can be made integrally with or joined to the cup.
  • the spigot 17 extends rearwardly from the cup through the epoxy resin infill 3 into the adaptor 8.
  • an insulating flanged sleeve 18 Between the front, annular face of the adaptor 8 and the infill 3 is an insulating flanged sleeve 18 which has a flange portion abutting the front face of the adaptor 8 and an axial portion which fits closely around the spigot and fits into the front passageway 15 of the adaptor 8.
  • the sleeve should be hydrophobic and may comprise polyethylene of high molecular weight.
  • a rubber gland seal 19 Disposed on the seat 14 formed within the bore of the adaptor is a rubber gland seal 19. This closely surrounds the rod extension. If necessary a PVC sleeve 20 may be fitted around the rod 17 inside the seal 19. A "nylon” (Registered Trade Mark) washer is disposed against the seal 19, which is forced against the seat to provide a close seal by means of an inner gland screw plug 22 which has an external screw threading engaging the first screw threaded portion 13 of the adaptor 8.
  • the inner gland screw plug 22 which may be made of a synthetic resin bonded fabric, has an internal bore 23 which accommodates a tubular connector 24, which connects a terminal portion of the rod 17 to the terminal portion of an electrical cable 29.
  • the connection between the rod 17 (and thereby the reference electrode) and the cable 29 is protected by a multiple seal (the seal 19 and the seat 25).
  • the inner gland screw Secured to and sealing the inside of the screw plug 22 the inner gland screw is a seat 25 which is a close fit within the chamber portion of the adaptor 8.
  • the seat has an internal bore, which accommodates the cable 29, and a part conical seat for the accommodation of a rubber gland seal 26.
  • the gland seal closely surrounds the cable and is forced into sealing relationship with the seat and the cable by means of an outer gland screw 27 which screws into the rear threaded portion 16 of the adaptor.
  • a nylon washer 28, to prevent undue distortion of the rubber gland seal may be disposed between the outer gland screw 27 and the rubber gland seal 26.
  • the reference electrode would usually be fitted into an aperture in the submarine hull or other deep-water structure which is to be protected.
  • the second seal 26 protects the interior of the hull against failure of the outer seal 19.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Immunology (AREA)
  • General Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Pathology (AREA)
  • General Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Environmental Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Ecology (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Prevention Of Electric Corrosion (AREA)
  • Laying Of Electric Cables Or Lines Outside (AREA)

Abstract

A reference electrode for use in corrosive protection includes a sintered body of silver/silver chloride material disposed in a cup secured in an epoxy resin body. A rigid member extends from the cup rearwardly of the body into a sealed chamber within an adaptor member. The adaptor member accommodates the terminal portion of the electric cable and includes a cable joint connecting the rear terminal portion of the extension member and the terminal part of the cable.

Description

REFERENCE ELECTRODES AND ELECTRODE ASSEMBLIES FOR PROTECTION OF SUBMARINE STRUCTURES
This invention relates to reference electrodes and also to assemblies of reference electrodes and associated components for use in the electrolytic protection against corrosion of submarine structures. The invention is particularly intended for use in the protection of the hull of a submarine vessel but the invention is intended to have utility in the protection of other submarine structures, particularly those intended for use at great depth.
The purpose of the reference electrode, as is well known, is to provide a measure of the potential difference between the electrode and sea water. This measure of potential may be employed by a control system to control the current impressed on an anode which is likewise associated with the structure.
It is commonplace to provide a reference electrode in the form of for example a sintered mixture of silver and silver choride within a cup or shallow retainer of the same metal and to provide at the rear of the cup a bundle of filaments of the reference metal. The filaments may be sintered to the cup. The purpose of the filaments is to provide by means of a tubular connector a connection of the reference electrode to an electrical cable which couples the electrode to the remainder of the control system. The cup may be mounted in a conformingly shaped recess in a support body which may be of a suitable synthetic, insulating material such as a glass-reinforced plastic or an epoxy resin.
Though reference electrodes of this generally known construction operate satisfactorily, they are, when used at substantial depths of water, potentially susceptible to ingress of water between the electrode and its insulating support, particularly between the metal cup and the surrounding material. This ingress of water degrades the electrical performance of the cell because the potential measured by the reference electrode will then be that between the material of the connector and seawater rather than between the reference electrode and seawater.
The present invention is concerned with an improved construction of reference electrode and a correspondingly improved design for an electrode assembly. The main object of the invention is to facilitate the exclusion of seawater from the region in which the silver/silver chloride reference electrode is connected to or is adapted to be connected to the electrical cable. A further or alternative object of the invention is to provide an electrode or electrode assembly which is more convenient to manufacture and/or assemble.
Summary of the Invention
The invention is based on a reference electrode for use in protection of submarine structures against corrosion comprising a body of a reference electrode material within an insulating support body and a rigid extension from the rear of the electrode through the body, the extension being adapted for connection at a terminal portion. The purpose of the extension is to enable the electrode to be accommodated in an assembly which includes a seal around the rigid extension so that an additional barrier to the ingress of water may be provided and thereby ensure that the connection between the terminal portion and the cable can be made in a dry region.
Other objects and advantages will be more clearly apparent from consideration of a detailed embodiment of the invention, which will be described with reference to the accompanying drawing.
Brief Description of the Drawing
The accompanying figure illustrates in section one embodiment of an electrode assembly according to the invention.
Description of a preferred embodiment
The single figure illustrates a particular embodiment by way of example of a reference electrode assembly which is primarily though not exclusively intended for use in the protection from corrosion of a submarine vessel or other submarine structure intended to be used or disposed at a substantial depth in seawater. The reference electrode itself is mainly constituted by a body or mass 1 of reference electrode material. This preferably consists of a sintered body of silver and silver chloride but other materials may be used. The body of reference electrode material is disposed within a shallow cup 2 of silver. The electrode itself is disposed in a facial recess 3 in an insulating body 4. This body may be formed by potting with epoxy resin in a container 5, which may be a shell in two parts 6 and 7. The shell is filled, apart from the components which are thereby embedded, with the epoxy resin so as to secure the reference electrode and a hollow body 8, constituting an adaptor, which is generally cylindrical in form and which has a radial flange 9 disposed within the epoxy body or infill 3.
The front of the reference electrode is protected by means of a mat 1A which may be of woven glass and which is held in place between the epoxy resin infill 3 and the front portion 6 of the shell.
The adaptor 8 has rearwardly of the flange an external annular portion 10 which is of substantially the same diameter as the internal diameter of the central aperture 11 of the rear portion 7 of the shell.
The adaptor 8 has an internal chamber 12. Forward of the chamber is an internally threaded portion 13, a bevelled annular shoulder 14 constituting a seat and a front passageway 15. Rearwardly of the chamber is a wider, internally threaded portion 16.
From the rear of the reference electrode extends a rod or spigot 17. The extension is substantially of the same material as the cup and can be made integrally with or joined to the cup. The spigot 17 extends rearwardly from the cup through the epoxy resin infill 3 into the adaptor 8. Between the front, annular face of the adaptor 8 and the infill 3 is an insulating flanged sleeve 18 which has a flange portion abutting the front face of the adaptor 8 and an axial portion which fits closely around the spigot and fits into the front passageway 15 of the adaptor 8. The sleeve should be hydrophobic and may comprise polyethylene of high molecular weight.
Disposed on the seat 14 formed within the bore of the adaptor is a rubber gland seal 19. This closely surrounds the rod extension. If necessary a PVC sleeve 20 may be fitted around the rod 17 inside the seal 19. A "nylon" (Registered Trade Mark) washer is disposed against the seal 19, which is forced against the seat to provide a close seal by means of an inner gland screw plug 22 which has an external screw threading engaging the first screw threaded portion 13 of the adaptor 8.
The inner gland screw plug 22, which may be made of a synthetic resin bonded fabric, has an internal bore 23 which accommodates a tubular connector 24, which connects a terminal portion of the rod 17 to the terminal portion of an electrical cable 29. The connection between the rod 17 (and thereby the reference electrode) and the cable 29 is protected by a multiple seal (the seal 19 and the seat 25).
Secured to and sealing the inside of the screw plug 22 the inner gland screw is a seat 25 which is a close fit within the chamber portion of the adaptor 8. The seat has an internal bore, which accommodates the cable 29, and a part conical seat for the accommodation of a rubber gland seal 26. The gland seal closely surrounds the cable and is forced into sealing relationship with the seat and the cable by means of an outer gland screw 27 which screws into the rear threaded portion 16 of the adaptor. A nylon washer 28, to prevent undue distortion of the rubber gland seal may be disposed between the outer gland screw 27 and the rubber gland seal 26.
The reference electrode would usually be fitted into an aperture in the submarine hull or other deep-water structure which is to be protected. The second seal 26 protects the interior of the hull against failure of the outer seal 19.

Claims

1. A reference electrode for use in protection against corrosion of a submarine structure, comprising a body (1) of reference electrode material supported in a compatible cup (2) of reference electrode material, and extending rearwardly of the cup a rigid extension member (17) of substantially the same material, and terminating in a portion adapted for connection.
2. An electrode assembly comprising an insulating body (3), having at one side a recess (4) including a reference electrode (1) , a hollow member (8) which at one end is disposed within the insulating body and which defines an internal chamber (12), an extension member (17) which is of similar material to that of the reference electrode and which extends from the reference electrode with the said chamber; and sealing means (19) between the extension member and the hollow member, to provide a barrier to ingress of water into the chamber.
3. An assembly according to claim 2, in which the said hollow member (8) includes a passageway (15) which leads to said chamber and includes a seat (14) for a sealing means, and further comprising means (22) engageable with the chamber to urge the sealing means against the seat.
4. An assembly according to claim 3 in which the means (22) engageable with the chamber comprises a screw plug.
5. An assembly according to any of claims 2 to 4 and comprising a connector (24) for connecting said extension member (17) to an electrical cable (29).
6. An assembly according to claim 4 and claim 5 in which the screw plug (22) accommodates the connector (24).
7. An assembly according to any of claims 2 to 6 further comprising a second sealing means (26) adapted to accommodate an electrical cable extending into the chamber.
8. An assembly according to claim 7 in which the second sealing means (26) comprises an annular sealing member for disposition between the cable (29) and the hollow member (8).
PCT/GB1991/001002 1990-06-25 1991-06-20 Reference electrodes and electrode assemblies for protection of submarine structures WO1992000400A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB909014123A GB9014123D0 (en) 1990-06-25 1990-06-25 Reference electrodes and electrode assemblies for protection of submarine structures
GB9014123.5 1990-06-25

Publications (1)

Publication Number Publication Date
WO1992000400A1 true WO1992000400A1 (en) 1992-01-09

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PCT/GB1991/001002 WO1992000400A1 (en) 1990-06-25 1991-06-20 Reference electrodes and electrode assemblies for protection of submarine structures

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GB (1) GB9014123D0 (en)
WO (1) WO1992000400A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19882506B4 (en) * 1997-07-02 2009-01-02 Mine Safety Appliances Co. Electrochemical sensor for detecting hydrogen cyanide and method for using the electrochemical sensor
US8231591B2 (en) 2006-04-21 2012-07-31 Kimberly-Clark Worldwide, Inc. Absorbent article with lengthwise, compact-fold

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3129161A (en) * 1958-10-10 1964-04-14 Engelhard Ind Inc Reference electrode assembly
US3625851A (en) * 1969-11-24 1971-12-07 Us Navy Underwater replaceable reference electrode

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3129161A (en) * 1958-10-10 1964-04-14 Engelhard Ind Inc Reference electrode assembly
US3625851A (en) * 1969-11-24 1971-12-07 Us Navy Underwater replaceable reference electrode

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19882506B4 (en) * 1997-07-02 2009-01-02 Mine Safety Appliances Co. Electrochemical sensor for detecting hydrogen cyanide and method for using the electrochemical sensor
US8231591B2 (en) 2006-04-21 2012-07-31 Kimberly-Clark Worldwide, Inc. Absorbent article with lengthwise, compact-fold

Also Published As

Publication number Publication date
GB9014123D0 (en) 1990-08-15

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