U.S. patent number 3,844,921 [Application Number 05/315,768] was granted by the patent office on 1974-10-29 for anode containing pin-type inserts.
This patent grant is currently assigned to Esso Production Research Company. Invention is credited to Risque L. Benedict.
United States Patent |
3,844,921 |
Benedict |
October 29, 1974 |
ANODE CONTAINING PIN-TYPE INSERTS
Abstract
An anode for use in a cathodic protection system or other
electrolytic process includes a body of lead or a lead alloy and a
plurality of pins or wire inserts of tantalum, titanium, niobium,
zirconium, vanadium or a similar metal coated with a thin outer
coating of platinum or other noble metal from Group VIII of the
Periodic Table. The inserts will normally range from about 50 to
about 250 mils in diameter and the coating will generally be from
about 1 to about 10,000 microinches in thickness.
Inventors: |
Benedict; Risque L. (Santa
Monica, CA) |
Assignee: |
Esso Production Research
Company (Houston, TX)
|
Family
ID: |
23225973 |
Appl.
No.: |
05/315,768 |
Filed: |
December 18, 1972 |
Current U.S.
Class: |
204/196.38;
204/288; 204/292; 204/290.12; 204/290.08; 204/280; 204/289 |
Current CPC
Class: |
C23F
13/02 (20130101); C25B 11/00 (20130101) |
Current International
Class: |
C25B
11/00 (20060101); C23F 13/02 (20060101); C23F
13/00 (20060101); C23f 013/06 (); B01k
003/06 () |
Field of
Search: |
;204/280,293,196,197,288,289,292 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Edmundson; F. C.
Attorney, Agent or Firm: Reed; James E.
Claims
1. An anode for a cathodic protection system or similar
electrolytic process which comprises a lead metal anode body; a
plurality of pins extending into said body from the outer surface
thereof, said pins being made of a base metal selected from the
group consisting of tantalum, titanium, niobium, zirconium,
vanadium and alloys thereof and being coated with a noble metal
from Group VIII of the Periodic Table; and means for
3. An anode as defined by claim 1 wherein said lead metal is a
lead-silver
4. An anode as defined by claim 1 wherein said lead metal is a
lead-antimony alloy containing up to about 10 percent antimony by
weight.
5. An anode as defined by claim 1 wherein said pins have diameters
between
6. An anode as defined by claim 1 wherein the thickness of the
noble metal
7. An anode as defined by claim 1 containing from about five to
about 50
8. An anode as defined by claim 1 wherein each of said pins is
provided
9. An anode for a cathodic protection system or similar
electrolytic process which comprises a lead metal anode body; a
plurality of pins extending from the outer surface of said anode
body completely through said anode body; said pins being made of a
base metal selected from the group consisting of tantalum,
titanium, niobium, zirconium, vanadium and alloys thereof and being
coated with a noble metal from Group VIII of the Periodic Table;
and means for applying an electric current to said anode
10. An anode as defined by claim 9 wherein the inner ends of said
pins extend beyond the inner surface of said anode body and are
bent over adjacent said surface.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to anodes for use in impressed current
cathodic protection systems and other electrolytic processes and is
particularly concerned with lead-type anodes containing wire or pin
inserts.
2. Description of the Prior Art
Lead and lead alloy anodes used in impressed current cathodic
protection systems and similar electrolytic processes tend to
deteriorate in the presence of brines. This deterioration is
manifested by the formation of coatings of lead chloride and other
salts which eventually deactivate the anodes and prevent further
electrolytic action. It is known that this difficulty can be
alleviated by providing such anodes with small pins or inserts of
platinum which will serve as nucleation sites and promote the
formation of lead peroxide in lieu of lead chloride and other
undesirable divalent salts. The improvements which can be obtained
in this manner are limited because of the high cost of platinum and
practical problems normally encountered in installing the pins and
holding them in place. Experience has shown that conventional
platinum pins are easily dislodged and are often lost from the
anodes long before the lead has been consumed. As a result of these
and related difficulties, efforts to prolong the useful life of
lead-type anodes through the use of platinum pins or inserts have
been only moderately successful.
SUMMARY OF THE INVENTION
The present invention provides an improved lead-type anode for use
in impressed current cathodic protection systems and similar
electrolytic processes which at least in part eliminates the
difficulties outlined above. This improved anode comprises a lead
metal anode body and a plurality of pins or wire inserts extending
into the anode body at spaced intervals over the outer surface
thereof. These pins or inserts are made of tantalum, titanium,
niobium, zirconium, vanadium or an alloy containing one or more of
these metals as the principal constituent and are coated with a
thin outer coating of platinum or a similar noble metal from Group
VIII of the Periodic Table. It has been found that these noble
metals have surprisingly low deterioration or attrition rates when
used on coated pins or inserts in lead metal anodes and that a
plurality of such inserts can be used to reduce the deterioration
rates of such anodes to a value of one-tenth or less that normally
obtained with anodes containing conventional platinum pins or
inserts. A conventional anode containing three platinum inserts per
square foot, for example, may have a useful life of about 6 years;
whereas an anode containing 15 of the coated pins of this invention
per square foot may have a useful life of 50 years. This makes
possible significant improvements in impressed current cathodic
protection systems and other electrolytic processes without
substantial increases in cost.
The pins or inserts used in the improved anodes of the invention
will normally have diameters of from about 50 to about 250 mils and
will be provided with coatings of platinum or a similar noble metal
between 1 and about 10,000 microinches in thickness. This use of
relatively large coated pins or inserts facilitates driving of the
inserts into the anode bodies, permits the use of longer inserts,
and makes the coated inserts more difficult to dislodge than the
smaller diameter platinum inserts generally employed heretofore. It
is preferred that the inserts extend through the anode body so that
fresh platinum is continually exposed as the lead metal
deteriorates and that the unexposed end of each insert be secured
to increase the resistance to forces generated by the formation of
lead peroxide which tend to extract the inserts from the anode
body. These and other features of the improved anodes responsible
for their improved performance will be described in detail
hereafter.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 in the drawing depicts one embodiment of the improved anode
of the invention which is particularly adapted for use on offshore
drilling and production platforms and other marine
installations;
FIG. 2 is an enlarged cross section of the anode of FIG. 1 taken
about the line 2--2;
FIG. 3 illustrates an alternate embodiment of the invention which
may be used on ships, underwater storage tanks, and similar marine
structures;
FIG. 4 is a cross sectional view of the anode of FIG. 3 taken about
the line 4--4;
FIG. 5 illustrates still another embodiment of the invention which
may be employed in impressed current cathodic protection systems
and other electrolytic processes; and,
FIG. 6 is a cross sectional view of the anode of FIG. 5 taken about
the line 6--6.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The anode depicted in FIG. 1 of the drawing comprises a cylindrical
lead metal anode body 11 which is suspended by means of an
insulated terminal member 12 and an insulated electrical conductor
13. The anode body may be made of metallic lead but will normally
be composed of a lead alloy containing small amounts of silver,
antimony, tellurium, bismuth and other metals. Experience has shown
that alloys of this type generally less prone than metallic lead to
form lead chloride in the presence of chloride ions and are
therefore somewhat more effective for use as anodes in electrolytic
processes. The preferred alloys will normally contain up to about 5
percent silver and up to about 10 percent antimony. Typical alloy
compositions which may be used include the following: (a) lead-98
percent, silver-2percent; (b) lead-99.5 percent, antimony-0.5
percent; (c) lead-93 percent, silver-1 percent, antimony-6 percent;
(d) lead-97.5 percent, silver-2 percent, tellurium-0.3 percent,
bismuth-0.2 percent; (e) lead-96 percent, sliver-2 percent,
antimony-1.5 percent, copper-0.4 percent, tellurium-0.1 percent;
and (f) lead-99.8 percent, tellurium-0.1 percent, bismuth 0.1
percent. All of these compositions may include other materials
present in small amounts as impurities. A variety of other lead
alloys suitable for use as anodes after treatment to provide a
surface coating of lead peroxide have been described in the
literature and will be familiar to those skilled in the art.
The anode body 11 is provided with a plurality of pins or wire
inserts 14 which are spaced at regular intervals over the outer
surface of the body. Each of these pins or inserts is made of
tantalum, titanium, niobium, zirconium, vanadium or an alloy
containing one or more of these metals as the principal constituent
and is coated with a thin outer coating of platinum or a similar
noble metal from Group VIII of the Periodic Table. The use of
titanium inserts coated with a layer of platinum or a
platinum-iridium alloy between about 1 and about 10,000 microinches
in thickness is generally preferred. These inserts will normally be
between about 50 and about 250 mils in diameter and will be spaced
to provide from about 5 to about 50 or more inserts per square foot
of anode surface area. As shown more clearly in FIG. 2, each insert
preferably extends through the wall of the lead body and if desired
may be provided with circumferential, longitudinal, or spiral
ridges 15 to aid in holding it in place.
The inserts used in the anode body are positioned by drilling holes
in the body at the desired locations and then driving the inserts
into place. In general, these holes should extend normal to the
outer surface of the body and be small enough to insure a very
tight fit. Otherwise, the formation of a thick layer of lead
peroxide on the surface of the body may result in the inserts being
pulled out of electrical contact with the lead alloy anode so that
no further nucleation of lead peroxide can take place. This will in
turn accelerate deterioration of the anode body, in some cases
perhaps by a factor of as much as 100 times.
The relatively large coated pins or inserts used for purposes of
the invention can be driven to much greater depths and are
considerably more difficult to dislodge from the anode body than
the platinum inserts used in the past. This is due in part to the
greater rigidity of the relatively large coated inserts. The
flexural rigidity of such an insert is a function of the modulus of
elasticity of the metal employed and the moment of inertia of the
cross sectional area about the transverse axis. Although the
modulus of elasticity of platinum is slightly higher than that of
titanium for example, the cost of platinum is such that the use of
platinum inserts greater than about 50 mils in diameter is
prohibitively expensive. Titanium inserts coated with 1 microinch
of platinum cost about 1/100 as much as platinum inserts of the
same size and hence the use of coated inserts with considerably
greater diameters than those of the platinum inserts employed
heretofore is feasible. The moment of inertia of an insert
increases as the fourth power of the diameter, so that doubling the
diameter will increase the flexural rigidity by a factor of 16. The
flexural rigidities of conventional platinum inserts and typical
coated inserts employed for purposes of the invention are set forth
below.
______________________________________ Modulus of Flexural Type of
Insert Elasticity Rigidity ______________________________________
Hard Drawn Platinum-50 mils Diameter 22.6 .times. 10.sup.6 6.95
Annealed Tantalum-100 mils Diameter 27.0 .times. 10.sup.6 133
Wrought Niobium-100 mils Diameter 15.0 .times. 10.sup.6 74
Titanium-100 mils Diameter 16.8 .times. 10.sup.6 83
______________________________________
It can be seen from the above table that the coated tantalum,
niobium and titanium inserts of 100 mils diameter have flexural
rigidities of from about 10 to 20 times those of the 50 mil
diameter platinum inserts. This greater rigidity permits driving of
the coated inserts much deeper than the 1/2 inch generally
considered a maximum for platinum inserts. For a given coefficient
of friction between an insert and the lead anode, the force
required to withdraw the insert is directly proportional to the
area of contact. The area of contact is a linear function of the
wire insert diameter and of its length. The force exerted on the
insert due to the formation of lead peroxide on the lead anode
surface is also proportional to the insert diameter and thus the
net resistance to withdrawal of the insert from the anode depends
upon the distance to which it is driven. The use of the coated
inserts of the invention makes possible useful anode lives many
times those that can be obtained with conventional lead anodes
containing relatively short platinum inserts.
As pointed out earlier, it is preferred that each of the coated
inserts be driven completely through the lead anode. Where the
inner surface of the lead is not exposed, the inner end of each
insert can be bent at a right angle to aid in holding the insert in
place. The increased flexural rigidity of the relatively large
coated inserts makes these inserts much more difficult to dislodge
from the anode than conventional platinum inserts. Before an insert
which is bent at the inner end as described above can be pulled out
of the lead anode, the inner end must be straightened out by
bending it through an angle of about 90.degree.. The maximum
bending or deflection which takes place under a given force is an
inverse function of the flexural rigidity of the insert and hence
doubling the insert diameter will reduce by a factor of 16 the
amount of bending or deflection that takes place. By using
relatively large coated inserts, the danger of losing the inserts
before substantially all of the lead is consumed can be
minimized.
The entire length of each of the wire inserts is substantially
covered with platinum or a similar noble metal. Tests in both the
laboratory and field have shown that platinum and platinum alloys
generally have deterioration rates of about 6 milligrams per ampere
year when used as anodes in the conventional fashion but that such
metals have negligible attrition rates of less than 1 milligram per
ampere year when employed on coated inserts in accordance with the
invention. Because there is thus virtually no loss of platinum or
other noble metal from the inserts, coatings of as little as 1
microinch in thickness are feasible. As the lead surrounding each
of the inserts deteriorates, new platinum is constantly being
uncovered and exposed to the electrolyte in the system. In the
event that the anode falls into the mud bottom where the rate of
anode deterioration will be much higher than in a circulating
aqueous environment, the exposed platinum may be destroyed. The
exposure of fresh platinum after the anode is returned to the
aqueous environment, however, will result in a return of the anode
to the former low deterioration rate.
The dimensions and configuration of the anode will depend primarily
upon the structure to be protected and the period over which
effective protection is required. As pointed out earlier, the
improved anodes of the invention are considerably less expensive
than conventional lead type anodes containing platinum inserts or
microanodes and permit the use of a much greater number of inserts
than has generally been considered feasible heretofore. This use of
more inserts results in a longer lasting anode, permits operation
of the anode at higher current densities, and for a given life
expectancy makes possible the use of a smaller diameter anode. The
ability of the improved anodes to operate at higher current
densities is particularly important because of the high initial
current densities required for the effective protection of steel in
sea water. The use of a smaller diameter anode for a given life
expectancy results in savings in anode costs, simplifies suspension
techniques, and makes the anodes more readily retrievable.
FIGS. 3 and 4 in the drawing illustrate an alternate embodiment of
the improved anode of the invention which is intended for use on
ships, underwater storage tanks and similar structures. The anode
shown in FIGS. 3 and 4 comprises a lead or lead alloy anode body 20
which is mounted upon a dielectric backing member 21 and held in
place by a gasket 22 and an apertured fixture or bracket 23, both
made of polyvinylchloride, polychloroprene, fiberglass reinforced
polyester and epoxy mastics or other suitable dielectric material.
The portion of the anode body exposed by the apertured fixture is
provided with a plurality of coated wire inserts 24. Each insert
includes an inner core of tantalum, titanium, niobium, zirconium,
vanadium or an alloy containing one of these metals as the
principal constituent and a thin outer coating of platinum or a
similar noble metal from Group VIII of the Periodic Table. The
inserts are preferably between about 100 and about 250 mils in
diameter and are spaced to provide between about 5 and about 50 or
more inserts per square foot of anode surface. As indicated in FIG.
4, each insert extends through the lead metal anode body and is
bent over parallel to the back of the body as indicated by
reference numeral 25. This aids in resisting forces generated by
the formation of lead peroxide on the exposed surface of the anode
which may otherwise tend to pull the insert from the anode. The
anode assembly will normally be mounted on a dielectric shield on
the surface of the member to be protected. It is generally
preferred that this shield extend for a distance of 10 feet or more
beyond the anode in all directions. The dielectric shield may
comprise a coating of coal tar epoxy resin, phenolic epoxy resin,
epoxy mastics fiberglass reinforced polyester material,
polyurethane, polyvinylchloride, neoprene rubber or other
dielectric material and may be applied by spraying, baking,
wrapping, or other conventional technique. The anode assembly may
be mechanically mounted on the surface to be protected by means of
countersunk brass screws which extend through holes 26 in the
assembly and are covered with polychloroprene putty or similar
dielectric material. Other mounting techniques may also be used.
Current will normally be supplied to the backside of the anode in
the conventional manner by means of a conductor which extends
through an opening in the hull or other surface on which the
assembly is mounted and is connected to the anode body.
Still another embodiment of the invention is shown in FIGS. 5 and 6
of the drawing. This embodiment comprises an elongated hollow anode
body 30 of lead or a lead alloy which is filled with an inner core
of epoxy resin or similar material 31. An insulated cap or terminal
member 32 provided with insulated electrical conductor 33 is
attached to the upper end of the anode body. Coated inserts 34 of
platinum coated titanium, tantalum, or niobium are positioned in
the anode body at regularly spaced intervals over its surface.
These inserts extend into the opening in the lead or lead alloy
body and are bent over before the opening is filled with the epoxy
resin. This aids in resisting forces due to the formation of lead
peroxide which tend to dislodge the inserts. In lieu of using an
epoxy resin core, a close fitting rod of titanium, tantalum,
niobium or similar metal can be driven into the opening in the body
after the inserts have been placed in order to bend them over and
provide the body with greater strength. The outer ends of the
inserts are substantially flush with the outer surface of the anode
body. Anodes of this type are useful in a variety of electrolytic
processes using lead type anodes.
It will be apparent from the foregoing that the improved anodes of
the invention can be constructed in a variety of different
configurations. Regardless of the particular configuration used,
the coated pins or inserts provide significantly longer anode life,
permit operation at higher current densities, and for a given anode
life make feasible the use of smaller anodes than do the platinum
inserts or microelectrodes employed heretofore.
* * * * *