CN117263658A - Oxide ceramic based on oxygen vacancy defect regulation and control and preparation method thereof - Google Patents
Oxide ceramic based on oxygen vacancy defect regulation and control and preparation method thereof Download PDFInfo
- Publication number
- CN117263658A CN117263658A CN202311215630.6A CN202311215630A CN117263658A CN 117263658 A CN117263658 A CN 117263658A CN 202311215630 A CN202311215630 A CN 202311215630A CN 117263658 A CN117263658 A CN 117263658A
- Authority
- CN
- China
- Prior art keywords
- sintering
- oxygen vacancy
- oxide ceramic
- powder
- phase
- 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.)
- Pending
Links
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 72
- 239000001301 oxygen Substances 0.000 title claims abstract description 72
- 229910052574 oxide ceramic Inorganic materials 0.000 title claims abstract description 65
- 239000011224 oxide ceramic Substances 0.000 title claims abstract description 63
- 230000007547 defect Effects 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 230000033228 biological regulation Effects 0.000 title claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 120
- 239000000843 powder Substances 0.000 claims abstract description 88
- 239000002994 raw material Substances 0.000 claims abstract description 35
- 238000007873 sieving Methods 0.000 claims abstract description 14
- 235000015895 biscuits Nutrition 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 238000009740 moulding (composite fabrication) Methods 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 87
- 238000000034 method Methods 0.000 claims description 38
- 239000004408 titanium dioxide Substances 0.000 claims description 30
- 239000010936 titanium Substances 0.000 claims description 27
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 16
- 238000006722 reduction reaction Methods 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000009694 cold isostatic pressing Methods 0.000 claims description 5
- 238000001272 pressureless sintering Methods 0.000 claims description 5
- 238000002490 spark plasma sintering Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000009768 microwave sintering Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000009832 plasma treatment Methods 0.000 claims description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 description 48
- 230000008569 process Effects 0.000 description 14
- 238000000498 ball milling Methods 0.000 description 11
- 206010021143 Hypoxia Diseases 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000002950 deficient Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 5
- 229910052582 BN Inorganic materials 0.000 description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 230000007954 hypoxia Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000013001 point bending Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002730 additional effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000000462 isostatic pressing Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000021384 green leafy vegetables Nutrition 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- -1 magnesium aluminate Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000013021 overheating Methods 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
- 238000005498 polishing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Abstract
The invention relates to oxide ceramic based on oxygen vacancy defect regulation and a preparation method thereof. The preparation method of the oxide ceramic based on oxygen vacancy defect regulation comprises the following steps: mixing a Magneli phase sintering aid containing oxygen vacancy defects with oxide ceramic raw material powder under an anaerobic condition to obtain an oxide ceramic mixed raw material, drying, sieving, forming into a biscuit, and sintering and aftertreatment to obtain the oxide ceramic based on oxygen vacancy defect regulation; the mass ratio of the Magneli phase sintering auxiliary agent containing oxygen vacancy defects and the oxide ceramic raw material powder is 0.5-10% and the mass ratio of the oxide ceramic raw material powder is 90-99.5% based on 100% of the total mass of the Magneli phase sintering auxiliary agent containing oxygen vacancy defects and the oxide ceramic raw material powder.
Description
Technical Field
The invention belongs to the technical field of oxide ceramic material preparation, and particularly relates to a preparation method for improving the density and mechanical strength of an oxide ceramic material based on the regulation and control of the oxygen vacancy defect concentration of a ceramic powder raw material.
Background
Oxide ceramics are ceramics made of one or more oxides, and can be divided into single oxide ceramics (such as alumina, beryllium oxide, titanium dioxide ceramics and the like) and composite oxide ceramics (such as spinel, mullite and the like) according to the components. Oxide ceramics generally have higher melting temperatures, are more stable in oxidizing atmospheres, and have higher mechanical strength, electrical insulating properties, and chemical stability, and are widely used. The oxide ceramic can be formed by adopting various forming methods such as hot die casting, dry pressing, isostatic pressing, casting, extrusion, grouting and the like according to the shape and performance requirements of the product. Most articles are fired in an oxidizing atmosphere, sometimes with vacuum, hydrogen or controlled atmosphere sintering, and the process of preparation includes the steps of presintering, formulation, milling, shaping, and sintering.
The high-performance ceramic has various excellent performances and is widely applied to industrial equipment. Oxide ceramics typified by alumina and titania are important components indispensable for high-performance ceramics. The preparation of high performance oxide ceramics has become an urgent need in the critical industries of aerospace, electronics, military equipment, medical machinery, and the like. In order to meet the requirements of high density, high performance and high efficiency of ceramics, the adjustment of the sintering mode and the optimization of the raw material proportion are two main research directions at present. In addition to adjusting the applied temperature field, the sintering mode can be adjusted by adopting a novel sintering technology with a plurality of external physical fields, including hot isostatic pressing sintering, spark plasma sintering, microwave sintering and the like. In the aspect of optimizing the raw material proportion, the addition of the sintering aid is a common method.
Titanium dioxide is an excellent sintering aid additive for various oxide ceramics, for example, the sintering of the alumina ceramics can be enhanced by forming an alumina-titanium dioxide solid solution, and the ceramic forming process of the ceramics can be promoted by promoting the crystallization and mineralization of magnesium aluminate spinel and mullite. However, ceramics prepared from the ceramic composition still have the problem of insufficient performance under severe environmental requirements. On this basis, it is necessary to develop a more effective sintering aid or sintering aid method.
Disclosure of Invention
Aiming at the technical problems, the invention provides a method for promoting the further densification of oxide ceramics based on the regulation and control of oxygen vacancy defects, and the ceramic material prepared by the preparation method provided by the invention has more excellent compactness and mechanical property and is easier to obtain functionality compared with ceramics prepared by adopting a non-defective sintering auxiliary agent under the same sintering system.
In a first aspect, the present invention provides a method for preparing an oxide ceramic based on oxygen vacancy defect control, the method comprising the steps of: mixing a Magneli phase sintering aid containing oxygen vacancy defects with oxide ceramic raw material powder under an anaerobic condition to obtain an oxide ceramic mixed raw material, drying, sieving, forming into a biscuit, and sintering and aftertreatment to obtain the oxide ceramic based on oxygen vacancy defect regulation;
the mass ratio of the Magneli phase sintering auxiliary agent containing oxygen vacancy defects and the oxide ceramic raw material powder is 0.5-10% and the mass ratio of the oxide ceramic raw material powder is 90-99.5% based on 100% of the total mass of the Magneli phase sintering auxiliary agent containing oxygen vacancy defects and the oxide ceramic raw material powder.
Preferably, the Magneli phase sintering aid containing oxygen vacancy defects is Magneli phase titanium oxide and Magneli phase vanadium oxide; preferably, the Magneli phase titanium oxide comprises Ti 4 O 7 、Ti 5 O 9 、Ti 6 O 11 、Ti 7 O 13 、Ti 8 O 15 、Ti 9 O 17 、Ti 10 O 19 A single phase or a mixed phase of said single phases.
Preferably, the Magneli phase sintering aid containing oxygen vacancy defects has an oxygen vacancy concentration of 5 to 12.5 mole fraction.
Preferably, the powder particle size of the Magneli phase sintering aid containing oxygen vacancy defects is 0.1-10 μm.
Preferably, the preparation method of the Magneli phase sintering aid containing oxygen vacancy defects adopts a mahalanobis phase preparation method, and is preferably carbothermic reduction, metal thermal reduction, reducing atmosphere reduction, metal oxidation, thermal plasma treatment and ultraviolet irradiation.
Preferably, the process for preparing Magneli-phase titanium oxide by carbothermal reduction reaction comprises the following steps: mixing titanium dioxide powder with nano carbon powder, grinding, drying, sieving, heating the sieved powder to 975-1100 ℃ at a speed of 3-10 ℃/min in a vacuum environment, and reacting for 2-6 h to obtain Magneli-phase titanium oxide powder.
Preferably, the oxide ceramic raw material powder comprises Al 2 O 3 、ZrO、TiO 2 At least one of ZnO; the particle size of the oxide ceramic raw material powder is 0.1-10 mu m.
Preferably, the biscuit forming mode comprises dry press forming, cold isostatic press forming and warm isostatic press forming; preferably, dry press molding is performed and then cold isostatic press molding is performed; the dry pressing forming pressure is 10-50MPa, and the pressure maintaining time is 1-10min; the pressure of the cold isostatic pressing is 100-500MPa, and the pressure maintaining time is 1-10min.
Preferably, the sintering mode comprises normal pressure sintering, pressureless sintering, hot press sintering, flash sintering, microwave sintering, spark plasma sintering and oscillating pressure sintering, and the sintering atmosphere comprises air, vacuum, inert gas and oxidizing gas; sintering is preferably performed under an atmospheric oxidizing gas atmosphere;
the sintering procedure is to heat up to 1000-1600 deg.C at the rate of 3-15 deg.C/min, then cool down to 900-1500 deg.C for 3-30min, keep the temperature for 1-12h, and finally cool down to room temperature at the rate of 3-15 deg.C/min.
In a second aspect, the present invention provides an oxide ceramic based on oxygen vacancy defect control obtained according to the above-described production method.
Advantageous effects
(1) According to the invention, mganeli phase sintering aids such as titanium dioxide are used for partially or completely replacing sintering aids such as titanium dioxide commonly used in oxide ceramics, so that oxygen vacancy defects with adjustable content are introduced into powder before ceramic sintering, the sintering performance and the conductivity of the ceramics are effectively enhanced due to the oxygen deficiency and the existence of a conductive phase, and the density and the mechanical property of a ceramic finished product are optimized;
(2) The oxide ceramic densification method based on oxygen vacancy defect regulation has certain universality, has universality on oxide ceramics which can use Mganeli phase sintering aids such as titanium dioxide and the like, and basically does not need to change the existing preparation flow;
(3) Compared with the traditional method, the ceramic prepared by the method has the advantages of obviously improved performance, obviously reduced sintering temperature, and simple and efficient implementation method.
Drawings
FIG. 1 is a TG/DTA plot of the Magneli-phase titanium oxide prepared in example 1;
FIGS. 2a and b are SEM pictures (magnification of 500) of samples T, TM-15%, respectively, prepared according to example 1;
FIG. 3 is a graph showing the sintering shrinkage of the pure phase ball milled titania added to example 2 with 10wt% magneli phase added.
Detailed Description
The invention is further illustrated by the following embodiments, it being understood that the following embodiments are merely illustrative of the invention and not limiting thereof.
The invention replaces the traditional sintering aids such as titanium dioxide and the like with the corresponding anoxic Magneli phases obtained after moderate reduction, thereby improving the anoxic degree in the sintering aid powder, and introducing oxygen vacancy defects with specific concentration when preparing the ceramic raw powder. The oxygen vacancy defects have different influences in different sintering methods of different sintering atmospheres, but the results can better promote the sintering of oxide ceramics, so that the prepared oxide ceramic sample has better properties such as compactness, mechanical strength and the like.
In the pressureless sintering process of air atmosphere, oxygen added into pores in a ceramic biscuit of Magneli phase powder fills oxygen vacancies to be converted into lattice oxygen so as to reduce the pores in the sintering process, and meanwhile, compared with the original powder, the volume expansion effect is 7.5%. In addition, even if oxidation occurs, more oxygen vacancies remain in the powder than in the ceramic greenware without the Magneli powder added, so that the sintering activity of the ceramic at higher temperatures can still be improved.
In the vacuum pressureless sintering process, the Magneli phase can reduce the sintering temperature of the oxide ceramic due to more defects, and the density of the oxide ceramic is improved under the same sintering condition.
During the flash process, the moderate Magneli phase acts as a conductive second phase, thereby lowering the critical temperature and critical current of the flash.
The following is an exemplary description of a method for preparing oxide ceramics based on oxygen vacancy defect control provided by the present invention. The preparation method can comprise the following steps: mixing a Magneli phase sintering aid containing oxygen vacancy defects with oxide ceramic raw material powder under the anaerobic condition to obtain an oxide ceramic mixed raw material, drying, sieving, forming into a biscuit, sintering and post-treating to obtain the oxide ceramic based on oxygen vacancy defect regulation.
Oxygen vacancy defects can be introduced into the ceramic material by adopting the Magneli phase sintering aid containing the oxygen vacancy defects so as to enhance the sintering activity of the oxide ceramic and further enhance the density and mechanical strength of the ceramic finished product after sintering.
In some embodiments, the Magneli phase sintering aid containing oxygen vacancy defects may be Magneli phase titanium oxide, magneli phase vanadium oxide; preferably, the Magneli phase titanium oxide may include Ti 4 O 7 、Ti 5 O 9 、Ti 6 O 11 、Ti 7 O 13 、Ti 8 O 15 、Ti 9 O 17 、Ti 10 O 19 A single phase or a mixed phase of said single phases.
In some embodiments, the Magneli phase sintering aid containing oxygen vacancy defects may have an oxygen vacancy concentration of 5 to 12.5 mole fraction. Wherein, the oxygen deficiency degree of the Magneli phase sintering aid containing oxygen vacancy defects can be analyzed by means of thermogravimetric analysis, XRD and the like of oxidation reaction, so as to help determine the oxygen deficiency powder consumption.
In some embodiments, the powder particle size of the Magneli phase sintering aid containing oxygen vacancy defects may be 0.1-10 μm to maintain good dispersion properties of the oxygen-deficient powder.
In some embodiments, the Magneli phase sintering aid containing oxygen vacancy defects may be prepared by a conventional mahalanobis phase preparation method, preferably carbothermic reduction, metallothermic reduction, reducing atmosphere reduction, metal oxidation, thermal plasma treatment, and ultraviolet irradiation.
As an example, the process for preparing Magneli phase titanium oxide using carbothermal reduction reaction may be: weighing 50-100 g of titanium dioxide powder with the particle size of 1-5 mu m and nano carbon powder accounting for 4-5% of the mass of the titanium dioxide powder, placing the titanium dioxide powder and the nano carbon powder into a polyurethane ball milling tank, adding zirconium oxide grinding balls with the diameter of 5-10 mm and absolute ethyl alcohol, and controlling the powder: grinding ball: absolute ethanol at 2: 3-4: 3-4, ball milling for 6-12h at a speed of 300-500 r/min, pouring out slurry, drying for 6-12h at a temperature of 60-100 ℃, sieving the dried powder with a 100-300 mesh sieve, placing the sieved powder into a boron nitride crucible, placing the boron nitride crucible into a vacuum carbon furnace, heating to 975-1100 ℃ at a speed of 3-10 ℃/min for reacting for 2-6 h, preferably heating to 1000-1050 ℃ at a speed of 5-10 ℃/min for reacting for 2-4 h, and obtaining the Magneli-phase titanium oxide powder.
In some embodiments, the oxide ceramic raw material powder may include Al 2 O 3 、ZrO、TiO 2 At least one of ZnO; the particle size of the oxide ceramic raw material powder can be 0.1-10 mu m.
The determination of the proportion of the Magneli phase sintering aid containing the oxygen vacancy defect can be performed according to the condition of the influence of the addition of the oxygen vacancy on the performance of the specific oxide ceramic in an actual test and the dosage proportion when the oxide ceramic is suitable for the corresponding non-defect state sintering aid, or can be performed according to the auxiliary determination of the phase diagram of elements in the target ceramic and the Magneli phase sintering aid containing the oxygen vacancy defect, the stacking density of the green body and the like, namely, the addition proportion of the Magneli phase powder is finally determined through the common analysis of the oxygen vacancy concentration and the oxygen deficiency of the Magneli phase based on the expected oxygen vacancy degree and the related phase diagram. And obtaining a qualitative/semi-quantitative relation between the performance of the ceramic sample and the concentration of oxygen vacancies through experiments and analysis, and determining the final oxygen-deficient powder adding amount according to the performance target.
In some embodiments, the Magneli phase sintering aid containing oxygen vacancy defects is present in an amount of 0.5 to 10% by mass and the oxide ceramic raw material powder is present in an amount of 90 to 99.5% by mass, based on 100% by mass of the total of the Magneli phase sintering aid containing oxygen vacancy defects and the oxide ceramic raw material powder.
In some embodiments, other kinds of sintering aids, binders, dispersants, plasticizers, coupling agents may also be included in the oxide ceramic mix raw materials.
In some embodiments, the mode of mixing the Magneli phase sintering aid containing oxygen vacancy defects and the oxide ceramic raw material powder can be planetary ball milling, and the planetary ball milling process can be ball milling for 3-12 hours at a rotating speed of 100-500 r/min, and meanwhile forward and reverse exchange is carried out every 15-20min to prevent local overheating.
The drying process under the anaerobic condition can be carried out for 12 hours at 60-80 ℃.
The powder which is basically uniform and has no obvious agglomeration can be obtained through sieving, the mesh number of the sieving can be 50-200 meshes, the mesh number of the sieving influences the thickness of the powder, and the sieving can be adjusted according to the condition of products.
In some embodiments, the manner in which the greens are formed may include dry press forming, cold isostatic forming, warm isostatic pressing; preferably, dry press molding is performed and then cold isostatic press molding is performed; the dry-pressing forming pressure can be 10-50MPa, preferably 15-20MPa, and the dwell time can be 1-10min, preferably 2-5min; the pressure of the cold isostatic pressing may be in the range of 100-500MPa, preferably 200-250MPa, and the dwell time may be in the range of 1-10min, preferably 2-5min. Of course, the raw material mixing mode can be adjusted to be added with dispersing agent, plasticizer or coupling agent, etc. after the ceramic slurry is prepared by adopting proper flow, 3D printing forming, tape casting forming, etc. can be adopted.
In some embodiments, the sintering mode may include normal pressure sintering, pressureless sintering, hot press sintering, flash sintering, microwave sintering, spark plasma sintering, oscillating pressure sintering; the sintering atmosphere may include air, vacuum, inert gas, oxidizing gas, etc.; preferably sintering under normal pressure oxidizing gas atmosphere, the sintering under oxygen-containing atmosphere can make the magneli phase powder contained in the powder absorb oxygen and expand, and the characteristic of the invention is fully utilized to exert good influence on the result.
In some embodiments, the sintering procedure may be: heating to 1000-1600 deg.C at a rate of 3-15 deg.C/min, cooling to 900-1500 deg.C for 3-30min, maintaining for 1-12h, and cooling to room temperature at a rate of 3-15 deg.C/min; preferably, the temperature is raised to 1400-1500 ℃ at a rate of 5-8 ℃/min, then the temperature is lowered to 1200-1400 ℃ for 5-15min, the temperature is kept for 6-10h, and finally the temperature is lowered to the room temperature at a rate of 5-10 ℃/min. The sintering schedule is different according to the different properties of the sintering method and the raw material powder, and different sintering schedules are required to be respectively formulated for different kinds of ceramics and different kinds of sintering methods.
In some embodiments, the post-treatment process may include tempering at a suitable temperature, excision polishing of the sample surface layer, and the like.
The preparation method provided by the invention can quantitatively or semi-quantitatively adjust the oxygen deficiency degree in the powder, and can also be used for preparing other types of oxide ceramic oxygen deficiency powder.
It should be noted that, unlike the case where a raw material powder with high defects is used as a reactant to directly participate in the formation of a main phase of ceramic, the scheme of using a raw material powder with high defects is limited to a certain extent in the reaction sintering that requires participation of a raw material powder with high defects of a special kind, and the action mechanism is mainly to promote the flash sintering process by improving the conductivity of the initial reactant due to the existence of defects. However, the highly defective Magneli phase sintering aid of the invention can be used in the preparation of oxide ceramics for which the corresponding non-defective sintering aid is suitable, and is also better than the corresponding non-defective sintering aidThe agent can play a better role in helping burning. Taking the defective titanium dioxide sintering aid as an example, the action mechanism is various, and besides the sintering aid effect of the titanium dioxide, oxygen defects in the magneli phase bring the following additional effects (and the additional effects which are not completely the same with the change of the sintering atmosphere and the sintering environment): (1) under an oxygen-containing atmosphere: magneli (4.27-4.5 g/cm) 3 ) Phase-meeting oxygen uptake oxidation occurs to rutile titanium dioxide (4.25 g/cm) 3 ) The mass increase density decreases, which brings about a volume expansion of more than 7%, so that the point contact between the powder particles increases to promote sintering; (2) self-characteristics: whether or not subjected to oxidation, the Magneli phase leaves more interstices Ti in the ceramic body 3+ And defects in the crystal such as oxygen vacancies, wherein the presence of the defects promotes the transport of substances and thus the sintering activity (the melting point and the sintering temperature of the magneli phase are both 150 ℃ lower than those of titanium dioxide in stoichiometric ratio); (3) under the action of an electric field: the magneli phase is a very good electric conductor (theoretical value can reach 1900S/cm at most), and under the sintering mode of using electromagnetic energy such as flash sintering, spark plasma sintering and the like, the existence of the magneli phase can promote the overall conductivity of reactants (such as ceramic greenware) so as to promote the sintering process under the action of an electric field.
The oxide ceramic based on oxygen vacancy defect regulation and control obtained by the preparation method provided by the invention has excellent density and mechanical property, and compared with ceramic prepared by using a conventional non-defective sintering aid with a stoichiometric ratio as a sintering aid, the oxide ceramic based on oxygen vacancy defect regulation and control has the advantages that the density is improved by 3-30%, the three-point bending strength is improved by 5-40%, and the compressive strength is improved by 5-50%.
The present invention will be described in more detail by way of examples. It should also be understood that the following examples are given by way of illustration only and are not to be construed as limiting the scope of the invention, since various insubstantial modifications and adaptations of the invention to those skilled in the art based on the foregoing disclosure are intended to be within the scope of the invention and the specific process parameters and the like set forth below are merely one example of a suitable range within which one skilled in the art would choose from the description herein without being limited to the specific values set forth below.
Example 1
The Magneli phase self-doped titanium dioxide ceramic is sintered in air in a pressureless manner to enhance the performance of the titanium dioxide ceramic, and the specific steps are as follows:
1. and preparing Magneli-phase titanium oxide powder by adopting carbothermic reduction reaction. Weighing 100g of titanium dioxide powder with the particle size of 1 mu m and nano carbon powder accounting for 5% of the mass of the titanium dioxide powder, placing the titanium dioxide powder and the nano carbon powder into a polyurethane ball milling tank, adding zirconia grinding balls with the diameter of 5-10 mm and absolute ethyl alcohol, and controlling the powder: grinding ball: absolute ethanol at 2:3:3, then carrying out planetary ball milling for 12 hours at a speed of 300r/min, pouring out slurry, drying at 80 ℃ for 12 hours, sieving the dried powder with a 100-mesh sieve, placing the sieved powder into a boron nitride crucible, placing the crucible into a vacuum carbon furnace, and heating to 1025 ℃ at a speed of 10 ℃ per minute for reaction for 2 hours to obtain blue-black Magneli phase powder.
Analysis of the hypoxia degree of the Magneli phase by TG/DTA as shown in FIG. 1 (mass increase after oxidation 4.69%) gave a hypoxia degree of between Ti 4 O 7 (5.2%) with Ti 5 O 9 (4.1%) of Ti 4 O 7 With Ti 5 O 9 Is presumed to be TiO based on the calculated specific chemical formula 1.77 . (calculated as titanium dioxide in strict adherence to stoichiometric ratio, ti 4 O 7 With Ti 5 O 9 The degree of hypoxia at a molar ratio of 12.5% to 10%,5.2% to 4.1% being the mass ratio of defects).
2. Mixing the anoxic powder with the matrix powder to prepare the powder. Because the Magneli phase doped titanium dioxide is self-doped, the oxygen in the air becomes in-phase with the matrix after oxidizing the Magneli, and the lattice matching is realized, so that the large-dose addition is adopted in the embodiment. 85g of titanium dioxide powder and 15g of Magneli powder are weighed, and 0.045mol of vacancy oxygen is equivalently introduced into 100g of powder. Placing the powder into a polyurethane ball milling tank, adding zirconia grinding balls with the diameter of 8mm and absolute ethyl alcohol, and adding the powder: grinding ball: absolute ethanol at 2:3:3, performing planetary ball milling for 12 hours at a speed of 300r/min, pouring out slurry, drying at 80 ℃ for 12 hours, sieving with a 100-mesh sieve, placing into a stainless steel die, performing dry pressing and pressure maintaining for 3 minutes at 20MPa, forming blocks, placing into a plastic package bag, performing plastic package, and performing pressure maintaining for 3 minutes at 250MPa by adopting a cold isostatic pressing method to obtain a ceramic biscuit. For comparison, a pure phase titania ceramic biscuit without added Magneli phase was prepared using the same procedure.
3. The biscuit is placed on an alumina support and placed in a muffle furnace. Setting a sintering program to heat up to 1400 ℃ at 5 ℃/min, then cooling to 1250 ℃ for 10min, preserving heat for 8h, and finally cooling to room temperature at a rate of 5 ℃/min, wherein the whole sintering process is all under the air atmosphere.
And processing the sintered ceramic and measuring the three-point bending strength and the compactness of the ceramic. The resulting ceramic with 15wt% of the powder of the Magneli phase added was designated as TM-15% and the pure titania ceramic without the Magneli phase added was designated as T, and the relevant parameters are shown in Table 1.
Table 1 parameters of the properties of the ceramic prepared in example 1:
| density/(g cm) -3 ) | Density/% | Flexural Strength/MPa | |
| T | 3.56 | 83.97 | 58.38 |
| TM-15％ | 3.63 | 85.60 | 132.19 |
。
Example 2
The performance of the titanium dioxide ceramic is enhanced by adopting Magneli phase self-doped titanium dioxide ceramic to be sintered in vacuum under no pressure, and the specific steps are as follows:
1. and preparing Magneli-phase titanium oxide powder by adopting carbothermic reduction reaction. This step is referred to as example 1 step 1.
2. Mixing the anoxic powder with the matrix powder to prepare powder: 80g of titanium dioxide powder with the particle size of 1 mu m and 20g of Magneli powder are weighed, placed into a polyurethane ball milling tank, zirconia grinding balls with the diameter of 8mm and absolute ethyl alcohol are added, and the powder is prepared by the steps of: grinding ball: absolute ethanol at 2:3:3, performing planetary ball milling for 12 hours at a speed of 300r/min, pouring out slurry, drying at 80 ℃ for 12 hours, sieving with a 100-mesh sieve, placing into a stainless steel die, performing dry pressing and pressure maintaining for 3 minutes at 20MPa, forming blocks, placing into a plastic package bag, performing plastic package, and performing pressure maintaining for 3 minutes at 250MPa by adopting a cold isostatic pressing method to obtain a ceramic biscuit. The same flow is adopted to prepare pure-phase titanium dioxide ceramic biscuit without adding Magneli phase, and the mass ratio of titanium dioxide powder to Magneli phase powder is 9: 1.
3. All three kinds of biscuit are placed in a boron nitride crucible and are placed in a vacuum sintering furnace. The sintering schedule was still two-step and the same as in example 1, with a sintering procedure of 5 ℃/min to 1400 ℃, 10min to 1250 ℃ and 8h incubation, and finally 5 ℃/min to room temperature. The whole sintering process is carried out in a near vacuum environment of <100 Pa.
And processing the sintered ceramic and measuring the three-point bending strength and the compactness of the ceramic. The obtained ceramics added with 10wt% and 20wt% of Magneli phase powder were respectively denoted as TMV-10% and TMV-20%, and pure titania ceramics without added with Magneli phase was denoted as TV, and the relevant performance parameters thereof are shown in Table 2.
Table 2 performance parameters of the ceramic prepared in example 2:
| density/(g cm) -3 ) | Density/% | Flexural Strength/MPa | |
| TV | 3.51 | 82.77 | 22.68 |
| TMV-10％ | 3.74 | 88.20 | 29.255 |
| TMV-20％ | 3.83 | 90.17 | 24.41 |
。
The higher density and poorer flexural strength of the results of example 2 compared with the results of example 1 are due to the stronger sintering activity of the titania ceramic in the vacuum environment, which results in an increase in density, while the mechanical strength decreases due to the occurrence of a degree of overburning, which proves that a reasonable and appropriate modification of the sintering schedule is required as the sintering mode changes. With the increase of the addition amount of the Magneli phase in the titanium dioxide, both the example 1 and the example 2 show higher and higher compactness, and particularly the results shown in the table 1 and the table 2 show that the Magneli has a practical burning assisting effect relative to the titanium dioxide under proper conditions. Fig. 3 demonstrates that the addition of Magneli phase can advance the densification process, the shrinkage of curve No. 2 is 100 ℃ earlier than that of curve No. 1, and the anoxic phase also affects the subsequent reaction process, and the shrinkage of curve No. 2 is significantly divided into two stages.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Many modifications and substitutions of the present invention will become apparent to those of ordinary skill in the art upon reading the foregoing. Accordingly, the scope of the invention should be limited only by the attached claims.
Claims (10)
1. The preparation method of the oxide ceramic based on oxygen vacancy defect regulation is characterized by comprising the following steps of: mixing a Magneli phase sintering aid containing oxygen vacancy defects with oxide ceramic raw material powder under an anaerobic condition to obtain an oxide ceramic mixed raw material, drying, sieving, forming into a biscuit, and sintering and aftertreatment to obtain the oxide ceramic based on oxygen vacancy defect regulation;
the mass ratio of the Magneli phase sintering auxiliary agent containing oxygen vacancy defects and the oxide ceramic raw material powder is 0.5-10% and the mass ratio of the oxide ceramic raw material powder is 90-99.5% based on 100% of the total mass of the Magneli phase sintering auxiliary agent containing oxygen vacancy defects and the oxide ceramic raw material powder.
2. The preparation method according to claim 1, wherein the Magneli phase sintering aid containing oxygen vacancy defects is Magneli phase titanium oxide or Magneli phase vanadium oxide; preferably, the Magneli phase titanium oxide comprises Ti 4 O 7 、Ti 5 O 9 、Ti 6 O 11 、Ti 7 O 13 、Ti 8 O 15 、Ti 9 O 17 、Ti 10 O 19 Single phase or mixture of said single phasesAnd (3) phase (C).
3. The preparation method according to claim 1 or 2, characterized in that the Magneli phase sintering aid containing oxygen vacancy defects has an oxygen vacancy concentration of 5-12.5% by mole fraction.
4. A production method according to any one of claims 1 to 3, wherein the powder particle size of the Magneli phase sintering aid containing oxygen vacancy defects is 0.1 to 10 μm.
5. The preparation method according to any one of claims 1 to 4, wherein the preparation method of Magneli phase sintering aid containing oxygen vacancy defects adopts a mahalanobis phase preparation method, preferably carbothermic reduction, metallothermic reduction, reducing atmosphere reduction, metal oxidation, thermal plasma treatment, ultraviolet irradiation.
6. The preparation method according to any one of claims 1 to 5, wherein the process for preparing Magneli-phase titanium oxide by carbothermal reduction reaction comprises: mixing titanium dioxide powder with nano carbon powder, grinding, drying, sieving, heating the sieved powder to 975-1100 ℃ at a speed of 3-10 ℃/min in a vacuum environment, and reacting for 2-6 h to obtain Magneli-phase titanium oxide powder.
7. The method according to any one of claims 1 to 6, wherein the oxide ceramic raw material powder comprises Al 2 O 3 、ZrO、TiO 2 At least one of ZnO; the particle size of the oxide ceramic raw material powder is 0.1-10 mu m.
8. The method according to any one of claims 1 to 7, wherein the biscuit forming means comprises dry press forming, cold isostatic forming, warm isostatic forming; preferably, dry press molding is performed and then cold isostatic press molding is performed; the dry pressing forming pressure is 10-50MPa, and the pressure maintaining time is 1-10min; the pressure of the cold isostatic pressing is 100-500MPa, and the pressure maintaining time is 1-10min.
9. The method according to any one of claims 1 to 8, wherein the sintering means comprises normal pressure sintering, pressureless sintering, hot press sintering, flash sintering, microwave sintering, spark plasma sintering, oscillating pressure sintering, the sintering atmosphere comprising air, vacuum, inert gas, oxidizing gas; sintering is preferably performed under an atmospheric oxidizing gas atmosphere;
the sintering procedure is to heat up to 1000-1600 deg.C at the rate of 3-15 deg.C/min, then cool down to 900-1500 deg.C for 3-30min, keep the temperature for 1-12h, and finally cool down to room temperature at the rate of 3-15 deg.C/min.
10. An oxide ceramic based on oxygen vacancy defect control obtained according to the production method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311215630.6A CN117263658A (en) | 2023-09-20 | 2023-09-20 | Oxide ceramic based on oxygen vacancy defect regulation and control and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311215630.6A CN117263658A (en) | 2023-09-20 | 2023-09-20 | Oxide ceramic based on oxygen vacancy defect regulation and control and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117263658A true CN117263658A (en) | 2023-12-22 |
Family
ID=89219015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311215630.6A Pending CN117263658A (en) | 2023-09-20 | 2023-09-20 | Oxide ceramic based on oxygen vacancy defect regulation and control and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117263658A (en) |
-
2023
- 2023-09-20 CN CN202311215630.6A patent/CN117263658A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2003004437A1 (en) | Translucent rare earth oxide sintered article and method for production thereof | |
| JPH07277814A (en) | Alumina-based ceramic sintered compact | |
| CN115745607A (en) | Infrared transparent ceramic material and preparation method thereof | |
| CN108863395B (en) | High-thermal-conductivity and high-strength silicon nitride ceramic material and preparation method thereof | |
| JPH05170532A (en) | Production of zirconia sintered product | |
| CN116854472A (en) | Microwave dielectric material and preparation method thereof | |
| CN115010491B (en) | High-entropy rare earth tantalate ceramic material and preparation method thereof | |
| CN115073186B (en) | Silicon nitride ceramic sintered body and preparation method thereof | |
| CN117263658A (en) | Oxide ceramic based on oxygen vacancy defect regulation and control and preparation method thereof | |
| CN114835473B (en) | Alumina ceramic and preparation method thereof | |
| CN112898022B (en) | Ultralow temperature sintered microwave dielectric material Ca2V2O7-H3BO3And method for preparing the same | |
| CN108147834A (en) | Regulatable lightweight silicon nitride antenna house of dielectric constant and preparation method thereof | |
| KR20190023485A (en) | Aluminum nitride sintered body and method for manufacturing the same | |
| CN112441830B (en) | High-quality-factor yttrium-doped zirconia microwave dielectric ceramic material and preparation method thereof | |
| JP2001089229A (en) | Electrically conductive ceramic and its production | |
| CN110818413A (en) | Aluminum molybdate based microwave dielectric composite ceramic sintered at extremely low temperature and preparation method thereof | |
| JP4065589B2 (en) | Aluminum nitride sintered body and manufacturing method thereof | |
| CN117447202B (en) | Single-phase microwave dielectric ceramic powder, microwave dielectric ceramic material and preparation method thereof | |
| CN115433008B (en) | Bismuth calcium niobate piezoelectric ceramic with high-voltage electrical property and high-temperature resistivity regulated and controlled by self components and preparation method thereof | |
| CN114057504B (en) | Low-thermal-conductivity calcium zirconate material and preparation method thereof | |
| CN117263665B (en) | Method for preparing cordierite ceramic by reaction sintering | |
| CN112410638B (en) | Zirconium oxide-based metal composite ceramic and preparation method thereof, zirconium oxide biological ceramic prosthesis and application thereof | |
| KR102510280B1 (en) | High Purity and High Density Yttrium Aluminum Garnet Sintered Body And Manufacturing Method Thereof | |
| JP4761693B2 (en) | Heat-resistant conductive ceramics | |
| JP4560328B2 (en) | Lanthanum chromite heating element having heating part and terminal part and method for manufacturing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |