CN113603477A - Perovskite type high-temperature thermal sensitive ceramic resistor material and preparation method thereof - Google Patents
Perovskite type high-temperature thermal sensitive ceramic resistor material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of perovskite type high-temperature thermal sensitive ceramic material, which takes barium carbonate, calcium carbonate, zirconium dioxide, titanium dioxide and manganese dioxide as raw materials, and the material is subjected to mixing grinding, calcination, cold isostatic pressing forming, high-temperature sintering and electrode coating and sintering to obtain the material with the material constant of B400℃/900℃12509-13303K, resistivity of 664.4-416.6 omega cm at 900 ℃, and aging coefficient of 0.19-0.76% when aging for 500 hours at 900 ℃. The thermistor material has stable performance and good consistency, has obvious negative temperature coefficient characteristic in the temperature range of 200-1100 ℃, and is suitable for manufacturing high-temperature thermistors.
Description
Technical Field
The invention relates to the technical field of thermal sensitive ceramic resistor materials, in particular to a perovskite type high-temperature thermal sensitive ceramic resistor material and a preparation method thereof.
Background
The Negative Temperature Coefficient (NTC) thermistor has the advantages of high temperature measurement precision, good interchangeability, high reliability, low cost and the like, is widely applied to various aspects such as temperature measurement, control, compensation, remote control of communication equipment and the like, is considered as an electronic component with great development potential, and has good application prospect.
Currently, widely used NTC thermistors are a multi-element spinel structure (AB2O4) material system mainly composed of Mn, Ni, Cu, Co, and other elements. The tetrahedral and octahedral cations of the spinel-structured NTC thermal sensitive ceramic are slowly redistributed over time at temperatures exceeding 473K, resulting in structural relaxation phenomena affecting the stability of the material and limiting the temperature range of use of such materials. The perovskite type NTC thermal sensitive ceramic structure has good temperature stability and is more suitable for application in a wider temperature environment, so the perovskite type NTC thermal sensitive ceramic attracts much attention and becomes one of research hotspots of NTC thermal sensitive materials.
The NTC thermal sensitive ceramic material has high resistance value and high thermal sensitive constant B value, and is difficult to realize high resistance and low B value or low resistance and high B value coexistence, but the NTC thermal sensitive resistor for the wide temperature area requires different combinations of the resistance value and the B value, and is one of the technical problems at present
Disclosure of Invention
In view of the above-mentioned disadvantages, the present invention provides a perovskite-type high-temperature thermal sensitive ceramic resistor material and a method for preparing the same, wherein barium carbonate, calcium carbonate, zirconium dioxide, titanium dioxide and manganese dioxide are used as raw materials, and the raw materials are subjected to mixing grinding, calcination, cold isostatic pressing, high-temperature sintering and electrode coating sintering to obtain a material with a material constant B400℃/900℃12509-13303K, resistivity of 377.6-664.4 omega cm at 900 ℃, and aging coefficient of 0.19-0.76% when aging for 500 hours at 900 ℃. The high-temperature thermal sensitive ceramic resistor material has stable performance, good consistency and obvious negative temperature coefficient in the temperature range of 200-1100 DEG CAnd the method is suitable for manufacturing high-temperature thermistors.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the perovskite type high-temperature thermal sensitive ceramic resistor material takes barium carbonate, calcium carbonate, zirconium dioxide, titanium dioxide and manganese dioxide as raw materials, and the chemical composition of the perovskite type high-temperature thermal sensitive ceramic resistor material is Ba0.85Ca0.15(Ti0.9Zr0.1)1- xMnxO3Wherein the value range of x is 0-0.015, and the prepared perovskite type high-temperature thermal sensitive ceramic resistor material has the material constant of B400 ℃/900 ℃12509-.
Furthermore, the perovskite type high-temperature thermal sensitive ceramic resistor material takes 62.9 wt% of barium carbonate, 5.7 wt% of calcium carbonate, 4.6 wt% of zirconium dioxide and 26.9 wt% of titanium dioxide as raw materials, and the chemical composition of the perovskite type high-temperature thermal sensitive ceramic resistor material is Ba0.85Ca0.15(Ti0.9Zr0.1)1-xMnxO3Wherein x is 0.
Furthermore, the perovskite type high-temperature thermal sensitive ceramic resistor material takes 62.8 wt% of barium carbonate, 5.6 wt% of calcium carbonate, 4.6 wt% of zirconium dioxide, 26.8 wt% of titanium dioxide and 0.2 wt% of manganese dioxide as raw materials, and the chemical composition of the perovskite type high-temperature thermal sensitive ceramic resistor material is Ba0.85Ca0.15(Ti0.9Zr0.1)1-xMnxO3Wherein x is 0.005.
Further, the perovskite-type high-temperature thermal sensitive ceramic resistor material uses 62.8 wt% of barium carbonate, 5.6 wt% of calcium carbonate, 4.5 wt% of zirconium dioxide, 26.7 wt% of titanium dioxide and 0.3 wt% of manganese dioxide as raw materials, and the chemical composition of the perovskite-type high-temperature thermal sensitive ceramic resistor material is Ba0.85Ca0.15(Ti0.9Zr0.1)1-xMnxO3Wherein x is 0.01.
Further, the perovskite type high temperature thermal sensitive ceramic resistance material comprises 62.9 wt% of barium carbonate, 5.6 wt% of calcium carbonate, 4.5 wt% of zirconium dioxide, 26.5 wt% of titanium dioxide and 0.5 wt% of manganese dioxideAs raw material, its chemical composition is Ba0.85Ca0.15(Ti0.9Zr0.1)1-xMnxO3Wherein the value of x is 0.015.
The preparation method of the perovskite high-temperature thermal sensitive ceramic resistor material comprises the following steps:
(1) push Ba0.85Ca0.15(Ti0.9Zr0.1)1-xMnxO3Weighing and mixing quantitative barium carbonate, calcium carbonate, zirconium dioxide, titanium dioxide and manganese dioxide respectively, and putting the mixed raw materials into an agate mortar for grinding for 6-10 hours to obtain powder;
(2) calcining the ground powder at 1000-1200 ℃ for 1-2 hours, and grinding for 5-8 hours to obtain the perovskite high-temperature heat-sensitive ceramic material Ba0.85Ca0.15(Ti0.9Zr0.1)1-xMnxO3Powder;
(3) prepared Ba0.85Ca0.15(Ti0.9Zr0.1)1-xMnxO3The powder is added with 10-20Kg/cm2The pressure is pressed into a block for 0.8-1.5min, the formed block material is subjected to cold isostatic pressing, the pressure is maintained at 250-350MPa for 1.5-2min, and then the block material is sintered at 1400 ℃ for 5 hours to prepare the perovskite type high-temperature heat-sensitive ceramic material;
(4) coating platinum slurry electrodes on the front and back surfaces of the prepared perovskite high-temperature thermosensitive ceramic material, and then annealing at 900 ℃ for 30 minutes to obtain the perovskite high-temperature thermosensitive ceramic material with the characteristics of negative temperature coefficient within the temperature range of 200-1100 ℃, and the material constant of B400℃/900℃12509-.
The invention has the beneficial effects that: the material takes barium carbonate, calcium carbonate, zirconium dioxide, titanium dioxide and manganese dioxide as raw materials, and is prepared by mixing, grinding, calcining, cold isostatic pressing, high-temperature sintering and electrode coating and sintering to obtain the material with the constant B400℃/900℃12509-13303K, a temperature of 900 ℃ and a resistivity of 377.6-664.4 omegacm, and aging at 900 ℃ for 500 hours, wherein the aging coefficient of the perovskite high-temperature thermal sensitive ceramic resistor material is 0.19-0.76%. The high-temperature thermal sensitive ceramic resistor material has stable performance and good consistency, has obvious negative temperature coefficient characteristic in the temperature range of 200-1100 ℃, and is suitable for manufacturing high-temperature thermal resistors.
Drawings
FIG. 1 is an XRD spectrum of a high temperature thermal sensitive ceramic material after sintering at 1400 ℃ in example 1 of the present invention;
FIG. 2 is an XRD spectrum of a high temperature thermal sensitive ceramic material after sintering at 1400 ℃ in example 2 of the present invention;
FIG. 3 is an XRD spectrum of a high temperature thermal sensitive ceramic material after sintering at 1400 ℃ in example 3 of the present invention;
FIG. 4 is an XRD spectrum of a high temperature thermal sensitive ceramic material after sintering at 1400 ℃ in example 4 of the present invention;
FIG. 5 is an SEM image of a high temperature heat-sensitive ceramic material after sintering at 1400 ℃ in example 1 of the present invention;
FIG. 6 is an SEM image of a high temperature heat-sensitive ceramic material of example 2 after sintering at 1400 ℃ in accordance with the present invention;
FIG. 7 is an SEM image of a high temperature heat-sensitive ceramic material of example 3 after sintering at 1400 ℃ in accordance with the present invention;
FIG. 8 is an SEM image of a high temperature heat-sensitive ceramic material of example 4 after sintering at 1400 ℃ in accordance with the present invention;
FIG. 9 is a Raman spectrum of the high temperature thermal sensitive ceramic material sintered at 1400 ℃ according to the present invention;
FIG. 10 is a graph showing the variation of DC resistance with temperature of the high temperature thermal sensitive ceramic resistor material according to the present invention;
FIG. 11 is a graph showing the aging curve of the high temperature thermal sensitive ceramic resistor material of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
The reagents or instruments used in the present invention are not indicated by manufacturers, and are all conventional products commercially available.
Example 1
1. Push Ba0.85Ca0.15Ti0.9Zr0.1O3Respectively weighing 62.9 wt% of barium carbonate, 5.7 wt% of calcium carbonate, 4.6 wt% of zirconium dioxide and 26.9 wt% of titanium dioxide, mixing, and grinding the mixed raw materials in an agate mortar for 6 hours to obtain powder;
2. calcining the powder ground in the step (1) at the temperature of 1000 ℃ for 2 hours, and grinding for 5 hours to obtain Ba0.85Ca0.15Ti0.9Zr0.1O3Powder;
3. the powder material obtained in the step (2) is added with 10Kg/cm2The pressure is pressed into a block for 0.8min, the formed block material is subjected to cold isostatic pressing, the pressure is maintained for 1.5min under the pressure of 350MPa, and then the block material is sintered for 5 hours at the temperature of 1400 ℃ to prepare the perovskite type high-temperature thermal sensitive ceramic material;
4. coating platinum slurry electrodes on the front and back surfaces of the thermosensitive ceramic material sintered in the step (3), and annealing at 900 ℃ for 30 minutes to obtain the thermosensitive ceramic material with the negative temperature coefficient characteristic in the temperature range of 200-1100 ℃, wherein the material constant is B400℃/900℃12696K, specific resistance 664.4 omega cm at 900 deg.C, ageing at 900 deg.C for 500 hr, and ageing coefficient 0.39%.
Example 2
1. Push Ba0.85Ca0.15(Ti0.9Zr0.1)0.995Mn0.005O3Respectively weighing 62.8 wt% of barium carbonate, 5.6 wt% of calcium carbonate, 4.6 wt% of zirconium dioxide, 26.8 wt% of titanium dioxide and 0.2 wt% of manganese dioxide, mixing, and grinding the mixed raw materials in an agate mortar for 8 hours to obtain powder;
2. calcining the powder ground in the step (1) at the temperature of 1200 ℃ for 1 hour, and grinding for 8 hours to obtain Ba0.85Ca0.15(Ti0.9Zr0.1)0.995Mn0.005O3Powder;
3. 15Kg/cm of the powder material obtained in the step (2)2The pressure is pressed into a block for 1min, the formed block material is subjected to cold isostatic pressing, the pressure is maintained for 2min under the pressure of 250MPa, and then the block material is sintered for 5 hours at the temperature of 1400 ℃ to prepare the perovskite high-temperature thermal sensitive ceramic material;
4. coating platinum slurry electrodes on the front and back surfaces of the thermosensitive ceramic material sintered in the step (3), and annealing at 900 ℃ for 30 minutes to obtain the thermosensitive ceramic material with the negative temperature coefficient characteristic in the temperature range of 200-1100 ℃, wherein the material constant is B400℃/900℃The perovskite type high-temperature thermal sensitive ceramic resistor material has the following characteristics that the resistivity is 458.3 omega cm at the temperature of 900 ℃, and the aging coefficient is 0.76 percent after aging for 500 hours at the temperature of 900 ℃.
Example 3
1. Push Ba0.85Ca0.15(Ti0.9Zr0.1)0.99Mn0.01O3Respectively weighing 62.8 wt% of barium carbonate, 5.6 wt% of calcium carbonate, 4.5 wt% of zirconium dioxide, 26.7 wt% of titanium dioxide and 0.3 wt% of manganese dioxide, mixing, and grinding the mixed raw materials in an agate mortar for 8 hours to obtain powder;
2. calcining the powder ground in the step (1) at the temperature of 1100 ℃ for 1.5 hours, and grinding for 6 hours to obtain Ba0.85Ca0.15(Ti0.9Zr0.1)0.99Mn0.01O3Powder;
3. 20Kg/cm of the powder material obtained in the step (2)2The pressure is pressed into blocks for 1.5min, the formed block material is subjected to cold isostatic pressing, the pressure is maintained for 1.8min under the pressure of 300MPa, and then the block material is sintered for 5 hours at the temperature of 1400 ℃ to prepare the perovskite type high-temperature thermal sensitive ceramic material;
4. coating platinum slurry electrodes on the front and back surfaces of the thermosensitive ceramic material sintered in the step (3), and annealing at 900 ℃ for 30 minutes to obtain the thermosensitive ceramic material with the negative temperature coefficient characteristic in the temperature range of 200-1100 ℃, wherein the material constant is B 400℃/900℃12624K, 900 deg.C resistivity 377.6 Ω cm, 900 deg.C aging 50The aging coefficient of 0 hour is 0.60 percent.
Example 4
1. Push Ba0.85Ca0.15(Ti0.9Zr0.1)0.985Mn0.015O3Respectively weighing 62.9 wt% of barium carbonate, 5.6 wt% of calcium carbonate, 4.5 wt% of zirconium dioxide, 26.5 wt% of titanium dioxide and 0.5 wt% of manganese dioxide, mixing, and grinding the mixed raw materials in an agate mortar for 10 hours to obtain powder;
2. calcining the powder ground in the step (1) at the temperature of 1150 ℃ for 1.5 hours, and grinding for 7 hours to obtain Ba0.85Ca0.15(Ti0.9Zr0.1)0.985Mn0.015O3Powder;
3. the powder material obtained in the step (2) is mixed with 16Kg/cm2The pressure is pressed into a block for 1.2min, the formed block material is subjected to cold isostatic pressing, the pressure is maintained for 2min under the pressure of 300MPa, and then the block material is sintered for 5 hours at the temperature of 1400 ℃ to prepare the perovskite high-temperature thermal sensitive ceramic material;
4. coating platinum slurry electrodes on the front and back surfaces of the thermosensitive ceramic material sintered in the step (3), and annealing at 900 ℃ for 30 minutes to obtain the thermosensitive ceramic material with the negative temperature coefficient characteristic in the temperature range of 200-1100 ℃, wherein the material constant is B400℃/900℃13303K, specific resistance of 416.6 omega cm at 900 deg.C, aging coefficient of 0.19% when aging 500 hours at 900 deg.C.
The structure of the perovskite high-temperature thermal sensitive ceramic material is analyzed by an XRD diffraction technology, an SEM method and a Raman spectrum analysis technology, and resistance tests and high-temperature aging tests of the perovskite high-temperature thermal sensitive ceramic resistance material at different temperatures are carried out.
As can be seen from the XRD patterns of the high-temperature thermal sensitive ceramic materials shown in figures 1-4, when x is more than or equal to 0.000 and less than or equal to 0.015, all ceramic samples form a pure perovskite structure and have obvious peaks of (100), (110), (111), (002), (210), (211) and (220), and the preferred orientation of the ceramic becomes more and more obvious as the content x is increased until x is 0.015 and is (110). The diffraction peak is sharp and clear at about 31 degrees, which shows that the crystallinity is good and the grain size is large. No secondary phase was observed in the spectrum, indicating that in this range the Mn ions had completely dissolved into the Ba-Ca-Zr-Ti-O lattice to form a homogeneous solid solution.
As shown in the SEM images of the high temperature heat-sensitive ceramic materials of fig. 5-8, each component exhibits a dense microstructure, which can provide good electrical characteristics and improve the electrical stability of the ceramic. The microstructure of pure Ba-Ca-Zr-Ti-O ceramics shows a grain size that is not uniform in size and a clear grain boundary, and the grain size gradually becomes uniform as the content of doped Mn ions increases.
As shown in FIG. 9, the Raman spectrum of the high-temperature heat-sensitive ceramic material shows that the perovskite type Ba-Ca-Zr-Ti-O has BaTiO3Thus, due to similar ABO3Perovskite structure, Raman mode assignment is considered to be with pure BaTiO3The same is true. According to previous reports, tetragonal phase BaTiO3The Raman optical lattice vibration of (2) is 3A1(TO) +3A1(LO) +3E (TO) +3E (LO) +1E (LO + TO) +1B 1. FIG. 9 shows a plot at 100--1Raman spectra of the range-measured Ba-Ca-Zr-Ti-Mn-O samples, due to Ba2+The long electrostatic forces induced by the lattice ionicity induced by the ions in Ba-Ca-Zr-Ti-O cause a splitting of the Longitudinal (LO) and Transverse (TO) components, the phase structure of the Ba-Ca-Zr-Ti-O ceramic doped with Mn ions is similar TO the pure Ba-Ca-Zr-Ti-O ceramic phase structure except for the different intensities, widths and positions of the peaks. In pure Ba-Ca-Zr-Ti-O, the peak-peak intensity of the Raman spectrum has obvious difference, and the vibration in the Raman pattern has a broadening effect, which shows that the structural disorder is caused by Mn4+To (Ti, Zr)4+Substitution of sites and lattice distortion.
As shown in fig. 10, the dc resistance of the high temperature thermistor material varies with temperature, and it can be seen from the graph that the ceramic has a typical NTC characteristic in which the resistivity decreases with increasing temperature in a wide temperature range, and when the Mn content x is 0.015, the resistivity is the smallest, indicating that Mn decreases the resistivity of the Ba-Ca-Zr-Ti-O system.
As shown in the aging curve chart of the high-temperature thermistor material shown in FIG. 11, it can be known that the aging coefficient of the sample increases first and then decreases within 0-200 h; within 200-500 hours, the aging coefficient tends to be stable, and the change range of the aging coefficient is 0.19-0.76 percent, which shows that the Ba-Ca-Zr-Ti-Mn-O ceramic sample has good high-temperature stability due to the special perovskite structure and the high-density microstructure.
Those skilled in the art to which the present invention pertains can also make appropriate alterations and modifications to the above-described embodiments, in light of the above disclosure. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (6)
1. A perovskite type high-temperature thermal sensitive ceramic resistor material is characterized in that: the perovskite high-temperature thermal sensitive ceramic resistor material takes barium carbonate, calcium carbonate, zirconium dioxide, titanium dioxide and manganese dioxide as raw materials, and the chemical composition of the perovskite high-temperature thermal sensitive ceramic resistor material is Ba0.85Ca0.15(Ti0.9Zr0.1)1-xMnxO3Wherein the value range of x is 0-0.015, and the constant of the prepared material is B400℃/900℃12509-.
2. The perovskite high-temperature thermal sensitive ceramic resistance material as claimed in claim 1, wherein: the perovskite high-temperature thermal sensitive ceramic resistor material takes 62.9 wt% of barium carbonate, 5.7 wt% of calcium carbonate, 4.6 wt% of zirconium dioxide and 26.9 wt% of titanium dioxide as raw materials, and the chemical composition of the perovskite high-temperature thermal sensitive ceramic resistor material is Ba0.85Ca0.15(Ti0.9Zr0.1)1-xMnxO3Wherein x is 0.
3. The perovskite high-temperature thermal sensitive ceramic resistance material as claimed in claim 1, wherein: the perovskite high-temperature thermal sensitive ceramic resistor material takes 62.8 wt% of barium carbonate, 5.6 wt% of calcium carbonate, 4.6 wt% of zirconium dioxide, 26.8 wt% of titanium dioxide and 0.2 wt% of manganese dioxide as raw materials, and the chemical composition of the perovskite high-temperature thermal sensitive ceramic resistor material is Ba0.85Ca0.15(Ti0.9Zr0.1)1- xMnxO3Wherein x is 0.005.
4. The perovskite high-temperature thermal sensitive ceramic resistance material as claimed in claim 1, wherein: the perovskite high-temperature thermal sensitive ceramic resistor material takes 62.8 wt% of barium carbonate, 5.6 wt% of calcium carbonate, 4.5 wt% of zirconium dioxide, 26.7 wt% of titanium dioxide and 0.3 wt% of manganese dioxide as raw materials, and the chemical composition of the perovskite high-temperature thermal sensitive ceramic resistor material is Ba0.85Ca0.15(Ti0.9Zr0.1)1- xMnxO3Wherein x is 0.01.
5. The perovskite high-temperature thermal sensitive ceramic resistance material as claimed in claim 1, wherein: the perovskite high-temperature thermal sensitive ceramic resistor material takes 62.9 wt% of barium carbonate, 5.6 wt% of calcium carbonate, 4.5 wt% of zirconium dioxide, 26.5 wt% of titanium dioxide and 0.5 wt% of manganese dioxide as raw materials, and the chemical composition of the perovskite high-temperature thermal sensitive ceramic resistor material is Ba0.85Ca0.15(Ti0.9Zr0.1)1- xMnxO3Wherein the value of x is 0.015.
6. The method for producing a perovskite-type high-temperature thermal sensitive ceramic resistance material according to any one of claims 1 to 5, characterized in that: the method comprises the following steps:
(1) push Ba0.85Ca0.15(Ti0.9Zr0.1)1-xMnxO3Weighing and mixing quantitative barium carbonate, calcium carbonate, zirconium dioxide, titanium dioxide and manganese dioxide respectively, and mixing the mixed raw materialsGrinding in agate mortar for 6-10 hr to obtain powder;
(2) calcining the ground powder at 1000-1200 deg.C for 1-2 hr, grinding for 5-8 hr to obtain Ba0.85Ca0.15(Ti0.9Zr0.1)1-xMnxO3Powder;
(3) prepared Ba0.85Ca0.15(Ti0.9Zr0.1)1-xMnxO3The powder is added with 10-20Kg/cm2The pressure is pressed into a block for 0.8-1.5min, the formed block material is subjected to cold isostatic pressing, the pressure is maintained at 250-350MPa for 1.5-2min, and then the block material is sintered at 1400 ℃ for 5 hours to prepare the perovskite type high-temperature heat-sensitive ceramic material;
(4) coating platinum slurry electrodes on the front and back surfaces of the prepared perovskite high-temperature thermosensitive ceramic material, and then annealing at 900 ℃ for 30 minutes to obtain the perovskite high-temperature thermosensitive ceramic material with the characteristics of negative temperature coefficient within the temperature range of 200-1100 ℃, and the material constant of B400℃/900℃12509-.
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