CN116023140B - Oxygen-insensitive negative temperature coefficient thermosensitive material based on high-entropy rare earth stannate - Google Patents
Oxygen-insensitive negative temperature coefficient thermosensitive material based on high-entropy rare earth stannate 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 stannate, which takes lanthanum oxide, neodymium oxide, samarium oxide, gadolinium oxide and tin dioxide as raw materials, respectively, and the materials are subjected to three-dimensional vibration mixing ball milling, calcination, secondary ball milling, cold isostatic pressing and high-temperature sintering to obtain pyrochlore structure (La) 0.2 Nd 0.2 Sm 0.2 Gd 0.2 M 0.2 ) 2 Sn 2 O 7 (m=eu, dy, ho or Yb) heat sensitive material. The electrical performance parameters of the series of materials are as follows: b (B) 400℃/1400℃ =11820~12519±2.31%K，ρ 1400℃ =3.22~5.67×10 2 (+ -1.56%) omega cm. The high-entropy rare earth stannate-based oxygen insensitive negative temperature coefficient thermosensitive material (La) 0.2 Nd 0.2 Sm 0.2 Gd 0.2 M 0.2 ) 2 Sn 2 O 7 (m=eu, dy, ho or Yb) has excellent negative temperature coefficient characteristics in a temperature range of 400 ℃ to 1400 ℃, and shows good aging stability at high temperature, and after aging for 500 hours at 1400 ℃, the resistance drift rate is less than 1.95%.
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 stannate 0.2 Nd 0.2 Sm 0.2 Gd 0.2 M 0.2 ) 2 Sn 2 O 7 (M＝Eu、Dy, ho or Yb). Further, the application provides a negative temperature coefficient thermosensitive material, a preparation method thereof and application thereof in the field of semiconductor sensors, wherein the thermosensitive material has obvious negative temperature coefficient characteristics and stable high-temperature aging characteristics in the temperature range of 400-1400 ℃, and the electric performance of the thermosensitive material does not change along with the change of oxygen partial pressure, and has oxygen insensitivity.
Background
The high temperature Negative Temperature Coefficient (NTC) thermistor is considered to be the most economical and wide choice in the field of temperature sensing test in a high temperature environment above 300 ℃ because of its simple structure and low power consumption. However, in recent years, with the vigorous development of fields such as automobiles, metallurgy, aerospace and the like, higher requirements are put forward on high-temperature negative temperature coefficient thermistors. Specifically, the method is firstly suitable for high-temperature environments at 1000 ℃ and above; and also should maintain high material constant B and resistivity at high temperatures to ensure measurement accuracy in extreme environments; more importantly, the test device must also have good aging characteristics at high temperatures, and electrical properties are not affected by changes in the oxygen partial pressure atmosphere in the test environment.
At present, reports of high temperature NTC materials are mainly focused on perovskite structure and scheelite structure materials. For the perovskite structure high-temperature NTC material, although the applicable temperature area is wider (25-900 ℃) and the highest upper limit of temperature measurement reaches 900 ℃, the series of materials are easy to volatilize elements in a high-temperature environment and have side reactions at grain boundaries, and the like, so that the resistivity drift is serious, and the poor high-temperature aging stability is shown. While the scheelite structure high temperature NTC material has the advantages of good ageing performance and flexible and adjustable electrical performance, the melting point is low, the high temperature resistivity is small, and the maximum upper limit temperature can only reach 800 ℃; in addition, the thermal constant B value of the two materials is about 4000K to 9000K, and in view of the tendency that the temperature coefficient α of resistance is exponentially decreased with the increase of temperature, if the higher B value cannot be maintained, the high temperature NTC materials of perovskite and scheelite structures often show poor temperature measurement precision at the same time in a high temperature environment. In addition, the electrical properties of the material systems of the two structures are also affected by the environmental atmosphere, especially the oxygen atmosphere, and the result is that the resistance and the resistivity of the thermistors processed by the material systems have obvious drift under different oxygen partial pressures, thereby reducing the measurement precision and accuracy. In view of the above, it is evident that perovskite and scheelite structural materials have failed to meet the increasingly stringent technical performance requirements currently proposed for high temperature NTC materials. 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 and scheelite structural materials, the pyrochlore structural material has higher B value and high-temperature resistivity, and can ensure that good sensitivity can be maintained at high temperature. Meanwhile, the material also has higher melting point and good structural stability at high temperature, 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. Among them, pyrochlore-type zirconates and titanates have been widely studied, while there have been less researches on pyrochlore-type stannates having similar structures and characteristics. 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). Then Mervini and Chiya et al speculate on the basis of the high temperature semiconductor properties of pyrochlore zirconates and their series materials, suggesting that such materials may be applied to thermistors (Chiya T j. The Synthesis and Characterisation of Pyrochlore Zirconates [ D]University of the Witwatersrand, faculty of Science, 2017), but lacks specific experimental data such as: key parameters such as temperature coefficient of resistance, resistivity and thermal constant. The research on zirconate by Wang et al of the subject group shows that the material does have excellent high-temperature NTC characteristics, the application temperature range is 400-1000 ℃ (Wang Y,Gao B,Wang Q,et al.A 2 Zr 2 O 7 (A＝Nd,Sm,Gd,Yb)zirconate ceramics with pyrochlore-type structure for high-temperature negative temperature coefficient thermistor[J]journal of Materials Science,2020,55 (32): 15405-15414), the maximum application temperature range still does not exceed 1000 ℃. Compared with zirconate, stannate has high temperature stability and oxygen insensitivity, lower oxygen ion migration activation energy and the potential of being used in the field of high temperature thermistor in a wider temperature area by virtue of the semiconductor characteristic of the stannate at high temperature, and the application temperature can reach 1100 ℃ (a stannate system negative temperature coefficient thermistor material and a preparation method thereof, and the patent application number is 202110212343.4). Although the stannate application temperature area is improved compared with that of zirconate, the expansion is not great. In addition, all pyrochlore materials inevitably undergo disordered structural transformation after long-term use in a high-temperature environment, and the electrical parameters of the pyrochlore materials are directly influenced.
In view of the above problems, the high entropy ceramics which have been developed in recent years have attracted attention from the inventors due to their excellent characteristics caused by the synergistic effect of multiple elements, such as the thermodynamic excellent structural stability caused by the high entropy effect provides a guarantee for better high temperature aging stability, the lattice distortion effect on the structure results in low thermal conductivity as a lower B value, the wider application temperature zone provides conditions, the oxidation resistance caused by the kinetic hysteresis effect, corrosion resistance and the like, which give them conditions for application in different oxygen atmospheres (Oses C, toher C, curtarolo S.high-entopy ceramics [ J ]. Nature Reviews Materials,2020,5 (4): 295-309). Therefore, according to a new strategy of multicomponent design of high-entropy ceramic, the application prepares pyrochlore-structured high-entropy rare earth stannate material which can be applied to the field of negative temperature coefficient thermistors with wide temperature area (400-1400 ℃) under high temperature and different oxygen partial pressure atmospheres.
Disclosure of Invention
The application aims at: in order to solve the problems, a series of oxygen-insensitive negative temperature coefficient thermosensitive materials (La 0.2 Nd 0.2 Sm 0.2 Gd 0.2 M 0.2 ) 2 Sn 2 O 7 (where m=eu, dy, ho or Yb). The high-entropy rare earth stannate-based oxygen insensitive negative temperature coefficient heat sensitive material prepared by the application has excellent negative temperature coefficient characteristics in a temperature range of 400-1400 ℃, and has good aging stability at high temperature, and the resistance drift rate is less than 1.95% after aging for 500 hours at 1400 ℃. Moreover, the electrical properties of the series of materials are not changed along with the change of the oxygen partial pressure, are insensitive to the oxygen partial pressure, and 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 above purpose, the present application adopts the following technical scheme:
high-entropy rare earth stannate-based oxygen insensitive negative temperature coefficient thermosensitive material with chemical formula of (La 0.2 Nd 0.2 Sm 0.2 Gd 0.2 M 0.2 ) 2 Sn 2 O 7 Wherein M is one of Eu, dy, ho or Yb;
the electrical performance parameters of the negative temperature coefficient thermosensitive material are as follows: b (B) 400℃/1400℃ ＝11820～12519±2.31％ K，ρ 1400℃ ＝3.22～5.67×10 2 The temperature range of the product is 400-1400 ℃ and is +/-1.56% omega cm.
The chemical formula is (La) 0.2 Nd 0.2 Sm 0.2 Gd 0.2 M 0.2 ) 2 Sn 2 O 7 (m=eu, dy, ho or Yb).
The negative temperature coefficient thermosensitive material is prepared by mixing and firing raw materials of tin dioxide, lanthanum oxide, neodymium oxide, samarium oxide and gadolinium oxide with europium oxide, dysprosium oxide, holmium oxide and ytterbium oxide respectively.
The high-entropy rare earth stannate-based oxygen insensitive negative temperature coefficient heat sensitive material is prepared by adopting a method comprising the following steps:
a. weighing oxide powder lanthanum oxide, neodymium oxide, samarium oxide, gadolinium oxide and tin dioxide according to the stoichiometric ratio of La, sm, gd, M, sn=1:1:1:1:1:5 (M=Eu, dy, ho or Yb) respectively, and mixing with the oxide of M to obtain a first mixture; carrying out wet three-dimensional vibration ball milling on the first mixture for 6-10 hours, drying the wet-milled slurry at the temperature of 100 ℃, taking out, and manually milling in an agate mortar for 2-4 hours to obtain precursor powder; the oxide of M is europium oxide, dysprosium oxide, holmium oxide or ytterbium oxide;
b. calcining the precursor powder obtained in the step a for 3-6 hours at 1400 ℃, performing wet three-dimensional vibration ball milling for 2-4 hours, and drying and 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 8-12 hours to obtain the high-entropy rare earth stannate-based oxygen insensitive negative temperature coefficient heat sensitive material.
In the step a, according to the stoichiometric ratio of La to Nd to Sm to M to Sn=1:1:1:1:5 (M=Eu, dy, ho or Yb), weighing oxide powder lanthanum oxide, neodymium oxide, samarium oxide, gadolinium oxide and tin dioxide, mixing with europium oxide, dysprosium oxide, holmium oxide or ytterbium oxide respectively, placing in a ball milling tank, taking agate as a ball milling medium, taking analytically pure absolute ethyl alcohol as a dispersing medium, carrying out wet three-dimensional vibration ball milling for 6-10 hours, drying the wet-milled slurry at 100 ℃, taking out, and manually grinding in an agate mortar for 2-4 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 ℃, and then is subjected to wet three-dimensional vibration ball milling for 2 to 4 hours, thus obtaining pyrochlore phase (La) 0.2 Nd 0.2 Sm 0.2 Gd 0.2 M 0.2 ) 2 Sn 2 O 7 (m=eu, dy, ho or Yb) 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; will bePerforming 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 8-12 hours to obtain the high-entropy rare earth stannate based oxygen insensitive negative temperature coefficient heat sensitive material (La) 0.2 Nd 0.2 Sm 0.2 Gd 0.2 M 0.2 ) 2 Sn 2 O 7 (m=eu, dy, ho or Yb).
The chemical formula is (La) 0.2 Nd 0.2 Sm 0.2 Gd 0.2 M 0.2 ) 2 Sn 2 O 7 (m=eu, dy, ho or Yb).
Application of high-entropy rare earth stannate-based oxygen insensitive negative temperature coefficient thermal material in the field of semiconductor sensors, wherein the chemical formula of the high-entropy rare earth stannate-based oxygen insensitive negative temperature coefficient thermal material is (La) 0.2 Nd 0.2 Sm 0.2 Gd 0.2 M 0.2 ) 2 Sn 2 O 7 Wherein M is one of Eu, dy, ho, yb.
The high-entropy rare earth stannate is used as an oxygen-insensitive high-temperature negative temperature coefficient thermosensitive material.
The inventors have found that high entropy rare earth stannate (La 0.2 Nd 0.2 Sm 0.2 Gd 0.2 M 0.2 ) 2 Sn 2 O 7 (m=eu, dy, ho or Yb) has a significant negative temperature coefficient characteristic in the temperature range of 400-1400 ℃, such high entropy materials exhibit a broad test temperature range, and the upper limit of the maximum temperature can reach 1400 ℃; meanwhile, due to the entropy-stable structure, excellent aging stability is exhibited. The material has stable electrical property, good linear relation, 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 stannate-based oxygen insensitive negative temperature coefficient thermosensitive material, a preparation method thereof and application thereof in the field of semiconductor sensors, which adopts a three-dimensional vibration ball milling method to respectively analyze pure tin dioxide, lanthanum oxide, neodymium oxide, samarium oxide and gadolinium oxideAnd performing three-dimensional vibration mixing ball milling on europium oxide, dysprosium oxide, holmium oxide and ytterbium oxide, drying, calcining, performing ball milling again, performing cold isostatic pressing molding on the powder sheet, sintering at high temperature, and performing high-temperature annealing to obtain the thermosensitive material. The thermosensitive material (La) 0.2 Nd 0.2 Sm 0.2 Gd 0.2 M 0.2 ) 2 Sn 2 O 7 The (m=eu, dy, ho or Yb) electrical performance parameters are: b (B) 400℃/1400℃ ＝11820～12519±2.31％ K，ρ 1400℃ ＝3.22～5.67×10 2 (+ -1.56%) omega cm. The thermosensitive material has obvious negative temperature coefficient characteristics in a temperature range of 400-1400 ℃ and good electrical property consistency; after the temperature is 1400 ℃ and aging is carried out for 500 hours, the resistivity drift rate is less than 1.95%, 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 stannate is suitable for manufacturing the 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 beneficial effects of the application are as follows:
(1) The thermosensitive material (La) 0.2 Nd 0.2 Sm 0.2 Gd 0.2 M 0.2 ) 2 Sn 2 O 7 (m=eu, dy, ho or Yb) has NTC characteristics in a temperature range of 400-1400 ℃ with a broad test temperature range;
(2) The thermosensitive material (La) 0.2 Nd 0.2 Sm 0.2 Gd 0.2 M 0.2 ) 2 Sn 2 O 7 (m=eu, dy, ho or Yb) aged at 1400 ℃ for 500 hours, the resistivity drift rate is less than 1.95%, exhibiting excellent high temperature aging stability;
(3) The thermosensitive material (La) 0.2 Nd 0.2 Sm 0.2 Gd 0.2 M 0.2 ) 2 Sn 2 O 7 The (m=eu, dy, ho or Yb) resistivity is not affected by the change of the oxygen partial pressure, and at the same time, the high material constant B value ensures that it is in a high temperature environmentAccuracy of the lower measurement.
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 Gd 0.2 M 0.2 ) 2 Sn 2 O 7 Resistivity versus temperature for (m=eu, dy, ho or Yb) materials.
FIG. 2 shows the process of the present application (La 0.2 Nd 0.2 Sm 0.2 Gd 0.2 Eu 0.2 ) 2 Sn 2 O 7 And the resistance drift rate of the material at 1400 ℃ with different oxygen partial pressures is plotted against aging time.
FIG. 3 shows the process of the present application (La 0.2 Nd 0.2 Sm 0.2 Gd 0.2 Dy 0.2 ) 2 Sn 2 O 7 And the resistance drift rate of the material at 1400 ℃ with different oxygen partial pressures is plotted against aging time.
FIG. 4 shows the process of the present application (La 0.2 Nd 0.2 Sm 0.2 Gd 0.2 Ho 0.2 ) 2 Sn 2 O 7 And the resistance drift rate of the material at 1400 ℃ with different oxygen partial pressures is plotted against aging time.
FIG. 5 shows the process of the present application (La 0.2 Nd 0.2 Sm 0.2 Gd 0.2 Yb 0.2 ) 2 Sn 2 O 7 And the resistance drift rate of the material at 1400 ℃ with different oxygen partial pressures is plotted against aging time.
FIG. 6 shows the structure of (La) 0.2 Nd 0.2 Sm 0.2 Gd 0.2 Eu 0.2 ) 2 Sn 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 Gd 0.2 Dy 0.2 ) 2 Sn 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 Gd 0.2 Ho 0.2 ) 2 Sn 2 O 7 Electric of materialsResistivity versus partial pressure of oxygen.
FIG. 9 shows the structure of example 4 (La 0.2 Nd 0.2 Sm 0.2 Gd 0.2 Yb 0.2 ) 2 Sn 2 O 7 And a plot of resistivity versus partial pressure of oxygen for the material.
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. According to the mass ratio of La to Sm to Eu to Sn=1:1:1:1:5, respectively weighing oxide powder lanthanum oxide, neodymium oxide, samarium oxide, gadolinium oxide, europium oxide and tin dioxide, and mixing to obtain a first mixture; and carrying out wet three-dimensional vibration ball milling on the first mixture for 6 hours, drying the wet-milled slurry at the temperature of 100 ℃, taking out, and manually milling in an agate mortar for 3 hours to obtain precursor powder.
b. And c, calcining the precursor powder obtained in the step a at 1400 ℃ for 3 hours, performing wet three-dimensional vibration ball milling for 3 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 8 hours to obtain the high-entropy rare earth stannate based oxygen insensitive negative temperature coefficient thermosensitive material (La) 0.2 Nd 0.2 Sm 0.2 Gd 0.2 Eu 0.2 ) 2 Sn 2 O 7 。
The obtained (La 0.2 Nd 0.2 Sm 0.2 Gd 0.2 Eu 0.2 ) 2 Sn 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℃/1400℃ ＝12519±1.71％ K，ρ 1400℃ ＝5.67×10 2 (+ -1.56%) omega cm. At the same time, for the prepared (La 0.2 Nd 0.2 Sm 0.2 Gd 0.2 Eu 0.2 ) 2 Sn 2 O 7 The resistivity drift rate and aging time, the resistivity and the oxygen partial pressure of the material at 1400 ℃ with different oxygen partial pressures are respectively measured to obtain the graphs of fig. 2 and 6.
Example 2
a. According to the mass ratio of La to Sm to Gd to Dy to Sn=1:1:1:1:5, respectively weighing oxide powder of lanthanum oxide, neodymium oxide, samarium oxide, gadolinium oxide, dysprosium oxide and tin dioxide, 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 three-dimensional vibration 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 280MPa to obtain a third static pressure block; sintering the third static pressure block at 1600 ℃ for 8 hours to obtain the high-entropy rare earth stannate based oxygen insensitive negative temperature coefficient thermosensitive material (La) 0.2 Nd 0.2 Sm 0.2 Gd 0.2 Dy 0.2 ) 2 Sn 2 O 7 。
The obtained (La 0.2 Nd 0.2 Sm 0.2 Gd 0.2 Dy 0.2 ) 2 Sn 2 O 7 Negative temperature coefficient heatThe sensitive ceramic material is subjected to electrical property test, and the obtained electrical parameter is B 400℃/1400℃ ＝12297±2.31％ K，ρ 1400℃ ＝4.72×10 2 (+ -1.23%) omega cm. At the same time, for the prepared (La 0.2 Nd 0.2 Sm 0.2 Gd 0.2 Dy 0.2 ) 2 Sn 2 O 7 The resistivity drift rate and aging time, the resistivity and the oxygen partial pressure of the material at 1400 ℃ with different oxygen partial pressures are respectively measured to obtain the graph 3 and the graph 7.
Example 3
a. According to the mass ratio of La to Sm to Gd to Ho and Sn=1:1:1:1:5, respectively weighing oxide powder lanthanum oxide, neodymium oxide, samarium oxide, gadolinium oxide, holmium oxide and tin dioxide, and mixing to obtain a first mixture; and carrying out wet three-dimensional vibration ball milling on the first mixture for 10 hours, drying the wet-milled slurry at the temperature of 100 ℃, taking out, and manually milling in an agate mortar for 4 hours to obtain precursor powder.
b. And c, calcining the precursor powder obtained in the step a at 1400 ℃ for 5 hours, performing wet three-dimensional vibration 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 20kg/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 300MPa to obtain a third static pressure block; sintering the third static pressure block at 1600 ℃ for 10 hours to obtain the high-entropy rare earth stannate based oxygen insensitive negative temperature coefficient thermosensitive material (La) 0.2 Nd 0.2 Sm 0.2 Gd 0.2 Ho 0.2 ) 2 Sn 2 O 7 。
The obtained (La 0.2 Nd 0.2 Sm 0.2 Gd 0.2 Ho 0.2 ) 2 Sn 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℃/1400℃ ＝12184±1.54％ K，ρ 1400℃ ＝4.23×10 2 ±1.07% Ω·cm. At the same time, for the prepared (La 0.2 Nd 0.2 Sm 0.2 Gd 0.2 Ho 0.2 ) 2 Sn 2 O 7 The resistivity drift rate and aging time, the resistivity and the oxygen partial pressure of the material at 1400 ℃ with different oxygen partial pressures are respectively measured to obtain the graphs of fig. 4 and 8.
Example 4
a. Weighing oxide powder lanthanum oxide, neodymium oxide, samarium oxide, gadolinium oxide, ytterbium oxide and tin dioxide respectively according to the stoichiometric ratio of La, nd, sm, gd, yb and Sn=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 10 hours, drying the wet-milled slurry at the temperature of 100 ℃, taking out, and manually milling in an agate mortar for 4 hours to obtain precursor powder.
b. And c, calcining the precursor powder obtained in the step a at 1400 ℃ for 6 hours, performing wet three-dimensional vibration ball milling for 4 hours, and drying and grinding to obtain pyrochlore phase powder.
c. The pyrochlore phase powder obtained in the step b is pressed at 20kg/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 300MPa to obtain a third static pressure block; sintering the third static pressure block at 1600 ℃ for 12 hours to obtain the high-entropy rare earth stannate based oxygen insensitive negative temperature coefficient thermosensitive material (La) 0.2 Nd 0.2 Sm 0.2 Gd 0.2 Yb 0.2 ) 2 Sn 2 O 7 。
The obtained (La 0.2 Nd 0.2 Sm 0.2 Gd 0.2 Yb 0.2 ) 2 Sn 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℃/1400℃ ＝11820±1.18％ K，ρ 1400℃ ＝3.22×10 2 (+ -1.25%) omega cm. At the same time, for the prepared (La 0.2 Nd 0.2 Sm 0.2 Gd 0.2 Yb 0.2 ) 2 Sn 2 O 7 The resistivity drift rate and aging time, and the resistivity and oxygen partial pressure of the material at 1400 ℃ with different oxygen partial pressures were measured respectively to obtain fig. 5 and 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. The high entropy rare earth stannate based oxygen insensitive negative temperature coefficient heat sensitive material is characterized in that the chemical formula is (La 0.2 Nd 0.2 Sm 0.2 Gd 0.2 M 0.2 ) 2 Sn 2 O 7 Wherein M is one of Eu, dy, ho, yb; the electrical performance parameters of the negative temperature coefficient thermosensitive material are as follows: b (B) 400℃/1400℃ =11820~12519±2.31% K，ρ 1400℃ =3.22~5.67×10 2 The temperature range of the heat exchanger is 400-1400 ℃ and is +/-1.56% omega cm.
2. The high-entropy rare earth stannate-based oxygen insensitive negative temperature coefficient thermal sensitive material according to claim 1, wherein the negative temperature coefficient thermal sensitive material is prepared by mixing and firing raw materials of tin dioxide, lanthanum oxide, neodymium oxide, samarium oxide and gadolinium oxide with oxides of M respectively; the oxide of M is europium oxide, dysprosium oxide, holmium oxide or ytterbium oxide.
3. The high-entropy rare earth stannate-based oxygen insensitive negative temperature coefficient thermal sensitive material according to claim 1, wherein the negative temperature coefficient thermal sensitive material is prepared by a method comprising the following steps:
a. weighing oxide powder lanthanum oxide, neodymium oxide, samarium oxide, gadolinium oxide, tin dioxide and oxides of M according to the mass ratio of La, nd, sm, M, sn=1:1:1:1:5, respectively, and mixing to obtain a first mixture; carrying out wet three-dimensional vibration ball milling on the first mixture for 6-10 hours, drying the wet-milled slurry at the temperature of 100 ℃, taking out, and manually milling in an agate mortar for 2-4 hours to obtain precursor powder; the oxide of M is europium oxide, dysprosium oxide, holmium oxide or ytterbium oxide; m=eu, dy, ho or Yb;
b. calcining the precursor powder obtained in the step a for 3-6 hours at 1400 ℃, performing wet three-dimensional vibration ball milling for 2-4 hours, and drying and 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 for 8-12 hours at 1600 ℃ to obtain the high-entropy rare earth stannate-based oxygen insensitive negative temperature coefficient heat sensitive material.
4. The high-entropy rare earth stannate-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 M to Sn=1:1:1:1:5, the oxides of oxide powder lanthanum oxide, neodymium oxide, samarium oxide, gadolinium oxide, tin dioxide and M are weighed and mixed, the mixture is placed in a ball milling tank, agate is taken as a ball milling medium, analytically pure absolute ethyl alcohol is taken as a dispersing medium, wet three-dimensional vibration ball milling is carried out for 6-10 hours, the wet-milled slurry is dried at the temperature of 100 ℃, and the wet-milled slurry is taken out and placed in an agate mortar for manual grinding for 2-4 hours, so that precursor powder is obtained; m=eu, dy, ho or Yb.
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, and then wet three-dimensional vibration ball milling is carried out for 2-4 hours, so as to obtain pyrochlore phase (La 0.2 Nd 0.2 Sm 0.2 Gd 0.2 M 0.2 ) 2 Sn 2 O 7 Powder, m=eu, dy, ho or Yb.
6. The negative temperature coefficient thermal device according to any one of claims 3 to 5The sensitive material is characterized in that in the step c, the pyrochlore phase powder obtained in the step b is pressed at 15-20 kg/cm by a single-shaft 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 250-300 MPa to obtain a third static pressure block; sintering the third static pressure block at 1600 ℃ for 8-12 hours to obtain the high-entropy rare earth stannate-based oxygen insensitive negative temperature coefficient heat sensitive material (La) 0.2 Nd 0.2 Sm 0.2 Gd 0.2 M 0.2 ) 2 Sn 2 O 7 M=eu, dy, ho or Yb.
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