CN103011811B - Method for preparing high temperature NTC (Negative Temperature Coefficient) thermistor material - Google Patents
Method for preparing high temperature NTC (Negative Temperature Coefficient) thermistor material Download PDFInfo
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- CN103011811B CN103011811B CN 201210523768 CN201210523768A CN103011811B CN 103011811 B CN103011811 B CN 103011811B CN 201210523768 CN201210523768 CN 201210523768 CN 201210523768 A CN201210523768 A CN 201210523768A CN 103011811 B CN103011811 B CN 103011811B
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Abstract
The invention discloses a method for preparing a high temperature NTC (Negative Temperature Coefficient) thermistor material, which comprises the following steps of: according to a formula of CaWO4-xCeTiyO2y+2, weighing and analyzing pure powdered CaCO3, CeO2, TiO2 and WO3, placing the powder into a ball milling tank, adding deionized water and zirconium ball grinding stone and carrying out ball milling for four hours; drying ball-milled slurry, grinding the dried powder and sieving the powder through a 80-mesh sieve; presintering the sieved powder, ball-grinding the presintered powder again, drying and grinding the powder and sieving the power through the 80-mesh sieve to obtain uniform and fine powder; and finally, placing a dry-pressed sample into a high temperature furnace to sinter so as to obtain the thermistor material. A main crystal phase of the thermistor material prepared by the method disclosed by the invention is a scheelite phase; the thermistor material has room temperature resistivity of 5.642*10<6> to 1.982*10<9> ohm.cm and has material constant of 5,077 to 7,275K; in the integral test temperature range, a resistor temperature relation curve LnRho-1000/T has good linearity; and the method is suitable for temperature measurement in the wide temperature range of room temperature to 1,000 DEG C.
Description
Technical field
The invention belongs to the thermo-sensitive material technical field, more specifically, relate to a kind of preparation method of high temperature negative temperature coefficient heat-sensitive resistance material.
Background technology
In recent years, along with being widely used of Exhaust Gas Catalytic Converter for Automobiles, it is more and more important that high-temperature NTC heat-sensitive resistance becomes.They are used to prepare the optimum temps monitor of vehicle exhaust temperature survey with temperature sensor and tail gas catalyzed transmodulator.Under the vehicle exhaust environment, the working temperature of sensor changes between room temperature to 1000 ℃, and being applicable to the temperature sensor that this temperature range measures has thermopair, NTC thermistor temperature sensor.The high-temperature NTC heat-sensitive resistance temperature sensor is large owing to having output signal, without the complicated advantages such as signal processing circuit, NTC thermistor low price, easy to prepare simultaneously, so the high-temperature NTC heat-sensitive resistance temperature sensor has very large advantage in exhaust temperature monitoring field.The actual NTC thermistor material used is nearly all by Mn at present
3o
4, Co
3o
4(the AB of spinel system formed with the transition metal oxide solid solution such as NiO
2o
4) stupalith.But spinel is that the NTC thermistor material is only suitable for for the temperature survey below 300 ℃, because under high temperature, ion is reset and irreversible transition causes room temperature resistivity that significantly drift occurs, thereby make the repeated and accuracy severe exacerbation of thermistor temperature detecting.The Fe that the people such as champion Qiao announce
1-xni
0.5mn
1.5cr
xo
4it is the serious problem of thermistor material high temperature ageing characteristic that still there is spinel in high-temperature NTC heat-sensitive resistance material.The Ni that the people such as Yang Jianfeng announce
0.6mn
2.0-xa1
0.4sn
xo
4high temperature NTC material is similarly spinel structure, and is only applicable to 300-500 ℃.The obvious high-temperature NTC heat-sensitive resistance product that more than 300 ℃, temperature survey is used also in the market.Therefore for meeting vehicle exhaust monitoring temperature demand, need to develop a kind of wide operating temperature range that has, the high temperature NTC thermo-sensitive material of stable performance under high temperature.
Summary of the invention
For the defect of prior art, the object of the present invention is to provide a kind of preparation method of high temperature negative temperature coefficient heat-sensitive resistance material, its thermistor prepared has wide operating temperature range, stable performance under high temperature.
For achieving the above object, the invention provides a kind of preparation method of high temperature negative temperature coefficient heat-sensitive resistance material, comprise the following steps:
(1) according to CaWO
4-xCeTi
yo
2y+2the analytically pure powder CaCO of formula weighing
3, CeO
2, TiO
2, WO
3,and powder is put into to ball grinder, and add deionized water, make ball-milling medium with the zirconium ball, ball milling four hours, mix powder;
(2) mixture after ball milling is placed on to drying in oven, obtains the dry powder body, powder rear mistake 80 mesh sieves of milling;
(3) powder step (2) obtained carries out pre-burning;
(4) by the ball milling oven dry again of the powder after pre-burning;
(5) after the powder after drying is milled, cross 80 mesh sieves, adding mass ratio in powder is that the PVA that 6%-10%, concentration are 5-10mol% evenly mixes as binding agent, and adopts dry-pressing formed method to be pressed into sheet sample the granulation powder obtained;
(6) dry-pressing formed sample is placed on to sintering in High Temperature Furnaces Heating Apparatus.
The mass ratio of the deionized water described in step (1) and powder is 1:2, and the mass ratio of powder and ball-milling medium is 1:3
Oven dry described in step (2) is dry 8h in 90 ℃ of baking ovens.
Pre-burning system described in step (3) is: be warmed up to 900-1100 ℃ of certain temperature value with 5 ℃/min from room temperature, insulation 2-5h, furnace cooling.
In step (4), ball milling condition is identical with step (1), and drying condition is identical with step (2).
To be the pressure that adopts 180MPa be pressed into diameter by granulation powder to dry-pressing formed method in step (5) is the slice of cylinder that 10mm thickness is 2-3mm.
The above technical scheme of conceiving by the present invention, compared with prior art, the present invention has following beneficial effect: the scheelite-type structure that the high-temperature thermistor material that 1) adopts the present invention to prepare has, scheelite-type structure is different from traditional spinel structure, irreversible transition can not occur under high temperature, have stable high-temperature performance; 2) adopt high-temperature thermistor prepared by the present invention to there is good linearity at the interval resistance temperature relation curve of whole probe temperature (Ln ρ-1000/T); 3) thermistor that prepared by the present invention has suitable room temperature resistivity and the resistivity under top temperature, and room temperature resistivity can be regulated and realize regulation and control continuously by formula.So the high-temperature thermistor that adopts the present invention to prepare meets temperature survey requirement in room temperature to 1000 ℃ temperature range.
The accompanying drawing explanation
Fig. 1 is the preparation method's of high temperature negative temperature coefficient heat-sensitive resistance material of the present invention schema.
Fig. 2 is the resistance temperature relation curve of the thermistor of the embodiment of the present invention two, five, seven preparations, and ordinate zou is the resistivity log value, the 1000/T reciprocal that X-coordinate is temperature.
Fig. 3 is the resistance temperature relation curve of the thermistor of the embodiment of the present invention ten, 11,12 preparations, and ordinate zou is the resistivity log value, the 1000/T reciprocal that X-coordinate is temperature.
Fig. 4 is the XRD figure of the thermistor material of the embodiment of the present invention five preparations, and ordinate zou is diffracted intensity, and X-coordinate is the twice diffraction angle.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
As shown in Figure 1, the preparation method of high temperature negative temperature coefficient heat-sensitive resistance material of the present invention comprises the following steps:
(1) according to CaWO
4-xCeTi
yo
2y+2the analytically pure powder CaCO of formula weighing
3, CeO
2, TiO
2, WO
3,and powder is put into to ball grinder, and add deionized water by powder and deionized water quality than 1:2, add ball milling stone, ball milling four hours by powder and ball milling stone mass ratio 1:3; Wherein the span of x is that 0.2 to 0.5, y span is 1 to 3, particularly, and according to CaWO
4-xCeTi
yo
2y+2formula can determine that the mol ratio of Ca, Ce, Ti, tetra-kinds of elements of W is 1:x:xy:1, thereby further determines powder CaCO according to these four kinds of elements
3, CeO
2, TiO
2, WO
3between mol ratio;
(2) mixture after ball milling is placed on to drying in oven, obtains the dry powder body, powder rear mistake 80 mesh sieves of milling;
(3) powder step (2) obtained is at 900-1100 ℃ of pre-burning 2-5h;
(4) by the ball milling oven dry again of the powder after pre-burning;
(5) after the powder after drying is milled, cross 80 mesh sieves, adding mass ratio in powder is that the PVA that 6%-10%, concentration are 5-10mol% evenly mixes as binding agent, and adopts dry-pressing formed method to be pressed into sheet sample the granulation powder obtained;
(6) dry-pressing formed sample is placed on to sintering in High Temperature Furnaces Heating Apparatus, the temperature increasing schedule that sintering adopts is as follows: adopt 3 ℃/min temperature rise rate to be warmed up to 600 ℃ from room temperature, remove PVA at 600 ℃ of insulation 2h, adopt 5 ℃/min temperature rise rate to be warmed up to 1200-1400 ℃ and be incubated 4h from 600 ℃, last furnace cooling is to room temperature.
Embodiment mono-
(1) according to CaWO
4-0.2CeTi
1o
4the analytically pure powder CaCO of formula weighing
3, CeO
2, TiO
2, WO
3,and powder is put into to ball grinder, and add deionized water by powder and deionized water quality than 1:2, add ball milling stone, ball milling four hours by powder and ball milling stone mass ratio 1:3;
(2) mixture after ball milling is placed on to drying in oven, obtains the dry powder body, powder rear mistake 80 mesh sieves of milling;
(3) by the fine powder body obtained of step (2) at 900-1100 ℃ of pre-burning 2-5h;
(4) by the ball milling oven dry again of the powder after pre-burning;
(5) after the powder after drying is milled, cross 80 mesh sieves, adding mass ratio in powder is that the PVA that 6%-10%, concentration are 5-10mol% evenly mixes as binding agent, and adopts dry-pressing formed method to be pressed into sheet sample the granulation powder obtained;
(6) dry-pressing formed sample is placed on to sintering in High Temperature Furnaces Heating Apparatus, the temperature increasing schedule that sintering adopts is as follows: adopt 3 ℃/min temperature rise rate to be warmed up to 600 ℃ from room temperature, remove PVA at 600 ℃ of insulation 2h, adopt 5 ℃/min temperature rise rate to be warmed up to 1200-1400 ℃ and be incubated 4h from 600 ℃, last furnace cooling is to room temperature.
Embodiment bis-
(1) according to CaWO
4-0.2CeTi
2o
6the analytically pure powder CaCO of formula weighing
3, CeO
2, TiO
2, WO
3,and powder is put into to ball grinder, and add deionized water by powder and deionized water quality than 1:2, add ball milling stone, ball milling four hours by powder and ball milling stone mass ratio 1:3;
(2) mixture after ball milling is placed on to drying in oven, obtains the dry powder body, powder rear mistake 80 mesh sieves of milling;
(3) by the fine powder body obtained of step (2) at 900-1100 ℃ of pre-burning 2-5h;
(4) by the ball milling oven dry again of the powder after pre-burning;
(5) after the powder after drying is milled, cross 80 mesh sieves, adding mass ratio in powder is that the PVA that 6%-10%, concentration are 5-10mol% evenly mixes as binding agent, and adopts dry-pressing formed method to be pressed into sheet sample the granulation powder obtained;
(6) dry-pressing formed sample is placed on to sintering in High Temperature Furnaces Heating Apparatus, the temperature increasing schedule that sintering adopts is as follows: adopt 3 ℃/min temperature rise rate to be warmed up to 600 ℃ from room temperature, remove PVA at 600 ℃ of insulation 2h, adopt 5 ℃/min temperature rise rate to be warmed up to 1200-1400 ℃ and be incubated 4h from 600 ℃, last furnace cooling is to room temperature.
Embodiment tri-
(1) according to CaWO
4-0.2CeTi
3o
8the analytically pure powder CaCO of formula weighing
3, CeO
2, TiO
2, WO
3,and powder is put into to ball grinder, and add deionized water by powder and deionized water quality than 1:2, add ball milling stone, ball milling four hours by powder and ball milling stone mass ratio 1:3;
(2) mixture after ball milling is placed on to drying in oven, obtains the dry powder body, powder rear mistake 80 mesh sieves of milling;
(3) by the fine powder body obtained of step (2) at 900-1100 ℃ of pre-burning 2-5h;
(4) by the ball milling oven dry again of the powder after pre-burning;
(5) after the powder after drying is milled, cross 80 mesh sieves, adding mass ratio in powder is that the PVA that 6%-10%, concentration are 5-10mol% evenly mixes as binding agent, and adopts dry-pressing formed method to be pressed into sheet sample the granulation powder obtained;
(6) dry-pressing formed sample is placed on to sintering in High Temperature Furnaces Heating Apparatus, the temperature increasing schedule that sintering adopts is as follows: adopt 3 ℃/min temperature rise rate to be warmed up to 600 ℃ from room temperature, remove PVA at 600 ℃ of insulation 2h, adopt 5 ℃/min temperature rise rate to be warmed up to 1200-1400 ℃ and be incubated 4h from 600 ℃, last furnace cooling is to room temperature.
Embodiment tetra-
(1) according to CaWO
4-0.25CeTi
1o
4the analytically pure powder CaCO of formula weighing
3, CeO
2, TiO
2, WO
3,and powder is put into to ball grinder, and add deionized water by powder and deionized water quality than 1:2, add ball milling stone, ball milling four hours by powder and ball milling stone mass ratio 1:3;
(2) mixture after ball milling is placed on to drying in oven, obtains the dry powder body, powder rear mistake 80 mesh sieves of milling;
(3) by the fine powder body obtained of step (2) at 900-1100 ℃ of pre-burning 2-5h;
(4) by the ball milling oven dry again of the powder after pre-burning;
(5) after the powder after drying is milled, cross 80 mesh sieves, adding mass ratio in powder is that the PVA that 6%-10%, concentration are 5-10mol% evenly mixes as binding agent, and adopts dry-pressing formed method to be pressed into sheet sample the granulation powder obtained;
(6) dry-pressing formed sample is placed on to sintering in High Temperature Furnaces Heating Apparatus, the temperature increasing schedule that sintering adopts is as follows: adopt 3 ℃/min temperature rise rate to be warmed up to 600 ℃ from room temperature, remove PVA at 600 ℃ of insulation 2h, adopt 5 ℃/min temperature rise rate to be warmed up to 1200-1400 ℃ and be incubated 4h from 600 ℃, last furnace cooling is to room temperature.
Embodiment five
(1) according to CaWO
4-0.25CeTi
2o
6the analytically pure powder CaCO of formula weighing
3, CeO
2, TiO
2, WO
3,and powder is put into to ball grinder, and add deionized water by powder and deionized water quality than 1:2, add ball milling stone, ball milling four hours by powder and ball milling stone mass ratio 1:3;
(2) mixture after ball milling is placed on to drying in oven, obtains the dry powder body, powder rear mistake 80 mesh sieves of milling;
(3) by the fine powder body obtained of step (2) at 900-1100 ℃ of pre-burning 2-5h;
(4) by the ball milling oven dry again of the powder after pre-burning;
(5) after the powder after drying is milled, cross 80 mesh sieves, adding mass ratio in powder is that the PVA that 6%-10%, concentration are 5-10mol% evenly mixes as binding agent, and adopts dry-pressing formed method to be pressed into sheet sample the granulation powder obtained;
(6) dry-pressing formed sample is placed on to sintering in High Temperature Furnaces Heating Apparatus, the temperature increasing schedule that sintering adopts is as follows: adopt 3 ℃/min temperature rise rate to be warmed up to 600 ℃ from room temperature, remove PVA at 600 ℃ of insulation 2h, adopt 5 ℃/min temperature rise rate to be warmed up to 1200-1400 ℃ and be incubated 4h from 600 ℃, last furnace cooling is to room temperature.
Embodiment six
(1) according to CaWO
4-0.25CeTi
3o
8the analytically pure powder CaCO of formula weighing
3, CeO
2, TiO
2, WO
3,and powder is put into to ball grinder, and add deionized water by powder and deionized water quality than 1:2, add ball milling stone, ball milling four hours by powder and ball milling stone mass ratio 1:3;
(2) mixture after ball milling is put to drying in oven, obtain the dry powder body, powder rear mistake 80 mesh sieves of milling;
(3) by the fine powder body obtained of step (2) at 900-1100 ℃ of pre-burning 2-5h;
(4) by the ball milling oven dry again of the powder after pre-burning;
(5) after the powder after drying is milled, cross 80 mesh sieves, adding mass ratio in powder is that the PVA that 6%-10%, concentration are 5-10mol% evenly mixes as binding agent, and adopts dry-pressing formed method to be pressed into sheet sample the granulation powder obtained;
(6) dry-pressing formed sample is placed on to sintering in High Temperature Furnaces Heating Apparatus, the temperature increasing schedule that sintering adopts is as follows: adopt 3 ℃/min temperature rise rate to be warmed up to 600 ℃ from room temperature, remove PVA at 600 ℃ of insulation 2h, adopt 5 ℃/min temperature rise rate to be warmed up to 1200-1400 ℃ and be incubated 4h from 600 ℃, last furnace cooling is to room temperature.
Embodiment seven
(1) according to CaWO
4-0.5CeTi
1o
4the analytically pure powder CaCO of formula weighing
3, CeO
2, TiO
2, WO
3,and powder is put into to ball grinder, and add deionized water by powder and deionized water quality than 1:2, add ball milling stone, ball milling four hours by powder and ball milling stone mass ratio 1:3;
(2) mixture after ball milling is put to drying in oven, obtain the dry powder body, powder rear mistake 80 mesh sieves of milling;
(3) by the fine powder body obtained of step (2) at 900-1100 ℃ of pre-burning 2-5h;
(4) by the ball milling oven dry again of the powder after pre-burning;
(5) after the powder after drying is milled, cross 80 mesh sieves, adding mass ratio in powder is that the PVA that 6%-10%, concentration are 5-10mol% evenly mixes as binding agent, and adopts dry-pressing formed method to be pressed into sheet sample the granulation powder obtained;
(6) dry-pressing formed sample is placed on to sintering in High Temperature Furnaces Heating Apparatus, the temperature increasing schedule that sintering adopts is as follows: adopt 3 ℃/min temperature rise rate to be warmed up to 600 ℃ from room temperature, remove PVA at 600 ℃ of insulation 2h, adopt 5 ℃/min temperature rise rate to be warmed up to 1200-1400 ℃ and be incubated 4h from 600 ℃, last furnace cooling is to room temperature.
Embodiment eight
(1) according to CaWO
4-0.5CeTi
2o
6the analytically pure powder CaCO of formula weighing
3, CeO
2, TiO
2, WO
3,and powder is put into to ball grinder, and add deionized water by powder and deionized water quality than 1:2, add ball milling stone, ball milling four hours by powder and ball milling stone mass ratio 1:3;
(2) mixture after ball milling is put to drying in oven, obtain the dry powder body, powder rear mistake 80 mesh sieves of milling;
(3) by the fine powder body obtained of step (2) at 900-1100 ℃ of pre-burning 2-5h;
(4) by the ball milling oven dry again of the powder after pre-burning;
(5) after the powder after drying is milled, cross 80 mesh sieves, adding mass ratio in powder is that the PVA that 6%-10%, concentration are 5-10mol% evenly mixes as binding agent, and adopts dry-pressing formed method to be pressed into sheet sample the granulation powder obtained;
(6) dry-pressing formed sample is placed on to sintering in High Temperature Furnaces Heating Apparatus, the temperature increasing schedule that sintering adopts is as follows: adopt 3 ℃/min temperature rise rate to be warmed up to 600 ℃ from room temperature, remove PVA at 600 ℃ of insulation 2h, adopt 5 ℃/min temperature rise rate to be warmed up to 1200-1400 ℃ and be incubated 4h from 600 ℃, last furnace cooling is to room temperature.
Embodiment nine
(1) according to CaWO
4-0.5CeTi
3o
8the analytically pure powder CaCO of formula weighing
3, CeO
2, TiO
2, WO
3,and powder is put into to ball grinder, and add deionized water by powder and deionized water quality than 1:2, add ball milling stone, ball milling four hours by powder and ball milling stone mass ratio 1:3;
(2) mixture after ball milling is put to drying in oven, obtain the dry powder body, powder rear mistake 80 mesh sieves of milling;
(3) by the fine powder body obtained of step (2) at 900-1100 ℃ of pre-burning 2-5h;
(4) by the ball milling oven dry again of the powder after pre-burning;
(5) after the powder after drying is milled, cross 80 mesh sieves, adding mass ratio in powder is that the PVA that 6%-10%, concentration are 5-10mol% evenly mixes as binding agent, and adopts dry-pressing formed method to be pressed into sheet sample the granulation powder obtained;
(6) dry-pressing formed sample is placed on to sintering in High Temperature Furnaces Heating Apparatus, the temperature increasing schedule that sintering adopts is as follows: adopt 3 ℃/min temperature rise rate to be warmed up to 600 ℃ from room temperature, remove PVA at 600 ℃ of insulation 2h, adopt 5 ℃/min temperature rise rate to be warmed up to 1200-1400 ℃ and be incubated 4h from 600 ℃, last furnace cooling is to room temperature.
Embodiment ten
(1) according to CaWO
4-0.33CeTi
1o
4the analytically pure powder CaCO of formula weighing
3, CeO
2, TiO
2, WO
3,and powder is put into to ball grinder, and add deionized water by powder and deionized water quality than 1:2, add ball milling stone, ball milling four hours by powder and ball milling stone mass ratio 1:3;
(2) mixture after ball milling is put in case and dried, obtain the dry powder body, powder rear mistake 80 mesh sieves of milling;
(3) by the fine powder body obtained of step (2) at 900-1100 ℃ of pre-burning 2-5h;
(4) by the ball milling oven dry again of the powder after pre-burning;
(5) after the powder after drying is milled, cross 80 mesh sieves, adding mass ratio in powder is that the PVA that 6%-10%, concentration are 5-10mol% evenly mixes as binding agent, and adopts dry-pressing formed method to be pressed into sheet sample the granulation powder obtained;
(6) dry-pressing formed sample is placed on to sintering in High Temperature Furnaces Heating Apparatus, the temperature increasing schedule that sintering adopts is as follows: adopt 3 ℃/min temperature rise rate to be warmed up to 600 ℃ from room temperature, remove PVA at 600 ℃ of insulation 2h, adopt 5 ℃/min temperature rise rate to be warmed up to 1200-1400 ℃ and be incubated 4h from 600 ℃, last furnace cooling is to room temperature.
Embodiment 11
(1) according to CaWO
4-0.33CeTi
2o
6the analytically pure powder CaCO of formula weighing
3, CeO
2, TiO
2, WO
3,and powder is put into to ball grinder, and add deionized water by powder and deionized water quality than 1:2, add ball milling stone, ball milling four hours by powder and ball milling stone mass ratio 1:3;
(2) mixture after ball milling is put in case and dried, obtain the dry powder body, powder rear mistake 80 mesh sieves of milling;
(3) by the fine powder body obtained of step (2) at 900-1100 ℃ of pre-burning 2-5h;
(4) by the ball milling oven dry again of the powder after pre-burning;
(5) after the powder after drying is milled, cross 80 mesh sieves, adding mass ratio in powder is that the PVA that 6%-10%, concentration are 5-10mol% evenly mixes as binding agent, and adopts dry-pressing formed method to be pressed into sheet sample the granulation powder obtained;
(6) dry-pressing formed sample is placed on to sintering in High Temperature Furnaces Heating Apparatus, the temperature increasing schedule that sintering adopts is as follows: adopt 3 ℃/min temperature rise rate to be warmed up to 600 ℃ from room temperature, remove PVA at 600 ℃ of insulation 2h, adopt 5 ℃/min temperature rise rate to be warmed up to 1200-1400 ℃ and be incubated 4h from 600 ℃, last furnace cooling is to room temperature.
(1) according to CaWO
4-0.33CeTi
3o
8the analytically pure powder CaCO of formula weighing
3, CeO
2, TiO
2, WO
3,and powder is put into to ball grinder, and add deionized water by powder and deionized water quality than 1:2, add ball milling stone, ball milling four hours by powder and ball milling stone mass ratio 1:3;
(2) mixture after ball milling is put in case and dried, obtain the dry powder body, powder rear mistake 80 mesh sieves of milling;
(3) by the fine powder body obtained of step (2) at 900-1100 ℃ of pre-burning 2-5h;
(4) by the ball milling oven dry again of the powder after pre-burning;
(5) after the powder after drying is milled, cross 80 mesh sieves, adding mass ratio in powder is that the PVA that 6%-10%, concentration are 5-10mol% evenly mixes as binding agent, and adopts dry-pressing formed method to be pressed into sheet sample the granulation powder obtained;
(6) dry-pressing formed sample is placed on to sintering in High Temperature Furnaces Heating Apparatus, the temperature increasing schedule that sintering adopts is as follows: adopt 3 ℃/min temperature rise rate to be warmed up to 600 ℃ from room temperature, remove PVA at 600 ℃ of insulation 2h, adopt 5 ℃/min temperature rise rate to be warmed up to 1200-1400 ℃ and be incubated 4h from 600 ℃, last furnace cooling is to room temperature.
NTC thermal sensitive ceramics lamellar body prepared by the present invention, adopt silk screen print method to print electrode in both ends of the surface.Adopt the Different electrodes slurry, the thermistor temperature detecting interval is not identical yet, and the highest thermometric temperature of high temperature silver electrode can reach 800 ℃, and the highest thermometric temperature of platinum electrode can reach 1000 ℃.The present invention adopts high temperature silver slurry and the high temperature resistant electrode of platinum slurry preparation.It is as follows that silk screen printing prepares high temperature resistant electrode process: 1) the thermosensitive resistor film both ends of the surface are removed to surperficial burr with sand papering; 2), by the ultrasonic washing of thermosensitive resistor film 10 minutes, dry; 3) adopt silk screen print method at the uniform electrode slurry of both ends of the surface printing a layer thickness (high temperature silver slurry or platinum slurry), dry 80 ℃ of bake out temperatures in baking oven; 4) burn electrode, while adopting high temperature silver slurry, electrode burning infiltration temperature increasing schedule is as follows: 2-5 ℃/min is warmed up to 850 ℃ from room temperature, 850 ℃ of insulation 10-20min, furnace cooling.Adopt the high temperature resistant electrode of platinum slurry preparation to burn the electrode temperature increasing schedule as follows: 2-5 ℃/min is warmed up to 1100 ℃ from room temperature, 1100 ℃ of insulation 10-20min, furnace cooling.
The high-temperature NTC heat-sensitive resistance of embodiment bis-, five, seven, ten, 11,12 preparations adopts high temperature silver slurry preparation silver electrode, and the electrical property of sample in 40-800 ℃ of temperature range as shown in Figure 2,3.All samples all have good linearity at whole temperature range internal resistance rate temperature curve, and resistivity is from 10
9-10
6Ω cm drops to 10
4-10
2Ω cm, in the time of 600 ℃, the temperature sensitivity coefficient of all samples all is greater than 0.7%, and such material meets the condition of high temperature NTC test.Room temperature resistivity and material constant value can be controlled by Ce, Ti content simultaneously, and room temperature resistivity is 5.642 * 10
6-1.982 * 10
9Ω cm changes, and material constant can change in 5077-7275K.High temperature NTC thermo-sensitive material prepared by the present invention is suitable for temperature survey in room temperature to 1000 ℃ temperature range.
As shown in Figure 4, the material principal crystalline phase of the thermistor of embodiment of the present invention five preparation is the sheelite phase, regulates the phase composite that the x value can regulation system.Scheelite-type structure has pyrochemistry stable performance characteristics.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (6)
1. the preparation method of a high temperature negative temperature coefficient heat-sensitive resistance material, is characterized in that, comprises the following steps:
(1) according to CaWO
4-xCeTi
yo
2y+2the analytically pure powder CaCO of formula weighing
3, CeO
2, TiO
2, WO
3,and powder is put into to ball grinder, and add deionized water, make ball-milling medium with the zirconium ball, ball milling four hours, mix powder, wherein 0.2≤x≤0.5,1≤y≤3;
(2) mixture after ball milling is placed on to drying in oven, obtains the dry powder body, powder rear mistake 80 mesh sieves of milling;
(3) powder step (2) obtained carries out pre-burning;
(4) by the ball milling oven dry again of the powder after pre-burning;
(5) after the powder after drying is milled, cross 80 mesh sieves, adding mass ratio in powder is that the PVA that 6%-10%, concentration are 5-10mol% evenly mixes as binding agent, and adopts dry-pressing formed method to be pressed into sheet sample the granulation powder obtained;
(6) dry-pressing formed sample is placed on to sintering in High Temperature Furnaces Heating Apparatus.
2. preparation method according to claim 1, it is characterized in that: the mass ratio of the deionized water described in step (1) and powder is 1:2, the mass ratio of powder and ball-milling medium is 1:3.
3. preparation method according to claim 1, it is characterized in that: the oven dry described in step (2) is dry 8 h in 90 ℃ of baking ovens.
4. preparation method according to claim 1, it is characterized in that: the pre-burning system described in step (3) is: be warmed up to 900-1100 ℃ of certain temperature value with 5 ℃/min from room temperature, insulation 2-5 h, furnace cooling.
5. preparation method according to claim 1 is characterized in that: in step (4), ball milling condition is identical with step (1), and drying condition is identical with step (2).
6. preparation method according to claim 1 is characterized in that: to be the pressure that adopts 180 MPa be pressed into diameter by granulation powder to the dry-pressing formed method in step (5) is the slice of cylinder that 10 mm thickness are 2-3 mm.
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| CN111533552B (en) * | 2020-05-12 | 2021-02-23 | 中南大学 | TiO 22NTC-based thermistor material and preparation method thereof |
| CN112851335B (en) * | 2021-02-19 | 2022-08-19 | 中国科学院新疆理化技术研究所 | Perovskite-like base composite high-temperature thermistor material and preparation method thereof |
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