U.S. patent number 3,751,296 [Application Number 05/144,906] was granted by the patent office on 1973-08-07 for electrode and coating therefor.
This patent grant is currently assigned to Chemnor Aktiengesellschaft. Invention is credited to Henri Bernard Beer.
United States Patent |
3,751,296 |
Beer |
* August 7, 1973 |
**Please see images for:
( Certificate of Correction ) ** |
ELECTRODE AND COATING THEREFOR
Abstract
An electrode for use in an electrolytic reaction. The electrode
has an electrically conductive base, preferably of a film-forming
metal, the outside of which is a conductive material other than a
film-forming metal, such as a layer of oxide of the base metal, and
which is resistant to the electrolyte. At least a portion of the
surface of said base has a coating of a mixed crystal material
consisting essentially of at least one oxide of a film-forming
metal and at least one oxide of a platinum group metal.
Inventors: |
Beer; Henri Bernard (Kalmthout,
BE) |
Assignee: |
Chemnor Aktiengesellschaft
(Vaduz, FL)
|
[*] Notice: |
The portion of the term of this patent
subsequent to January 4, 1989 has been disclaimed. |
Family
ID: |
26240739 |
Appl.
No.: |
05/144,906 |
Filed: |
May 19, 1971 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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702695 |
Feb 2, 1968 |
3632498 |
|
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Foreign Application Priority Data
|
|
|
|
|
Feb 10, 1967 [GB] |
|
|
6,490/67 |
|
Current U.S.
Class: |
204/290.12;
428/472; 976/DIG.184; 204/290.13; 428/209; 204/290.14 |
Current CPC
Class: |
C23F
13/02 (20130101); C25D 9/06 (20130101); C25B
11/091 (20210101); C01B 35/023 (20130101); C25B
11/093 (20210101); C25D 13/02 (20130101); Y10T
428/24917 (20150115) |
Current International
Class: |
C25B
11/00 (20060101); C23F 13/02 (20060101); C23F
13/00 (20060101); C25B 11/04 (20060101); C25D
13/02 (20060101); C25D 9/06 (20060101); C25D
9/00 (20060101); C01B 35/02 (20060101); C01B
35/00 (20060101); B01k 003/04 (); B01k
003/06 () |
Field of
Search: |
;117/230,201
;204/29F,29R ;136/84 ;252/472 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Kendall; Ralph S.
Assistant Examiner: Esposito; M. F.
Parent Case Text
This application is a Division of application Ser. No. 702,695
filed Feb. 2, 1968 now U.S. Pat. No. 3,632,498.
Claims
I claim:
1. An electrode for use in an electrolytic reaction comprising an
electrically conductive base selected from the group consisting of
aluminum, tantalum, titanium, zirconium, bismuth, tungsten, niobium
and alloys thereof, at least a portion of the surface of said
electrode having a coating of a mixed crystal material consisting
essentially of at least one oxide of a film-forming metal and at
least one oxide of a platinum group metal.
2. An electrode according to claim 1 wherein said oxide of a
film-forming metal is an oxide of a metal selected from the group
consisting of aluminum, tantalum, titanium, zirconium, bismuth,
tungsten and niobium.
3. An electrode according to claim 1 wherein said oxide of a
platinum group metal is an oxide of a metal selected from the group
consisting of palladium, platinum, rhodium, iridium, ruthenium and
osmium.
4. An electrode according to claim 1 wherein the coating contains
oxides of a plurality of film-forming metals selected from the
group consisting of aluminum, tantalum, titanium, zirconium,
bismuth, tungsten and niobium.
5. An electrode according to claim 1 wherein the coating contains
oxides of a plurality of platinum group metals selected from the
group consisting of palladium, platinum, rhodium, iridium,
ruthenium and osmium.
6. An electrode according to claim 1 wherein the oxide of the
film-forming metal is present in a proportion higher than 50 mol
percent of the materials of the coating.
7. An electrode according to claim 1 wherein the coating covers at
least 2 percent of the surface of the electrode adapted to be
placed in an electrolyte.
8. An electrode according to claim 1 wherein the electrically
conductive base is selected from the group consisting of titanium
and tantalum, and the surface of said electrode has a mixed crystal
material coating consisting essentially of titanium oxide and
ruthenium oxide.
9. An electrode according to claim 1 wherein said oxide of a
film-forming metal is titanium oxide and is present in a proportion
of 70 mol percent of the material of the coating, and said oxide of
a platinum group metal is ruthenium oxide and is present in a
proportion of 30 mol percent of the material of the coating.
Description
This invention relates to an electrode for use in an electrolytic
process, particularly in the electrolytic production of chlorine
and alkali metal in mercury cells and diaphragm cells, the
electrolytic production of chlorates, hypochlorites, persulphates,
perborates, the oxidation of organic compounds, fuel cells,
desalination and purification of water, galvanic processes, and
cathodic protection systems. Further the electrode has a long life,
a low overvoltage and catalytic properties.
The invention also relates to processes for making the electrode,
and to methods of carrying out electrolyses employing the
electrode.
Hitherto it has been believed that the best electrode for use as
anode in many electrolytic reactions was a solid metallic electrode
of a noble metal, such as a metal of the group of the platinum
metals. However, by reason of the cost of such metals and certain
undesirable technical properties, such as undesirable over-voltage,
poor mechanical properties and structural difficulties, ways have
been sought to provide electrodes plated with a platinum metal.
In recent years there have been developed electrodes on the basis
of titanium and coated with a platinum metal, which have proved to
be satisfactory for many uses. It has been found, however, that the
electrodes having a titanium base and coated with a platinum metal
deteriorate in use at a rate which, although not harmful in many
kinds of electrolyses, nevertheless results in the necessity of
replacing the electrodes from time to time at considerable
expense.
In addition, there are other processes, in which the products of
the electrolysis should preferably not be contaminated with the
material given off by the electrodes. If such a material is present
in the products of the electrolysis, it must be removed by a
separate treatment.
It is one object of the present invention to provide an electrode
for use in electrolytic processes, whereby to eliminate
substantially the disadvantages of the prior electrodes, said
electrode being inexpensive and easy to manufacture.
It is another object of the invention to provide such an electrode
which utilizes relatively inexpensive metal in the coating thereon,
and which is nevertheless excellent for carrying out electrolytic
processes, has a long life, and is stable in operation.
Still another object of the invention is to provide processes for
making the electrode, methods for the use of the electrode and for
carrying out electrolytic processes employing the electrode.
These and other objects are achieved, according to the invention,
by an electrode based on the discovery that when the electrode
comprises a conductive base with a coating consisting essentially
of a combination of one or more oxides of one or more film-forming
metals with one or more non-film-forming conductors, there is
obtained an electrode having excellent characteristics of
resistancy, durability and efficiency.
By film-forming metals are understood metals which when connected
as an anode in an electrolyte form an oxide coating on their
surface which seals off the subjacent metal in such a manner as to
practically bar the passage of current after a period of a few
minutes.
By non-film-forming conductors are understood conductors which when
connected as an anode is an electrolyte continue to transport the
current into or out of the electrolyte practically without
losses.
The invention will now be described in greater detail with
reference to the accompanying drawings, in which
FIG. 1 is a cross-section of the electrode according to the
invention; and
FIG. 2 is a graph in which the performance of prior electrodes is
compared with that of an electrode according to the invention.
Referring to the drawings, the electrode according to the invention
consists of a base or core 10 having a coating 11 thereon, which
two parts consist of materials which will be described more fully
hereinafter.
The electrode is shown as having a simple rectangular shape, but it
will be understood that the electrode is not limited to such a
configuration, but may have any configuration suitable for the
electrolysis apparatus in which the electrode is to be used.
Furthermore, there is shown a simple cavity 12 at the top for
connecting the current conductor thereto, but this feature does not
constitute part of the invention and may be changed as desired.
The base or core of the electrode according to the invention
consists of a conductive material which at least on the outside is
resistant to the electrolyte in which it is to be used. Thus, for
example, the base may consist of any of the film-forming metals,
such as, aluminum, tantalum, titanium, zirconium, bismuth,
tungsten, niobium, or alloys of two or more of these metals.
However, I may use other conductive materials which will not be
affected by the electrolyte and the products formed during the
dissociation thereof, it being possible to use metals such as iron,
nickel or lead, and non-metallic conductive materials, such as
graphite, in suitable electrolytes.
It is an essential feature of the coating 11 that is behaves as a
mixed-crystal material which contains one or more oxides of one or
more of the film-forming materials set out hereinbefore, and
preferably more than 50 mol percent of such an oxide or oxides. By
mixed-crystal material is generally understood that the molecular
lattices of the oxide of the film-forming metal are intertwined
with the molecular lattices of the other material constituting the
coating. There are various methods of achieving such a structure,
some of which will be described hereinafter in connection with the
processes for making the electrode according to the invention, but
this is not intended to restrict the scope of the invention.
The other material of the mixture consists of one or more
representatives of the non-film-forming conductors. This other
material may consist of a mixture of a metal and the oxide of the
metal, or of a mixture of two metals, or of a mixture of a metal
and an oxide of a different metal, or other permutations and
combinations of conductors and oxides. Preferably the conductors
belong to the group consisting of gold, silver, platinum,
palladium, iridium, ruthenium, osmium, rhodium, iron, nickel,
chromium, copper, lead, manganese, and the oxides thereof,
graphite, nitrides, carbides, and sulfides.
The coating according to the invention need not cover the entire
surface of the electrode to be immersed in the electrolyte. As a
matter of fact, the coating need only cover 2 percent of the
immersed zone, and the electrode will still operate effectively and
efficiently.
There are a number of methods of forming the coating on the base to
produce the mixed-crystal material. The most practical one thereof
comprises the coprecipitation of an oxide of a film-forming metal
with the other material of the mixture constituting the coating,
which coprecipitation may be effected chemically, thermally,
electrically, or by a combination of these methods. One method of
effecting such a coprecipitation consists in preparing a solution
containing materials from which one or more oxides of the
film-forming metal can be precipitated, and further materials from
which non-film-forming conductors can be precipitated and
thereafter treating the solutions in such a manner that the oxide
or oxides of the film-forming metal are coprecipitated with the
conductors of the non-film-forming type. Among the methods of
treating the solution are evaporation of the solvent followed by
the thermal formation of the mixed crystals, whereby, when the
solution is first applied to the surface of the electrode to be
coated, by a treatment such as brushing, immersion, or spraying,
the coprecipitated mixture remains behind on the surface of the
electrode. Alternatively, the acidity of the solution can be so
adjusted that the materials of the mixture are precipitated to form
a suspension and then the portion of the electrode to be coated can
be immersed in the suspension and an electrophoresis effected to
precipitate the materials onto the electrode. Such a method is
preferably followed by sintering to promote the adhesion of the
deposited mixture of the material of the core of the electrode.
A particular method of co-precipitating the materials to form the
mixed-crystal material comprises preparing a solution containing a
solvent and a soluble compound or compounds of a film-forming
metal, which will precipitate when the solvent is evaporated, and a
soluble compound or compounds of a non-film-forming conductor,
which will also precipitate when the solvent is evaporated. The
solution is applied to the surface of the electrode base to be
coated, and the base thus coated is heated one or more times,
preferably several times, in a non-reducing atmosphere.
Alternatively, only one of the materials in the solvent need be
evaporated, that is to say, either a compound from which an oxide
of a film-forming metal can be deposited, or a compound from which
a non-film-forming conductor can be deposited, the other compound
or compounds being suspended in the solution. The subsequent
treatments are the same as in the case that all materials are in
the dissolved state.
A different method of making the electrode consists in the use of
the so-called vacuum-sputtering techniques, in which the base is
placed in a vacuum and connected as a cathode, and anodes of one or
more film-forming metals, are placed in the vacuum together with an
anode of an electrolytic non-film-forming metal or an oxide
thereof, or anodes of electrolytic non-film-forming metals or
oxides thereof, and the sputtering current is conducted through the
anodes and the cathode so that the electrolytic film-forming metal
oxide or oxides are sputtered onto the cathode together with the
electrolytic non-film-forming metal or metals or oxide or oxides
thereof.
Still another method of making the electrode according to the
invention consists in the use of an electrolysis. The base of the
electrode is immersed in an electrolyte consisting of a solution of
salts or other compounds of one or more film-forming metals, from
which solution the oxide or the oxides will co-precipitate onto the
electrode when the solution is subjected to electrolysis. The
solution also contains a soluble compound of a non-film-forming
metal or metals or of an oxide or oxides of such metals which will
also co-precipitate during the electrolysis. The electrolysis can
be effected either by passing an alternating current through the
electrode, or by using the electrode as an anode and conducting a
direct current through it.
Generally speaking, the formation of the mixtures of the oxides
according to the invention can be effected thermally by heating in
the air, but in some cases this can be beneficially affected by
conducting the heat treatment under sub-atmospheric or
super-atmospheric pressure. The heating may be effected by
resistance heating or high-frequency heating.
When the mixtures are applied alectrolytically, this is best
effected under anodic conditions, and preferably so that one or
more hydroxides of the metals are deposited on the base, such
hydroxides being subsequently sealed by boiling in demineralized
water or by heating.
Generally speaking, the starting products are salts of the metals,
which are converted into the desired oxides thermally. The acid
residue is preferably so selected that the salt is converted into
an oxide at a temperature of from 400.degree.-1,200.degree.C. I
preferably use acid residues of volatile acids, such as HCl, HBr,
or acetic acid.
The manner in which the electrode according to the invention is
used will be readily apparent to those skilled in the art. For most
uses, the electrode is placed as an anode in an electrolysis
apparatus, and the electrolysis is carried out in the conventional
manner and under conventional conditions, the product or products
of the electrolysis being yielded in the conventional manner, or
the purified electrolyte being recovered, as desired. Examples of
processes in which the electrode is thus used are the electrolysis
of brine in mercury cells or diaphragm cells for the production of
chlorine and alkali metal, the electrolytic production of
chlorates, hydrochlorites, persulphates, and perborates, the
electrolytic oxidation of organic compounds, such as liquid or
gaseous hydrocarbons, for example, propylene or ethylene, the
electrolytic deposition of metals, desalination of water,
sterilization of water, and fuel cells. The electrode is also
excellently suitable for use as an anode in cathode protection
systems and as a cathode in bi-polar cells.
As explained above, the provision of the mixed-crystal coating is
the particular feature accounting for the outstanding performance
of the electrode according to the invention. The importance of the
restriction that the coating must behave as a mixed-crystal
material rather than as a mere mixture of the two oxides can be
shown by means of several examples. Iron oxide itself is highly
sensitive to hydrochloric acid at room temperature, and so are
several titanium oxides. It has been found, however, that when a
co-precipitated mixture of iron oxide and titanium oxide is applied
to a basis of conductive material it is only affected by
hydrochloric acid at room temperature to a very small extent.
Similarly, ruthenium oxide coated on a titanium base, connected as
an anode in an alkali metal chloride electrolysis, which anode is
contacted with the amalgam formed in a mercury cell, loses a part
of its thickness after a prolonged period of electrolysis, because
the reductive properties of the amalgam convert the ruthenium oxide
into metallic ruthenium, and the metallic ruthenium is readily
dissolved in the amalgam from the surface of the titanium and is
not resistant to the electrolyte. Co-precipitated mixed oxides of
titanium oxide and ruthenium oxide, however, which are in contact
with such an amalgam are resistant to the amalgam because these
oxides when in mixed-crystal form are not reduced and so do not
dissolve in the amalgam or in the generated chlorine.
It should be noted that the mixed crystals which are applied to the
electrodes according to the present invention are quite different
from those obtained, for example, by mere heating in the air of the
solid noble metals, or when these are superimposed in discontinuous
layers in finely divided condition on other metals. Generally
speaking, it may be said that the oxidation of the solid metals by
mere heating is very difficult, and that, although finely divided
noble metals may be oxidized, the adhesion of such oxides to the
substrate is often very poor. Electrolytic oxidation is also very
difficult, and in addition layers produced in this manner also show
poor adhesion, so that a mechanically weak electrode is formed. The
problem of rendering the oxides of the noble metals and other
metals in finely divided condition adhesive and at the same time
resistant is now solved by virtue of the co-precipitation of the
non-film-forming conductors with the oxides of the film-forming
metals. It is surprising, for example, that palladium oxide,
platinum oxide, and ruthenium oxide are then fully resistant.
Therefore, it is decidedly not so that platinum, applied to a
metallic base, when heated in the air or used as an anode in the
electrolysis of alkali metal chloride, just acquires the condition
required according to the present invention, that is to say, that
an adhering mixture is co-precipitated thereon.
The following Table A clearly indicates the difference between the
co-precipitated oxides according to the present invention and the
other oxides which may be formed thermally or electrolytically
when, for example, an electrode consisting of a base of metallic
titanium and a coating of a platinum metal is oxidized in the air
or used to electrolyse a dilute solution of an alkali metal
chloride or dilute hydrochloric acid.
Chemical and electrolytic properties of singular oxides as
compared with the mixed oxides according to the invention
Thermal oxidation in air at 500.degree.C of Pt/Pd/Ag/Fe/Ru in
finely-divided condition on titanium base Formation of oxide
B/B/B/B/G Adhesion to base metal B/B/B/B/B Resistance to 0.2%
sodium amalgam B/B/B/B/B Overvoltage in chlorine electrolysis at
8,000 amps/m.sup.2 B/B/--/--/B Loss of oxides per ton of chlorine
at 8,000 amps/m.sup.2 M/M/--/--/M Chemical resistance to aqua regia
without current B/B/--/--/B Resistance to reduction B/B/B/B/B
Catalytic properties in the oxidation of organic compounds
B/B/B/B/B Mechanical strength B/B/B/B/B Key: E -- excellent B --
bad G -- good N -- practically no oxide formed M -- much L -- very
little
Electrolytic oxidation in dilute sulphuric acid of Pt/Pd/Ag/Fe/Ru
in finely-divided state on titanium base Formation of oxide
N/B/B/--/G Adhesion to base metal --/--/B/--/B Resistance to 0.2%
sodium amalgam --/B/B/--/B Overvoltage in chlorine electrolysis at
8,000 amps/m.sup.2 --/B/--/--/G (for a short time) Loss of oxides
per ton of chlorine at 8,000 amps/m.sup.2 --/M/--/--/M Chemical
resistance to aqua regia without current --/B/--/--/B Resistance to
reduction --/B/--/--/B Catalytic properties in the oxidation of
organic compounds --/B/B/B/B Mechanical strength --/B/B/B/B
co-precipitated oxides of Ru/Ti, Pt/Zr, Pd/Ta, Ag/Ti, Fe/Ti, and
Pt/Ti in finely-divided state on titanium base. Formation of oxide
E/E/E/E/E/E Adhesion to base metal E/E/E/E/E/E Resistance to 0.2%
sodium amalgam E/E/E/--/E/E Overvoltage in chlorine electrolysis at
8,000 amps/m.sup.2 E/E/E/--/--/E Loss of oxides per ton of chlorine
at 8,000 amps/m.sup.2 L/L/L/--/--/L Chemical resistance to aqua
regia without current E/E/E/--/--/E Resistance to reduction
E/E/E/--/--/E Catalytic properties in the oxidation of organic
compounds E/E/E/--/--/E Mechanical strength E/E/E/--/--/E
in a test designed to show quantitatively the improvement obtained
by electrodes according to the invention as compared with other
electrodes in contact with 0.2 percent sodium amalgam under a
constant electric load of 10.000 Amp/m.sup.2 during electrolysis
and of 80.000 Amp/m.sup.2 during short-circuiting with the amalgam,
a number of titanium bases were respectively coated with (1)
metallic ruthenium, (2) a mixture of platinum and iridium (70/30
weight/weight), (3) a co-precipitated mixture of ruthenium oxide
and titanium oxide (90 mol % / 10 mol %), and (4) a co-precipitated
mixture of ruthenium oxide and titanium oxide (30 mol % / 70 mol
%). All these materials were present in a thickness of 10
g/m.sup.2. The electrodes were introduced into a brine test cell
containing 0.2 percent sodium amalgam, which quantity was kept
constant, the brine in the cell having a concentration of 28
percent and a temperature of 80.degree.C, the applied current
density being 10.000 Amp/m.sup.2. These conditions are the same as
may be the case in a large-scale cell. FIG. 2 shows the overvoltage
in millivolts plotted against the time. It will be seen that,
whereas the overvoltage of the first, second and third electrodes
increased relatively rapidly owing to the contact with the amalgam,
the overvoltage of the electrode according to the invention, i.e.,
containing more than 50 percent titanium oxide, only increased
gradually during a long period of time.
The invention is illustrated, but not limited, by the following
examples.
EXAMPLE I
6.2 cc butyl alcohol
0.4 cc HCl 36 percent
3 cc butyl titanate
1 g RuCl.sub.3
The solution was several times brushed on to a cleaned titanium
plate (grain size titanium 0.04-0.06 mm; ASTM 6) of 10 .times. 10
cm and a thickness of 1 mm, the plate being first pickled in hot
aqueous oxalic acid, subjected to ultrasonorous vibration in water,
and dried. The plate thus treated was heated in the air at a
temperature of 300.degree. - 500.degree.C for 1 - 5 minutes.
The resulting electrode had a coating of ruthenium oxide
coprecipitated with titanium oxide, the titanium oxide being
present in a proportion of 70 mol %, the balance being
RuO.sub.2.
The resulting electrode was placed in a hydrochloric acid cell as
an anode, the cathode being a silver plated titanium electrode.
Flowing hydrochloric acid of 25 percent was electrolyzed at
70.degree.C and 2,500 Amp/m.sup.2 for practically one year with
excellent results and with losses of less than 0.1 g ruthenium per
ton of chlorine.
The resulting electrode was placed in a brine electrolysis cell as
an anode, the cathode being mercury and the brine having a
concentration of 28 percent a pH of about 2.5, and a temperature of
80.degree.C. The spacing between anode and cathode was less than
2.5 mm. When a current density of 10.000 Amp/m.sup.2 was applied,
the anode had an extremely low overvoltage of about 80 millivolts,
measured against a calomel reference electrode, and this was
maintained for a long period of time, even after various
short-circuitings with the amalgam.
The resulting electrode was placed in a brine diaphragm cell as an
anode, the cathode being iron, and the brine having a concentration
of 28 percent, a pH of about 3.5, and a temperature of 80.degree.C.
At a current density of 1,000 Amp/m.sup.2, the anode had an
extremely low overvoltage of 60 mVolts and maintained this for a
long period of time. The losses of metallic ruthenium were less
than 0.15 g per ton of produced chlorine, in the mercury cell and
less than 0.1 g of produced chlorine in the diaphragm cell.
The resulting electrode was also used in a cathodic protection
system as anode for the protection of a ship. The electric design
was a conventional system well-known to those skilled in the art.
The anode showed good electrical and mechanical properties.
The resulting electrode was extremely suitable for the oxidation of
unsaturated organic compounds, such as ethylene and propylene, as
well as for the preparation of chlorates.
The resulting electrode was also suitable for electrodialysis,
because it readily admits of pole changing.
The resulting electrode was also used in a galvanic metal
deposition process, in which gold was deposited on copper from a
bath having the following composition: gold chloride 30 g/l, nitric
acid (specific gravity 1.19) 25 cc/l, sodium chloride 12 g/l,
sulphuric acid (specific gravity 1.025) 13 g/l (+ organic
brighteners). By means of this bath, at 70.degree.C, and a current
density of 8-10 Amp/m.sup. 2, an excellent plating on the cathode
was obtained, the overvoltage at the anode being such that no
damage was done to the bath.
EXAMPLE II
80 cc TiCl.sub.3 -solution in H.sub.2 O (25% TiO.sub.2)
1 g RuCl.sub.3
This mixture was absorbed in a graphite anode at a subatmospheric
pressure this anode being previously subjected to ultrasonorous
vibrations for 10 minutes. Subsequently the anode was heated in a
stream of air for one-half hour at a temperature of 300.degree. -
800.degree.C. This treatment was repeated four times. The resulting
electrode had a coating of ruthenium oxide, co-precipitated with
titanium oxide, the titanium oxide being present in a proportion of
98.4 mol % TiO.sub.2, there being 1.6 mol % RuO.sub.2.
An untreated graphite anode was placed in an alkali metal chloride
cell containing 28 percent brine of a pH of about 2.5 and a
temperature of 80.degree.C as the electrolyte and a mercury
cathode. The distance between the anode and the cathode was less
than 2.5 mm.
A current of a density of 8.000 Amp/m.sup.2 was passed through the
cell. The anode first had an overvoltage of about 400 mV, which
decreased to 360 and after a considerable time increased to 450 mV.
Furthermore, the untreated anode showed marked erosion after a
short while, and as a result the brine solution became black with
the graphite released. In addition to the contamination of the bath
liquid, the loose graphite caused stray currents, resulting in loss
of efficiency and discharge of the amalgam. Furthermore, the
spacing between the anode and the cathode required adjustment at
regular intervals, because this spacing changed as a result of the
erosion of the anode, resulting in loss of energy in the
electrolyte.
The electrode according to this example, placed in the same
electrolyte under the same conditions, had an overvoltage of only
70 mV, which overvoltage remained constant during a considerable
time. Moreover, the bath remained clear and the anode showed no
erosion. Accordingly, not only was the electrolyte not
contaminated, but the electrodes did not require adjustment.
The electrode according to the invention was also used as an anode
in a cathode protection system of a conventional type and operated
excellently.
EXAMPLE III
A tantalum plate was cleansed well and mechanically roughened, and
a coating mixture was prepared as follows:
18 cc isopropyl alcohol
1 g iridium chloride
2 g platinum chloride
4 g isopropyl titanate
3 cc anise-oil (reducing agent)
Lavender oil or linalool may be used instead of the anise-oil.
The mixture was brushed onto the tantalum plate several times, and
the coated base was subsequently heated at a temperature of
600.degree.C for several minutes. The resulting electrode had an
oxide coating of iridium and platinum, co-precipitated with
titanium oxide, the titanium oxide being present in a proportion of
65.8 mol percent in addition to 12.65 mol percent iridium and 21.55
mol percent platinum.
This electrode operated excellently in electrolytic processes for
the preparation of chlorine, oxygen, oxidation of organic
compounds, and in galvanic baths.
EXAMPLE IV
A zirconium plate was degreased and a coating mixture was prepared
as follows:
10 cc water
1 g gold chloride
3 cc 25 percent titanium chloride solution
0.1 cc wetting agent
This mixture was brushed onto the degreased plate and the plate was
heated in the air at a temperature of 200.degree. - 300.degree.C
and at a superatomspheric pressure. This treatment was repeated
eight times.
The resulting electrode had a coating of gold oxide coprecipitated
with titanium oxide, the titanium oxide being present in a
proportion of 74 mol percent and the gold oxide in a proportion of
26 mol percent.
This electrode operated excellently in dilute sulphuric acid
solutions.
EXAMPLE V
A titanium rod was degreased and then pickled for 8 hours in a 10
percent oxalic acid solution at 90.degree.C. The rod was
subsequently brushed with the following mixture:
30 cc TiCl.sub.3 solution in water
3 g anhydrous ferric chloride
1 g ferrous chloride
The resulting rod was subsequently heated in a space filled with a
mixture of steam and air at a temperature of 450.degree. -
600.degree.C for 1-2 hours.
The resulting rod was connected in a cathodic protection system.
The electrode operated excellently in alkaline solutions at current
densities upto 1,000 Amp/m.sup.2.
EXAMPLE VI
6.2 cc butyl alcohol
0.4 cc hydrochloric acid 36 percent
1 g zirconium acetyl acetonate
1 g iridium chloride, dry
The solution was applied to a zirconium base as described in
Example I, the base being previously degreased, pickled, and
subjected to ultrasonorous vibrations. After the application of the
solution the base was heated at 500.degree. - 700.degree.C for
several minutes by clamping the base between two copper plates
heated throughout their surface. This resulted in a highly uniform
heating of the overall surface, which was highly beneficial to the
quality of the anode. The treatment was repeated several times. The
ratio of zirconium oxide to iridium oxide in the mixture had been
so selected that more than 50 mol percent of zirconium oxide was
present in it. The anode thus made was excellently suitable for all
kinds of electrolytic processes, particularly for the electrolysis
of sulfuric acid solutions and solutions of sulfates.
EXAMPLE VII
9 cc butyl alcohol
0.4 cc hydrochloric acid 36 percent
1 g palladium chloride
3 cc pentaethyl tantalate.
A tantalum base was dipped into the above solution and after drying
heated at 500.degree. - 800.degree.C to deposit a mixture thereon
of 62 mol % tantalum oxide and 38 mol % palladium oxide. This
treatment was repeated six times. The tantalum base was a thin tube
which after the completion of the coating was provided with a
copper rod acting as a current conductor, because the tantalum tube
comprised insufficient metal for it to be able to transport current
without undue losses. In order to ensure proper contact between the
tantalum tube and the copper rod, the inner surface of the tantalum
tube was electrolytically copper-plated. Intimate contact between
the copper rod and the copper inner coating was obtained by
applying molten tin therebetween and allowing the tin to
solidify.
The anode made in this manner was excellently suitable for cathodic
protection purposes with an applied voltage of higher than 20
volts, and also is an excellent anode for the preparation of
hypochlorites.
EXAMPLE VIII
6.2 cc butyl alcohol
0.4 cc hydrochloric acid 36 percent
1 g ruthenium chloride
3 cc niobium pentaethylate.
A niobium base was degreased and connected as an anode in an
electrolyte to form an oxide coating thereon. This coating was
subsequently rinsed thoroughly and dried. The anode with the oxide
coating thereon was dipped into the above solution and subjected to
high-frequency heating at 600.degree.C at a subatmospheric pressure
of 100 mm Hg to convert the reactants to the desired mixture. This
treatment was repeated several times until the desired mixture was
present on the niobium in a thickness of 2 microns.
The anode thus made was excellently suitable for all kinds of
electrolytic processes, such as for the preparation of chlorine,
chlorates, and hypochlorites, for the sterilization of
swimming-pools, etc.
EXAMPLE IX
A titanium plate was degreased and pickled and subsequently an
oxide coating of about 1 mm thickness was applied to it by means of
electrolysis.
A mixture of:
10 cc butyl alcohol
1 g ruthenium oxide powder
3 cc butyl titanate
was painted onto it and converted into the desired mixture at a
temperature of 300.degree. - 600.degree.C. This treatment was
repeated so many times that 10g/m.sup.2 of the desired mixture was
present on the surface of the titanium plate.
The anode made in this manneer was excellently suitable for the
electrolytic preparation of chlorine, and chlorine compounds, and
for cathodic protection purposes.
The electrolytically formed oxide on the titanium highly promotes
the adhesion of the mixture formed.
EXAMPLE X
A niobium expanded metal plate was pre-treated in known manner and
subsequently brushed with a solution of:
10 cc water
1 g ruthenium chloride
1/2 cc hydrochloric acid (35 percent)
2 g titanium hydroxide.
The plate was subsequently heated at 400.degree. - 700.degree.C for
several minutes until the desired mixture formed. This treatment
was repeated until 6g/m.sup.2 of the mixture was present on the
surface.
This anode was excellently suitable for the electrolysis of
alkaline solutions.
EXAMPLE XI
An aluminum plate was degreased and pickled in a conventional
manner. There was then prepared a mixture of:
10 cc isopropyl alcohol
1 g aluminum bromide
1 g platinum chloride
0.01 g iodine.
The aluminum plate was dipped into this mixture and heated at
400.degree.C to form the required mixture, the latter consisting of
62.2 mol % Al.sub.2 0.sub.3 and 37.8 mol % PtO.sub.2.
This treatment was repeated several times, the mixture being
applied to the plate either by dripping or painting.
The electrode thus made is excellently suitable for the
electrolysis of boric acid compounds.
EXAMPLE XII
The following mixture was prepared:
10 cc butyl alcohol
6 cc butyl titanate
2 g graphite (can be replaced by titanium nitride or tantalum
carbide or rhenium sulfide)
This mixture was painted onto a titanium base and heated at a
temperature of 400.degree. - 700.degree.C, which treatment was
repeated a number of times.
An anode thus coated with graphite and titanium oxide is
particularly suitable for electrolyses in which a low current
density is desirable, for example, cathodic protection of
subterraneous objects.
Anodes in which the coating contains in addition to titanium oxide
a nitride, carbide, or sulfide are resistant to high current
densities in various electrolytes.
EXAMPLE XIII
2 g titanium chelate
1 g ruthenium chelate
These two chelates were intimately admixed in the dry state and
subsequently placed on the bottom of a vessel which can be closed
and heated. A degreased, pickled titanium rod, covered as to 98
percent with a heat-resistant silicon lacquer layer, was introduced
into the vessel. By heating the chelates, a mixture of titanium
oxide and ruthenium oxide was evaporated onto the 2 percent of
exposed titanium, and the required crystal form was obtained by
sintering. A small quantity of hydrochloric acid vapour in the
vessel promotes the adhesion of the mixed oxide. Subsequently the
lacquer layer was removed. The resulting electrode has an active
surface area of about 2 percent.
This electrode is excellently suitable as an anode for the
sterilization of water in swimming-pools or for the electrolysis of
two layers of liquid, in which a local electrolysis of either of
the liquids is desired.
Naturally, partly coated anodes may also be made in different
manners from that described in this example.
EXAMPLE XIV
10 cc butyl alcohol
2 cc butyl titanate
1 cc pentaethyl tantalate
1 cc pentaethyl niobate
1 g ruthenium chloride, bromide, or iodide
0.1 g hydrogen chloride
A zirconium base was degreased and pickled in known manner. The
above mixture was painted onto the base and converted by heating at
400.degree. - 700.degree.C in air. This treatment was repeated
until 40 g/m.sup.2 of the desired mixture was present on the
surface. The mixed crystal consisted of the oxides of titanium,
tantalum, and niobium as oxides of film-forming metals and
ruthenium oxide as the oxide of a non-film-forming conductor.
In addition, some zirconium oxide had formed thermally on the
boundary surface of the mixture and the zirconium rod. The quantity
of oxides of film-forming metals was more than 50 mol %, calculated
on the overall mixture.
Such an anode is particularly suitable for all kinds of
electrolyses, such as of sulphuric acid compounds, for the
purification of water, and for the preparation of chlorates.
EXAMPLE XV
A titanium plate was degreased, pickled, and subjected to
ultra-sonorous vibrations. Subsequently the plate was placed as an
electrode in a stirred emulsion consisting of:
100 cc water
100 cc acetone
5 g extremely finely divided mixture of co-precipitated platinum
oxide (3 g) and titanium oxide (2 g)
1 g emulsifying agent
The second electrode was constituted by a platinum plate. By
applying an electric voltage of 10 - 100 volts, the titanium was
electrophoretically coated with a mixed oxide from the emulsion.
After being removed from the bath, the titanium with the coating
deposited thereon was carefully dried and subsequently heated at
400.degree.C for several minutes. Thereafter the
electrophoretically deposited layer had an excellent adhesion to
the titanium, and the anode thus made is suitable for various kinds
of electrolyses.
The adhesion is highly promoted by pre-oxidizing the titanium base
by means of heat or electrolytically, and then applying the mixed
oxide by electrophoresis.
This example was repeated using a mixture of co-precipitated
platinum oxide, titanium oxide, and manganese dioxide. There is
thus obtained an anode having a high overvoltage and catalytic
properties.
EXAMPLE XVI
Two titanium rods were degreased and pickled and subsequently
placed in a galvanic bath having the following composition:
100 cc ethanol
100 cc water
1 g ruthenium chloride
10 g titanium chloride and subsequently connected to a source of
alternating current of 13 volts and a current density of 15
Amp/m.sup.2, temperature 20.degree. - 30.degree.C, for a period of
time of about 20 minutes.
After about 20 minutes both rods were coated with a mixture of
titanium oxide and ruthenium oxide, the adhesion of which was still
further improved by heating at 400.degree.C for 5 minutes.
The anode thus made is excellently suitable for use in various
electrolyses effected at low current densities.
EXAMPLE XVII
A titanium rod was degreased and subsequently electrolytically
provided with an oxide coating of a thickness of about 5 microns.
The rod thus treated was placed as an anode in a bath
(80.degree.C), containing:
100 cc water
5 g yellow lead oxide
5 g sodium hydroxide
3 cc hydrogen peroxide
10 cc titanium chloride solution (25% TiO.sub.2)
This bath is regularly insufflated with air. The treated titanium
rod was connected as anode, an iron plate being used as the
cathode. The voltage differential between the anode and the cathode
was about 2 - 3 volts, and the current density was about 5
Amp/m.sup.2.
After about an half hour, the titanium anode was coated with a
mixture of titanium oxide and lead oxide, the properties of which
could be considerably improved by heating at 200.degree. -
600.degree.C.
An anode thus treated is suitable for use in electrolyses in which
no high-current densities are necessary.
EXAMPLE XVIII
Titanium expanded metal was degreased and pickled, and then painted
with the following mixture:
10 cc butyl alcohol
1 g ruthenium chloride
3 cc zirconium acetyl acetonate.
Subsequently the product was heated at 400.degree. - 700.degree.C.
This treatment was repeated until the mixture on the titanium had a
thickness of one-half micron.
An electrode thus made is excellently suitable for the electrolysis
of solutions of sulphuric acid compounds, the resistance of the
titanium to sulphuric acid being greatly increased by virtue of the
mixed surface coating containing zirconium oxide.
EXAMPLE XIX
A tantalum wire was degreased and pickled, and then dipped into a
mixture of
10 cc butyl alcohol
3 cc butyl titanate
1 g iridium chloride
The wire was then heated at a temperature of 500.degree. -
700.degree.C, and the treatment was repeated until at least 2.5 g
of the mixture of the oxides per m.sup.2 was present on the surface
of the tantalum.
A tantalum wire thus treated is excellently suitable for use as an
anode for the cathodic protection of ships.
EXAMPLE XX
A titanium plate was degreased, pickled, subjected to ultrasonoric
vibrations and then rinsed thoroughly and dried. This plate was
subsequently connected as a cathode in an apparatus in which metals
can be vacuum deposited. As anodes, a bar of platinum and bars of
titanium were connected, the ambient atmosphere containing so much
oxygen that the anodic materials were deposited on the titanium
cathode as oxides (a detailed description of this apparatus is
contained in the book by L. Holland, Vacuum Deposition, 1963, pages
454 - 458).
After several minutes a mixture of titanium oxide and platinium
oxide had deposited on the titanium, and the titanium thus treated
is excellently suitable for the electrolysis of aqueous
electrolytes.
EXAMPLE XXI
Niobium was degreased and subsequently provided with an oxide
coating of a thickness of at least 1 micron. This can be effected
either electrolytically or thermally.
Subsequently a paste was prepared of:
10 cc ethanol
1 g ruthenium oxide
4 g titanium oxide.
This mixture was intimately admixed, heated, sintered, comminuted,
and again mixed with 10 cc ethanol. The resulting paste was applied
to the oxidized niobium in a thin layer, and subsequently heated at
a temperature of 450.degree. - 700.degree.C. This treatment was
repeated until at least 10 g of the desired mixture per m.sup.2 was
present on the surface.
A niobium plate thus treated is excellently suitable for the
electrolysis of electrolytes.
EXAMPLE XXII
A soft-quality titanium rod was degreased and then a mixture of
more than 50 mol percent titanium oxide and less than 50 mol
percent palladium oxide was rolled into it under pressure.
Alternatively, this may be effected by hammering.
The oxides were prepared by dissolving water-soluble salts of the
metals in water in the required proportions, from which solution
they were precipitated with lye, washed, and carefully dried. In
this manner a very fine mixed oxide was obtained, which could be
hammered or rolled into the titanium without undue trouble. Other
conventional methods of preparing these mixed oxides can naturally
be used as well.
Furthermore, other mtals than titanium can naturally be treated in
this manner.
EXAMPLE XXIII
6.2 cc butyl alcohol
0.4 cc water
3 cc butyl titanate
1 g ruthenium chloride.
The above solution was painted onto a titanium base and heated as
described in Example I.
An anode thus made is particularly suitable for the electrolysis of
zinc sulphate or copper sulphate solutions, which may be
contaminated with nitrate or chloride, for the manufacture of the
metals concerned.
EXAMPLE XXIV
A zirconium plate was degreased and subsequently provided with the
desired mixture of oxides by means of a so-called plasma
burner.
There is thus obtained a very thin, but excellently adhering layer,
and a zirconium plate provided with such a coating is excellently
suitable for all kinds of electrolyses.
* * * * *