CN112939597A - PTCR thermal sensitive ceramic material and preparation method thereof - Google Patents

PTCR thermal sensitive ceramic material and preparation method thereof Download PDF

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CN112939597A
CN112939597A CN202110367358.8A CN202110367358A CN112939597A CN 112939597 A CN112939597 A CN 112939597A CN 202110367358 A CN202110367358 A CN 202110367358A CN 112939597 A CN112939597 A CN 112939597A
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powder
biscuit
ceramic
ptcr
resistance
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宋泽君
盛晨浩
王谦
朱兴文
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University of Shanghai for Science and Technology
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Abstract

The application discloses a PTCR thermal sensitive ceramic material and a preparation method thereof, wherein the method comprises the following steps: a. to BaTiO3、PbTiO3、MnO2In which Z mol% of Ta is added2O5As powder, the value range of z is more than 0 and less than or equal to 0.05; b. weighing materials according to a material formula, taking zirconia balls and deionized water as media, ball-milling the powder and the ingredients for a preset time, and drying to obtain mixed powder; c. adding polyvinyl alcohol with the weight of 3.0-12.0 wt% of the mixed powder and the concentration of 10 wt% into the mixed powder for granulation, and pressing into a biscuit at the pressure of 10-15 MPa; d. and (3) placing the pressed biscuit in an air atmosphere at 1230-1300 ℃ to fully sinter the biscuit into ceramic. In the present application, with the addition of Ta, the voltage resistance and room temperature of the PTCR ceramic sheet before and after reductionThe rate of change of resistance is continuously reduced and the reduction resistance of the manufactured heater is obviously improved.

Description

PTCR thermal sensitive ceramic material and preparation method thereof
Technical Field
The application relates to a functional ceramic material, in particular to a PTCR thermal sensitive ceramic material and a preparation method thereof.
Background
PTCR ceramics generally refer to thermistor materials or components having a Positive Temperature Coefficient of resistance (Positive Temperature Coefficient). The PTCR ceramic has the advantages of temperature sensitivity, energy conservation, no open fire, safety and the like, and is widely applied to the fields of household appliances, communication, automobiles, automatic control and the like. The heater manufactured by using the PTC as the constant temperature heating element has high reliability and high safety, and the heating value can be automatically adjusted along with the change of the environmental temperature.
In the industrial PTC heating element, silica gel is generally bonded with an electrode plate to make the PTC heating element conductive, the silica gel component contains organic volatile substances, and when the silica gel is cured at 180-285 ℃ and works for a long time by electrifying, the organic silica gel can volatilize dimethyl cyclosiloxane (DMC) at the temperature range to make the PTC ceramic plate work in a weak reducing atmosphere, so that the electrical property of the PTC is deteriorated, and the room temperature resistivity of the PTC heating element can be reduced to different degrees. During the use, the performances of the PTC heating element, such as voltage resistance, impact current, heating power, and surface temperature, change with the influence of the reducing atmosphere, thereby greatly affecting the use reliability of the PTC element.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present application provides a method for preparing a PTCR thermal sensitive ceramic material, and a PTCR thermal sensitive ceramic material prepared by the method, for the purpose of achieving improved performance.
The preparation method of the PTCR thermal sensitive ceramic material comprises the following steps:
a. to BaTiO3、PbTiO3、MnO2In which Z mol% of Ta is added2O5As powder, the value range of z is more than 0 and less than or equal to 0.05;
b. weighing materials according to a material formula, taking zirconia balls and deionized water as media, ball-milling the powder and the ingredients for a preset time, and drying to obtain mixed powder;
c. adding polyvinyl alcohol with the weight of 3.0-12.0 wt% of the mixed powder and the concentration of 10 wt% into the mixed powder for granulation, and pressing into a biscuit at the pressure of 10-15 MPa;
d. and (3) placing the pressed biscuit in an air atmosphere at 1230-1300 ℃ to fully sinter the biscuit into ceramic.
Optionally, in the step a, a semiconducting agent and/or a sintering aid are added as ingredients, wherein the doping amount of the semiconducting agent is 0.05-0.50 atom% of the powder, and the sintering aid accounts for 0-2.5 mol% of the total substance amount of the powder.
Optionally, the formula of the powder is (100-x) BaTiO3+xPbTiO3+yMnO2+zTa2O5Wherein x is 0 to 50 mol% and y is 0.03 to 0.20 mol%.
Optionally, in the step b, the preset time is 12-24 hours.
Optionally, in step c, the biscuit has a dimension of phi 10 mm.
Optionally, in step d, the sintering time of the biscuit is 10-30 minutes.
Optionally, the biscuit is a circular biscuit.
Optionally, the method further comprises:
f. grinding the surface of the ceramic, spraying an electrode on the surface of the ceramic, sintering the ceramic with the electrode in an air atmosphere at 480-520 ℃, and preserving heat for 8 min.
Optionally, in step d, the electrode is an Ag electrode.
The PTCR thermal sensitive ceramic material provided by the application is prepared by adopting the method.
Compared with the prior art, the advantage of this application is:
1. the method of the application is realized by changing the formula of the material, namely, (Ba, Pb) TiO3System PTCR ceramic material with Ta doped2O5Reducing the prepared PTCR ceramic wafer, wherein the resistance change rate before and after reduction is reduced from-41.36% to-5.01%;
2. the reduction resistance of the manufactured heater is obviously improved, and the change rate of the reduced withstand voltage intensity is changed from-19.19% to-1.46%;
3. the method is simple to operate, easy to control, low in cost and easy to implement industrially, and has great significance for research on improvement of the reduction resistance of the PTCR heating ceramic.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It should be clear that the drawings in the following description are only intended to illustrate some embodiments of the present application, and that for a person skilled in the art, it is possible to derive from these drawings, without inventive effort, technical features, connections or even method steps not mentioned in the other drawings.
FIG. 1 shows the content of PbTiO3 (14.85%) and Ta2O5A curve showing that the room temperature resistance change rate of a sample with the content of 0-0.05 mol% changes before and after reduction;
FIG. 2 shows the content of PbTiO3 (14.85%) and Ta2O5A curve that the change rate of the withstand voltage strength of a sample with the content of 0-0.05 mol% changes before and after reduction;
FIG. 3 shows 21.34% of PbTiO3 and Ta2O5A curve showing that the room temperature resistance change rate of a sample with the content of 0-0.05 mol% changes before and after reduction;
FIG. 4 shows 21.34% of PbTiO3 and Ta2O5A curve that the change rate of the withstand voltage strength of a sample with the content of 0-0.05 mol% changes before and after reduction;
FIG. 5 shows 34.31% of PbTiO3 and Ta2O5A curve showing that the room temperature resistance change rate of a sample with the content of 0-0.05 mol% changes before and after reduction;
FIG. 6 shows 34.31% of PbTiO3 and Ta2O5A curve that the change rate of the withstand voltage strength of a sample with the content of 0-0.05 mol% changes before and after reduction;
FIG. 7 shows 43.23% of PbTiO3 and Ta2O5A curve showing that the room temperature resistance change rate of a sample with the content of 0-0.05 mol% changes before and after reduction;
FIG. 8 shows 43.23% of PbTiO3 and Ta2O5And (3) a curve that the change rate of the withstand voltage strength of the sample with the content of 0-0.05 mol% changes before and after reduction.
Detailed Description
To make the purpose, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The application provides a preparation method of a PTCR thermal sensitive ceramic material and the PTCR thermal sensitive ceramic material prepared by the method.
The preparation method of the PTCR thermal sensitive ceramic material comprises the following steps:
a. to BaTiO3、PbTiO3、MnO2In which Z mol% of Ta is added2O5As powder, the value range of z is more than 0 and less than or equal to 0.05;
b. weighing materials according to a material formula, taking zirconia balls and deionized water as media, ball-milling the powder and the ingredients for a preset time, and drying to obtain mixed powder;
c. adding polyvinyl alcohol with the weight of 3.0-12.0 wt% of the mixed powder and the concentration of 10 wt% into the mixed powder for granulation, and pressing into a biscuit at the pressure of 10-15 MPa;
d. and (3) placing the pressed biscuit in an air atmosphere at 1230-1300 ℃ to fully sinter the biscuit into ceramic.
Optionally, in the step a, a semiconducting agent and/or a sintering aid are added as ingredients, wherein the doping amount of the semiconducting agent is 0.05-0.50 atom% of the powder, and the sintering aid accounts for 0-2.5 mol% of the total substance amount of the powder.
Optionally, the formula of the powder is (100-x) BaTiO3+xPbTiO3+yMnO2+zTa2O5Wherein x is 0 to 50 mol% and y is 0.03 to 0.20 mol%.
Optionally, in the step b, the preset time is 12-24 hours.
Optionally, in step c, the biscuit has a dimension of phi 10 mm.
Optionally, in step d, the sintering time of the biscuit is 10-30 minutes.
Optionally, the biscuit is a circular biscuit.
Optionally, the method further comprises:
f. grinding the surface of the ceramic, spraying an electrode on the surface of the ceramic, sintering the ceramic with the electrode in an air atmosphere at 480-520 ℃, and preserving heat for 8 min.
Optionally, in step d, the electrode is an Ag electrode.
The PTCR thermal sensitive ceramic material provided by the application is prepared by adopting the method. Next, the preparation process of the PTCR thermosensitive ceramic material will be described with a specific example.
Implementation mode one
a. Preparing ingredients: according to the mass ratio of the raw material powder, the following raw material powder formula is adopted:
85.15 mol% of BaTiO3Powder, 14.85 mol% PbTiO3Powder of material, 0.05 mol% MnO2Powder zTa2O5Dosing with 1.647 mol% of other sintering aids, wherein z is 0.00, 0.01, 0.02, 0.03, 0.04, 0.05; the weights were calculated in terms of molar ratios in the formula and were weighed as given in table 1 below:
TABLE 1 ingredient Table (unit: g) of example one method
Numbering I # Material II # Material MnO2 Other sintering aids Ta2O5
Ta0.00％ 49.4083 11.2489 0.0130 0.2670 0.0000
Ta0.005％ 49.4083 11.2489 0.0130 0.2670 0.0055
Ta0.01％ 49.4083 11.2489 0.0130 0.2670 0.0110
Ta0.015％ 49.4083 11.2489 0.0130 0.2670 0.0166
Ta0.02％ 49.4083 11.2489 0.0130 0.2670 0.0221
Ta0.03％ 49.4083 11.2489 0.0130 0.2670 0.0331
Ta0.04％ 49.4083 11.2489 0.0130 0.2670 0.0442
Ta0.05％ 49.4083 11.2489 0.0130 0.2670 0.0552
b. Weighing raw material ingredients according to the formula proportion in the table, taking zirconia balls and deionized water as media, carrying out ball milling on the mixture for 24 hours, then drying the ball grinding materials, adding polyvinyl alcohol (PVA) with the concentration of 10 wt% and the weight of 8.0 wt% of the total weight of the dried powder, granulating, and tabletting under the pressure of 10MPa to prepare a round biscuit with the size of phi 10 mm;
c. sintering the pressed round biscuit at 1260 ℃ in air atmosphere, and carrying out heat preservation sintering for 30min to fully sinter the round biscuit and realize solid-phase reaction; and then spraying an Ag electrode on the surface of the ceramic wafer, sintering the electrode at 480-520 ℃ for 8min, and solidifying the electrode to finally obtain the PTCR heating ceramic wafer with optimized reduction resistance.
d. Will be doped with Ta2O5The resistance at room temperature was measured in a room temperature environment.
e. Will be doped with Ta2O5The PTCR ceramic sample is tested for voltage resistance by a direct current power supply.
f. Sealing and wrapping Ta with insulating paper at 180 DEG C2O5Heating the PTCR ceramic sample for 1min, then cooling the sample to room temperature, measuring room temperature resistance, and calculating the resistance change rate; and then testing the withstand voltage strength of the sample by using a direct current power supply, and calculating the variation rate of the withstand voltage strength.
Test analysis:
the PTCR ceramic samples were heated at a temperature rise rate of 2 ℃/min, and the resistance-temperature characteristics thereof were measured, and the results are shown in Table 2.
The voltage resistance was measured by applying a DC voltage to a PTCR ceramic sample at a step-up rate of 20V/min until the sample broke down, and the results are shown in Table 3.
TABLE 2 comparison of Electrical Property measurements for PTCR ceramic test specimens of different Ta contents
Figure BDA0003008042710000061
Sealing and wrapping Ta with insulating paper at 180 DEG C2O5Heating the PTCR ceramic sample for 1min, then cooling the sample to room temperature, measuring the resistance at room temperature, and calculating the resistance change rate; and then testing the withstand voltage strength of the sample by using a direct current power supply, and calculating the variation rate of the withstand voltage strength.
TABLE 3 specific values of room temperature resistance and withstand voltage strength change rate of samples with different Ta contents after electrification
Figure BDA0003008042710000071
And (4) conclusion: as shown in Table 3, Ta was not added2O5The room temperature resistance change rate after reduction is-56.22%, the withstand voltage change rate is-27.95%, and the change rate is along with Ta2O5The content is increased, the change rate of the room temperature resistance and the voltage-resistant strength of the sample is reduced, the room temperature resistance change reaches the minimum value of-11.50% when the Ta content is 0.015 mol%, and the voltage-resistant strength change reaches the minimum value of-8.15%. The above experimental results show that Ta2O5The addition of (A) has a remarkable effect on improving the reduction resistance of the PTC heating ceramic with the Curie temperature of about 180 ℃.
Second embodiment
a. Preparing ingredients: according to the mass ratio of the raw material powder, the following raw material powder formula is adopted:
78.66 mol% of BaTiO3Powder, 21.34 mol% PbTiO3Powder of material, 0.05 mol% MnO2Powder zTa2O5Dosing with 1.647 mol% of other sintering aids, wherein z is 0.00, 0.01, 0.02, 0.03, 0.04, 0.05; weights were calculated as molar ratios in the formula and weighed as in table 4 below:
TABLE 4 raw materials compounding Table for example two methods (unit: g)
Numbering I # Material II # Material MnO2 Other sintering aids Ta2O5
Ta 0.00％ 45.6425 16.1651 0.0130 0.2670 0.0000
Ta 0.005％ 45.6425 16.1651 0.0130 0.2670 0.0055
Ta 0.01％ 45.6425 16.1651 0.0130 0.2670 0.0110
Ta 0.015％ 45.6425 16.1651 0.0130 0.2670 0.0166
Ta 0.02％ 45.6425 16.1651 0.0130 0.2670 0.0221
Ta 0.03％ 45.6425 16.1651 0.0130 0.2670 0.0331
Ta 0.04％ 45.6425 16.1651 0.0130 0.2670 0.0442
Ta 0.05％ 45.6425 16.1651 0.0130 0.0375 0.0552
b. Weighing raw material ingredients according to the formula proportion in the table, taking zirconia balls and deionized water as media, carrying out ball milling on the mixture for 24 hours, then drying the ball grinding materials, adding polyvinyl alcohol (PVA) with the concentration of 10 wt% and the weight of 8.0 wt% of the total weight of the dried powder, granulating, and tabletting under the pressure of 10MPa to prepare a round biscuit with the size of phi 10 mm;
c. sintering the pressed round biscuit at 1260 ℃ in air atmosphere, and carrying out heat preservation sintering for 30min to fully sinter the round biscuit and realize solid-phase reaction; and then spraying an Ag electrode on the surface of the ceramic wafer, sintering the electrode at 480-520 ℃ for 8min, and solidifying the electrode to finally obtain the PTCR heating ceramic wafer with optimized reduction resistance.
d. Will be doped with Ta2O5The resistance at room temperature was measured in a room temperature environment.
e. Will be doped with Ta2O5The PTCR ceramic sample is tested for voltage resistance by a direct current power supply.
f. Sealing and wrapping Ta with insulating paper at 204 deg.C2O5Heating the PTCR ceramic sample for 1min, then cooling the sample to room temperature, measuring room temperature resistance, and calculating the resistance change rate; and then testing the withstand voltage strength of the sample by using a direct current power supply, and calculating the variation rate of the withstand voltage strength.
Test analysis:
the PTCR ceramic samples were heated at a temperature rise rate of 2 ℃/min, and the resistance-temperature characteristics thereof were measured, and the results are shown in Table 5.
The voltage resistance was measured by applying a DC voltage to a PTCR ceramic sample at a step-up rate of 20V/min until the sample broke down, and the results are shown in Table 6.
TABLE 5 comparison of Electrical Property measurements for PTCR ceramic test specimens of different Ta contents
Figure BDA0003008042710000091
Sealing and wrapping Ta with insulating paper at 250 DEG C2O5Heating the PTCR ceramic sample for 1min, then cooling the sample to room temperature, measuring the resistance at room temperature, and calculating the resistance change rate; and then testing the withstand voltage strength of the sample by using a direct current power supply, and calculating the variation rate of the withstand voltage strength.
TABLE 6 specific values of room temperature resistance and withstand voltage strength change rate of samples with different Ta contents after electrification
Figure BDA0003008042710000092
And (4) conclusion: as shown in Table 6, Ta was not added2O5Change in resistance at room temperature after time reductionThe rate is-58.12%, the change rate of the withstand voltage is-36.72%, along with Ta2O5The content is increased, the change rate of the room temperature resistance and the voltage-resistant strength of the sample is reduced, the room temperature resistance change reaches the minimum value of-9.16% when the Ta content is 0.015 mol%, and the voltage-resistant strength change reaches the minimum value of-7.88%. The above experimental results show that Ta2O5The addition of (A) has a remarkable effect on improving the reduction resistance of the PTC heating ceramic with the Curie temperature of about 204 ℃.
Third embodiment
a. Preparing ingredients: according to the mass ratio of the raw material powder, the following raw material powder formula is adopted:
65.69 mol% of BaTiO3Powder, 34.31 mol% PbTiO3Powder of material, 0.05 mol% MnO2Powder zTa2O5Dosing with 1.647 mol% of other sintering aids, wherein z is 0.00, 0.01, 0.02, 0.03, 0.04, 0.05; weights were calculated in terms of molar ratios in the formula and were weighed as in table 7 below:
TABLE 7 raw materials compounding Table for the three methods of example (unit: g)
Numbering I # Material II # Material MnO2 Other sintering aids Ta2O5
Ta 0.00％ 38.1183 25.9907 0.0130 0.2670 0.0000
Ta 0.005％ 38.1183 25.9907 0.0130 0.2670 0.0055
Ta 0.01％ 38.1183 25.9907 0.0130 0.2670 0.0110
Ta 0.015％ 38.1183 25.9907 0.0130 0.2670 0.0166
Ta 0.02％ 38.1183 25.9907 0.0130 0.2670 0.0221
Ta 0.03％ 38.1183 25.9907 0.0130 0.2670 0.0331
Ta 0.04％ 38.1183 25.9907 0.0130 0.2670 0.0442
Ta 0.05％ 38.1183 25.9907 0.0130 0.2670 0.0552
b. Weighing raw material ingredients according to the formula proportion in the table, taking zirconia balls and deionized water as media, carrying out ball milling on the mixture for 24 hours, then drying the ball grinding materials, adding polyvinyl alcohol (PVA) with the concentration of 10 wt% and the weight of 8.0 wt% of the total weight of the dried powder, granulating, and tabletting under the pressure of 10MPa to prepare a round biscuit with the size of phi 10 mm;
c. sintering the pressed round biscuit at 1260 ℃ in air atmosphere, and carrying out heat preservation sintering for 30min to fully sinter the round biscuit and realize solid-phase reaction; and then spraying an Ag electrode on the surface of the ceramic wafer, sintering the electrode at 480-520 ℃ for 8min, and solidifying the electrode to finally obtain the PTCR heating ceramic wafer with optimized reduction resistance.
d. Will be doped with Ta2O5The resistance at room temperature was measured in a room temperature environment.
e. Will be provided withDoped with Ta2O5The PTCR ceramic sample is tested for voltage resistance by a direct current power supply.
f. Sealing and wrapping Ta with insulating paper at 252 DEG C2O5Heating the PTCR ceramic sample for 1min, then cooling the sample to room temperature, measuring room temperature resistance, and calculating the resistance change rate; and then testing the withstand voltage strength of the sample by using a direct current power supply, and calculating the variation rate of the withstand voltage strength.
Test analysis:
the PTCR ceramic samples were heated at a temperature rise rate of 2 ℃/min, and the resistance-temperature characteristics thereof were measured, and the results are shown in Table 8.
The voltage resistance was measured by applying a DC voltage to a PTCR ceramic sample at a step-up rate of 20V/min until the sample broke down, and the results are shown in Table 9.
TABLE 8 comparison of Electrical Property measurements for PTCR ceramic test specimens of different Ta contents
Figure BDA0003008042710000111
Sealing and wrapping Ta with insulating paper at 252 deg.C2O5Heating the PTCR ceramic sample for 1min, then cooling the sample to room temperature, measuring the resistance at room temperature, and calculating the resistance change rate; and then testing the withstand voltage strength of the sample by using a direct current power supply, and calculating the variation rate of the withstand voltage strength.
TABLE 9 specific values of room temperature resistance and withstand voltage strength change rate after electrification of samples with different Ta contents
Figure BDA0003008042710000121
And (4) conclusion: as shown in Table 9, Ta was not added2O5The room temperature resistance change rate after reduction is-41.36 percent, the withstand voltage change rate is-19.20 percent, and the change rate is along with Ta2O5The content is increased, the change rate of the room-temperature resistance and the voltage-resistant strength of the sample are reduced, and the room-temperature resistance is reduced when the content of Ta is 0.01mol percentThe variation reaches the minimum value of-5.01 percent, the variation of the withstand voltage strength reaches the minimum value of-1.47 percent, and when the content of Ta is continuously increased, the variation rate of the room temperature resistance and the withstand voltage strength is increased, but is still reduced compared with the control group. The above experimental results show that Ta2O5The addition of (A) has a remarkable effect on improving the reduction resistance of the PTC heating ceramic with the Curie temperature of about 252 ℃.
Embodiment IV
a. Preparing ingredients: according to the mass ratio of the raw material powder, the following raw material powder formula is adopted:
56.77mol percent of BaTiO3Powder, 43.23 mol% PbTiO3Powder of material, 0.05 mol% MnO2Powder zTa2O5Dosing with 1.647 mol% of other sintering aids, wherein z is 0.00, 0.01, 0.02, 0.03, 0.04, 0.05; weights were calculated as molar ratios in the formula and weighed as in table 10 below:
TABLE 10 raw materials compounding Table for example four methods (unit: g)
Numbering I # Material II # Material MnO2 Other sintering aids Ta2O5
Ta 0.00％ 32.9408 32.7467 0.0130 0.2670 0.0000
Ta 0.005％ 32.9408 32.7467 0.0130 0.2670 0.0055
Ta 0.01％ 32.9408 32.7467 0.0130 0.2670 0.0110
Ta 0.015％ 32.9408 32.7467 0.0130 0.2670 0.0166
Ta 0.02％ 32.9408 32.7467 0.0130 0.2670 0.0221
Ta 0.03％ 32.9408 32.7467 0.0130 0.2670 0.0331
Ta 0.04％ 32.9408 32.7467 0.0130 0.2670 0.0442
Ta 0.05％ 32.9408 32.7467 0.0130 0.2670 0.0552
b. Weighing raw material ingredients according to the formula proportion in the table, taking zirconia balls and deionized water as media, carrying out ball milling on the mixture for 24 hours, then drying the ball grinding materials, adding polyvinyl alcohol (PVA) with the concentration of 10 wt% and the weight of 8.0 wt% of the total weight of the dried powder, granulating, and tabletting under the pressure of 10MPa to prepare a round biscuit with the size of phi 10 mm;
c. sintering the pressed round biscuit at 1260 ℃ in air atmosphere, and carrying out heat preservation sintering for 30min to fully sinter the round biscuit and realize solid-phase reaction; and then spraying an Ag electrode on the surface of the ceramic wafer, sintering the electrode at 480-520 ℃ for 8min, and solidifying the electrode to finally obtain the PTCR heating ceramic wafer with optimized reduction resistance.
d. Will be doped with Ta2O5The resistance at room temperature was measured in a room temperature environment.
e. Will be doped with Ta2O5The PTCR ceramic sample is tested with a direct current power supplyThe intensity of the voltage.
f. Sealing and wrapping Ta with insulating paper at 285 deg.C2O5Heating the PTCR ceramic sample for 1min, then cooling the sample to room temperature, measuring room temperature resistance, and calculating the resistance change rate; and then testing the withstand voltage strength of the sample by using a direct current power supply, and calculating the variation rate of the withstand voltage strength.
Test analysis:
the PTCR ceramic samples were heated at a temperature rise rate of 2 ℃/min, and the resistance-temperature characteristics thereof were measured, and the results are shown in Table 11.
The voltage resistance was measured by applying a DC voltage to a PTCR ceramic sample at a step-up rate of 20V/min until the sample broke down, and the results are shown in Table 12.
TABLE 11 comparison of measured data for electrical properties of PTCR ceramic test specimens of varying Ta contents
Figure BDA0003008042710000141
Sealing and wrapping Ta with insulating paper at 285 deg.C2O5Heating the PTCR ceramic sample for 1min, then cooling the sample to room temperature, measuring the resistance at room temperature, and calculating the resistance change rate; and then testing the withstand voltage strength of the sample by using a direct current power supply, and calculating the variation rate of the withstand voltage strength.
TABLE 12 specific values of room temperature resistance and withstand voltage strength change rate after electrification for samples with different Ta contents
Figure BDA0003008042710000142
In summary, compared with the prior art, the application has the advantages that:
1. the method of the application is realized by changing the formula of the material, namely, (Ba, Pb) TiO3System PTCR ceramic material with Ta doped2O5Reducing the prepared PTCR ceramic wafer, wherein the resistance change rate before and after reduction is reduced from-41.36% to-5.01%;
2. the reduction resistance of the manufactured heater is obviously improved, and the change rate of the reduced withstand voltage intensity is changed from-19.19% to-1.46%;
3. the method is simple to operate, easy to control, low in cost and easy to implement industrially, and has great significance for research on improvement of the reduction resistance of the PTCR heating ceramic.
And (4) conclusion: as shown in Table 12, Ta was not added2O5The room temperature resistance change rate after reduction is-49.11%, the withstand voltage change rate is-26.35%, and the change rate is along with Ta2O5The content is increased, the change rates of the room temperature resistance and the voltage resistance strength of the sample are both reduced, the change amount of the room temperature resistance reaches the minimum value of-9.95% when the content of Ta is 0.01 mol%, the change amount of the voltage resistance strength reaches the minimum value of-2.26%, and when the content of Ta is continuously increased, the change rates of the room temperature resistance and the voltage resistance strength are increased but still reduced compared with a control group. The above experimental results show that Ta2O5The addition of (A) has a remarkable effect on improving the reduction resistance of the PTC heating ceramic with the Curie temperature of about 285 ℃.
Finally, it should be noted that those skilled in the art will appreciate that embodiments of the present application present many technical details for the purpose of enabling the reader to better understand the present application. However, the technical solutions claimed in the claims of the present application can be basically implemented without these technical details and various changes and modifications based on the above-described embodiments. Accordingly, in actual practice, various changes in form and detail may be made to the above-described embodiments without departing from the spirit and scope of the present application.

Claims (10)

1. A preparation method of a PTCR thermal sensitive ceramic material is characterized by comprising the following steps:
a. to BaTiO3、PbTiO3、MnO2In which Z mol% of Ta is added2O5As powder, the value range of z is more than 0 and less than or equal to 0.05;
b. weighing materials according to a material formula, taking zirconia balls and deionized water as media, ball-milling the powder and the ingredients for a preset time, and drying to obtain mixed powder;
c. adding polyvinyl alcohol with the weight of 3.0-12.0 wt% of the mixed powder and the concentration of 10 wt% into the mixed powder for granulation, and pressing into a biscuit at the pressure of 10-15 MPa;
d. and (3) placing the pressed biscuit in an air atmosphere at 1230-1300 ℃ to fully sinter the biscuit into ceramic.
2. The method according to claim 1, wherein in the step a, a semi-conducting agent and/or a sintering aid are added as ingredients, wherein the doping amount of the semi-conducting agent is 0.05-0.50 atom% of the powder, and the sintering aid accounts for 0-2.5 mol% of the total substance amount of the powder.
3. The method of claim 1, wherein the powder has a formula of (100-x) BaTiO3+xPbTiO3+yMnO2+zTa2O5Wherein x is 0 to 50 mol% and y is 0.03 to 0.20 mol%.
4. The method according to claim 1, wherein in the step b, the preset time is 12-24 hours.
5. The method according to claim 1, wherein in step c the biscuit has a dimension of phi 10 mm.
6. The method according to claim 1, wherein in step d, the green body is sintered for a period of time between 10 and 30 minutes.
7. The method of claim 1, wherein the biscuit is a circular biscuit.
8. The method of claim 1, further comprising:
f. grinding the surface of the ceramic, spraying an electrode on the surface of the ceramic, sintering the ceramic with the electrode in an air atmosphere at 480-520 ℃, and preserving heat for 8 min.
9. The method of claim 8, wherein in step d, the electrode is an Ag electrode.
10. A PTCR heat-sensitive ceramic material, characterised in that it is prepared by a process as claimed in any one of claims 1 to 9.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114031394A (en) * 2021-10-22 2022-02-11 江苏钧瓷科技有限公司 Method for improving reduction resistance of PTCR (thermal sensitive ceramic)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01234360A (en) * 1988-03-15 1989-09-19 Matsushita Electric Ind Co Ltd Production of ceramic material containing lead
CN106866135A (en) * 2017-03-13 2017-06-20 中国地质大学（北京） A kind of unleaded high-curie temperature BaTiO3The preparation method of base positive temperature coefficient thermal sensitive ceramics
CN107512906A (en) * 2016-06-17 2017-12-26 清华大学 A kind of anti-reduction X9R type ceramic capacitor dielectric materials and preparation method thereof
CN108975907A (en) * 2018-09-05 2018-12-11 天津大学 The method for improving barium titanate dielectric material resistance to reduction is adulterated by transition-metal ions
CN111410529A (en) * 2020-04-30 2020-07-14 上海大学 Addition of CeO2Method for improving power aging of PTC heating ceramic

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01234360A (en) * 1988-03-15 1989-09-19 Matsushita Electric Ind Co Ltd Production of ceramic material containing lead
CN107512906A (en) * 2016-06-17 2017-12-26 清华大学 A kind of anti-reduction X9R type ceramic capacitor dielectric materials and preparation method thereof
CN106866135A (en) * 2017-03-13 2017-06-20 中国地质大学（北京） A kind of unleaded high-curie temperature BaTiO3The preparation method of base positive temperature coefficient thermal sensitive ceramics
CN108975907A (en) * 2018-09-05 2018-12-11 天津大学 The method for improving barium titanate dielectric material resistance to reduction is adulterated by transition-metal ions
CN111410529A (en) * 2020-04-30 2020-07-14 上海大学 Addition of CeO2Method for improving power aging of PTC heating ceramic

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
杨梦梦: "高性能无铅BaTiO3基正温度系数热敏电阻陶瓷材料的研究", 《中国优秀博硕士学位论文全文数据库（硕士）工程科技I辑》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114031394A (en) * 2021-10-22 2022-02-11 江苏钧瓷科技有限公司 Method for improving reduction resistance of PTCR (thermal sensitive ceramic)

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