U.S. patent number 3,868,313 [Application Number 05/334,317] was granted by the patent office on 1975-02-25 for cathodic protection.
Invention is credited to Philip James Gay.
United States Patent |
3,868,313 |
Gay |
February 25, 1975 |
Cathodic protection
Abstract
A cathodic protection system for a metal substrate has an anode
which is normally electrically insulated from the substrate but
which is disposed very close to the substrate. Cathodic protection
only becomes effective when the electrical insulation breaks down
and the metal substrate would otherwise be subject to corrosion.
The system comprises an electrically insulating coating on the
metal substrate and an electrically conducting coating applied over
the insulating coating, a D.C. voltage being applied between the
metal substrate and the conductive coating. The conductive coating
or the insulating coating or both may be paint, the conductive
layer being rendered conductive by the incorporation of an
electrically conductive material such as elemental carbon.
Inventors: |
Gay; Philip James (Hull,
Yorkshire, EN) |
Family
ID: |
9858967 |
Appl.
No.: |
05/334,317 |
Filed: |
February 21, 1973 |
Foreign Application Priority Data
|
|
|
|
|
Feb 25, 1972 [GB] |
|
|
8771/72 |
|
Current U.S.
Class: |
204/196.36;
204/196.38 |
Current CPC
Class: |
C23F
13/02 (20130101) |
Current International
Class: |
C23F
13/02 (20060101); C23F 13/00 (20060101); C23f
013/00 () |
Field of
Search: |
;204/147,148,196,197 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Tung; T.
Attorney, Agent or Firm: Hall and Myers
Claims
I claim:
1. A cathodic protection system comprising a metal to be protected,
an electrically non-conductive coating applied in fluid form over
the metal, an electrically conductive coating applied in fluid form
over the non-conductive coating, said conductive coating being
rendered electrically conductive by the incorporation of elemental
carbon therein, such that the metal and electrically conductive
coating are electrically insulated one from the other, a source of
D.C. voltage being connected between the metal and the electrically
conductive coating such that the electrically conductive coating is
anodic with respect to the metal.
2. A cathodic protection system according to claim 1, wherein said
conductive coating is a paint composition.
3. A cathodic protection system according to claim 2 in which the
electrically conductive coating has a resistivity of up to 1,000
ohms/ft. sq.
4. A cathodic protection system according to claim 2 wherein the
carbon content is up to 50 percent by volume of dried coating.
5. A cathodic protection system according to claim 2 wherein the
conductive paint composition is a carbon-containing chlorinated
rubber paint.
6. A cathodic protection system according to claim 2 wherein the
conductive paint composition is a carbon-containing epoxy ester
paint.
7. A cathodic protection system according to claim 2 in which the
conductive paint composition is a carbon-containing chemically
cured pitch epoxy paint.
8. A cathodic protection system according to claim 1 wherein there
is another coating over the electrically conductive coating.
9. A cathodic protection system according to claim 1 in which the
D.C. voltage source is of sufficient size to provide sufficient
voltage to liberate chlorine from sea water.
10. A cathodic protection system according to claim 9 wherein the
D.C. voltage source is of a size sufficient to provide at least 1.4
volts.
Description
The present invention relates to a cathodic protection system for
the protection of metals such as the steel framework of buildings,
ships or pipelines.
The phenomenon of cathodic protection has been known and applied
industrially for many years. In a simple form, an iron/copper
couple is immersed in a sodium chloride solution and an auxiliary
anode is provided in electrical contact with the couple. The
auxiliary anode is capable of readily providing a supply of
electrons. The dissolution of the iron is reduced and the rate of
hydroxyl ion production at the copper raised, so that the
potentials of both the anode and the cathode are lowered.
By impressing an external cathodic current on the couple, the
anodic current is reduced and the cathodic current increased. The
corrosion current of the couple can be reduced to zero if the
cathode is polarized down to the unpolarized potential of the
anode.
A supply of electrons to protect a corroding metal can be provided
from a D.C. source, the negative terminal of which is joined to the
metal to be protected and the positive terminal to an anode, for
example, scrap iron or graphite, located adjacent the metal to be
protected and in a conducting medium.
One disadvantage with known cathodic protection systems is that the
anodes must be immersed or buried in a conducting electrolytic
medium and there must be a continuous conducting medium between the
anodes and the metal to be protected. The known systems cannot,
therefore, be applied to metal exposed to an air environment, such
as structural steelwork for buildings.
A further disadvantage is that the anodes are of small size in
relation to the metal to be protected, and in many cases are
somewhat remote. Much of the driving potential is, therefore,
absorbed in overcoming the resistance of the medium which, in the
case of land based structures, can vary widely. Current
distribution at the metal surface is, therefore, variable.
Generally the greatest current density appears at the parts of the
metal nearest to the anodes. Moreover there is always danger from
interference by and with other metal structures and considerable
study has to be made to overcome such interference. So important is
this matter, particularly with pipelines in industrial areas, that
it is sometimes deemed necessary to provide strip anodes of
aluminium or other metal in an adjacent trench alongside
pipelines.
According to the present invention there is provided a cathodic
protection system which comprises a metal to be protected, an
electrically non-conductive coating applied over the metal, an
electrically-conductive coating applied over the non-conductive
coating such that the metal and the electrically-conductive coating
are electrically insulated one from the other, a source of D.C.
voltage being applied between the metal and the
electrically-conductive coating such that the
electrically-conductive coating is anodic with respect to the
metal.
Hence, a permanent impressed current electrode is applied close to
all parts of the steel surface. Where any part of the steel is
subjected to corrosive influences as by damage to the protective
coating or by its saturation with aggressive aqueous solutions that
part of the anode closest to the point of potential corrosion
becomes effective. Thus the resistance of the circuit is
independent of the resistance of the surrounding medium except at
the immediate point of damage since virtually the whole of the
impressed current is carried by the conductive paint layer. It is,
therefore, not necessary to apply excessive potential to overcome
the resistance of the surrounding medium.
The anode and cathodic steel are so close that sufficient
electrolyte to maintain the protective current can be supplied by a
film of condensed moisture, or by rain or condensed water droplets.
On the other hand the system operates with equal effect when the
conducting medium at the point of damage is damp soil or aqueous
solution such as seawater in bulk. Thus the system is effective for
underwater protection, underground protection and overground
protection. Because of the continuous close proximity between anode
and cathode there is no requirement for long "throw" (the distance
over which current from the anodes is effective) to give
protection, and the system is effective on the insides of water
carrying pipes.
The invention will now be described further by way of example.
The metal such as steel to be protected is first prepared and
coated according to a known method typically by blast cleaning
through the impact of high velocity grit, abrasive slag or shot to
remove mill scale, rust etc., or by chemically pickling using an
inhibited acid solution or other chemical process. Alternatively
the metal may be cleaned by manual means to the required standard.
After cleaning the metal may be further chemically treated as by a
phosphate or chromate dip. Following the prescribed treatment the
metal is coated with an electrically insulating type material.
Apart from this, there is no limitation beyond the normal known
requirements of metal protection. Suitable coating materials are
bituminous compositions, many types of paints, particularly, though
not necessarily, those based on epoxy resins or chlorinated rubber,
natural and synthetic rubber, polyvinyl chloride, and other
synthetic resins, and certain wrapping materials. The
above-mentioned protective coating, which may be a single or
multiple application is then overcoated with an
electrically-conductive paint. The coating must be applied in such
a way that it is not in direct contact with the steel to be
protected, and should cover either the whole surface to be
protected or such part as is deemed necessary to give the required
protection. The conductive paint thickness is such as to produce
the required conductivity of the surface. In general, low
resistivity is desirable for protecting large areas or long
lengths, but very low resistivity is not always necessary nor
economically suitable. For many purposes a resistivity of not more
than 200 ohms per square (i.e. per square measuring one foot by one
foot) is adequate but resistivity of below 20 ohms per foot square
gives more control of the process. The conductive paints need to be
durable in the conditions of use and particular types must be used
with this in view so that sometimes it is necessary to sacrifice a
measure of conductivity to maintain durability.
Certain metal pigmented paints are suitable for use with the
present invention, though the selection of a particular type will
depend upon the conditions to which the system is to be exposed.
Non-metallic conductive paints are preferred to avoid loss of anode
and of conductivity.
Among the paints which can be used for the conductive coating are
chlorinated rubber paint, epoxy ester paint and chemically cured
pitch epoxy paint, each of which being compounded with the
incorporation of elemental carbon. A typical chlorinated rubber
paint is formed by grinding together 40 percent by weight of a
medium having the three components 30 percent by weight of a medium
viscosity grade chlorinated rubber or chlorinated synthetic rubber
such as alloprene R20, 10 percent by weight of a chlorinated
hydrocarbon plasticiser such as cereclor S52 and 60 percent by
weight of an aromatic hydrocarbon solvent having a boiling range of
165.degree. to 185.degree.C, such as shellsol A; 3 to 4 percent by
weight of a dispersible gas carbon black pigment such as carbon
black XC 72; 0.2 to 0.25 percent by weight of an
N-alkyltrimethylene diamine such as duomeen TDO; and 26 to 30
percent by weight of the aromatic solvent. 15 to 20 percent by
weight graphite is then added and fully dispersed by further
grinding. The composition is then thinned to the required
consistency with more of the aromatic solvent.
The electrical resistivity of a coating of chlorinated rubber paint
depends on the carbon content in the dried film. At 33 percent by
volume of pigment in the dried film, the resistivity is 10 to 12
ohms per foot square at 50 microns film thickness.
A typical epoxy ester paint is formed by mixing 0.02 grms
rosaniline base (an amine dyestuff base) with 18.3 grms of a 60
percent by weight solution of a linseed oil fatty acid ester of
epoxy resin and warming the mixture to 100.degree.C, 6 to 8 grms of
carbon black XC 72, 25 to 35 grms of white spirit and 30 to 35 grms
xylol are then added and the whole is ground in a pebble mill for
at least 24 hours, 12 to 16 grms of a coarse pigment grade lamellar
graphite such as graphite foliac X1204 is then added and the
mixture is further ground until the graphite is fully dispersed. An
epoxy ester paint having a pigment content of 45 percent by volume
in a dried film has an electrical resistivity of 7 ohms per foot
square at 50 microns film thickness.
Chemically cured pitch epoxy paint is formed in two packs, pack A
typically being formed by grinding together 3 to 4 percent by
weight of carbon black XC72, 15 to 20 percent by weight of a coarse
pigment grade lamellar graphite such as graphite 152S, 18 to 25
percent by weight of a 5 to 1 by weight mixture of xylol and
N-butanol, and a medium which comprises 14.3 percent by weight of
an epoxy resin, such as epikote resin 1001, having an epoxy
equivalent 450 to 525, 14.3 percent by weight of an epoxy resin,
such as epikote resin 828, having an epoxy equivalent of 175 to
210, 40 to 50 percent by weight of a coal tar pitch, such as orgol
pitch which has viscosity of approximately 100 poise at
15.5.degree.C, 20 to 25 percent by weight xylol, and 3 to 6 percent
by weight of N-butanol. Pack B comprises 93.5 percent by weight of
a 50 percent by weight solution of beckalide resin (a polyamide
resin of amine number 140 to 150) in a solvent such as 5 to 1 by
weight xylol and N-butanol or 4 to 1 by weight xylol and propanol,
and 6.5 percent by weight of a curing agent such as curing agent
K54 which is 2:4:6 tris(dimethylaminomethyl)phenol. Pack B is added
to pack A in a ratio to give optimum reaction with the epoxy resin.
The electrical resistivity of such a paint is 300 ohms per foot
square at 50 microns dry film thickness and 80 ohms per foot square
at 125 microns dry film thickness, at 42.5 percent by volume
pigment content in the dried film.
In each case, a sufficient pigment content must be used to give a
sufficiently low electrical resistivity. The lower limit of
resistivity for a given film thickness is determined by a fall off
in durability of the film at pigment contents in excess of 50
percent by volume in the dried film. The useful range of dry film
resistivity is in the order of 1 to 1,000 ohms per foot square.
Electrical connections for a direct current supply usually of 1-2
volts, are made with the steel as for normal cathodic protection
systems, and with the conductive paint coating. Connection with the
conductive paint coating may be made either by (a) connecting the
supply cables to bus-bars which are held in close electrical
contact with the paint coating while it is still tacky and bolted
to the structure with insulated bolts, washers and sleeves or (b)
by welding or soldering connecting cables to metal foil embedded in
the coating while it is wet, or (c) by embedding connecting cables
in a suitable conductive mastic adhering to the paint coating. It
is desirable in order to make use of the maximum conductive area of
the paint coating, to use a linear contact such as a bus-bar rather
than a point contact with the conductive paint. The electrical
connections are such that the layer of conductive paint is anodic
with respect to the metal. Monitoring and control are the same as
for normal cathodic protection systems.
If required, the electrically-conductive paint coating may be
further overcoated with decorative paint as required for special
effects, though such over-coating is not necessary for protection.
In such cases the anodic electrically-conductive paint coat acts as
the middle layer of a "sandwich."
While the protective coatings are intact or in such a condition
that they are not electrically-conductive when wet, the cathodic
protection system does not operate and no current is consumed. When
there is breakdown of the coating, or metal is exposed, or the
coating develops pores, the electrically conductive coating
operates as a node when wet, and so prevents corrosion. The anode
coating itself is non-corrodible and so is not wasted. A single
droplet of water falling on a crack in the protective coating
system or on edges where the coating may have broken down, will
provide the electrolyte for the current, and protect the wet area
which would normally corrode. Thus it is not necessary to have a
bulk of electrolyte for the system to be effective, and it would
accordingly afford cathodic protection against corrosion on aerial
exposure as well as in immersed or buried conditions. Even when
overcoated with decorative paint the exposed edge of the conductive
paint is sufficient to act as an effective anode at crakcs in the
film.
It has been found that when immersed in salt water under conditions
of electrolysis at a potential difference of approximately 1.4
volts or greater chlorine is produced over the surface of the
anodic paint coating in quantity dependent upon the current
flowing. The quantity of chlorine produced can be controlled
electrically and can be seen visually by bleaching action on
dyestuffs placed on the surface. This offers a means of sterilising
the painted surface and keeping it free from many living organisms
without releasing quantities of dangerous or unpleasant materials
into the environment.
The invention is further described, by way of example, with
reference to the following specific compositions, and Examples, and
with reference to the accompanying drawings, in which:
FIG. 1 is a section through a steel sheet provided with a cathodic
protection system in accordance with one embodiment of the present
invention, and
FIG. 2 is a section on the line II--II in FIG. 1.
Composition 1 Chlorinated Rubber Paint
______________________________________ Medium 39.7% Carbon Black
XC72 3.6% Duomeen TDO 0.2% Shellsol A 27.9% Grind all the above in
a pebble mill for 24 hours. Add Graphite 17.9% and grind in the
pebble mill until fully dispersed and thin with Shellsol A 10.7%
The medium consists of: Alloprene R20 30% Cereclor S52 10% Shellsol
A 60% ______________________________________
All percentages are by weight.
This paint has a resistance of 10 to 12 ohms per foot square when
applied at 50 microns dry film thickness and 4 to 5 ohms per foot
square when applied at 125 microns dry film thickness. It is
suitable for use in continuous immersion or atmosphere
exposure.
______________________________________ Composition 2 Epoxy Ester
Paint ______________________________________ Rosaline base 0.02
grms mixed with a 60% solution of Epoxy Ester in white spirit 18.3
grms and warmed to 100.degree.C Carbon Black XC72 6.9 grms White
Spirit 29.0 grms Xylol 32.0 grms are added and the mixture is
ground together in a pebble mill for at least 24 hours Graphite
Foliac X2104 13.8 grms is then added and the mixutre further ground
until the Graphite is dispersed.
______________________________________
This paint has a resistance of approximately 7 ohms per foot square
when applied at a dry film thickness of 50 microns. It is suitable
for use on metal frequently wet but not for continuous
immersion.
______________________________________ Composition 3 Chemically
Cured Pitch Epoxy Paint ______________________________________ This
paint consists of two packs. Pack A, this base paint, is made as
follows: Medium 31.8 grms Carbon Black XC72 3.4 grms Graphite 152S
17.2 grms Xylol 17.2 grms n-Butanol 3.4 grms are milled together in
a pebble mill for 24 hours or until the pigments are dispersed.
Then a further quantity of Xylol 17.2 grms n-Butanol 3.4 grms is
added. The medium consists of: Epikote Resin 1001 14.3% Epikote
Resin 828 14.3% Orgol Pitch 42.9% n-Butanol 4.8% Xylol 23.7% To
93.6 grms of the above base paint, Pack A, is added 6.4 grms of
Reactor, and after thorough mixing the paint is used immediately.
The Reactor consists of Beckalide Resin 50% solution 93.5% Curing
Agent K54 6.5% ______________________________________
This paint has a resistance of 300 ohms per foot square when
applied at 50 microns dry film thickness and 80 ohms per foot
square when applied at 125 microns dry film thickness.
EXAMPLE 1
A steel structure was blast-cleaned to B.S. 4232 second quality or
Swedish Standard SIS.05.59.00.1967 Sa21/2 and the cleaned surface
primed with an alkali resisting blast primer such as a chemically
cured epoxy resin based blast primer. Two or three coats of a
non-metal-pigmented chemically cured epoxy enamel were applied to
the primed surface at such thickness that the metal was fully
covered and electrically insulated. One good coat of electrically
conductive chlorinated rubber paint was then applied at 50 microns
dry film thickness. A second coat of the conductive paint was then
over a band onto which a bus-bar was fitted. Fabric or metal foil
was embedded into the paint and laid in contact with the bus-bar,
the bus-bar and fabric or foil then being overpainted with the
conductive paint. The bus-bar and the steel structure were then
connected across a D.C. electrical supply with the conductive paint
coating anodic with respect to the steel structure.
EXAMPLE 2
A steel structure was blast-cleaned to B.S. 4232 second quality or
Swedish Standard SIS.05.59.00.1967 Sa 21/2 and the cleaned surface
primed with an alkali resisting blast primer such as a chemically
cured epoxy resin based blast primer. Two or three coats of
non-metal-pigmented chlorinated rubber paint were applied so that
the metal was fully covered and electrically insulated. One good
coat of electrically conductive chlorinated rubber paint was then
applied at 50 microns dry film thickness. A second coat of the
conductive paint was applied over a band onto which a bus-bar was
fitted. Fabric or metal foil was embedded into the paint and laid
in contact with the bus-bar, the bus-bar and fabric or foil then
being overpainted with the conductive paint. The bus-bar and the
steel structure were then connected across a D.C. electrical supply
with the conductive paint coating anodic with respect to the steel
structure.
EXAMPLE 3
A steel structure was blast-cleaned to B.S. 4232 second quality or
Swedish Standard SIS.05.59.00.1967 Sa 21/2 and the cleaned surface
primed with an alkali resisting blast primer such as a chemically
cured epoxy resin based blast primer. Oleo resin varnish based
primers and undercoats, not metal-pigmented, were applied so that
the metal surface was fully covered and electrically insulated. One
or two good coats of electrically conductive epoxy ester paint were
then applied to give a minimum dry film thickness of conductive
paint of 50 microns. A second coat of the conductive paint was
applied over a band onto which a bus-bar was fitted. Fabric or
metal foil was embedded into the paint and laid in contact with the
bus-bar, the bus-bar and fabric or foil then being overpainted with
the conductive paint. The bus-bar and the steel structure were then
connected across a D.C. electrical supply with the conductive paint
coating anodic with respect to the steel structure.
EXAMPLE 4
For Steel to be Only Partly Immersed in Water
A steel structure was blast-cleaned to B.S. 4232 second quality or
Swedish Standard SIS.05.59.00.1967 Sa 21/2 and the cleaned surface
primed with an alkali resisting blast primer such as a chemically
cured epoxy resin based blast primer. Two or three coats of a
non-metal-pigmented chemically cured epoxy enamel was applied to
the primed surface at such thickness that the steel surface was
fully covered and electrically insulated. One good coat of
electrically conductive chlorinated rubber paint was then applied
at 50 microns dry film thickness. A second coat of the conductive
paint was applied over a band onto which a bus-bar was fitted.
Fabric or metal foil was embedded into the paint and laid in
contact with the bus-bar the bus-bar and fabric or foil then being
overpainted with the conductive paint. A decorative paint was
applied over that part of the surface not to be immersed in water,
completely covering the conductive paint and the bus-bar, but
leaving terminals on the bus-bar clean for electrical connections.
The bus-bar and the steel structure were then connected across a
D.C. electrical supply with the conductive paint coating anodic
with respect to the steel structure.
The drawings show a steel sheet 10 which has been provided with a
cathodic protection system in accordance with the invention. The
surface of the sheet 10 intended to be exposed to a corrosive
environment, has a first coating 12 of electrically insulating
paint and a second, overlying coating 14 of electrically conducting
paint. An electrically conducting bus-bar 16 is fixed to the sheet
10 so as to be in intimate electrically conducting contact with the
conducting layer 14. A further coating 18 of electrically
conducting paint is applied over the bus-bar 16 and the adjacent
region of the coating 14, a layer of sheet material such as fabric
or foil being embedded in the coating 18.
The bus-bar 16 is secured to the steel sheet 10 by bolts 20 and
nuts 22 which are electrically insulated from the sheet 10 by
insulating sleeves 24 and insulating washers 26 respectively. The
nut and bolt assemblies are protected at their exposed ends by an
electrically insulating covering 28 of a material such as mastic or
an epoxy resin.
A D.C. electrical supply (not shown) is applied across the bus-bar
16 and steel sheet 10 with the bus-bar anodic with respect to the
steel sheet. Electrical connection is made to the bus-bar 16 by way
of a connector 30 and to the steel sheet by, for example, welding
or mechanical means.
The system thus provides an anode which is normally insulated from
but is disposed very close to the entire surface of a cathodic
substrate. Cathodic protection of the substrate only becomes
effective when the insulation between the anode and the substrate
breaks down owing, for example, to physical damage or pore
formation. By virtue of the invention, an anode for providing
cathodic protection is immediately available at any point on the
protected substrate surface when required. As the insulating layer
between the anode and the substrate is very thin, even moisture
condensation from the atmosphere can be sufficient to provide the
necessary electrolyte link between the anode and substrate.
* * * * *