US3234110A - Electrode and method of making same - Google Patents

Electrode and method of making same Download PDF

Info

Publication number
US3234110A
US3234110A US36218064A US3234110A US 3234110 A US3234110 A US 3234110A US 36218064 A US36218064 A US 36218064A US 3234110 A US3234110 A US 3234110A
Authority
US
Grant status
Grant
Patent type
Prior art keywords
core
titanium
barrier layer
electrode
noble 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 - Lifetime
Application number
Inventor
Beer Henri Bernard
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AMALGAMATED CURACAO PATENTS CO
AMALGAMATED CURACAO PATENTS Co NV
Original Assignee
AMALGAMATED CURACAO PATENTS CO
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Grant date

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31Coating with metals
    • C23C18/42Coating with noble metals
    • C23C18/44Coating with noble metals using reducing agents
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/02Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
    • C23F13/06Constructional parts, or assemblies of cathodic-protection apparatus
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/02Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
    • C23F13/06Constructional parts, or assemblies of cathodic-protection apparatus
    • C23F13/08Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
    • C23F13/12Electrodes characterised by the material
    • C23F13/14Material for sacrificial anodes
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/041Electrodes; Manufacture thereof not otherwise provided for characterised by the material characterised by the material of the substrate
    • C25B11/0426Electrodes; Manufacture thereof not otherwise provided for characterised by the material characterised by the material of the substrate consisting of plurality elements or compounds
    • C25B11/0431Metal alloys
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/0442Electrodes; Manufacture thereof not otherwise provided for characterised by the material characterised by the material of the coating
    • C25B11/0447Coatings consisting of a single component
    • C25B11/0473Noble metals
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/0442Electrodes; Manufacture thereof not otherwise provided for characterised by the material characterised by the material of the coating
    • C25B11/0478Coatings consisting of two or more components
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/0442Electrodes; Manufacture thereof not otherwise provided for characterised by the material characterised by the material of the coating
    • C25B11/0478Coatings consisting of two or more components
    • C25B11/0484Coatings consisting of two or more components comprising at least a noble metal or noble metal oxide and a non-noble metal oxide
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02Anodisation
    • C25D11/26Anodisation of refractory metals or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/56Electroplating: Baths therefor from solutions of alloys
    • C25D3/58Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F2213/00Aspects of inhibiting corrosion of metals by anodic or cathodic protection
    • C23F2213/30Anodic or cathodic protection specially adapted for a specific object
    • C23F2213/31Immersed structures, e.g. submarine structures

Description

United States Patent O 8 Claims. (Cl. 204-38 The present invention relates to' an electrode having a base or core oftitanium or titanium with small amounts of alloying metals therein,.which core is covered with a barrier layer of titanium oxide and coated with a noble metal coating, and to a method of producing such an electrode.

This application is a continuation in-part of my application Serial No. 6,351, filed'February 3, 1960, now abandoned.

In several of my prior copending applications, there has been disclosed an electrode particularly suitable for use as an anode which has such a core or base of titanium, either substantially pure titanium or titanium with small amounts of alloying metals therein, anda coating of a noble met-a1, such as platinum, iridium, rodium, or alloys of these metals. In making such electrodes, the core of titanium is treated so as to remove any oxide coating therefrom and the noble metal-coating is formed thereon. Since such coatings are at best slightlyporous, there are places in the'coating at which the titanium core is exposed. At these pores there is formed a barrier layer of titanium oxide. This barrier layer is for-med by placing the electrode in an electrolyte and electrolytically forming the barrier layer. Alternatively, the barrier layer can be formed by a chemical and/ or a thermal treatment which makes a more stable and chemically inert barrier layer than forming the barrier layer electrolytically.

During the use of such electrodes-as'anodes in such electrolytical processes as, for example, brine electrolysis, or as anodes in cathodic protection arrangements, ionic current flow can take place through the noble metal coating and electronic current flow will take place" from the noble metal coating to the titanium core. The barrier layer over theutitanium core which is exposed through the pores in the noble metal coating will prevent ionic current flow directly to the titanium core, and will thereby prevent a chemical attack by the electrolyte, which is usually quite corrosive on the titanium of the core. In addition the noble metal coating is chemically resistant so that the titanium core is protected from chemical attack where it is coated by the noble metal.

When the noble metal coating is damaged. during electrolysis so that the bare titaniumot the core is exposed, an electrolytically formed barrier layer will be produced over the exposed area, b-utthere will be a short period of time when the titanium is exposed to attack by the electrolyte, and this is detrimental to the life of the electrode. i

I have now discovered that the titanium or titanium alloy core of such an electrode can be'entirely covered with a barrier layer of titanium oxide, and thereafter coated with a noble metal coatinggand it will still act as an electrode, particularly as an anode in electrolytic processes suchas, for example, brine electrolysis, and as an anode in cathodic protection methods. The existence of a barrier layer of titanium oxide between the noble metal coating and the titanium core or base does not. interfere with the electronic flow of current from the noble metal coating to the titanium base, while at the places where the noble metal coating is imperfectly formed or has pores in it, the barrier layer prevents ionic flow of current from the electrolyte to the titanium base.

metal.

3234,11 1h Patented Feb. 8,1966

This characteristic is generally not true of the other socalled film forming metals, i.e. the metals which have their surfaces easily oxidized by contact with the air. When these metals are coated with an oxide film, the film otters great-resistance to both ionic current flow, i.e. flow of current from an electrolyte into the metal itself, an electronic current, i.e. flow of current from a conducting metal which is in metal to metal contact with the film forming Thus, an electrode having a core of aluminum whichhas been oxidized in air or has been intentionally provided with a layer of oxide for example by anodizing, and which has been coatedwith a noble metal, offers a high resistance to the passage of electric current from the noble metal coating to the aluminum core.

The electrode according to the invention is particularly valuable in that if, during use, the noble metal coating should be damaged, for example by peeling off, 'there will be a barrier layer already formed beneath the noble metal coating which will immediately resist attack by the electrolyte, and the electrode will accordingly be preserved and itslife extended.

It is therefore an object of the present invention to provide an electrode particularly suitable for use as an anode which-has acore or base of titanium or titanium with small amounts of alloying metals therein, a barrier 1 layer of titanium'oxide covering said core or base, and a noble metal coating over the barrier layer, the noble metal being taken from the group consisting of platinum, rhodium, iridium, and alloys of these metals.

his a further'object of the present invention to provide a method of making an electrode particularly suitable for use as an anode by forming a barrier layer of titanium oxide on such a core or base, and then coating a noble have vanadium or aluminum therein in an amount up to 4% by weight, or it can have zirconium therein up to 10% by weight. These percentages of metals other than titan- ..ium will not inhibit the film forming characteristic of the titanium. Accordingly, where reference is made to a core or base of titanium in this specification, it -is to be under 'stood'th'at such a core or base includes a base of substantially pure titanium aswell as a base of titanium and an alloying metal as herein described. n t a By the term barrier layer as used to describe the oxide layer formed on the titanium core of the electrode of the present invention, is meant a layer of oxide which resists attack by the electrolyte in which the electrode is used, and at-the same time prevents passage'of current directly from the electrolyte to the titanium core but permits passage of current from the noble metal coating to the core.

In connection with the following examples, it is essential to understand that in forming the barrier layer on the titanium core by placing the core in an electrolyte as an anode and passing a current through it, the voltage which is impressed on the core must be below the breakdown, voltage for titanium in the electrolyte in'question. Otherwise, if the breakdown voltage for titanium in the particular electrolyte is exceeded, the form of oxide which will be produced is not that which produces a barrier layer, but rather is one which, when itis coated with a conducting-metal, will not permit electronic current conduction therethrough from a noble metal coating to the titanium core at the normal operating voltages of the electrodes during their use in electrolysis.

It is further necessary to understand that the breakdown voltage will vary depending on the particular elec trolyte in which the barrier layer is being formed on the titanium core, and in fact the breakdown voltage will. be further dependent on the metal of the core, should it be, for example, an alloy of titanium. For this reason,

in the examples, thevoltages at which the barrier layer is formed can vary from example to example.

invention, the voltage utilized will amount to to 60% of the breakdown voltage depending on the concentration and temperature of the electrolyte.

The method of making the electrodes according tothe invention comprises at least partially immersing a core of'titanium in an electrolyte, impressing a voltage on said core, which voltage is below the breakdown-voltage for titanium in said electrolyte, but :sufiicient 'to form a barrier layer of titanium oxide on the portion of the core which is immersed in the electrolyte, painting a solution of at least one salt of a noble metal taken from.

the group consisting of platinum, rhodium and iridium or alloys thereof in an organic volatile solvent onto the barrierilayer thus formed on said core, heatingsaid painted core to evaporate the volatile solvent,'and then. firing the ,core in an atmosphere for converting the deposited salt to metal.

The method will now be set forth'in 'detail in connection with the following examples. In these examples,

a' plurality of specimens of substantially pure titaniumplate'each 1 cm. x 2 cm. were prepared according to the conditions set forth in Table I, there being used.100. cc.:

of electrolyte in each instance, and the electricpower being supplied from an accumulator at the indicated voltages which are below the .breakdown voltages for However, for purposes of illustration, it can be mentioned that thevoltage for formingthe barrier layer herein plates were heated in airvat a temperature of 250" C. for

After: the last application of the paint and the heating in air, the painted plates'were each heated in a closedturnace in an atmosphere. of ammonia and a reducing gas,.for .ex--

ample illuminating or lighting, gas, at. a temperature of 11 minutes to evaporate and burn off the solvent.

330 for l0minutes in order to form on the plates a coating of a platinum and iridium alloy without-adversely aft footing the underlying barrier layer. :of titanium oxide. Thereafter. the plates were gradually cooled.

The thus treated specimens 1, 3,v 5 and 6 were then used as anodes in theelectrolysis of 30% brine solutions at a temperature of 60 C; and a current density of 1500 amperes per square meter, at an applied voltage of 2.8. volts. The anode'sperforrned excellently, and at a low and constant overvoltage-this current, density could "be maintained. Specimens 2 and 4 were used as anodes in-a similar chloride alkali electrolysis with excellent results.

Examples 7-1-2 Specimens -7l2 were each coated four times withta paintzwhich contained 2 gramsof rhodiumin the form. I

of a rhodium compound,'for example rhodiumchloride,

per 10 cc. of organicsolvent, for example ethanol. After" each coating the plates were heated ;in air at atempera ture of 250 C. for'l0'minutes; to evaporate, and burnoif the solvent. After the last-application,ofthe paint and the heating in :air to evaporate and .burn the solvent the painted plates were each heated in air at a temperature 1 of 650 C. for 10 minutes in order. to form :on the plates a coatingofmetallic rhodium. Thereafter the plates were gradually cooleda were mechanically very strong;

Examples 13.18

Specimens 13-18 were :each'coated twice: with a paint f l I whichcontaine'd 10% by weight platinum chloride, 20%

of. an ethereal oil (lavender) and the remainder an or v ganic diluent, for example acetone and isopropyl alcohol.

After each coating the plates were heated inc-airat 390- trtamum 111 the respective electrolytes. C. for 1 nnnute to evaporate and burn'oif the solvent, and

TABLE I i 7 Immediately after voltage is After 15 minutes I applled Resistance 7 Specimen Volt. Electrolyte C across barrier,

aqueous solution or oxide layer Intensity .ln Ionic resistance Intensity in Ionic resistance in 1 ohms rmcroamperes in ohms microamperes in ohms 4 36,000 111 57 70,250 1% NaCLQ 20" 0. 001-0. 005 6 100,000 37, 500 5% N aCl 0. 001-0. 005 6 25,000 240 52, 700 1% NaCl 0. (101-0005 4 45, 000 89 S0 50, 000 1% H450 0. 001-0. 005 4 100,000 40 100 40, 000 10% H2304. 0. 001-0. 005 4 115,000 35 130 80, 800 10% NaOH 0. 001-0. 005 6 50, 000 46, 200 1% NaCll. 0. 001-0. 005 4 45, 000 89 75 53, 300 36% NaCL. 0. 001-0. 005 4 50, 000 80 45 88, 900 5% NaCl.-- 0. 001-0. 005. 4 100, 000 40 100 40, 000 10% H 0. 001-0. 005 4 90, 000 44 90 44, 500 5% NaO 0. 001-0. 005 4 34, 000 118 20 200, 000 10% tartaric a 0. 001-0. 005 4 55,000 73 85 7,100 5% NaC 0. 001-0. 005 6 100, 000 60 42, 800 36% NaCL. 0. 001-0. 005 4 15, 000 267 85 47, 100 1 0 NaCl 0. 001-0. 005 p 4 100,000 40 70 57, 200 5% Has 4. 0. 001-0. 005 4 60, 000 67 85 47, 100' 1% NaOH 0. 001-0. 005 4 300, 000 13 15 267, 000 10% oxalic acid I 0. 001-0. 005 4 60, 000 67 55 72, 750 1% N aCl 0. 001-0. 005 4 75, 000 53 55 72, 750 5% NaCl--- 80- 0.'00l0. 005 a Examples 1-6 Specimens.16 were each coated four times with a 70 paint which contained 1 gram of platinum in the form.

of a platinum salt, for example platinum tetraiodide, and v 0. 03 gram of iridium in the form of an iridium salt, for 7 example iriditun tetrachloride, per 10 cc. of an organicv to deposit a layer of metallic platinum on the barrier" layer on the titanium. cores;

solvent, for. exampleethanol. After each coating the -water, and proved very satisfactory.

Thereafter the platinum coated titaniu'm'electrodes were heated in air at 350 C. for 48 Example 19 A plate of substantially pure titanium was partly coated with platinum, and was at least partially immersed as an anode in an electrolyte which was an aqueous solution having 5% NaCl at a temperature of 70 C. so that at least part of the platinum coated portion of the electrode was in the electrolyte. A voltage of 4 volts was applied to the electrode to form a barrier layer on the uncoated portions of the electrode which were immersed in the electrolyte. Immediately after the application of the voltage, the current intensity was 1,000,000 microamperes and the ionic resistance was 4 ohms. After the voltage had been applied for minutes, the current intensity was still1,000,000rnicroamperes and the ionic resistance was still 4 ohms. A barrier layer was formed on the uncoated parts of the electrode-which had a resistance as measured A plate of titanium metal is thoroughly degreased by rinsing it with e.g. petrol or carbon tetrachloride. The plate is dried and placed as anode between two graphite cathodes in a solution of 95 parts by volume of concentrated phosphoric acid (98% or more) and 5 parts by volume of concentrated nitric acid. The voltage between the titanium anode and the graphite cathodes is gradually raised to 100 volts, a barrier layer of titanium oxide forming which also after the termination of the electrolysis remains of excellent quality.

On to the plate of titanium provided with said electrolytically formed barrier layer a homogeneous mixture is sprayed which is composed of 100 parts by volume of absolute ethanol,

10 parts by volume of rhodium trichloride,

2 parts by volume of colored Venetian turpentine,

5 parts by volume of hydrazine-monohydrochloride.

When from the color it appears that the entire plate is covered by the mixture, the plate is dried and the whole is heated in an open flame to a temperature of at most 700 C. A rhodium coating of about 2 microns will form.

The electrode thus manufactured is found to be very satisfactory when used as anode for carrying out electro lyses of all kinds of electrolytes, more particularly also of baths containing chloride, with the exception only of electrolyses evolving fluorine. The allowable current density is 70 amperes per square decimeter or higher.

Instead of the mixturementioned above it is also possible to apply by means of a brush mixture of 100 parts by volume of absolute ethanol, 10 parts by volume of platinum tetraiodide, 2 parts by volume of rhodium trichloride, 1 part by volume of lavender oil,

3 parts by volume of colophonium resin, 5 parts by volume of hydrazine.

By the method according to the invention there has been produced an electrode in which there is a barrier layer completely covering the titanium of the base, so that where there are pores or breaks in the noble metal coating on the electrode, the titanium of the base is protected by the barrier layer. Should the coating peel or otherwise be removed, all that is exposed is the barrier layer, the titanium of the core being protected from attack by the electrolyte in which the electrode is immersed.

In addition, it is possible with this type of electrode to provide the electrode with a fresh coating of noble metal a substantially unlimited number of times, if desired. The barrier layer remains intact once it has been formed, so that it is not necessary to pickle the electrode before applying a new noble metal coating, as has heretofore been done with this type of electrode. Moreover, there will be no loss of the core material during recoating, since the noble metal is simply added to the barrier layer covered core.

A further advantage of the electrodes according to the invention is that the adherence of the coating of noble metal is enhanced because the surface of the oxide barrier layer is rougher than the surface of the bare titanium metal.

It is thought that the invention and its advantages will be understood from the foregoing description and it is apparent that various changes may be made in the method without departing from the spirit and scope of the invention or sacrificing its material advantages, the forms of the method hereinbefore described and set forth in the examples being merely preferred embodiments thereof.

I claim:

1. An electrode, comprising a core of a metal taken from the group consisting of 'titanium and an alloy of titanium and small amounts of alloying metals, a high ionic resistance, low electronic resistance barrier layer of titanium oxide covering at least a part of said core, and a noble metal coating over said barrier layer, the noble metal being selected from the group consisting of platnium, rhodium, iridium, and alloys thereof, said barrier layer being electrolytically deposited on said core by impressing thereon a voltage below the breakdown voltage of the metal of the core in the electrolyte used for the formation of the barrier layer.

2. An electrode, comprising a core of a metal taken from the group consisting of titanium and an alloy of titanium and small amounts of alloying metals, a high ionic resistance, low electronic resistance barrier layer of titanium oxide covering at least part of said core, and a noble metal coating over said barrier layer, the noble metal being selected from the group consisting of platinum, rhodium, iridium, and alloys thereof, said barrier layer being electrolytically deposited on said core by im pressing thereon a voltage below the breakdown voltage of the metal of the core in the electrolyte used for the formation of the barrier layer, and the noble metal coating being deposited on the barrier layer by painting onto the barrier layer a solution containing a compound of the noble metal and evaporating the solvent.

3. An electrode as claimed in claim 2 in which the alloying metals are taken from the group consisting of up to 4% vanadium, up to 4% aluminum, and up to 10% zirconium.

4. An electrode, comprising a core of a metal taken from the group consisting of titanium and an alloy of titanium and small amounts of alloying metals, a barrier layer of titanium oxide covering at least a part of said core, and a noble metal coating over said barrier layer, the noble metal being selected from the group consisting of platinum, rhodium, iridium, and alloys thereof, said barrier layer having an electronic resistance in the range of about 0.001 to 0.005 ohm and an ionic resistance of at least about 35,000 ohms which is formed by immersing the core in .a sodium chloride electrolyte for about 15 minutes with an impressed voltage of about 4 volts.

5. A method of making an electrode, comprising the steps of immersing at least a part of a core of a metal taken from the group consisting of titanium and an alloy of titanium and small amounts of alloying metals in an electrolyte as an anode, impressing a voltage on said core, which voltage is below the breakdown voltage for titanium in said electrolyte, to thereby form a high ionic resistance, low electronic resistance barrier layer of titanium oxide on the immersed part of said core, and then coating over said barrier layer a noble metal taken from the group consisting of platinum, rhodium, iridium, and alloys thereof.

6. A method of making an electrode, comprising the steps of immersing at least a part of a core of a metal taken from the group consisting of titanium and an alloy 7 t of titaniumand small amounts of alloying metals in an electrolyte as an anode, impressing a voltage .on said core,

which voltage is below the breakdown voltage for titani-' um in said electrolyte, to thereby form a high ionic resistance, low electronic resistance barrier layer of titanium oxide on the immersed part of said core, and then paintinggonto said barrier layer covered core a solution containing a compound of a noble metal taken from-the group consisting of platinum, rhodium, iridium, and alloys thereof, andheating the painted core for evaporating the solventand converting the compound to a metallic coating while retaining the barrier layer undisturbed. V

7. A method as claimed in claim 6 in which the painted core is heated in air for evaporating and. burning the solvent, and then is heated in a reducing atmosphere for reducing thecornpound of the noble metal while leaving the barrier layer unaifected.

8. A method of making an electrode, comprising the steps of partly coating a core of a metal taken'fromthe group consisting of titanium and an alloy of titaniumand small amounts of alloying metals with a noble metal,

immersing at least a part of the core including a part of Y the noble metal coated portion in an-electrolyte as an anode, impressing a voltage onsaid core, which voltage is below the breakdown voltageior, titanium in ,said i electrolyte, for forming a high ionic resistance, lowelecrhodium, iridium, and alloys thereof.

References Cited by the Examiner 10 ,UNITED STATES PATENTS 2,955,999 10/1960 Tirrell 204-290 2,965,551; 12/1960 'Richa'ud 204-32 2,991,234 7/1961 Andrus -204-3s 3,085,052 4/1963 Sibert 204--38 3,096,272v 7/1963 Beer 204-290 3,103,484 9/1963 Messner 204-290 OTHER REFERENCES 20 Chemical Age, page 9, January 3,4959,

WINSTON r A. DoUGLAsrimar Examiner.

' JOHN H. MACKQExaminrQ

Claims (1)

1. AN ELECTRODE, COMPRISING A CORE OF A METAL TAKEN FROM THE GROUP CONSISTING OF TITANIUM AND AN ALLOY OF TITANIUM AND SMALL AMOJNTS OF ALLOYING METALS, A HIGH IONIC RESISTANCE, LOW ELECTRONIC RESISTANCE BARRIER LAYER OF TITANIUM OXIDE COVERING AT LEAST A PART OF SAID CORE, AND A NOBLE METAL COATING OVER SAID BARRIER LAYER, THE NOBLE METAL BEING SELECTED FROM THE GROUP CONSISTING OF PLATNIUM, RHODIUM, IRIDIUM, AND ALLOYS THEREOF, SAID BARRIER LAYER BEING ELECTROLYTICALLY DEPOSITED ON SAID CORE BY IMPRESSING THEREON A VOLTAGE BELOW THE BREAKDOWN VOLTAGE OF THE METAL OF THE CORE IN THE ELECTROLYTE USED FOR THE FORMATION OF THE BARRIER LAYER.
US3234110A 1959-02-06 1964-04-23 Electrode and method of making same Expired - Lifetime US3234110A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
NL235848 1959-02-06

Publications (1)

Publication Number Publication Date
US3234110A true US3234110A (en) 1966-02-08

Family

ID=19751552

Family Applications (1)

Application Number Title Priority Date Filing Date
US3234110A Expired - Lifetime US3234110A (en) 1959-02-06 1964-04-23 Electrode and method of making same

Country Status (7)

Country Link
US (1) US3234110A (en)
BE (1) BE587237A (en)
DE (1) DE1115721B (en)
DK (1) DK98880C (en)
FR (1) FR1311108A (en)
GB (1) GB925080A (en)
NL (2) NL122179C (en)

Cited By (56)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3467584A (en) * 1966-10-24 1969-09-16 Ernest H Lyons Jr Plating platinum metals on chromium
US3497426A (en) * 1964-07-02 1970-02-24 Nippon Carbide Kogyo Kk Manufacture of electrode
US3497425A (en) * 1964-07-20 1970-02-24 Imp Metal Ind Kynoch Ltd Electrodes and methods of making same
US3751296A (en) * 1967-02-10 1973-08-07 Chemnor Ag Electrode and coating therefor
US3786680A (en) * 1972-11-01 1974-01-22 D Clark Voltage sensing system
US3878072A (en) * 1973-11-01 1975-04-15 Hooker Chemicals Plastics Corp Electrolytic method for the manufacture of chlorates
US3884777A (en) * 1974-01-02 1975-05-20 Hooker Chemicals Plastics Corp Electrolytic process for manufacturing chlorine dioxide, hydrogen peroxide, chlorine, alkali metal hydroxide and hydrogen
US3897320A (en) * 1973-11-01 1975-07-29 Hooker Chemicals Plastics Corp Electrolytic manufacture of chlorates, using a plurality of electrolytic cells
US3920551A (en) * 1973-11-01 1975-11-18 Hooker Chemicals Plastics Corp Electrolytic method for the manufacture of dithionites
US4005003A (en) * 1975-04-15 1977-01-25 Olin Corporation Multi-component metal electrode
FR2349664A1 (en) * 1976-04-28 1977-11-25 Diamond Shamrock Techn Electrodes high breakdown voltage for electrolytes containing a bromide
US4217195A (en) * 1979-05-02 1980-08-12 General Electric Company Electrophoretic electrode for use in laser doppler shift spectroscopy, and method
US4362707A (en) * 1981-04-23 1982-12-07 Diamond Shamrock Corporation Preparation of chlorine dioxide with platinum group metal oxide catalysts
US4585540A (en) * 1984-09-13 1986-04-29 Eltech Systems Corporation Composite catalytic material particularly for electrolysis electrodes and method of manufacture
US4696731A (en) * 1986-12-16 1987-09-29 The Standard Oil Company Amorphous metal-based composite oxygen anodes
US4702813A (en) * 1986-12-16 1987-10-27 The Standard Oil Company Multi-layered amorphous metal-based oxygen anodes
US4705610A (en) * 1985-06-24 1987-11-10 The Standard Oil Company Anodes containing iridium based amorphous metal alloys and use thereof as halogen electrodes
US4781803A (en) * 1985-02-26 1988-11-01 The Standard Oil Company Electrolytic processes employing platinum based amorphous metal alloy oxygen anodes
US4797182A (en) * 1986-04-17 1989-01-10 Eltech Systems Corporation Electrode with a platinum metal catalyst in surface film and its use
US5004626A (en) * 1986-10-27 1991-04-02 Huron Technologies, Inc. Anodes and method of making
US5324407A (en) * 1989-06-30 1994-06-28 Eltech Systems Corporation Substrate of improved plasma sprayed surface morphology and its use as an electrode in an electrolytic cell
US5328584A (en) * 1992-06-19 1994-07-12 Water Regeneration Systems, Inc. Passive circulation in electrolytic fluid treatment systems
EP0576402B1 (en) * 1992-06-25 1997-03-05 Eltech Systems Corporation Electrodes of improved service life
WO2002038833A1 (en) * 2000-11-13 2002-05-16 Akzo Nobel N.V. Gas diffusion electrode
US20020110726A1 (en) * 2000-11-13 2002-08-15 Bernd Busse Electrode
US6527939B1 (en) 1999-06-28 2003-03-04 Eltech Systems Corporation Method of producing copper foil with an anode having multiple coating layers
US20030168348A1 (en) * 2001-03-14 2003-09-11 Yasuhito Kondo Method and apparatus for generating ozone by electrolysis
US20040211676A1 (en) * 2001-07-16 2004-10-28 Miox Corporation Electrolytic cell for surface and point of use disinfection
US20040226873A1 (en) * 2001-07-16 2004-11-18 Miox Corporation Gas drive electrolytic cell
US20050131509A1 (en) * 2003-12-16 2005-06-16 Liliana Atanassoska Coatings for implantable electrodes
DE102004015633A1 (en) * 2004-03-31 2005-10-20 Studiengesellschaft Kohle Mbh A process for the production of coatings of iridium oxides
US20060037869A1 (en) * 2004-08-19 2006-02-23 Miox Corporation Scented electrolysis product
US20060137973A1 (en) * 2004-11-24 2006-06-29 Miox Corporation Device and method for instrument steralization
US20070261968A1 (en) * 2005-01-27 2007-11-15 Carlson Richard C High efficiency hypochlorite anode coating
US20080116146A1 (en) * 2006-11-17 2008-05-22 Miox Corproation Water purification system
US20080156658A1 (en) * 2004-06-10 2008-07-03 Miox Corporation Method and Apparatus for Scale and Biofilm Control
WO2008080118A1 (en) 2006-12-23 2008-07-03 Miox Corporation Internal flow control in electrolytic cells
US20080237054A1 (en) * 2006-11-28 2008-10-02 Miox Corporation Low Maintenance On-Site Generator
US20090095635A1 (en) * 2007-07-20 2009-04-16 Siemens Medical Solutions Usa, Inc. Microfluidic radiosynthesis of a radiolabeled compound using electrochemical trapping and release
US20090159436A1 (en) * 2007-12-25 2009-06-25 Mikuni Corporation Electrolyzed water generating and spraying device
US20090205972A1 (en) * 2008-01-04 2009-08-20 Miox Corporation Electrolytic Purifier
US20090229992A1 (en) * 2006-11-28 2009-09-17 Miox Corporation Reverse Polarity Cleaning and Electronic Flow Control Systems for Low Intervention Electrolytic Chemical Generators
US20090283417A1 (en) * 2008-05-19 2009-11-19 Miox Corporation Electrolytic Cell with Gas Driven Pumping
US20100044219A1 (en) * 2003-05-07 2010-02-25 Eltech Systems Corporation Smooth Surface Morphology Chlorate Anode Coating
CN101048535B (en) 2004-09-01 2012-05-30 埃尔塔克系统公司 PD-containing coating for low chlorine overvoltage
US20130037417A1 (en) * 2011-08-11 2013-02-14 Toyota Motor Engineering & Manufacturing North America, Inc. Efficient water oxidation catalysts and methods of energy production
US8455010B1 (en) 2007-10-31 2013-06-04 Reoxcyn Discoveries Group, Inc Product and method for producing an immune system supplement and performance enhancer
CN103173835A (en) * 2011-12-22 2013-06-26 中国科学院大连化学物理研究所 Treating method of metallic titanium material
US8580091B2 (en) 2010-10-08 2013-11-12 Water Star, Inc. Multi-layer mixed metal oxide electrode and method for making same
US8663705B2 (en) 2007-10-30 2014-03-04 Reoxcyn Discoveries Group, Inc. Method and apparatus for producing a stabilized antimicrobial non-toxic electrolyzed saline solution exhibiting potential as a therapeutic
EP2765221A1 (en) 2013-02-11 2014-08-13 Unilever N.V. An electrolytic method for production of bleaching agent
US20150021243A1 (en) * 2012-01-30 2015-01-22 Rodney E Herrington Personal Water Purifier
US9255336B2 (en) 2007-10-31 2016-02-09 Reoxcyn Discoveries Group, Inc. Method and apparatus for producing a stabilized antimicrobial non-toxic electrolyzed saline solution exhibiting potential as a therapeutic
US9593026B2 (en) 2011-05-06 2017-03-14 Johnson Matthey Public Limited Company Organic contaminant destruction using chlorine or mixed oxidant solution and ultraviolet light
US9775992B2 (en) 2015-02-13 2017-10-03 Cardiac Pacemakers, Inc. Implantable electrode
EP3257819A1 (en) 2010-08-06 2017-12-20 Johnson Matthey Public Limited Company Electrolytic on-site generator

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2035212C2 (en) * 1970-07-16 1987-11-12 Conradty Gmbh & Co Metallelektroden Kg, 8505 Roethenbach, De
FR2272469B1 (en) * 1974-05-20 1980-03-21 Suisse Horlogerie
DE3068540D1 (en) * 1979-10-08 1984-08-16 Diamond Shamrock Corp Coated metal electrode with improved barrier layer and methods of manufacture and use thereof
LU88516A1 (en) * 1993-07-21 1996-02-01 Furukawa Electric Co Ltd Oxygen generating electrode and process the same to produce

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2955999A (en) * 1957-09-04 1960-10-11 Ionics Self-rectifying electrodialysis unit
US2965551A (en) * 1956-08-08 1960-12-20 Pechiney Prod Chimiques Sa Metal plating process
US2991234A (en) * 1958-08-11 1961-07-04 Croname Inc Enameled aluminum and process for manufacture thereof
US3085052A (en) * 1960-09-09 1963-04-09 Lockheed Aircraft Corp Method for making film capacitors
US3096272A (en) * 1957-10-24 1963-07-02 Amalgamated Curacao Patents Co Noble metal coated titanium electrode and method of making and using it
US3103484A (en) * 1959-10-10 1963-09-10 Anodes for electrolytic chlorine

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2965551A (en) * 1956-08-08 1960-12-20 Pechiney Prod Chimiques Sa Metal plating process
US2955999A (en) * 1957-09-04 1960-10-11 Ionics Self-rectifying electrodialysis unit
US3096272A (en) * 1957-10-24 1963-07-02 Amalgamated Curacao Patents Co Noble metal coated titanium electrode and method of making and using it
US2991234A (en) * 1958-08-11 1961-07-04 Croname Inc Enameled aluminum and process for manufacture thereof
US3103484A (en) * 1959-10-10 1963-09-10 Anodes for electrolytic chlorine
US3085052A (en) * 1960-09-09 1963-04-09 Lockheed Aircraft Corp Method for making film capacitors

Cited By (72)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3497426A (en) * 1964-07-02 1970-02-24 Nippon Carbide Kogyo Kk Manufacture of electrode
US3497425A (en) * 1964-07-20 1970-02-24 Imp Metal Ind Kynoch Ltd Electrodes and methods of making same
US3467584A (en) * 1966-10-24 1969-09-16 Ernest H Lyons Jr Plating platinum metals on chromium
US3751296A (en) * 1967-02-10 1973-08-07 Chemnor Ag Electrode and coating therefor
US3786680A (en) * 1972-11-01 1974-01-22 D Clark Voltage sensing system
US3878072A (en) * 1973-11-01 1975-04-15 Hooker Chemicals Plastics Corp Electrolytic method for the manufacture of chlorates
US3897320A (en) * 1973-11-01 1975-07-29 Hooker Chemicals Plastics Corp Electrolytic manufacture of chlorates, using a plurality of electrolytic cells
US3920551A (en) * 1973-11-01 1975-11-18 Hooker Chemicals Plastics Corp Electrolytic method for the manufacture of dithionites
US3884777A (en) * 1974-01-02 1975-05-20 Hooker Chemicals Plastics Corp Electrolytic process for manufacturing chlorine dioxide, hydrogen peroxide, chlorine, alkali metal hydroxide and hydrogen
US4005003A (en) * 1975-04-15 1977-01-25 Olin Corporation Multi-component metal electrode
FR2349664A1 (en) * 1976-04-28 1977-11-25 Diamond Shamrock Techn Electrodes high breakdown voltage for electrolytes containing a bromide
US4217195A (en) * 1979-05-02 1980-08-12 General Electric Company Electrophoretic electrode for use in laser doppler shift spectroscopy, and method
US4362707A (en) * 1981-04-23 1982-12-07 Diamond Shamrock Corporation Preparation of chlorine dioxide with platinum group metal oxide catalysts
US4585540A (en) * 1984-09-13 1986-04-29 Eltech Systems Corporation Composite catalytic material particularly for electrolysis electrodes and method of manufacture
US4781803A (en) * 1985-02-26 1988-11-01 The Standard Oil Company Electrolytic processes employing platinum based amorphous metal alloy oxygen anodes
US4705610A (en) * 1985-06-24 1987-11-10 The Standard Oil Company Anodes containing iridium based amorphous metal alloys and use thereof as halogen electrodes
US4797182A (en) * 1986-04-17 1989-01-10 Eltech Systems Corporation Electrode with a platinum metal catalyst in surface film and its use
US5004626A (en) * 1986-10-27 1991-04-02 Huron Technologies, Inc. Anodes and method of making
US4702813A (en) * 1986-12-16 1987-10-27 The Standard Oil Company Multi-layered amorphous metal-based oxygen anodes
US4696731A (en) * 1986-12-16 1987-09-29 The Standard Oil Company Amorphous metal-based composite oxygen anodes
US5324407A (en) * 1989-06-30 1994-06-28 Eltech Systems Corporation Substrate of improved plasma sprayed surface morphology and its use as an electrode in an electrolytic cell
US5672394A (en) * 1989-06-30 1997-09-30 Eltech Systems Corporation Electrodes of improved service life
US6071570A (en) * 1989-06-30 2000-06-06 Eltech Systems Corporation Electrodes of improved service life
US5328584A (en) * 1992-06-19 1994-07-12 Water Regeneration Systems, Inc. Passive circulation in electrolytic fluid treatment systems
EP0576402B1 (en) * 1992-06-25 1997-03-05 Eltech Systems Corporation Electrodes of improved service life
US6527939B1 (en) 1999-06-28 2003-03-04 Eltech Systems Corporation Method of producing copper foil with an anode having multiple coating layers
US20020110726A1 (en) * 2000-11-13 2002-08-15 Bernd Busse Electrode
US6733639B2 (en) 2000-11-13 2004-05-11 Akzo Nobel N.V. Electrode
WO2002038833A1 (en) * 2000-11-13 2002-05-16 Akzo Nobel N.V. Gas diffusion electrode
US20030168348A1 (en) * 2001-03-14 2003-09-11 Yasuhito Kondo Method and apparatus for generating ozone by electrolysis
US20040211676A1 (en) * 2001-07-16 2004-10-28 Miox Corporation Electrolytic cell for surface and point of use disinfection
US20040226873A1 (en) * 2001-07-16 2004-11-18 Miox Corporation Gas drive electrolytic cell
US7740749B2 (en) 2001-07-16 2010-06-22 Miox Corporation Gas drive electrolytic cell
US20060157342A1 (en) * 2001-07-16 2006-07-20 Miox Corporation Gas drive electrolytic cell
US7008523B2 (en) 2001-07-16 2006-03-07 Miox Corporation Electrolytic cell for surface and point of use disinfection
US7005075B2 (en) 2001-07-16 2006-02-28 Miox Corporation Gas drive electrolytic cell
US20100044219A1 (en) * 2003-05-07 2010-02-25 Eltech Systems Corporation Smooth Surface Morphology Chlorate Anode Coating
US8142898B2 (en) 2003-05-07 2012-03-27 De Nora Tech, Inc. Smooth surface morphology chlorate anode coating
US20060035026A1 (en) * 2003-12-16 2006-02-16 Cardiac Pacemakers, Inc. Coatings for implantable electrodes
US8017179B2 (en) 2003-12-16 2011-09-13 Cardiac Pacemakers, Inc. Coatings for implantable electrodes
US8017178B2 (en) 2003-12-16 2011-09-13 Cardiac Pacemakers, Inc. Coatings for implantable electrodes
US20050131509A1 (en) * 2003-12-16 2005-06-16 Liliana Atanassoska Coatings for implantable electrodes
DE102004015633A1 (en) * 2004-03-31 2005-10-20 Studiengesellschaft Kohle Mbh A process for the production of coatings of iridium oxides
US20080156658A1 (en) * 2004-06-10 2008-07-03 Miox Corporation Method and Apparatus for Scale and Biofilm Control
US20060037869A1 (en) * 2004-08-19 2006-02-23 Miox Corporation Scented electrolysis product
CN101048535B (en) 2004-09-01 2012-05-30 埃尔塔克系统公司 PD-containing coating for low chlorine overvoltage
US20060137973A1 (en) * 2004-11-24 2006-06-29 Miox Corporation Device and method for instrument steralization
US20070261968A1 (en) * 2005-01-27 2007-11-15 Carlson Richard C High efficiency hypochlorite anode coating
US20080116146A1 (en) * 2006-11-17 2008-05-22 Miox Corproation Water purification system
US20080237054A1 (en) * 2006-11-28 2008-10-02 Miox Corporation Low Maintenance On-Site Generator
US20090229992A1 (en) * 2006-11-28 2009-09-17 Miox Corporation Reverse Polarity Cleaning and Electronic Flow Control Systems for Low Intervention Electrolytic Chemical Generators
US7922890B2 (en) 2006-11-28 2011-04-12 Miox Corporation Low maintenance on-site generator
WO2008080118A1 (en) 2006-12-23 2008-07-03 Miox Corporation Internal flow control in electrolytic cells
US20080164152A1 (en) * 2006-12-23 2008-07-10 Miox Corporation Internal flow control in electrolytic cells
US7955481B2 (en) 2006-12-23 2011-06-07 Miox Corporation Internal flow control in electrolytic cells
US20090095635A1 (en) * 2007-07-20 2009-04-16 Siemens Medical Solutions Usa, Inc. Microfluidic radiosynthesis of a radiolabeled compound using electrochemical trapping and release
US8663705B2 (en) 2007-10-30 2014-03-04 Reoxcyn Discoveries Group, Inc. Method and apparatus for producing a stabilized antimicrobial non-toxic electrolyzed saline solution exhibiting potential as a therapeutic
US9255336B2 (en) 2007-10-31 2016-02-09 Reoxcyn Discoveries Group, Inc. Method and apparatus for producing a stabilized antimicrobial non-toxic electrolyzed saline solution exhibiting potential as a therapeutic
US8455010B1 (en) 2007-10-31 2013-06-04 Reoxcyn Discoveries Group, Inc Product and method for producing an immune system supplement and performance enhancer
US20090159436A1 (en) * 2007-12-25 2009-06-25 Mikuni Corporation Electrolyzed water generating and spraying device
US20090205972A1 (en) * 2008-01-04 2009-08-20 Miox Corporation Electrolytic Purifier
US20090283417A1 (en) * 2008-05-19 2009-11-19 Miox Corporation Electrolytic Cell with Gas Driven Pumping
WO2009155044A2 (en) 2008-05-28 2009-12-23 Miox Corporation Reverse polarity cleaning and electronic flow control systems for low intervention electrolytic chemical generators
EP3257819A1 (en) 2010-08-06 2017-12-20 Johnson Matthey Public Limited Company Electrolytic on-site generator
US8580091B2 (en) 2010-10-08 2013-11-12 Water Star, Inc. Multi-layer mixed metal oxide electrode and method for making same
US9593026B2 (en) 2011-05-06 2017-03-14 Johnson Matthey Public Limited Company Organic contaminant destruction using chlorine or mixed oxidant solution and ultraviolet light
US20130037417A1 (en) * 2011-08-11 2013-02-14 Toyota Motor Engineering & Manufacturing North America, Inc. Efficient water oxidation catalysts and methods of energy production
CN103173835B (en) * 2011-12-22 2016-01-06 中国科学院大连化学物理研究所 Method for processing a titanium material
CN103173835A (en) * 2011-12-22 2013-06-26 中国科学院大连化学物理研究所 Treating method of metallic titanium material
US20150021243A1 (en) * 2012-01-30 2015-01-22 Rodney E Herrington Personal Water Purifier
EP2765221A1 (en) 2013-02-11 2014-08-13 Unilever N.V. An electrolytic method for production of bleaching agent
US9775992B2 (en) 2015-02-13 2017-10-03 Cardiac Pacemakers, Inc. Implantable electrode

Also Published As

Publication number Publication date Type
BE587237A (en) 1960-05-30 grant
FR1311108A (en) 1962-12-07 grant
BE587237A2 (en) grant
GB925080A (en) 1963-05-01 application
NL122179C (en) 1966-12-15 grant
DE1115721B (en) 1961-10-26 application
NL235848A (en) application
DK98880C (en) 1964-06-01 grant

Similar Documents

Publication Publication Date Title
US3663379A (en) Method and electrolytes for anodizing titanium and its alloys
US3620934A (en) Method of electrolytic tinning sheet steel
Lin et al. Electrodeposition of zinc from a Lewis acidic zinc chloride-1-ethyl-3-methylimidazolium chloride molten salt
US3834999A (en) Electrolytic production of glassy layers on metals
US3933616A (en) Coating of protected electrocatalytic material on an electrode
Yerokhin et al. Spatial characteristics of discharge phenomena in plasma electrolytic oxidation of aluminium alloy
US6267861B1 (en) Method of anodizing valve metals
Conway et al. Determination of the adsorption behaviour of ‘overpotential-deposited’hydrogen-atom species in the cathodic hydrogen-evolution reaction by analysis of potential-relaxation transients
El Abedin et al. A study on the electrodeposition of tantalum on NiTi alloy in an ionic liquid and corrosion behaviour of the coated alloy
US3645862A (en) Method of making an electrode
US4668347A (en) Anticorrosive coated rectifier metals and their alloys
US6328874B1 (en) Anodically formed intrinsically conductive polymer-aluminum oxide composite as a coating on aluminum
US3309292A (en) Method for obtaining thick adherent coatings of platinum metals on refractory metals
US4128463A (en) Method for stripping tungsten carbide from titanium or titanium alloy substrates
US3711385A (en) Electrode having platinum metal oxide coating thereon,and method of use thereof
US6071570A (en) Electrodes of improved service life
US3956080A (en) Coated valve metal article formed by spark anodizing
US3773554A (en) Electrodes for electrochemical processes
US4184926A (en) Anti-corrosive coating on magnesium and its alloys
US3663414A (en) Electrode coating
US6251254B1 (en) Electrode for chromium plating
US5545262A (en) Method of preparing a metal substrate of improved surface morphology
US4140813A (en) Method of making long-term electrode for electrolytic processes
US4052271A (en) Method of making an electrode having a coating containing a platinum metal oxide thereon
US3961111A (en) Method of increasing corrosion resistance of anodized aluminum