AU463572B2 - Electrodes for electrochemical processes - Google Patents
Electrodes for electrochemical processesInfo
- Publication number
- AU463572B2 AU463572B2 AU39853/72A AU3985372A AU463572B2 AU 463572 B2 AU463572 B2 AU 463572B2 AU 39853/72 A AU39853/72 A AU 39853/72A AU 3985372 A AU3985372 A AU 3985372A AU 463572 B2 AU463572 B2 AU 463572B2
- Authority
- AU
- Australia
- Prior art keywords
- film
- layer
- coating
- forming metal
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electrolytic Production Of Metals (AREA)
- Inert Electrodes (AREA)
- Chemically Coating (AREA)
- Secondary Cells (AREA)
Description
3 9. 85. -2
MD.23700
The present invention relates to electrodes for
electrochemical processes. More particularly it relates.
to electrodes comprising a support member of a film-forming
metal carrying a coating which is active in transferring
an electric current from the support member to ions of an
electrolyte and is resistant to electrochemical attack.
It is known to employ oxides of the platinum group
metals as coatings on electrodes of the aforesaid type
because they have a high intrinsic resistance to electro-
chemical dissolution in a variety of corrosive media and
they are active in discharging ions from an electrolyte.
The present invention provides improved electrodes incor-
4 63 72
39,853/72 porating coatings comprising platinum group metal oxides.
The electrodes of the invention are very useful as anodes
in cells for the electrolysis of alkali metal chloride
solutions. They are particularly useful in cells with
flowing mercury cathodes, because the electrodes have a
high resistance to damage by short-circuit contact with
the cathode, such as may occur accidentally even during
the normal course of operation in these cells. The
electrodes can also be used in other electrochemical
processes, including other electrolytic processes, electro-
catalysis, as for instancein fuel cells, electrosynthesis
and cathodic protection.
According to the present invention we provide an
electrode for use in electrochemical processes which com-
prises a support member made of a film-forming metal or
alloy and a coating thereon consisting of a layer of a
mixture of the oxide(s) of at least one platinum group
metal in a proportion of 20-80% by weight and a film-
forming metal oxide and superimposed on the said layer a
layer of a film-forming metal oxide.
In a preferred form of the electrode the ratio of
platinum group metal oxides:film-forming metal oxide in
the layer of the said mixture is not less than 1:1 but is
less than 2:1 by weight.
By a film-forming metal we mean one of the metals
titanium, zirconium, niobium, tantalum and tungsten. By
a film-forming alloy we mean an alloy containing a major
39,853/72 p. ip ion of of these mrietals ald having anodic
polari.sation properties similar to the coimmiec-cially-
pure n.cta]. Thie support member of the electrode is
preferably made of titanium or a titanium alloy having titanium. ainodic polarisation properties similar to Lhose of
By the oxide(s) of. at least one platinum group metal
we mean the oxide(s) of at least one of the metals ruthenium,
rhodiumn, palladium, osmium, iridium and platinum.
In a preferred form of the electrode according to
the invention the layer of the said mixture consists of
ruthenium dioxide and titanium dio.ide and the super-
imposed layer consists of titanium dioxide.
The preferred method of forming the layer of mixed
oxides on the support member is as follows. A coating of
a paint compositici comprising a thermally-decomposable compound of at least one platinum group metal and a
thermally-decomposable organo-compound of a film-forming
metal in an organic liquid vehicle and optionally also
comprising a reducing agent, e.g. linalool, is applied to
the support member, the coating is dried by evaporation
of the liquid vehicle and the coated support is then
heated in an oxidising atmosphere, e.g. in air, at a 0 the range temperature of at least 350 C and preferably in
400-550°C to convert the compounds of the platinum group
neta].s and the film-forming metal to oxides of these metals.
Further coats of the paint composition may then be applied
to the coated support, dried and heated in the same manner
A 463 72 l'j increase the th-i':kners *of the 1mixeo o:'Ade ly(rto arty desired extent. Foi- examiple for eIlec trt dIes that ace to be used as anode! in mercury-ca thzcde cells eJ.2 I roll.y Inj~ alkali metal chlcridc solutions we prefer to builed up a thickness of- this layer in the range J-rjm of tile coated surfa.:e of the support inemnber. This thiickniess is, however, in no way critical. Thinrner or thicker coatings may be employed and the thickness will gencrally be chojen having regard to the wear to which the electrode will be submitted during use in the cell, which itself wil.l be related inter alia to the current density at w,.hich the electrode will be required to operate.
The preferred method of forming the superimposed
layer of film-forming metal oxide is by applying over
the mixed oxide la;7er a coating of a thermally-decomposable
organo-compound of the film-forming metal in an organic
liquid vehicle, drying the coating by evaporation of the
liquid vehicle and then heating the coating in an oxidising
atmosphere, e.g. air, to convert the organo-compound of the
film-forming metal to the oxide of the metal. The preferred
thickness of this superimposed layer of film-forming metal
oxide is in the range 2-1lm2 of the coated surface. The
desired thickness of this layer may be obtained by adjust-
ing the viscosity of the coating composition by adding nore
or less of the organic liquid vehicle and/or by repeated
application of thinner layers of coating composition,
drying and hcatin6j each coating, to build tip the desired
thickness,
4635.72 s.ta. IfIq 7iu ;~pl d i forming I h e ssuj~fi. ii:pj.Scd ofci 1 'rc L~l o-'.ide in a~co;.rpne th the pr i Lfl pz:.;r .ph are MoCst su~itabJ y thp titanateS the alk'l bale tita.nates whcorcin the ;,.LoJon is chlorine, bromin;z or £1 noiine (alter natively ki-cwrn as titanum alkoxides and aidz-a d )and tht! corresponding alkyl cor; pound!s of other filin-fori-iinq mctas. Other suitable the(rmial ly-dec.co-niposabie organo-compounds are resinites of the film-forriirg iretals, The preferred compo'ands are the alkyl titanates and halotitanates, especially those in
%w.hich the alky]. groups contain 2-4 carbon atoms each.
Coatings ofL these preferred compoundMs applied in an
organic liquid vehicle as aforesaid are suitably dried
at a temperature cf 100-2001C and then heated in an 0 oxidising atmosphere at 250-800 C, preferably at 350-5500C,
to convert the titanate compounds to titanium dioxide.
Any of the thermally decomposable Compounds of the
film-forming metals listed in the preceding paragraph
may also be employed in the paint compositions used for
forming the under-layer of mixed oxides on the electrode
support miember. Again the alkyl titanates and the alkyl
halotitanates wherein the halogen is chlorine, bromine or
fluorine, especially those in which the alkcyl groups con-
tain 2-4 carbon atoms each, ate preferred. The theynmdly-
d~oopc'salle compounds of the platinum group metals use_-d
in these paint compositions may stiitably be halides,
4 635.72
39.853/72 e.g. ruthcnium trichloridiA, halo-acid complexes, e.g. hlia-
chlorcpl.atiiic acid, or resina.tes these metals. The pre-
csi:rtle platinum agroup metal con:ipoun.d is ruthenium trichloride.
The invention is further illustrated by the follow-
ing Ex.mple
EXAMPLE 1
A strip of titanium 35 cm long, cross section
6 mm x 1 mm was etched in oxalic acid soluti.on, washed, dried and then painted with a mi,:ture of 4.3g partly
hydrated ruthenium trichloride, 12.0g n-pentanol and
6.4g tetrabutyl ortho titanate. The paint layer was dried at 180 0C and then fired by heating in air at 450 0 C
for 15 minutes. A total of six layers of this paint was
applied, each layer being dried and heated in the same
manner, to give a loading on the titanium surface of 2 14g/m of a coating consisting of 60% ruthenium dioxide
and 40% titanium dioxide by weight. Over this mixed oxide coating was painted a mixture of 5g tetrabutyl
ortho titanate in 5g n-pentanol. This paint was also 0 dried at 180 C and then fired by heated in air at 450 0 C
for 15 minutes. A total of three layers of this second
paint was applied, each layer being dried and heated in
the same manner, to give a loading of 4g/m 2 of titanium
dioxide over the mixed oxide layer.
Samplcs cut from the coated strip were tested as
anodes for chlorine production in sodium chloride brine
containing 21.5, NaCI at pHl 2-3 and a temperature of 650 C.
4 635.72
39 8 5 /72 7Thi samp.i.s operaltd with low overpotential (50 mV at
a current density o. 8 kA/m 2 and they also showed
excellent resistance to damage when contacted wxith the
cathode amalgam in a mercury cell electrolysing sodium
chloride brine.
EXAMPLE 2
An anode whose working surface was in the form of
a grid made up of titanium strips and having a projected
area of 0.1 m 2 was in oxalic acid solution for 16 hours,
washed and dried. The anode grid was then sprayed with a
paint composition consisting of 60.5 g ruthenium trichloride
and 90.0 g tetra-n-butyl ortho titanate in 300 g n-pentanol. 0 The paint layer was dried in an oven at 180 C and was then
converted to a layer of composition 60% Ru02/40% TiO 2 by
weight by heating in air in a furnace at 450°C for 20 minutes
A further five layers of the same paint composition were
then sprayed on to the anode, each layer being dried and
then fired by heating in air as was the first layer. An
outer layer consisting of titanium dioxide alone was then
applied to the anode grid by spraying on to it three coats
of a paint composition consisting of 25 g tetra-n-butyl 0 titanate in.75 g n-pentanol, each being dried at 180 C and 0 The total then fired in air at 450 C for 20 minutes.
loading of oxides deposited on the titanium grid was then
32 g/m2 projected area.
The coated titanium anode was installed in a mercury-
cathode cell electrolysing sodium brine, as a replacement
a 463572
39.853 /7 for a graphite anode, and after operating satisfactorily for six months with an anode current of up to 900 amp.
there was no apparent wear nor decline in performance.
EXAMPLE 3 22 A titanium grid anode of 0.1 m projected area was
coated as in Example 2 except that the paint composition used
for the first six coats consisted of 55 g rutheniuhi tri-
chloride and 101 g tetra-n-butyl ortho titanate in 300 g
n-pentanol. This composition, after drying and firing,
produced an underlayer on the titanium grid of composition
Ru02/45% TiO 2 by weight.. The outer layer consisting
of titanium dioxide alone was then deposited as in
Example 2. This anode was also operated in a mercury-
cathode cell electrolysing sodium chloride brine and also
showed no signs of wear nor decline in performance after
six months' use with an anode current of up to 900 amp.
Claims (4)
1. An elecLrode for use in electrochemical processes
which co!.:.rises a support mem-ber made of a film-forming metal or alloy as hereinbefore 6efiied and a coating
thereon consisting of a layer of a mixture of the oxide(s) of at least one platinum group metal in a
proportion of 20-80% by weight and a film-forming metal oxide and superimposed on the said layer a
layer of a film-forming metal oxide.
2. An electrode according to claim 1, wherein the ratio
of platinum group metal oxides:film-forning metal
oxide in the layer of the said mixture is not less
-than 1:1 but is less than 2:1 by weight.
3. An electrode according to either of the preceding
claims, wherein the said support member is made of
titanium or a titanium alloy having anodic polarisation
properties similar to those of titanium.
4. An electrode according to any one of the preceding claims,
wherein the layer of the said mixture consists of
ruthenium dioxide and titanium dioxide and the super-
imposed layer consists of titanium dioxide.
An electrode according to any one of the preceding claims, wherein the weight of the layer of the said
mixture is in the range 10-15 g/m 2 of the coated surface, 6. An electrode according to any one of the preceding claims
wherein the weight of the said superimposed layer is in
the range 2-10 g/m 2 of the coated surface.
4 635,79
39,853 7. A method for the manulacture of an electrode
according to claim 1, which comprises the steps of
applying on a support member made of a film- forming metal or alloy at least one coating of a
composition comprising a thernally-decomposable
compound of at least one platinum group metal and
a thermally-decomposable organo-compound of a film-
forming metal in an organic liquid vehicle, drying
each coating by evaporation of the liquid vehicle
and then heating each coating in an oxidising atmos- 0 phere at a temperature of at least 350 C to convert
the compounds of the platinum group metals and the
film-forming metal to oxides of these metals, and
applying over the layer of mixed oxides thus produced on tLe support member at least one coating
of a thermally-decomposable organo-.compound of a film-
forming metal in an organic liquid vehicle, drying
each coating by evaporation of the liquid vehicle
and then heating each coating in an oxidising atmos-
phere to convert the organo-compound of the film-
forming metal to the oxide of the metal.
8. A method according to claim 7, wherein the said
support member is made of titanium or a titanium alloy
having anodic polarisation properties similar to those
of titanium.
9. A method according to either of claims 7 and 8 wherein
in step the said composition comprises a reducing agent. 4 6 5.7 2
398 53 72 7-9, vwherein A method according to any one of claims at in step the thermally-decomposable compound of trichloride. least one platinum group metal is ruthenium 7-10, wherein 11. A method according to any one of claims in step the temperature at which each coating is
heated in an oxidising atmosphere is in the range
400-550 0°C. 7-11, wherein 12. A method according to any one of claims in step the number of coatings of the said com-
position applied, dried and heated on the support
member is sufficient to build up a layer of mixed 2 oxides amounting to 10-15 g/m of the coated surface
of the support member. wherein 13. A method according to any one of claims 7-12, in step the thermally-decomposable organo-compound
of a film-forming metal is an alkyl titanate or an
alkyl halotitanate wherein the halogen is chlorine,
bromine or fluorine.
14. A method according to claim 13, wherein the alkyl
groups of the said alkyl titanate or alkyl halotitanate
contain 2-4 carbon atoms each.
A method according to any one of claims 7-14, wherein
the proportions of tjyIgroup metal compounds and film-forming metal compound in the said composition
in step are chosen so that the ratio of platinum
group metal oxides:film-forming metal oxide in the is not said layer of mixed oxides produced in step
less than 1:1 but is less than 2:1 by weight.
4635.72
39.853/72 16. Amethod according to any one of claims 7-15, wherein
the total amount of coating which is applied over
the said layer of mixed oxides is sufficient to prod-
uce in step a layer of film-forming metal oxide 2 2 amounting to 2-10 g/m of the coated surface.
17. A method according to any one of claims 7-16, wherein in step the thermally-decomposable organo-.
compound of a film-forming metal is an alkyl titanate
or an alkyl halotitanate wherein the halogen is
chlorine, bromine or fluorine.
18. A method according to claim 17, wherein'the alkyl
groups of the said alkyl titanate or alkyl halotitanate
contain 2-4 carbon atoms each.
19. A method according to either of claims 17 and 18,
wherein in step each coating is dried at 100-200°C
in an oxidising atmosphere.
A method according to claim 19, wherein in step (2) 0 each coating after drying is heated at 350-550 C
in an oxidising atmosphere.
21. An electrode for use in electrochemical processes,
substantially as hereinbefore described with reference
to any one of the foregoing Examples.
22. A method for the manufacture of an electrode, substan-
tially as hereinbefore described with reference to
any one of the foregoing Examples.
463572
39853f7I2ai 23. A cell for the electrolfsis of alkali n metal chloride solutions, wherein electrodes according to any one
of claims 1-6 and 21 constitute the anodes of the
cell.
24. A cell according to claim 23, wherein the cathode is
a flowing mercury cathode. An electrochemical process using an electrode as claimed
in any one of claims 1 to 6 and claim 21. 26. A process for the electrolysis of alkali metal chloride
solutions using an electrode as claimed in any one of
claims 1 to 6 and claim 21.
DATED: 7th March, 1972
PHILLIPS ORMONDE AND FITZPATRICK Attorneys for: IMPERIAL CHEMICAL INDUSTRIES LIITED
4 63472
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB721171 | 1971-03-18 | ||
| GBGB7211/71 | 1971-03-18 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU3985372A AU3985372A (en) | 1973-09-13 |
| AU463572B2 true AU463572B2 (en) | 1975-07-14 |
Family
ID=9828761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU39853/72A Expired AU463572B2 (en) | 1971-03-18 | 1972-03-10 | Electrodes for electrochemical processes |
Country Status (21)
| Country | Link |
|---|---|
| US (1) | US3869312A (en) |
| JP (1) | JPS559471B1 (en) |
| AR (1) | AR194834A1 (en) |
| AT (1) | AT312633B (en) |
| AU (1) | AU463572B2 (en) |
| BE (1) | BE780756A (en) |
| BR (1) | BR7201555D0 (en) |
| CA (1) | CA976505A (en) |
| CH (1) | CH578625A5 (en) |
| DD (1) | DD99934A5 (en) |
| DE (1) | DE2213083A1 (en) |
| ES (1) | ES400915A1 (en) |
| FR (1) | FR2130419B1 (en) |
| GB (1) | GB1352872A (en) |
| IL (1) | IL38958A (en) |
| IT (1) | IT950343B (en) |
| MY (1) | MY7400318A (en) |
| NL (1) | NL7203580A (en) |
| NO (1) | NO140235C (en) |
| TR (1) | TR17134A (en) |
| ZA (1) | ZA721481B (en) |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3793164A (en) * | 1973-04-19 | 1974-02-19 | Diamond Shamrock Corp | High current density brine electrolysis |
| JPS5137877A (en) * | 1974-09-27 | 1976-03-30 | Asahi Chemical Ind | Denkaiyodenkyoku oyobi sonoseizoho |
| FR2289632A1 (en) * | 1974-10-29 | 1976-05-28 | Marston Excelsior Ltd | PROCESS FOR REALIZING ELECTRODES FOR ELECTROLYTIC OPERATIONS |
| US3969216A (en) * | 1974-12-27 | 1976-07-13 | Doreen Veronica Barrett | Flotation separation |
| US4112140A (en) * | 1977-04-14 | 1978-09-05 | The Dow Chemical Company | Electrode coating process |
| US4214971A (en) * | 1978-08-14 | 1980-07-29 | The Dow Chemical Company | Electrode coating process |
| US4331528A (en) * | 1980-10-06 | 1982-05-25 | Diamond Shamrock Corporation | Coated metal electrode with improved barrier layer |
| JPS582175A (en) * | 1981-06-27 | 1983-01-07 | フジテック株式会社 | Controller for elevator |
| US4871703A (en) * | 1983-05-31 | 1989-10-03 | The Dow Chemical Company | Process for preparation of an electrocatalyst |
| US4615913A (en) * | 1984-03-13 | 1986-10-07 | Kaman Sciences Corporation | Multilayered chromium oxide bonded, hardened and densified coatings and method of making same |
| IL73536A (en) * | 1984-09-13 | 1987-12-20 | Eltech Systems Corp | Composite catalytic material particularly for electrolysis electrodes,its manufacture and its use in electrolysis |
| EP0174413A1 (en) * | 1984-09-17 | 1986-03-19 | Eltech Systems Corporation | Composite catalytic material particularly for electrolysis electrodes and method of manufacture |
| US6000982A (en) * | 1995-07-31 | 1999-12-14 | Casio Computer Co., Ltd. | Method of manufacturing a cold-cathode for a discharge device |
| US5707715A (en) * | 1996-08-29 | 1998-01-13 | L. Pierre deRochemont | Metal ceramic composites with improved interfacial properties and methods to make such composites |
| US6323549B1 (en) | 1996-08-29 | 2001-11-27 | L. Pierre deRochemont | Ceramic composite wiring structures for semiconductor devices and method of manufacture |
| US6143432A (en) * | 1998-01-09 | 2000-11-07 | L. Pierre deRochemont | Ceramic composites with improved interfacial properties and methods to make such composites |
| US7247229B2 (en) * | 1999-06-28 | 2007-07-24 | Eltech Systems Corporation | Coatings for the inhibition of undesirable oxidation in an electrochemical cell |
| KR100407710B1 (en) * | 2001-11-08 | 2003-12-01 | (주) 테크윈 | Catalytic oxide anode manufacturing method by high temperature sintering |
| US8124556B2 (en) * | 2008-05-24 | 2012-02-28 | Freeport-Mcmoran Corporation | Electrochemically active composition, methods of making, and uses thereof |
| CN102443818B (en) | 2010-10-08 | 2016-01-13 | 水之星公司 | Multi-layer mixed metal oxide electrode and manufacture method thereof |
| ITMI20102354A1 (en) * | 2010-12-22 | 2012-06-23 | Industrie De Nora Spa | ELECTRODE FOR ELECTROLYTIC CELL |
| CN104005047B (en) * | 2014-06-11 | 2017-02-15 | 中国船舶重工集团公司第七二五研究所 | Novel mixed metal oxide electrode for low-temperature sea water electrolysis antifouling |
| CN106099047A (en) * | 2016-08-25 | 2016-11-09 | 深圳市贝特瑞纳米科技有限公司 | A kind of surface coating method of electrode material and application thereof |
| US11668017B2 (en) | 2018-07-30 | 2023-06-06 | Water Star, Inc. | Current reversal tolerant multilayer material, method of making the same, use as an electrode, and use in electrochemical processes |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1195871A (en) * | 1967-02-10 | 1970-06-24 | Chemnor Ag | Improvements in or relating to the Manufacture of Electrodes. |
| GB1246447A (en) * | 1967-09-26 | 1971-09-15 | Imp Metal Ind Kynoch Ltd | Improvements in or relating to the manufacture of oxide-coated electrodes for use in electrolytic processes |
| US3616445A (en) * | 1967-12-14 | 1971-10-26 | Electronor Corp | Titanium or tantalum base electrodes with applied titanium or tantalum oxide face activated with noble metals or noble metal oxides |
| GB1206863A (en) * | 1968-04-02 | 1970-09-30 | Ici Ltd | Electrodes for electrochemical process |
| US3562008A (en) * | 1968-10-14 | 1971-02-09 | Ppg Industries Inc | Method for producing a ruthenium coated titanium electrode |
| GB1327760A (en) * | 1969-12-22 | 1973-08-22 | Imp Metal Ind Kynoch Ltd | Electrodes |
| GB1294373A (en) * | 1970-03-18 | 1972-10-25 | Ici Ltd | Electrodes for electrochemical processes |
| US3711385A (en) * | 1970-09-25 | 1973-01-16 | Chemnor Corp | Electrode having platinum metal oxide coating thereon,and method of use thereof |
| US3684543A (en) * | 1970-11-19 | 1972-08-15 | Patricia J Barbato | Recoating of electrodes |
-
1971
- 1971-03-18 GB GB721171*[A patent/GB1352872A/en not_active Expired
-
1972
- 1972-03-06 ZA ZA721481A patent/ZA721481B/en unknown
- 1972-03-06 NO NO707/72A patent/NO140235C/en unknown
- 1972-03-10 AU AU39853/72A patent/AU463572B2/en not_active Expired
- 1972-03-12 IL IL38958A patent/IL38958A/en unknown
- 1972-03-14 AR AR240928A patent/AR194834A1/en active
- 1972-03-15 TR TR17134A patent/TR17134A/en unknown
- 1972-03-16 BE BE780756A patent/BE780756A/en not_active IP Right Cessation
- 1972-03-17 CH CH396672A patent/CH578625A5/xx not_active IP Right Cessation
- 1972-03-17 DE DE19722213083 patent/DE2213083A1/en not_active Ceased
- 1972-03-17 BR BR1555/72A patent/BR7201555D0/en unknown
- 1972-03-17 JP JP2659972A patent/JPS559471B1/ja active Pending
- 1972-03-17 CA CA137,422A patent/CA976505A/en not_active Expired
- 1972-03-17 FR FR7209511A patent/FR2130419B1/fr not_active Expired
- 1972-03-17 IT IT7222049A patent/IT950343B/en active
- 1972-03-17 DD DD161624A patent/DD99934A5/xx unknown
- 1972-03-17 NL NL7203580A patent/NL7203580A/xx active Search and Examination
- 1972-03-18 ES ES400915A patent/ES400915A1/en not_active Expired
- 1972-03-20 AT AT235172A patent/AT312633B/en not_active IP Right Cessation
-
1973
- 1973-09-04 US US394394A patent/US3869312A/en not_active Expired - Lifetime
-
1974
- 1974-12-31 MY MY1974318A patent/MY7400318A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NL7203580A (en) | 1972-09-20 |
| NO140235C (en) | 1984-02-14 |
| GB1352872A (en) | 1974-05-15 |
| ZA721481B (en) | 1972-11-29 |
| IL38958A (en) | 1974-12-31 |
| IL38958A0 (en) | 1972-05-30 |
| AR194834A1 (en) | 1973-08-24 |
| DD99934A5 (en) | 1973-09-05 |
| US3869312A (en) | 1975-03-04 |
| DE2213083A1 (en) | 1972-09-21 |
| FR2130419A1 (en) | 1972-11-03 |
| FR2130419B1 (en) | 1974-08-02 |
| CH578625A5 (en) | 1976-08-13 |
| CA976505A (en) | 1975-10-21 |
| BR7201555D0 (en) | 1973-06-14 |
| AT312633B (en) | 1974-01-10 |
| JPS4733076A (en) | 1972-11-16 |
| NO140235B (en) | 1979-04-17 |
| ES400915A1 (en) | 1975-01-16 |
| BE780756A (en) | 1972-09-18 |
| AU3985372A (en) | 1973-09-13 |
| IT950343B (en) | 1973-06-20 |
| TR17134A (en) | 1974-04-25 |
| JPS559471B1 (en) | 1980-03-10 |
| MY7400318A (en) | 1974-12-31 |
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