WO2002075023A2 - Materiau d'electrode inerte sous forme de poudre nanocristalline - Google Patents

Materiau d'electrode inerte sous forme de poudre nanocristalline Download PDF

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Publication number
WO2002075023A2
WO2002075023A2 PCT/CA2002/000395 CA0200395W WO02075023A2 WO 2002075023 A2 WO2002075023 A2 WO 2002075023A2 CA 0200395 W CA0200395 W CA 0200395W WO 02075023 A2 WO02075023 A2 WO 02075023A2
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Prior art keywords
process according
carbide
nitride
group
oxide
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PCT/CA2002/000395
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English (en)
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WO2002075023A3 (fr
Inventor
Sabin Boily
Houshang Darvishi Alamdari
Marco Blouin
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Groupe Minutia Inc.
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Priority to JP2002574408A priority Critical patent/JP2004531644A/ja
Priority to CA002441578A priority patent/CA2441578A1/fr
Priority to EP02706576A priority patent/EP1466039A2/fr
Priority to BR0208273-0A priority patent/BR0208273A/pt
Priority to US10/472,590 priority patent/US20040045402A1/en
Publication of WO2002075023A2 publication Critical patent/WO2002075023A2/fr
Publication of WO2002075023A3 publication Critical patent/WO2002075023A3/fr
Priority to NO20034198A priority patent/NO20034198L/no

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
    • C04B35/2666—Other ferrites containing nickel, copper or cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/002—Making metallic powder or suspensions thereof amorphous or microcrystalline
    • B22F9/004—Making metallic powder or suspensions thereof amorphous or microcrystalline by diffusion, e.g. solid state reaction
    • B22F9/005—Transformation into amorphous state by milling
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the present invention pertains to improvements in the field of electrodes for metal electrolysis. More particularly, the invention relates to an inert electrode material in nanocrystalline powder form for use in the manufacture of such electrodes.
  • Aluminum is produced conventionally in a Hall-Heroult reduction cell by the electrolysis of alumina dissolved in molten cryolite (Na 3 AlF 6 ) 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. Typically, for each ton of aluminum produced, 0.5 ton of carbon anode is required.
  • the carbon anode is consumed leading to the evolution of greenhouse gases such as CO and CO 2 .
  • 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.
  • the carbon blocks are subjected to erosion and electrolyte penetration.
  • a sodium intercalation in the graphitic structure occurs, which causes swelling and deformation of the cathode carbon blocks.
  • the increase of voltage between the electrodes adversely affects the energy efficiency of the process.
  • the proposed materials include metals such as proposed in US Patent No. 6,162,334, ceramics such as proposed in US Patent Nos. 3,960,678 and 4,399,008, and cermets such as proposed in US Patent No. 5,865,980.
  • metals such as proposed in US Patent No. 6,162,334, ceramics such as proposed in US Patent Nos. 3,960,678 and 4,399,008, and cermets such as proposed in US Patent No. 5,865,980.
  • Ceramics are generally brittle and do not resist to the thermal shocks during start-up and operation of a Hall-Heroult cell.
  • Metal oxide ceramics are generally resistant to oxidation, but they are not good electrical conductors.
  • Cermets are very good conductors but the corrosion rate of metallic anodes in cryolite is very high. Cermets, on the other hand, seem to be promising materials for anode applications. Cermets combine the good properties of metals (conductivity, toughness) with good properties of ceramics (corrosion resistance).
  • US Patent No. 5,865,980 describes a cermet comprising a ferrite, copper and silver which can be used as an inert anode. These cermet anodes exhibit a good corrosion resistance due to the ceramic part and a good electrical conductivity due to the metallic part. Fabrication process of such a cermet is complex and consists of several steps. At least two metal oxides, such as NiO and Fe 2 O 3 , are mixed and calcined at high temperatures (1300-1400 °C) for a relatively long period of time (12 h) in order to synthesize a nickel ferrite spinel with or without excess of NiO.
  • NiO and Fe 2 O 3 are mixed and calcined at high temperatures (1300-1400 °C) for a relatively long period of time (12 h) in order to synthesize a nickel ferrite spinel with or without excess of NiO.
  • the resulting material is grinded to reduce the average particle size to about 10 microns, mixed with a polymeric binder and water, spray dried, and mixed with copper and silver powder.
  • the powder mixture thus obtained is then pressed and sintered at about ' 1350 °C for 2-4 hours.
  • the resulting cermet has ceramic phase portions and alloy phase portions.
  • Segregation is a serious problem when powders having a large average particle size are mixed together. Segregation is more pronounced when the difference between the densities of the particles or their size is larger. Metal particles having a density greater than that of ceramic particles tend to segregate from the low-density ceramic particles. This results in a non-homogeneous powder mixture and, consequently, in a non-homogeneous sintered anode. Since the conductivity of the ceramic phase is much lower than that of the metal phase, any non-homogeneity results in a non-homogeneous current density during use of the anode. On the other hand, the corrosion or erosion rates of the ceramic and metal phase portions of the cermet in cryolite are not the same. Therefore, any non-homogeneity results in an excessive local degradation of the anode.
  • sintering The purpose of sintering is to obtain a solid product having maximum density and homogeneity.
  • densification pore elimination
  • grain growth Higher sintering temperatures and longer sintering times generally lead to high densification but, on the other hand, favor grain growth.
  • the sintering temperature and/or time must be increased. This results in a cermet with a coarse microstructure which decreases the thermal shock resistance of the cermet.
  • Coarse structured cermets also exhibit low mechanical properties and non-homogeneous corrosion rates.
  • an inert electrode material in powder form comprising particles having an average particle size of 0.1 to 100 ⁇ m and each formed of an agglomerate of grains of a ceramic material and grains of a metal or alloy with each grain of ceramic material comprising a nanocrystal of the ceramic material and each grain of metal or alloy comprising a nanocrystal of the metal or alloy.
  • an inert electrode material in powder form comprising particles having an average particle size of 0.1 to 100 ⁇ m and each formed of an agglomerate of grains with each grain comprising a nanocrystal of a single phase ceramic material.
  • an inert electrode material in powder form comprising particles having an average particle size of 0.1 to 100 ⁇ m and each formed of an agglomerate of grains with each grain comprising a nanocrystal of a metal.
  • an inert electrode material in powder form comprising particles having an average particle size of 0.1 to 100 ⁇ m and each formed of an agglomerate of grains with each grain comprising a nanocrystal of an alloy.
  • nanocrystalline refers to a crystal having a size of 100 nanometers or less.
  • the nanocrystalline microstructure considerably favors densification, even without sintering aids, when the electrode material in powder form according to the invention is compacted and sintered to produce dense electrodes.
  • Nanocrystalline powders also minimize grain growth ⁇ since sintering can be effected at lower temperatures.
  • the sintering time is also much shorter than that required for densification of the conventional coarse-grained (about 10 ⁇ m) powder mixtures for a same densification level. Thus, the overall cost of the sintering process is considerably decreased.
  • the resulting electrode Since the time and the temperature of the sintering are considerably low, the resulting electrode has a fine microstructure. The finer the microstructure, the higher the toughness and the resistance to thermal shock, and consequently the longer the electrode life time.
  • each particle is formed of an agglomerate of grains with each grain comprising a nanocrystal of a metal
  • the nanocrystalline metals are more resistant to corrosion than polycrystalline metals because of the growth of a passivation layer.
  • This protective layer grows faster at the surface of a nanocrystalline metal than in a polycrystalline metal.
  • the present invention also provides, in a further aspect thereof, a process for producing an inert electrode material in powder form as previously defined, wherein each particle is formed of an agglomerate of grains of a ceramic material and grains of a metal.
  • the process of the invention comprises the steps of: a) subjecting at least one metal oxide, nitride or carbide to high-energy ball milling to form a first powder comprising particles having an average particle size of 0.1 to 100 ⁇ m and each formed of an agglomerate of grains of a ceramic material; b) subjecting a metal to high-energy ball milling to form a second powder comprising particles having an average particle size of 0.1 to 100 ⁇ m and each formed of an agglomerate of grains with each grain comprising a nanocrystal of the metal; c) mixing the first and second powders to form a powder mixture; and
  • step (c) subjecting the powder mixture obtained in step (c) to high- energy ball milling to form a nanocrystalline powder comprising particles having an average particle size of 0.1 to 100 ⁇ m and each formed of an agglomerate of grains of the ceramic material and grains of the metal, wherein each grain of ceramic material comprises a nanocrystal of the ceramic material and each grain of metal comprises a nanocrystal of the metal.
  • a process for producing an inert electrode material as previously defined, wherein each particle is formed of an agglomerate of grains of a ceramic material and grains of an alloy comprises the steps of: a) subjecting at least one metal oxide, nitride or carbide to high-energy ball milling to form a first powder comprising particles having an average particle size of 0.1 to 100 ⁇ m and each formed of an agglomerate of grains of a ceramic material; b) subjecting at least two metals to high-energy ball milling to form a second powder comprising particles having an average particle size of 0.1 to 100 ⁇ m and each formed of an agglomerate of grains with each grain comprising a nanocrystal of an alloy of the metals; c) mixing the first and second powders to form a powder mixture; and d) subjecting the powder mixture obtained in step (c) to high- energy ball milling to form a nanocrystalline powder comprising particles having an average particle size
  • the process of the invention comprises subjecting a metal oxide, nitride or carbide to high-energy ball milling to form a nanocrystalline powder comprising particles having an average particle size of 0.1 to 100 ⁇ m and each formed of an agglomerate of grains with each grain comprising a nanocrystal of a single phase ceramic material.
  • a process for producing an inert electrode material in powder form as previously defined, wherein each particle is formed of an agglomerate of grains each comprising a nanocrystal of a metal comprises subjecting a metal to high-energy ball milling to form a nanocrystalline powder comprising particles having an average particle size of 0.1 to 100 ⁇ m and each formed of an agglomerate of grains with each grain comprising a nanocrystal of the metal.
  • the process of the invention comprises subjecting at least two metals to high-energy ball milling to form a nanocrystalline powder comprising particles having an average particle size of 0.1 to 100 ⁇ m and each formed of an agglomerate of grains with each grain comprising a nanocrystal of an alloy of the metals.
  • high-energy ball milling refers to a ball milling process capable of forming the aforesaid particles within a period of time of about 40 hours.
  • the high-energy ball milling is carried out for a period of time sufficient to break the agglomerates formed in steps (a) and (b), and to form new agglomerates comprising nanocrystalline grains of the ceramic material and nanocrystalline grains of the metal or alloy.
  • a period of time is about one hour.
  • suitable ceramic materials include oxides, nitrides and carbides of transition metals such as Ag, Co, Cu, Cr, Fe, Ir,
  • the metal can be for example chromium, cobalt, copper, gold, iridium, iron, nickel, niobium, palladium, platinum, rubidium, ruthenium, silicon, silver, titanium, yttrium or zirconium.
  • the alloy can be for example a Cu-Ag, Cu-Ag-Ni, Cu-Ni, Cu-Ni-Fe, Cu-Pd, Cu-Pt or Ni-Fe alloy. When these particles are sintered, they will form a cermet material having ceramic phase portions and metal or alloy phase portions.
  • the ceramic material advantageously includes a dopant for improving the sinterability of the powder and/or for increasing the conductivity of the electrode eventually made from the ceramic powder.
  • suitable dopants include those comprising an element selected from the group of Al, Co, Cr, Cu, Fe, Mo, Nb, Ni, Sb, Si, Sn, Ti, V, W, Y, Zn and Zr.
  • the dopant is generally present in an amount of about 0.002 to about 1 wt.%, preferably between about 0.005 and about 0.05 wt.%. Since the corrosion, erosion and thermal expansion of a single phase ceramic material are uniform, electrodes produced from the nanocrystalline powder according to the invention, comprising such a material, have a longer life time.
  • each particle is formed of an agglomerate of grains with each grain comprising a nanocrystal of a metal
  • the metal can be for example chromium, cobalt, copper, gold, iridium, iron, nickel, niobium, palladium, platinum, rubidium, ruthenium, silicon, silver, titanium, yttrium or zirconium. Copper is preferred.
  • the alloy in the case where each particle is formed of an agglomerate of grains with each grain comprising a nanocrystal of an alloy, the alloy can be for example a Cu-Ag, Cu-Ag-Ni, Cu-Ni, Cu-Ni-Fe, Cu-Pd, Cu-Pt or Ni-Fe alloy.
  • the high-energy ball milling 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 carry out such a ball milling in a rotary ball mill operated at a speed of 100 to 2000 r.p.m., preferably about 1200 r.p.m.
  • the high-energy ball milling is carried out under an inert gas atmosphere such as a gas atmosphere comprising argon or helium.
  • an atmosphere of argon is preferred.
  • the electrode material in powder form according to the invention can be used to produce dense electrode by powder metallurgy.
  • powder metallurgy 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.
  • the dense electrodes thus obtained have improved thermal shock and corrosion resistance properties.
  • the electrode material in powder form according to the invention can also be used to produce electrodes by thermal deposition applications.
  • thermal deposition refers to a technique in which powder particles are injected in a torch and sprayed on a conductive substrate such as graphite or copper, to form thereon a highly dense coating. The particles acquire a high velocity and are partially or totally melted during the flight path. The coating is built by the solidification of the droplets on the substrate surface. Examples of such techniques include plasma spray, arc spray and high velocity oxy-fuel.
  • the electrodes produced from the nanocrystalline powder according to the invention have a high density, the electrolyte does not penetrate into the electrode via pores and, consequently, the degradation of the electrode is minimized.
  • a NiFe 2 O spinel powder was produced by ball milling 51.7 wt.% NiO and 48.3 wt.% Fe 2 O 3 in a tungsten carbide crucible with a ball-to- powder mass ratio of 15:1 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. The crucible was closed and sealed with a rubber O-ring. After 10 hours of high-energy ball milling, a nanocrystalline structure comprising a NiFe 2 O spinel with excess NiO was formed. The particle size varied between 0.1 and 5 ⁇ m and the crystallite size, measured by X-ray diffraction, was about 30 nm.
  • a Cu-Ag alloy powder was also produced by ball milling 69.5 wt.% Cu and 29.5 wt.% Ag in a tungsten carbide crucible with a ball-to- powder mass ratio of 10:1 using a SPEX 8000 vibratory ball mill operated at a frequency of about 17 Hz. The operation was performed under a controlled argon atmosphere. 1 wt.% of stearic acid was added as a lubricant. After 10 hours of high-energy ball milling, a nanocrystalline structure comprising an alloy of copper and silver was formed. The particle size varied between 10 and 30 ⁇ m and the crystallite size, measured by X-ray diffraction, was about 40 nm.
  • a NiFe 2 O 4 ferrite powder was produced by ball milling 51.7 wt.% of NiO and 48.3 wt.% Fe 2 O 3 in a steel crucible with a ball-to-powder mass ratio of 10:1 using a SIMOLOYER (trademark) rotary ball mill operated at a speed of 1200 r.p.m.. The operation was performed under a controlled argon atmosphere by continously flushing the crucible with argon. After 5 hours of high-energy ball milling, an amorphous NiFe 2 O 4 spinel was produced with an excess of nanocrystalline NiO. The particle size varied between 0.1 and 5 ⁇ m.
  • a Cu-Ag alloy powder was also produced by ball milling 98 wt.% Cu and 2 wt.% Ag in a steel crucible with a ball-to-powder mass ratio of 10:1 using a SIMOLOYER rotary ball mill operated at a speed of 1200 r.p.m. The operation was performed under a controlled argon atmosphere. 1 wt.% stearic acid was added as a lubricant. After 5 hours of high-energy ball milling, a nanocrystalline structure comprising an alloy of copper and silver was formed. The particle size varied between 5 to 30 ⁇ m and the crystallite size, measured by X-ray diffraction, was about 20 nm.
  • the particle size varied between 5 and 10 ⁇ m.
  • This nanocrystalline powder was then cold isostatically pressed at 138 Mpa.
  • the compacted powder was then sintered at a temperature of 1050°C for one hour to produce a dense electrode having excellent thermal shock and corrosion resistance properties.
  • a NiFe 2 O 4 ferrite powder was produced by ball milling 51.7 wt.% of NiO and 48.3 wt.% Fe 2 O 3 in a steel crucible with a ball-to-powder mass ratio of 10: 1 using a SIMOLOYER rotary ball mill operated at a speed of 1200 r.p.m.. The operation was performed under a controlled argon atmosphere by continously flushing the crucible with argon. After 5 hours of high-energy ball milling, an amorphous NiFe 2 O 4 spinel was produced with an excess of nanocrystalline NiO. The particle size varied between 0.1 and 5 ⁇ m.
  • a Cu-Ag alloy powder was also produced by ball milling
  • a coarse-grained ZnO powder (99.9% pure) having an average grain size of 1 ⁇ m and a specific surface area of 3 m 2 /g was used as starting material.
  • 0.008 wt.% Al 2 O 3 and 2 wt.% PVA were added as dopant and binder, respectively.
  • the powder mixture was ball milled in a tungsten carbide crucible using a SPEX 8000 vibratory ball mill operated at a frequency of about 17 Hz. After 15 hours of high-energy ball milling, a nanocrystalline ZnO powder having a particle size between 1 and 5 ⁇ m and an average grain size smaller than 100 nm was obtained.
  • the specific surface area of the nanocrystalline grains was 40 m 2 /g.
  • This nanocrystalline powder was then pressed uniaxially at a pressure of 400 MPa.
  • the compacted powder was then sintered at a temperature of 1250°C for one hour to produce a dense electrode having excellent thermal shock and corrosion resistance properties.
  • a nanocrystalline Cu-Ni alloy powder was produced by ball milling 70 wt.% Cu and 30 wt.% Ni in a steel crucible with a ball-to- powder mass ratio of 10:1 using a SIMOLOYER rotary ball mill operated at a speed of 1200 r.p.m.. 1 wt.% stearic acid was added as a lubricant. After 5 hours of high-energy ball milling, a nanocrystalline powder comprising particles each formed of an agglomerate of grains comprising nanocrystals of an alloy of copper and nickel was obtained. The particle size varied between 5 to 30 ⁇ m and the crystallite size, measured by X-ray diffraction, was about 20 nm. This nanocrystalline powder was mixed with 2 wt.% of CAPLUBE G and uniaxially pressed at 300 Mpa. The compacted powder was then sintered at a temperature of 1000°C for one hour to produce a dense electrode.

Abstract

La présente invention concerne un matériau d'électrode inerte, se présentant sous forme de poudre et comprenant des particules de taille moyenne allant de 0,1 à 100 νm, chacune constituée d'un agglomérat de grains d'une matière céramique et de grains d'un métal ou d'un alliage. Chaque grain de matière céramique comprend un nanocristal de la matière céramique et chaque grain de métal ou d'alliage comprend un nanocristal du métal ou de l'alliage. En variante, chaque particule peut être constituée d'un agglomérat de grains, chaque grain comprenant un nanocristal d'une matière céramique à une phase, d'un métal ou d'un alliage. Le matériau d'électrode sous forme de poudre selon cette invention est utilisé dans la production d'électrodes inertes présentant des propriétés de résistance au choc thermique et à la corrosion améliorées.
PCT/CA2002/000395 2001-03-20 2002-03-20 Materiau d'electrode inerte sous forme de poudre nanocristalline WO2002075023A2 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP2002574408A JP2004531644A (ja) 2001-03-20 2002-03-20 ナノ結晶性粉末形状の不活性電極材料
CA002441578A CA2441578A1 (fr) 2001-03-20 2002-03-20 Materiau d'electrode inerte sous forme de poudre nanocristalline
EP02706576A EP1466039A2 (fr) 2001-03-20 2002-03-20 Materiau inerte d'electrode en forme de poudre nanocristalline
BR0208273-0A BR0208273A (pt) 2001-03-20 2002-03-20 Material de eletrodo inerte em forma pulverizada nanocristalina
US10/472,590 US20040045402A1 (en) 2001-03-20 2002-03-20 Inert electrode material in nanocrystalline powder form
NO20034198A NO20034198L (no) 2001-03-20 2003-09-19 Inert elektrodemateriale i nanokrystallionsk pulverform

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CA002341779A CA2341779A1 (fr) 2001-03-20 2001-03-20 Matiere inerte, sous forme de poudre nanocristalline, pour fabrication d'electrodes
CA2,341,779 2001-03-20

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Publication Number Publication Date
WO2002075023A2 true WO2002075023A2 (fr) 2002-09-26
WO2002075023A3 WO2002075023A3 (fr) 2003-07-17

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EP (1) EP1466039A2 (fr)
JP (1) JP2004531644A (fr)
CN (1) CN1498287A (fr)
BR (1) BR0208273A (fr)
CA (1) CA2341779A1 (fr)
NO (1) NO20034198L (fr)
RU (1) RU2003130746A (fr)
WO (1) WO2002075023A2 (fr)

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CN100507091C (zh) * 2005-11-10 2009-07-01 东北大学 一种铝电解用金属基复合材料惰性阳极及其制备方法
WO2007111793A2 (fr) * 2006-02-17 2007-10-04 Steward Advanced Materials, Inc. Procédé et appareil de projection à flamme oxygaz à faible vitesse (lvof) pour l'élaboration de produits de ferrite et produits ainsi obtenus
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CA2850856C (fr) * 2011-10-20 2019-09-17 Institut National De La Recherche Scientifique Anodes inertes pour l'electrolyse de l'aluminium et leur procede de production
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US10443265B2 (en) 2015-11-06 2019-10-15 Winloc Ag Set of profile members in combination with a key plug, a method to manufacture such a key plug and a combination also including an associated key
CN108863368A (zh) * 2018-07-12 2018-11-23 百色皓海碳素有限公司 开槽预焙阳极的生产工艺
CN111974986A (zh) * 2020-08-06 2020-11-24 东莞材料基因高等理工研究院 一种铝金属复合粉末及利用该粉末制备的激光增材

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