CN114538925A - 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

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CN114538925A
CN114538925A CN202210082967.3A CN202210082967A CN114538925A CN 114538925 A CN114538925 A CN 114538925A CN 202210082967 A CN202210082967 A CN 202210082967A CN 114538925 A CN114538925 A CN 114538925A
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oxide
vanadium oxide
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vanadium
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CN114538925B (en
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陈吉堃
周轩弛
张秀兰
姜勇
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University of Science and Technology Beijing USTB
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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 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 TMITHereinafter, the insulating phase with a monoclinic structure [ Science,2008,318(5857): 1750-. In addition to temperature-induced triggering, VO2The electronic phase change of (9), (2018), (nat. Commun.,) (2018), (201818) can be triggered by hydrogen atmosphere, an external electric field, ion droplet gating, an ultrahigh magnetic field, high voltage and the like; nat. nanotechnol, 2014, Doi: 10.1038/nnano.2014.71; commun, 2020,11(1). VO, a typical material for strongly associated systems2The complex coupling of charges, spins, orbitals and crystal lattices in the system causes the electric, optical, thermal and magnetic properties thereof to be TMITMutations nearby [ Nature,2013,500(7463):431-431 ]. At the same time, VO2The phase change characteristic of the material can be further adjusted by a plurality of methods such as element doping, oxygen vacancy, interface stress field, environmental oxygen partial pressure, ion implantation and the like. These unique advantages greatly enhance VO2The material has application prospect in the fields of abrupt change thermistors, non-refrigeration type infrared detector self-supporting bridge membranes, intelligent window coatings and the like [ Science 374, 1504-1509 (2021) ]; j. Eur. Central. Soc.,2003,23(9): 1435-. Recently, domestic and foreign companies such as Hitachi make use of VO2Sensitive 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 VO2The phase change property of the material has considerable application prospect in the fields of sensitive resistance devices and the like, but VO2The material has poor electronic phase change function stability, low mechanical strength, insufficient fatigue resistance and thermal shock resistance and the likeThe problem is always a core difficult problem in the field. The main reason is VO2The 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 inevitably lead to VO2The 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 reduced2The mechanical strength and the electronic phase change function stability of the material.
In summary, the biggest difficulty that the vanadium oxide electronic phase change material is restricted to be applied 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 method have higher electronic phase change function stability, ageing resistance, irradiation resistance and thermal shock resistance, and the service life of the sensitive 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 (V) oxide2O3) 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 be generated under the triggering of characteristic temperatureThe phase transition characteristic of the raw metal insulator, the electrical resistivity of which can be suddenly changed under the triggering of 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 transition characteristics, and the phase transition temperature of the metal insulator is reduced 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)2O3) Hafnium oxide (HfO)2) Cerium oxide (CeO)2) Terbium oxide (Tb)4O7) Praseodymium oxide (Pr)6O11) Lanthanum oxide (La)2O3) Lutetium oxide (Lu)2O3) Samarium oxide (Sm)2O3) Neodymium oxide (Nd)2O3) Thulium oxide (Tm)2O3) Holmium oxide (Ho)2O3) Erbium oxide (Er)2O3) Europium oxide (Eu)2O3) Yttrium oxide (Y)2O3) Gadolinium oxide (Gd)2O3) Dysprosium oxide (Dy)2O3) 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, the relative chemical reaction degree and the like 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, the electronic ceramic obtained by mixing vanadium dioxide and hafnium dioxide powder and co-sintering by using the method provided by the invention 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 composite phase crystal grains and the parent phase crystal grains of the vanadium oxide composite electronic phase-change ceramic material prepared by the method provided by the invention are bridged in a three-dimensional space in a coherent form, and a coherent interface can form a new compound due to a certain degree of solid-phase reaction in sintering. 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 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 to the valence 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 phase change function stability 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 process2O3A 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 defined or stated otherwise, 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 reactor2Powder and CeO2The powder is prepared according to the proportion of 9.5: 0.5; 9: 1; fully grinding and uniformly mixing the mixture in an agate mortar according to the molar ratio of 8:2, sintering the mixed powder into a ceramic material in a protective atmosphere, and applying 300A pulses in the sintering processFurther increase of VO by current2The 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 process2O3The 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 CeO2VO of powder2Compared 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. 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 no defects such as obvious holes exist, as shown in figure 4.
Example 2:
VO is introduced into a reactor2Powder and Tb4O7Fully 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 micrometer, and the defects of obvious holes and the like are overcome.
Example 3:
VO is introduced into a reactor2Powder and alumina (Al)2O3) Fully grinding and uniformly mixing the powder in an agate mortar, and sintering the mixed powder into a ceramic material in a protective atmosphereAnd respectively applying 50A pulse current and 500A pulse current in the sintering process, and sintering for 60 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 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 reactor2Powder and lanthanum oxide (La)2O3) 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 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 5:
VO is introduced into a reactor2Mixing the powder with lutetium oxide (Lu)2O3) 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 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 6:
VO is introduced into a reactor2Mixing the powder with samarium oxide (Sm)2O3) Powder is in the horseFully grinding and uniformly mixing the mixture 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 for 100 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 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 introduced into a reactor2Powder and neodymium oxide (Nd)2O3) Fully grinding and uniformly mixing the powder in an agate mortar, sintering the mixed powder into a ceramic material in a protective atmosphere, applying 3000A pulse current in the sintering process, and sintering at 1500 ℃ for 200 minutes under the pressure of 1Mpa 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 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 8:
VO is introduced into a reactor2Powder and thulium oxide (Tm)2O3) 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 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 hasThe typical temperature-induced phase transition characteristic is that the phase transition temperature is not changed, and meanwhile, the sharpness degree of phase transition 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 introduced into a reactor2Powder and holmium oxide (Ho)2O3) 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, 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 10:
VO is introduced into a reactor2Powder and erbium oxide (Er)2O3) 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 introduced into a reactor2Powder and europium oxide (Eu)2O3) 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 micron-scale, and the defects of obvious holes and the like are avoided.
Example 12:
VO is introduced into a reactor2Mixing the powder with yttrium oxide (Y)2O3) 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. 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 reactor2Powder 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. CompoundingThe ceramic still has typical temperature-induced phase transition characteristics, and the phase transition temperature of the 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 reactor2Powder 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. 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 15:
VO is introduced into a reactor2Powder and praseodymium oxide (Pr)6O11) 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 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 reactor2The powder and nickel oxide (NiO) powder are fully ground and uniformly mixed in an agate mortar, and the mixed powder is sintered into a ceramic material in a protective atmosphere. During sinteringAdding 100A pulse current, sintering at 5Mpa pressure and 1300 deg.C for 120 min 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 micrometer, and the defects of obvious holes and the like are overcome.
Example 17:
VO is introduced into a reactor2Powder 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. The prepared composite ceramic is mainly compounded by vanadium oxide and titanium vanadium oxide. The composite electronic ceramic with larger sintering pressure has better radiation resistance and mechanical property, and the phase change temperature can be regulated and controlled.
Example 18:
VO is introduced into a reactor2Powder and niobium oxide (Nb)2O5) 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 at 1Mpa and 1300 ℃ for 120 minutes 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 reactor2Powder and iron oxide (Fe)2O3) Fully grinding and uniformly mixing the powder in an agate mortar, and putting the mixed powder in protective gasSintering into ceramic material in 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 treated2Powder and molybdenum oxide (MoO)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 800A pulse current in the sintering process, and sintering for 200 minutes at 1300 ℃ and 2Mpa to obtain the composite ceramic material. 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 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 21:
VO is introduced into a reactor2Fully 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 reactor2Powder and gadolinium oxide (Gd)2O3) 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. 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 reactor2Powder and dysprosium oxide (Dy)2O3) 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 (7)

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 matrix 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 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 coherence of a mother phase and a composite phase interface can be further improved and the relative solid phase reaction degree of the vanadium oxide mother phase and the composite phase interface can be adjusted by applying continuous or pulse current, a magnetic field and a high-energy ray external field 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 the generation and the expansion of crack defects in the ceramic material, thereby greatly improving the mechanical property and the thermal shock resistance of the prepared vanadium oxide composite ceramic material.
2. The method for preparing vanadium oxide electronic phase change composite ceramic of claim 1, wherein the oxidation process of vanadium element in the +4 valence state to +5 valence state in air or the reduction process to +3 valence state in reducing atmosphere in the material can be substantially slowed down by adjusting the polarity of the interface between the composite phase oxide and 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.
3. The method for preparing the high-strength high-stability vanadium oxide electronic phase change composite ceramic according to claim 1, wherein a matrix material in the composite ceramic is vanadium oxide, and the method comprises the following steps: vanadium dioxide (VO)2) Vanadium (V) oxide2O3) And a compound in which the vanadium oxide compound is further doped with a transition element; the doping elements in the vanadium oxide doped by the transition group elements comprise tungsten (W) and niobium (N)b) Molybdenum (Mo), titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), aluminum (Al), hafnium (Hf); 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.
4. The method for preparing high-strength high-stability vanadium oxide electronic phase change composite ceramic according to claim 1, wherein the composite phase material in the composite ceramic is an oxide having a crystal structure and lattice parameters similar to those of a corresponding parent vanadium oxide on a crystal plane, and comprises titanium oxide (TiO)2) Nickel oxide (NiO), aluminum oxide (Al)2O3) Hafnium oxide (HfO)2) Cerium oxide (CeO)2) Terbium oxide (Tb)4O7) Praseodymium oxide (Pr)6O11) Lanthanum oxide (La)2O3) Lutetium oxide (Lu)2O3) Samarium oxide (Sm)2O3) Neodymium oxide (Nd)2O3) Thulium oxide (Tm)2O3) Holmium oxide (Ho)2O3) Erbium oxide (Er)2O3) Europium oxide (Eu)2O3) Yttrium oxide (Y)2O3) Gadolinium oxide (Gd)2O3) Dysprosium oxide (Dy)2O3) (ii) a 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.
5. The method for preparing the vanadium oxide electronic phase change composite ceramic with high strength and high stability as claimed in claim 1, wherein the spatial distribution, the coherent state and the relative chemical reaction degree characteristic of the composite phase in the ceramic relative to the parent phase material can be regulated and controlled by adjusting the chemical components, the particle size distribution, the morphology and the composite proportion of the selected oxide composite powder, and the mechanical property and the electrical stability of the prepared 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 crack defect expansion of the vanadium oxide caused by the structural change in the electronic phase change is inhibited.
6. The preparation method of the high-strength high-stability vanadium oxide electronic phase change composite ceramic as claimed in claim 1, wherein the control of the composite powder sintering process technology can realize the regulation and control of the spatial distribution, coherent state and relative reaction degree characteristics of composite phases in the ceramic relative to the parent phase material, and further realize the improvement of the mechanical properties and electrical stability of the prepared composite vanadium oxide electronic phase change ceramic; the sintering process comprises sintering temperature, sintering pressure, and the form and strength of an external current field applied in the sintering process; wherein the applied current intensity range is 10-3000A, the applied pressure range is 1-50MPa, the in-situ annealing temperature range is 1200-1500 ℃, and the in-situ annealing time range is 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.
7. The preparation method of the high-strength high-stability vanadium oxide electronic phase change composite ceramic as claimed in claim 1, wherein the sintered composite phase grains and the mother phase grains are bridged in a three-dimensional space in a coherent form, and a coherent interface thereof can form a new compound due to a certain degree of solid phase reaction during sintering; 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 prepared vanadium oxide composite ceramic electronic phase change material has higher mechanical strength, more stable metal insulator phase transition characteristic, and higher thermal shock resistance, aging resistance and irradiation resistance.
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