US20040052713A1 - 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 PDFInfo
- Publication number
- US20040052713A1 US20040052713A1 US10/250,499 US25049903A US2004052713A1 US 20040052713 A1 US20040052713 A1 US 20040052713A1 US 25049903 A US25049903 A US 25049903A US 2004052713 A1 US2004052713 A1 US 2004052713A1
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- United States
- Prior art keywords
- process according
- powder form
- refractory hard
- 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
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 44
- 239000002184 metal Substances 0.000 title claims abstract description 44
- 239000000843 powder Substances 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 150000002739 metals Chemical class 0.000 title description 9
- 239000002245 particle Substances 0.000 claims abstract description 24
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052796 boron Inorganic materials 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052799 carbon Chemical group 0.000 claims abstract description 18
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 16
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 12
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 11
- 150000003624 transition metals Chemical class 0.000 claims abstract description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 10
- 239000011651 chromium Substances 0.000 claims abstract description 10
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 10
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002159 nanocrystal Substances 0.000 claims abstract description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 239000011733 molybdenum Substances 0.000 claims abstract description 7
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
- 239000010955 niobium Substances 0.000 claims abstract description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 7
- 239000010937 tungsten Substances 0.000 claims abstract description 7
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 48
- 150000001875 compounds Chemical class 0.000 claims description 35
- 239000010936 titanium Substances 0.000 claims description 24
- 239000003153 chemical reaction reagent Substances 0.000 claims description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 18
- 229910052719 titanium Inorganic materials 0.000 claims description 18
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims description 15
- 229910033181 TiB2 Inorganic materials 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 13
- 238000000713 high-energy ball milling Methods 0.000 claims description 13
- -1 AlB12 Inorganic materials 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910016459 AlB2 Inorganic materials 0.000 claims description 2
- 229910019918 CrB2 Inorganic materials 0.000 claims description 2
- 229910003862 HfB2 Inorganic materials 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910015425 Mo2B5 Inorganic materials 0.000 claims description 2
- 229910015173 MoB2 Inorganic materials 0.000 claims description 2
- 229910004835 Na2B4O7 Inorganic materials 0.000 claims description 2
- 229910019742 NbB2 Inorganic materials 0.000 claims description 2
- 229910004533 TaB2 Inorganic materials 0.000 claims description 2
- 229910010039 TiAl3 Inorganic materials 0.000 claims description 2
- 229910010055 TiB Inorganic materials 0.000 claims description 2
- 229910010068 TiCl2 Inorganic materials 0.000 claims description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 2
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 238000003746 solid phase reaction Methods 0.000 claims description 2
- 238000010671 solid-state reaction Methods 0.000 claims description 2
- 229910000048 titanium hydride Inorganic materials 0.000 claims description 2
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 claims description 2
- 238000004663 powder metallurgy Methods 0.000 abstract description 4
- 238000002207 thermal evaporation Methods 0.000 abstract description 4
- 238000000498 ball milling Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000005056 compaction Methods 0.000 description 2
- 229910001610 cryolite Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910000760 Hardened steel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910007948 ZrB2 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000007582 slurry-cast process Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000003826 uniaxial pressing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/907—Oxycarbides; Sulfocarbides; Mixture of carbides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/921—Titanium carbide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/02—Boron; Borides
- C01B35/04—Metal borides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
- C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
- C25C3/12—Anodes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/60—Compounds characterised by their crystallite size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Definitions
- the present invention pertains to improvements in the field of electrodes for metal electrolysis. More particularly, the invention relates to refractory hard metals in powder form for use in the manufacture of such electrodes.
- a Hall-Héroult reduction 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.
- refractory hard metals such as TiB 2
- electrode materials As electrode materials.
- TiB 2 and other refractory hard metals are practically insoluble in aluminum, have a low electrical resistance and are wetted by aluminum.
- the shaping of TiB 2 and similar refractory hard metals is difficult because these materials have high melting temperatures and are highly covalent.
- a refractory hard metal in powder form comprising particles having an average particle size of 0.1 to 30 ⁇ m and each formed of an agglomerate of grains with each grain comprising a nanocrystal of a refractory hard metal of the formula:
- 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
- z ranges from 1 to 6.
- nanoclaystal refers to a crystal having a size of 100 nanometers or less.
- thermal deposition 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 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.
- pellet 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 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:
- high-energy ball milling 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.
- FIGURE shows the X-ray diffraction of the refractory hard metal in powder form obtained in Example 1.
- Typical examples of refractory hard metals of the formula (I) include TiB 1.8 , TiB 2 , TiB 2.2 , TiC, Ti 0.5 Zr 0.5 B 2 , Ti 0.9 Zr 0.1 B 2 , Ti 0.5 Hf 0.5 B 2 and Zr 0.8 V 0.2 B 2 .
- TiB 2 is preferred.
- Examples of suitable compounds which may be used as the aforesaid third reagent include HfB 2 , VB 2 , NbB 2 , TaB 2 , CrB 2 , MoB 2 , MnB 2 , Mo 2 B 5 , W 2 B 5 , CoB, ZrC, TaC, WC and HfC.
- step (d) of the process according to the invention 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.
- 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.
- a sintering aid such as Y 2 O 3 can be added during step (d).
- these two compounds can be used as starting material.
- 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 ⁇ m, each particle being formed of an agglomerate of grains with each grain comprising a nanocrystal of TiB 2 or TiC.
- 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.
- a TiB 2 powder was produced by ball milling 3.45 g of titanium and 1.55 g 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 TiB 2 structure was formed, as shown on the X-ray diffraction pattern in the accompanying drawing. The structure of TiB 2 is hexagonal with the space group P6/mmm (191). The particle size varied between 1 and 5 ⁇ m and the crystallite size, measured by X-ray diffraction, was about 30 nm.
- a TiB 2 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.
- 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.
- a TiB 2 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.
- a TiB 1.8 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.
- a TiB 2.2 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.
- a Ti 0.5 Zr 0.5 B 2 powder was according to the same procedure as described in Example 1 and under the same operating conditions, with the exception that 1.9 g of titanium, 3.1 g of zirconium diboride and 0.8 g of boron were milled.
- a Ti 0.9 Zr 0.1 B 2 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.
- a Ti 0.5 Hf 0.5 B 2 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.
- a Zr 0.8 V 0.2 B 2 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.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
- Carbon And Carbon Compounds (AREA)
- Crushing And Grinding (AREA)
- Electrolytic Production Of Metals (AREA)
Applications Claiming Priority (3)
| 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 |
| CA2,330,352 | 2001-01-05 | ||
| PCT/CA2002/000013 WO2002053495A1 (en) | 2001-01-05 | 2002-01-02 | Refractory hard metals in powder form for use in the manufacture of electrodes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20040052713A1 true US20040052713A1 (en) | 2004-03-18 |
Family
ID=4168043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US10/250,499 Abandoned US20040052713A1 (en) | 2001-01-05 | 2002-01-02 | Refractory hard metals in powder form for use in the manufacture of electrodes |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20040052713A1 (en22) |
| EP (1) | EP1347939A1 (en22) |
| JP (1) | JP2004516226A (en22) |
| CN (1) | CN1484613A (en22) |
| BR (1) | BR0206306A (en22) |
| CA (1) | CA2330352A1 (en22) |
| NO (1) | NO20033076L (en22) |
| RU (1) | RU2003124183A (en22) |
| WO (1) | WO2002053495A1 (en22) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090017332A1 (en) * | 2006-02-17 | 2009-01-15 | Newcastle Innovation Limited | Crystalline ternary ceramic precursors |
| US20100122903A1 (en) * | 2008-11-17 | 2010-05-20 | Kennametal, Inc. | Readily-Densified Titanium Diboride and Process for Making Same |
| CN110655408A (zh) * | 2019-11-13 | 2020-01-07 | 哈尔滨工业大学 | 一种单相碳硼化物固溶体陶瓷材料的制备方法 |
| US11041250B2 (en) * | 2009-07-28 | 2021-06-22 | Alcoa Usa Corp. | Composition for making wettable cathode in aluminum smelting |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100546041B1 (ko) * | 2005-05-31 | 2006-01-26 | 가야에이엠에이 주식회사 | 로터리 킬른형 노를 사용한 탄화티타늄 분말의 제조방법 |
| JP5780540B2 (ja) * | 2010-12-24 | 2015-09-16 | 国立研究開発法人物質・材料研究機構 | 二ホウ化ジルコニウム粉末及びその合成方法 |
| CN102430757A (zh) * | 2011-11-25 | 2012-05-02 | 天津大学 | 一种高能球磨制备发动机活塞环表面喷涂用TiB2/TiC超细粉的方法 |
| JP2015174046A (ja) * | 2014-03-17 | 2015-10-05 | Ｊｆｅマテリアル株式会社 | 粉末冶金用クロムの製造方法 |
| KR101659823B1 (ko) * | 2014-12-17 | 2016-09-27 | 한국기계연구원 | HfC 복합체 및 이의 제조방법 |
| CN105297069A (zh) * | 2015-11-18 | 2016-02-03 | 上海大学 | 一种精确可控直接制备金属碳化物的电化学方法 |
| CN108165858B (zh) * | 2017-11-15 | 2022-03-25 | 常德永 | 一种高温敏感纳米材料及其制备方法 |
| CN109896861A (zh) * | 2019-04-11 | 2019-06-18 | 哈尔滨工业大学 | 一种高纯度、小粒度硼化铪耐烧蚀粉体的制备方法 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2634475B1 (fr) * | 1988-07-22 | 1990-10-12 | Centre Nat Rech Scient | Procede de preparation de poudres de composes d'elements de la colonne iv a et produits obtenus |
| JPH0674126B2 (ja) * | 1989-11-20 | 1994-09-21 | 科学技術庁金属材料技術研究所長 | 遷移金属炭化物の製造方法 |
| CN1147478A (zh) * | 1996-05-17 | 1997-04-16 | 浙江大学 | 碳化钨、碳化钛超细粉的常温合成方法 |
| US6214309B1 (en) * | 1997-09-24 | 2001-04-10 | University Of Connecticut | Sinterable carbides from oxides using high energy milling |
-
2001
- 2001-01-05 CA CA002330352A patent/CA2330352A1/en not_active Abandoned
-
2002
- 2002-01-02 CN CNA028035011A patent/CN1484613A/zh active Pending
- 2002-01-02 WO PCT/CA2002/000013 patent/WO2002053495A1/en not_active Application Discontinuation
- 2002-01-02 EP EP02726977A patent/EP1347939A1/en not_active Withdrawn
- 2002-01-02 US US10/250,499 patent/US20040052713A1/en not_active Abandoned
- 2002-01-02 JP JP2002554621A patent/JP2004516226A/ja active Pending
- 2002-01-02 RU RU2003124183/15A patent/RU2003124183A/ru not_active Application Discontinuation
- 2002-01-02 BR BR0206306-9A patent/BR0206306A/pt not_active Application Discontinuation
-
2003
- 2003-07-04 NO NO20033076A patent/NO20033076L/no not_active Application Discontinuation
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090017332A1 (en) * | 2006-02-17 | 2009-01-15 | Newcastle Innovation Limited | Crystalline ternary ceramic precursors |
| US20100122903A1 (en) * | 2008-11-17 | 2010-05-20 | Kennametal, Inc. | Readily-Densified Titanium Diboride and Process for Making Same |
| WO2010056976A3 (en) * | 2008-11-17 | 2010-08-19 | Kennametal Inc. | Readily-densified titanium diboride and process for making same |
| GB2477233A (en) * | 2008-11-17 | 2011-07-27 | Kennametal Inc | Readily-densified titanium diboride and process for making same |
| US8142749B2 (en) | 2008-11-17 | 2012-03-27 | Kennametal Inc. | Readily-densified titanium diboride and process for making same |
| GB2477233B (en) * | 2008-11-17 | 2014-04-30 | Kennametal Inc | Readily-densified titanium diboride and process for making same |
| AU2009313897B2 (en) * | 2008-11-17 | 2014-11-20 | Kennametal Inc. | Readily-densified titanium diboride and process for making same |
| US11041250B2 (en) * | 2009-07-28 | 2021-06-22 | Alcoa Usa Corp. | Composition for making wettable cathode in aluminum smelting |
| CN110655408A (zh) * | 2019-11-13 | 2020-01-07 | 哈尔滨工业大学 | 一种单相碳硼化物固溶体陶瓷材料的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| NO20033076L (no) | 2003-09-05 |
| CN1484613A (zh) | 2004-03-24 |
| JP2004516226A (ja) | 2004-06-03 |
| CA2330352A1 (en) | 2002-07-05 |
| EP1347939A1 (en) | 2003-10-01 |
| RU2003124183A (ru) | 2005-01-10 |
| NO20033076D0 (no) | 2003-07-04 |
| WO2002053495A1 (en) | 2002-07-11 |
| BR0206306A (pt) | 2004-02-17 |
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