WO1994001361A1 - Method and apparatus for making nanometer sized particles - Google Patents
Method and apparatus for making nanometer sized particles Download PDFInfo
- Publication number
- WO1994001361A1 WO1994001361A1 PCT/US1993/006415 US9306415W WO9401361A1 WO 1994001361 A1 WO1994001361 A1 WO 1994001361A1 US 9306415 W US9306415 W US 9306415W WO 9401361 A1 WO9401361 A1 WO 9401361A1
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- WIPO (PCT)
- Prior art keywords
- recited
- solution
- particles
- precursor
- solvent
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Links
- 239000002245 particle Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims description 42
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000009826 distribution Methods 0.000 claims abstract description 6
- 230000006872 improvement Effects 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000007788 liquid Substances 0.000 claims description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 claims description 2
- 150000001860 citric acid derivatives Chemical class 0.000 claims description 2
- 230000003993 interaction Effects 0.000 claims description 2
- 229910000765 intermetallic Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims 4
- 230000000977 initiatory effect Effects 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 1
- 229910000000 metal hydroxide Inorganic materials 0.000 claims 1
- 150000004692 metal hydroxides Chemical class 0.000 claims 1
- 229910052976 metal sulfide Inorganic materials 0.000 claims 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 11
- 238000010924 continuous production Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000002244 precipitate Substances 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000010923 batch production Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 48
- 239000000047 product Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017147 Fe(CO)5 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910017333 Mo(CO)6 Inorganic materials 0.000 description 1
- 238000004813 Moessbauer spectroscopy Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- JZQOJFLIJNRDHK-CMDGGOBGSA-N alpha-irone Chemical compound CC1CC=C(C)C(\C=C\C(C)=O)C1(C)C JZQOJFLIJNRDHK-CMDGGOBGSA-N 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052575 non-oxide ceramic Inorganic materials 0.000 description 1
- 239000011225 non-oxide ceramic Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
-
- 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
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/32—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/36—Methods for preparing oxides or hydroxides in general by precipitation reactions in aqueous solutions
- C01B13/366—Methods for preparing oxides or hydroxides in general by precipitation reactions in aqueous solutions by hydrothermal processing
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/20—Methods for preparing sulfides or polysulfides, in general
-
- 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
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/60—Compounds characterised by their crystallite size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Definitions
- the present invention relates generally to a method and apparatus for making nanometer-sized particles. More specifically, the method is making a solution of a soluble precursor in a liquid solvent, then continuously flowing the solution through a heated vessel and forming particles within the heated vessel, then recovering the particles by quenching the solution in a cooled region.
- Production of nanometer-sized particles is currently accomplished in a variety of ways, including gas phase condensation, laser synthesis processes, freeze drying methods, flame or plasma torch reactions, vacuum synthesis methods utilizing sputtering, laser ablation, liquid metal ion sources, reverse micelle solutions, solidification from the liquid state, and hydrothermal methods.
- These techniques are typically batch techniques and have limited particle production rate (on the order of gram quantities or less per day) and limited overall production quantity. Additionally, relatively wide ranges of particle sizes are produced by these techniques.
- Hydrothermal methods utilize conditions of elevated temperatures and/or elevated pressures wherein particles are formed by nucleation and grown under these conditions to produce powder products.
- Termination of particle growth is achieved by stopping the reaction, generally by cooling the heated solution. Remaining liquid is decanted and the particles dried and recovered. Particle sizes are a result of concentrations of reactants, the amount of time that the reactants are in contact, and the temperature and pressure of the reactant solution. Using current methods, it is difficult to control the amount of time reactants are in contact at given conditions of temperature and pressure because of large total heat capacity of vessels and equipment.
- Particles are made of materials including but not limited to oxides and hydroxides by hydrolysis or oxidation reactions in aqueous solvent systems, and metals in non-aqueous systems; for example, organometallic species, as well as non-oxide ceramic particles formed by reaction of a precursor with a solvent. More specifically, particle products include but are not limited to iron oxide, titanium oxide, nickel oxide, zirconium oxide, aluminum oxide and silicon oxide. Precursor solutions from which particles are made include but are not limited to aqueous nitrate solutions, sulfate solutions, and oxalate solutions. For example, iron oxide particles may be made from Fe(NO 3 ) 3 or Fe(NH 4 ) (SO 4 ) 2 .
- the Smith process is useful for soluble polymers, organic compounds, and many inorganic compounds, it is not useful for insoluble or substantially insoluble ceramic materials, metal oxides, and other above mentioned sybstantially insoluble materials.
- the Smith process requires carrier solutions which have no liquid droplet formation upon expansion to low pressure, whereas the present invention does not require this limitation.
- the invention is an improvement to hydrothermal methods wherein a solution of precursor and solvent continuously flow through a heated vessel and chemically react to nucleate particle precipitates within the vessel, then flow into a cooled region for recovery of the particles.
- a solution of precursor and solvent continuously flow through a heated vessel and chemically react to nucleate particle precipitates within the vessel, then flow into a cooled region for recovery of the particles.
- FIG. 1 is a schematic of an embodiment of the present invention.
- FIG. 2 is a schematic of a second embodiment of the present invention.
- the invention is an improvement to hydrothermal methods wherein a solution of precursor and solvent continuously flow through a heated vessel and the solute chemically reacts to nucleate particle precipitates, then flows into a cooled region for recovery of the particles.
- An apparatus for carrying out the present invention is shown in FIG. 1.
- Solution (1) within reservoir (2) flows into a first tube (3) and is pressurized by a pump (4).
- Pressurized solution flows into a reaction vessel (6) that may be any type of closed and pressurizeable continuous flow vessel having an inlet and outlet, but is preferably a tube.
- the reaction vessel (6) is heated by a heater (8).
- Pressure may be maintained within the reaction vessel (6) by any pressure control means, but preferably with a flow restrictor (10) located downstream of both the pump (4) and the heater (8).
- the heated solution is cooled by ejection from the end (12) of the reaction vessel (6) into a chamber (14) having walls (16) that are cooled.
- the heated solution is rapidly cooled within the chamber (14). Particles and reacted solution accumulate within the chamber (14). Particles are recovered by any method including but not limited to settling, filtering, or centrifugation. Remaining liquid is decanted and the particles dried under flowing nitrogen or air.
- the heater (8) may be of any type including but not limited to electrical resistance heaters, induction heaters, microwave heaters, fuel fired heaters, and steam coils. It is preferred that the heater be the tube itself resistively heated with electricity.
- the flow restrictor (10) may be of any type including but not limited to an adjustable valve, or a non-adjustable orifice such as a nozzle or lengths of small diameter tubing.
- the walls (16) may be cooled by any means including but not limited to refrigeration coils, water/ice bath, liquid nitrogen, and dry ice.
- FIG. 2 A second embodiment of an apparatus according to the present invention is shown in FIG. 2. Instead of an open chamber (14) for cooling and particle collection, a section of the reaction vessel (6) is cooled by a cooling means (21) downstream from the heater (8). Upon exiting the cooled section of reaction vessel (6), the solution (1) enters a filter means (22) wherein particles are collected while remaining liquid flows through the flow restrictor (10) to a catch basin (24).
- the cooling means (21) may be any means including but not limited to low temperature baths, including water and ice baths, and dry ice, as well as refrigeration cooling coils.
- the solution (1) is pressurizeable by any means including but not limited to mechanical pistons with weights on them, overpressure of a gas, and hydraulic head.
- the first two embodiments disclose a reservoir (2) holding a solution (1).
- the reaction vessel tube (3) may be provided with multiple ports for staged injection of precursors and solvents.
- the tube (3) itself may be a concentric tube having an inner and outer tube with an annular space therebetween.
- Co-processing of precursors, solvents, or reagents having different reaction temperatures may be accomplished with a multi-port or concentric tube reaction vessel.
- the heated region of the reaction vessel tube may be controlled to exhibit a temperature variation along its length wherein various compounds may be added into an appropriate temperature zone.
- particle size is determined by many factors including temperature, pressure, type of flow restrictor, and concentration and type of precursor in the solution.
- Flow rate of solution to achieve a particle production rate depends upon the same factors recited above and may vary over a wide range.
- flow rates and tube lengths are selected to provide a residence time of solution (1) within the vessel (3) of less than one minute, and preferably about 2 to 3 seconds.
- the temperature and pressure of the solution within the vessel may also vary widely depending upon the type of solution and the size of particles desired. Temperatures may range from about 25°C (ambient) to greater than 500°C, but are preferably from about 200°C to about 400°C. Pressures are sufficient to prevent substantial vaporization of the solution thereby maintaining the solution substantially in the liquid phase.
- the terms "substantial” and “substantially” are used because it is recognized that vaporization may not be completely avoided. Furthermore, some vaporization of solution is not harmful to the process of the present invention.
- the process of the present invention is not limited to the type of chemical reaction occurring within the reaction vessel. It is preferred, however, that the reaction take place within the reaction vessel and not within the inlet reservoir or the outlet.
- the chemical reaction may be an interaction of the precursor with the solvent at elevated temperature conditions, for example oxide formation.
- the chemical reaction may be a thermal breakdown of the precursor into an insoluble form, for example formation of iron particles from an iron pentacarbonyl/carbon dioxide solution.
- the chemical reaction may be thermal decomposition of an additional reactant, for example addition of urea decomposing into ammonia in a solution of iron nitrate and forming iron hydroxite particles.
- Solvents may be selected from inorganic and organic liquids.
- Inorganic liquids include but are not limited to water (aqueous solvent) and ammonia.
- Precursors that are aqueous soluble include but are not limited to ferric or ferrous salt, for example, ferric halide, ferric sulfate, ferric (periodic chart column 1A element) sulfate; oxalates of potassium, sodium, ammonium, lithium, oxotitanium, zirconium, hafnium, and citrates of zirconium and titanium.
- Precursors that are soluble in carbon dioxide, especially supercritical carbon dioxide include but are not limited to Fe(CO) 5 and Mo(CO) 6 .
- An additional solute may be oxidizing like urea or reducing like hydrazine, hydrogen gas or sodium borohydride.
- An aqueous solution of iron nitrate (0.1M Fe(NO 3 ) 3 ) was pressurized with a reciprocating pump (4) to a pressure of about 510 Bar (7500 psi) and transported through a reaction vessel (6).
- the reaction vessel (6) was 316 stainless steel tubing having an outside diameter of 0.32 cm, a wall thickness of 0.09 cm, and a length of 90 cm.
- the reaction vessel (6) was heated by resistive electrical heating.
- the solution had a flow rate of about 50 cc/min.
- the tube temperature was held constant for each run and several runs having temperatures ranging from about 225°C to about 400°C were made.
- the flow restrictor (10) was constructed of a short length (length less than about 2.5 cm) of capillary tubing having an inside diameter from about 60 micrometers to about 100 micrometers.
- the heated solution was ejected into a flask immersed in a water/ice bath.
- Phase identification and size of the particles was performed using X-ray particle diffraction. Diffraction patterns were obtained using a Philips X-ray diffractometer with a copper source operated at 40 kV and 25 mA. Particle size estimates were made by calculations based upon the Scherrer formula as may be found in the book entitled ELEMENTS OF X-RAY DIFFRACTION, 2d edition, by BD Cullity, published by Addison Wesley, Reading, Mass. in 1978. A correction for instrument broadening was made to the Scherrer formula. Particle size and particle size distribution were obtained using transmission electron microscopy micrographs of particles deposited upon 3 mm carbon coated grids.
- the particles were micrographed in a Philips EM400T electron microscope operated at 120 keV. Particle size distributions were also obtained using variable temperature Mossbauer spectroscopy as described in the article entitled MOSSBAUER EFFECT STUDIES OF SURFACE IONS OF ULTRAFINE ALPHA-IRON(III) OXIDE PARTICLES, by AM Van der Kraan, published in Phys. Stat. Sol. A, Vol. 18, pp 215, 226 in 1973.
- Results are shown in Table 1. For the identified sample numbers, processing parameters of temperature and pressure are shown. Results of yield, material phase, and particle size are also shown. Particle diameters are reported for three independent measurements along with confirmatory surface area measurements. From Table 1, one can see that particle sizes are larger for higher processing temperature. One also sees that the particle size range is narrow, showing size range variations of from 8 to 50 nm. EXAMPLE 2
- Results are shown in Table 2. From Table 2, one can see that the particle size range is narrow, showing range variations of 5 nm.
- Example 2 Another experiment was conducted according to the method and using the apparatus of Example 1. In this experiment, a solution of aluminum nitrate (0.1 M) Al(NO 3 ) 3 ) was used. The solution was processed at a temperature of about 400°C and produced very few particles.
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US91184292A | 1992-07-10 | 1992-07-10 | |
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Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998051613A1 (en) * | 1997-05-15 | 1998-11-19 | Commissariat A L'energie Atomique | Method for making single or mixed metal oxides or silicon oxide |
US6010977A (en) * | 1998-06-24 | 2000-01-04 | Eastman Chemical Company | Preparation of sub-visual molecular aggregrates composed of antimony phosphate derivatives |
EP1428896A2 (en) * | 2002-12-13 | 2004-06-16 | General Electric Company | Method for producing a metallic alloy by dissolution, oxidation and chemical reduction |
US7217400B2 (en) | 2002-08-16 | 2007-05-15 | Albemarle Netherlands B.V. | Preparation of iron compounds by hydrothermal conversion |
US7241437B2 (en) | 2004-12-30 | 2007-07-10 | 3M Innovative Properties Company | Zirconia particles |
JP2008504202A (en) * | 2004-06-27 | 2008-02-14 | ヨーマ・ケミカル・アー・エス | Method for producing iron oxide nanoparticles |
US7833621B2 (en) | 2005-03-11 | 2010-11-16 | 3M Innovative Properties Company | Light management films with zirconia particles |
CN102773496A (en) * | 2012-08-22 | 2012-11-14 | 厦门大学 | Method for preparing gold-silver alloy nano particle by continuous reaction kettle |
RU2633582C1 (en) * | 2016-06-23 | 2017-10-13 | Общество с ограниченной ответственностью "Инновационные Технологии Синтеза" | Method of producing nanodispersed metal oxides |
US10100386B2 (en) | 2002-06-14 | 2018-10-16 | General Electric Company | Method for preparing a metallic article having an other additive constituent, without any melting |
US10604452B2 (en) | 2004-11-12 | 2020-03-31 | General Electric Company | Article having a dispersion of ultrafine titanium boride particles in a titanium-base matrix |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55136130A (en) * | 1979-04-06 | 1980-10-23 | Nakamichi Yamazaki | Slag gamma-fe2o3 formed by wet metallurgy of chromite |
WO1989003365A1 (en) * | 1987-10-09 | 1989-04-20 | Allied-Signal Inc. | Continuous process for production of fine particulate ceramics |
-
1993
- 1993-07-07 WO PCT/US1993/006415 patent/WO1994001361A1/en active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55136130A (en) * | 1979-04-06 | 1980-10-23 | Nakamichi Yamazaki | Slag gamma-fe2o3 formed by wet metallurgy of chromite |
WO1989003365A1 (en) * | 1987-10-09 | 1989-04-20 | Allied-Signal Inc. | Continuous process for production of fine particulate ceramics |
Non-Patent Citations (3)
Title |
---|
E.M.ADKINS: "LIGHT METALS 1983", March 1983, METALLURGICAL SOCIETY OF AIME, UNITED ARAB EMIRATES * |
PATENT ABSTRACTS OF JAPAN * |
TADAFUMI ADSCHIRI: "RAPID AND CONTINUOUS HYDROTHERMAL CRYSTALLISATION OF METAL OXIDE PARTICLES IN SUPERCRITICAL WATER", JOURNAL OF THE AMERICAN CERAMIC SOCIETY., vol. 75, no. 4, April 1992 (1992-04-01), COLUMBUS US, pages 1019 - 1022, XP002540462, DOI: doi:10.1111/j.1151-2916.1992.tb04179.x * |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2763258A1 (en) * | 1997-05-15 | 1998-11-20 | Commissariat Energie Atomique | PROCESS FOR THE MANUFACTURING OF METAL OXIDES, SINGLE OR MIXED, OR OF SILICON OXIDE |
WO1998051613A1 (en) * | 1997-05-15 | 1998-11-19 | Commissariat A L'energie Atomique | Method for making single or mixed metal oxides or silicon oxide |
US6010977A (en) * | 1998-06-24 | 2000-01-04 | Eastman Chemical Company | Preparation of sub-visual molecular aggregrates composed of antimony phosphate derivatives |
US10100386B2 (en) | 2002-06-14 | 2018-10-16 | General Electric Company | Method for preparing a metallic article having an other additive constituent, without any melting |
US7217400B2 (en) | 2002-08-16 | 2007-05-15 | Albemarle Netherlands B.V. | Preparation of iron compounds by hydrothermal conversion |
EP1428896A2 (en) * | 2002-12-13 | 2004-06-16 | General Electric Company | Method for producing a metallic alloy by dissolution, oxidation and chemical reduction |
EP1428896A3 (en) * | 2002-12-13 | 2004-11-17 | General Electric Company | Method for producing a metallic alloy by dissolution, oxidation and chemical reduction |
US7510680B2 (en) | 2002-12-13 | 2009-03-31 | General Electric Company | Method for producing a metallic alloy by dissolution, oxidation and chemical reduction |
JP2008504202A (en) * | 2004-06-27 | 2008-02-14 | ヨーマ・ケミカル・アー・エス | Method for producing iron oxide nanoparticles |
US10604452B2 (en) | 2004-11-12 | 2020-03-31 | General Electric Company | Article having a dispersion of ultrafine titanium boride particles in a titanium-base matrix |
US7429422B2 (en) | 2004-12-30 | 2008-09-30 | 3M Innovative Properties Company | Zirconia particles |
US7674523B2 (en) | 2004-12-30 | 2010-03-09 | 3M Innovative Properties Company | Zirconia particles |
US7241437B2 (en) | 2004-12-30 | 2007-07-10 | 3M Innovative Properties Company | Zirconia particles |
US7833621B2 (en) | 2005-03-11 | 2010-11-16 | 3M Innovative Properties Company | Light management films with zirconia particles |
CN102773496A (en) * | 2012-08-22 | 2012-11-14 | 厦门大学 | Method for preparing gold-silver alloy nano particle by continuous reaction kettle |
RU2633582C1 (en) * | 2016-06-23 | 2017-10-13 | Общество с ограниченной ответственностью "Инновационные Технологии Синтеза" | Method of producing nanodispersed metal oxides |
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