CN114538925B - Preparation method of high-strength high-stability vanadium oxide electronic phase change composite ceramic - Google Patents

Preparation method of high-strength high-stability vanadium oxide electronic phase change composite ceramic Download PDF

Info

Publication number
CN114538925B
CN114538925B CN202210082967.3A CN202210082967A CN114538925B CN 114538925 B CN114538925 B CN 114538925B CN 202210082967 A CN202210082967 A CN 202210082967A CN 114538925 B CN114538925 B CN 114538925B
Authority
CN
China
Prior art keywords
oxide
composite
vanadium oxide
phase
composite ceramic
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.)
Active
Application number
CN202210082967.3A
Other languages
Chinese (zh)
Other versions
CN114538925A (en
Inventor
陈吉堃
周轩弛
张秀兰
姜勇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Science and Technology Beijing USTB
Original Assignee
University of Science and Technology Beijing USTB
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by University of Science and Technology Beijing USTB filed Critical University of Science and Technology Beijing USTB
Priority to CN202210082967.3A priority Critical patent/CN114538925B/en
Publication of CN114538925A publication Critical patent/CN114538925A/en
Application granted granted Critical
Publication of CN114538925B publication Critical patent/CN114538925B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C04B35/495—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 vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • 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
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
    • 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
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
    • 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
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3229—Cerium oxides or oxide-forming salts thereof
    • 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
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • 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
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • 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
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
    • 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
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3256—Molybdenum oxides, molybdates or oxide forming salts thereof, e.g. cadmium molybdate
    • 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
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
    • 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
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
    • 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
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3279—Nickel oxides, nickalates, or oxide-forming salts thereof
    • 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
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • 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
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/666—Applying a current during sintering, e.g. plasma sintering [SPS], electrical resistance heating or pulse electric current sintering [PECS]
    • 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
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/786—Micrometer sized grains, i.e. from 1 to 100 micron

Abstract

The invention belongs to the fields of metal functional semiconductor oxides, sensitive resistance materials and devices, electronic ceramics and the like, and particularly relates to a technical method for realizing coherent sintering of an oxide composite phase and vanadium oxide grains by a rapid thermal treatment process. The method is characterized in that an oxide composite phase with a certain proportion and a crystal structure and lattice parameters similar to those of vanadium oxide powder is added, and coherent sintering between vanadium oxide matrix crystal grains and composite phase oxides is realized through a high-energy scale heat treatment process, so that the mechanical strength, the electronic phase change functional stability, the fatigue resistance and the thermal shock resistance of the vanadium oxide electronic phase change material are greatly improved. Sensitive components such as a mutation type thermistor, a pressure sensitive resistor and the like further prepared from the composite vanadium oxide electronic phase change material have higher electronic phase change functional stability, mechanical property, aging resistance and thermal shock resistance, and the service life of the composite vanadium oxide electronic phase change material is obviously prolonged under extreme environments such as low temperature, high pressure, high radiation and the like.

Description

Preparation method of high-strength high-stability vanadium oxide electronic phase change composite ceramic
Technical Field
The invention belongs to the fields of metal functional semiconductor oxides, sensitive resistance materials and devices, electronic ceramics and the like, and particularly relates to a technical method for realizing coherent sintering and spatial bridging of an oxide composite phase and vanadium oxide crystal grains by a rapid heat treatment process so as to greatly improve the mechanical strength, the electronic phase change functional stability, the fatigue resistance and the thermal shock resistance of a vanadium oxide electronic phase change material.
Background
Vanadium dioxide (VO) 2 ) Is a classical metal-insulator transition (MIT) strongly correlated electron oxide with temperature-induced phase transition characteristic, i.e. at the metal-insulator transition temperature (T) MIT ) The above is a metal phase having a rutile structure, at T MIT The following is an insulating phase with a monoclinic structure [ Science,2008,318 (5857): 1750-1753 ]. In addition to temperature-induced triggering, VO 2 The electronic phase transition of (9) can also be triggered by means of hydrogen atmosphere, external electric field, ion droplet gating, ultra-high magnetic field, high voltage, etc. (nat. Commun., (2018) 9; nat. Nanotechnol.,2014, doi:10.1038/nnano.2014.71; commun.,2020,11 (1). Typical material as strong correlation systemMaterial, VO 2 The complex coupling of charges, spins, orbitals and crystal lattices in the system causes the electric, optical, thermal and magnetic properties thereof to be T MIT Mutations [ Nature,2013,500 (7463): 431-431 ] were made nearby. At the same time, VO 2 The phase change property of the material can be further adjusted by various methods such as element doping, oxygen vacancy, interface stress field, ambient oxygen partial pressure, ion implantation and the like. These unique advantages greatly improve VO 2 The material has application prospect in the fields of abrupt change type thermistors, non-refrigeration type infrared detectors self-supporting bridge membranes, intelligent window coatings and the like [ Science 374,1504-1509 (2021) ]; j. Eur. Ceram. Soc.,2003,23 (9): 1435-1439 ]. Recently, domestic and foreign companies such as Hitachi Japan utilize VO 2 Sensitive resistance devices such as critical temperature resistors with excellent performance are developed successively by materials, the sensitive resistance devices have negative resistance temperature coefficients, and resistance mutation (Jpn. J. Appl. Phys,1965,4,28) with 2-3 orders of magnitude can be generated at about 68 ℃.
Albeit VO 2 The phase change characteristic has considerable application prospect in the fields of sensitive resistance devices and the like, but VO 2 The problems of poor stability of electronic phase change function, low mechanical strength, insufficient fatigue resistance and thermal shock resistance and the like of the material are a core difficult problem in the field. The main reason is VO 2 The electronic phase change generated after the periodic thermal field cycling also generates structural phase change, the volume change generated by the crystal lattice is about 1%, and the structural change further causes the mechanical stress to be formed at the grain boundary. These mechanical stresses will inevitably lead to VO 2 The electronic ceramic material forms micro crack and other defects at the grain boundary, so that the electronic ceramic material is difficult to maintain a stable structural state when the electronic ceramic material is subjected to phase change, and VO is reduced 2 The mechanical strength and the electronic phase change function stability of the material.
In summary, the biggest difficulty restricting the application of the vanadium oxide electronic phase change material to the discrete sensitive resistor device at present is that the material crystal structure change accompanied by the electronic phase change is easy to generate micro cracks and other defects in the vanadium oxide ceramic material, so that the mechanical property of the material is gradually reduced in use, the basic resistance of the material is increased, and the resistivity change rate triggered by the electronic phase change is reduced at the same time. How to solve the problems from the material technical level becomes the key point for improving the functional stability and the service life of the vanadium oxide-based abrupt thermistor.
Disclosure of Invention
The invention aims to provide a preparation method of a composite vanadium oxide electronic phase change material with high strength and high stability, which is characterized in that a certain proportion of oxide composite phase with a crystal structure and lattice parameters similar to those of vanadium oxide powder is added into the vanadium oxide powder, and coherent sintering between vanadium oxide parent crystal grains and composite phase oxide is realized through a high-energy scale heat treatment process.
A preparation method of high-strength high-stability vanadium oxide electronic phase change composite ceramic is characterized by firstly providing vanadium oxide matrix material powder and one or more oxide composite phase powder, wherein the crystal structure and lattice parameters of the surface of the oxide composite phase powder and the surface of the vanadium oxide matrix are similar. The powder is uniformly mixed according to a certain proportion and sintered into a ceramic material at a preferred temperature and pressure, and the coherent nature of the interface of the parent phase and the composite phase can be further improved and the relative solid phase reaction degree of the interface of the vanadium oxide parent phase and the composite phase can be adjusted by applying the action of external fields such as continuous or pulse current, a magnetic field, high-energy rays and the like in the sintering process. Through coherent space bridging between the composite phase and the parent phase, the structural change of vanadium oxide in the process of triggering electronic phase change in a periodic thermal field can be inhibited, and crystal boundaries are pinned and strengthened so as to prevent generation and expansion of defects such as cracks in the ceramic material, thereby greatly improving the mechanical property and the thermal shock resistance of the prepared vanadium oxide composite ceramic material.
Furthermore, the oxidation process of the vanadium element in the intermediate valence state of +4 in the material to the valence of +5 in the air or the reduction process of the vanadium element in the intermediate valence state of +3 in the reducing atmosphere can be greatly slowed down by adjusting the polarity of the interface of the composite phase oxide and the vanadium oxide, so that the prepared vanadium oxide composite ceramic material has higher chemical stability and higher stability of the phase change function of the metal insulator.
Compared with the traditional vanadium oxide pure-phase ceramic, the vanadium oxide composite ceramic electronic phase change material prepared by the invention has higher chemical stability, functional characteristic stability and mechanical strength. Sensitive components such as a sudden change type thermistor, a pressure sensitive resistor, a non-refrigeration type infrared detector self-supporting bridge membrane and the like which are further prepared by the invention have higher electronic phase change function stability, aging resistance, irradiation resistance and thermal shock resistance, and the service life of the components is obviously prolonged under extreme environments such as low temperature, high pressure, high radiation and the like. In a preferred embodiment, vanadium dioxide and cerium dioxide powder are mixed and co-sintered by using the method provided by the invention, and the obtained electronic ceramic has higher electronic phase change functional stability, aging resistance, irradiation resistance and thermal shock resistance compared with a pure vanadium oxide material.
Further, the parent material in the composite ceramic is vanadium oxide, and comprises: vanadium dioxide (VO) 2 ) Vanadium trioxide (V) 2 O 3 ) And a compound in which the vanadium oxide compound is further doped with a transition element. The doping elements in the vanadium oxide doped with the transition group elements comprise tungsten (W), niobium (Nb), molybdenum (Mo), titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), aluminum (Al), hafnium (Hf) and the like. The vanadium oxide compound can generate the phase transition characteristic of a metal insulator under the trigger of characteristic temperature, and the resistivity of the vanadium oxide compound can generate mutation under the trigger of the characteristic temperature; the phase transition temperature of the metal insulator can be further regulated and controlled through the doping effect. In a preferred embodiment, vanadium dioxide and P25 type titanium dioxide powder with the particle size of about 10 nanometers are mixed and sintered by using the method provided by the invention, the sintered electronic ceramic material has typical temperature-induced phase change characteristics, and the reduction of the phase change temperature of the metal insulator is realized by continuously increasing the relative doping amount of the titanium dioxide.
Furthermore, the composite phase material in the composite ceramic is an oxide with a crystal structure and a lattice parameter close to those of the corresponding parent vanadium oxide on a certain crystal face, preferably titanium oxide (TiO) 2 ) Nickel oxide (NiO), aluminum oxide (Al) 2 O 3 ) Hafnium oxide (HfO) 2 ) Cerium oxide (CeO) 2 ) Terbium oxide (Tb) 4 O 7 ) Praseodymium oxide (Pr) 6 O 11 ) Lanthanum oxide (La) 2 O 3 ) Lutetium oxide (Lu) 2 O 3 ) Samarium oxide (Sm) 2 O 3 ) Neodymium oxide (Nd) 2 O 3 ) Thulium oxide (Tm) 2 O 3 ) Holmium oxide (Ho) 2 O 3 ) Erbium oxide (Er) 2 O 3 ) Europium oxide (Eu) 2 O 3 ) Yttrium oxide (Y) 2 O 3 ) Gadolinium oxide (Gd) 2 O 3 ) Dysprosium oxide (Dy) 2 O 3 ) Etc.; the surface of the used oxide composite powder and the surface of the vanadium oxide parent phase powder have similar two-dimensional crystal structures and lattice parameters.
Furthermore, by adjusting the chemical components, the particle size distribution, the morphology and the composite proportion of the selected oxide composite powder, the characteristics of the composite phase in the ceramic, such as the space distribution, the coherent state and the relative chemical reaction degree of the composite phase relative to the parent phase material, can be regulated, and the mechanical property and the electrical stability of the prepared composite vanadium oxide electronic phase change ceramic can be further improved. In the sintering process, the composite phase crystal face and the vanadium oxide parent phase crystal face are sintered together in a coherent form, and a certain degree of solid phase reaction occurs at an interface, so that the mechanical property of the vanadium oxide is reinforced, and the defect expansion of cracks and the like caused by structural change of the vanadium oxide in the electronic phase change is inhibited. In a preferred embodiment, vanadium dioxide and hafnium dioxide powder are mixed and co-sintered by using the method provided by the invention, and the obtained electronic ceramic has better mechanical properties compared with a pure vanadium oxide material.
Furthermore, by controlling the composite powder sintering process technology, the characteristics of spatial distribution, coherent state, relative reaction degree and the like of composite phases in the ceramic relative to a parent phase material can be regulated and controlled, and the mechanical property and the electrical stability of the prepared composite vanadium oxide electronic phase change ceramic are further improved. The sintering process comprises sintering temperature, sintering pressure, and the form and strength of an external field such as current applied in the sintering process. Wherein the applied current intensity is preferably 10-3000A, the applied pressure is preferably 1-50MPa, the in-situ annealing temperature is preferably 1200-1500 ℃, and the in-situ annealing time is preferably 5-200 minutes. By comprehensively controlling the sintering process conditions and the applied external field in the sintering process, the coherent state between the composite phase and the vanadium oxide matrix phase and the relative solid phase reaction degree can be regulated and controlled. In a preferred embodiment, vanadium dioxide and alumina powder are mixed, and a larger current is applied in the sintering process, so that the alumina powder is more uniformly distributed in the ceramic relative to the space of the parent phase material, and the mechanical and electrical stability of the alumina powder can be further improved.
Furthermore, the vanadium oxide composite electronic phase change ceramic material prepared by the method provided by the invention has the advantages that the sintered composite phase crystal grains and the mother phase crystal grains are bridged in a three-dimensional space in a coherent form, and a coherent interface can generate a certain degree of solid phase reaction in sintering to form a new compound. The coherent bridging or interface part solid phase reaction effect initiated by the composite phase crystal grains can inhibit the structural change of vanadium oxide in electronic phase change, pin the crystal boundary and inhibit the defect expansion in the material, thereby greatly improving the mechanical strength, functional stability, thermal shock resistance and irradiation resistance of the prepared material.
The invention provides a preparation method of a high-strength composite vanadium oxide electronic phase change material through extensive and intensive research, and the conception is that coherent sintering and spatial bridging of an oxide composite phase and vanadium oxide crystal grains are realized through a rapid heat treatment process, so that the mechanical strength, the electronic phase change functional stability, the fatigue resistance and the thermal shock resistance of the vanadium oxide electronic phase change material are greatly improved. The key technology is that a certain proportion of oxide composite phase with a crystal structure and lattice parameter similar to that of vanadium oxide powder is added, and the coherent sintering between vanadium oxide parent crystal grains and composite phase oxide is realized through a high-energy-scale heat treatment process. On one hand, the structural change of vanadium oxide in the periodic thermal field triggered electronic phase change process is inhibited through the spatial bridging action of the composite phase, and the crystal boundary is pinned and strengthened so as to prevent the generation and the expansion of the defects such as cracks in the ceramic material, and the mechanical property and the functional stability of the prepared vanadium oxide composite ceramic material are greatly improved. On the other hand, the oxidation process of vanadium element in the +4 valence state to +5 valence state in the air or the reduction process of vanadium element in the +3 valence state in the reducing atmosphere can be greatly slowed down by adjusting the polarity of the interface of the composite phase oxide and the vanadium oxide, so that the stability of the phase change function of the metal insulator of the prepared vanadium oxide ceramic material is stabilized. Compared with the traditional vanadium oxide pure-phase ceramic, sensitive components such as a sudden change type thermistor, a pressure sensitive resistor, a non-refrigeration type infrared detector self-supporting bridge membrane and the like further prepared from the vanadium oxide composite ceramic electronic phase-change material have higher electronic phase-change functional stability, ageing resistance, irradiation resistance and thermal shock resistance, and the service life of the electronic phase-change material is obviously prolonged under extreme environments such as low temperature, high pressure and high radiation.
Drawings
FIG. 1 is an X-ray spectrum of a vanadium oxide and cerium oxide composite ceramic. It can be seen that the prepared composite ceramic is mainly compounded by vanadium oxide and cerium vanadium oxide, and a small amount of V is also generated in the sintering process 2 O 3 A second phase.
FIG. 2 is a graph of Vickers hardness of the vanadium oxide and cerium oxide composite ceramic. It can be seen that the mechanical properties of the prepared composite ceramic are greatly improved compared with vanadium oxide pure-phase ceramic. The Vickers hardness of the composite ceramic material with the molar fraction of cerium oxide being 0.05 is improved by 1.84 times compared with that of pure vanadium oxide ceramic.
FIG. 3 is a graph of resistivity versus temperature for a vanadium oxide and cerium oxide composite ceramic. It can be seen that the prepared composite ceramic still has typical temperature-induced phase transition characteristics, namely, the electrical resistivity is suddenly changed at the phase transition temperature, and the sharpness degree and the phase transition temperature of the phase transition are almost consistent with those of the pure vanadium oxide ceramic material. This shows that the ceramic material of oxide composite vanadium oxide is still a typical electronic phase-change ceramic material.
FIG. 4 is a field emission scanning electron microscope (FE-SEM) spectrum of the vanadium oxide and cerium oxide composite ceramic. It can be seen that the prepared composite ceramic is mainly formed by sintering an oxide composite phase and vanadium oxide crystal grains in a coherent manner, the grain size of the composite ceramic is micron level, and the composite ceramic has no defects of obvious holes and the like.
Detailed Description
Unless otherwise specified, various starting materials used in the present invention may be commercially available or prepared according to a conventional method in the art. Unless otherwise defined or stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention.
Other aspects of the invention will be apparent to those skilled in the art in view of the disclosure herein.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not specified, in the following examples are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
Example 1:
VO is introduced into a reactor 2 Powder and CeO 2 The powder is prepared according to the weight ratio of 9.5; 9:1; the molar ratio of 8:2 is fully ground and uniformly mixed in an agate mortar, the mixed powder is sintered into a ceramic material in protective atmosphere, and 300A pulse current is applied in the sintering process to further improve VO 2 The compatibility with the composite phase interface and the relative solid phase reaction degree of the vanadium oxide parent phase and the composite phase interface are adjusted, and finally the compact composite ceramic material is obtained. Sintering the mixture for 100 minutes at 1300 ℃ under the pressure of 2Mpa to obtain the composite ceramic material. The prepared composite ceramic is mainly compounded by vanadium oxide and cerium vanadium oxide, and a small amount of V is also generated in the sintering process 2 O 3 The second phase, as shown in FIG. 1. The hardness of the composite ceramic was significantly increased compared to the bulk material of vanadium dioxide, as shown in figure 2. The resistivity curve of the composite ceramic along with the temperature is measured to find that the composite ceramic still has the typical temperature-induced phase transition characteristic, the phase transition temperature of the composite ceramic is about 340K, as shown in figure 3, and the composite ceramic is not added with CeO 2 VO of powder 2 Compared with the electric transport property of the ceramic material, the phase transition temperature of the ceramic material is not changed, and meanwhile, the phase transition sharpness degree and the room temperature resistivity are changed. Simultaneous composite ceramic bodyThe vanadium oxide composite material is formed by spatial bridging of an oxide composite phase and vanadium oxide crystal grains, the grain size is micrometer, and no defects such as obvious holes exist, as shown in figure 4.
Example 2:
VO is introduced into a reactor 2 Powder and Tb 4 O 7 Fully grinding and uniformly mixing the powder in an agate mortar, sintering the mixed powder into a ceramic material in a protective atmosphere, applying pulse current of 300A in the sintering process, and sintering at the pressure of 3Mpa and the temperature of 1200 ℃ for 100 minutes to obtain the composite ceramic material. Compared with the block material of vanadium dioxide, the hardness of the composite ceramic is obviously improved. The resistivity of the composite ceramic is measured along with a temperature change curve to find that the composite ceramic still has typical temperature-induced phase change characteristics, the phase change temperature of the composite ceramic is not changed, and meanwhile, the phase change sharpness degree and the room temperature resistivity are changed. Meanwhile, the composite ceramic is mainly formed by spatial bridging of an oxide composite phase and vanadium oxide crystal grains, the grain size is micron-scale, and the defects of obvious holes and the like are avoided.
Example 3:
VO is introduced into a reactor 2 Powder and alumina (Al) 2 O 3 ) Fully grinding and uniformly mixing the powder in an agate mortar, sintering the mixed powder into a ceramic material in a protective atmosphere, respectively applying 50 and 500A pulse current in the sintering process, and sintering at the pressure of 3Mpa and the temperature of 1300 ℃ for 60 minutes to obtain the composite ceramic material. The prepared composite ceramic is mainly compounded by vanadium oxide and aluminum vanadium oxide, and the phase change temperature of the composite ceramic is adjustable. The composite ceramic material applied with large current has better mechanical and thermal cycle resistance.
Example 4:
VO is introduced into a reactor 2 Powder and lanthanum oxide (La) 2 O 3 ) Fully grinding and uniformly mixing the powder in an agate mortar, sintering the mixed powder into a ceramic material in a protective atmosphere, applying pulse current of 300A in the sintering process, and sintering at the pressure of 5Mpa and the temperature of 1200 ℃ for 100 minutes to obtain the composite ceramic material. Compared with the block material of vanadium dioxide, the hardness of the composite ceramic is obviously improved. The composite ceramic still has typical temperature-induced phase change characteristics, the phase change temperature of the composite ceramic is not changed, and the composite ceramic has the characteristic that the composite ceramic has the typical temperature-induced phase change characteristicsMeanwhile, the sharpness of phase change and the room temperature resistivity are changed. Meanwhile, the composite ceramic is mainly formed by spatial bridging of an oxide composite phase and vanadium oxide crystal grains, the grain size is micron-scale, and the defects of obvious holes and the like are avoided.
Example 5:
VO is introduced into a reactor 2 Powder and lutetium oxide (Lu) 2 O 3 ) Fully grinding and uniformly mixing the powder in an agate mortar, sintering the mixed powder into a ceramic material in a protective atmosphere, applying 500A pulse current in the sintering process, and sintering at the pressure of 5Mpa and the temperature of 1200 ℃ for 100 minutes to obtain the composite ceramic material. The prepared composite ceramic is mainly compounded by vanadium oxide and lutetium vanadium oxide. Compared with the block material of vanadium dioxide, the hardness of the composite ceramic is obviously improved. The composite ceramic still has typical temperature-induced phase change characteristics, the phase change temperature of the composite ceramic is not changed, and meanwhile, the phase change sharpness degree and the room temperature resistivity are changed. Meanwhile, the composite ceramic is mainly formed by spatial bridging of an oxide composite phase and vanadium oxide crystal grains, the grain size is micron-scale, and the defects of obvious holes and the like are avoided.
Example 6:
VO is introduced into a reactor 2 Mixing the powder with samarium oxide (Sm) 2 O 3 ) Fully grinding and uniformly mixing the powder in an agate mortar, sintering the mixed powder into a ceramic material in a protective atmosphere, applying pulse current of 300A in the sintering process, and sintering at the pressure of 5Mpa and the temperature of 1300 ℃ for 100 minutes to obtain the composite ceramic material. The prepared composite ceramic is mainly compounded by vanadium oxide and samarium vanadium oxide. Compared with the block material of vanadium dioxide, the hardness of the composite ceramic is obviously improved. The composite ceramic still has typical temperature-induced phase transition characteristics, the phase transition temperature of the composite ceramic is not changed, and meanwhile, the phase transition sharpness degree and the room temperature resistivity are changed. Meanwhile, the composite ceramic is mainly formed by spatial bridging of an oxide composite phase and vanadium oxide crystal grains, the grain size is micron-scale, and the defects of obvious holes and the like are avoided.
Example 7:
VO is treated 2 Powder and neodymium oxide (Nd) 2 O 3 ) Fully grinding and uniformly mixing the powder in an agate mortar, and mixingSintering the powder in protective atmosphere to obtain ceramic material, applying pulse current of 3000A in the sintering process, and sintering at 1MPa and 1500 ℃ for 200 min to obtain the composite ceramic material. The prepared composite ceramic is mainly compounded by vanadium oxide and neodymium vanadium oxide. Compared with the block material of vanadium dioxide, the hardness of the composite ceramic is obviously improved. The composite ceramic still has typical temperature-induced phase change characteristics, the phase change temperature of the composite ceramic is not changed, and meanwhile, the phase change sharpness degree and the room temperature resistivity are changed. Meanwhile, the composite ceramic is mainly formed by spatial bridging of an oxide composite phase and vanadium oxide crystal grains, the grain size is micrometer, and the defects of obvious holes and the like are overcome.
Example 8:
VO is introduced into a reactor 2 Powder and thulium oxide (Tm) 2 O 3 ) The powder is fully ground and uniformly mixed in an agate mortar, and the mixed powder is sintered into a ceramic material in a protective atmosphere. And applying a pulse current of 100A in the sintering process, and sintering for 100 minutes at the pressure of 5Mpa and the temperature of 1200 ℃ to obtain the composite ceramic material. The prepared composite ceramic is mainly compounded by vanadium oxide and thulium vanadium oxide. Compared with the block material of vanadium dioxide, the hardness of the composite ceramic is obviously improved. The composite ceramic still has typical temperature-induced phase transition characteristics, the phase transition temperature of the composite ceramic is not changed, and meanwhile, the phase transition sharpness degree and the room temperature resistivity are changed. Meanwhile, the composite ceramic is mainly formed by spatial bridging of an oxide composite phase and vanadium oxide crystal grains, the grain size is micron-scale, and the defects of obvious holes and the like are avoided.
Example 9:
VO is treated 2 Powder and holmium oxide (Ho) 2 O 3 ) The powder is fully ground and uniformly mixed in an agate mortar, and the mixed powder is sintered into a ceramic material in a protective atmosphere. And applying 1000A pulse current in the sintering process, and sintering for 5 minutes at the pressure of 2Mpa and the temperature of 1300 ℃ to obtain the composite ceramic material. The prepared composite ceramic is mainly compounded by vanadium oxide and holmium vanadium oxide. Compared with the block material of vanadium dioxide, the hardness of the composite ceramic is obviously improved. The composite ceramic still has typical temperature-induced phase transition characteristics, and the phase transition temperature is not higher thanChanges occur, and at the same time, the sharpness of the phase change and the room temperature resistivity change. Meanwhile, the composite ceramic is mainly formed by spatial bridging of an oxide composite phase and vanadium oxide crystal grains, the grain size is micron-scale, and the defects of obvious holes and the like are avoided.
Example 10:
VO is treated 2 Powder and erbium oxide (Er) 2 O 3 ) The powder is fully ground and uniformly mixed in an agate mortar, and the mixed powder is sintered into a ceramic material in a protective atmosphere. And applying 500A pulse current in the sintering process, and sintering for 160 minutes under the pressure of 4Mpa and 1300 ℃ to obtain the composite ceramic material. The prepared composite ceramic is mainly compounded by vanadium oxide and erbium vanadium oxide. Compared with the block material of vanadium dioxide, the hardness of the composite ceramic is obviously improved. The composite ceramic still has typical temperature-induced phase transition characteristics, the phase transition temperature of the composite ceramic is not changed, and meanwhile, the phase transition sharpness degree and the room temperature resistivity are changed. Meanwhile, the composite ceramic is mainly formed by spatial bridging of an oxide composite phase and vanadium oxide crystal grains, the grain size is micron-scale, and the defects of obvious holes and the like are avoided.
Example 11:
VO is treated 2 Powder and europium oxide (Eu) 2 O 3 ) The powder is fully ground and uniformly mixed in an agate mortar, and the mixed powder is sintered into a ceramic material in a protective atmosphere. And applying 100A pulse current in the sintering process, and sintering for 160 minutes at 1300 ℃ and 4Mpa to obtain the composite ceramic material. The prepared composite ceramic is mainly compounded by vanadium oxide and europium vanadium oxide. Compared with the block material of vanadium dioxide, the hardness of the composite ceramic is obviously improved. The composite ceramic still has typical temperature-induced phase transition characteristics, the phase transition temperature of the composite ceramic is not changed, and meanwhile, the phase transition sharpness degree and the room temperature resistivity are changed. Meanwhile, the composite ceramic is mainly formed by spatial bridging of an oxide composite phase and vanadium oxide crystal grains, the grain size is micrometer, and the defects of obvious holes and the like are overcome.
Example 12:
VO is treated 2 Mixing the powder with yttrium oxide (Y) 2 O 3 ) The powder is fully ground in an agate mortarGrinding and mixing evenly, and sintering the mixed powder in protective atmosphere to obtain the ceramic material. And applying pulse current of 300A in the sintering process, and sintering for 160 minutes at the pressure of 1Mpa and the temperature of 1300 ℃ to obtain the composite ceramic material. The prepared composite ceramic is mainly compounded by vanadium oxide and yttrium vanadium oxide. Compared with the block material of vanadium dioxide, the hardness of the composite ceramic is obviously improved. The composite ceramic still has typical temperature-induced phase transition characteristics, the phase transition temperature of the composite ceramic is not changed, and meanwhile, the phase transition sharpness degree and the room temperature resistivity are changed. Meanwhile, the composite ceramic is mainly formed by spatial bridging of an oxide composite phase and vanadium oxide crystal grains, the grain size is micron-scale, and the defects of obvious holes and the like are avoided.
Example 13:
VO is introduced into a reactor 2 Powder and titanium oxide (TiO) 2 ) The powder is fully ground and uniformly mixed in an agate mortar, and the mixed powder is sintered into a ceramic material in a protective atmosphere. And applying 500A pulse current in the sintering process, and sintering for 100 minutes at the pressure of 5Mpa and the temperature of 1500 ℃ to obtain the composite ceramic material. The prepared composite ceramic is mainly compounded by vanadium oxide and titanium vanadium oxide. Compared with the block material of vanadium dioxide, the hardness of the composite ceramic is obviously improved. The composite ceramic still has typical temperature-induced phase transition characteristics, and the phase transition temperature of the composite ceramic can be regulated and controlled. Meanwhile, the composite ceramic is mainly formed by spatial bridging of an oxide composite phase and vanadium oxide crystal grains, the grain size is micron-scale, and the defects of obvious holes and the like are avoided.
Example 14:
VO is introduced into a reactor 2 Powder and hafnium oxide (HfO) 2 ) The powder is fully ground and uniformly mixed in an agate mortar, and the mixed powder is sintered into a ceramic material in a protective atmosphere. And applying pulse current of 300A in the sintering process, and sintering for 100 minutes at the pressure of 3Mpa and the temperature of 1300 ℃ to obtain the composite ceramic material. The prepared composite ceramic is mainly compounded by vanadium oxide and hafnium vanadium oxide. Compared with the block material of vanadium dioxide, the hardness of the composite ceramic is obviously improved. The composite ceramic still has typical temperature-induced phase transition characteristics, and the phase transition temperature of the composite ceramic can be regulated and controlled. While the composite ceramic is mainly an oxide compositeThe phase mixture is spatially bridged with vanadium oxide crystal grains, the grain size is micron order, and no defects such as obvious holes and the like exist.
Example 15:
VO is introduced into a reactor 2 Powder and praseodymium oxide (Pr) 6 O 11 ) The powder is fully ground and uniformly mixed in an agate mortar, and the mixed powder is sintered into a ceramic material in a protective atmosphere. And applying a pulse current of 300A in the sintering process, and sintering for 120 minutes at the pressure of 5Mpa and the temperature of 1300 ℃ to obtain the composite ceramic material. The prepared composite ceramic is mainly compounded by vanadium oxide and praseodymium vanadium oxide. Compared with the block material of vanadium dioxide, the hardness of the composite ceramic is obviously improved. The composite ceramic still has typical temperature-induced phase transition characteristics, the phase transition temperature of the composite ceramic is not changed, and meanwhile, the phase transition sharpness degree and the room temperature resistivity are changed. Meanwhile, the composite ceramic is mainly formed by spatial bridging of an oxide composite phase and vanadium oxide crystal grains, the grain size is micron-scale, and the defects of obvious holes and the like are avoided.
Example 16:
VO is introduced into a reactor 2 Fully grinding and uniformly mixing the powder and nickel oxide (NiO) powder in an agate mortar, and sintering the mixed powder in a protective atmosphere to obtain the ceramic material. And applying a pulse current of 100A in the sintering process, and sintering for 120 minutes at the pressure of 5Mpa and the temperature of 1300 ℃ to obtain the composite ceramic material. The prepared composite ceramic is mainly compounded by vanadium oxide and nickel vanadium oxide. Compared with the block material of vanadium dioxide, the hardness of the composite ceramic is obviously improved. The composite ceramic still has typical temperature-induced phase transition characteristics, and the phase transition temperature of the composite ceramic can be regulated and controlled. Meanwhile, the composite ceramic is mainly formed by spatial bridging of an oxide composite phase and vanadium oxide crystal grains, the grain size is micron-scale, and the defects of obvious holes and the like are avoided.
Example 17:
VO is introduced into a reactor 2 Powder and titanium oxide (TiO) 2 ) The powder is fully ground and uniformly mixed in an agate mortar, and the mixed powder is sintered into a ceramic material in a protective atmosphere. And applying 3000A pulse current in the sintering process, and sintering at the pressure of 1Mpa and the temperature of 1500 ℃ for 10 minutes to obtain the composite ceramic material. Preparation of compoundThe composite ceramic is mainly compounded by vanadium oxide and titanium vanadium oxide. The composite electronic ceramic applied with larger sintering pressure has better radiation resistance and mechanical property, and the phase change temperature of the composite electronic ceramic can be regulated and controlled.
Example 18:
VO is introduced into a reactor 2 Powder and niobium oxide (Nb) 2 O 5 ) The powder is fully ground and uniformly mixed in an agate mortar, and the mixed powder is sintered into a ceramic material in a protective atmosphere. And applying a pulse current of 100A in the sintering process, and sintering for 120 minutes at the pressure of 1Mpa and the temperature of 1300 ℃ to obtain the composite ceramic material. The prepared composite ceramic is mainly compounded by vanadium oxide and niobium vanadium oxide. Compared with the block material of vanadium dioxide, the hardness of the composite ceramic is obviously improved. The composite ceramic still has typical temperature-induced phase transition characteristics, and the phase transition temperature of the composite ceramic can be regulated and controlled. Meanwhile, the composite ceramic is mainly formed by spatial bridging of an oxide composite phase and vanadium oxide crystal grains, the grain size is micron-scale, and the defects of obvious holes and the like are avoided.
Example 19:
VO is introduced into a reactor 2 Powder and iron oxide (Fe) 2 O 3 ) The powder is fully ground and uniformly mixed in an agate mortar, and the mixed powder is sintered into a ceramic material in a protective atmosphere. And applying 1000A pulse current in the sintering process, and sintering for 200 minutes at the pressure of 5Mpa and the temperature of 1300 ℃ to obtain the composite ceramic material. The prepared composite ceramic is mainly compounded by vanadium oxide and iron vanadium oxide. Compared with the block material of vanadium dioxide, the hardness of the composite ceramic is obviously improved. The composite ceramic still has typical temperature-induced phase transition characteristics, and the phase transition temperature of the composite ceramic can be regulated and controlled. Meanwhile, the composite ceramic is mainly formed by spatial bridging of an oxide composite phase and vanadium oxide crystal grains, the grain size is micron-scale, and the defects of obvious holes and the like are avoided.
Example 20:
VO is introduced into a reactor 2 Powder and molybdenum oxide (MoO) 3 ) The powder is fully ground and uniformly mixed in an agate mortar, and the mixed powder is sintered into the ceramic material in protective atmosphere. Applying 800A pulse current in the sintering process, sintering at 2Mpa pressure and 1300 deg.C for 2After 00 minutes, a composite ceramic material was obtained. The prepared composite ceramic is mainly compounded by vanadium oxide and molybdenum-vanadium oxide. Compared with the block material of vanadium dioxide, the hardness of the composite ceramic is obviously improved. The composite ceramic still has typical temperature-induced phase change characteristics, and the phase change temperature of the composite ceramic can be regulated and controlled. Meanwhile, the composite ceramic is mainly formed by spatial bridging of an oxide composite phase and vanadium oxide crystal grains, the grain size is micron-scale, and the defects of obvious holes and the like are avoided.
Example 21:
VO is introduced into a reactor 2 Fully grinding and uniformly mixing the powder and cobalt oxide (CoO) powder in an agate mortar, and sintering the mixed powder in a protective atmosphere to obtain the ceramic material. And applying 800A pulse current in the sintering process, and sintering for 100 minutes at the pressure of 1Mpa and the temperature of 1200 ℃ to obtain the composite ceramic material. The prepared composite ceramic is mainly compounded by vanadium oxide and cobalt vanadium oxide. Compared with the block material of vanadium dioxide, the hardness of the composite ceramic is obviously improved. The composite ceramic still has typical temperature-induced phase transition characteristics, and the phase transition temperature of the composite ceramic can be regulated and controlled. Meanwhile, the composite ceramic is mainly formed by spatial bridging of an oxide composite phase and vanadium oxide crystal grains, the grain size is micron-scale, and the defects of obvious holes and the like are avoided.
Example 22:
VO is introduced into a reactor 2 Powder and gadolinium oxide (Gd) 2 O 3 ) The powder is fully ground and uniformly mixed in an agate mortar, and the mixed powder is sintered into a ceramic material in a protective atmosphere. And applying pulse current of 300A in the sintering process, and sintering for 120 minutes at the pressure of 5Mpa and the temperature of 1300 ℃ to obtain the composite ceramic material. The prepared composite ceramic is mainly compounded by vanadium oxide and gadolinium vanadium oxide. Compared with the block material of vanadium dioxide, the hardness of the composite ceramic is obviously improved. The composite ceramic still has typical temperature-induced phase transition characteristics, the phase transition temperature of the composite ceramic is not changed, and meanwhile, the phase transition sharpness degree and the room temperature resistivity are changed. Meanwhile, the composite ceramic is mainly formed by spatial bridging of an oxide composite phase and vanadium oxide crystal grains, the grain size is micron-scale, and the defects of obvious holes and the like are avoided.
Example 23:
VO is introduced into a reactor 2 Powder and dysprosium oxide (Dy) 2 O 3 ) The powder is fully ground and uniformly mixed in an agate mortar, and the mixed powder is sintered into a ceramic material in a protective atmosphere. And applying 500A pulse current in the sintering process, and sintering for 20 minutes at the pressure of 10Mpa and the temperature of 1300 ℃ to obtain the composite ceramic material. The prepared composite ceramic is mainly compounded by vanadium oxide and dysprosium vanadium oxide. Compared with the block material of vanadium dioxide, the hardness of the composite ceramic is obviously improved. The composite ceramic still has typical temperature-induced phase transition characteristics, the phase transition temperature of the composite ceramic is not changed, and meanwhile, the phase transition sharpness degree and the room temperature resistivity are changed. Meanwhile, the composite ceramic is mainly formed by spatial bridging of an oxide composite phase and vanadium oxide crystal grains, the grain size is micron-scale, and the defects of obvious holes and the like are avoided.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the scope of the invention, which is defined by the claims appended hereto, and any other technical entity or method that is encompassed by the claims as broadly defined herein, or equivalent variations thereof, is contemplated as being encompassed by the claims.

Claims (1)

1. A preparation method of vanadium oxide electronic phase change composite ceramic with high strength and high stability is characterized by firstly providing vanadium oxide parent material powder and one or more oxide composite phase powder, wherein the crystal structure and the lattice parameter of the surface of the oxide composite phase powder and the surface of the vanadium oxide parent material powder are similar; uniformly mixing the powder in a certain proportion, sintering the mixture into a ceramic material at 1200-1500 ℃ and 1-50MPa, further improving the compatibility of a parent phase and a composite phase interface and adjusting the relative solid phase reaction degree of the vanadium oxide parent phase and the composite phase interface by applying continuous or pulse current in the sintering process, wherein the applied current intensity range is 10-3000A, and the sintering time range is 5-200 minutes; structural change of vanadium oxide in the periodic thermal field triggered electronic phase change process is inhibited through the co-lattice space bridging of the composite phase and the mother phase, and grain boundaries are pinned and strengthened so as to prevent generation and expansion of crack defects in the ceramic material, so that the mechanical property and the thermal shock resistance of the prepared vanadium oxide composite ceramic material are greatly improved, the mother material is vanadium dioxide, and the composite phase powder comprises hafnium oxide, cerium oxide, terbium oxide, praseodymium oxide, lanthanum oxide, lutetium oxide, samarium oxide, neodymium oxide, thulium oxide, holmium oxide, erbium oxide, europium oxide, yttrium oxide, gadolinium oxide and dysprosium oxide.
CN202210082967.3A 2022-01-25 2022-01-25 Preparation method of high-strength high-stability vanadium oxide electronic phase change composite ceramic Active CN114538925B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210082967.3A CN114538925B (en) 2022-01-25 2022-01-25 Preparation method of high-strength high-stability vanadium oxide electronic phase change composite ceramic

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210082967.3A CN114538925B (en) 2022-01-25 2022-01-25 Preparation method of high-strength high-stability vanadium oxide electronic phase change composite ceramic

Publications (2)

Publication Number Publication Date
CN114538925A CN114538925A (en) 2022-05-27
CN114538925B true CN114538925B (en) 2023-01-31

Family

ID=81671957

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210082967.3A Active CN114538925B (en) 2022-01-25 2022-01-25 Preparation method of high-strength high-stability vanadium oxide electronic phase change composite ceramic

Country Status (1)

Country Link
CN (1) CN114538925B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115124277B (en) * 2022-05-30 2023-04-25 北京科技大学 Preparation method of organic-inorganic composite vanadium oxide electronic phase change material
CN115536273B (en) * 2022-10-22 2023-09-01 佛山市三水宏源陶瓷企业有限公司 Antibacterial glaze powder and preparation process thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150251948A1 (en) * 2011-01-21 2015-09-10 Shanghai Institute Of Ceramics, Chinese Academy Of Sciences Preparation method of doped vanadium dioxide powder
CN107162591A (en) * 2017-03-28 2017-09-15 华中科技大学 Nb5+The monoclinic phase VO of doping2Metal insulator Phase transformation ceramics and preparation method thereof
CN109368695A (en) * 2018-11-19 2019-02-22 五邑大学 A kind of doping preparation method of high-activity nano vanadium oxide powder
CN110105068A (en) * 2019-04-30 2019-08-09 合肥工业大学 A kind of molding method of thermoelectric material Fast Sintering
CN110451990A (en) * 2019-09-06 2019-11-15 西北工业大学 A kind of method that Fast Sintering prepares metal oxide texture ceramic material under room temperature
CN110498399A (en) * 2019-09-06 2019-11-26 西北工业大学 The method that composite oxide of metal powder is prepared using heating effect of current direct sintering under no furnace room temperature
CN110606732A (en) * 2019-09-06 2019-12-24 西北工业大学 Method for preparing oxide ceramic by furnace-free rapid sintering at normal temperature
CN112939591A (en) * 2021-01-22 2021-06-11 北京科技大学 Synthetic method of mixed valence state rare earth iron-based oxide bulk material

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150251948A1 (en) * 2011-01-21 2015-09-10 Shanghai Institute Of Ceramics, Chinese Academy Of Sciences Preparation method of doped vanadium dioxide powder
CN107162591A (en) * 2017-03-28 2017-09-15 华中科技大学 Nb5+The monoclinic phase VO of doping2Metal insulator Phase transformation ceramics and preparation method thereof
CN109368695A (en) * 2018-11-19 2019-02-22 五邑大学 A kind of doping preparation method of high-activity nano vanadium oxide powder
CN110105068A (en) * 2019-04-30 2019-08-09 合肥工业大学 A kind of molding method of thermoelectric material Fast Sintering
CN110451990A (en) * 2019-09-06 2019-11-15 西北工业大学 A kind of method that Fast Sintering prepares metal oxide texture ceramic material under room temperature
CN110498399A (en) * 2019-09-06 2019-11-26 西北工业大学 The method that composite oxide of metal powder is prepared using heating effect of current direct sintering under no furnace room temperature
CN110606732A (en) * 2019-09-06 2019-12-24 西北工业大学 Method for preparing oxide ceramic by furnace-free rapid sintering at normal temperature
CN112939591A (en) * 2021-01-22 2021-06-11 北京科技大学 Synthetic method of mixed valence state rare earth iron-based oxide bulk material

Also Published As

Publication number Publication date
CN114538925A (en) 2022-05-27

Similar Documents

Publication Publication Date Title
CN114538925B (en) Preparation method of high-strength high-stability vanadium oxide electronic phase change composite ceramic
Kong et al. Preparation of Bi4Ti3O12 ceramics via a high-energy ball milling process
Yang et al. High energy storage density and ultrafast discharge in lead lutetium niobate based ceramics
Jiang et al. Ultrahigh piezoelectric coefficient of a lead-free K 0.5 Na 0.5 NbO 3-based single crystal fabricated by a simple seed-free solid-state growth method
Liu et al. Comprehensively enhanced energy-storage properties in (Pb 1− 3x/2 La x)(Zr 0.995 Ti 0.005) O 3 antiferroelectric ceramics via composition optimization
US20060217259A1 (en) Aluminum nitride sintered body, semiconductor manufacturing member, and method of manufacturing aluminum nitride sintered body
Jin et al. Enhanced energy storage performance of Ba0. 4Sr0. 6TiO3 ceramics: influence of sintering atmosphere
Sultan et al. Effect of Mn doping on structural, morphological and dielectric properties of EuFeO 3 ceramics
Wang et al. Effect of rare-earth Nd/Sm doping on the structural and multiferroic properties of BiFeO3 ceramics prepared by spark plasma sintering
Pokharel et al. Irreversibility of the antiferroelectric to ferroelectric phase transition in (Pb 0.90 Ba 0.10) ZrO 3 ceramics
CN114538924A (en) Method for preparing electronic phase-change ceramic material by doping transition metal oxide with vanadium oxide
CN114436655A (en) Composite modification method for strength of rare earth nickel-based oxide electronic phase change material
Kim et al. Effects of non-stoichiometry and chemical inhomogeneity on the order-disorder phase formation in the complex perovskite compounds, Ba (Ni 1/3 Nb 2/3) O 3 and Ba (Zn 1/3 Nb 2/3) O 3
CN111018516A (en) Barium titanate-based high-energy-density electronic ceramic and preparation method thereof
Qian et al. Enhanced ferromagnetic, ferroelectric, and dielectric properties in BiFeO 3-SrTiO 3-Bi 0.5 Na 0.5 TiO 3 ceramics
Takahashi et al. Fabrication and electrical properties of Bi4Ti3O12 ceramics by spark plasma sintering
KR101797232B1 (en) Electrostatic chuck
Vilarinho et al. Dielectric Properties of Pb (Fe2/3W1/3) O3–PbTiO3 Solid‐Solution Ceramics
Matizamhuka Fabrication of fine-grained functional ceramics by two-step sintering or Spark Plasma Sintering (SPS)
Babu et al. Rare earth co-doped nanocrystalline ceria electrolytes for intermediate temperature solid oxide fuel cells (IT-SOFC)
Chan et al. Microstructural evolution and macroscopic property relationship in antiferroelectric lead lanthanum stannate zirconate titanate ceramics
CN104193323A (en) Preparation method of SrTiO3/TiO2 composite thermoelectric ceramic material
CN107840659A (en) A kind of tungsten bronze pure phase room temperature multiferroic ceramics and preparation method thereof
Deptula et al. Sintering of ZrO2‐CeO2 Spherical Powders Prepared by a Water Extraction Variant of the Sol‐Gel Process
KR101559942B1 (en) Method of enhancing the thermoelectric properties and electrical conductivity in Ca-V oxide perovskite system by means of synthesizing the single phase

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
GR01 Patent grant
GR01 Patent grant