CA2330352A1 - Refractory hard metals in powder form for use in the manufacture of electrodes - Google Patents

Refractory hard metals in powder form for use in the manufacture of electrodes Download PDF

Info

Publication number
CA2330352A1
CA2330352A1 CA002330352A CA2330352A CA2330352A1 CA 2330352 A1 CA2330352 A1 CA 2330352A1 CA 002330352 A CA002330352 A CA 002330352A CA 2330352 A CA2330352 A CA 2330352A CA 2330352 A1 CA2330352 A1 CA 2330352A1
Authority
CA
Canada
Prior art keywords
process according
refractory hard
powder form
hard metal
containing compounds
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.)
Abandoned
Application number
CA002330352A
Other languages
French (fr)
Inventor
Sabin Boily
Marco Blouin
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.)
GROUPE MINUTIA Inc
Original Assignee
GROUPE MINUTIA Inc
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
Application filed by GROUPE MINUTIA Inc filed Critical GROUPE MINUTIA Inc
Priority to CA002330352A priority Critical patent/CA2330352A1/en
Publication of CA2330352A1 publication Critical patent/CA2330352A1/en
Application status is Abandoned legal-status Critical

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/90Carbides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/90Carbides
    • C01B32/907Oxycarbides; Sulfocarbides; Mixture of carbides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/90Carbides
    • C01B32/914Carbides of single elements
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/90Carbides
    • C01B32/914Carbides of single elements
    • C01B32/921Titanium carbide
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00Boron; Compounds thereof
    • C01B35/02Boron; Borides
    • C01B35/04Metal borides
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/06Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C25C3/08Cell construction, e.g. bottoms, walls, cathodes
    • C25C3/12Anodes
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/60Compounds characterised by their crystallite size
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/50Agglomerated particles
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/61Micrometer sized, i.e. from 1-100 micrometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/62Submicrometer sized, i.e. from 0.1-1 micrometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer

Abstract

The invention relates to a refractory hard metal in powder form comprising particles having an average particle size of 0.1 to 30 µm and each formed of an agglomerate of refractory hard metals of the formula:
A x B y X z (I) wherein A is a transition metal, B is a metal selected from the group consisting of zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, manganese, tungsten and cobalt, X is boron or carbon, x ranges from 0.1 to 3, y ranges from 0 to 3 and z from 1 to 6. The refractory hard metal in powder form according to the invention is suitable for use in the manufacture of electrodes by thermal deposition or powder metallurgy.

Description

REFRACTORY HARD METALS IN POWDER FORM FOR
USE IN THE MANUFACTURE OF ELECTRODES
The present invention pertains to improvements in the field of electrodes for metal electrolysis. More particularly, the invention relates to a refractory hard metals in powder form for use in the manufacture of such electrodes.
Aluminum is produced conventionally in a Hall-Heroult reduction cells by the electrolysis of alumina dissolved in molten cryolite (Na3A1F6) at temperatures of up to about 950 °C. A Hall-Heroult cell typically has a steel shell provided with an insulating lining of refractory material, which in turn has a lining made of prebaked carbon blocks contacting the molten constituents of the electrolyte. The carbon lining acts as the cathode substrate and the molten aluminum pool acts as the cathode. The anode is a consumable carbon electrode, usually prebaked carbon made by coke calcination.
During electrolysis, in Hall-Heroult cells, the carbon anode is consumed leading to the evolution of greenhouse gases such as CO and C02.
The anode has to be periodically changed and the erosion of the material modifies the anode-cathode distance, which increases the voltage due to the electrolyte resistance. On the cathode side, the carbon blocks are subjected to erosion and electrolyte penetration. A sodium intercalation in the graphitic structure occurs, which cause swelling and deformation of the cathode carbon blocks. The increase of voltage between the electrodes adversely affects the energy efficiency of the process.
Extensive research has been carried out with refractory hard metals such as TiBz, as electrode materials. TiB2 and other refractory hard metals are practically insoluble in aluminum, have a low electrical resistance and are wetted by aluminum. However, the shaping of TiB2 and similar refractory hard metals is difficult because these materials have high melting temperatures and are highly covalent.
It is therefore an object of the present invention to overcome the above drawbacks, and to provide a refractory hard metal in powder form suitable for the manufacture of electrode by thermal deposition or powder metallurgy.
According to one aspect of the invention, there is provided a refractory hard metal in powder form comprising particles having an average particle size of 0.1 to 30 dm and each formed of an agglomerate of grains with each grain comprising a nanocrystal of a refractory hard metal of the formula:
AXByXZ ~I) wherein A is a transition metal, B is a metal selected from the group consisting of zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, manganese, tungsten and cobalt, X is boron or carbon, x ranges from 0.1 to 3, y ranges from 0 to 3 and z from 1 to 6.
The term "nanocrystal" as used herein refers to a crystal having a size of 100 nanometers or less.
The expression "thermal deposition" as used herein refers to a technique in which powder particles are injected in a torch and sprayed on a substrate. The particles acquire a high velocity and are partially or totally melted during the flight path. The coating is budded by the solidification of the droplets on the substrate surface. Examples of such techniques include plasma spray, arc spray and high velocity oxy-fuel.

-2-The expression "powder metallurgy" as used herein refers to a technique in which the bulk powders are transformed into preforms of a desired shape by compaction or shaping followed by a sintering step. Compaction refers to techniques where pressure is applied to the powder, as, for example, cold uniaxial pressing, cold isostatic pressing or hot isostatic pressing. Shaping refers to techniques executed without the application of external pressure such as powder filling or slurry casting.
Typical examples of refractory hard metals of the formula (I) include TiBl.s, TiB2, TiC, Tio.sZro.sBz~ Tio.9Zro.~Bz~ Tio.sHfo.sBz and Zro.sVo.2B2~
TiB2 is preferred.
The present invention also provides, in another aspect thereof, a process for producing a refractory hard metal in powder form as defined above.
The process of the invention comprises the steps of:
a) providing a first reagent selected from the group consisting of transition metals and transition metal-containing compounds;
b) providing a second reagent selected from the group consisting of boron, boron-containing compounds, carbon and carbon-containing compounds;
c) providing an optional third reagent selected from the group consisting of zirconium, zirconium-containing compounds, hafnium, hafnium-containing compounds, vanadium, vanadium-containing compounds, niobium, niobium-containing compounds, chromium, chromium-containing compounds, molybdenum, molybdenum-containing compounds, manganese, manganese-containing compounds, tungsten, tungsten-containing compounds, cobalt and cobalt-containing compounds; and

-3-d) subjecting the first, second and third reagents to high-energy ball milling to cause solid state reaction therebetween and formation of particles having an average particle size of 0.1 to 30 Vim, each particle being formed of an agglomerate of grains with each grain comprising a nanocrystal of a refractory hard metal of formula (I) defined above.
The expression "high-energy ball milling" as used herein refers to a ball milling process capable of forming the aforesaid particles comprising nanocrystalline grains of the refractory hard metal of formula (I), within a period of time of about 40 hours.
Examples of suitable transition metals which may be used as the aforesaid first reagent include titanium, chromium, zirconium and vanadium.
Titanium is preferred. It is also possible to use a titanium-containing compound such as TiH2, TiAl3, TiB and TiCl2.
Examples of suitable boron-containing compounds which may be used as the aforesaid second reagent include A1B2, A1B,2, BH3, BN, VB, H2B03 and Na2B40~. It is also possible to use tetraboron carbide (B4C) as either a boron-containing compound or a carbon-containing compound.
Examples of suitable compounds which may be used as the aforesaid third reagent include HfB2, VBZ, NbB2, TaB2, CrB2, MoB2, MnB2, Mo2B5, W2B5, CoB, ZrC, TaC, WC and HfC.
According to a preferred embodiment, step (d) is carried out in a vibratory ball mill operated at a frequency of 8 to 25 Hz, preferably about 17 Hz. It is also possible to conduct step (d) in a rotary ball mill operated at a speed of 150 to 1500 r.p.m., preferably about 1000 r.p.m.

-4-According to another preferred embodiment, step (d) is carried out under an inert gas atmosphere such as a gas atmosphere comprising argon or helium, or under a reactive gas atmosphere such as a gas atmosphere comprising hydrogen, ammonia or a hydrocarbon, in order to saturate dangling bonds and thereby prevent oxidation of the refractory hard metal. An atmosphere of argon, helium or hydrogen is preferred. It is also possible to coat the particles with a protective film or to admix a sacrificial element such as Mg or Ca with the reagents. In addition, a sintering aid such as Y203 can be added during step (d).
In the particular case of TiB2 or TiC wherein titanium and boron or carbon are present in stoichiometric quantities, these two compounds can be used as starting material. Thus, they can be directly subjected to high-energy ball milling to cause formation of particles having an average particle size of 0.1 to 30 Vim, each particle being formed of an agglomerate of grains with each grain comprising a nanocrystal of TiB2 or TiC.
The high-energy ball milling described above enables one to obtain refractory hard metals in powder form having either non-stoichiometric or stoichiometric compositions.
The refractory hard metals in powder form according to the invention are suitable for use in the manufacture of electrodes by thermal deposition or powder metallurgy. Due to the properties of refractory hard metals, the emission of toxic and greenhouse effect gases during metal electrolysis is lowered and the lifetime of the electrodes is increased, thus lowering maintenance costs. A lower and constant inter-electrode distance is also possible, thereby decreasing the electrolyte ohmic drop.

-5-The following non-limiting examples illustrate the invention, reference being made to the accompanying drawing in which the sole figure shows the X-ray diffraction of the refractory hard metal in powder form obtained in Example 1.
EXAMPLE 1.
A TiB2 powder was produced by ball milling 3.45g of titanium and I.SSg of boron in a hardened steel crucible with a ball-to-powder mass ratio of 4.5:1 using a SPEX 8000 (trademark) vibratory ball mill operated at a frequency of about 17 Hz. The operation was performed under a controlled argon atmosphere to prevent oxidization. The crucible was closed and sealed with a rubber O-ring. After 5 hours of high-energy ball milling, a TiB2 structure was formed, as shown on the X-ray diffraction pattern in the accompanying drawing. The structure of TiB2 is hexagonal with the space group P6/mmm ( 191 ). The particle size varied between 1 and 5 pm and the crystallite size, measured by X-ray diffraction, was about 30 nm.
EXAMPLE 2.
A TiB2 powder was produced according to the same procedure as described in Example 1 and under the same operating conditions, with the exception that the ball milling was carried out for 20 hours instead of 5 hours.
The resulting powder was similar to that obtained in Example 1. The crystallite size, however, was lower (about 16 nm).

-6-EXAMPLE 3.
A TiC powder was produced according to the same procedure as described in Example 1 and under the same operating conditions, with the exception that titanium and graphite were milled.
EXAMPLE 4.
A TiB2 powder was produced by ball milling titanium diboride under the same operating conditions as in Example 1, with the exception that the ball milling was carried out for 20 hours instead of 5 hours. The starting structure was maintained, but the crystallite size decreased to 15 nm.
EXAMPLE 5.
A TiB 1.g powder was according to the same procedure as described in Example 1 and under the same operating conditions, with the exception that 3.6 g of titanium and 1.4 g of boron were milled.
EXAMPLE 6.
A TiB2.2 powder was according to the same procedure as described in Example 1 and under the same operating conditions, with the exception that 3.4 g of titanium and 1.7 g of boron were milled.
EXAMPLE 7.
A TiBo.SZro.5B2 powder was according to the same procedure as described in Example 1 and under the same operating conditions, with the _7_ exception that 1.9 g of titanium, 3.1 g of zirconium diboride and 0.8 g of boron were milled.
EXAMPLE 8.
A TiBo.9Zro,lBz powder was according to the same procedure as described in Example 1 and under the same operating conditions, with the exception that 2.9 g of titanium, 0.6 g of zirconium and 1.5 g of boron were milled.
EXAMPLE 9.
A TiBo.SHfo,5B2 powder was according to the same procedure as described in Example 1 and under the same operating conditions, with the exception that 0.9 g of titanium, 3.3 g of hafnium and 0.8 g of boron were milled.
EXAMPLE 10.
A Zro,gVo.2B2 powder was according to the same procedure as described in Example 1 and under the same operating conditions, with the exception that 3.5 g of zirconium, 0.5 g of vanadium and 1.0 g of boron were milled.
_g_

Claims (45)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A refractory hard metal in powder form comprising particles having an average particle size of 0.1 to 30 µm and each formed of an agglomerate of refractory hard metals of the formula:
A x B y X z (I) wherein A is a transition metal, B is a metal selected from the group consisting of zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, manganese, tungsten and cobalt, X is boron or carbon, x ranges from 0.1 to 3, y ranges from 0 to 3 and z from 1 to 6.
2. A refractory hard metal in powder form according to claim 1, wherein A is a transition metal selected from the group consisting of titanium, chromium, zirconium and vanadium.
3. A refractory hard metal in powder form according to claim 2, wherein A is titanium, X is boron and y is 0.
4. A refractory hard metal in powder form according to claim 3, wherein x is 1 and z is 1.8.
5. A refractory hard metal in powder form according to claim 3, wherein x is 1 and z is 2.
6. A refractory hard metal in powder form according to claim 3, wherein x is 1 and z is 2.2.
7. A refractory hard metal in powder form according to claim 2, wherein A is titanium, X is carbon and y is 0.
8. A refractory hard metal in powder form according to claim 8, wherein x is 1 and z is 1.
9. A refractory hard metal in powder form according to claim 2, wherein A is titanium, B is zirconium or hafnium, X is boron and y is other than 0.
10. A refractory hard metal in powder form according to claim 9, wherein B is zirconium, x is 0.5, y is 0.5 and z is 2.
11. A refractory hard metal in powder form according to claim 9, wherein B is zirconium, x is 0.9, y is 0.1 and z is 2.
12. A refractory hard metal in powder form according to claim 2, wherein B is hafnium, x is 0.5, y is 0.5 and z is 2.
13. A refractory hard metal in powder form according to claim 2, wherein A is zirconium, B is vanadium, X is boron and y is other than 0.
14. A refractory hard metal in powder form according to claim 13, wherein x is 0.8, y is 0.2 and z is 2.
15. A refractory hard metal in powder form according to claim 1, wherein said average particle size ranges from 1 to 5 µm.
16. A process for producing a refractory hard metal in powder form as defined in claim 1, comprising the steps of:

a) providing a first reagent selected from the group consisting of transition metals and transition metal-containing compounds;

b) providing a second reagent selected from the group consisting of boron, boron-containing compounds, carbon and carbon-containing compounds;

c) providing an optional third reagent selected from the group consisting of zirconium, zirconium-containing compounds, hafnium, hafnium-containing compounds, vanadium, vanadium-containing compounds, niobium, niobium-containing compounds, chromium, chromium-containing compounds, molybdenum, molybdenum-containing compounds, manganese, manganese-containing compounds, tungsten, tungsten-containing compounds, cobalt and cobalt-containing compounds; and d) subjecting said first, second and third reagents to high-energy ball milling to cause solid state reaction therebetween and formation of particles having an average particle size of 0.1 to 30 µm, each particle being formed of an agglomerate of grains with each grain comprising a nanocrystal of a refractory hard metal of the formula (I) as defined in claim 1.
17. A process according to claim 16, wherein said first reagent comprises a transition metal selected from the group consisting of titanium, chromium, zirconium and vanadium.
18. A process according to claim 17, wherein said transition metal is titanium.
19. A process according to claim 16, wherein said first reagent comprises a titanium-containing compound selected from the group TiH2, TiA13, TiB and TiC12.
20. A process according to claim 16, wherein said second reagent comprises boron.
21. A process according to claim 16, wherein said second reagent comprises a boron-containing compound selected from the group consisting of A1B2, A1B12, BH3, BN, VB2, H2BO3 and Na2BO7.
22. A process according to claim 16, wherein said second reagent comprises carbon.
23. A process according to claim 16, wherein said second reagent comprises tetraboron carbide.
24. A process according to claim 16, wherein said third reagent is a compound selected from the group consisting of HfB2, VB2, NbB2, TaB2, CrB2, MoB2, MnB2, Mo2B5, W2B5, CoB, ZrC, TaC, WC and HfC.
25. A process according to claim 16, wherein step (d) is carried out in a vibratory ball mill operated at a frequency of 8 to 25 Hz.
26. A process according to claim 25, wherein said vibratory ball mill is operated at a frequency of about 17 Hz.
27. A process according to claim 16, wherein step (d) is carried out in a rotary ball mill operated at a speed of 150 to 1500 r.p.m.
28. A process according to claim 27, wherein said rotary ball mill is operated at a speed of about 1000 r.p.m.
29. A process according to claim 16, wherein step (d) is carried out under an inert gas atmosphere.
30. A process according to claim 29, wherein said inert gas atmosphere comprises argon or helium.
31. A process according to claim 16, wherein step (d) is carried out under a reactive gas atmosphere.
32. A process according to claim 31, wherein said reactive gas atmosphere comprises hydrogen, ammonia or a hydrocarbon.
33. A process according to claim 16, wherein step (d) is carried out for a period of time of about 5 hours.
34. A process according to claim 16, wherein a sintering aid is added during step (d).
35. A processd of preparing a grain refining agent as defined in claim or 8, comprising subjecting TiB2 or TiC to high-energy ball milling to cause formation of particles having an average particle size of 0.1 to 30 µm, each particle being formed of an agglomerate of grains with each grain comprising a nanocrystal of TiB2 or TiC.
36. A process according to claim 35, wherein said high-energy ball milling is carried out in a vibratory ball mill operated at a frequency of 8 to 25 Hz.
37. A process according to claim 36, wherein said vibratory ball mill is operated at a frequency of about 17 Hz.
38. A process according to claim 35, wherein said high-energy ball milling is carried out in a rotary ball mill operated at a speed of 150 to r.p.m.
39. A process according to claim 38, wherein said rotary ball mill is operated at a speed of about 1000 r.p.m.
40. A process according to claim 35, wherein said high-energy ball milling is carried out under an inert gas atmosphere.
41. A process according to claim 35, wherein said inert gas atmosphere comprises argon or helium.
42. A process according to claim 35, wherein said high-energy ball milling is carried out under a reactive gas atmosphere.
43. A process according to claim 42, wherein said reactive gas atmosphere comprises hydrogen, ammonia or a hydrocarbon.
44. A process according to claim 35, wherein said high-energy ball milling is carried out for a period of time of about 20 hours.
45. A process according to claim 35, wherein a sintering aid is added during said high-enery bal milling.
CA002330352A 2001-01-05 2001-01-05 Refractory hard metals in powder form for use in the manufacture of electrodes Abandoned CA2330352A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CA002330352A CA2330352A1 (en) 2001-01-05 2001-01-05 Refractory hard metals in powder form for use in the manufacture of electrodes

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
CA002330352A CA2330352A1 (en) 2001-01-05 2001-01-05 Refractory hard metals in powder form for use in the manufacture of electrodes
US10/250,499 US20040052713A1 (en) 2001-01-05 2002-01-02 Refractory hard metals in powder form for use in the manufacture of electrodes
JP2002554621A JP2004516226A (en) 2001-01-05 2002-01-02 Refractory hard alloy in powder form for electrode production
EP02726977A EP1347939A1 (en) 2001-01-05 2002-01-02 Refractory hard metals in powder form for use in the manufacture of electrodes
RU2003124183/15A RU2003124183A (en) 2001-01-05 2002-01-02 Refractory solid alloys in the form of powder for use in the manufacture of electrodes
PCT/CA2002/000013 WO2002053495A1 (en) 2001-01-05 2002-01-02 Refractory hard metals in powder form for use in the manufacture of electrodes
BR0206306-9A BR0206306A (en) 2001-01-05 2002-01-02 Refractory powdered hard metals for use in electrode manufacturing
CNA028035011A CN1484613A (en) 2001-01-05 2002-01-02 Refractory hard metals in powder form for use in the manufacture of electrodes
NO20033076A NO20033076L (en) 2001-01-05 2003-07-04 Refractory hard metals in powder form for use in the manufacture of electrodes

Publications (1)

Publication Number Publication Date
CA2330352A1 true CA2330352A1 (en) 2002-07-05

Family

ID=4168043

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002330352A Abandoned CA2330352A1 (en) 2001-01-05 2001-01-05 Refractory hard metals in powder form for use in the manufacture of electrodes

Country Status (9)

Country Link
US (1) US20040052713A1 (en)
EP (1) EP1347939A1 (en)
JP (1) JP2004516226A (en)
CN (1) CN1484613A (en)
BR (1) BR0206306A (en)
CA (1) CA2330352A1 (en)
NO (1) NO20033076L (en)
RU (1) RU2003124183A (en)
WO (1) WO2002053495A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102430757A (en) * 2011-11-25 2012-05-02 天津大学 Method for preparing TiB2/TiC (titanium diboride/titanium carbide) ultrafine powder for surface spraying of engine piston ring by means of high energy ball milling

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100546041B1 (en) * 2005-05-31 2006-01-18 가야에이엠에이 주식회사 Method for manufacturing titanium carbide using a rotary kiln furnace
AU2007215394B2 (en) * 2006-02-17 2013-06-27 Gravitas Technologies Pty Ltd Crystalline ternary ceramic precursors
US8142749B2 (en) * 2008-11-17 2012-03-27 Kennametal Inc. Readily-densified titanium diboride and process for making same
JP5780540B2 (en) * 2010-12-24 2015-09-16 国立研究開発法人物質・材料研究機構 Zirconium diboride powder and synthesis method thereof
JP2015174046A (en) * 2014-03-17 2015-10-05 Jfeマテリアル株式会社 Manufacturing method of chromium for powder metallurgy
KR101659823B1 (en) * 2014-12-17 2016-09-27 한국기계연구원 A HfC Composites and A Manufacturing method of the same
CN105297069A (en) * 2015-11-18 2016-02-03 上海大学 Electrochemical method for directly preparing metal carbide accurately and controllably

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2634475B1 (en) * 1988-07-22 1990-10-12 Centre Nat Rech Scient Process for preparing compounds of powders of elements of the column and iv products obtained
JPH0674126B2 (en) * 1989-11-20 1994-09-21 科学技術庁金属材料技術研究所長 The method of manufacturing a transition metal carbide
CN1147478A (en) * 1996-05-17 1997-04-16 浙江大学 Normal-temp composition process of ultrafine tungsten carbide and titanium carbide powder
US6214309B1 (en) * 1997-09-24 2001-04-10 University Of Connecticut Sinterable carbides from oxides using high energy milling

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102430757A (en) * 2011-11-25 2012-05-02 天津大学 Method for preparing TiB2/TiC (titanium diboride/titanium carbide) ultrafine powder for surface spraying of engine piston ring by means of high energy ball milling

Also Published As

Publication number Publication date
EP1347939A1 (en) 2003-10-01
JP2004516226A (en) 2004-06-03
RU2003124183A (en) 2005-01-10
BR0206306A (en) 2004-02-17
NO20033076L (en) 2003-09-05
US20040052713A1 (en) 2004-03-18
CN1484613A (en) 2004-03-24
WO2002053495A1 (en) 2002-07-11
NO20033076D0 (en) 2003-07-04

Similar Documents

Publication Publication Date Title
Senderoff Electrodeposition of refractory metals
AU2004267452B2 (en) Thermal and electrochemical process for metal production
US6402926B1 (en) Application of refractory protective coatings on the surface of electrolytic cell components
Basu et al. Processing and properties of monolithic TiB2 based materials
AU678040B2 (en) Densified micrograin refractory metal or solid solution (mixed metal) carbide ceramics
Schwandt et al. Determination of the kinetic pathway in the electrochemical reduction of titanium dioxide in molten calcium chloride
Yan et al. Production of niobium powder by direct electrochemical reduction of solid Nb 2 O 5 in a eutectic CaCl 2-NaCl melt
EP0122160A2 (en) Composition suitable for inert electrode
Sun Progress in research and development on MAX phases: a family of layered ternary compounds
US4595545A (en) Refractory metal borides and composites containing them
EP0072043A1 (en) Electrolytic production of aluminum
US6372119B1 (en) Inert anode containing oxides of nickel iron and cobalt useful for the electrolytic production of metals
Mishra et al. Defect structures in zirconium diboride powder prepared by self-propagating high-temperature synthesis
US5585041A (en) Electrically-conductive titanium suboxides
EP2770086A2 (en) Reduction of metal oxides in an electrolytic cell
JP2012517531A (en) Polycrystalline diamond
EP0593512B1 (en) Method for preparing composite electrode for electrochemical processing having improved high temperature properties and use of the electrode
EP0569407B1 (en) Composite electrode for electrochemical processing and method for preparation by combustion synthesis without a die
AU2002338623C1 (en) Electrolytic production of high purity aluminum using ceramic inert anodes
Sonber et al. Synthesis and consolidation of zirconium diboride
WO2000067936A1 (en) Metal powders produced by the reduction of the oxides with gaseous magnesium
Fang et al. Powder metallurgy of titanium–past, present, and future
CA1235001A (en) Reaction sintered cermet
Zhang et al. Effect of TiC content on the microstructure and properties of Ti3SiC2–TiC composites in situ fabricated by spark plasma sintering
Helle et al. Structure and high-temperature oxidation behaviour of Cu–Ni–Fe alloys prepared by high-energy ball milling for application as inert anodes in aluminium electrolysis

Legal Events

Date Code Title Description
FZDE Dead