US20160089724A1 - Process for manufacturing metal containing powder - Google Patents
Process for manufacturing metal containing powder Download PDFInfo
- Publication number
- US20160089724A1 US20160089724A1 US14/892,478 US201414892478A US2016089724A1 US 20160089724 A1 US20160089724 A1 US 20160089724A1 US 201414892478 A US201414892478 A US 201414892478A US 2016089724 A1 US2016089724 A1 US 2016089724A1
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- Prior art keywords
- powder
- metal
- hydride
- mixture
- atmosphere
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- 239000000843 powder Substances 0.000 title claims abstract description 171
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 72
- 239000002184 metal Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 239000012298 atmosphere Substances 0.000 claims abstract description 36
- 239000008187 granular material Substances 0.000 claims abstract description 34
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 29
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 29
- 239000011575 calcium Substances 0.000 claims abstract description 27
- 229910052987 metal hydride Inorganic materials 0.000 claims abstract description 24
- 150000004681 metal hydrides Chemical class 0.000 claims abstract description 24
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 14
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 49
- 229910052719 titanium Inorganic materials 0.000 claims description 24
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- 229910052804 chromium Inorganic materials 0.000 claims description 14
- 229910052758 niobium Inorganic materials 0.000 claims description 11
- 239000011777 magnesium Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- 229910012375 magnesium hydride Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- RSHAOIXHUHAZPM-UHFFFAOYSA-N magnesium hydride Chemical compound [MgH2] RSHAOIXHUHAZPM-UHFFFAOYSA-N 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 35
- 239000002245 particle Substances 0.000 description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 238000010438 heat treatment Methods 0.000 description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 239000010936 titanium Substances 0.000 description 23
- 239000007789 gas Substances 0.000 description 21
- 239000001257 hydrogen Substances 0.000 description 20
- 229910052739 hydrogen Inorganic materials 0.000 description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 17
- 239000012467 final product Substances 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 229910001092 metal group alloy Inorganic materials 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000011651 chromium Substances 0.000 description 13
- 150000004678 hydrides Chemical class 0.000 description 13
- 229910052786 argon Inorganic materials 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 10
- 239000007858 starting material Substances 0.000 description 10
- 239000012535 impurity Substances 0.000 description 9
- 239000010955 niobium Substances 0.000 description 9
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- -1 hydride compound Chemical class 0.000 description 7
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 229910000765 intermetallic Inorganic materials 0.000 description 5
- 229910000048 titanium hydride Inorganic materials 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000006356 dehydrogenation reaction Methods 0.000 description 4
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 3
- 229910002335 LaNi5 Inorganic materials 0.000 description 3
- 229910052776 Thorium Inorganic materials 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 229910003074 TiCl4 Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 2
- 238000009838 combustion analysis Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010038 TiAl Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005049 combustion synthesis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- 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
-
- B22F1/0003—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
-
- 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
- B22F2201/00—Treatment under specific atmosphere
- B22F2201/01—Reducing atmosphere
- B22F2201/013—Hydrogen
-
- 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
- B22F2201/00—Treatment under specific atmosphere
- B22F2201/10—Inert gases
- B22F2201/11—Argon
-
- 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
- B22F2301/00—Metallic composition of the powder or its coating
-
- 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
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/05—Light metals
- B22F2301/052—Aluminium
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- 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
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/20—Refractory metals
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- 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
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/20—Refractory metals
- B22F2301/205—Titanium, zirconium or hafnium
-
- 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
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/30—Low melting point metals, i.e. Zn, Pb, Sn, Cd, In, Ga
-
- 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
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/45—Rare earth metals, i.e. Sc, Y, Lanthanides (57-71)
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- 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
- B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
- B22F2302/45—Others, including non-metals
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- 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 concerns a new method for producing metal powders, metal alloy powders, intermetallic powders and/or their hydride powders, by a simplified, cost efficient process, preferably by performing the reduction reaction of metal oxides under hydrogen gas protection, using specific reducing agents and specific reduction conditions.
- Powder metallurgical (PM) techniques are well established routes for efficient production of complex metal based components. These techniques are commonly used in applications where alloys based on iron, stainless steel, copper or nickel are required. However, the use of PM techniques where material such as titanium, chromium and tantalum are required has so far been limited due to lack of availability of corresponding powders of high quality.
- Titanium metal base alloys and non-titanium metal base alloy powders are amongst the advanced materials, which are key to performance improvements and have many favorable properties such as high strength to weight ratio, good ductility and fracture toughness, high corrosion resistance and high melting point, making them important engineering materials for many applications in aerospace, chemical processing industry, architecture, and terrestrial systems.
- a major concern with titanium-based materials is high cost compared to competing materials.
- the present invention relates to a cost effective production of metal powders, metal alloy powders, intermetallic powders and/or their hydride powders, resulting in high levels of purity.
- the conventional method of producing titanium alloy powder today involves producing titanium sponge by the Kroll process, vacuum arc melting the sponge followed by gas atomising.
- the Kroll process involves the reaction of TiO 2 and carbon under chlorine gas at temperatures around 800° C., thus forming titanium chloride, TiCl 4 .
- TiCl 4 produced in the reaction is in the form of liquid and must first be purified by distillation. This means that this process is complex and uses products difficult to handle, such as Mg and/or chlorine.
- U.S. Pat. No. 6,264,719 discloses a method of producing a titanium-alumina composite, which results in the formation of Al 2 O 3 particles in a Ti-rich metallic or intermetallic phase.
- JP 05299216 relates to the preparation of rare earth based alloy magnetic material, and describes a method in which a rare earth oxide, a reducing agent, and a metal are mixed, a reduction-diffusion reaction treatment is conducted in a hydrogen-containing reducing atmosphere, and the obtained cake-like reaction product is cooled.
- the reducing atmosphere is switched to an inert gas atmosphere when the cake-like reaction product is cooled.
- This switch is conducted in the temperature window of 770 to 870° C. Conducting the switch in this specific temperature window is said to lead to the rare earth alloy product having good magnetic characteristics. In particular, conducting the switch in this temperature window is said to be important to ensure that the product does not contain any undesirable metal hydride product.
- WO2008/010733 describes a process for producing titanium alloy powders.
- TiO 2 and Al powder are mixed and heat-treated to form a TiAl/Al 2 O 3 metal matrix ceramic composite material.
- Said composite is further reduced in a second heat treatment step using CaH 2 .
- the present invention is based on the realization that it is possible to completely reduce metal oxides under hydrogen atmosphere, using calcium and/or calcium hydride granules or powders, at a specified temperature to obtain pure metal or metal alloy powders at a high rate.
- the process of the invention particularly in the context of the preferred metal oxides discussed herein, enables excellent control over the reaction conditions, meaning that there is no need to take extra steps that may have been employed in previous methods.
- extra steps may include the provision of “buffer” substances that do not contribute to the reaction step, to act as a buffer during heat absorption/generation in order to avoid sharp rises/falls in temperature.
- the process of the invention also enables the preparation of metal powders, metal alloy powders, intermetallic powders and/or their hydride powders, which are of a very high quality, particularly in terms of purity and particle size distribution.
- the process may be applied to the production of a wide range of metal containing powders, such as metal powders, metal hydride powders, and/or metal alloy powders.
- metal oxides in powder form, are mixed with a reducing agent, such as calcium or magnesium in powder form or in the form of granules.
- a reducing agent such as calcium or magnesium in powder form or in the form of granules.
- the powder mixture should preferably not be compacted.
- the powder mixture is heated to a temperature in the range of 1000° C. to 1500° C., and kept under a hydrogen atmosphere. This results in the formation of metal hydrides which are optionally subsequently dehydrated under a vacuum, or under an inert gas atmosphere (e.g. argon).
- the final product is of a higher purity than what is achieved with previously known technologies. This makes it possible to use the resulting metal powder in a variety of different applications within the powder metallurgy industry.
- FIG. 1 is an SEM micrograph of the final product powder from TiO 2 +1.3XCa granules at 1100° C., 2 hr under argon gas atmosphere.
- FIG. 2 shows an EDS spectrum of the final product powder from TiO 2 +1.3XCa granules at 1100° C., 2 hr under argon gas atmosphere.
- FIG. 3 shows an XRD pattern of the final product material for the reduction of TiO 2 and 1.2XCa granules heat treated at 1100° C. for 2 hrs under argon gas protection.
- FIG. 4 is an SEM micrograph of the final product powder from TiO 2 +1.3X Ca granules at 1100° C., 2 hr under H 2 then switched to Ar gas.
- FIG. 5 shows an EDS spectrum of the final product powder from TiO 2 +1.3X Ca granules at 1100° C., 2 hr under H 2 then switched to Ar gas
- FIG. 6 shows the XRD pattern of the final product powder from TiO 2 +1.3xCa granules at 1100° C., 2hr under H 2 gas then switched to argon gas.
- the XRD pattern shows that titanium metal is the major constituent in the final product, with little or no contaminants.
- FIG. 7 is an SEM micrograph of the Cr from the Cr203 and 1.3X CaH 2 powder at 1100° C. for 2 hrs under H 2 gas for both heating and cooling sessions.
- the particles have a spheroidal shape.
- FIG. 8 shows the EDS spectrum of the final product powder from the Cr 2 O 3 and 1.3X CaH 2 powder at 1100° C. for 2 hrs under H 2 gas for both heating and cooling sessions.
- FIG. 9 shows the XRD of the final product of chromium powder from the Cr 2 O 3 and 1.3X CaH 2 powder at 1100° C. for 2 hrs under H 2 gas for both heating and cooling sessions.
- FIG. 10 is an SEM micrograph of Nb metal powder from Nb 2 O 5 +1.2CaH 2 -heating Ar for both heating and cooling sessions.
- FIG. 11 shows an EDS spectrum of the final product powder Nb 2 O 5 +1.2CaH 2 -heating Ar for both heating and cooling sessions.
- FIG. 12 is an SEM micrograph of tantalum powder made according to Example 12.
- the invention concerns a cost-efficient method of producing metal powders and their hydrides or alloys consisting or comprising the following steps:
- the present invention provides a process for manufacturing metal containing powder, the process comprising the steps of:
- the metal containing powder is a metal hydride powder or a hydride of a metal alloy or intermetallic.
- the invention provides a process as defined above, wherein metal hydride powder is recovered.
- the present invention provides a process for manufacturing metal hydride powder, comprising the steps of;
- the metal containing powder is a metal powder, a metal alloy or an intermetallic.
- the invention provides a process as defined above, further further comprising between steps (b) and (c):
- step (a) comprises mixing at least one metal oxide powder with Ca or Mg granules and/or calcium hydride or magnesium hydride in granule or powder form to form a mixture.
- Said at least one metal oxide is preferably chosen from oxides of:
- said at least one metal oxide is chosen from oxides of Sc, Ti, V, Cr, Mn, Y, Zr, Nb, Hf, Ta, rare earth metals, Th, U, and/or Si.
- oxides which may be used as starting material are oxides of Al, In, Sb, Sn, Ge, Bi, and/or Pb.
- oxides which may be used as starting material are oxides of Ti, Cr, Al, V, La, Nb and/or Ta.
- the temperature range in which to maintain the mixture under an H 2 atmosphere is preferably between 1000° C. and 1500° C., more preferably 1020° C. and 1400° C., more preferably 1020° C. and 1300° C., more preferably 1020° C. and 1200° C., still more preferably 1020° C. and 1100° C.
- the time for which the mixture is maintained under an H 2 atmosphere is preferably 1-10 hours, more preferably 1-5 hours, more preferably 2-4 hours and most preferably around 3 hours.
- the invention provides a process for manufacturing metal hydride powder, comprising the steps of:
- the invention also provides a process for manufacturing metal powder, comprising steps a) and b) above, followed by;
- step d) involves maintaining the mixture under a temperature of from 1000° C. to 1500° C., preferably 1020° C. to 1400° C., more preferably 1020° C. to 1300° C., yet more preferably 1020° C. to 1200° C., and yet more preferably still 1020° C. to 1100° C.
- the temperature maintained in step d) is substantially the same as that used in step b).
- the mixture is maintained under an Ar atmosphere preferably for around 1 hour, but this may vary between 20 minutes and 5 hours, preferably 40 minutes to 3 hours, preferably 50 minutes to 2 hours, still more preferably 55 minutes to 80 minutes.
- the ratio between number of oxygen atoms in said metal oxide and the number of calcium atoms (O:Ca) is in the range of 1:1.7-1.1 or 1:1.5-1:1.1 or 1:1.5-1:1.05, or 1:1.4-1:2, or 1:1.2.
- said metal oxide powder is TiO 2 powder and said powder mixture is maintained in step b) under an H 2 atmosphere, at a temperature between 1020° C. and 1100° C. for around 3 hours.
- the invention also includes the metal powder or metal hydride powder produced according to the above methods.
- the invention provides a metal powder or metal hydride powder wherein the metal is as defined herein subject to being other than Ti.
- the invention includes a metal powder or metal hydride powder so produced, wherein the metal is Ti, Cr, Nb, or Ta. In a particularly preferred aspect the metal is Cr.
- the invention includes a metal powder or metal hydride powder so produced, wherein the metal is substantially free from oxygen.
- the invention includes a metal powder or metal hydride powder so produced, having an amount of oxygen lower than 0.35% by weight.
- metal oxide may also include metal particles that contain substantial amounts of oxygen in the form of dissolved oxygen, oxide inclusions and/or oxide coatings, in such amounts that make them unfit for use in production using PM techniques.
- the Ca or Mg granules are preferably in the size range of 0.03-2 mm.
- Ca hydride (CaH 2 ) and/or magnesium hydride granules in the same size range may also be used.
- the term “powder” is meant to describe a collection of particles having a size range of 50 nm-1 mm.
- Particle size distribution X50 (sometimes denoted D50) is also known as the median diameter or the medium value of the particle size distribution, and is the value of the particle diameter at 50% in the cumulative distribution.
- the particle size distribution of the products produced by the present method typically has an X50 of less than 40 ⁇ m, or less than 35 ⁇ m, or less than 25 ⁇ m, or less than 20 ⁇ m.
- Particle size and size distribution may be determined by e.g. light scattering.
- the amount of contaminants (e.g. oxygen or nitrogen) in the final product may be determined by combustion analysis and detection by way of IR absorption (to determine oxygen levels) or by thermic conductivity (to determine nitrogen levels).
- the starting materials may, in addition to only one metal oxide, also include one or more additional metal containing reagents, which could be one or more metals or metal oxides (preferably metal oxides).
- the final product may be a metal alloy or an intermetallic compound.
- metal alloy is therefore meant to include pure metals, metal alloys and also intermetallic compounds.
- elemental metal powders such as iron, aluminum, nickel, copper etc, may be added to the reaction mix to provide a source of additional elements (e.g. to provide alloying elements). Oxides of these elements may also be used, e.g. Fe 3 O 4 .
- the resulting end product is a metal alloy powder or intermetallic compound powder.
- the metal oxide powder is TiO 2 powder.
- the product is a hydride
- the product of step b is recovered (without the subsequent possible steps of switching to an Ar atmosphere, cooling under Ar atmosphere, and then recovering metal powder).
- the starting materials may, in addition to only one metal oxide, also include one or more additional metal containing reagents, which could be one or more metals or metal oxides (preferably metal oxides).
- the final product may be a metal alloy hydride or an intermetallic hydride compound.
- elemental metal powders such as iron, aluminum, nickel, copper etc, may be added to the reaction mix to provide a source of additional elements (e.g. to provide alloying elements). Oxides of these elements may also be used, e.g. Fe 3 O 4 .
- the resulting end product is a hydride of a metal alloy or intermetallic compound (in powder form).
- Said one or more additional metal containing reagents are preferably included in the reaction mixture in powder or granular form, most preferably powder form.
- the hydrogen may be part of a substantially regular crystalline structure, but alternatively the hydrogen may be contained within the metal(s) in the form of a solid solution.
- percentages given in connection with the content of a given component in an alloy preferably indicate percentages by weight
- percentages given in connection with the content of a given component of an intermetallic compound preferably indicate percentages by mol. Unless indicated otherwise, percentage figures mentioned herein follow this general rule.
- the metal oxides may be present on the surface of metal particles or components, e.g. as a surrounding layer on a metal particle having been exposed to oxidizing conditions.
- the powder mixture in step b is preferably maintained under an H 2 atmosphere, at a temperature between 1020° C. and 1100° C., preferably for 3 hours.
- a strong exothermic reaction is interpreted as an un-controlled, thermal runaway reaction. It is believed that such an uncontrolled exothermic reaction (e.g. self-ignition combustion synthesis) leads to less pure material.
- the resulting powders may be subjected to a drying step to remove water.
- the resulting metal powder typically has a particle size less than 25 ⁇ m. Furthermore, the metal powder is of high purity, having an oxygen content lower than 0.35%, by weight.
- furnace suitable for working under temperatures for the reduction reaction, i.e. up to 1500° C.
- the furnace should also be fitted with means for supplying various types of gases, or in some cases applying vacuum.
- a muffle open furnace was used to perform the heat treatment processes to achieve the reduction reaction of the oxides being used at different stages of work.
- a rectangular cross section crucible with a flat base was used.
- the crucible was made of high temperature resistant material such as e.g. chromium nickel steel (253 MA).
- the crucible was introduced to the furnace at each heat treatment process.
- the heat treatment was performed at different temperatures and time according to the examples below.
- the real temperature of the furnace was measured using a thermocouple to compare it with the set temperature.
- the difference in temperature between real temperature and set temperature was below 10° C.
- Containers filled with water were used for washing.
- the intermediate product after heat treatment was added to the water and washed.
- the containers were equipped with stirrers to stir the mixture of water and the intermediate material.
- Acetic acid was added to the slurry with continuous stirring.
- Calcium hydride may be prepared from its elements by direct combination of calcium and hydrogen at 300 to 400° C. Calcium granules were obtained from Mashinostroitelny Zavod (Elektrostal, Moskovskaya oblast,144001, Russia).
- the amount of contaminants e.g. oxygen or nitrogen
- the amount of contaminants was determined by combustion analysis, followed by detection by way of IR absorption (to determine oxygen levels) or by thermic conductivity (to determine nitrogen levels).
- the io instrument used was a LECO TC436DR.
- the calcium content was 2.9% as shown by ICP analysis.
- This example was carried out with the above mentioned heat treatment conditions with the only exception of heating being carried out under hydrogen gas and for 2hrs also, and then switched to argon gas.
- the resulting titanium powder particles had a particle size with X50 of 117.64 ⁇ m, and did not form agglomerates.
- the oxygen content was 0.30%, nitrogen content 0.08%, and hydrogen content 0.28%.
- XRD pattern showed that titanium was obtained without impurities. This confirms that heat treatment of the TiO 2 and calcium granules at the same heat treatment conditions but under hydrogen gas protection and then performing the dehydrogenation under argon atmosphere was successful.
- the calcium content was 0.25% as shown by ICP analysis.
- TiO 2 100 gram
- CaH 2 granules 145 gram
- TiO 2 in Powder Form Aldrich
- CaH 2 Granules 0.4- ⁇ 2 mm
- the mixture was heated at 1100° C. during 2 hrs under hydrogen gas in an open muffle furnace. After heating, the mixture was cooled for one hour under argon atmosphere.
- the resulting titanium powder particles had a particle size with X50 of 20.06 ⁇ m, and did not form agglomerates.
- the oxygen content was 0.27%, nitrogen content 0.016%, and hydrogen content 0.17%.
- XRD pattern showed that titanium was obtained without impurities.
- the calcium content was 0.22% as shown by ICP analysis.
- the resulting titanium hydride powder particles had a particle size with X50 of 6.35 ⁇ m, and did not form agglomerates.
- the oxygen content was 0.17%, nitrogen content 0.73%, and hydrogen content 3.63%.
- XRD pattern showed that titanium hydride was obtained without impurities.
- the calcium content was 0.17% as shown by ICP analysis.
- the mixture was heated at 1100° C. during 2 hrs under hydrogen gas in an open muffle furnace. Both heating and cooling sessions were performed under hydrogen gas protection.
- the resulting chromium metal powder particles had a particle size with X50 of 5.93 ⁇ m, and did not form agglomerates.
- the oxygen content was 0.08%, nitrogen content 0.003%, and hydrogen content 0.006%.
- XRD pattern showed that chromium was obtained without impurities.
- the calcium content was 0.004% as shown by ICP analysis.
- the resulting titanium hydride powder particles had a particle size with X50 of 8.06 ⁇ m, and did not form agglomerates.
- the oxygen content was 0.12%, nitrogen content 0.72%, and hydrogen content 3.42% .
- XRD pattern showed that titanium io hydride was obtained without impurities.
- the calcium content was 0.19% as shown by ICP analysis.
- the mixture was heated at 1100° C. during 2 hrs under hydrogen gas, followed by argon gas, in an open muffle furnace.
- the resulting Ti19Al powder particles had a particle size with X50 of 16.4 ⁇ m, and did not form agglomerates.
- the oxygen content was 0.28%, nitrogen content 0.03%, and hydrogen content 0.27%.
- XRD pattern showed that Ti19Al was obtained without impurities.
- the calcium content was 0.03% as shown by ICP analysis.
- the resulting ferrotitanium powder particles had a particle size with X50 of 10.69 ⁇ m, and did not form agglomerates.
- the oxygen content was 0.13%, nitrogen content 0.06%, and hydrogen content 2.07%.
- XRD pattern showed that ferro titanium hydride powder was obtained without impurities.
- the calcium content was 0.026% as shown by ICP analysis
- TiO 2 in powder form (Aldrich) was mixed with 7.1 grams of V 2 O 5 powder and 6 gram of Al(Aldrich) powders were mixed with 245 grams of CaH 2 granules (Höganäs AB) size of 0.4- ⁇ 2 mm.
- the mixture was heated at 1100° C. during 3 hrs under hydrogen gas, then switched to argon gas environment, in an open muffle furnace.
- the switching of gases was performed in the open muffle furnace, with no need for transfer to another furnace for the dehydrogenation processing step.
- the resulting Ti6Al4V powder particles had a particle size with X50 of 9.73 ⁇ m, and did not form agglomerates.
- the oxygen content was 0.24%, nitrogen content 0.05%, and hydrogen content 0.08%.
- XRD pattern showed that Ti6Al4V was obtained without impurities.
- the calcium content was 0.017% as shown by ICP analysis
- the mixture was heated at 1080° C. for a period of 6 hrs under hydrogen gas protection, then switched to argon gas environment, in an open muffle furnace. Switching gases performed in the same furnace, with no need for another furnace foe dehydrogenation processing step.
- the resulting LaNi 5 powder particles had a particle size with X50 of 9.57 ⁇ m, and did not form agglomerates.
- the oxygen content was 0.17%, nitrogen content 0.08%, and hydrogen content 0.04%.
- XRD pattern showed that LaNi 5 was obtained without impurities.
- the calcium content was 0.06% as shown by ICP analysis
- Niobium metal powder was produced using heat treatment at 1050° C. of the starting materials Nb 2 O 5 and CaH 2 granules (as 1.2 of the stoichiometric ratio) for 2 hrs under hydrogen followed by switching gases for the cooling session to be performed under argon gas protection.
- Tantalum metal powder from Ta 2 O 5 and CaH 2 granules (as 1.2 of the stoichiometric ratio). Heat treatment was at 1050° C. for 2 hrs. Heating was under hydrogen gas protection followed by switching to argon gas environment (in the same furnace without changing the furnace) for the dehydrogenation. SEM micrographs showed that the material is consisted of different sizes of agglomerates. These agglomerates were mostly consisted of very fine size particles but with few big sizes of the large agglomerates. In general the agglomerates were of very fine particles sizes as shown in FIG. 12 .
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Abstract
A process for manufacturing metal containing powder, the process including the steps of: (a) mixing at least one metal oxide powder with Ca or Mg granules and/or calcium hydride in granule or powder form to form a mixture; (b) maintaining said mixture under an H2 atmosphere, at a temperature between 1000° C. and 1500° C. for 1-10 hours, followed by: (c) recovering metal containing powder. Metal hydride powder may be recovered. The process may further include between steps (b) and (c): (d) switching the H2 atmosphere to an Ar atmosphere and maintaining the mixture thereunder for a period of 20 minutes to 5 hours, followed by: (e) cooling under Ar atmosphere, wherein metal powder is recovered in step (c).
Description
- The present invention concerns a new method for producing metal powders, metal alloy powders, intermetallic powders and/or their hydride powders, by a simplified, cost efficient process, preferably by performing the reduction reaction of metal oxides under hydrogen gas protection, using specific reducing agents and specific reduction conditions.
- Powder metallurgical (PM) techniques are well established routes for efficient production of complex metal based components. These techniques are commonly used in applications where alloys based on iron, stainless steel, copper or nickel are required. However, the use of PM techniques where material such as titanium, chromium and tantalum are required has so far been limited due to lack of availability of corresponding powders of high quality.
- Titanium metal base alloys and non-titanium metal base alloy powders are amongst the advanced materials, which are key to performance improvements and have many favorable properties such as high strength to weight ratio, good ductility and fracture toughness, high corrosion resistance and high melting point, making them important engineering materials for many applications in aerospace, chemical processing industry, architecture, and terrestrial systems. However, a major concern with titanium-based materials is high cost compared to competing materials.
- The present invention relates to a cost effective production of metal powders, metal alloy powders, intermetallic powders and/or their hydride powders, resulting in high levels of purity.
- The conventional method of producing titanium alloy powder today involves producing titanium sponge by the Kroll process, vacuum arc melting the sponge followed by gas atomising. The Kroll process involves the reaction of TiO2 and carbon under chlorine gas at temperatures around 800° C., thus forming titanium chloride, TiCl4.
- TiCl4 produced in the reaction is in the form of liquid and must first be purified by distillation. This means that this process is complex and uses products difficult to handle, such as Mg and/or chlorine.
- There have been many attempts to produce titanium alloys in a more cost efficient way, but attempts so far require the use of more than one heat treatment step, lasting for several hours.
- U.S. Pat. No. 6,264,719 discloses a method of producing a titanium-alumina composite, which results in the formation of Al2O3 particles in a Ti-rich metallic or intermetallic phase.
- JP 05299216 relates to the preparation of rare earth based alloy magnetic material, and describes a method in which a rare earth oxide, a reducing agent, and a metal are mixed, a reduction-diffusion reaction treatment is conducted in a hydrogen-containing reducing atmosphere, and the obtained cake-like reaction product is cooled. The reducing atmosphere is switched to an inert gas atmosphere when the cake-like reaction product is cooled. This switch is conducted in the temperature window of 770 to 870° C. Conducting the switch in this specific temperature window is said to lead to the rare earth alloy product having good magnetic characteristics. In particular, conducting the switch in this temperature window is said to be important to ensure that the product does not contain any undesirable metal hydride product.
- There is no suggestion that any intermediate metal hydride product that may form during the reduction step would have any useful attributes.
- WO2008/010733 describes a process for producing titanium alloy powders. In a first heat treatment step TiO2 and Al powder are mixed and heat-treated to form a TiAl/Al2O3 metal matrix ceramic composite material. Said composite is further reduced in a second heat treatment step using CaH2.
- Attempts have also been made to produce various metal powders from their metal oxides by using the so-called self-ignition synthesis method. (Akiyama et al). These methods usually lead to products which suffer from low purity.
- Consequently, there is still a need for a more cost efficient process to produce high quality metal powders, metal alloy powders, intermetallic powders and/or their hydride powders, with high purity.
- The present invention is based on the realization that it is possible to completely reduce metal oxides under hydrogen atmosphere, using calcium and/or calcium hydride granules or powders, at a specified temperature to obtain pure metal or metal alloy powders at a high rate. Surprisingly, it has been found that the process of the invention, particularly in the context of the preferred metal oxides discussed herein, enables excellent control over the reaction conditions, meaning that there is no need to take extra steps that may have been employed in previous methods. Such extra steps may include the provision of “buffer” substances that do not contribute to the reaction step, to act as a buffer during heat absorption/generation in order to avoid sharp rises/falls in temperature. The process of the invention also enables the preparation of metal powders, metal alloy powders, intermetallic powders and/or their hydride powders, which are of a very high quality, particularly in terms of purity and particle size distribution. The process may be applied to the production of a wide range of metal containing powders, such as metal powders, metal hydride powders, and/or metal alloy powders.
- As starting materials, metal oxides, in powder form, are mixed with a reducing agent, such as calcium or magnesium in powder form or in the form of granules. The powder mixture should preferably not be compacted. The powder mixture is heated to a temperature in the range of 1000° C. to 1500° C., and kept under a hydrogen atmosphere. This results in the formation of metal hydrides which are optionally subsequently dehydrated under a vacuum, or under an inert gas atmosphere (e.g. argon).
- The invention is defined in the claims.
- The final product is of a higher purity than what is achieved with previously known technologies. This makes it possible to use the resulting metal powder in a variety of different applications within the powder metallurgy industry.
- The invention will now be described by way of non-limitative example only, with reference to the accompanying drawings, in which:
-
FIG. 1 is an SEM micrograph of the final product powder from TiO2+1.3XCa granules at 1100° C., 2 hr under argon gas atmosphere. -
FIG. 2 shows an EDS spectrum of the final product powder from TiO2+1.3XCa granules at 1100° C., 2 hr under argon gas atmosphere. -
FIG. 3 shows an XRD pattern of the final product material for the reduction of TiO2 and 1.2XCa granules heat treated at 1100° C. for 2 hrs under argon gas protection. - The above XRD pattern showed that titanium was the first major phase of material, but in the same time showed calcium titanium oxide as the second phase of material. This means that the reduction reaction process was not successfully processed under the above mentioned conditions.
-
FIG. 4 is an SEM micrograph of the final product powder from TiO2+1.3X Ca granules at 1100° C., 2 hr under H2 then switched to Ar gas. -
FIG. 5 shows an EDS spectrum of the final product powder from TiO2+1.3X Ca granules at 1100° C., 2 hr under H2 then switched to Ar gas -
FIG. 6 shows the XRD pattern of the final product powder from TiO2+1.3xCa granules at 1100° C., 2hr under H2 gas then switched to argon gas. The XRD pattern shows that titanium metal is the major constituent in the final product, with little or no contaminants. -
FIG. 7 is an SEM micrograph of the Cr from the Cr203 and 1.3X CaH2 powder at 1100° C. for 2 hrs under H2 gas for both heating and cooling sessions. The particles have a spheroidal shape. -
FIG. 8 shows the EDS spectrum of the final product powder from the Cr2O3 and 1.3X CaH2 powder at 1100° C. for 2 hrs under H2 gas for both heating and cooling sessions. -
FIG. 9 shows the XRD of the final product of chromium powder from the Cr2O3 and 1.3X CaH2 powder at 1100° C. for 2 hrs under H2 gas for both heating and cooling sessions. -
FIG. 10 is an SEM micrograph of Nb metal powder from Nb2O5+1.2CaH2-heating Ar for both heating and cooling sessions. -
FIG. 11 shows an EDS spectrum of the final product powder Nb2O5+1.2CaH2-heating Ar for both heating and cooling sessions. -
FIG. 12 is an SEM micrograph of tantalum powder made according to Example 12. The invention concerns a cost-efficient method of producing metal powders and their hydrides or alloys consisting or comprising the following steps: - The present invention provides a process for manufacturing metal containing powder, the process comprising the steps of:
-
- a. mixing at least one metal oxide powder with Ca, Mg, calcium hydride, magnesium hydride or a mixture thereof, in the form of granules or powder;
- b. maintaining said mixture under an H2 atmosphere, at a temperature between 1000° C. and 1500° C. for 1-10 hours; then
- c. recovering metal containing powder.
- In one aspect the metal containing powder is a metal hydride powder or a hydride of a metal alloy or intermetallic. In this aspect, the invention provides a process as defined above, wherein metal hydride powder is recovered.
- The present invention provides a process for manufacturing metal hydride powder, comprising the steps of;
-
- a. mixing at least one metal oxide powder with Ca or Mg granules and/or calcium hydride in granule or powder form to form a mixture;
- b. maintaining said mixture under an H2 atmosphere, at a temperature between 1020° C. and 1100° C. for 2-4 hours, followed by;
- c. recovering metal hydride powder.
- In another aspect the metal containing powder is a metal powder, a metal alloy or an intermetallic. In this aspect, the invention provides a process as defined above, further further comprising between steps (b) and (c):
-
- (d) switching the H2 atmosphere to an Ar atmosphere and maintaining the mixture thereunder for a period of from 20 minutes to 5 hours (preferably at least 1 hour, typically around 1 hour), followed by:
- (e) cooling under Ar atmosphere,
wherein metal powder is recovered in step (c).
- In one aspect, step (a) comprises mixing at least one metal oxide powder with Ca or Mg granules and/or calcium hydride or magnesium hydride in granule or powder form to form a mixture.
- Said at least one metal oxide is preferably chosen from oxides of:
-
- Al, Si, Ti, V, Cr, Mn, Ge, Zr, Nb, In, Sn, Sb, Hf, Ta, W, Pb, Bi, rare earth metals (i.e. Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb), Th and/or U;
- more preferably Al, Si, Ti, V, Cr, Mn, Ge, Zr, Nb, In, Sn, Sb, Hf, Ta, W, Pb, Bi, Th and/or U;
- yet more preferably Al, Si, Ti, Cr, Mn, Ge, Zr, Nb, In, Sn, Sb, Hf, Ta, W, Pb, Bi, Th and/or U;
- yet more preferably still Ti, Cr, Nb, Ta, and/or W; and
- most preferably Ti, Cr, Nb and/or Ta.
- In one embodiment said at least one metal oxide is chosen from oxides of Sc, Ti, V, Cr, Mn, Y, Zr, Nb, Hf, Ta, rare earth metals, Th, U, and/or Si. In another embodiment oxides which may be used as starting material are oxides of Al, In, Sb, Sn, Ge, Bi, and/or Pb. In another embodiment oxides which may be used as starting material are oxides of Ti, Cr, Al, V, La, Nb and/or Ta.
- The above preferences for the metal(s) present in the metal oxide(s) apply correspondingly to the metal(s) present in the product.
- The temperature range in which to maintain the mixture under an H2 atmosphere is preferably between 1000° C. and 1500° C., more preferably 1020° C. and 1400° C., more preferably 1020° C. and 1300° C., more preferably 1020° C. and 1200° C., still more preferably 1020° C. and 1100° C.
- The time for which the mixture is maintained under an H2 atmosphere is preferably 1-10 hours, more preferably 1-5 hours, more preferably 2-4 hours and most preferably around 3 hours.
- More particularly, the invention provides a process for manufacturing metal hydride powder, comprising the steps of:
-
- a) mixing at least one metal oxide powder with Ca or Mg granules or powder and/or calcium hydride or magnesium hydride in granule or powder form, to form a mixture;
- b) maintaining said mixture under an H2 atmosphere, at a temperature between 1020° C. and 1100° C. for 2-4 hours, followed by;
- c) recovering metal hydride powder.
- The invention also provides a process for manufacturing metal powder, comprising steps a) and b) above, followed by;
-
- d) switching the H2 atmosphere to an Ar atmosphere and maintaining the mixture thereunder for a period of at least 1 hour, followed by:
- e) cooling under Ar atmosphere, and;
- f) recovering metal powder.
- In this regard, step d) involves maintaining the mixture under a temperature of from 1000° C. to 1500° C., preferably 1020° C. to 1400° C., more preferably 1020° C. to 1300° C., yet more preferably 1020° C. to 1200° C., and yet more preferably still 1020° C. to 1100° C. Typically, the temperature maintained in step d) is substantially the same as that used in step b).
- The mixture is maintained under an Ar atmosphere preferably for around 1 hour, but this may vary between 20 minutes and 5 hours, preferably 40 minutes to 3 hours, preferably 50 minutes to 2 hours, still more preferably 55 minutes to 80 minutes.
- Optionally, the ratio between number of oxygen atoms in said metal oxide and the number of calcium atoms (O:Ca) is in the range of 1:1.7-1.1 or 1:1.5-1:1.1 or 1:1.5-1:1.05, or 1:1.4-1:2, or 1:1.2.
- Optionally, said metal oxide powder is TiO2 powder and said powder mixture is maintained in step b) under an H2 atmosphere, at a temperature between 1020° C. and 1100° C. for around 3 hours.
- The invention also includes the metal powder or metal hydride powder produced according to the above methods.
- In one aspect the invention provides a metal powder or metal hydride powder wherein the metal is as defined herein subject to being other than Ti. The invention includes a metal powder or metal hydride powder so produced, wherein the metal is Ti, Cr, Nb, or Ta. In a particularly preferred aspect the metal is Cr.
- The invention includes a metal powder or metal hydride powder so produced, wherein the metal is substantially free from oxygen.
- The invention includes a metal powder or metal hydride powder so produced, having an amount of oxygen lower than 0.35% by weight.
- The term “metal oxide” may also include metal particles that contain substantial amounts of oxygen in the form of dissolved oxygen, oxide inclusions and/or oxide coatings, in such amounts that make them unfit for use in production using PM techniques.
- The Ca or Mg granules are preferably in the size range of 0.03-2 mm. Ca hydride (CaH2) and/or magnesium hydride granules in the same size range may also be used.
- As defined herein, the term “powder” is meant to describe a collection of particles having a size range of 50 nm-1 mm.
- Particle size distribution X50 (sometimes denoted D50) is also known as the median diameter or the medium value of the particle size distribution, and is the value of the particle diameter at 50% in the cumulative distribution. The particle size distribution of the products produced by the present method typically has an X50 of less than 40 μm, or less than 35 μm, or less than 25 μm, or less than 20 μm. Particle size and size distribution may be determined by e.g. light scattering.
- The X50 distribution is discussed at pages 216-218 of “Metals Handbook”, 9th Edition, Volume 7, Powder Metallurgy, American Society for Metals, Metals Park, Ohio 44073, ISBN 0-87170-013-1.
- The amount of contaminants (e.g. oxygen or nitrogen) in the final product may be determined by combustion analysis and detection by way of IR absorption (to determine oxygen levels) or by thermic conductivity (to determine nitrogen levels).
- The starting materials may, in addition to only one metal oxide, also include one or more additional metal containing reagents, which could be one or more metals or metal oxides (preferably metal oxides). In that case, the final product may be a metal alloy or an intermetallic compound. Preferably it is a metal alloy. The term “metal powder” is therefore meant to include pure metals, metal alloys and also intermetallic compounds. In this regard, elemental metal powders such as iron, aluminum, nickel, copper etc, may be added to the reaction mix to provide a source of additional elements (e.g. to provide alloying elements). Oxides of these elements may also be used, e.g. Fe3O4. The resulting end product is a metal alloy powder or intermetallic compound powder. In a preferred embodiment, the metal oxide powder is TiO2 powder.
- Similar considerations apply to embodiments of the invention in which the product is a hydride, i.e. wherein the product of step b is recovered (without the subsequent possible steps of switching to an Ar atmosphere, cooling under Ar atmosphere, and then recovering metal powder). Thus, the starting materials may, in addition to only one metal oxide, also include one or more additional metal containing reagents, which could be one or more metals or metal oxides (preferably metal oxides). In that case, the final product may be a metal alloy hydride or an intermetallic hydride compound. In this regard, elemental metal powders such as iron, aluminum, nickel, copper etc, may be added to the reaction mix to provide a source of additional elements (e.g. to provide alloying elements). Oxides of these elements may also be used, e.g. Fe3O4. The resulting end product is a hydride of a metal alloy or intermetallic compound (in powder form).
- Said one or more additional metal containing reagents are preferably included in the reaction mixture in powder or granular form, most preferably powder form.
- When the product of the method of the invention is a hydride, the hydrogen may be part of a substantially regular crystalline structure, but alternatively the hydrogen may be contained within the metal(s) in the form of a solid solution.
- As a general rule, percentages given in connection with the content of a given component in an alloy preferably indicate percentages by weight, and percentages given in connection with the content of a given component of an intermetallic compound preferably indicate percentages by mol. Unless indicated otherwise, percentage figures mentioned herein follow this general rule.
- The metal oxides may be present on the surface of metal particles or components, e.g. as a surrounding layer on a metal particle having been exposed to oxidizing conditions.
- The powder mixture in step b is preferably maintained under an H2 atmosphere, at a temperature between 1020° C. and 1100° C., preferably for 3 hours.
- It is preferred to perform the reduction under conditions which will avoid the initiation of a strong exothermic reaction. In this sense, a “strong” exothermic reaction is interpreted as an un-controlled, thermal runaway reaction. It is believed that such an uncontrolled exothermic reaction (e.g. self-ignition combustion synthesis) leads to less pure material.
- These unwanted reactions can be avoided by e.g. using a specific ratio between oxygen and calcium, and optionally maintaining the reactants in non-compacted form. Furthermore, the reduction reaction should ideally take place under hydrogen atmosphere. In case a compacted form of reactants is to be used, this should ideally be in the form of thin plates, pellets, or granules.
- The resulting powders may be subjected to a drying step to remove water. The resulting metal powder typically has a particle size less than 25 μm. Furthermore, the metal powder is of high purity, having an oxygen content lower than 0.35%, by weight.
- The equipment used to perform the experimental work was as follows:
- Any type of furnace suitable for working under temperatures for the reduction reaction, i.e. up to 1500° C. may be used. The furnace should also be fitted with means for supplying various types of gases, or in some cases applying vacuum. For the work herein, a muffle open furnace was used to perform the heat treatment processes to achieve the reduction reaction of the oxides being used at different stages of work.
- A rectangular cross section crucible with a flat base was used. The crucible was made of high temperature resistant material such as e.g. chromium nickel steel (253 MA). The crucible was introduced to the furnace at each heat treatment process.
- The heat treatment was performed at different temperatures and time according to the examples below. The real temperature of the furnace was measured using a thermocouple to compare it with the set temperature. The difference in temperature between real temperature and set temperature was below 10° C.
- Containers filled with water were used for washing. The intermediate product after heat treatment was added to the water and washed. The containers were equipped with stirrers to stir the mixture of water and the intermediate material. Acetic acid was added to the slurry with continuous stirring.
- After washing, the resulting powder were dried to yield the final product. Starting materials used for making different metals, metal hydrides and their alloy powder were as follows:
-
TABLE 1 Starting materials used in the following examples. Powder Purity Particle Size Manufacturer Aluminum Powder 99.5% −325 mesh Aldrich Rutile (TiO2) powder 99% −325 mesh Aldrich Ca granules 99.5% 0.04-2 mm Mashinostroitelny Zavod CaH2 granules 99.5% 0.04-1 mm Hoganas Cr2O3 powder 98% <50 micron Aldrich Fe3O4 powder 98% <20 micron Hoganas Fe powder 99% −325 mesh Hoganas V2O5 powder 99.6% −325 mesh Aldrich CaH2 powder 99.5% −325 mesh Aldrich - Calcium hydride may be prepared from its elements by direct combination of calcium and hydrogen at 300 to 400° C. Calcium granules were obtained from Mashinostroitelny Zavod (Elektrostal, Moskovskaya oblast,144001, Russia).
- The amount of contaminants (e.g. oxygen or nitrogen) was determined by combustion analysis, followed by detection by way of IR absorption (to determine oxygen levels) or by thermic conductivity (to determine nitrogen levels). The io instrument used was a LECO TC436DR.
- Comparative example of preparation of titanium from TiO2 powder and calcium granules as starting materials.
- 100 g TiO2 in powder form, 99% purity, 325 mesh, (Aldrich) was mixed with 130 g grams of calcium granules 0.4-2 mm (Mashinostroitel'nyi zavod, Russia). The powder and granules were mixed thoroughly and placed in a crucible as described above. The mixture was heated at 1100° C. during 2 hrs under argon gas in an open muffle furnace. The resulting titanium powder particles had a particle size with X50 of 35 μm, and formed agglomerates. The oxygen content was 2.7%, nitrogen content 0.38%, and hydrogen content 0.26%. The XRD pattern showed that titanium is the first major phase of material, and also showed that calcium titanium oxide is the second phase of material. This means that the reduction reaction process was not fully processed under the above mentioned conditions.
- The calcium content was 2.9% as shown by ICP analysis.
- This example was carried out with the above mentioned heat treatment conditions with the only exception of heating being carried out under hydrogen gas and for 2hrs also, and then switched to argon gas. The resulting titanium powder particles had a particle size with X50 of 117.64 μm, and did not form agglomerates. The oxygen content was 0.30%, nitrogen content 0.08%, and hydrogen content 0.28%. XRD pattern showed that titanium was obtained without impurities. This confirms that heat treatment of the TiO2 and calcium granules at the same heat treatment conditions but under hydrogen gas protection and then performing the dehydrogenation under argon atmosphere was successful.
- The calcium content was 0.25% as shown by ICP analysis.
- The mixture was heated at 1100° C. during 2 hrs under hydrogen gas in an open muffle furnace. After heating, the mixture was cooled for one hour under argon atmosphere.
- The resulting titanium powder particles had a particle size with X50 of 20.06 μm, and did not form agglomerates. The oxygen content was 0.27%, nitrogen content 0.016%, and hydrogen content 0.17%. XRD pattern showed that titanium was obtained without impurities.
- The calcium content was 0.22% as shown by ICP analysis.
- 100 grams of TiO2 in powder form (Aldrich) was mixed with 145 grams of calcium hydride granules, size of 0.4-2 mm (Höganäs AB). The mixture of powders and granules was heated at 1100° C. during 2 hrs under hydrogen gas in an open muffle furnace. After heating, the mixture was cooled for one hour under hydrogen atmosphere.
- The resulting titanium hydride powder particles had a particle size with X50 of 6.35 μm, and did not form agglomerates. The oxygen content was 0.17%, nitrogen content 0.73%, and hydrogen content 3.63%. XRD pattern showed that titanium hydride was obtained without impurities.
- The calcium content was 0.17% as shown by ICP analysis.
- The mixture was heated at 1100° C. during 2 hrs under hydrogen gas in an open muffle furnace. Both heating and cooling sessions were performed under hydrogen gas protection.
- The resulting chromium metal powder particles had a particle size with X50 of 5.93 μm, and did not form agglomerates. The oxygen content was 0.08%, nitrogen content 0.003%, and hydrogen content 0.006%. XRD pattern showed that chromium was obtained without impurities.
- The calcium content was 0.004% as shown by ICP analysis.
- 100 grams of TiO2 in powder form(Aldrich) was mixed with 145 grams of calcium hydride powder at −325 mesh(Aldrich). The mixture was heated at 1100° C. during 2 hrs under hydrogen gas in an open muffle furnace. Both heating and cooling sessions were maintained under hydrogen gas protection.
- The resulting titanium hydride powder particles had a particle size with X50 of 8.06 μm, and did not form agglomerates. The oxygen content was 0.12%, nitrogen content 0.72%, and hydrogen content 3.42% . XRD pattern showed that titanium io hydride was obtained without impurities.
- The calcium content was 0.19% as shown by ICP analysis.
- 135 grams of TiO2 in powder form(Aldrich) was mixed with 19 grams of Al powder(Aldrich) was mixed with 141.7 grams of calcium granules (Mashinostroitel'nyi zavod, Russia).
- The mixture was heated at 1100° C. during 2 hrs under hydrogen gas, followed by argon gas, in an open muffle furnace.
- The resulting Ti19Al powder particles had a particle size with X50 of 16.4 μm, and did not form agglomerates. The oxygen content was 0.28%, nitrogen content 0.03%, and hydrogen content 0.27%. XRD pattern showed that Ti19Al was obtained without impurities.
- The calcium content was 0.03% as shown by ICP analysis.
- 103.5 grams of TiO2 in powder form (Aldrich) was mixed with 100 grams of Fe3O4 powder(Aldrich) was mixed with 218.1 grams of CaH2 powder (Aldrich). The mixture was heated at 1100° C. during 3hrs under hydrogen gas, in an open muffle furnace. Both heating and cooling processing steps were maintained under hydrogen gas protection.
- The resulting ferrotitanium powder particles had a particle size with X50 of 10.69 μm, and did not form agglomerates. The oxygen content was 0.13%, nitrogen content 0.06%, and hydrogen content 2.07%. XRD pattern showed that ferro titanium hydride powder was obtained without impurities.
- The calcium content was 0.026% as shown by ICP analysis
- 150 grams of TiO2 in powder form (Aldrich) was mixed with 7.1 grams of V2O5 powder and 6 gram of Al(Aldrich) powders were mixed with 245 grams of CaH2 granules (Höganäs AB) size of 0.4-<2 mm.
- The mixture was heated at 1100° C. during 3 hrs under hydrogen gas, then switched to argon gas environment, in an open muffle furnace. The switching of gases was performed in the open muffle furnace, with no need for transfer to another furnace for the dehydrogenation processing step.
- The resulting Ti6Al4V powder particles had a particle size with X50 of 9.73 μm, and did not form agglomerates. The oxygen content was 0.24%, nitrogen content 0.05%, and hydrogen content 0.08%. XRD pattern showed that Ti6Al4V was obtained without impurities.
- The calcium content was 0.017% as shown by ICP analysis
- 55.5 grams of La2O3 in powder form (Aldrich) was mixed with 100 grams of Ni powder were mixed with 43 grams of CaH2 granules (Höganäs AB) size of 0.4-2 mm.
- The mixture was heated at 1080° C. for a period of 6 hrs under hydrogen gas protection, then switched to argon gas environment, in an open muffle furnace. Switching gases performed in the same furnace, with no need for another furnace foe dehydrogenation processing step.
- The resulting LaNi5 powder particles had a particle size with X50 of 9.57 μm, and did not form agglomerates. The oxygen content was 0.17%, nitrogen content 0.08%, and hydrogen content 0.04%. XRD pattern showed that LaNi5 was obtained without impurities.
- The calcium content was 0.06% as shown by ICP analysis
- Niobium metal powder was produced using heat treatment at 1050° C. of the starting materials Nb2O5 and CaH2 granules (as 1.2 of the stoichiometric ratio) for 2 hrs under hydrogen followed by switching gases for the cooling session to be performed under argon gas protection.
- Tantalum metal powder from Ta2O5 and CaH2 granules (as 1.2 of the stoichiometric ratio). Heat treatment was at 1050° C. for 2 hrs. Heating was under hydrogen gas protection followed by switching to argon gas environment (in the same furnace without changing the furnace) for the dehydrogenation. SEM micrographs showed that the material is consisted of different sizes of agglomerates. These agglomerates were mostly consisted of very fine size particles but with few big sizes of the large agglomerates. In general the agglomerates were of very fine particles sizes as shown in
FIG. 12 .
Claims (12)
1. Process for manufacturing metal containing powder, the process comprising the steps of:
a. mixing at least one metal oxide powder with Ca, Mg, calcium hydride, magnesium hydride or a mixture thereof, in the form of granules or powder, to form a mixture;
b. maintaining said mixture under an H2 atmosphere, at a temperature between 1000° C. and 1500° C. for 1-10 hours, followed by:
c. recovering metal containing powder.
2. Process according to claim 1 , which is a process for manufacturing metal hydride powder, comprising the steps of:
a. mixing at least one metal oxide powder with Ca, Mg, calcium hydride, magnesium hydride or a mixture thereof, in the form of granules or powder, to form a mixture;
b. maintaining said mixture under an H2 atmosphere, at a temperature between 1020° C. and 1100° C. for 2-4 hours, followed by:
c. recovering metal hydride powder.
3. Process according to claim 1 , which is a process for manufacturing metal powder, comprising steps a) and b), followed by:
d. switching the H2 atmosphere to an Ar atmosphere and maintaining the mixture thereunder at a temperature between 1000° C. and 1500° C. for a period of from 20 minutes to 5 hours, followed by;
e. cooling under Ar atmosphere, and;
f. recovering metal powder.
4. Process according to claim 1 , wherein the ratio between number of oxygen atoms in said metal oxide and number of calcium atoms (O:Ca) is in the range of 1:1.7-1.1 or 1:1.5-1:1.1 or 1:1.5-1:1.05, or 1:1.4-1:2, or 1:1.2.
5. Process according to claim 1 , wherein the metal is Al, Si, Ti, V, Cr, Mn, Ge, Zr, Nb, In, Sn, Sb, Hf, Ta, W, Pb, Bi, rare earth metals (i.e. Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb), Th and/or U
6. Process according to claim 5 , wherein the metal is Ti, Cr, Nb, W, or Ta.
7. Process for manufacturing metal powder according to claim 1 , wherein:
said metal oxide powder is TiO2 powder and said powder mixture is maintained in step b) under an H2 atmosphere, at a temperature between 1020° C. and 1100° C. for 3 hours.
8. Process according to claim 1 , wherein step a comprises including one or more additional reagents within the mixture, said one or more additional reagents being one or more metals or metal oxides.
9. Metal powder or metal hydride powder produced according to claim 1 .
10. Metal powder or metal hydride powder according to claim 9 , wherein the metal is Ti, Cr, Nb, W, or Ta.
11. Metal powder or metal hydride powder according to claim 9 , wherein the metal is substantially free from oxygen.
12. Metal powder or metal hydride powder according to claim 1 , having an amount of oxygen lower than 0.35% by weight.
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AU2014330007C1 (en) | 2013-08-19 | 2018-05-10 | University Of Utah Research Foundation | Producing a titanium product |
CA2931842A1 (en) | 2013-11-26 | 2015-06-04 | Scoperta, Inc. | Corrosion resistant hardfacing alloy |
WO2015191458A1 (en) | 2014-06-09 | 2015-12-17 | Scoperta, Inc. | Crack resistant hardfacing alloys |
CN107532265B (en) | 2014-12-16 | 2020-04-21 | 思高博塔公司 | Ductile and wear resistant iron alloy containing multiple hard phases |
CN105063394B (en) * | 2015-08-06 | 2017-05-31 | 王海英 | A kind of preparation method of titanium or titanium alloy material |
CA2997367C (en) | 2015-09-04 | 2023-10-03 | Scoperta, Inc. | Chromium free and low-chromium wear resistant alloys |
JP7049244B2 (en) | 2015-09-08 | 2022-04-06 | エリコン メテコ(ユーエス)インコーポレイテッド | Non-magnetic strong carbide forming alloy for powder production |
US10954588B2 (en) | 2015-11-10 | 2021-03-23 | Oerlikon Metco (Us) Inc. | Oxidation controlled twin wire arc spray materials |
US9669464B1 (en) * | 2016-02-10 | 2017-06-06 | University Of Utah Research Foundation | Methods of deoxygenating metals having oxygen dissolved therein in a solid solution |
CA3017642A1 (en) | 2016-03-22 | 2017-09-28 | Scoperta, Inc. | Fully readable thermal spray coating |
CN109290586A (en) * | 2018-10-19 | 2019-02-01 | 重庆大学 | A kind of preparation method of high-purity vanadium powder |
EP3870727A1 (en) | 2018-10-26 | 2021-09-01 | Oerlikon Metco (US) Inc. | Corrosion and wear resistant nickel based alloys |
KR102028184B1 (en) * | 2018-12-18 | 2019-10-04 | 주식회사 엔에이피 | Method for preparing titanium metal powder or titanium alloy powder |
KR101991499B1 (en) * | 2018-12-18 | 2019-06-20 | 주식회사 엔에이피 | Method for preparing calcium hydride |
JP7285024B2 (en) * | 2019-07-08 | 2023-06-01 | 国立研究開発法人科学技術振興機構 | Method for producing metal oxyhydride, metal oxyhydride, and method for synthesizing ammonia using the same |
KR102205493B1 (en) * | 2019-09-25 | 2021-01-21 | 주식회사 엔에이피 | Method for preparing nonferrous metal powderr |
CN110802237B (en) * | 2019-09-29 | 2021-06-15 | 中南大学 | Preparation method of high-purity zirconium metal powder |
US10907239B1 (en) * | 2020-03-16 | 2021-02-02 | University Of Utah Research Foundation | Methods of producing a titanium alloy product |
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