AU625225B2 - Cermet anode with continuously dispersed alloy phase and process for making - Google Patents

Description

OPI DATE 01/06/89 APPLN. ID 28046 89 PCT wo T Wo AOJP DATE 06/07/89 PCT NUMBER PCT/US88/03937 INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TIKA1 Y (Pk'I) (51) International Patent Classification 4: (11) International Publication Number: WO 89/ 04384 3/12, 7/02 Al (43) International Publication Date: 18 May 1989 (18.05.89) (21) International Application Number: PCT/US88/03937 (81) Designated States: AT (European patent), AU, BE (European patent), BJ (OAPI patent), BR, CF (OAPI pa- (22) International Filing Date: 3 November 1988 (03.11.88) tent), CG (OAPI patent), CH (European patent), CM (OAPI patent), DE (European patent), FR (European patent), GA (OAPI patent), GB (European patent), (31) Priority Application Number: 116,475 IT (European patent), JP, KR, LU (European patent), ML (OAPI patent), MR (OAPI patent), NL (Euro- (32) Priority Date: 3 November 1987 (03.11.87) pean patent), NO, SE (European patent), SN (OAPI patent), TD (OAPI patent), TG (OAPI patent).

(33) Priority Country: US Published (71) Applicant: BATTELLE MEMORIAL INSTITUTE With international search report.

[US/US]; 505 King Avenue, Columbus, OH Before the expiration of the time limit for amending the 43201-2693 claims and to be republished in the event of the receipt of amendments.

(72) Inventors: DAVIS, Norman, C. 2212 Tinkle, Richland, WA 99352 MARSCHMAN, Steven, C. 1155 Dos Palos Ct., Richland, WA 99352 (US).

(74) Agents: SHAWEKER, Kenneth, Battelle Memorial Institute, 505 King Avenue, Columbus, OH 43201-2693 (US) et al.

(54) Title: CERMET ANODE WITH CONTINUOUSLY DISPERSED ALLOY PHASE AND PROCESS FOR MAK-

ING

(57) Abstract Cermet electrode compositions and methods for making are disclosed which comprise NiO-NiFe 2 04-Cu-Ni. Addition of an effective amount of a metallic catalyst-reactant to a composition of a nickel/iron/oxide, NiO, copper, and nickel produces a stable electrode having significantly increased electrical conductivity. The metallic catalyst functions to disperse the copper and nickel as an alloy continuously throughout the oxide phase of the cermet to render the electrode composition more highly electrically conductive than were the third metal not present in the base composition. The third metal is preferably added to the base composition as elemental metal and includes aluminum, magnesium, sodium and gallium.

The elemental metal is converted to a metal oxide during the sintering process.

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I i 1 BA4-708.M01 CERMET ANODE WITH CONTINUOUSLY DISPERSED ALLOY PHASE AND PROCESS FOR MAKING Technical Field This invention relates to cermet electrodes for use in the electrolytic reduction of a metal from a metal compound dissolved in a molten salt. The invention has specific application in the production s of anodes and the electrolytic process for manufacture of aluminum in Hall-Heroult cells.

*o: Backeround of the Invention 1 0 T h i s i v e Contract No. DE-AC06-76RLO e the U.S. Department Electrolytic cells, such as a Hall-Heroult cell for aluminum production by the electrolysis of alumina in molten cryolite.

15 conventionally employ conductive carbon electrodes. The Hall-Heroult process reduces aluminum metal from alumina in a molten salt electrolyte and consumes carbon from a carbon anode in the process.

The anode liberates oxygen from the alumina, which results in aluminum metal being collected on the cathode. The oxygen combines with carbon to produce CO and CO,. The overall reaction in its simplest form is represented as follows: 940 0 -1000°C 2ALO, 3C 4A1 NaA1F Approximately 0.33 pounds of carbon are consumed for every pound of aluminum produced. The life of carbon anodes is typically two to three weeks.

Carbon obtained from petroleum coke is typically used for fabrication of such anodes. Such material is becoming increasingly 0 30o _expensive. The petroleum coke also WO 89/04384 PCT/US88/03937 i 2 typically contains significant quantities of impurities such as sulfur, silicon, vanadium, titanium, iron and nickel. Such impurities can contaminate the metal being produced as well as cause environmental problems and poor working conditions. Removal of excess quantities of such impurities requires extra and costly steps when high purity aluminum is to be produced.

If no carbon were consumed in the reduction of alumina, the overall reaction would be: 2A1203 4A1 302. Accordingly, non-consumable anodes could be used in a process where carbon does not enter into the electrolytic reaction. Such anodes would have a life limited only by corrosion due to the cryolite electrolyte and electrochemical degradation mechanisms. It is anticipated that the life of such anodes could be extended to several months or even a year or more as compared to the two to three week life of a carbon anode which is consumed in the electrolytic reduction reaction. Furthermore, nonconsumable anodes would presumably not add the same significant quantities of impurities as do carbon anodes.

Numerous attempts have been made to develop an inert electrode, but apparently without the required degree of success to make it commercially feasible. The entire aluminum industry still uses consumable carbon anodes in the production of aluminum. Many of the newly developed inert electrodes apparently are reactive or corroded by the electrolyte to an extent which results in contamination of the metal being produced as well as consumption of the anode due to corrosion.

There have been numerous suggestions for nonconsumable anode compositions based on various ceramic oxides and oxy compounds. Such materials typically behave as a semi-conductor having inherently low electrical -1 -1 conductivities on the order of 1 ohm-cm Attempts have

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WO 89/04384 PCT/US88/03937 3 been made to fabricate non-consumable electrodes with special compositions known as cermets. A cermet composition includes both metallic and ceramic phases.

Cermets typically have higher electrical conductivity than pure ceramic compositions, and improved corrosion resistance as compared to metals. The conventional method of preparing cermet compositions is to mix metal and ceramic powders, cold press a preform, and sinter the preform at an elevated temperature in a controlled atmosphere. Alternatively, the cermet can be prepared by hot pressing or hot isostatic pressing wherein the sintering operation is carried out under pressure. Other densification methods for forming oxides and metals into cermets may also be usable.

One promising oxide system identified for use with cermets is the NiO-NiFe204 system. However, most cermets using this oxide system, or other oxide systems, still have low electrical conductivities, on the order of 1 to 10 ohm-1cm 1 Prior art oxide systems containing nickel in the metal phase (a NiO-NiFe204-Ni cermet) have been fabricated by reaction sintering processes and exhibit excellent electrical conductivity on the order of 300 oh-1 -1 ohm cm This is even an improvement over the conductivity of carbon anodes which typically average approximately 200 ohm- cm 1 However, typical cermets have a discontinuous metal phase distributed throughout the oxide phase and are susceptible to anodic dissolution by corrosion. This causes anodes of such material to fail prematurely and also contaminate the produced aluminum with nickel.

Copper has also been incorporated into the NiO-NiFe204 matrix creating an NiO-NiFe204-Cu cermet, The Cu metal phase is discontinuously distributed within the oxide matrix, but still provides improved electrical I WO 89/04384 PCT/US88/03937 4 conductivity on the order of 60 to 70 ohm- cm 1 Such a material had a copper content of 17 weight percent.

For example, U.S. Patent No. 4,620,905 to Tarcy et al. discloses an NiO-NiFe404-Cu-Ni cermet wherein 17% of the composition is comprised of a metal alloy of copper and nickel. The nickel metal is understood to arise primarily from the reduction of excess NiO in the oxide phase induced by the presence of carbon-based binders used to produce the oxide powders (col. 5, lines 3-14).

U.S. Patent Nos. 4,374,761; 4,478,693; 4,399,008; and 4,374,050 to Ray and 4,455,211 to Ray et al. also disclose non-consumable cermet electrodes for use in molten salt electrolysis. The electrodes disclosed are stated to be comprised of ceramic oxide compositions having at least one metal powder disbursed therethrough for purposes of increasing electrical conductivity. The metal powder is stated to be selected from the group consisting of Co, Fe, Ni, Cu, Pt, Rh, In, and Ir or alloys thereof. The metal is also stated to be provided in the electrode composition in amounts not constituting more than 30 volume percent metal.

Additionally, elemental cooper is stated to be includable in an amount up to 30 weight percent of the finished composition using the Ray processes. However, no example in any of these patents supports the broad statements concerning achieving high metal content in a cermet.

Further, the metal is indicated as being coated with a wax binder to prevent the metal particles from oxidizing during the sintering step. Additionally, the electrical i conductivities of the example electrodes range from 0.4 ohm- cm to 32 ohm cm Prior to the present invention, 17% metal alloy of copper and nickel was understood to be at or close to the practical upper limit of including an alloy of copper t I UI., iWO 89/04384 PCT/US88/03937 5 and nickel or pure copper within a NiO-NiFe204 oxide system, despite statements in the above prior art patents.

Apparently in these processes, additions of copper above this limit merely bled out of the composite during sintering, forming small copper metal beads on the surface of the cermet. Further, the alloy phase is discontinuously distributed throughout the oxide phase.

Detailed Description of Preferred Embodiments The following disclosure of the invention is submitted in compliance with the constitutional purpose of the Patent Laws "to promote the progress of science and useful arts" (Article 1, Section 8).

It has been discovered that addition of an effective amount of a metallic catalyst/reactant to a base composition of a nickel/iron/oxide, NiO, copper, and nickel provides a stable electrode having significantly increased electrical conductivity. The metallic catalyst/reactant functions to disperse the copper and nickel as an alloy continuously throughout the oxide phase of the cermet to render the electrode composition more highly electrically conductive than were the third metal not present in the base composition. The third metal is preferably added to the base mixture as elemental metal in micronized form which is converted to a metal oxide during the sintering process. Metallic catalyst/reactants anticipated to be usable in accordance with the invention include aluminum, magnesium, sodium, and gallium.

In a preferred process for producing such an electrode, NiO and NiFe204 powders are first combined to provide a mixture having a weight concentration of NiO to NiFe204 preferably from 2:3 to 3:2. Other oxide powder combinations would also be usable, but a combination that produces a NiO-NiFe204 oxide phase in the finished product WO 89/04384 PCT/US88/03937 6 is preferred. The NiO-NiFe204 oxide used in this process was a fully reacted, calcined, and spray-dried powder with agglomerates of approximately 50 microns. This was used due to availability, and is of little importance since these agglomerates were broken down to micron size particles during milling. However, small and high surface area particles with a binder provided during spray-drying are considered important in achieving optimum results. The oxide powder combination could also be prepared during milling along with addition of the metals or metal alloy powders, then spray dried to provide the agglomerates to improve powder flowability or packing.

The NiO and NiFe204 mixture is combined with quantities of elemental copper powder and elemental nickel powder with an average particle size of approximately 2 microns. Alternatively, a copper-nickel alloy powder can be combined with the combined oxide powders. The third micronized catalyzing metal is also combined with the other materials to produce a base mixture. Broad concentrations of the base mixture should be from 10 to 30 weight percent copper, 0.1 to 10 weight percent nickel, and from 0.5 to weight percent of the third catalyzing metal. The remainder of the mixture consists essentially of NiO- NiFe204 powder. Preferred concentration ranges are from 20.0 to 30.0 weight percent copper, from 2.0 to 4.0 weight percent nickel, and from 0.5 to 1.5 weight percent of the catalyzing metal.

The base powder mixture is blended by simple shaker-mixing techniques or more preferably vibrationally milled to more intimately mix the various constituents.

Simple blending procedures are typically performed dry.

Vibration milling can be used to produce cermets which have a more uniform, homogeneous distribution of the metal phase than possible by using simpler shaker-mixing blending WO 89/04384 PCT/US88/03937 7 7 procedures. For vibration milling, stainless steel mixing balls are added to a mixing bottle containing the base powder mixture. A Freon (tm) based liquid solution is preferably used as a milling solution, or the mixture can be milled dry. The Freon (tm) solution functions as a lubricant which volatilizes from the mixture after completion of the milling. The base mixture-solution is vibratory milled from 0.5 hours to 24 hours and allowed to dry.

The milled base powder mixture is then formed into desired green-body shapes using conventional pressing techniques. The final pressure of the formed mixture will preferably be approximately 25 Kpsi which provides sufficient strength for handling and machining of such green-bodies. The green-bodies are next placed into a sintering furnace having controlled atmosphere capabilities. The furnace preferably has alumina walls as opposed to metal walls which have been shown to cause excessive reduction of nickel and iron from the oxides.

The furnace atmosphere is preferably relatively inert containing either argon or nitrogen. Some oxygen is necessary in the range of 100 ppm to 500 ppm, but preferably not higher than 250 ppm to obtain optimum results. The furnace is also preferably ramped to a hold temperature just below the melting point of copper, and held for a period of time up to 50% of the sintering time.

The heating rate and hold period allow the alloy to stabilize which contributes to the reduction of metal phase bleedout. This heating cycle is increased to sintering temperatures up to 1300 0 C for a holding period of up to 8 hours. This hold time at temperature, as well as heating and cooling down rates, is dependent upon the physical size and mass of the anode being produced.

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WO 89/04384 PCT/US88/03937 8 At the sintering temperatures, the catalyzing metal combines with copper, nickel, NiO, and NiFe204 powders to produce a composition of NiO-NiFe204-Cu-Ni having Cu and Ni continuously dispersed as an alloy.

Where the third catalyzing metal is aluminum, the reaction is represented as follows: 2A1 Ni Cu NiFe204 (excess) NiyFe lyO NiyFelyO NiFe204 CuxNil-x A1203 The amount of Fe in NiyFelyO is typically negligible, resulting in the industry accepted abbreviation NiO. The CuxNil-x alloy phase generated typically also contains a negligible amount of iron. The quantity of A1203 formed in the finished system is also negligible.

However, the sintering produces a continuous Cu-Ni alloy phase dispersed throughout the oxide matrix which gives the sintered material metallic properties in terms of electrical conductivity. Electrical conductivities well in -1 -1 excess of 100 ohm cm are achievable.

Although this disclosure refers primarily to the combination of NiO with NiFe204, alternate NiO based oxide systems would be usable by skilled artisans without departing from the principles and scope of the invention.

Example An electrode was produced using the abovedescribed process wherein the third catalyzing metal was aluminum. The concentrations in the base powder mixture were as follows: 71 weight percent NiO-NiFe204 powder (spray dried, approximately 50 microns agglomerates) SWO 89/04384 PCT/US88/03937 9 weight percent copper (average 2 microns particles) 3 weight percent nickel (average 3 micron particles) 1 weight percent elemental micronized aluminum.

The base powder mixture was vibratory milled using a Freon (tm) based solution for 2.5 hours. The milled powder was pressed into desired shapes to a final pressure of 25 Kpsi using standard pressing techniques. The sample was slowly heated over a 16 hr period to a diffusion soak temperature below the melting point of copper, (preferably about 10750C) and allowed to hold for 2 hrs. The sample was then further heated at a rate of approximately 100 0 C per hr to a sintering temperature of 1200 0 C over a period of 8 hours.

Oxygen content in the furnace ranged from 150 to 200 ppm.

The remainder of the furnace atmosphere consisted essentially of argon. The sample was maintained under these conditions at 1200oC for a holding period of an additional 8 hours. The material was then furnaced cooled at a rate of approximately 100oC per hour.

Electrical conductivity of the sample was determined to be in excess of 410 ohm cm at 9500C. The sample was also tested as an anode in a small Hall-Heroult aluminum electrolysis cell. No wear or corrosion was evident after 6 hours of continuous operation at a current density of 1 A/cm 2 In compliance with the statute, the invention has been described in language more or less specific as to structural and methodical features. It is to be understood, however, that the invention is not limited to the specific features described, since the methods herein disclosed comprise a preferred form of putting the I i 1 s il a~ WO 89/04384 PCT/US88/03937 10 invention into effect. The invention is, therefore, claimed in any of its forms or modifications within the proper scope of the appended claims, appropriately interpreted in accordance with the doctrine of equivalents.

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Claims (38)

1. A cermet electrode composition produced by forming a base mixture into a desired shape followed by sintering the formed base mixture for use in the electrolytic reduction of a metal from a metal compound dissolved in a molten salt, the electrode composition comprising: an oxide phase of nickel/iron/oxide and NiO; an alloy phase of copper and nickel; a third metal oxide formed by the sintering, the third metal oxide containing a third metal added to the base mixture in an effective amount to disperse the copper- nickel alloy phase continuously throughout the oxide phase to render the electrode composition more highly electrically conductive than were the third metal not present in the base mixture.

2. The cermet electrode composition of claim 1 wherein the electrode has an electrical conductivity in excess of 100 ohm-lcm

3. The cermet electrode composition of claim 1 wherein copper in the alloy phase is present in a weight concentration in excess of 20% of the composition.

4. The cermet electrode composition of claim 1 wherein, the electrode has an electrical conductivity in excess of 100 ohm- 1 cm-1; and copper in the alloy phase is present in a weight concentration in excess of 20% of the composition. C The cermet electrode composition of claim 1 I _i i -ci- ~II WO 89/04384 PCT/US88/03937 12 wherein the base mixtu e weight ratio of NiO to nickel/iron/oxide is from 2:3 to 3:2.

6. The cermet electrode composition of claim 1 wherein, copper is present in a base mixture weight concentration of from 10% to nickel is present in a base mixture weight concentration of from 0.1% to 10%; and the third metal is present in a base mixture weight concentration of from 0.1% to

7. The cermet electrode composition of claim 6 wherein copper in the alloy phase is present in a weight concentration in excess of 20% of the composition.

8. The cermet electrode composition of claim 6 wherein the third metal is present in a base mixture weight concentration of from 0.5% to

9. The cermet electrode composition of claim 1 wherein, copper is present in a base mixture weight concentration of from 10% to nickel is present in a base mixture weight concentration of from 0.1% to the third metal is present in a base mixture weight concentration of from 0.1% to and the remainder of the base mixture consists essentially of NiO-nickel/iron/oxide. The cermet electrode composition of claim 1 wherein, mI m WO 89/04384 PCT/US88/03937 13 copper is present in a base mixture weight concentration of from 20% to nickel is present in a base mixture weight concentration of from 0.1% to the third metal is present in a base mixture weight concentration of from 0.5% to and the remainder of the base mixture consists essentially of NiO-nickel/iron/oxide in a weight ratio of NiO to nickel/iron/oxide between 2:3 to 3:2.

11. The cermet electrode composition of claim 1 wherein the third metal is selected from the group consisting of aluminum, magnesium, sodium, and gallium.

12. The cermet electrode composition of claim 1 wherein the third metal comprises aluminum.

13. The cermet electrode composition of claim 1 wherein, copper is present in a base mixture weight concentration of from 10% to nickel is present in a base mixture weight concentration of from 0.1% to the third metal is present in a base mixture weight concentration of from 0.5% to the remainder of the base mixture consists essentially of NiO-nickel/iron/oxide; and the third metal is selected from the group consisting of aluminum, magnesium, sodium, and gallium.

14. The cermet electrode composition of claim 1 wherein, copper is present in a base mixture weight concentration of from 10% to s i WO 89/04384 PCT/US88/03937 14 nickel is present in a base mixture weight concentration of from 0.1% to the third metal is present in a base mixture weight concentration of from 0.5% to the remainder of the base mixture consists essentially of NiO-nickel/iron/oxide; and the third metal comprises aluminum. The cermet electrode composition of claim 14 wherein copper in the alloy phase is present in a weight concentration in excess of 20% of the composition.

16. The cermet electrode composition of claim 1 wherein the third metal oxide is present in a negligible amount in the finished electrode composition.

17. An apparatus for producing metal by a reduction process in which oxygen is removed, comprising: a molten salt electrolyte comprising an oxide of a metal to be collected; a cathode for collecting the metal to be collected; and a cermet anode produced by sintering a base mixture for liberating the metal and oxygen from the oxide in the molten salt electrolyte, the composition of the anode comprising: an oxide phase of nickel/iron/oxide and NiO; an alloy phase of copper and nickel; and a third metal oxide formed by the sintering, the third metal oxide containing a third metal added to the base mixture as elemental metal in an effective amount to disperse the copper-nickel alloy phase continuously throughout the oxide phase the I 1--8 WO 89/04384 PCT/US88/03937 i 15 render the electrode composition more highly electrically conductive than were the third metal not present in the base mixture.

18. The apparatus of claim 17 wherein the anode has an electrical conductivity in excess of 100 ohm-lcm- 1 and copper in the alloy phase is present in a weihbt concentration in excess of 20% of the anode composition.

19. The apparatus of claim 17 wherein, copper is present in the anode composition in a base mixture weight concentration of from 10% to nickel is present in the anode composition in a base mixture weight concentration of from 0.1% to the third metal is present in a base mixture weight concentration of from 0.1% to 5% of the anode composition; and the remainder of the anode base mixture consists essentially of NiO-nickel/iron/oxide. The apparatus of claim 19 wherein copper in the alloy phase is present in a weight concentration in excess of 20% of the anode composition.

21. The apparatus of claim 17 wherein, copper is present in the anode composition in a base mixture weight concentration of from 20% to nickel is present in the anode composit'ion in a base mixture weight concentration of from 0.1% to the third metal is present in a base mixture weight concentration of from 0.1% to the remainder of the anode base mixture consists essentially of NiO-nickel/iron/oxide; and 4i i i WO 89/04384 PCT/US88/03937 16 the third metal is selected from the group consisting of aluminum, magnesium, sodium, and gallium.

22. The apparatus of claim 17 wherein copper is present in the anode composition in a base mixture weight concentration of from 20% to nickel is present in the anode composition in a base mixture weight concentration of from 0.1% to the third metal is present in a base mixture weight concentration of from 0.1% to the remainder of the anode base mixture consists essentially of NiO-nickel/iron/oxide; and the third metal comprises aluminum. proe==s-fs producing an-electri-ally, conductive cermet electrode having an oxide phase and n alloy phase for use in the electrolytic reduction of a metal from a metal compound dissolved in a molten alt, the process comprising the following steps: combining NiO-nickel/iron/oxide powder with copper and nickel powder to produce a b e mixture; forming the base mixture i o a desired shape; sintering the shaped se mixture to produ2a a desired NiO-nickel/iron/oxide u-Ni cermet having an oxide phase of NiO-nickel/iron/x de and an alloy phase of Cu-Ni; and catalyzin the reaction sintering step by including in t base mixture an effective amount of at least one a itional metal which functions to disperse the copper d nickel continuously throughout the NiO- nick iron/oxide phase as an alloy to produce a cermet e ctrode having higher electrical conductivity than were S&theadditional metal net included in the bao .mixtere-. C) m LC- I R 7 SEP 199 16/1 BA4-708.M 01i

23. A process for producing an electrically conductive cermet electrode having an oxide phase and an alloy phase for use in the electrolytic reduction of a metal from a metal compound dissolved in a molten salt, the process comprising the following steps: combining NiO-nickel/iron/oxide powder with copper and nickel powder to produce a base mixture; forming the base mixture into a desired shape; sintering the shaped base mixture to produce a desired NiO-nickel/iron/oxide-Cu-Ni cermet having an oxide phase of NiO- nickel/iron/oxide and an alloy phase of Cu-Ni; and catalyzing the reaction sintering step by including in the base mixture an effective amount of at least one additional metal which reacts to disperse the copper and nickel continuously throughout the NiO-nickel/iron/oxide phase as an alloy to produce a cermet electrode having higher electrical conductivity than were the additional metal not included in the base mixture, the effective amount of one additional metal being transformed to a metal oxide in the process. VJTi MT SI IPEA/US P E Av I -1L* r o.l/ u S2 ,7;:';989 17 BA4-708.MOI

24. The process of claim 23 wherein copper in the alloy phase is present in a weight concentration in excess of 20%. of the electrode composition.

25. The process of claim 23 wherein the one additional metal is selected from the group consisting of aluminum, magnesium, sodium, and gallium.

26. The process of claim 23 wherein the one additional metal comprises aluminum.

27. The process of claim 23 wherein, copper is present in the base mixture in a weight concentration of from 10% to nickel is present ;n the base mixture in a weight concentration of from 0.1% to the one additional metal is present in the base mixture in a weight concentration of from 0.1% to and the remainder of the base mixture consists essentially of NiO-nickel/iron/oxide.

28. The process of claim 27 wherein copper is present in a weight concentration in excess of 20% of the base mixture.

29. A cermet electrode produced by the process of claim 23. A process for producing an electrically conductive cermet electrode having an oxide phase and an alloy phase for use in the electrolytic reduction of a metal from a metal compound dissolved in a molten salt, the process comprising the following steps: 4 K4-k ./03957 SIPEAfl.'r StPEA! 1989 17/1 BA4-708.M01 combining NiO-nickel/iron/oxide powder with copper and nickel powder to produce a base mixture; forming the base mixture into a desired shape; sintering the shaped base mixture to produce a desired NiO-nickel/iron/oxide-Cu-Ni cermet having an oxide phase of NiO-nickel/iron/oxide and an alloy phase of Cu-Ni; catalyzing the reaction sintering step by including in the base mixture an effective amount of at least one additional metal which reacts to disperse the copper and nickel continuously throughout the Ni-nickel/iron/oxide oxide phase as an alloy to produce a cermet electrode having higher electrical conductivity than were the additional metal not included in the base mixture; and wherein the step of sintering comprises: raising the temperature to a value just below the melting point of elemental copper, and holding the formed base mixture at such value to allow the copper-nickel alloy to form and stabilize; and ;C A .ITUTE St y i IFEFA/US PCT/US 8./03 937 L IPEA!' 3 7sE-1989 18 BA4.708 MO0 then, raising the temperature of the formed base mixture to a sintering temperature.

31. A cermet electrode produced by the process of claim claim 24.

32. A cermet electrode

33. A cermet electrode produced by the process of produced by the process of claim claim 26.

34. A cermet electrode A cermet electrode produced by the process of produced by the process of claim 27.

36. A cermet electrode produced by the process of claim 28.

37. The process of claim 23 wherein the pre-sinter base mixture weight ratio of NiO to nickel/iron/oxide is from 2:3 to 3:2.

38. The process of claim 23 wherein the one additional metal is present in the base mixture in a weight concentration of from to

39. The process of claim 23 wherein, copper is present in the base mixture in a weight concentration of from 20% to IPA/US I i~ i,, I J PRT/US 8 8/03 93 7 IPEA/. 27 SEP1989 18/1 BA4-708.M01 nickel is present the base mixture in a weight concentration of from 0.1% to the one additional metal is present in the base mixture in a weight concentration of from 0.5% to and the remainder of the pre-sinter base mixture consists essentially of NiO-nickel/iron/oxide in a weight ratio of NiO to nickel/iron/oxide between 2:3 and 3:2. The process of claim 23 wherein, copper is present in the base mixture in a weight concentration of from 10% to nickel is present in the base mixture in a weight concentration of from 0.1% to the one additional metal is present in the base mixture in a weight concentration of from 0.5% to the remainder of the pre-sinter base mixture consists essentially of NiO-nickel/iron/oxide; and the one additional metal comprises aluminum.

41. The process of claim 23 wherein the metal oxide in the electrode resulting from the one additional metal is present as a small amount of the finished electrode composition.

42. A cermet electrode produced by the process of claim 37.

43. A cermet electrode produced by the process of claim 38.

44. A cermet electrode produced by the prc ess of claim 39. Of E S1UEET LEA U Si' I PAP 27 SE,989 BA4 708.MOI 18/2 A cermet electrode produced by the process of claim

46. A cermet electrode produced by the process of claim 41. ~)1~LLT a, Ii INTERNATIONAL SEARCH REPORT International Application No PCT/US 88/03937 I. CLASSIFICATION OF SUBJECT MATTER (it several classlicaton symools aoply, indicate all) According to International Patent Classification (IPC) or to both National Classification and IPC iPC 4 C 25 C 3/12; C 25 C 7/02 II. FIELDS SEARCHED Minimum Documentation Searched Classification System Classification Symbols 4 IPC C 25 C 3; C 25 C 7; C 04 B Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included In the Fields Searched III. DOCUMENTS CONSIDERED TO BE RELEVANT' Category Citation of Document, i with Indication, where approoriate, of the relevant pasaages 1 Relevant to Claim No. A EP, A, 0139087 (GREAT LAKES CARBON CORP.) 1 2 May 1985 see page 1; claims 1-4 ii I Special categories of cited documents: 1o later document published after the International filing date or priority date and not in conflict with the application but document defining the general state of the art which is not o pioit understand the principle or theory undalyiin the considered to be of particular relevance cited to understand the principle or theory underlying the considered to be of particular relevance invention earlier document but published on or after the international document of particular relevance; the claimed invention riling date cannot be considered novel or cannot be consiaered to document which may throw doubts on priority claim(s) or Involve an inventive rtep which is cited to establisn the publication date of another document of particular relevance;' the claimed invention citation or other special reason (as specified) cannot be considered to Involve an inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior to the International filing date but in the art later than the priority date claimed document member of the same patent family IV. CERTIFICATION Dale of the Actual Completion of the International Search Date of Mai of this nternona Search Report 13th March 1989 1 4. 3 International Searching Authority Atho Officer EUROPEAN PATENT OFFICE G.VANDERPUTTEN Form PCT/ISA/210 (second sheet) (January 195) ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. US 8803937 SA 25641 This annex lists the patent family members relating to the patent documents cited in the abow-ementioned international search report. Thc members are as contained in the European Patent Office EDiP file on 05/04/89 The European Patent office is in no Aav liable for these particulars ishich are merely given for the purpose of information. Patent document Publication Patent family Publication citcd in search rcpok't date member(s) date EP-A- 0139087 02-05-85 US-A- 4462889 31-07-84 JP-A- 60082685 10-05-85 AU-A- 3086484 18-04-85 ZFor more details aboui this annex see Official Journal of the lxurolpean Patent Office, No. 12/82 'I