U.S. patent number 3,676,325 [Application Number 05/044,044] was granted by the patent office on 1972-07-11 for anode assembly for electrolytic cells.
This patent grant is currently assigned to Imperial Chemical Industries Limited. Invention is credited to John Hubert Entwisle, Frank Smith.
United States Patent |
3,676,325 |
Smith , et al. |
July 11, 1972 |
ANODE ASSEMBLY FOR ELECTROLYTIC CELLS
Abstract
An anode assembly for electrolytic cells comprising: a
downwardly-facing, open-ended, horizontally-elongated titanium
channel member having a web portion and two depending flange
portions integral with the web portion; a titanium tube secured at
one end to said web portion in a fluid-tight manner so that said
web portion closes said end, said web portion having at least one
gas escape opening therethrough located intermediate said tube and
each end of said channel an aluminum current lead-in rod at least
partially within the tube coaxially therewith having one end
friction-welded to said web portion; and a foraminate titanium
structure lying in a plane parallel to said web portion and
electrically connected to the lower edges of the flange portions,
said foraminate structure carrying on at least a part of its
surface a coating comprising an operative electrode material.
Inventors: |
Smith; Frank (Runcorn,
EN), Entwisle; John Hubert (Runcorn, EN) |
Assignee: |
Imperial Chemical Industries
Limited (London, EN)
|
Family
ID: |
10340232 |
Appl.
No.: |
05/044,044 |
Filed: |
June 8, 1970 |
Foreign Application Priority Data
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Jun 27, 1969 [GB] |
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32,544/69 |
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Current U.S.
Class: |
204/288;
204/290.13; 204/290.09; 204/219; 204/250; 204/284 |
Current CPC
Class: |
C25B
11/03 (20130101) |
Current International
Class: |
C25B
11/00 (20060101); C25B 11/03 (20060101); B01k
003/04 (); C23g 005/68 (); B01r 003/04 () |
Field of
Search: |
;204/288,281,29F,29R,219,250 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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668,618 |
|
Sep 1950 |
|
GB |
|
453,750 |
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Dec 1927 |
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DD |
|
Primary Examiner: Mack; John H.
Assistant Examiner: Fay; Regan J.
Claims
What we claim is:
1. An anode assembly for electrolytic cells which comprises a
titanium tube having a flat titanium closure attached in
fluid-tight manner across one end, an aluminum current lead-in rod
at least partially within the tube and coaxial therewith having one
end friction-welded to the titanium closure, and a foraminate
titanium structure carrying on at least a part of its surface a
coating comprising an operative electrode material, the said
foraminate titanium structure lying in a plane parallel to the said
titanium closure and being electrically connected thereto by
titanium members which together with the said closure define an
inverted channel shape.
2. An anode assembly according to claim 1, wherein the said
titanium members and the titanium closure which together define an
inverted channel shape have been fabricated from one integral piece
of titanium metal.
3. An anode assembly according to claim 1, wherein the edges of the
titanium channel shape are welded at intervals to the foraminate
titanium structure.
4. An anode assembly according to claim 1, wherein the foraminate
titanium structure is a sheet of expanded titanium metal.
5. An anode assembly according to claim 1, wherein the foraminate
titanium structure has been built up from longitudinally-extending
titanium members spaced apart with their long axes parallel to each
other.
6. An anode assembly according to claim 5, wherein the
longitudinally-extending titanium members are flat strips which
each have one long edge welded to the edges of the titanium channel
shape.
7. An anode assembly according to claim 6, wherein at least half
the coating comprising an operative electrode material is carried
on the faces of the said flat strips.
8. An anode assembly according to claim 1, wherein the foraminate
titanium structure is louvred structure formed by pressing a series
of of louvre slats from a titanium sheet.
9. An anode assembly according to claim 8, wherein the louvre slats
have been turned at right angles to the original plane of the
titanium sheet.
10. An anode assembly according to claim 1, wherein the foraminate
titanium structure comprises a titanium sheet having a plurality of
louvre slats pressed out so as to form a plurality of corresponding
slots, the slats having rolled edges so as to form a series of
approximately hemicylindrical members which alternate with the
slots.
11. An anode assembly according to claim 1, wherein the operative
electrode material in selected from the group consisting of
platinum group metals and oxides thereof.
12. An anode assembly according to claim 1, wherein the coating
comprising an operative electrode material consists of at least one
oxide of at least one platinum group metal as the operative
electrode material and titanium dioxide.
13. An anode assembly according to claim 12, wherein the said
operative electrode material is ruthenium dioxide.
14. An anode assembly for electrolytic cells comprising:
a downwardly-facing, open-ended, horizontally-elongated titanium
channel member having a web portion and two depending flange
portions integral with the web portion;
a titanium tube secured at one end to said web portion in a
fluid-tight manner so that said web portion closes said end, said
web portion having at least one gas escape opening therethrough
located intermediate said tube and each end of said channel;
an aluminum current lead-in rod at least partially within the tube
coaxially therewith having one end friction-welded to said web
portion; and
a foraminate titanium structure lying in a plane parallel to said
web portion and electrically connected to the lower edges of the
flange portions, said foraminate structure carrying on at least a
part of its surface a coating comprising an operative electrode
material.
Description
The present invention relates to an anode assembly for electrolytic
cells. More particularly it relates to an anode assembly which is
particularly suitable for use in cells where gas is evolved at the
anode.
In recent years it has been proposed to employ as anodes,
particularly in cells electrolyzing aqueous alkali metal chloride
solutions, structures in which a layer of a platinum group metal or
metals and/or the oxides thereof constitutes the working anode
surface and is carried on a support made of a film-forming metal,
usually titanium. The anode conductor leading the current to the
anode within the cell may also be constructed of titanium since
this metal is resistant to electrochemical attack under the severe
anodic conditions ruling in the cell, but in order to reduce
capital expenditure and running costs it is desirable to use as far
as possible a cheaper and better conducting metal. It has therefore
been proposed to use as the current lead-in a composite structure
in which a core of copper, steel or aluminum is protected from
electrochemical attack by a casing or sheath of titanium. Aluminum
is generally the most desirable core metal on the basis of
cost/weight for adequate electrical conductivity but such a
structure presents the problem of making a mechanically strong and
low-resistance electrical connection between the aluminum core and
the titanium of the casing or the titanium support member of the
anode structure. This is important because the current carried
principally by the good-conducting aluminum core must pass in some
region across an interface between the aluminum of the core and the
titanium of the casing or the anode structure itself in order to
reach the working anode surface.
It has been proposed to solve this problem by melting and alloying
an aluminum core inside a titanium casing and by soldering an
aluminum core into a titanium casing after coating the juxtaposed
surfaces of the core and casing with a solderable metal. Melting
and alloying is a high temperature process which can cause
distortion. Soldering introduces problems of shrinkage between the
core and the casing on cooling and is expensive in labor because of
the pre-coating operations that are needed.
The present invention overcomes these problems by providing a
friction-welded joint between an aluminum current lead-in and a
titanium member which supports the anode structure proper. Other
advantageous features of the invention will appear hereinafter.
According to the present invention we provide an anode assembly for
electrolytic cells which comprises a titanium tube having a flat
titanium closure attached in fluid-tight manner across one end, an
aluminum current lead-in at least partially within the tube and
coaxial therewith having one end friction-welded to the titanium
closure, and a foraminate titanium structure carrying on at least a
part of its surface a coating comprising an operative electrode
material, the said foraminate titanium structure lying in a plane
parallel to the said titanium closure and being electrically
connected thereto by titanium members which together with the said
closure define an inverted channel shape.
In this specification by "titanium" we mean titanium alone or an
alloy based on titanium and having anodic polarization properties
comparable to those of titanium.
The operative electrode material may be any material which is
active in transferring electrons from an electrolyte to the
underlying titanium structure of the anode assembly and which is
resistant to electrochemical attack under the conditions ruling in
the cell where the anode is to be used. For use in very corrosive
media, for instance in chloride electrolytes, the operative
electrode material may suitably consist of one or more platinum
group metals i.e. platinum, rhodium, iridium, ruthenium, osmium and
palladium, and/or oxides thereof, or another metal or a compound
which will function as an anode and which is resistant to
electrochemical dissolution in the cell, for instance rhenium,
rhenium trioxide, magnetite, titanium nitride, the borides,
phosphides or silicides of the platinum group metals, or an oxidic
semiconducting compound. The coating comprising an operative
electrode material may also contain electronically non-conducting
oxides, particularly oxides of the film-forming metals such as
titanium, as is known in the art, to anchor the operative electrode
material more securely to the supporting titanium structure and to
increase its resistance to dissolution in the working cell. A
preferred coating comprising an operative electrode material for
anodes that are to be used in mercury-cathode cells electrolyzing
alkali metal chloride solutions consists of at least one oxide of
at least one platinum group metal, particularly ruthenium dioxide,
as the operative electrode material, and titanium dioxide.
When an anode assembly according to the invention is installed in a
cell, the titanium tube passes through sealing means in the cell
casing, for instance the cover of the cell, so that the aluminum
current lead-in rod is protected from contact with the cell
contents. In general the aluminum current lead-in rod is made of
sufficient length to protrude from the titanium tube for easy
connection of an electrical bus-bar to the end of the rod outside
the cell.
In preferred embodiments of the invention the titanium closure and
the titanium members together defining an inverted channel shape
are fabricated from one integral piece of titanium metal.
Furthermore, the inverted channel shape may extend both laterally
and longitudinally well beyond the limits defined by the
cross-section of the end of the titanium tube to which the base of
the channel forms a closure, and usually will so extend, in order
to support a coated foraminate titanium structure of sufficient
area to provide the desired working anode area when installed in
the cell. Such embodiments are illustrated in the accompanying
drawings FIG. 1-7, which are not to scale and in which like parts
are numbered alike.
FIG. 1 and FIG. 2 show vertical sections at right angles to each
other through the center of an electrode assembly. In these figures
the center part of an inverted titanium channel 1 forms a
fluid-tight closure across the lower end of titanium tube 2 by
virtue of a peripheral weld around the end of the tube indicated as
3. (Other suitable forms, not shown, for the weld 3 are electrical
resistance welding and friction welding). An aluminum current
lead-in rod 4 has its lower end attached to the center of the
channel 1 by a friction weld indicated at 5. The edges of the
channel 1 are welded at intervals as indicated at 6 to a
horizontally-disposed foraminate titanium structure 7 which carries
on at least a part of its surface a coating (not shown) comprising
an operative electrode material as defined hereinbefore. The
foraminate titanium structure 7 may suitably be a multi-holed
titanium sheet, for instance a sheet of expanded titanium metal.
Alternatively the foraminate structure may be built up from
longitudinally-extended titanium members spaced apart with their
long axes parallel to each other, each one being welded to both
bottom edges of the inverted channel. These members may be for
instance flat strips, rods, hemicylindrical channels which are
convex upwards or convex downwards or channels of U-shaped or
inverted U-shaped, the closed end of the U being optionally
flattened. Yet again, an arrangement approximating to the said
built-up structure of longitudinally-extending members spaced apart
with their long axes parallel to each other may be produced by
pressing from a titanium sheet by means of a slotting and forming
tool, whereby a structure with pressed-out louvres is obtained. The
louvre slats so obtained may suitably be turned at right angles to
the original plane of the titanium sheet or they may have each of
their edges rolled round to form approximately hemicylindrical
members which alternate with the slots from which the metal forming
them has been pressed out. FIG. 3 shows an anode assembly in which
the foraminate titanium structure is built up from parallel-spaced
titanium strips 8, which each have one long edge welded to both
bottom edges of the inverted titanium channel 1 as again indicated
at 6. The other parts of FIG. 3 correspond to those of FIG. 2. When
the foraminate titanium structure is built up in this manner, at
least half of the coating thereon comprising an operative electrode
material may suitably be carried on the faces of the strips 8 (the
vertical surfaces in the configuration in the drawing), as taught
for instance in British Patent Specification No. 1,076,973 for
coatings of the platinum group metals on anode surfaces formed from
titanium ribs.
If desired, within the scope of the invention the titanium tube
which surrounds the aluminum current lead-in may be provided with a
flange at its lower end, the fluid-tight joint between the titanium
tube and the inverted titanium channel then being made by welding
the flange to the channel. Likewise each of the sides of the
inverted channel may be terminated by a flange, the foraminate
titanium structure carrying the coating comprising an operative
electrode material then being welded to these flanges. An anode
assembly incorporating these optional features is illustrated in
FIG. 4, with the flange 8 and weld 9 replacing the weld 3 of FIG. 1
and the flanges 10 and welds 11 replacing the welds 6 of FIG.
1.
In FIG. 1-4 the aluminum current lead-in rod 4 is shown
substantially filling the cross-section of titanium tube 2. In
general we prefer this arrangement, in which only sufficient
clearance is provided between the rod and the tube for easy
assembly of these parts, so as to obtain the lowest electrical
resistance in the aluminum rod commensurate with the diameter of
the tube employed. It is not, however, essential for the rod to be
a close fit within the tube and a wider gap may be provided between
these two members if desired.
An anode assembly according to the invention is very suitable for
use in a cell wherein gas is evolved at the anode, with the working
anode structure of coated foraminate titanium arranged parallel to
a substantially horizontal cathode, e.g. a flowing mercury cathode,
since gas evolved beneath the current lead-in can pass freely
upwards through the foraminate structure into the space beneath the
inverted titanium channel. The gas may be allowed to flow out from
under the ends of the inverted channel or, if desired, one or more
openings to assist the escape of gas may be provided in the top of
the channel between the centrally disposed titanium tube and each
end of the channel. Suitable arrangements of opening are shown in
FIG. 5-7, which are plan views showing only the titanium
channel-shaped member 1 and the current lead-in 4 with its
surrounding titanium tube 2. In the arrangement of FIG. 5 there is
one large opening 12 provided towards each end of the channel. In
the arrangement of FIG. 6 there is a plurality of small openings 13
towards each end of the channel and in the arrangement of FIG. 7
the channel is cut away at each end in approximately a V-shape 14
to assist the escape of gas.
* * * * *