CN115894029A - 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 invention relates to a series of oxygen-insensitive negative temperature coefficient thermal sensitive materials based on high-entropy rare earth zirconate, which take lanthanum oxide, neodymium oxide, samarium oxide, europium oxide and zirconium dioxide and gadolinium oxide, dysprosium oxide, holmium oxide or erbium oxide as raw materials, through wet three-dimensional vibration ball milling, powder calcining, secondary ball milling, cold isostatic pressing and high-temperature sintering, the pyrochlore structure (La) can be obtained 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 series of materials have the following electrical performance parameters: b is 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 thermal sensitive material (La) prepared by the invention 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 within the temperature range of 400-1500 ℃, and shows good aging stability at high temperature, and the resistance drift rate is less than 0.6% after aging for 500 hours at 1500 ℃.
Description
Technical Field
The invention relates to the field of semiconductor sensors, in particular to a series of oxygen-insensitive negative temperature coefficient thermal sensitive 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 range of 400-1500 ℃, the electrical property of the thermistor material does not change along with the change of oxygen partial pressure, and the thermistor material has oxygen-insensitive characteristics.
Background
Compared with the traditional noble metal resistor and thermocouple, the Negative Temperature Coefficient (NTC) thermistor is considered to be the most economical and wide choice in the fields of temperature sensing, compensation, surge current suppression and the like due to small volume, low cost and short response time. However, in recent years, with national industrial adjustment and technical upgrading, the operating temperature of components in various fields of aerospace, automotive electronics and military science is gradually increased, so that higher requirements are placed on the upper limit of temperature measurement of a high-temperature Negative Temperature Coefficient (NTC) thermistor. To obtain a high-temperature NTC thermistor meeting the requirement of high-temperature measurement, work should be done from the following aspects: firstly, a material system with stable structure under a high-temperature environment is selected; secondly, the material should keep higher material constant B value and resistivity at high temperature to ensure the measurement accuracy in extreme environment; and thirdly, the high-temperature aging stability is required, and the electrical property is not influenced by the change of the oxygen partial pressure atmosphere in the testing environment.
At present, reports of high-temperature NTC materials mainly focus on perovskite and composite structures thereof and scheelite structural materials. For the high-temperature NTC material with the perovskite structure, although the applicable temperature zone is wider (25 ℃ -900 ℃), and the electrical property is adjustable; however, the perovskite is easy to volatilize elements in a high-temperature environment, so that the material is difficult to sinter and compact in air, poor in uniformity, and side reaction can occur at a crystal boundary, so that the resistance value of the thermistor is dispersed and continuously drifted due to serious drift of the resistivity, the poor high-temperature aging stability is shown, and the large-scale manufacturing is not facilitated. For the perovskite compound of the high-resistance phase oxide and the low-resistance phase, a high-temperature NTC material suitable for a wide temperature zone and high temperature measurement upper limit is expected to be obtained according to an electrical property mixing rule, but subsequent researches find that the grain boundary resistance inside the composite material and the carrier concentration inside a bulk phase are changed due to the seepage effect and ion migration between the two phases at high temperature of the composite phase, so that the resistivity of the material is continuously reduced, and the high-temperature stability is still poor. Although the high-temperature NTC material with the scheelite structure has the advantages of good aging performance and flexible and adjustable electrical property, the high-temperature NTC material has a low melting point and small high-temperature resistivity, and the electrical conduction mechanism of the high-temperature NTC material with the scheelite structure is changed at 800 ℃, so that the electrical property of the material is changed, the resistivity is nonlinear in a temperature region, and the maximum upper limit temperature of the material can only reach 800 ℃. In addition, the thermal constant B value of these materials is often about 4000K to 9000K, and in view of the tendency that the temperature coefficient of resistance α value is inversely proportional to the square of the temperature (α = -B/T) 2 ) Therefore, if a high B value cannot be maintained, the temperature measurement accuracy is often poor in a high-temperature environment. In addition, the electrical properties of the material systems of the above-mentioned structures are also affected by the ambient atmosphere, especially the oxygen atmosphere, which results in that the thermistors based on their processing have a significant drift in resistance and resistivity at different oxygen partial pressures, thereby causing a decrease in measurement accuracy and precision. In summary, it is obvious that both perovskite and its composite structure and scheelite structure materials can not meet the increasingly demanding technical performance requirements for high temperature NTC materials at the present stage. Therefore, the number of the first and second electrodes is increased,the research and development of a novel high-temperature NTC material with higher temperature measurement upper limit, good aging stability and higher precision at high temperature and strong tolerance to oxygen environment change is imperative.
Pyrochlore structural ceramic materials are a new class of high temperature NTC materials discovered in recent years. Research has found that compared with perovskite and its composite structure and scheelite structure materials, pyrochlore structure ceramic materials have high melting points and excellent high temperature semiconductor properties, and their electrical properties are not sensitive to oxygen partial pressure. Meanwhile, the pyrochlore material has higher thermal constant B value and resistivity at high temperature, and ensures higher upper limit of temperature measurement and good sensitivity. Meanwhile, the electrical property of the material can be adjusted by replacing or doping to change the structural disorder degree of the zirconate, thereby providing necessary guarantee for researching and developing a novel high-temperature NTC thermistor with higher applicable upper temperature limit and good high-temperature aging characteristic. Subramanian et al reported Bi 2 Ru 2 O 7 And Ln 2 W 2 O 7 The application temperature range of the pyrochlore material as the thermistor is 25-900 ℃ (Subramanian M A, aravamdan G, rao G V.oxide pyrochlores-a review [ J ]]Progress in Solid State Chemistry,1983,15 (2): 55-143). Pyrochlore structure Nd was prepared by Farheen N.Sayed et al, cambridge university, UK 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 electrical property of the system (N.S. farheen, J.Dheiej, flexibility of structure from organized to distributed and object on-ic communication property in the Nd is researched by combining diffraction and spectrum analysis technologies 2-y Ho y Zr 2 O 7 (0.0≤y≤2.0)system[J]RSC Advance,2012,2, 8341-8351), found with Ho 3+ The doping proportion is increased, the structural order degree is reduced, and the material constant B value is increased. The material shows negative temperature coefficient characteristic at 300-800 deg.c and has relatively high resistivity at high temperature. However, in the pyrochlore material under long-term high temperature, due to thermal activation, cation site mixing and 48f site oxygen occupancy rate increase are caused, partial disorder of anion sublattice in the structure can occur, and thus inevitable structural order degree transformation can occur at high temperature, so that oxygen vacancy migration can be causedThe energy barrier increases, affecting the electrical parameters of the material.
Disclosure of Invention
Aiming at the problems, the excellent characteristics of the emerging high-entropy ceramics caused by the multi-element synergistic action arouse the attention of the inventor in recent years, for example, the high-entropy effect on thermodynamics enables the material to have better high-temperature phase/structure stability, the lattice distortion effect on the structure causes the low thermal conductivity to be a lower B value, and conditions are provided for a wider application temperature zone; the oxidation and corrosion resistance characteristics due to the kinetic hysteresis effect make it possible to apply to different oxygen atmospheres (H.M. Xiaong, Y.C. Zhou, high-entry Ceramics: present status, pulleys, and a look forward, [ J ]. Journal of Advanced Ceramics 2021,10 (3): 385-441). Therefore, according to a new strategy of multi-component design of the high-entropy ceramic, the pyrochlore structure high-entropy rare earth zirconate material which can be applied to the field of negative temperature coefficient thermistors with wide temperature zones (400-1500 ℃) under high temperature and different oxygen partial pressure atmospheres is prepared.
The invention aims to: the high-entropy zirconate negative temperature coefficient thermistor material is provided for solving the problems that the high-temperature aging stability is still to be improved when perovskite type and composite phase thermosensitive ceramics are applied in a high-temperature environment for a long time, the maximum upper limit temperature of a high-temperature NTC material with a scheelite structure can only reach 1000 ℃, and the application requirements in a higher environment cannot be met. 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 characteristic within 400-1500 ℃, and has the highest temperature upper limit and high sensitivity. 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 does not change along with the change of oxygen partial pressure at different temperatures, and the system can be used for manufacturing high-temperature negative temperature coefficient thermistors with high stability suitable for different oxygen partial pressure atmospheres.
In order to achieve the purpose, the invention adopts the following technical scheme:
an oxygen-insensitive negative temperature coefficient thermosensitive material based on high-entropy rare earth zirconate and has a chemical formula of (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 and Er;
the electrical performance parameters of the high-entropy zirconate negative temperature coefficient thermistor material are as follows: b is 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 ℃.
The negative temperature coefficient thermal sensitive material is prepared by mixing and firing raw materials of zirconium dioxide, lanthanum trioxide, neodymium trioxide, samarium trioxide and europium trioxide and gadolinium trioxide, dysprosium trioxide, holmium trioxide and erbium trioxide according to the molar ratio of a chemical formula.
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. respectively weighing and mixing oxide powders of lanthanum sesquioxide, neodymium sesquioxide, samarium sesquioxide, europium sesquioxide, oxides of A and zirconium dioxide according to the stoichiometric ratio of La to Nd to Sm to Eu to A to Zr = 1; carrying out wet three-dimensional vibration ball milling on the first mixture for 5-15 hours, drying the slurry after wet milling at the temperature of 100 ℃, taking out the slurry and placing the slurry in an agate mortar for manual milling for 1-5 hours to obtain precursor powder; the oxide of A is gadolinium oxide, dysprosium oxide, holmium oxide or erbium oxide;
b. calcining the precursor powder obtained in the step a at 1400 ℃ for 3-6 hours, performing wet ball milling for 2 hours, and drying and manually grinding to obtain pyrochlore phase powder;
c. b, briquetting and molding the pyrochlore phase powder obtained in the step b to obtain a second molded block; carrying out cold isostatic pressing on the second formed block body for 3min under the pressure of 250-300 MPa to obtain a third hydrostatic block body; and sintering the third static pressure block at 1600 ℃ for 20-24 h to obtain the oxygen-insensitive negative temperature coefficient thermal sensitive material of the high-entropy rare earth zirconate.
In the step a, according to the stoichiometric ratio of La: nd: sm: eu: A: zr = 1.
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 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).
In the step c, the pyrochlore phase powder obtained in the step b is processed by a uniaxial oil press at the speed of 15-20 kg/cm 2 The pressure is used for briquetting and forming for 2 minutes to obtain a second formed briquette; carrying out cold isostatic pressing on the second formed block, and maintaining the pressure for 3 minutes under the pressure of 250-300 MPa to obtain a third hydrostatic block; sintering the third static pressure block body for 20-24 hours at 1600 ℃ to obtain the oxygen-insensitive negative temperature coefficient heat-sensitive 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).
Has a chemical formula of (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).
The application of high-entropy rare earth zirconate based oxygen-insensitive negative temperature coefficient thermosensitive material in the field of semiconductor sensorsThe entropy rare earth zirconate based oxygen-insensitive negative temperature coefficient thermosensitive material has the chemical formula of (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).
The high-entropy rare earth zirconate 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 obvious negative temperature coefficient characteristic in the temperature range of 400-1500 ℃, the high-entropy material shows a wide testing temperature zone, and the upper limit of the highest temperature can reach 1500 ℃; meanwhile, excellent aging stability is exhibited due to the entropy-stable structure. The material has stable electrical property, high linear correlation degree, good consistency and insensitivity to oxygen, and is suitable for manufacturing thermosensitive components used in high-temperature different oxygen partial pressure atmospheres.
In summary, the present application provides a high-entropy rare earth zirconate oxygen-insensitive negative temperature coefficient thermal sensitive material, a preparation method thereof and an application thereof in the field of semiconductor sensors, wherein analytically pure lanthanum trioxide, neodymium trioxide, samarium trioxide, europium trioxide and zirconium dioxide are respectively mixed and ball-milled with gadolinium trioxide, dysprosium trioxide, holmium trioxide or erbium trioxide by a wet three-dimensional vibration ball milling method, and then the powder is subjected to drying, powder calcination and ball milling again, sheet-type cold isostatic pressing, high-temperature sintering and high-temperature annealing to obtain the thermal sensitive material. Thermosensitive material (La) prepared by the invention 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) electrical property parameters: b is 400℃/1500℃ ＝10413～11957±1.97％K，ρ 1500℃ ＝1.20～1.28×10 2 +/-2.13% of omega cm, the thermosensitive material has obvious negative temperature coefficient characteristic within the temperature range of 400-1500 ℃, and the consistency of electrical property is good; after the material is aged for 500 hours at the temperature of 1500 ℃, the resistance drift rates are all less than 0.6 percent,the high-temperature electrical property is stable, and the sensitivity is high; meanwhile, the electrical property of the material is not changed along with the change of oxygen partial pressure, and the material has the characteristic of insensitivity to oxygen. Therefore, the high-entropy rare earth zirconate is a high-temperature negative temperature coefficient thermosensitive material with high stability in different oxygen partial pressure atmospheres.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
(1) Thermosensitive Material (La) of the present invention 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 NTC characteristic in the temperature range of 400 ℃ -1500 ℃, and has a wider test temperature zone;
(2) Heat-sensitive Material (La) of the present invention 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) is aged for 500 hours at 1500 ℃, the resistance drift rate is less than 0.6%, and the high-temperature aging stability is excellent;
(3) Thermosensitive Material (La) of the present invention 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 the change of oxygen partial pressure, and at the same time, the higher value of the material constant B ensures its accuracy of measurement in a high temperature environment.
Drawings
The invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 shows the present invention (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 A 0.2 ) 2 Zr 2 O 7 Resistivity versus temperature plot of (a = Gd, dy, ho, or Er) material.
FIG. 2 shows the present invention (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Gd 0.2 ) 2 Zr 2 O 7 Graph of resistance drift rate and aging time of the material at different oxygen partial pressures of 1500 ℃.
FIG. 3 shows the present invention (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Dy 0.2 ) 2 Zr 2 O 7 Graph of resistance drift rate and aging time of the material at different oxygen partial pressures of 1500 ℃.
FIG. 4 shows the present invention (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Ho 0.2 ) 2 Zr 2 O 7 The resistance drift rate of the material at different oxygen partial pressures of 1500 ℃ is plotted against aging time.
FIG. 5 shows the present invention (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Er 0.2 ) 2 Zr 2 O 7 Graph of resistance drift rate and aging time of the material at different oxygen partial pressures of 1500 ℃.
FIG. 6 shows (La) in example 1 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Gd 0.2 ) 2 Zr 2 O 7 Resistivity of the material is plotted against oxygen partial pressure.
FIG. 7 shows (La) in example 2 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Dy 0.2 ) 2 Zr 2 O 7 Resistivity of the material is plotted against oxygen partial pressure.
FIG. 8 shows (La) in example 3 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Ho 0.2 ) 2 Zr 2 O 7 Resistivity of the material is plotted against oxygen partial pressure.
FIG. 9 shows (La) in example 4 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Er 0.2 ) 2 Zr 2 O 7 Resistivity of the material is plotted against oxygen partial pressure.
FIG. 10 shows the present invention (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 A 0.2 ) 2 Zr 2 O 7 Resistivity of (a = Gd, dy, ho, er) material is plotted against oxygen partial pressure.
Detailed Description
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features.
Example 1
a. Respectively weighing and mixing oxide powders of lanthanum oxide, neodymium oxide, samarium oxide, europium oxide, gadolinium oxide and zirconium dioxide according to the mass ratio of La to Nd to Sm to Eu to Gd to Zr = 1; and (3) carrying out wet three-dimensional vibration ball milling on the first mixture for 8 hours, drying the slurry after wet milling at the temperature of 100 ℃, taking out the slurry, and manually milling the slurry 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 3 hours, then carrying out wet ball milling for 2 hours, and drying and grinding to obtain pyrochlore phase powder.
c. C, using a uniaxial oil press to perform the step b on the pyrochlore phase powder at 15kg/cm 2 The pressure is used for briquetting and forming for 2 minutes to obtain a second formed briquette; carrying out cold isostatic pressing on the second forming block, and maintaining the pressure for 3 minutes under the pressure of 250MPa to obtain a third hydrostatic block; sintering the third static pressure block body at 1600 ℃ for 20 hours to obtain the high-entropy rare earth zirconate based oxygen-insensitive negative temperature coefficient thermal sensitive material (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Gd 0.2 ) 2 Zr 2 O 7 。
Will obtain (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 to obtain an electrical parameter B 400℃/1500℃ ＝10413±1.52％K，ρ 1500℃ ＝1.20×10 2 . + -. 1.24% Ω. 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 Resistance value of material is floated at 1500 ℃ under different oxygen partial pressuresThe relationship between the migration rate and the aging time, and the resistivity and the oxygen partial pressure were measured, respectively, to obtain FIGS. 2 and 6.
Example 2
a. Respectively weighing and mixing oxide powders of lanthanum trioxide, neodymium trioxide, samarium trioxide, europium trioxide, dysprosium trioxide and zirconium dioxide according to the mass ratio of La to Nd to Sm to Eu to Dy to Zr = 1; and (3) carrying out wet three-dimensional vibration ball milling on the first mixture for 8 hours, drying the slurry after wet milling at the temperature of 100 ℃, taking out the slurry, and manually milling the slurry 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 4 hours, then carrying out wet ball milling for 2 hours, and drying and grinding to obtain pyrochlore phase powder.
c. B, using a single-shaft oil press to perform the step of grinding the pyrochlore phase powder obtained in the step b at the speed of 15kg/cm 2 The pressure is used for briquetting and forming for 2 minutes to obtain a second formed briquette; carrying out cold isostatic pressing on the second forming block, and keeping the pressure for 3 minutes under the pressure of 270MPa to obtain a third hydrostatic 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 thermal sensitive material (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Dy 0.2 ) 2 Zr 2 O 7 。
Will obtain (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 to obtain an electrical parameter B 400℃/1500℃ ＝11241±1.37％K，ρ 1500℃ ＝1.25×10 2 . + -. 1.28% Ω. 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 relationship between the resistance drift rate and the aging time of the material at different oxygen partial pressures of 1500 ℃, and the resistivity and the oxygen partial pressure are respectively measured to obtain figures 3 and 7.
Example 3
a. Respectively weighing and mixing oxide powders of lanthanum trioxide, neodymium trioxide, samarium trioxide, europium trioxide, holmium trioxide and zirconium dioxide according to the mass ratio of La to Nd to Sm to Eu to Ho to Zr = 1; and (3) carrying out wet three-dimensional vibration ball milling on the first mixture for 8 hours, drying the slurry after wet milling at the temperature of 100 ℃, taking out the slurry, and manually milling the slurry 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 5 hours, then carrying out wet ball milling for 2 hours, and drying and grinding to obtain pyrochlore phase powder.
c. C, using a uniaxial oil press to perform the step b on the pyrochlore phase powder at 15kg/cm 2 The pressure is used for briquetting and forming for 2 minutes to obtain a second formed briquette; carrying out cold isostatic pressing on the second forming block, and keeping the pressure for 3 minutes under the pressure of 290MPa to obtain a third hydrostatic block; sintering the third static pressure block body at 1600 ℃ for 22 hours to obtain the high-entropy rare earth zirconate based oxygen-insensitive negative temperature coefficient thermal sensitive material (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Ho 0.2 ) 2 Zr 2 O 7 。
Will obtain (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 to obtain an electrical parameter B 400℃/1500℃ ＝11646±1.46％K，ρ 1500℃ ＝1.27×10 2 . + -. 1.35% Ω. 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 relationship between the resistance drift rate and the aging time of the material at different oxygen partial pressures of 1500 ℃, and the resistivity and the oxygen partial pressure are respectively measured to obtain the graphs of FIG. 4 and FIG. 8.
Example 4
a. Respectively weighing and mixing oxide powders of lanthanum trioxide, neodymium trioxide, samarium trioxide, europium trioxide, erbium trioxide and zirconium dioxide according to the mass ratio of La to Nd to Sm to Eu to Er to Zr = 1; and (3) performing wet three-dimensional vibration ball milling on the first mixture for 8 hours, drying the slurry after wet milling at the temperature of 100 ℃, taking out the slurry, and manually milling the slurry 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, then carrying out wet ball milling for 2 hours, and drying and grinding to obtain pyrochlore phase powder.
c. B, using a single-shaft oil press to perform the step of grinding the pyrochlore phase powder obtained in the step b at the speed of 15kg/cm 2 The pressure is used for briquetting and forming for 2 minutes to obtain a second formed briquette; carrying out cold isostatic pressing on the second forming block, and keeping the pressure for 3 minutes under the pressure of 300MPa to obtain a third hydrostatic block; sintering the third static pressure block body at 1600 ℃ for 24 hours to obtain the high-entropy rare earth zirconate based oxygen-insensitive negative temperature coefficient thermal sensitive material (La) 0.2 Nd 0.2 Sm 0.2 Eu 0.2 Er 0.2 ) 2 Zr 2 O 7 。
Will obtain (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 to obtain an electrical parameter B 400℃/1500℃ ＝11957±1.55％K，ρ 1500℃ ＝1.28×10 2 . + -. 1.31% Ω. 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 relationship between the resistance drift rate and the aging time of the material at different oxygen partial pressures of 1500 ℃, and the resistivity and the oxygen partial pressure are respectively measured to obtain figures 5 and 9.
The invention is not limited to the foregoing embodiments. The invention extends to any novel feature or any novel combination of features disclosed in this specification and any novel method or process steps or any novel combination of features disclosed.
Claims (7)
1. Oxygen-insensitive negative temperature coefficient thermosensitive material based on high-entropy rare earth zirconateThe material 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 and Er; the electrical performance parameters of the high-entropy zirconate negative temperature coefficient thermistor material are as follows: b is 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. An oxygen-insensitive negative temperature coefficient thermal material based on high entropy rare earth zirconate as claimed in claim 1, wherein 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).
3. The oxygen-insensitive negative temperature coefficient thermal sensitive material based on the high-entropy rare earth zirconate is characterized in that the negative temperature coefficient thermal sensitive material is formed by respectively mixing and firing raw materials of lanthanum sesquioxide, neodymium sesquioxide, samarium sesquioxide, europium sesquioxide and zirconium dioxide with an oxide of A; the oxide of A is gadolinium oxide, dysprosium oxide, holmium oxide or erbium oxide.
4. An oxygen-insensitive negative temperature coefficient thermal material of high entropy rare earth zirconate according to claim 1, 2 or 3, wherein the negative temperature coefficient thermal material is prepared by a method comprising the following steps:
a. respectively weighing and mixing oxide powders of lanthanum oxide, neodymium oxide, samarium oxide, europium oxide, A oxide and zirconium dioxide according to the mass ratio of La to Nd to Sm to Eu to Zr to =1 to 1; carrying out wet three-dimensional vibration ball milling on the first mixture for 5-15 hours, drying the slurry after wet milling at the temperature of 100 ℃, taking out the slurry, placing the slurry in an agate mortar, and manually milling the slurry for 1-5 hours to obtain precursor powder; the oxide of A is gadolinium oxide, dysprosium oxide, holmium oxide or erbium oxide;
b. calcining the precursor powder obtained in the step a at 1400 ℃ for 3-10 hours, then carrying out wet ball milling for 2 hours, and drying and manually grinding to obtain pyrochlore phase powder;
c. b, briquetting and molding the pyrochlore phase powder obtained in the step b to obtain a second molded block; carrying out cold isostatic pressing on the second formed block to obtain a third hydrostatic block; and sintering the third static pressure block at 1600 ℃ for 20-24 h to obtain the oxygen-insensitive negative temperature coefficient thermal sensitive material of the high-entropy rare earth zirconate.
5. The high-entropy rare-earth zirconate oxygen-insensitive negative temperature coefficient thermal sensitive material according to claim 4, wherein in the step a, the oxide powders of lanthanum trioxide, neodymium trioxide, samarium trioxide, europium trioxide, A oxide and zirconium dioxide are weighed according to the mass ratio of La, nd, eu, A, zr = 1.
6. The negative temperature coefficient thermal sensitive material of claim 4, 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 ground to obtain pyrochlore phase (La) which is a rare earth element 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).
7. The negative temperature coefficient thermal material according to any one of claims 4 to 6, wherein in the step c, the pyrochlore phase powder obtained in the step b is pressed by a uniaxial oil press at 15 to 20kg/cm 2 The pressure is used for briquetting and forming for 2 minutes to obtain a second formed briquette; carrying out cold isostatic pressing on the second forming block, and maintaining the pressure for 3 minutes under the pressure of 250-300 MPa to obtain a third isostatic pressing block; sintering the third static pressure block body for 20-24 hours at 1600 ℃ to obtain the high-entropy rare earth zirconate based oxygen insensitive negative temperature coefficient thermal sensitive 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).
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