JP4690638B2 - 耐熱金属酸化物のメタロサーミック還元 - Google Patents
耐熱金属酸化物のメタロサーミック還元 Download PDFInfo
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- JP4690638B2 JP4690638B2 JP2002587141A JP2002587141A JP4690638B2 JP 4690638 B2 JP4690638 B2 JP 4690638B2 JP 2002587141 A JP2002587141 A JP 2002587141A JP 2002587141 A JP2002587141 A JP 2002587141A JP 4690638 B2 JP4690638 B2 JP 4690638B2
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- powder
- metal
- reaction
- oxide
- magnesium
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- 150000004706 metal oxides Chemical class 0.000 title claims description 16
- 229910044991 metal oxide Inorganic materials 0.000 title claims description 15
- 239000003870 refractory metal Substances 0.000 title claims description 14
- 230000009467 reduction Effects 0.000 title description 45
- 239000000843 powder Substances 0.000 claims description 83
- 238000006243 chemical reaction Methods 0.000 claims description 58
- 238000006722 reduction reaction Methods 0.000 claims description 52
- 239000011777 magnesium Substances 0.000 claims description 50
- 229910052749 magnesium Inorganic materials 0.000 claims description 47
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- 239000003638 chemical reducing agent Substances 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 229910052758 niobium Inorganic materials 0.000 claims description 8
- 239000010955 niobium Substances 0.000 claims description 8
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 7
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical group [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 5
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 5
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 3
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims 2
- 229910001092 metal group alloy Inorganic materials 0.000 claims 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims 2
- 229940117975 chromium trioxide Drugs 0.000 claims 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000012535 impurity Substances 0.000 claims 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 description 46
- 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 26
- 239000011734 sodium Substances 0.000 description 26
- 229910052708 sodium Inorganic materials 0.000 description 26
- 239000008188 pellet Substances 0.000 description 22
- 239000002245 particle Substances 0.000 description 21
- 230000002829 reductive effect Effects 0.000 description 19
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 15
- 239000003990 capacitor Substances 0.000 description 14
- 238000009826 distribution Methods 0.000 description 13
- 239000011148 porous material Substances 0.000 description 10
- 238000011946 reduction process Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 229910052715 tantalum Inorganic materials 0.000 description 10
- 239000011575 calcium Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002048 anodisation reaction Methods 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229910001936 tantalum oxide Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910002593 Fe-Ti Inorganic materials 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910004446 Ta2 O5 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- IXQWNVPHFNLUGD-UHFFFAOYSA-N iron titanium Chemical compound [Ti].[Fe] IXQWNVPHFNLUGD-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- -1 oxides Chemical class 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003482 tantalum compounds Chemical class 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
- H01G9/052—Sintered electrodes
- H01G9/0525—Powder therefor
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/043—Titanium sub-oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/02—Oxides or hydrates thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P2006/00—Physical properties of inorganic compounds
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- C01P2006/12—Surface area
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/32—Thermal properties
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- C01P2006/34—Melting temperatures
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- C01P2006/40—Electric properties
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/80—Compositional purity
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Powder Metallurgy (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
本発明は、自立した、高い発熱反応(連続的マグネシウム還元)を達成するために、酸化物および還元剤の混合物を直接反応器に供給することにより耐熱金属酸化物還元の課題を解決する。酸化物/還元剤混合物の使用はガス状金属の生成および反応帯域への搬送に関係する問題を取り除く。この方法により還元の終了および金属粉末の物理的特性を調節できる。
図1は本発明の方法を実施する装置を示す。垂直管形炉10は、混合ブレンド14として用意される耐熱金属酸化物粉末および還元剤粉末(他の実施例では反応物質を別々に供給することができる)を保持するホッパー12、ブレンド14をホッパー12の外部に一定に排出するスクリュー供給器16、スクリュー供給器16から供給される酸化物粒子を分解する酸化物分散装置18、自立反応を行う3帯域電気炉26により加熱される酸化物分散装置18に結合したパイプまたは反応器24、還元生成物30が集められる反応器24に結合した受け器28および未処理の(凝縮した)還元剤粉末が集められるトラップ32を有する。反応器の熱帯域の長さは約5フィート(約1.5m)である。
本発明を以下の限定されない実施例により説明する。
図2に示されるように五酸化タンタルを気体のマグネシウムで還元した。マグネシウム溶融装置内の温度は975℃であり、炉内の温度はマグネシウムが冷却部分に凝縮することを避けるために985℃に維持した。アルゴンが溶融装置を流動し、炉は55scfhであった。平均酸化物供給速度は1.5kg/hであった。還元は3時間継続した。不活性化の後に受け器を開放し、生成物を希釈硫酸で浸出し、残りのマグネシウムおよび酸化マグネシウムを除去した。引き続きケーキを炉内で65℃で乾燥し、分析した。還元した粉末の表面積は17m2/gであり、かさ密度は26.8g/in3であり、酸素含量は13.2W/W%であった。一定の酸化物およびマグネシウム供給速度を維持できないために還元は60%のみ終了し、これが試験の経過中に自立反応で不安定性を生じた。
反応帯域温度をエネルギーバランス計算から計算し、結果を図3に混合物供給速度の関数としてプロットした。以下の前提条件を使用した。
(1)エネルギー損失の値をエネルギー供給量の30%であると評価した。これは使用される炉の構成に理論的に近い。
(2)化学反応の動力学は瞬間的であり。酸化物またはマグネシウム粒度の関数でない。
(3)アルゴン流動速度は1.8Nm3/hである。
(4)炉の温度は1150℃であった。
図4は数種の混合物供給速度の時間の関数としてマグネシウム粉末を用いるTa2O5の還元の間の炉出力の示度を示す。このグラフは混合物供給速度の関数として出力の変化の値を示す。供給速度が高いほど、出力の低下が大きい。実際に混合物供給速度20kg/hで電気的出力供給が46%から6%に低下した。言い換えると炉は装置にエネルギーを供給しなかった。これは反応器で安定な自立反応が存在することを強く証拠づける。
表4は種々の混合物供給速度で行われる試験の結果を示す。マグネシウム化学量は100.5%であった。例5〜7で製造した粉末はコンデンサグレードのタンタル粉末の製造に適した特性を有した。反応帯域温度は五酸化タンタルの融点より低かった(表2および図3)。低い供給速度および高い供給速度および関係する反応帯域温度で製造した粉末は還元しなかった。還元は高い供給速度および関係する反応帯域温度で製造した粉末では特に少なかった(例8)。
表5は例4〜8に記載される粉末の粒度分布を示す。粒度分布はMalvern Mastersizer2000粒度分析器を使用して測定し、超音波で処理しなかった。比較のために、酸化物のバッチ還元により製造した粉末およびナトリウム還元法により製造した100KCVクラスの粉末の結果も記載する。バッチマグネシウム還元を管形炉内で100℃で6時間実施した。使用したナトリウム還元法は当業者に周知である。
表6は本発明により(連続的マグネシウム還元)、バッチ式マグネシウム還元によりおよび30Vおよび50Vで陽極処理した前および後のナトリウム還元により製造した粉末から製造した焼結ペレットの計算した平均孔径(APD)を示す。ペレットは生密度5.0g/ccに圧縮し、1210℃で20分間焼結した。ペレットを0.1V/V%H3PO4溶液中で、80℃、電流密度100mA/gで2時間かけて陽極処理し、形成電圧に保持した。Micromiretics Auto Pore IIIモデル水銀細孔計を使用して孔径分布を測定した。バッチ式マグネシウム還元法およびナトリウム還元法により製造した焼結したペレットがより高い平均孔径を有するにもかかわらず、30Vおよび50Vに陽極処理する際のAPD損失は本発明の連続的マグネシウム還元法により製造した粉末から製造したペレットがより少ない。これはバッチ式マグネシウム還元法またはナトリウム還元法により製造した粉末から製造したペレットに対する本発明の連続的マグネシウム還元法から製造したペレットの形状の改良による徴候である。
表7は例10〜13の粉末の湿潤容量および固体容量を示す。本発明の連続的還元粉末から製造したコンデンサの固体コンデンサ30V〜50Vの容量変化(CC)はナトリウム還元粉末ペレットのこの変化より少ない。本発明の連続的マグネシウム還元粉末から製造したコンデンサは、バッチ式マグネシウム還元粉末コンデンサおよびナトリウム還元粉末コンデンサより固体に対する湿潤容量回復率(CR)が高い。本発明の連続的還元粉末の固体に対する湿潤容量回復率は混合物供給速度が増加するとともに高まる。最後に本発明の連続的還元粉末から製造したコンデンサの等価連続抵抗(ESR)は、特に50Vでナトリウム還元粉末から製造した固体コンデンサのESRよりはるかに低い。これらの結果は本発明の連続的還元法により製造した粉末から製造したペレットの良好な形状の徴候であり、高い混合物供給速度で(20kg/hまで)製造した粉末が固体コンデンサを製造する最良の形状特性を有することを示す。
表8は例4〜8に記載される粉末の金属元素化学の一覧表である。比較のために典型的な100KCVナトリウム還元粉末のデータを記載する。本発明の連続的還元法により製造した粉末のクロム含量、鉄含量、ニッケル含量、カリウム含量およびナトリウム含量は検出限界より低い。対照的にナトリウム還元法により製造した粉末のこれらの元素の濃度は検出可能である。
提案された方法はマグネシウム化学量および混合物供給速度のような還元パラメーターの調節により金属亜酸化物の製造に使用することができる。
Claims (1)
- 連続的還元反応により粉末を製造する方法において、前記粉末が耐熱金属粉末、弁金属粉末、耐熱金属合金粉末、弁金属合金、耐熱金属亜酸化物粉末、または弁金属亜酸化物粉末であり、
a)耐熱金属酸化物または弁金属酸化物を金属還元剤とともに連続的粉末混合物として供給し、
b)その際前記耐熱金属酸化物または弁金属酸化物が五酸化タンタル、五酸化ニオブ、ニオブ亜酸化物、三酸化タングステン、三酸化クロム、三酸化モリブデン、五酸化バナジウム、酸化ニオブまたはこれらの混合物からなる群から選択され、前記金属還元剤がマグネシウムであり、
c)前記混合物を反応容器中で加熱することにより発熱反応が引き起こされ、一定の供給速度を維持することにより、高い自立発熱反応を生じ、高温安定反応帯域が、前記耐熱金属酸化物または弁金属酸化物の融点を上回らず、前記金属還元剤の沸点を上回る温度を有するように調節し、前記耐熱金属酸化物または弁金属酸化物を前記反応帯域中で還元し、かつ
d)実質的に不純物を含まない高い表面積の前記粉末を回収する
ことを特徴とする連続的還元反応により粉末を製造する方法。
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US09/849,717 US6849104B2 (en) | 2000-10-10 | 2001-05-04 | Metalothermic reduction of refractory metal oxides |
PCT/US2001/031726 WO2002090024A1 (en) | 2001-05-04 | 2001-10-11 | Metalothermic reduction of refractory metal oxides |
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Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6849104B2 (en) | 2000-10-10 | 2005-02-01 | H. C. Starck Inc. | Metalothermic reduction of refractory metal oxides |
DE10307716B4 (de) | 2002-03-12 | 2021-11-18 | Taniobis Gmbh | Ventilmetall-Pulver und Verfahren zu deren Herstellung |
US7655214B2 (en) * | 2003-02-26 | 2010-02-02 | Cabot Corporation | Phase formation of oxygen reduced valve metal oxides and granulation methods |
WO2005077573A1 (ja) * | 2004-02-16 | 2005-08-25 | Cabot Supermetals K.K. | バルブ金属の製造方法 |
GB2414729A (en) * | 2004-06-01 | 2005-12-07 | Atraverda Ltd | Method of producing sub-oxides with a substantially moisture free gas |
US7354472B2 (en) * | 2004-06-21 | 2008-04-08 | H.C. Starck Inc. | Metalothermic reduction of refractory metal oxides |
DE102004049039B4 (de) * | 2004-10-08 | 2009-05-07 | H.C. Starck Gmbh | Verfahren zur Herstellung feinteiliger Ventilmetallpulver |
KR101352371B1 (ko) * | 2012-05-29 | 2014-01-22 | 충남대학교산학협력단 | 자전연소합성법을 이용한 저산소 티타늄 분말 제조방법 |
US9260765B2 (en) * | 2013-03-15 | 2016-02-16 | Ati Properties, Inc. | Process for producing tantalum alloys |
US9994929B2 (en) | 2013-03-15 | 2018-06-12 | Ati Properties Llc | Processes for producing tantalum alloys and niobium alloys |
CN104096847A (zh) * | 2013-04-03 | 2014-10-15 | 北京有色金属研究总院 | 一种低氧、大尺寸高纯铪粉的制备方法 |
KR101500069B1 (ko) | 2013-04-11 | 2015-03-06 | 현대자동차주식회사 | 연료전지용 촉매전극을 위한 티타늄 서브옥사이드 지지체와 이의 저온 합성방법 |
WO2017127950A1 (zh) | 2016-01-27 | 2017-08-03 | 王娜 | 一种熔盐化学法回收废硬质合金的方法 |
CN106006743B (zh) * | 2016-05-31 | 2017-07-18 | 上海应用技术学院 | 一种正交相黑色wo3的制备方法 |
CN106830065B (zh) * | 2017-03-02 | 2019-01-22 | 攀枝花学院 | 制备Magnéli相低价钛氧化物的方法 |
CN108624782A (zh) * | 2017-03-23 | 2018-10-09 | 江苏展钛科技有限公司 | 一种制备生物钛合金的方法 |
RU2655560C1 (ru) * | 2017-06-13 | 2018-05-28 | Федеральное государственное бюджетное учреждение науки Федеральный исследовательский центр "Кольский научный центр Российской академии наук" (ФИЦ КНЦ РАН) | Способ получения порошка сплава молибдена и вольфрама |
KR102041496B1 (ko) * | 2017-12-26 | 2019-11-07 | 전북대학교산학협력단 | 저산소 티타늄 제조를 위한 다층 탈산 장치 |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2516863A (en) * | 1946-07-15 | 1950-08-01 | Gardner Daniel | Process of producing tantalum, columbium, and compounds thereof |
US3658507A (en) * | 1968-02-26 | 1972-04-25 | Onera (Off Nat Aerospatiale) | Process for the manufacture of chrome powder |
US3934179A (en) * | 1972-09-20 | 1976-01-20 | Fansteel Inc. | Tantalum anode for electrolytic devices |
US4045216A (en) * | 1975-11-03 | 1977-08-30 | Amax Inc. | Direct reduction of molybdenum oxide to substantially metallic molybdenum |
DE3232245A1 (de) * | 1982-08-30 | 1984-03-01 | Hermann C. Starck Berlin, 1000 Berlin | Verbesserung der fliessfaehigkeit und erhoehung der schuettdichte von hochkapazitiven ventilmetallpulvern |
US4441927A (en) * | 1982-11-16 | 1984-04-10 | Cabot Corporation | Tantalum powder composition |
US4684399A (en) * | 1986-03-04 | 1987-08-04 | Cabot Corporation | Tantalum powder process |
US4740238A (en) * | 1987-03-26 | 1988-04-26 | Fansteel Inc. | Platelet-containing tantalum powders |
DE3820960A1 (de) * | 1988-06-22 | 1989-12-28 | Starck Hermann C Fa | Feinkoernige hochreine erdsaeuremetallpulver, verfahren zu ihrer herstellung sowie deren verwendung |
US5082491A (en) * | 1989-09-28 | 1992-01-21 | V Tech Corporation | Tantalum powder with improved capacitor anode processing characteristics |
CN1017123B (zh) * | 1990-08-20 | 1992-06-24 | 中国科学院化工冶金研究所 | 超细钨粉的制备方法 |
IT1270828B (it) * | 1993-09-03 | 1997-05-13 | Chon Int Co Ltd | Processo per la sintesi di polveri ceramiche cristalline di composti di perovskite |
US5707599A (en) * | 1996-02-13 | 1998-01-13 | Santiam Electroactive Materials | Process for purifying tantalum oxide and other metal oxides |
US5769922A (en) * | 1996-04-12 | 1998-06-23 | Reading Alloys, Inc. | Method for producing vanadium-aluminum-ruthenium master alloys and master alloy compositions |
US5954856A (en) * | 1996-04-25 | 1999-09-21 | Cabot Corporation | Method of making tantalum metal powder with controlled size distribution and products made therefrom |
EP0933434A1 (fr) * | 1998-01-28 | 1999-08-04 | Sidmar N.V. | Procédé de réduction d'oxydes de fer et installation à cet effet |
WO2000067936A1 (en) * | 1998-05-06 | 2000-11-16 | H.C. Starck, Inc. | Metal powders produced by the reduction of the oxides with gaseous magnesium |
DE19847012A1 (de) * | 1998-10-13 | 2000-04-20 | Starck H C Gmbh Co Kg | Niobpulver und Verfahren zu dessen Herstellung |
CN2516863Y (zh) * | 2002-03-04 | 2002-10-16 | 梁广仁 | 空气调节电扇 |
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IL198900A (en) | 2010-06-30 |
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DE60138228D1 (de) | 2009-05-14 |
AU2008246253B2 (en) | 2010-06-17 |
KR100957248B1 (ko) | 2010-05-12 |
CZ307638B6 (cs) | 2019-01-30 |
MXPA03010043A (es) | 2004-12-06 |
CN1524022A (zh) | 2004-08-25 |
CZ20032981A3 (cs) | 2004-04-14 |
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AU2001296793B2 (en) | 2008-08-21 |
KR100893415B1 (ko) | 2009-04-17 |
AU2008246253A1 (en) | 2008-12-11 |
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