CN115894029B - Oxygen-insensitive negative temperature coefficient thermosensitive material based on high-entropy rare earth zirconate - Google Patents
Oxygen-insensitive negative temperature coefficient thermosensitive material based on high-entropy rare earth zirconate Download PDFInfo
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Abstract
The application relates to a series of oxygen insensitive negative temperature coefficient thermosensitive materials based on high-entropy rare earth zirconate, which takes lanthanum oxide, neodymium oxide, samarium oxide, europium oxide and zirconium dioxide as raw materials, and respectively carries out wet three-dimensional vibration ball milling, powder calcination, secondary ball milling, cold isostatic pressing and high-temperature sintering to obtain pyrochlore structure (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 A 0.2 ) 2 Zr 2 O 7 (a=gd, dy, ho or Er) heat sensitive material. The electrical performance parameters of the series of materials are as follows: b (B) 400℃/1500℃ =10413~11957±1.97%K，ρ 1500℃ =1.20~1.28×10 2 2.13% Ω·cm. The high-entropy rare earth zirconate-based oxygen insensitive negative temperature coefficient thermosensitive material (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 A 0.2 ) 2 Zr 2 O 7 (a=gd, dy, ho or Er) has excellent negative temperature coefficient characteristics in a temperature range of 400 ℃ to 1500 ℃, and exhibits good aging stability at high temperature, and after aging for 500 hours at 1500 ℃, the resistance drift rate is less than 0.6%.
Description
Technical Field
The application relates to the field of semiconductor sensors, in particular to a series of oxygen-insensitive negative temperature coefficient thermosensitive materials (La) based on high-entropy rare earth zirconate 0.2 Nd 0.2 Sm 0.2 Eu 0.2 A 0.2 ) 2 Zr 2 O 7 (a=gd, dy, ho or Er). Further, the application provides a high-entropy zirconate negative temperature coefficient thermistor material, a preparation method thereof and application thereof in the field of semiconductor sensors, wherein the thermistor material has obvious negative temperature coefficient characteristics and stable high-temperature aging characteristics within the temperature range of 400-1500 ℃, and the electrical property of the thermistor material does not change along with the change of oxygen partial pressure, and has oxygen insensitivity.
Background
Compared with the traditional noble metal resistor and thermocouple, the Negative Temperature Coefficient (NTC) thermistor has small volume, low cost and short response time, and is considered to be the most economical and wide choice in the fields of temperature sensing, compensation, surge current suppression and the like. But in recent years, with national industry adjustment and technology upgrading, the working temperatures of components in various fields of aerospace, automotive electronics and military science are gradually increased, so that higher requirements are imposed on the upper limit of temperature measurement of a high-temperature Negative Temperature Coefficient (NTC) thermistor. To obtain a high temperature NTC thermistor that meets the high temperature measurement requirements, work should be done from several aspects: firstly, selecting a material system with stable phase structure in a high-temperature environment; secondly, the material should also maintain higher material constant B value and resistivity at high temperature to ensure the measurement accuracy in extreme environment; thirdly, the aging stability at high temperature is required to be good, and the electrical performance is not affected by the change of the oxygen partial pressure atmosphere in the test environment.
At present, reports of high-temperature NTC materials are mainly focused on perovskite and composite structures and scheelite structure materials. For the perovskite structure high-temperature NTC material, the applicable temperature area is wider (25-900 ℃) and the electrical property is adjustable; however, perovskite is easy to volatilize elements in a high-temperature environment, so that the material is difficult to sinter and compact in air and has poor uniformity, side reactions can occur in grain boundaries, the resistivity drift seriously causes the dispersion and continuous drift of the resistance value of the thermistor, the poor high-temperature aging stability is shown, and the large-scale manufacturing is not facilitated. For perovskite complexes of high-resistance phase oxides with low-resistance phase, it is desirable to obtain, according to the rule of electrical property mixingThe method is suitable for high-temperature NTC materials with wide temperature range and high upper limit of temperature measurement, but subsequent researches find that the composite phase is still poor in high-temperature stability due to the change of grain boundary resistance and carrier concentration in bulk phase inside the composite material caused by the seepage effect and ion migration between two phases at high temperature. The high-temperature NTC material with the scheelite structure has the advantages of good ageing performance and flexible and adjustable electrical performance, but has low melting point and low high-temperature resistivity, and the electrical conductivity mechanism of the high-temperature NTC material with the scheelite structure can be changed at 800 ℃, so that the electrical performance of the material can be changed, the resistivity is nonlinear in a temperature zone, and the upper limit temperature of the material can only reach 800 ℃ at most. In addition, the thermal constant B value of these materials is more about 4000K to 9000K, considering the tendency that the temperature coefficient of resistance α value is inversely proportional to the square of temperature (α= -B/T) 2 ) Therefore, if a high B value cannot be maintained, poor temperature measurement accuracy is often exhibited at the same time in a high-temperature environment. In addition, the electrical properties of the material system with the structure are also affected by the environmental atmosphere, especially the oxygen atmosphere environment, and the result is that the resistance value and the resistivity of the thermistor processed by the material system with the structure have obvious drift under different oxygen partial pressures, so that the measurement precision and accuracy are reduced. In summary, it is evident that perovskite and its composite structure and scheelite structure materials cannot meet the increasingly stringent technical performance requirements for high temperature NTC materials at the present stage. Therefore, it is imperative to develop a novel high-temperature NTC material with higher upper temperature measurement limit, good aging stability and higher precision at high temperature and strong tolerance to oxygen environment change.
Pyrochlore-structured ceramic materials are a new class of high temperature NTC materials discovered in recent years. The research shows that compared with perovskite, a composite structure thereof and a scheelite structure material, the pyrochlore structure ceramic material has high melting point and excellent high-temperature semiconductor property, and the electrical property is insensitive to oxygen partial pressure. Meanwhile, the pyrochlore material has higher thermosensitive constant B value and resistivity at high temperature, and ensures higher upper temperature measurement limit and good sensitivity. At the same time can be communicated withThe structural disorder degree of zirconate is changed by substitution or doping so as to adjust the electrical property of the material, thereby providing necessary guarantee for developing a novel high-temperature NTC thermistor with higher upper limit of applicable temperature and good high-temperature aging characteristic. Subramannian et al reported Bi 2 Ru 2 O 7 And Ln 2 W 2 O 7 The application temperature area of the isopyrochlore material as the thermistor is 25-900 ℃ (Subramannian M A, aravaamuman G, rao G V S.oxide pyrochlores-a review [ J)]Progress in Solid State Chemistry,1983,15 (2): 55-143). Pyrochlore structure Nd was prepared by Farrhen N. Sayd et al, university of Cambridge, england 2-y Ho y Zr 2 O 7 (y is more than or equal to 0 and less than or equal to 2.0), and the change rule of the system electrical property is researched by combining diffraction and spectrum analysis technology (N.S.Farheen, J.Dheeraj, tunability of structure from ordered to disordered and its impact on ionic conductivity behavior in the Nd) 2-y Ho y Zr 2 O 7 (0.0≤y≤2.0)system[J]RSC Advance,2012,2,8341-8351), found to follow Ho 3+ The doping proportion is increased, the structural order is reduced, and the material constant B value is increased. The material shows negative temperature coefficient characteristics at 300-800 ℃ and has higher resistivity at high temperature. However, under the condition of long-term high temperature, the pyrochlore material can cause cation site mixing and increase the oxygen occupancy rate of 48f sites, and the anion sub-lattices in the structure can generate local disorder, so that the structural order degree is inevitably changed under the high temperature, the oxygen vacancy migration energy barrier can be increased, and the electrical parameters of the material are affected.
Disclosure of Invention
In view of the above problems, the high entropy ceramic which is emerging in recent years has attracted attention from the inventor due to the excellent characteristics of the multi-element synergistic effect, such as the high entropy effect on thermodynamics leads to better high temperature phase/structural stability of the material, the lattice distortion effect on structure leads to low thermal conductivity to be lower B value, and the wider application temperature area provides conditions; the oxidation resistance and corrosion resistance properties of the kinetic hysteresis effect give the device conditions for application in different oxygen atmospheres (H.M.Xiang, Y.C.Zhou, high-entopy ceramics: present status, changes, and a look forward, [ J ]. Journal of Advanced Ceramics 2021,10 (3): 385-441.). Therefore, according to a new strategy of multicomponent design of high-entropy ceramic, the application prepares pyrochlore-structured high-entropy rare earth zirconate materials which can be applied to the field of negative temperature coefficient thermistors with wide temperature range (400-1500 ℃) under high temperature and different oxygen partial pressure atmospheres.
The application aims at: aiming at the problems that when perovskite type and composite phase thermosensitive ceramics thereof are applied for a long time in a high-temperature environment, the high-temperature aging stability still needs to be improved, and the maximum upper limit temperature of a high-temperature NTC material with a scheelite structure can only reach 1000 ℃ and cannot meet the application requirements in a higher environment, the high-entropy zirconate negative temperature coefficient thermosensitive resistor material is provided. The application discloses a negative temperature coefficient thermistor material (La 0.2 Nd 0.2 Sm 0.2 Eu 0.2 A 0.2 ) 2 Zr 2 O 7 (a=gd, dy, ho, er), the material system has negative temperature coefficient characteristics at 400-1500 ℃, with the highest upper temperature limit and high sensitivity so far. Meanwhile, the high-entropy zirconate-based negative temperature coefficient thermistor material has excellent aging stability at 1500 ℃, and the resistance drift rate is less than 0.6% after aging for 500 hours. In addition, the electrical property of the system at different temperatures does not change with the change of the oxygen partial pressure, and the system can be used for manufacturing high-temperature negative temperature coefficient thermistors with high stability suitable for the atmospheres with different oxygen partial pressures.
In order to achieve the above purpose, the present application adopts the following technical scheme:
oxygen-insensitive negative temperature coefficient thermosensitive material based on high-entropy rare earth zirconate and chemical formula of oxygen-insensitive negative temperature coefficient thermosensitive material is (La 0.2 Nd 0.2 Sm 0.2 Eu 0.2 A 0.2 ) 2 Zr 2 O 7 Wherein a is one or more of Gd, dy, ho, er;
the electrical performance parameters of the high-entropy zirconate negative temperature coefficient thermistor material are as follows: b (B) 400℃/1500℃ ＝10413～11957±1.97％K，ρ 1500℃ ＝1.20～1.28×10 2 2.13% omega cm, the applicable temperature range is 400 DEG C-1500℃。
The negative temperature coefficient thermosensitive material is prepared by mixing and firing raw materials of zirconium dioxide, lanthanum oxide, neodymium oxide, samarium oxide and europium oxide respectively with gadolinium oxide, dysprosium oxide, holmium oxide and erbium oxide according to a chemical formula molar ratio.
The oxygen-insensitive negative temperature coefficient thermosensitive material of the high-entropy rare earth zirconate is prepared by adopting a method comprising the following steps of:
a. weighing oxide powder of lanthanum oxide, neodymium oxide, samarium oxide, europium oxide and oxide of zirconium dioxide respectively according to the stoichiometric ratio of La, sm, eu and A of Zr=1:1:1:1:1:5 (A=Gd, dy, ho and Er) to obtain a first mixture; carrying out wet three-dimensional vibration ball milling on the first mixture for 5-15 hours, drying the wet-milled slurry at the temperature of 100 ℃, taking out, and manually milling in an agate mortar for 1-5 hours to obtain precursor powder; the oxide of the A is gadolinium oxide, dysprosium oxide, holmium oxide or erbium oxide;
b. calcining the precursor powder obtained in the step a for 3-6 hours at 1400 ℃, performing wet ball milling for 2 hours, and drying and manually grinding to obtain pyrochlore phase powder;
c. performing briquetting and forming on the pyrochlore phase powder obtained in the step b to obtain a second formed block; cold isostatic pressing the second molding block for 3min under 250-300 MPa to obtain a third static pressure block; sintering the third static pressure block at 1600 ℃ for 20-24 hours to obtain the oxygen-insensitive negative temperature coefficient thermosensitive material of the high-entropy rare earth zirconate.
In the step a, according to the stoichiometric ratio of La to Nd to Sm to Eu to Zr=1:1:1:1:5 (A=Gd, dy, ho or Er), weighing oxide powder lanthanum oxide, neodymium oxide, samarium oxide, europium oxide and zirconium oxide, respectively mixing with gadolinium oxide, dysprosium oxide, holmium oxide or erbium oxide, placing in a ball milling tank, taking agate as a ball milling medium, taking analytically pure absolute ethyl alcohol as a dispersion medium, carrying out wet three-dimensional vibration ball milling for 8 hours, drying the wet milled slurry at 100 ℃, taking out, and manually grinding in an agate mortar for 2 hours to obtain precursor powder.
In the step b, the precursor powder obtained in the step a is calcined for 3 to 6 hours at 1400 ℃, ball-milled for 2 hours by a wet method, and then baked and manually ground to obtain pyrochlore phase (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 A 0.2 ) 2 Zr 2 O 7 (a=gd, dy, ho or Er) powder.
In the step c, the pyrochlore phase powder obtained in the step b is pressed by a single-shaft oil press at a speed of 15-20 kg/cm 2 Briquetting is carried out for 2 minutes under the pressure of the mixture to obtain a second formed block; carrying out cold isostatic pressing on the second molding block, and maintaining the pressure for 3 minutes under the pressure of 250-300 MPa to obtain a third static pressure block; sintering the third static pressure block at 1600 ℃ for 20-24 hours to obtain the oxygen-insensitive negative temperature coefficient thermosensitive material (La) of the high-entropy rare earth zirconate 0.2 Nd 0.2 Sm 0.2 Eu 0.2 A 0.2 ) 2 Zr 2 O 7 (a=gd, dy, ho or Er).
The chemical formula is (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 A 0.2 ) 2 Zr 2 O 7 (a=gd, dy, ho or Er).
Application of high-entropy rare earth zirconate-based oxygen insensitive negative temperature coefficient thermosensitive material in the field of semiconductor sensors, wherein the chemical formula of the high-entropy rare earth zirconate-based oxygen insensitive negative temperature coefficient thermosensitive material is (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 A 0.2 ) 2 Zr 2 O 7 (a=one of Gd, dy, ho or Er).
The high-entropy rare earth zirconate salt is used as an oxygen-insensitive high-temperature negative temperature coefficient thermosensitive material.
The inventor researches and discovers that the high-entropy rare earth zirconate (La 0.2 Nd 0.2 Sm 0.2 Eu 0.2 A 0.2 ) 2 Zr 2 O 7 (a=gd, dy, ho or Er) has a significant negative value in the temperature range 400 ℃ to 1500 °cThe temperature coefficient characteristic, such high-entropy materials show a wide test temperature zone, and the upper limit of the highest temperature can reach 1500 ℃; meanwhile, due to the entropy-stable structure, excellent aging stability is exhibited. The material has stable electrical property, high linear relativity, good consistency and insensitivity to oxygen, and is suitable for manufacturing thermosensitive components used in high-temperature atmospheres with different oxygen partial pressures.
In summary, the application provides a high-entropy rare earth zirconate-based oxygen insensitive negative temperature coefficient thermosensitive material, a preparation method thereof and application thereof in the field of semiconductor sensors, which adopts a wet three-dimensional vibration ball milling method to mix and ball mill analytically pure lanthanum oxide, neodymium oxide, samarium oxide, europium oxide and zirconium dioxide with gadolinium oxide, dysprosium oxide, holmium trioxide or erbium trioxide respectively, and then the thermosensitive material is obtained through drying, powder calcination, ball milling again, powder sheet cold isostatic pressing molding, high-temperature sintering and high-temperature annealing. The thermosensitive material (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 A 0.2 ) 2 Zr 2 O 7 The (a=gd, dy, ho or Er) electrical performance parameters are: b (B) 400℃/1500℃ ＝10413～11957±1.97％K，ρ 1500℃ ＝1.20～1.28×10 2 2.13 percent of omega cm, the thermosensitive material has obvious negative temperature coefficient characteristics in a temperature interval of 400-1500 ℃ and good electrical property consistency; after the temperature is 1500 ℃ for 500 hours, the resistivity drift rate is less than 0.6%, the high Wen Dianxing can be stable, and the sensitivity is high; meanwhile, the electrical property of the material does not change along with the change of the oxygen partial pressure, and has the characteristic of oxygen insensitivity. Therefore, the high-entropy rare earth zirconate is suitable for manufacturing high-temperature negative temperature coefficient thermosensitive materials with high stability in different oxygen partial pressure atmospheres.
In summary, due to the adoption of the technical scheme, the beneficial effects of the application are as follows:
(1) The thermosensitive material (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 A 0.2 ) 2 Zr 2 O 7 (A=Gd, dy, ho or Er) in the temperature range of 400-1500 DEG CThe NTC characteristic is achieved, and a wider test temperature zone is achieved;
(2) The thermosensitive material (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 A 0.2 ) 2 Zr 2 O 7 (a=gd, dy, ho or Er) aged at 1500 ℃ for 500 hours, the resistivity drift rate being less than 0.6%, exhibiting excellent high temperature aging stability;
(3) The thermosensitive material (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 A 0.2 ) 2 Zr 2 O 7 The (a=gd, dy, ho or Er) resistivity is not affected by changes in oxygen partial pressure, while the higher material constant B value ensures its accuracy of measurement in high temperature environments.
Drawings
The application will now be described by way of example and with reference to the accompanying drawings in which:
FIG. 1 shows the structure of the present application (La 0.2 Nd 0.2 Sm 0.2 Eu 0.2 A 0.2 ) 2 Zr 2 O 7 Resistivity versus temperature for (a=gd, dy, ho or Er) materials.
FIG. 2 shows the process of the present application (La 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Gd 0.2 ) 2 Zr 2 O 7 And the relation diagram of the resistance drift rate and aging time of the material at 1500 ℃ with different oxygen partial pressures.
FIG. 3 shows the process of the present application (La 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Dy 0.2 ) 2 Zr 2 O 7 And the relation diagram of the resistance drift rate and aging time of the material at 1500 ℃ with different oxygen partial pressures.
FIG. 4 shows the process of the present application (La 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Ho 0.2 ) 2 Zr 2 O 7 And the relation diagram of the resistance drift rate and aging time of the material at 1500 ℃ with different oxygen partial pressures.
FIG. 5 shows the process of the present application (La 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Er 0.2 ) 2 Zr 2 O 7 Resistance value drift of material at 1500 ℃ with different oxygen partial pressuresAnd (5) a graph of the relation between the mobility and the aging time.
FIG. 6 shows the structure of (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Gd 0.2 ) 2 Zr 2 O 7 And a plot of resistivity versus partial pressure of oxygen for the material.
FIG. 7 shows the structure of example 2 (La 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Dy 0.2 ) 2 Zr 2 O 7 And a plot of resistivity versus partial pressure of oxygen for the material.
FIG. 8 shows the structure of example 3 (La 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Ho 0.2 ) 2 Zr 2 O 7 And a plot of resistivity versus partial pressure of oxygen for the material.
FIG. 9 shows the structure of example 4 (La 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Er 0.2 ) 2 Zr 2 O 7 And a plot of resistivity versus partial pressure of oxygen for the material.
FIG. 10 shows the structure of the present application (La 0.2 Nd 0.2 Sm 0.2 Eu 0.2 A 0.2 ) 2 Zr 2 O 7 Resistivity versus oxygen partial pressure for (a=gd, dy, ho, er) materials.
Detailed Description
All of the features disclosed in this specification, or all of the steps in a method or process disclosed, may be combined in any combination, except for mutually exclusive features and/or steps.
Any feature disclosed in this specification may be replaced by alternative features serving the same or equivalent purpose, unless expressly stated otherwise. That is, each feature is one example only of a generic series of equivalent or similar features, unless expressly stated otherwise.
Example 1
a. Weighing oxide powder lanthanum oxide, neodymium oxide, samarium oxide, europium oxide, gadolinium oxide and zirconium oxide respectively according to the mass ratio of La to Sm to Eu to Gd to Zr=1:1:1:1:1:5, and mixing to obtain a first mixture; and carrying out wet three-dimensional vibration ball milling on the first mixture for 8 hours, drying the wet-milled slurry at the temperature of 100 ℃, taking out, and manually milling in an agate mortar for 2 hours to obtain precursor powder.
b. And c, calcining the precursor powder obtained in the step a for 3 hours at 1400 ℃, performing wet ball milling for 2 hours, and drying and grinding to obtain pyrochlore phase powder.
c. The pyrochlore phase powder obtained in the step b is pressed at 15kg/cm by a uniaxial oil press 2 Briquetting is carried out for 2 minutes under the pressure of the mixture to obtain a second formed block; carrying out cold isostatic pressing on the second molding block, and maintaining the pressure for 3 minutes under the pressure of 250MPa to obtain a third static pressure block; sintering the third static pressure block at 1600 ℃ for 20 hours to obtain the high-entropy rare earth zirconate-based oxygen insensitive negative temperature coefficient thermosensitive material (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Gd 0.2 ) 2 Zr 2 O 7 。
The obtained (La 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Gd 0.2 ) 2 Zr 2 O 7 The negative temperature coefficient thermal sensitive ceramic material is subjected to electrical property test, and the obtained electrical parameter is B 400℃/1500℃ ＝10413±1.52％K，ρ 1500℃ ＝1.20×10 2 (+ -1.24%) omega cm. At the same time, for the prepared (La 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Gd 0.2 ) 2 Zr 2 O 7 The relation between the resistance drift rate and aging time of the material at 1500 ℃ with different oxygen partial pressures, and the resistivity and the oxygen partial pressure are measured respectively to obtain the graph 2 and the graph 6.
Example 2
a. Weighing oxide powder lanthanum oxide, neodymium oxide, samarium oxide, europium oxide, dysprosium oxide and zirconium oxide respectively according to the mass ratio of La to Sm to Eu to Dy to Zr=1:1:1:1:1:5, and mixing to obtain a first mixture; and carrying out wet three-dimensional vibration ball milling on the first mixture for 8 hours, drying the wet-milled slurry at the temperature of 100 ℃, taking out, and manually milling in an agate mortar for 2 hours to obtain precursor powder.
b. And c, calcining the precursor powder obtained in the step a for 4 hours at 1400 ℃, performing wet ball milling for 2 hours, and drying and grinding to obtain pyrochlore phase powder.
c. The pyrochlore phase powder obtained in the step b is pressed at 15kg/cm by a uniaxial oil press 2 Briquetting is carried out for 2 minutes under the pressure of the mixture to obtain a second formed block; carrying out cold isostatic pressing on the second molding block, and maintaining the pressure for 3 minutes under 270MPa to obtain a third static pressure block; sintering the third static pressure block at 1600 ℃ for 21 hours to obtain the high-entropy rare earth zirconate-based oxygen insensitive negative temperature coefficient thermosensitive material (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Dy 0.2 ) 2 Zr 2 O 7 。
The obtained (La 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Dy 0.2 ) 2 Zr 2 O 7 The negative temperature coefficient thermal sensitive ceramic material is subjected to electrical property test, and the obtained electrical parameter is B 400℃/1500℃ ＝11241±1.37％K，ρ 1500℃ ＝1.25×10 2 (+ -1.28%) omega cm. At the same time, for the prepared (La 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Dy 0.2 ) 2 Zr 2 O 7 The relation between the resistance drift rate and aging time of the material at 1500 ℃ with different oxygen partial pressures, and the resistivity and the oxygen partial pressure are measured respectively to obtain the graph 3 and the graph 7.
Example 3
a. Weighing oxide powder lanthanum oxide, neodymium oxide, samarium oxide, europium oxide, holmium oxide and zirconium dioxide respectively according to the mass ratio of La to Nd to Sm to Eu to Ho, wherein Zr=1:1:1:1:1:5, and mixing to obtain a first mixture; and carrying out wet three-dimensional vibration ball milling on the first mixture for 8 hours, drying the wet-milled slurry at the temperature of 100 ℃, taking out, and manually milling in an agate mortar for 2 hours to obtain precursor powder.
b. And c, calcining the precursor powder obtained in the step a for 5 hours at 1400 ℃, performing wet ball milling for 2 hours, and drying and grinding to obtain pyrochlore phase powder.
c. The pyrochlore phase powder obtained in the step b is pressed at 15kg/cm by a uniaxial oil press 2 Briquetting is carried out for 2 minutes under the pressure of the mixture to obtain a second formed block; carrying out cold isostatic pressing on the second molding block, and maintaining the pressure for 3 minutes under 290MPa to obtain a third static pressure block; sintering the third static pressure block at 1600 ℃ for 22 hours to obtain the high-entropy rare earth zirconate-based oxygen insensitive negative temperature coefficient thermosensitive material (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Ho 0.2 ) 2 Zr 2 O 7 。
The obtained (La 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Ho 0.2 ) 2 Zr 2 O 7 The negative temperature coefficient thermal sensitive ceramic material is subjected to electrical property test, and the obtained electrical parameter is B 400℃/1500℃ ＝11646±1.46％K，ρ 1500℃ ＝1.27×10 2 (+ -1.35%) omega cm. At the same time, for the prepared (La 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Ho 0.2 ) 2 Zr 2 O 7 The relation between the resistance drift rate and aging time of the material at 1500 ℃ with different oxygen partial pressures, and the resistivity and the oxygen partial pressure are measured respectively to obtain the graph 4 and the graph 8.
Example 4
a. Weighing oxide powder lanthanum oxide, neodymium oxide, samarium oxide, europium oxide, erbium oxide and zirconium oxide respectively according to the mass ratio of La to Sm to Eu to Er, wherein Zr=1:1:1:1:1:5, and mixing to obtain a first mixture; and carrying out wet three-dimensional vibration ball milling on the first mixture for 8 hours, drying the wet-milled slurry at the temperature of 100 ℃, taking out, and manually milling in an agate mortar for 2 hours to obtain precursor powder.
b. And c, calcining the precursor powder obtained in the step a at 1400 ℃ for 6 hours, performing wet ball milling for 2 hours, and drying and grinding to obtain pyrochlore phase powder.
c. The pyrochlore phase powder obtained in the step b is pressed at 15kg/cm by a uniaxial oil press 2 Briquetting is carried out for 2 minutes under the pressure of the mixture to obtain a second formed block; will be secondPerforming cold isostatic pressing on the formed block, and maintaining the pressure for 3 minutes under the pressure of 300MPa to obtain a third static pressure block; sintering the third static pressure block at 1600 ℃ for 24 hours to obtain the high-entropy rare earth zirconate-based oxygen insensitive negative temperature coefficient thermosensitive material (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Er 0.2 ) 2 Zr 2 O 7 。
The obtained (La 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Er 0.2 ) 2 Zr 2 O 7 The negative temperature coefficient thermal sensitive ceramic material is subjected to electrical property test, and the obtained electrical parameter is B 400℃/1500℃ ＝11957±1.55％K，ρ 1500℃ ＝1.28×10 2 (+ -1.31%) omega cm. At the same time, for the prepared (La 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Er 0.2 ) 2 Zr 2 O 7 The relation between the resistance drift rate and aging time of the material at 1500 ℃ with different oxygen partial pressures, and the resistivity and the oxygen partial pressure are measured respectively to obtain the graph 5 and the graph 9.
The application is not limited to the specific embodiments described above. The application extends to any novel one, or any novel combination, of the features disclosed in this specification, as well as to any novel one, or any novel combination, of the steps of the method or process disclosed.
Claims (6)
1. Oxygen-insensitive negative temperature coefficient thermosensitive material based on high-entropy rare earth zirconate is characterized in that the chemical formula is (La 0.2 Nd 0.2 Sm 0.2 Eu 0.2 A 0.2 ) 2 Zr 2 O 7 Wherein A is one of Gd, dy, ho, er; the electrical performance parameters of the high-entropy rare earth zirconate negative temperature coefficient thermistor material are as follows: b (B) 400℃/1500℃ =10413~11957 ±1.97% K，ρ 1500℃ =1.20~1.28×10 2 2.13% omega cm, and the applicable temperature range is 400-1500 ℃.
2. The oxygen-insensitive negative temperature coefficient thermal sensitive material based on high-entropy rare earth zirconate according to claim 1, wherein the negative temperature coefficient thermal sensitive material is prepared by mixing and firing raw materials of lanthanum oxide, neodymium oxide, samarium oxide, europium oxide, zirconium oxide and oxides of A respectively; the oxide of A is gadolinium oxide, dysprosium oxide, holmium oxide or erbium oxide.
3. The oxygen-insensitive negative temperature coefficient thermosensitive material of the high-entropy rare earth zirconate according to claim 1 or 2, wherein the negative temperature coefficient thermosensitive material is prepared by a method comprising the following steps:
a. weighing and mixing lanthanum oxide powder, neodymium oxide, samarium oxide, europium oxide, oxide of A and zirconium dioxide according to the mass ratio of La, nd, sm, eu and Zr=1:1:1:1:1:5, wherein A is one of Gd, dy, ho, er, so as to obtain a first mixture; carrying out wet three-dimensional vibration ball milling on the first mixture for 5-15 hours, drying the wet-milled slurry at the temperature of 100 ℃, taking out, and manually milling in an agate mortar for 1-5 hours to obtain precursor powder; the oxide of the A is gadolinium oxide, dysprosium oxide, holmium oxide or erbium oxide;
b. calcining the precursor powder obtained in the step a for 3-10 hours at 1400 ℃, performing wet ball milling for 2 hours, and drying and manually grinding to obtain pyrochlore phase powder;
c. performing briquetting and forming on the pyrochlore phase powder obtained in the step b to obtain a second formed block; carrying out cold isostatic pressing on the second molding block to obtain a third static pressure block; and sintering the third static pressure block at 1600 ℃ for 20-24 hours to obtain the oxygen-insensitive negative temperature coefficient heat-sensitive material of the high-entropy rare earth zirconate.
4. The high-entropy rare earth zirconate-based oxygen insensitive negative temperature coefficient heat sensitive material according to claim 3, wherein in the step a, according to the mass ratio of La to Sm to Eu to Zr=1:1:1:1:5, wherein A is one of Gd, dy, ho, er, the oxides of lanthanum oxide powder, neodymium oxide, samarium oxide, europium oxide and zirconium dioxide are weighed and mixed, the mixture is placed in a ball milling tank, agate is used as a ball milling medium, analytically pure absolute ethyl alcohol is used as a dispersion medium, wet three-dimensional vibration ball milling is carried out for 8 hours, the wet milled slurry is dried at 100 ℃, and the wet milled slurry is taken out and is manually milled in an agate mortar for 2 hours, so as to obtain precursor powder.
5. The negative temperature coefficient heat-sensitive material according to claim 3, wherein in the step b, the precursor powder obtained in the step a is calcined at 1400 ℃ for 3-6 hours, ball-milled for 2 hours by a wet method, and dried and manually milled to obtain pyrochlore phase (La 0.2 Nd 0.2 Sm 0.2 Eu 0.2 A 0.2 ) 2 Zr 2 O 7 Powder, wherein A is one of Gd, dy, ho, er.
6. The negative temperature coefficient heat-sensitive material according to claim 3, wherein in said step c, the pyrochlore phase powder obtained in step b is pressed with a uniaxial oil press at 15-20 kg/cm 2 Briquetting is carried out for 2 minutes under the pressure of the mixture to obtain a second formed block; carrying out cold isostatic pressing on the second molding block, and maintaining the pressure for 3 minutes under the pressure of 250-300 MPa to obtain a third static pressure block; sintering the third static pressure block at 1600 ℃ for 20-24 hours to obtain the high-entropy rare earth zirconate-based oxygen insensitive negative temperature coefficient heat sensitive material (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 A 0.2 ) 2 Zr 2 O 7 Wherein A is one of Gd, dy, ho, er.
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