GB1282307A - Method of preparation of homogeneous oxides of two or more elements in a fineley divided form and products obtained - Google Patents

Method of preparation of homogeneous oxides of two or more elements in a fineley divided form and products obtained

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Publication number
GB1282307A
GB1282307A GB3322269A GB3322269A GB1282307A GB 1282307 A GB1282307 A GB 1282307A GB 3322269 A GB3322269 A GB 3322269A GB 3322269 A GB3322269 A GB 3322269A GB 1282307 A GB1282307 A GB 1282307A
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GB
United Kingdom
Prior art keywords
solution
oxides
moo
acid
elements
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
GB3322269A
Inventor
Philippe Courty
Bernard Delmon
Christian Marcilly
Andre Sugier
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique CEA
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Publication date
Priority claimed from FR6918997A external-priority patent/FR2045612A2/en
Application filed by Commissariat a lEnergie Atomique CEA filed Critical Commissariat a lEnergie Atomique CEA
Publication of GB1282307A publication Critical patent/GB1282307A/en
Expired legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14Methods for preparing oxides or hydroxides in general
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14Methods for preparing oxides or hydroxides in general
    • C01B13/18Methods for preparing oxides or hydroxides in general by thermal decomposition of compounds, e.g. of salts or hydroxides
    • C01B13/185Preparing mixtures of oxides
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/10Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure
    • H01F1/11Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials non-metallic substances, e.g. ferrites, e.g. [(Ba,Sr)O(Fe2O3)6] ferrites with hexagonal structure in the form of particles
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/02Amorphous compounds
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/50Agglomerated particles
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/61Micrometer sized, i.e. from 1-100 micrometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/62Submicrometer sized, i.e. from 0.1-1 micrometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/64Nanometer sized, i.e. from 1-100 nanometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/10Solid density
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/12Surface area
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/60Optical properties, e.g. expressed in CIELAB-values

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Structural Engineering (AREA)
  • Composite Materials (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Power Engineering (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Catalysts (AREA)
  • Compounds Of Iron (AREA)

Abstract

1282307 Oxidation catalysts COMMISSARIAT A L'ENERGIE ATOMIQUE INSTITUT FRANCAIS DU PETROLE DES CARBURANTS ET LIBRIFIANTS 1 July 1969 [2 July 1968 9 June 1969] 33222/69 Heading B1E [Also in Divisions C1 C2 and H1] Homogeneous oxides of two or more elements are made in a finely-divided state by (1) forming a solution containing salts of the elements to be combined and an organic complexing agent; (2) concentrating the solution in less than 30 mins to a viscosity greater than 200 centipoises at 20‹C; (3) further concentrating the viscous solution to an amorphous product and (4) thermally decomposing the precursor thus passed at temperatures above 200‹C in an atmosphere which is inert or contains O 2 in about the same proportions as in air. The complexing agent is a polybasic acid, amino-acid, keto-acid or ammonium or organic base salts thereof. Citric, glycollic, malic, tartaric, lactic and pyruric acids, and alanine are used in the Examples. The solvent may be aqueous (neutral, acidic or basic) or non-aqueous e.g. DMF, DMS n-methylpyrrolidone, nitro-compounds, alcohols, ketones or nitrites. An additional acid and/or base may be used to aid e.g. Fe 1À72 Co 0À28 (MoO 3 ) 2À7 (WO 3 ) 0 . 3 . Solid solutions: 20 mole % MoO 3 in V 2 O 5 ; 0.5In 2 O 3 -0.5Y 2 O 3 ; 10 wt% ThO 2 in Y.O,; 10 wt% ZrO 2 in Y 2 O 3 and MoO 3 , WO 3 and P 2 O 5 in V 2 O 5 . Examples describe the preparation of:- Chromites: CuCr 2 O 4 ; ZnCr 2 O 4 . Ferrites: CuFe 2 O 4 ; NiFe 2 O 4 ; CoFe 2 O 4 ; BaFe 12 O 19 ; Ni 0À8 Zn 0À2 Fe 2 O 4 ; Li 0À5 Al 0À95 Fe 1À55 O 4 ; Mn 0À6 Zn 0À4 Fe 2 O 4 . Aluminates: MgAl 2 O 4 . Zirconates and titanates: MgTi 2 O 4 ; PbTiO 3 ; BaTiO 3 PbZrO 3 ; BaZrO 3 ; Pb(Zr x Ti 1-x-y Sn y )O 3 where X=0-0.9; 1-X-Y=0.1-0.6, Y=0- 0.65; Pb 1-a M a (Zr x Ti 1-x-y Sn y )O 3 where M=Ca, Sr or Ba, a =0-0.25; also the above compounds doped with less than 0.5% MnO or .less than 0.3% IrO 2 . Manganites: CoMnO 3 . Molybdates: CoMaO 4 ; Cr-Fe molybdate (MoO 3 /Fe 2 O 3 + Cr 2 O 3 =24.7; Cr/Fe+Cr= 0.08). Pyrochlore: La 2 Sn 2 O 7 . Garnets: Y 3 Fe 5 O 12 ; Y 3 Al 5 O 12 ; Nd 0À1 Y 2À9 Fe 5 O 12 ; Gd 0À68 Y 2À32 Fe 4À58 Al 0À42 O 12 . Perooskites: YFeO 3 ; TbFeO 3 ; TmFeO 3 ; SmAlO 3 ; LaDyO 3 ; YCrO 3 ; TbAl 0À5 Co 0À5 O 3 . Mixed phases: AO-BO 3 and Fe 2 O 3 -3(BO 3 ) where A=Co, Ni or Mn and B=Mo or W The solution may also be made by mechanical trituration, using little or no solvent other than the water of crystallisation of the salts. The solution may be concentrated at atmospheric pressure or in vacuo at temperatures of -50 to 200‹C, in 2 stages or in a single stage. The single stage process may comprise spray-drying or freeze-drying, or trituration and dehydration of the resulting solution, in the same apparatus. The dehydrated precursor is a vitreous lacquer or foam, which may be in the form of flakes or spherules 10-750 microns diam. Thermal decomposition may be carried out in a fixed or fluidised bed at temperatures approaching 600‹C. Dehydration and thermal decomposition may be effected simultaneously by spray atomising the solution in a hot atmosphere. The oxides always appear as a light ash of fine particles or particle aggregates. The oxides may have specific gravity 0.01-0.5, particle size 10-10,000Š and specific surface area more than 0.1m<SP>2</SP>/g. The oxides are used as oxidation catalysts e.g. methanol to formaldehyde.
GB3322269A 1968-07-02 1969-07-01 Method of preparation of homogeneous oxides of two or more elements in a fineley divided form and products obtained Expired GB1282307A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR157487 1968-07-02
FR6918997A FR2045612A2 (en) 1969-06-09 1969-06-09 Finely divided homogeneous mixed oxide prepn

Publications (1)

Publication Number Publication Date
GB1282307A true GB1282307A (en) 1972-07-19

Family

ID=26182093

Family Applications (1)

Application Number Title Priority Date Filing Date
GB3322269A Expired GB1282307A (en) 1968-07-02 1969-07-01 Method of preparation of homogeneous oxides of two or more elements in a fineley divided form and products obtained

Country Status (10)

Country Link
JP (1) JPS496040B1 (en)
BE (1) BE735476A (en)
BG (1) BG17281A3 (en)
CA (1) CA936676A (en)
CH (1) CH513769A (en)
DE (1) DE1933331A1 (en)
GB (1) GB1282307A (en)
LU (1) LU59000A1 (en)
NL (1) NL6910093A (en)
RO (1) RO56114A (en)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4231231A (en) 1979-04-13 1980-11-04 Corning Glass Works Cryogenic ceramic and apparatus
US4266978A (en) * 1979-06-25 1981-05-12 General Electric Company Synthesis of mixed oxide composition
US4285726A (en) * 1978-04-08 1981-08-25 Bayer Aktiengesellschaft Active anti-corrosion pigments based on calcium oxide, aluminium oxide and iron oxide
US4301020A (en) * 1978-08-01 1981-11-17 Bell Telephone Laboratories, Incorporated Process of slurrying and spray drying ceramic oxides with polyethyleneimine dispersants
US4330332A (en) 1977-08-09 1982-05-18 Battelle Memorial Institute Process for the preparation of molybdenum-tungsten carbides
US4429051A (en) 1981-03-11 1984-01-31 United Kingdom Atomic Energy Authority Ceramic materials by sol-gel route
GB2154248A (en) * 1984-01-31 1985-09-04 Permelec Electrode Ltd Improvements in the manufacture of electrodes
US4608350A (en) * 1983-10-27 1986-08-26 E. I. Du Pont De Nemours And Company Precursor solutions for biologically active glass
US4786555A (en) * 1983-10-27 1988-11-22 E. I. Du Pont De Nemours And Company Support particles coated with or particles of precursors for or of biologically active glass
EP0422105A1 (en) * 1988-06-09 1991-04-17 Battelle Memorial Institute Metal oxide ceramic powders and methods of making same.
FR2670770A1 (en) * 1990-12-20 1992-06-26 Bellon Labor Sa Roger PROCESS FOR PREPARING AN OXIDE OF AT LEAST TWO DIFFERENT METALS.
EP0990621A2 (en) * 1998-09-30 2000-04-05 Kabushiki Kaisha Toyota Chuo Kenkyusho Spinel powder and spinel slurry
EP1450425A1 (en) * 2001-11-15 2004-08-25 Seimi Chemical Co., Ltd. Composite oxide for solid oxide fuel cell and method for preparation thereof
CN109806881A (en) * 2017-11-20 2019-05-28 中国科学院大连化学物理研究所 A kind of iron-molybdic catalyst and preparation method thereof for prepn. of formaldehyde by oxidation of methanol
CN112876238A (en) * 2021-02-25 2021-06-01 中国科学院新疆理化技术研究所 Stannate system negative temperature coefficient thermistor material and preparation method thereof
CN113275017A (en) * 2021-05-28 2021-08-20 内蒙古大学 Preparation method and application of composite pyrochlore catalyst
CN115920889A (en) * 2022-11-07 2023-04-07 上海交通大学 Preparation and application of foamed spinel catalyst
RU2815312C1 (en) * 2023-09-06 2024-03-13 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский государственный университет" Method of producing magnesium titanates

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* Cited by examiner, † Cited by third party
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US4377424A (en) * 1980-05-26 1983-03-22 Chuetsu Metal Works Co., Ltd. Mold of precipitation hardenable copper alloy for continuous casting mold
JPS57116936U (en) * 1981-12-23 1982-07-20
US4778671A (en) * 1986-07-14 1988-10-18 Corning Glass Works Preparation of unagglomerated metal oxide particles with uniform particle size
DE4217818C1 (en) * 1992-05-29 1993-09-16 H.C. Starck Gmbh & Co Kg, 3380 Goslar, De
JP5176084B2 (en) * 2000-11-30 2013-04-03 中部キレスト株式会社 Method for producing metal oxide phosphor
FR2865576B1 (en) 2004-01-28 2006-04-28 Commissariat Energie Atomique PROCESS FOR THE PREPARATION OF COMPOSITE MATERIALS COMPRISING AN ELECTRODE ACTIVE COMPOUND AND AN ELECTRONIC CONDUCTING COMPOUND SUCH AS CARBON PARTICULARLY FOR LITHIUM ACCUMULATORS
US20090269585A1 (en) * 2005-03-31 2009-10-29 Mitsui Mining & Smelting Co., Ltd. Black complex oxide particles
EP1873118A1 (en) * 2005-04-01 2008-01-02 Mitsui Mining and Smelting Co., Ltd Black double oxide particles, process for production thereof, black pastes, and black matrixes
JP4839043B2 (en) * 2005-08-30 2011-12-14 三井金属鉱業株式会社 Composite oxide black particles, method for producing the same, black paint and black matrix
JP5483898B2 (en) * 2009-02-19 2014-05-07 住友金属鉱山株式会社 Method for producing oxide phosphor
JP7454425B2 (en) * 2019-05-24 2024-03-22 日鉄鉱業株式会社 Method for producing cobalt ferrite particles and cobalt ferrite particles produced thereby
CN114149068B (en) * 2021-11-23 2023-08-29 武汉理工大学 High-valence iron-containing Fe (IV) perovskite type composite oxide and low-temperature roasting synthesis method and application thereof
CN115784315B (en) * 2022-06-24 2024-04-30 西北大学 Oxygen carrier for efficient carbon dioxide trapping based on chemical looping combustion and preparation method and application thereof

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4330332A (en) 1977-08-09 1982-05-18 Battelle Memorial Institute Process for the preparation of molybdenum-tungsten carbides
US4285726A (en) * 1978-04-08 1981-08-25 Bayer Aktiengesellschaft Active anti-corrosion pigments based on calcium oxide, aluminium oxide and iron oxide
US4301020A (en) * 1978-08-01 1981-11-17 Bell Telephone Laboratories, Incorporated Process of slurrying and spray drying ceramic oxides with polyethyleneimine dispersants
US4231231A (en) 1979-04-13 1980-11-04 Corning Glass Works Cryogenic ceramic and apparatus
US4266978A (en) * 1979-06-25 1981-05-12 General Electric Company Synthesis of mixed oxide composition
US4429051A (en) 1981-03-11 1984-01-31 United Kingdom Atomic Energy Authority Ceramic materials by sol-gel route
US4608350A (en) * 1983-10-27 1986-08-26 E. I. Du Pont De Nemours And Company Precursor solutions for biologically active glass
US4786555A (en) * 1983-10-27 1988-11-22 E. I. Du Pont De Nemours And Company Support particles coated with or particles of precursors for or of biologically active glass
GB2154248A (en) * 1984-01-31 1985-09-04 Permelec Electrode Ltd Improvements in the manufacture of electrodes
AU567789B2 (en) * 1984-01-31 1987-12-03 Permelec Electrode Ltd. Electrode coated by organic metal complex
EP0422105A1 (en) * 1988-06-09 1991-04-17 Battelle Memorial Institute Metal oxide ceramic powders and methods of making same.
EP0422105A4 (en) * 1988-06-09 1992-01-08 Battelle Memorial Institute Metal oxide ceramic powders and thin films and methods of making same
FR2670770A1 (en) * 1990-12-20 1992-06-26 Bellon Labor Sa Roger PROCESS FOR PREPARING AN OXIDE OF AT LEAST TWO DIFFERENT METALS.
WO1992011223A1 (en) * 1990-12-20 1992-07-09 Institut Français Du Petrole Isosynthesis method in the presence of a catalyst based on an oxide of at least two different metals
EP0990621A2 (en) * 1998-09-30 2000-04-05 Kabushiki Kaisha Toyota Chuo Kenkyusho Spinel powder and spinel slurry
EP0990621A3 (en) * 1998-09-30 2000-06-28 Kabushiki Kaisha Toyota Chuo Kenkyusho Spinel powder and spinel slurry
US6306360B1 (en) 1998-09-30 2001-10-23 Kabushiki Kaisha Toyota Chuo Kenkyusho Spinel powder and spinel slurry
EP1450425A1 (en) * 2001-11-15 2004-08-25 Seimi Chemical Co., Ltd. Composite oxide for solid oxide fuel cell and method for preparation thereof
EP1450425A4 (en) * 2001-11-15 2009-01-28 Seimi Chem Kk Composite oxide for solid oxide fuel cell and method for preparation thereof
CN109806881A (en) * 2017-11-20 2019-05-28 中国科学院大连化学物理研究所 A kind of iron-molybdic catalyst and preparation method thereof for prepn. of formaldehyde by oxidation of methanol
CN112876238A (en) * 2021-02-25 2021-06-01 中国科学院新疆理化技术研究所 Stannate system negative temperature coefficient thermistor material and preparation method thereof
CN112876238B (en) * 2021-02-25 2023-04-18 中国科学院新疆理化技术研究所 Stannate system negative temperature coefficient thermistor material and preparation method thereof
CN113275017A (en) * 2021-05-28 2021-08-20 内蒙古大学 Preparation method and application of composite pyrochlore catalyst
CN115920889A (en) * 2022-11-07 2023-04-07 上海交通大学 Preparation and application of foamed spinel catalyst
RU2815312C1 (en) * 2023-09-06 2024-03-13 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский государственный университет" Method of producing magnesium titanates

Also Published As

Publication number Publication date
BE735476A (en) 1969-12-16
DE1933331A1 (en) 1970-01-29
JPS496040B1 (en) 1974-02-12
BG17281A3 (en) 1973-07-25
RO56114A (en) 1974-04-29
NL6910093A (en) 1970-01-06
LU59000A1 (en) 1969-11-14
CH513769A (en) 1971-10-15
CA936676A (en) 1973-11-13

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