CN108288529B - Bear the preparation method of low ageing rate negative temperature coefficient thermistor ceramic material - Google Patents

Bear the preparation method of low ageing rate negative temperature coefficient thermistor ceramic material Download PDF

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CN108288529B
CN108288529B CN201810052930.XA CN201810052930A CN108288529B CN 108288529 B CN108288529 B CN 108288529B CN 201810052930 A CN201810052930 A CN 201810052930A CN 108288529 B CN108288529 B CN 108288529B
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temperature
ceramic material
preparation
per minute
coefficient thermistor
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CN108288529A (en
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李栋才
朱绍峰
钱尼燕
石青
刘柄辰
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Anhui University of Architecture
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Abstract

The invention discloses a kind of preparation method for bearing low ageing rate negative temperature coefficient thermistor ceramic material, the nominal chemical composition of the thermal resistor ceramic material is Mn3-x-y-zNixFeyMzO4, and M represents Cu, Ti, Sn, Al；It is to form the oxide of cation as starting material, ball milling, by repeatedly calcining, after organic binder granulating and forming is added, it fires, after being burnt into sheet sample, silver electrode in both ends of the surface, after electrode burning infiltration, the electrodeless place of sample is covered at cylinder with medium temperature glass glaze sealing-in under oxygen-enriched environment.It is 3-1000 Ω m in 25 DEG C of resistivity, the B value of 25-85 DEG C of warm area is 3000-4000K, 150 DEG C of one week ageing rates: -3.0~-0.1% by thermal resistor ceramic material prepared by the preparation process.

Description

Bear the preparation method of low ageing rate negative temperature coefficient thermistor ceramic material
Technical field
The present invention relates to the preparation field of negative temperature coefficient thermal-sensitive ceramic material, especially one kind to bear low ageing rate negative temperature The preparation method of coefficient thermal resistor ceramic material.
Background technique
Negative temperature coefficient (NTC) thermal sensitive ceramics is mainly used in thermometric, temperature-compensating and inhibits surge current.NTC at present Thermal sensitive ceramics main problem is stability problem, i.e. problem of aging.The aging of General N TC thermal sensitive ceramics is with the time used Extend, resistance value becomes larger.Chinese patent focuses mostly on about the research and development of NTC thermal sensitive ceramics and is forming variation by material at present The resistance value or B value of controlled material, as Chinese patent (CN200910060128.6, CN200710172253.7, CN200710113771.1, CN200710113773.0, CN201210182425.X) to disclose a kind of high B value of low-resistivity negative Temperature coefficient thermistor material and preparation method；Chinese patent (CN201210181462.9, CN200910013605.3, CN200910113608.4, CN 201010131358.X) disclose a kind of high resistivity and low B value negative tempperature coefficient thermistor Material and preparation method.The above invention has the NTC thermal sensitive ceramic material of p-type conductance under the conditions of normal ageing, material resistance value Become larger at any time.
Present invention is generally directed to MnNiFeO4The temperature sensitive ceramic material of base p-type, at preparation method appropriate and sealing-in heat Low ageing rate negative temperature coefficient thermistor ceramic material is born in the acquisition of science and engineering skill.General preparation method, it is normal pressure-sintered to be obtained MnNiFeO4Thermal sensitive ceramics resistivity at room temperature is in 80-500 Ω m, B value in 3000-4000K, and ageing rate Δ ρ/ρ is in 2-5%.
Summary of the invention
The purpose of the present invention is to provide a kind of preparations for bearing low ageing rate negative temperature coefficient thermistor ceramic material Method.
Above-mentioned purpose is realized by following scheme:
A kind of preparation method for bearing low ageing rate negative temperature coefficient thermistor ceramic material, thermal resistor ceramics The nominal chemical composition of material is Mn3-x-y-zNixFeyMzO4, and M represents Cu, Ti, Sn, Al, x:0.9-1.1；y:0.9-1.1； z:0.03-0.1；It is to be milled to certain fineness to form the oxide of cation as starting material, by repeatedly calcining, add It is fired under certain temperature system after certain organic binder granulating and forming, after being burnt into sheet sample, silver electricity in both ends of the surface Pole after burning electrode, covers at electrodeless place at cylinder with medium temperature glass glaze sealing-in under oxygen-enriched environment.
The preparation method for bearing low ageing rate negative temperature coefficient thermistor ceramic material, comprising the following steps:
(1) it using the oxide for forming cation as starting material, using alcohol as abrasive media, is milled under 300 meshes, obtains Powder drying after ball milling is stand-by；
(2) powder after gained ball milling is sintered into phase twice, and first time calcination temperature is 800-900 DEG C, soaking time 4-6 hours；Second calcination temperature is 950-1050 DEG C, soaking time 4-6 hour, through dry ball milling to 300 after calcining every time Under mesh；
(3) it is granulated to being sintered into the ceramic powder after phase, the use of solid content is the water-soluble of 3-10wt%PVA or CMC Liquid is granulating agent, and granulating agent dosage is 2-6wt%；
(4) dry-pressing formed, pressure 150-250MPa after being granulated；
(5) sintering processing of dry-pressing formed rear green body uses atmospheric air atmosphere, the temperature schedule of sintering are as follows: with per minute 1-1.5 DEG C is raised to 300 DEG C, keeps the temperature 1 hour；800 DEG C are raised to 2-3 DEG C per minute later, keeps the temperature 1 hour；Later with per minute 3-4 DEG C is raised to 1240-1280 DEG C, keeps the temperature 4-6 hours；850 DEG C are dropped to 1 DEG C per minute later, then is dropped with 10-20 DEG C per minute To room temperature；
(6) burn electrode: sintered sheets sample brushes silver paste, is raised to 850 DEG C with 2-3 DEG C per minute, keeps the temperature 0.5 hour, then with every 10-20 DEG C of minute drops to room temperature；
(7) it thermal resistor sealing-in: in atmosphere furnace, will be sealed at electrodeless covering with medium temperature glass glaze under oxygen-enriched environment It connects.
Wherein, described in step (7) under oxygen-enriched environment by the cylinder of electrodeless covering with cryogenic glass glaze sealing-in, In glass-glazed firing temperature at 620-680 DEG C；Oxygen-enriched environment are as follows: oxygen content 22-40%vol.
The preparation method for bearing low ageing rate negative temperature coefficient thermistor ceramic material, design principle are: institute The thermal resistor ceramic material of preparation can make the crystal boundary of sample and phase boundary director's time be in oxygen-enriched by the oxygen-enriched sealing-in of medium temperature Acceptor state, then it can balance grain boundary acceptor state to resistance variations caused by micropore diffusion in application process.
The invention has the benefit that
The present invention is by Mn3-x-y-zNixFeyMzO4 system thermal sensitive ceramics prepared by the preparation process, by oxygen-enriched Sealing-in obtains the thermal resistor material for bearing low ageing rate negative temperature coefficient；Material obtained is 3- in 25 DEG C of resistivity 1000 Ω m, the B value of 25-85 DEG C of warm area are 3000-4000K, and 150 DEG C of one week ageing rates are -3.0~-0.1%.
Specific embodiment
Embodiment 1: name group becomes Mn0.97NiFeSn0.03O4(x=1, y=1, z=0.03) bears low ageing rate negative temperature The preparation of coefficient thermal resistor ceramic material:
1, quality formula: with MnO2、Ni2O3、Fe2O3、SnO2For starting material, Mn is calculated0.97NiFeSn0.03O4Batch Quality formula are as follows:
MnO2: Ni2O3: Fe2O3:SnO2=33.53%:32.89%:31.78%:1.80%；
2, ball milling: with material: alcohol: ball=1:0.8:1.8 ratio wet ball grinding 10 hours, cross 300 meshes after, drying to With；
3, calcine twice: first time calcination temperature is 850 DEG C, soaking time 6 hours, is taken out after cooling, with material: ball=1: 300 meshes are crossed after 1.4 dry ball millings 3 hours waits for second of calcining；Second calcination temperature is 950 DEG C, soaking time 6 hours, It is taken out after cooling, with material: ball=1:1.4 dry ball milling 3 hours is crossed after 300 meshes for use；
4, be granulated: by the 5wt% of powder quality ratio, addition concentration is 10wt%PVA aqueous solution, is granulated by hand, crosses 180 mesh Sieve；
5, it forms: being formed with uniaxial tension, briquetting pressure 300MPa, Φ 8mm × (1.5~2.5) mm piece sample is made；
6, be burnt into: it seems in resistance furnace that piece sample blanks body, which is put into Elema, and sintering temperature curve is as follows:
- 300 DEG C of room temperature, 1.5 DEG C/min of heating rate；
300 DEG C -300 DEG C, keep the temperature 60min；
300 DEG C -800 DEG C, 2.5 DEG C/min of heating rate；
800 DEG C -800 DEG C, keep the temperature 60min
800 DEG C -1250 DEG C, 4 DEG C/min of heating rate；
1250 DEG C -1250 DEG C, keep the temperature 300min；
1250 DEG C -800 DEG C, 1 DEG C/min of rate of temperature fall minute；
800 DEG C-room temperature, 10 DEG C/min of rate of temperature fall minute.
7, silver ink firing: using firing temperature to coat the two sides of tile for 850 DEG C of silver paste, and silver ink firing soaking time is 30min.
8, sealing-in: in atmosphere furnace by electrodeless covering cylinder with cryogenic glass glaze sealing-in, oxygen content 30%vol, 650 DEG C of sealing temperature.
9, electric performance test: sample being placed in 25 ± 0.1 DEG C and 85 ± 0.1 DEG C of constant temperature oil baths and measures its resistance value, meter Calculate resistivity, B value, 150 DEG C of one week ageing rate Δ ρ/ρ25℃, sample tests such as table 1:
1 Mn of table0.97NiFeSn0.03O4Sample tests
Embodiment 2: name group becomes MnNiFe0.94Cu0.06O4(x=1, y=0.94, z=0.06) bears low ageing rate subzero temperature Spend the preparation of coefficient thermal resistor ceramic material:
1, the quality formula of the present embodiment thermal resistor ceramic material batch:
MnO2: Ni2O3: Fe2O3: CuO=34.84%:33.15%:30.11%:1.90%；
2, by the identical technique of 2-9 in embodiment 1, the oxygen content for only changing the step sealing-in in 8 is 22%vol, sealing-in Temperature is 620 DEG C, remaining process is all identical, prepared sample tests such as the following table 2.
2 MnNiFe of table0.94Cu0.06O44Sample tests
Embodiment 3: name group becomes Mn0.97NiFe0.94Ti0.09O4(x=1, y=0.94, z=0.09) bears low ageing rate The preparation of negative temperature coefficient thermistor ceramic material:
1, the formula of the present embodiment thermal resistor ceramic material batch:
MnO2: Ni2O3: Fe2O3: TiO2=33.51%:31.88%:30.78%:3.83%.
2, it is only changed the step in 8 by the identical technique of 2-8 in embodiment 1 by the identical technique of 2-9 in embodiment 1 is implemented The oxygen content of sealing-in is 40%vol, and sealing temperature is 640 DEG C, remaining process is all identical, sample tests such as following table 3:
3 Mn of table0.97NiFe0.94Ti0.09O4Sample tests
Embodiment 4: name group becomes MnNi0.97FeAl0.03O4(x=0.97, y=1, z=0.03) bears low ageing rate subzero temperature Spend the preparation of coefficient thermal resistor ceramic material:
1, the formula of the present embodiment thermal resistor ceramic material batch:
MnO2: Ni2O3: Fe2O3: Al2O3=30.10%:28.64%:27.65%:13.61%.
2, it is only changed the step in 8 by the identical technique of 2-8 in embodiment 1 by the identical technique of 2-9 in embodiment 1 is implemented The oxygen content of sealing-in is 25%vol, and sealing temperature is 680 DEG C, remaining process is all identical, sample tests such as following table 4:
4 MnNi of table0.97FeAl0.03O4Sample tests

Claims (3)

1. a kind of preparation method for bearing low ageing rate negative temperature coefficient thermistor ceramic material, which is characterized in that its be with The oxide of composition cation is starting material, is milled to certain fineness, by repeatedly calcining, certain organic binder is added to be granulated It is fired under certain temperature system after molding, after being burnt into sheet sample, silver electrode in both ends of the surface, after electrode burning infiltration, in richness Under oxygen environment by the cylinder of electrodeless covering with medium temperature glass glaze sealing-in；
The following steps are included:
(1) it using the oxide for forming cation as starting material, using alcohol as abrasive media, is milled under 300 meshes, obtains ball milling Powder drying afterwards is stand-by；
(2) powder after gained ball milling is sintered into phase twice, and first time calcination temperature is 800-900 DEG C, and soaking time 4-6 is small When；Second calcination temperature is 950-1050 DEG C, soaking time 4-6 hour, through dry ball milling to 300 meshes after calcining every time Under；
(3) it is granulated to being sintered into the ceramic powder after phase, using solid content be 3-10wt%PVA or the aqueous solution of CMC is to make Granula, granulating agent dosage are 2-6wt%；
(4) dry-pressing formed, pressure 150-250MPa after being granulated；
(5) sintering processing of dry-pressing formed rear green body uses atmospheric air atmosphere, the temperature schedule of sintering are as follows: with 1- per minute 1.5 DEG C are raised to 300 DEG C, keep the temperature 1 hour；800 DEG C are raised to 2-3 DEG C per minute later, keeps the temperature 1 hour；Later with 3-4 per minute It DEG C is raised to 1240-1280 DEG C, keeps the temperature 4-6 hours；850 DEG C are dropped to 1 DEG C per minute later, then is dropped to 10-20 DEG C per minute Room temperature；
(6) burn electrode: sintered sheets sample brushes silver paste, is raised to 850 DEG C with 2-3 DEG C per minute, keeps the temperature 0.5 hour, then with per minute 10-20 DEG C drops to room temperature；
(7) thermal resistor sealing-in: in atmosphere furnace, under oxygen-enriched environment by electrodeless covering with medium temperature glass glaze sealing-in, Glass-glazed firing temperature is at 620-680 DEG C.
2. a kind of preparation side for bearing low ageing rate negative temperature coefficient thermistor ceramic material according to claim 1 Method, which is characterized in that the chemical composition of the thermal resistor ceramic material is Mn3-x-y-zNixFeyMzO4, wherein M represent Cu, Ti, Sn or Al, x:0.9-1.1, y:0.9-1.1, z:0.03-0.1.
3. a kind of preparation method for bearing low ageing rate negative temperature coefficient thermistor ceramic material according to claim 1, It is characterized in that, cover at electrodeless place at cylinder with medium temperature glass glaze sealing-in under oxygen-enriched environment described in step (7), wherein Oxygen-enriched environment are as follows: oxygen content 22-40%vol.
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Publication number Priority date Publication date Assignee Title
CN201196910Y (en) * 2008-05-29 2009-02-18 成都宏明电子股份有限公司 Packaging body used for sheet-type multilayer ceramic capacitor and sheet-type multi-layer piezoresistor
US7992285B2 (en) * 2007-12-26 2011-08-09 Industrial Technology Research Institute Method for fabricating negative temperature coefficient thermistor
CN102674826A (en) * 2012-06-05 2012-09-19 安徽建筑工业学院 Low-resistivity high-B-value negative temperature coefficient heat-sensitive ceramic material and preparation process thereof
CN103632781A (en) * 2013-12-13 2014-03-12 深圳顺络电子股份有限公司 Chip component tip packaging paste and preparation method of chip component

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7992285B2 (en) * 2007-12-26 2011-08-09 Industrial Technology Research Institute Method for fabricating negative temperature coefficient thermistor
CN201196910Y (en) * 2008-05-29 2009-02-18 成都宏明电子股份有限公司 Packaging body used for sheet-type multilayer ceramic capacitor and sheet-type multi-layer piezoresistor
CN102674826A (en) * 2012-06-05 2012-09-19 安徽建筑工业学院 Low-resistivity high-B-value negative temperature coefficient heat-sensitive ceramic material and preparation process thereof
CN103632781A (en) * 2013-12-13 2014-03-12 深圳顺络电子股份有限公司 Chip component tip packaging paste and preparation method of chip component

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