CN108863346A - A kind of NTC thermal sensitive ceramic material and the preparation method and application thereof of novel high B value - Google Patents

A kind of NTC thermal sensitive ceramic material and the preparation method and application thereof of novel high B value Download PDF

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CN108863346A
CN108863346A CN201810819102.4A CN201810819102A CN108863346A CN 108863346 A CN108863346 A CN 108863346A CN 201810819102 A CN201810819102 A CN 201810819102A CN 108863346 A CN108863346 A CN 108863346A
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赵景畅
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Yunnan University YNU
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Abstract

The invention discloses a kind of NTC thermal sensitive ceramic materials and the preparation method and application thereof of novel high B value, and the raw material of the NTC thermal sensitive ceramic material includes XCu3Ti4O12, the X is one of Ca, Sr, Ba or a variety of.The present invention is by the way that by the preparation applied to NTC thermal sensitive ceramic material of perovskite-like structure material creativeness, not only simple process, raw material are easy to get, and effectively increase the B value of NTC ceramic element, reach 6000 ~ 9000K.

Description

A kind of NTC thermal sensitive ceramic material and the preparation method and application thereof of novel high B value
Technical field
The invention belongs to thermo-sensitive material technical fields, and in particular to a kind of using perovskite-like structure material as the novel height of base NTC thermal sensitive ceramic material of B value and the preparation method and application thereof.
Background technique
Resistance is known as thermal sensitive ceramics with the ceramic material that significant changes occur for temperature, and wherein resistivity is in operating temperature range It is interior to be reduced to thermistor NTCR with temperature increase（Negative Temperature Coefficient Resistor）.As electronic equipment develops towards the directions such as miniaturization, slimming, integrated, highly sensitive NTC temperature-sensitive electricity Resistance material has been a concern.This kind of semiconductive ceramic has special resistance v. temperature, and current-voltage and current-vs-time are special Property, it can be made as multiple sensors element, for temperature detection, inhibition surge current, temperature-compensating etc., be widely used in leading to News, medical treatment, automobile, electronic equipment and household electrical appliance etc. occupy the biggish market share in Thermosensor field.Its In, rise using with environment temperature, the resistance-temperature characteristics that the resistance of element exponentially declines, by turning the variation of resistance Become signal output, can be used to high-precision temperature measurement.In addition, for high-power electric appliance, such as Switching Power Supply, motor, change Depressor or mains lighting supply etc. are being connected instantaneously, and biggish surge current can be generated, and are entered at room temperature by series connection for high resistance NTC thermistor, so that starting current is inhibited, effective protection core component.Meanwhile utilizing its current-voltage and electricity Stream-time response, self-heating will be such that the temperature of NTC thermistor device increases and resistance decline, and electric current gradually increases in circuit, reaches To normal operating condition.
NTC thermistor material is Mn-Co-Ni-Cu-Fe system transition metal oxide mostly at present, mostly uses raw material mixed High temperature solid-phase sintering is prepared after conjunction.B constant is generallyd use to characterize its sensitivity to temperature of NTC thermistor, Value is defined as：.The B value of mainstream NTC thermistor product is 2000 ~ 5000K both at home and abroad at present.High B value then can be mentioned further The sensitivity and measurement accuracy of high negative tempperature coefficient thermistor.But there is material in existing NTC thermistor material mostly The disadvantages of system is complex, and cost of material is higher, and B constant is lower and problem.Meanwhile existing CCTO ceramics are mainly situated between in electricity It is studied and is applied in terms of material, be not used for the application report of NTC thermal sensitive ceramics.
In summary problem, it is necessary to invent a kind of using perovskite-like structure material as the high temperature NTC thermal sensitive ceramics material of base Material and preparation method thereof.
Summary of the invention
The first object of the present invention is to provide a kind of NTC thermal sensitive ceramic material of novel high B value, and the second purpose is to mention For a kind of preparation method of the NTC thermal sensitive ceramic material of novel high B value, third is designed to provide a kind of NTC of novel high B value The application of thermal sensitive ceramic material.
The first object of the present invention is achieved in that the raw material of the NTC thermal sensitive ceramic material includes XCu3Ti4O12, the X is one of Ca, Sr, Ba or a variety of.
The second object of the present invention, which is achieved in that, to be included the following steps：
1）Take the raw material and 3 ~ 6wt%（Weight ratio）After polyvinyl alcohol is uniformly mixed, is granulated, with powder compressing machine 100 ~ 300MPa pressure depresses to the disk of 10 ~ 14mm of diameter, 1 ~ 1.5mm of thickness, then with 200 DEG C/h from room temperature 1050 DEG C ~ 1100 DEG C, heat preservation sintering 4 ~ 10 hours in air atmosphere；
2）The ceramic upper and lower surface that sintering obtains is polished, polished, is cleaned by ultrasonic, silver electrode paste is then coated with, with 200 ~ 250 DEG C/h is warming up to 850 ~ 900 DEG C, keeps the temperature 15 ~ 30 minutes, forms surface electrode.
The third object of the present invention is achieved in that the NTC thermal sensitive ceramic material of the novel high B value is examined in temperature The application surveyed component, surge current component, temperature-compensating component is inhibited to prepare.
The third object of the present invention is achieved in that the NTC thermal sensitive ceramic material of the novel high B value in NTC heat Application in quick resistance preparation.
Compared with prior art, beneficial effects of the present invention：
1, the present invention is by by the preparation applied to NTC thermal sensitive ceramic material of perovskite-like structure material creativeness, not only work Skill is simple, and raw material is easy to get, and effectively increases the B value of NTC ceramic element, reaches 6000 ~ 9000K.
2, obtained high B value NTC thermal sensitive ceramic material of the invention effectively increases and improves the sensitive of NTC thermistor Degree and measurement accuracy.
3, NTC thermistor of the invention is prepared using the NTC thermal sensitive ceramic material of the perovskite-like structure, Using multi-laminate slice structure, thermo-sensitive material and interior electrode are subjected to lamination, form the series and parallel of interlayer structure, and pass through control Preparative layer spacing and the number of plies etc. can get the high B value with different room temperature resistances, highly sensitive thermal-sensitive electric resistance device, and different The application range of NTC device is effectively expanded in the combination of the thermistor of performance parameter.
Detailed description of the invention
Fig. 1 is process flow chart of the invention；
Fig. 2 is using Regaku D/max IIIB X-ray diffractometer（Cu target）Analysis measurement CaCu3Ti4O12Ceramic material X-ray diffraction pattern, the material has cubic phase perovskite-like structure at room temperature as shown in Figure 2；
Fig. 3 is using Regaku D/max IIIB X-ray diffractometer（Cu target）Analysis measurement SrCu3Ti4O12Ceramic material X-ray diffraction pattern, the material has cubic phase perovskite-like structure at room temperature as shown in Figure 3；
Fig. 4 is to measure resulting CaCu using four probe method3Ti4O12The NTCR performance map of ceramics；Measure temperature range：Room temperature ~ 500 DEG C, the B value of the NTC ceramic element of preparation is 6000 ~ 9000K；
Fig. 5 is to measure resulting SrCu using four probe method3Ti4O12The NTCR performance map of ceramics；Measure temperature range：Room temperature ~ 500 DEG C, the B value of the NTC ceramic element of preparation is 6000 ~ 9000K；
Fig. 6 is NTC thermistor multi-laminate chip structure chart.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is further illustrated, but is not subject in any way to the present invention Limitation, based on present invention teach that it is made it is any transform or replace, all belong to the scope of protection of the present invention.
The raw material of the NTC thermal sensitive ceramic material of novel high B value of the present invention includes XCu3Ti4O12, the X is One of Ca, Sr, Ba or a variety of.
The XCu3Ti4O12For CaCu3Ti4O12, the CaCu3Ti4O12Preparation method be sol-gel method, tool Body is that preparation molar ratio is 1：3：4 calcium nitrate, copper nitrate and butyl titanate, first dissolves in anhydrous second for calcium nitrate and copper nitrate It in pure and mild distilled water, stirs, is allowed to form homogeneous solution A；Butyl titanate is dissolved in dehydrated alcohol again, uses magnetic Power blender is sufficiently stirred 10 ~ 30 minutes, is evenly distributed on butyl titanate in dehydrated alcohol, forms homogeneous B liquid；Then, Under violent stirring, solution A is slowly instilled in solution B, and distilled water is added and glacial acetic acid is added dropwise, adjusts the PH of solution It is worth to 2 ~ 3；It is sufficiently stirred 0.5 ~ 1.0 hour, obtains the colloidal sol of blue, gel is formed after standing 1 ~ 2 day, then in 70 ~ 85 In DEG C baking oven it is dry after obtain blue xerogel presoma, xerogel presoma is put into high temperature furnace, with 200 DEG C/h from room Temperature is warming up to 900 ~ 950 DEG C, and keeps the temperature 4 ~ 8 hours, and CaCu is obtained after furnace cooling3Ti4O12Powder.
The XCu3Ti4O12For CaCu3Ti4O12, the CaCu3Ti4O12Preparation method be solid-phase synthesis, tool Body is with CaCO3, CuO and TiO2Powder is raw material, with electronic balance with CaCO3, CuO and TiO2Molar ratio 1:3:4 weighings are mixed Merge to initial CuO excessive 2 ~ 5%（Molar ratio）To compensate the loss in calcination process, mixed powder is placed on agate It is fully ground in mortar 48 ~ 72 hours, wherein expecting：Ball：Ethyl alcohol mass ratio=1:2:1, then dried in 70 ~ 85 DEG C of drying boxes, And powder of the drying after finely ground is put into crucible, with 200 DEG C/h from room temperature to 900 ~ 950 DEG C, and it is small to keep the temperature 8 ~ 12 When, obtain kermesinus CaCu3Ti4O12Powder.
The XCu3Ti4O12For Sr Cu3Ti4O12, the Sr Cu3Ti4O12Preparation method be sol-gel method, Specially preparing molar ratio is 1：3：4 strontium carbonate, copper nitrate and butyl titanate first dissolves in strontium carbonate and copper nitrate anhydrous It in ethyl alcohol and distilled water, stirs, is allowed to form homogeneous solution A；Butyl titanate is dissolved in dehydrated alcohol again, is used Magnetic stirring apparatus is sufficiently stirred 10 ~ 30 minutes, is evenly distributed on butyl titanate in dehydrated alcohol, forms homogeneous B liquid；With Afterwards, under violent stirring, solution A is slowly instilled in solution B, and distilled water is added and glacial acetic acid is added dropwise, adjusts solution PH value to 2 ~ 3；It is sufficiently stirred 0.5 ~ 1.0 hour, obtains the colloidal sol of blue, gel is formed after standing 1 ~ 2 day, then in 70 In ~ 85 DEG C of baking ovens it is dry after obtain blue xerogel presoma, xerogel presoma is put into high temperature furnace, with 200 DEG C/h from Room temperature keeps the temperature 4 ~ 8 hours to 900 ~ 950 DEG C, and SrCu is obtained after furnace cooling3Ti4O12Powder.
The XCu3Ti4O12For SrCu3Ti4O12, the CaCu3Ti4O12Preparation method be solid-phase synthesis, tool Body is with SrCO3, CuO and TiO2Powder is raw material, with electronic balance with SrCO3, CuO and TiO2Molar ratio 1:3:4 weighings are mixed Merge to initial CuO excessive 2 ~ 5%（Molar ratio）To compensate the loss in calcination process, mixed powder is placed on agate It is fully ground in tank 48 ~ 72 hours, wherein expecting：Ball：Ethyl alcohol mass ratio=1:2:1, then dried in 70 ~ 85 DEG C of drying boxes, and Powder of the drying after finely ground is put into crucible, with 200 DEG C/h from room temperature to 900 ~ 950 DEG C, and it is small to keep the temperature 8 ~ 12 When, obtain kermesinus SrCu3Ti4O12Powder.
The preparation method of the NTC thermal sensitive ceramic material of novel high B value of the present invention, includes the following steps：
1）Take the raw material and 3 ~ 6wt%（Weight ratio）After polyvinyl alcohol is uniformly mixed, is granulated, with powder compressing machine 100 ~ 300MPa pressure depresses to the disk of 10 ~ 14mm of diameter, 1 ~ 1.5mm of thickness, then with 200 DEG C/h from room temperature 1050 DEG C ~ 1100 DEG C, heat preservation sintering 4 ~ 10 hours in air atmosphere；
2）The ceramic upper and lower surface that sintering obtains is polished, polished, is cleaned by ultrasonic, silver electrode paste is then coated with, with 200 ~ 250 DEG C/h is warming up to 850 ~ 900 DEG C, keeps the temperature 15 ~ 30 minutes, forms surface electrode.
The NTC thermal sensitive ceramic material of the novel high B value temperature detection component, inhibit surge current component, Application in the preparation of temperature-compensating component.
Application of the NTC thermal sensitive ceramic material of the novel high B value in NTC thermistor preparation.
The NTC thermistor is prepared using multi-laminate slice structure, and preparation method is by the NTC temperature-sensitive Material and interior electrode carry out lamination, form the series and parallel of interlayer structure, interlamellar spacing is 1 ~ 10 μm and the number of plies is 100 ~ 500 layers.
The lamination is that NTC heat-sensitive material layer is formed using casting technology, and silk-screen printing makes internal electrode layer.Described Termination electrode also uses silk-screen printing to make to obtain.
Embodiment 1
CaCu3Ti4O12The preparation of powder：Using sol-gel technology, 11.9268g calcium nitrate is weighed（0.05mol, purity >= 99%）It is dissolved in 100ml dehydrated alcohol with 36.422g copper nitrate (0.15mol, purity >=99%), 20ml distilled water is added, sufficiently It stirs evenly, is allowed to form homogeneous solution A；Claim the butyl titanate of 68.0720g again（0.2mol, purity >=98%）It dissolves in In the dehydrated alcohol of 100mL, it is sufficiently stirred 30 minutes with magnetic stirring apparatus, butyl titanate is made to be evenly distributed on dehydrated alcohol In, B liquid is formed, then 20ml glacial acetic acid is added drop-wise in B liquid, to prevent from precipitating during solution A is added dropwise；Most Afterwards, under violent stirring, solution A is slowly instilled in solution B, and distilled water is added, adjusts the pH value of solution to 3.Through It is sufficiently stirred 1 hour, obtains the colloidal sol of blue, form gel after standing 1 day, then obtain blue after drying in 70 DEG C of baking ovens Xerogel presoma.Xerogel presoma is put into high temperature furnace, with 200 DEG C/h from room temperature to 900 DEG C, and keeps the temperature 4h, with CaCu is obtained after furnace is cooling3Ti4O12Powder.
The preparation of NTC thermal sensitive ceramic material：The CaCu that will be obtained3Ti4O12Polycrystal powder is uniformly mixed with 5wt% polyvinyl alcohol After closing, being granulated, the disk of 10 ~ 14mm of diameter, 1 ~ 1.5mm of thickness are depressed in 100MPa pressure with powder compressing machine；Then with 200 DEG C/h is from room temperature to 1050 DEG C, heat preservation sintering 4h in air atmosphere；The ceramic upper and lower surface that sintering obtains is beaten Mill, polishing, ultrasonic cleaning, are then coated with silver electrode paste, are warming up to 850 DEG C with 250 DEG C/h, keep the temperature 15 minutes, form surface Electrode.
Using Regaku D/max IIIB X-ray diffractometer（Cu target）Analysis measures the CaCu of above-mentioned preparation3Ti4O12Pottery The x-ray diffraction pattern of ceramic material such as Fig. 2, the material has cubic phase perovskite-like knot at room temperature as shown in Figure 2 Structure.
Resulting CaCu is measured using four probe method3Ti4O12NTCR performance such as Fig. 4 of ceramics；Measure temperature range：Room temperature ~ 500 DEG C, such as scheme, the B value of the NTC ceramic element of preparation is 6000 ~ 9000K.
The application of NTC thermal sensitive ceramic material produced above in NTC thermistor preparation.The NTC thermistor It is prepared using multi-laminate slice structure, preparation method is that the NTC thermo-sensitive material and interior electrode are carried out lamination（Curtain coating Technology forms NTC heat-sensitive material layer, and silk-screen printing makes electrode layer）, form the series and parallel of interlayer structure, interlamellar spacing be 1 μm and The number of plies is 100 layers.The termination electrode also uses silk-screen printing to make to obtain.Resulting NTC thermistor multi-laminate chip knot Structure schematic diagram such as Fig. 6.
Embodiment 2
SrCu3Ti4O12The preparation of powder：Using sol-gel technology, 7.4580g strontium carbonate is weighed（0.05mol, purity >= 99%）With 36.422g copper nitrate (0.15mol, purity >=99%), 100ml distilled water and 20ml nitric acid is added, is sufficiently stirred It is even, it is allowed to form homogeneous solution A.Claim the butyl titanate of 68.0720g again（0.2mol, purity >=98%）Dissolve in the nothing of 100mL It in water-ethanol, is sufficiently stirred 30 minutes with magnetic stirring apparatus, is evenly distributed on butyl titanate in dehydrated alcohol, form B liquid. Finally, solution A is slowly instilled in solution B under violent stirring.It is sufficiently stirred 1 hour, obtains the colloidal sol of blue, Gel is formed after standing 1 day, then obtains blue xerogel presoma after drying in 70 DEG C of baking ovens.Xerogel presoma is put Enter high temperature furnace, with 200 DEG C/h from room temperature to 925 DEG C, and keeps the temperature 4h, SrCu is obtained after furnace cooling3Ti4O12Powder.
The preparation of NTC thermal sensitive ceramic material：The SrCu that will be obtained3Ti4O12Polycrystal powder is uniformly mixed with 5wt% polyvinyl alcohol After closing, being granulated, the disk of 10 ~ 14mm of diameter, 1 ~ 1.5mm of thickness are depressed in 100MPa pressure with powder compressing machine；Then with 200 DEG C/h is from 1050 DEG C of room temperature, heat preservation sintering 4h in air atmosphere；The ceramic upper and lower surface that sintering obtains is beaten Mill, polishing, ultrasonic cleaning, are then coated with silver electrode paste, are warming up to 850 DEG C with 250 DEG C/h, keep the temperature 15 minutes, form surface Electrode.
Using Regaku D/max IIIB X-ray diffractometer（Cu target）Analysis measures the SrCu of above-mentioned preparation3Ti4O12Pottery The x-ray diffraction pattern of ceramic material such as Fig. 3, the material has cubic phase perovskite-like knot at room temperature as shown in Figure 3 Structure.
Resulting SrCu is measured using four probe method3Ti4O12NTCR performance such as Fig. 5 of ceramics；Measure temperature range：Room temperature ~ 500 DEG C, the B value of the NTC ceramic element of preparation is 6000 ~ 9000K.
Embodiment 3
CaCu3Ti4O12The preparation of powder：Using process for solid phase synthesis, with CaCO3, CuO and TiO2Powder is raw material, is closed by solid phase At 200gCaCu3Ti4O12（Molecular weight 614.1768）It calculates, with electronic balance with molar ratio 1:3:4 weigh mixing and to initial CuO excessive 2% to compensate the loss in calcination process（32.9224gCaCO3, purity >=99%；80.0688gCuO purity >= 99%；105.6195g TiO2, purity >=98.5%）.Mixed powder is placed in agate pot and is fully ground 48 hours（Material： Ball：Ethyl alcohol mass ratio=1:2:1）, it is then dried in 75 DEG C of drying boxes, and powder of the drying after finely ground is put into crucible, with 200 DEG C/h keeps the temperature 8h from room temperature to 900 DEG C, obtains kermesinus CaCu3Ti4O12Powder.
The preparation of NTC thermal sensitive ceramic material：The CaCu that will be obtained3Ti4O12Polycrystal powder is uniformly mixed with 5wt% polyvinyl alcohol After closing, being granulated, the disk of 10 ~ 14mm of diameter, 1 ~ 1.5mm of thickness are depressed in 100MPa pressure with powder compressing machine；Then with 200 DEG C/h is from 1050 DEG C of room temperature, heat preservation sintering 4h in air atmosphere；The ceramic upper and lower surface that sintering obtains is beaten Mill, polishing, ultrasonic cleaning, are then coated with silver electrode paste, are warming up to 850 DEG C with 250 DEG C/h, keep the temperature 15 minutes, form surface Electrode.
The application of NTC thermal sensitive ceramic material produced above in NTC thermistor preparation.The NTC thermistor It is prepared using multi-laminate slice structure, preparation method is that the NTC thermo-sensitive material and interior electrode are carried out lamination（Curtain coating Technology forms NTC heat-sensitive material layer, and silk-screen printing makes electrode layer）, the series and parallel of interlayer structure is formed, interlamellar spacing is 10 μm And the number of plies is 500 layers.
Embodiment 4
SrCu3Ti4O12The preparation of powder：With SrCO3, CuO and TiO2Powder is raw material, by synthesis in solid state 200gSrCu3Ti4O12 （Molecular weight 664.7168）It calculates, with electronic balance with molar ratio 1:3:4 weigh mixing and to initial CuO excessive 2% with compensation Loss in calcination process（44.8676gSrCO3, purity >=99%；73.9809gCuO purity >=99%；97.5890g TiO2, Purity >=98.5%）.Mixed powder is placed in agate pot and is fully ground 48 hours（Material：Ball：Ethyl alcohol mass ratio=1:2: 1）, then dried in 75 DEG C of drying boxes, and powder of the drying after finely ground is put into crucible, with 200 DEG C/h from room temperature To 925 DEG C, and 8 ~ 12h is kept the temperature, obtains kermesinus SrCu3Ti4O12Powder.
The preparation of NTC thermal sensitive ceramic material：The SrCu that will be obtained3Ti4O12Polycrystal powder is uniformly mixed with 5wt% polyvinyl alcohol After closing, being granulated, the disk of diameter 10mm, thickness 1mm are depressed in 300MPa pressure with powder compressing machine；Then with 200 DEG C/h From 1100 DEG C of room temperature, heat preservation sintering 10h in air atmosphere；The ceramic upper and lower surface that sintering obtains is polished, is polished, Ultrasonic cleaning, is then coated with silver electrode paste, is warming up to 850 DEG C with 250 DEG C/h, keeps the temperature 15 minutes, forms surface electrode, i.e., It can.
The application of NTC thermal sensitive ceramic material produced above in NTC thermistor preparation.The NTC thermistor It is prepared using multi-laminate slice structure, preparation method is that the NTC thermo-sensitive material and interior electrode are carried out lamination（Curtain coating Technology forms NTC heat-sensitive material layer, and silk-screen printing makes electrode layer）, the series and parallel of interlayer structure is formed, interlamellar spacing is 2 μm, The number of plies is 200 layers.
Embodiment 5
A kind of NTC thermal sensitive ceramic material of novel high B value, the raw material of the NTC thermal sensitive ceramic material includes XCu3Ti4O12, The XCu3Ti4O12For CaCu3Ti4O12, the CaCu3Ti4O12Preparation method be sol-gel method, specially prepare Molar ratio is 1：3：4 calcium nitrate, copper nitrate and butyl titanate, first dissolves in dehydrated alcohol and distillation for calcium nitrate and copper nitrate Water（The volume ratio of dehydrated alcohol and distilled water is 5:1）In, it stirs, is allowed to form homogeneous solution A；Again by metatitanic acid four Butyl ester dissolves in dehydrated alcohol, is sufficiently stirred 30 minutes with magnetic stirring apparatus, butyl titanate is made to be evenly distributed on dehydrated alcohol In, form homogeneous B liquid；Then, under violent stirring, solution A is slowly instilled in solution B, and distilled water and drop is added Acetic acid on the rocks adjusts the pH value of solution to 2；It is sufficiently stirred 0.5 hour, obtains the colloidal sol of blue, formed after standing 1 day solidifying Glue then obtains blue xerogel presoma in 70 DEG C of baking ovens, xerogel presoma is put into high temperature furnace, with 200 after drying DEG C/h from room temperature to 900 DEG C, and 5 hours are kept the temperature, CaCu is obtained after furnace cooling3Ti4O12Powder.
The preparation method of the NTC thermal sensitive ceramic material of the novel high B value, includes the following steps：
1）Take the raw material and 3wt%（Weight ratio）After polyvinyl alcohol is uniformly mixed, is granulated, with powder compressing machine in 300MPa Pressure depresses to the disk of diameter 10mm, thickness 1mm, then with 200 DEG C/h from 1100 DEG C of room temperature, in air atmosphere Heat preservation sintering 10 hours；
2）The ceramic upper and lower surface that sintering obtains is polished, polished, is cleaned by ultrasonic, silver electrode paste is then coated with, with 250 DEG C/h is warming up to 900 DEG C, 30 minutes are kept the temperature, surface electrode is formed.
Application of the NTC thermal sensitive ceramic material of the novel high B value in the preparation of temperature detection component.
The B value of the resulting NTC thermal sensitive ceramic material of the present embodiment reaches 6000 ~ 8800K.
Embodiment 6
A kind of NTC thermal sensitive ceramic material of novel high B value, the raw material of the NTC thermal sensitive ceramic material includes XCu3Ti4O12, The X is one of Ca, Sr, Ba or a variety of.
The XCu3Ti4O12For CaCu3Ti4O12, the CaCu3Ti4O12Preparation method be sol-gel method, tool Body is that preparation molar ratio is 1：3：4 calcium nitrate, copper nitrate and butyl titanate, first dissolves in anhydrous second for calcium nitrate and copper nitrate It in pure and mild distilled water, stirs, is allowed to form homogeneous solution A；Butyl titanate is dissolved in dehydrated alcohol again, uses magnetic Power blender is sufficiently stirred 20 minutes, is evenly distributed on butyl titanate in dehydrated alcohol, forms homogeneous B liquid；Then, in play Under strong stirring, solution A is slowly instilled in solution B, and distilled water is added and glacial acetic acid is added dropwise, adjusts the pH value of solution extremely 3；It is sufficiently stirred 1.0 hours, obtains the colloidal sol of blue, form gel after standing 2 days, then obtained after drying in 80 DEG C of baking ovens Blue xerogel presoma is obtained, xerogel presoma is put into high temperature furnace, with 200 DEG C/h from room temperature to 950 DEG C, and Heat preservation 6 hours, obtains CaCu after furnace cooling3Ti4O12Powder.
A kind of preparation method of the NTC thermal sensitive ceramic material of novel high B value, includes the following steps：
1）Take the raw material and 6wt%（Weight ratio）After polyvinyl alcohol is uniformly mixed, is granulated, with powder compressing machine in 200MPa Pressure depresses to the disk of diameter 12mm, thickness 1.1mm, then with 200 DEG C/h from 1075 DEG C of room temperature, air atmosphere Middle heat preservation sintering 8 hours；
2）The ceramic upper and lower surface that sintering obtains is polished, polished, is cleaned by ultrasonic, silver electrode paste is then coated with, with 225 DEG C/h is warming up to 875 DEG C, 20 minutes are kept the temperature, surface electrode is formed.
The NTC thermal sensitive ceramic material of the novel high B value is inhibiting the application in the preparation of surge current component.
The B value of the resulting NTC thermal sensitive ceramic material of the present embodiment reaches 6000 ~ 8200K.
Embodiment 7
A kind of NTC thermal sensitive ceramic material of novel high B value, the raw material of the NTC thermal sensitive ceramic material includes XCu3Ti4O12, The XCu3Ti4O12For CaCu3Ti4O12, the CaCu3Ti4O12Preparation method be solid-phase synthesis, specially with CaCO3, CuO and TiO2Powder is raw material, with electronic balance with CaCO3, CuO and TiO2Molar ratio 1:3:4 weighing mixing are simultaneously right Initial CuO excessive 2%（Molar ratio）To compensate the loss in calcination process, mixed powder is put and is filled in the agate mortar Divide grinding 48 hours, wherein expecting：Ball：Ethyl alcohol mass ratio=1:2:1, then dried in 85 DEG C of drying boxes, and will it is dry it is finely ground after Powder be put into crucible, with 200 DEG C/h from room temperature to 900 DEG C, and keep the temperature 8 hours, obtain kermesinus CaCu3Ti4O12Powder.
A kind of preparation method of the NTC thermal sensitive ceramic material of novel high B value, includes the following steps：
1）Take the raw material and 4wt%（Weight ratio）After polyvinyl alcohol is uniformly mixed, is granulated, with powder compressing machine in 150MPa Pressure depresses to the disk of diameter 11mm, thickness 1.2mm, then with 200 DEG C/h from 1100 DEG C of room temperature, air atmosphere Middle heat preservation sintering 6 hours；
2）The ceramic upper and lower surface that sintering obtains is polished, polished, is cleaned by ultrasonic, silver electrode paste is then coated with, with 220 DEG C/h is warming up to 900 DEG C, 25 minutes are kept the temperature, surface electrode is formed.
Application of the NTC thermal sensitive ceramic material of the novel high B value in the preparation of temperature-compensating component.
The B value of the resulting NTC thermal sensitive ceramic material of the present embodiment reaches 5800 ~ 8600K.
Embodiment 8
A kind of NTC thermal sensitive ceramic material of novel high B value, the raw material of the NTC thermal sensitive ceramic material includes XCu3Ti4O12, The XCu3Ti4O12For CaCu3Ti4O12, the CaCu3Ti4O12Preparation method be solid-phase synthesis, specially with CaCO3, CuO and TiO2Powder is raw material, with electronic balance with CaCO3, CuO and TiO2Molar ratio 1:3:4 weighing mixing are simultaneously right Initial CuO excessive 5%（Molar ratio）To compensate the loss in calcination process, mixed powder is put and is filled in the agate mortar Divide grinding 72 hours, wherein expecting：Ball：Ethyl alcohol mass ratio=1:2:1, then dried in 70 DEG C of drying boxes, and will it is dry it is finely ground after Powder be put into crucible, with 200 DEG C/h from room temperature to 925 DEG C, and keep the temperature 10 hours, obtain kermesinus CaCu3Ti4O12Powder.
A kind of preparation method of the NTC thermal sensitive ceramic material of novel high B value, includes the following steps：
1）Take the raw material and 5wt%（Weight ratio）After polyvinyl alcohol is uniformly mixed, is granulated, with powder compressing machine in 250MPa Pressure depresses to the disk of diameter 13mm, thickness 1.3mm, then with 200 DEG C/h from 1050 DEG C of room temperature, air atmosphere Middle heat preservation sintering 9 hours；
2）The ceramic upper and lower surface that sintering obtains is polished, polished, is cleaned by ultrasonic, silver electrode paste is then coated with, with 200 DEG C/h is warming up to 900 DEG C, 28 minutes are kept the temperature, surface electrode is formed.
Application of the NTC thermal sensitive ceramic material of the novel high B value in NTC thermistor preparation.The NTC heat Quick resistance is prepared using multi-laminate slice structure, and preparation method is to fold the NTC thermo-sensitive material with interior electrode Layer, forms the series and parallel of interlayer structure, interlamellar spacing is 3 μm and the number of plies is 300 layers.The lamination is using casting technology shape At NTC heat-sensitive material layer, silk-screen printing makes internal electrode layer.
The B value of the resulting NTC thermal sensitive ceramic material of the present embodiment reaches 6200 ~ 8900K.
Embodiment 9
A kind of NTC thermal sensitive ceramic material of novel high B value, the raw material of the NTC thermal sensitive ceramic material includes XCu3Ti4O12, The XCu3Ti4O12For Sr Cu3Ti4O12, the Sr Cu3Ti4O12Preparation method be sol-gel method, it is specific subject to Standby molar ratio is 1：3：4 strontium carbonate, copper nitrate and butyl titanate, first dissolves in dehydrated alcohol and steaming for strontium carbonate and copper nitrate It in distilled water, stirs, is allowed to form homogeneous solution A；Butyl titanate is dissolved in dehydrated alcohol again, uses magnetic agitation Device is sufficiently stirred 30 minutes, is evenly distributed on butyl titanate in dehydrated alcohol, forms homogeneous B liquid；Then, it is stirred in violent It mixes down, solution A is slowly instilled in solution B, and distilled water is added and glacial acetic acid is added dropwise, adjust the pH value of solution to 3；Through filling Divide and stir 1.0 hours, obtain the colloidal sol of blue, form gel after standing 1 day, then acquisition is blue after drying in 75 DEG C of baking ovens Xerogel presoma is put into high temperature furnace by xerogel presoma, and with 200 DEG C/h from room temperature to 925 DEG C, and it is small to keep the temperature 6 When, SrCu is obtained after furnace cooling3Ti4O12Powder.
A kind of preparation method of the NTC thermal sensitive ceramic material of novel high B value, includes the following steps：
1）Take the raw material and 3wt%（Weight ratio）After polyvinyl alcohol is uniformly mixed, is granulated, with powder compressing machine in 100MPa Pressure depresses to the disk of diameter 10mm, thickness 1.5mm, then with 200 DEG C/h from 1050 DEG C of room temperature, air atmosphere Middle heat preservation sintering 7 hours；
2）The ceramic upper and lower surface that sintering obtains is polished, polished, is cleaned by ultrasonic, silver electrode paste is then coated with, with 230 DEG C/h is warming up to 850 DEG C, 15 minutes are kept the temperature, surface electrode is formed.
Application of the NTC thermal sensitive ceramic material of the novel high B value in NTC thermistor preparation.The NTC heat Quick resistance is prepared using multi-laminate slice structure, and preparation method is to fold the NTC thermo-sensitive material with interior electrode Layer, forms the series and parallel of interlayer structure, interlamellar spacing is 4 μm and the number of plies is 400 layers.The lamination is using casting technology shape At NTC heat-sensitive material layer, silk-screen printing makes internal electrode layer.
The B value of the resulting NTC thermal sensitive ceramic material of the present embodiment reaches 6000 ~ 8400K.
Embodiment 10
A kind of NTC thermal sensitive ceramic material of novel high B value, the raw material of the NTC thermal sensitive ceramic material includes XCu3Ti4O12, The XCu3Ti4O12For Sr Cu3Ti4O12, the Sr Cu3Ti4O12Preparation method be sol-gel method, it is specific subject to Standby molar ratio is 1：3：4 strontium carbonate, copper nitrate and butyl titanate, first dissolves in dehydrated alcohol and steaming for strontium carbonate and copper nitrate It in distilled water, stirs, is allowed to form homogeneous solution A；Butyl titanate is dissolved in dehydrated alcohol again, uses magnetic agitation Device is sufficiently stirred 10 minutes, is evenly distributed on butyl titanate in dehydrated alcohol, forms homogeneous B liquid；Then, it is stirred in violent It mixes down, solution A is slowly instilled in solution B, and distilled water is added and glacial acetic acid is added dropwise, adjust the pH value of solution to 2；Through filling Divide and stir 0.5 hour, obtain the colloidal sol of blue, form gel after standing 1 day, then acquisition is blue after drying in 70 DEG C of baking ovens Xerogel presoma is put into high temperature furnace by xerogel presoma, and with 200 DEG C/h from room temperature to 950 DEG C, and it is small to keep the temperature 4 When, SrCu is obtained after furnace cooling3Ti4O12Powder.
A kind of preparation method of the NTC thermal sensitive ceramic material of novel high B value, includes the following steps：
1）Take the raw material and 3wt%（Weight ratio）After polyvinyl alcohol is uniformly mixed, is granulated, with powder compressing machine in 100MPa Pressure depresses to the disk of diameter 10mm, thickness 1mm, then with 200 DEG C/h from 1050 DEG C of room temperature, in air atmosphere Heat preservation sintering 4 hours；
2）The ceramic upper and lower surface that sintering obtains is polished, polished, is cleaned by ultrasonic, silver electrode paste is then coated with, with 200 DEG C/h is warming up to 850 DEG C, 15 minutes are kept the temperature, surface electrode is formed.
Application of the NTC thermal sensitive ceramic material of the novel high B value in NTC thermistor preparation.The NTC heat Quick resistance is prepared using multi-laminate slice structure, and preparation method is to fold the NTC thermo-sensitive material with interior electrode Layer, forms the series and parallel of interlayer structure, interlamellar spacing is 5 μm and the number of plies is 500 layers.The lamination is using casting technology shape At NTC heat-sensitive material layer, silk-screen printing makes internal electrode layer.
The B value of the resulting NTC thermal sensitive ceramic material of the present embodiment reaches 6000 ~ 8200K.
Embodiment 11
A kind of NTC thermal sensitive ceramic material of novel high B value, the raw material of the NTC thermal sensitive ceramic material includes XCu3Ti4O12, The X is one of Ca, Sr, Ba or a variety of.
The XCu3Ti4O12For SrCu3Ti4O12, the CaCu3Ti4O12Preparation method be solid-phase synthesis, tool Body is with SrCO3, CuO and TiO2Powder is raw material, with electronic balance with SrCO3, CuO and TiO2Molar ratio 1:3:4 weighings are mixed Merge to initial CuO excessive 3%（Molar ratio）To compensate the loss in calcination process, mixed powder is placed on agate pot In be fully ground 48 hours, wherein expecting：Ball：Ethyl alcohol mass ratio=1:2:1, it is then dried in 70 DEG C of drying boxes, and drying is ground Powder after thin is put into crucible, with 200 DEG C/h from room temperature to 900 DEG C, and is kept the temperature 8 hours, is obtained kermesinus SrCu3Ti4O12Powder.
A kind of preparation method of the NTC thermal sensitive ceramic material of novel high B value, includes the following steps：
1）Take the raw material and 3wt%（Weight ratio）After polyvinyl alcohol is uniformly mixed, is granulated, with powder compressing machine in 200MPa Pressure depresses to the disk of diameter 10mm, thickness 1.2mm, then with 200 DEG C/h from 1050 DEG C of room temperature, air atmosphere Middle heat preservation sintering 5 hours；
2）The ceramic upper and lower surface that sintering obtains is polished, polished, is cleaned by ultrasonic, silver electrode paste is then coated with, with 240 DEG C/h is warming up to 900 DEG C, 18 minutes are kept the temperature, surface electrode is formed.
Application of the NTC thermal sensitive ceramic material of the novel high B value in NTC thermistor preparation.The NTC heat Quick resistance is prepared using multi-laminate slice structure, and preparation method is to fold the NTC thermo-sensitive material with interior electrode Layer, forms the series and parallel of interlayer structure, interlamellar spacing is 7 μm and the number of plies is 250 layers.The lamination is using casting technology shape At NTC heat-sensitive material layer, silk-screen printing makes internal electrode layer.
The B value of the resulting NTC thermal sensitive ceramic material of the present embodiment reaches 6000 ~ 9000K.
Embodiment 12
A kind of NTC thermal sensitive ceramic material of novel high B value, the raw material of the NTC thermal sensitive ceramic material includes XCu3Ti4O12, The XCu3Ti4O12For SrCu3Ti4O12, the CaCu3Ti4O12Preparation method be solid-phase synthesis, specially with SrCO3, CuO and TiO2Powder is raw material, with electronic balance with SrCO3, CuO and TiO2Molar ratio 1:3:4 weighing mixing are simultaneously right Initial CuO excessive 5%（Molar ratio）To compensate the loss in calcination process, mixed powder is placed in agate pot sufficiently Grinding 72 hours, wherein expecting：Ball：Ethyl alcohol mass ratio=1:2:1, then dried in 80 DEG C of drying boxes, and by drying it is finely ground after Powder is put into crucible, with 200 DEG C/h from room temperature to 950 DEG C, and is kept the temperature 12 hours, is obtained kermesinus SrCu3Ti4O12Powder.
A kind of preparation method of the NTC thermal sensitive ceramic material of novel high B value, includes the following steps：
1）Take the raw material and 6wt%（Weight ratio）After polyvinyl alcohol is uniformly mixed, is granulated, with powder compressing machine in 100MPa Pressure depresses to the disk of diameter 13mm, thickness 1mm, then with 200 DEG C/h from 1100 DEG C of room temperature, in air atmosphere Heat preservation sintering 10 hours；
2）The ceramic upper and lower surface that sintering obtains is polished, polished, is cleaned by ultrasonic, silver electrode paste is then coated with, with 250 DEG C/h is warming up to 900 DEG C, 25 minutes are kept the temperature, surface electrode is formed.
Application of the NTC thermal sensitive ceramic material of the novel high B value in NTC thermistor preparation.The NTC heat Quick resistance is prepared using multi-laminate slice structure, and preparation method is to fold the NTC thermo-sensitive material with interior electrode Layer, forms the series and parallel of interlayer structure, interlamellar spacing is 8 μm and the number of plies is 350 layers.The lamination is using casting technology shape At NTC heat-sensitive material layer, silk-screen printing makes internal electrode layer.
The B value of the resulting NTC thermal sensitive ceramic material of the present embodiment reaches 6000 ~ 9000K.

Claims (10)

1. a kind of NTC thermal sensitive ceramic material of novel high B value, it is characterised in that the raw material packet of the NTC thermal sensitive ceramic material Include XCu3Ti4O12, the X is one of Ca, Sr, Ba or a variety of.
2. the NTC thermal sensitive ceramic material of novel high B value according to claim 1, it is characterised in that the XCu3Ti4O12 For CaCu3Ti4O12, the CaCu3Ti4O12Preparation method be sol-gel method, specially preparation molar ratio be 1：3：4 Calcium nitrate, copper nitrate and butyl titanate, first dissolve in calcium nitrate and copper nitrate in dehydrated alcohol and distilled water, are sufficiently stirred It is even, it is allowed to form homogeneous solution A；Butyl titanate is dissolved in dehydrated alcohol again, is sufficiently stirred 10 ~ 30 points with magnetic stirring apparatus Clock is evenly distributed on butyl titanate in dehydrated alcohol, forms homogeneous B liquid；Then, under violent stirring, solution A is delayed It slowly instills in solution B, and distilled water is added and glacial acetic acid is added dropwise, adjust the pH value of solution to 2 ~ 3；It is sufficiently stirred 0.5 ~ 1.0 hours, the colloidal sol of blue is obtained, forms gel after standing 1 ~ 2 day, then obtains blue after drying in 70 ~ 85 DEG C of baking ovens Xerogel presoma is put into high temperature furnace by xerogel presoma, with 200 DEG C/h from room temperature to 900 ~ 950 DEG C, and is protected Temperature 4 ~ 8 hours, obtains CaCu after furnace cooling3Ti4O12Powder.
3. the NTC thermal sensitive ceramic material of novel high B value according to claim 1, it is characterised in that the XCu3Ti4O12 For CaCu3Ti4O12, the CaCu3Ti4O12Preparation method be solid-phase synthesis, specially with CaCO3, CuO and TiO2Powder End is raw material, with electronic balance with CaCO3, CuO and TiO2Molar ratio 1:3:4 weigh mixing and to initial CuO excessive 2 ~ 5% （Molar ratio）To compensate the loss in calcination process, mixed powder is put and is fully ground in the agate mortar 48 ~ 72 hours, Wherein expect：Ball：Ethyl alcohol mass ratio=1:2:1, it is then dried in 70 ~ 85 DEG C of drying boxes, and powder of the drying after finely ground is put into In crucible, with 200 DEG C/h from room temperature to 900 ~ 950 DEG C, and 8 ~ 12 hours is kept the temperature, obtain kermesinus CaCu3Ti4O12 Powder.
4. the NTC thermal sensitive ceramic material of novel high B value according to claim 1, it is characterised in that the XCu3Ti4O12 For SrCu3Ti4O12, the Sr Cu3Ti4O12Preparation method be sol-gel method, specially preparation molar ratio be 1：3：4 Strontium carbonate, copper nitrate and butyl titanate, first strontium carbonate and copper nitrate are dissolved in dehydrated alcohol and distilled water, are sufficiently stirred Uniformly, it is allowed to form homogeneous solution A；Butyl titanate is dissolved in dehydrated alcohol again, is sufficiently stirred 10 ~ 30 with magnetic stirring apparatus Minute, it is evenly distributed on butyl titanate in dehydrated alcohol, forms homogeneous B liquid；Then, under violent stirring, by solution A It slowly instills in solution B, and distilled water is added and glacial acetic acid is added dropwise, adjust the pH value of solution to 2 ~ 3；It is sufficiently stirred 0.5 ~ 1.0 hours, the colloidal sol of blue is obtained, forms gel after standing 1 ~ 2 day, then obtains blue after drying in 70 ~ 85 DEG C of baking ovens Xerogel presoma is put into high temperature furnace by xerogel presoma, with 200 DEG C/h from room temperature to 900 ~ 950 DEG C, and is protected Temperature 4 ~ 8 hours, obtains SrCu after furnace cooling3Ti4O12Powder.
5. the NTC thermal sensitive ceramic material of novel high B value according to claim 1, it is characterised in that the XCu3Ti4O12 For SrCu3Ti4O12, the CaCu3Ti4O12Preparation method be solid-phase synthesis, specially with SrCO3, CuO and TiO2Powder End is raw material, with electronic balance with SrCO3, CuO and TiO2Molar ratio 1:3:4 weigh mixing and to initial CuO excessive 2 ~ 5% （Molar ratio）To compensate the loss in calcination process, mixed powder is placed in agate pot and is fully ground 48 ~ 72 hours, Middle material：Ball：Ethyl alcohol mass ratio=1:2:1, it is then dried in 70 ~ 85 DEG C of drying boxes, and powder of the drying after finely ground is put into earthenware In crucible, with 200 DEG C/h from room temperature to 900 ~ 950 DEG C, and 8 ~ 12 hours is kept the temperature, obtain kermesinus SrCu3Ti4O12Powder End.
6. a kind of preparation method of the NTC thermal sensitive ceramic material of the novel high B value any according to claim 1 ~ 5, special Sign is that the preparation method includes the following steps：
1）After taking the raw material uniformly to mix, be granulated with 3 ~ 6wt% polyvinyl alcohol, pressed with powder compressing machine in 100 ~ 300MPa Power depresses to the disk of 10 ~ 14mm of diameter, 1 ~ 1.5mm of thickness, then with 200 DEG C/h from room temperature 1050 DEG C ~ 1100 DEG C, heat preservation sintering 4 ~ 10 hours in air atmosphere；
2）The ceramic upper and lower surface that sintering obtains is polished, polished, is cleaned by ultrasonic, silver electrode paste is then coated with, with 200 ~ 250 DEG C/h is warming up to 850 ~ 900 DEG C, keeps the temperature 15 ~ 30 minutes, forms surface electrode.
7. a kind of NTC thermal sensitive ceramic material of the novel high B value any according to claim 1 ~ 5 is in temperature detection member device Part, the application for inhibiting surge current component, temperature-compensating component to prepare.
8. a kind of NTC thermal sensitive ceramic material of the novel high B value any according to claim 1 ~ 5 is in NTC thermistor system Standby upper application.
9. the application of the NTC thermal sensitive ceramic material of novel high B value according to claim 8, it is characterised in that the NTC Thermistor is prepared using multi-laminate slice structure, and preparation method is to carry out the NTC thermo-sensitive material and interior electrode Lamination forms the series and parallel of interlayer structure, and interlamellar spacing is 1 ~ 10 μm and the number of plies is 100 ~ 500 layers.
10. the application of the NTC thermal sensitive ceramic material of novel high B value according to claim 9, it is characterised in that described is folded For layer to form NTC heat-sensitive material layer using casting technology, silk-screen printing makes internal electrode layer.
CN201810819102.4A 2018-07-24 2018-07-24 A kind of NTC thermal sensitive ceramic material and the preparation method and application thereof of novel high B value Pending CN108863346A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109974883A (en) * 2019-04-19 2019-07-05 济南大学 A kind of NTC temperature sensor and preparation method and application suitable for concrete temperature monitoring
CN111620689A (en) * 2020-06-08 2020-09-04 中国科学院新疆理化技术研究所 Perovskite-like high-temperature thermistor material with different A-site elements and preparation method thereof
CN112851335A (en) * 2021-02-19 2021-05-28 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
CN115849898A (en) * 2021-09-24 2023-03-28 华为技术有限公司 Thermal sensitive ceramic material, preparation method thereof and thermistor
CN116230340A (en) * 2023-03-03 2023-06-06 肇庆市金龙宝电子有限公司 High-temperature-resistant ceramic film NTC thermistor and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109974883A (en) * 2019-04-19 2019-07-05 济南大学 A kind of NTC temperature sensor and preparation method and application suitable for concrete temperature monitoring
CN109974883B (en) * 2019-04-19 2021-05-07 济南大学 NTC temperature sensor suitable for concrete temperature monitoring and preparation method and application thereof
CN111620689A (en) * 2020-06-08 2020-09-04 中国科学院新疆理化技术研究所 Perovskite-like high-temperature thermistor material with different A-site elements and preparation method thereof
CN112851335A (en) * 2021-02-19 2021-05-28 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
CN115849898A (en) * 2021-09-24 2023-03-28 华为技术有限公司 Thermal sensitive ceramic material, preparation method thereof and thermistor
CN115849898B (en) * 2021-09-24 2024-06-04 华为技术有限公司 Thermal sensitive ceramic material, preparation method thereof and thermistor
CN116230340A (en) * 2023-03-03 2023-06-06 肇庆市金龙宝电子有限公司 High-temperature-resistant ceramic film NTC thermistor and preparation method thereof
CN116230340B (en) * 2023-03-03 2024-02-13 肇庆市金龙宝电子有限公司 High-temperature-resistant ceramic film NTC thermistor and preparation method thereof

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