CN104649681A - Method for preparing NTC (negative temperature coefficient) thermosensitive ceramic material through two-step solid-phase chemical reaction - Google Patents
Method for preparing NTC (negative temperature coefficient) thermosensitive ceramic material through two-step solid-phase chemical reaction Download PDFInfo
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- CN104649681A CN104649681A CN201510101679.8A CN201510101679A CN104649681A CN 104649681 A CN104649681 A CN 104649681A CN 201510101679 A CN201510101679 A CN 201510101679A CN 104649681 A CN104649681 A CN 104649681A
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Abstract
The invention relates to a method for preparing an NTC (negative temperature coefficient) thermosensitive ceramic material through two-step solid-phase chemical reaction. The method comprises the following steps: by taking manganese acetate tetrahydrate, nickel nitrate hexahydrate, magnesium nitrate hexahydrate, aluminium nitratenonahydrate and ammonium citrate as raw materials, carrying out solid-phase chemical reaction at room temperature, calcining the reaction product at a high temperature to obtain composite oxide powder with uniform size and good dispersibility, prepressing the composite oxide powder, pressing isostatically, and calcining to obtain the NTC thermosensitive ceramic material. The NTC thermosensitive ceramic material can be made into an NTC thermosensitive resistor by adopting a conventional method according to the procedures of slicing, coating with electrodes, scribing, welding and encapsulating. The NTC thermosensitive resistor has good consistent resistance value and B value, interchangeability, stability and repeatability and can be widely used for controlling and detecting the temperature of induction cookers, electric pressure cookers, electric rice cookers, electric ovens, disinfection cabinets, water dispensers, microwave ovens, electric heaters and other household appliances.
Description
Technical field
The present invention relates to a kind of method that two step solid state reactions prepare negative temperature coefficient thermal-sensitive ceramic material, belong to semiconductor functional material product scope.
Background technology
Negative tempperature coefficient thermistor (NTC) is that a kind of resistance raises and the electronic ceramic component of decline with temperature, be widely used in conditioning unit, steam heating, Medical Instruments, temperature control instrument, electronic gift, electronics Hygrothermograph, automobile thermometric, electronic calendar, the therm-param method of rechargeable battery set and charger.Along with the development of technology, have higher requirement to the precision of negative tempperature coefficient thermistor element, reliability and yield rate in market.
The performance of negative tempperature coefficient thermistor element depends on the quality of ceramic powder material to a great extent.The powder preparation method of current widespread use is conventional high-temperature solid phase method, but the method exists powder body material particle diameter is large, chemical uniformity is poor shortcoming.Often chemical coprecipitation is adopted in prepared by high precision thermosensitive resistor element, the method is that precipitation agent is added in mixed metal salt solution, make two or more the positively charged ion coprecipitation contained in solution, generate precipitation mixture or sosoloid presoma, filtration, washing, thermolysis, obtain composite oxides.But adding of precipitation agent may make partial concn too high, produce and reunite or form even not.Powder body material granularity prepared by this kind of method is little, be evenly distributed.But the pH value precipitated due to each element is different, easily cause fractional precipitation and the powder element ratio be settled out and original formulation variant, be difficult to the powder obtaining actual stoichiometry ratio.
Summary of the invention
The object of the invention is to, a kind of two step solid state reactions are provided to prepare the method for negative temperature coefficient thermal-sensitive ceramic material, the method is that four kinds of metallic cations and ammonium citrate at ambient temperature solid state reaction are occurred, and instead of the chemical reaction occurred in the solution.This not only reduces the process of precipitation, filtration, washing, shorten reaction time, and the method can make positively charged ion keep the mol ratio of design, obtains stoichiometric ratio accurately.React by adding ammonium citrate and tensio-active agent and metal ion, through calcining, acquisition mixes, particle diameter is consistent, the powder of good crystallinity, the powder obtained is carried out shaping, sintering, section, be coated with electrode, scribing complete processing, resistance value and the good negative temperature coefficient thermal-sensitive ceramic material of B value consistence can be obtained.The method technique is simple, reproducible, easy handling amplifies and can effectively improve thermo-sensitive material quality, has commercial scale production prospect.
A kind of two step solid state reactions of the present invention prepare the method for negative temperature coefficient thermal-sensitive ceramic material, and concrete operations follow these steps to carry out:
A, in molar ratio manganese: nickel: magnesium: aluminium=2-3.1: 1.4-2.5: 1.4-2: 0.1 takes raw material four water manganous acetate, six water nickelous nitrates, magnesium nitrate hexahydrate and nine water aluminum nitrates, mixed grinding 2 hours in planetary ball mill;
Ammonium citrate and surfactant polyethylene-800 add in the mixture that step a obtains by b, in molar ratio 5:0.2, continue grinding 4-8 hour, make it occur green viscous thing that solid state reaction becomes uniform color;
C, the dope obtained in step b is placed in temperature 100 DEG C of baking ovens dehydrations after, pulverize, be and then placed in temperature 400-500 DEG C of clock hood type furnace and decompose 3-6 hour, after having decomposed, powder body material is placed in pre-burning 2-4 hour in temperature 700-850 DEG C of clock hood type furnace;
D, then carry out pre-molding, isostatic pressed, at temperature 1100-1220 DEG C of sintering 2-5 hour, negative tempperature coefficient thermistor stupalith can be obtained.
The thermistor ceramic material obtained by the method for the invention is through cutting into slices, being coated with electrode, scribing, welding, encapsulation, the NTC thermistor element B made
25/50=4060-4300 × (1 ± 0.5%) K; Resistance value R
25 DEG Cat 20-40k Ω, the yield rate of resistance value in 1% is 60%-80%, and the yield rate within 3% reaches 85%-95%.
A kind of two step solid state reactions of the present invention prepare the method for negative temperature coefficient heat-sensitive resistance material, simple to operate, reaction does not need solvent, energy-conservation, productive rate is high, be convenient to amplify the feature such as production.By the stupalith that the method for the invention obtains, through ordinary method section, painting electrode, scribing, welding, encapsulation, resistance value and the B value consistence of the NTC thermistor product made are higher, exchange better performances.Can be applied to electromagnetic oven, electric pressure cooking saucepan, electric cooker, electric oven, sterilizing-cabinet, water dispenser, microwave oven, the temperature of the household electrical appliance such as Electric heating range controls and temperature detection.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) photograph of the present invention;
Fig. 2 is thermistor ceramic material resistance of the present invention and temperature characteristics figure;
Fig. 3 is the linear relationship chart of thermistor ceramic material resistance logarithm of the present invention and inverse temperature.
Embodiment
Embodiment 1
Manganese in molar ratio: nickel: magnesium: aluminium=2:2.5:1.4:0.1 takes four water manganous acetates, six water nickelous nitrates, magnesium nitrate hexahydrate and nine water aluminum nitrates and prepares burden, mixed grinding 2 hours in planetary ball mill;
5:0.2 is by ammonium citrate and surfactant polyethylene-800(PEG-800 in molar ratio) add in the mixture of gained and continue grinding 8 hours, make it occur green viscous thing that solid state reaction becomes uniform color;
After the dope obtained being placed in the dehydration of temperature 100 DEG C of baking ovens, pulverize, be and then placed in temperature 500 DEG C of clock hood type furnaces and decompose 3 hours, after having decomposed, powder body material to be placed in 850 DEG C of clock hood type furnaces pre-burning 2 hours;
Then carry out pre-molding, isostatic pressed, sinter 5 hours temperature 1100 DEG C, negative tempperature coefficient thermistor stupalith can be obtained;
By the negative tempperature coefficient thermistor stupalith obtained, through ordinary method section, be coated with electrode, scribing, welding lead and encapsulation, the NTC thermistor element B made
25/50=4060 × (1 ± 0.5%) K, resistance value R
25 DEG C=20 k Ω, the yield rate of resistance value in 1% is 60%, and the yield rate within 3% reaches 85%, and this product can be applied to electromagnetic oven, electric pressure cooking saucepan, electric cooker, electric oven, sterilizing-cabinet, water dispenser, microwave oven, the temperature of the household appliance technical field such as Electric heating range controls and temperature detection.
Embodiment 2
Manganese in molar ratio: nickel: magnesium: aluminium=3.1:1.4:1.4:0.1 takes four water manganous acetates, six water nickelous nitrates, magnesium nitrate hexahydrate and nine water aluminum nitrates and prepares burden, mixed grinding 2 hours in planetary ball mill;
5:0.2 is by ammonium citrate and surfactant polyethylene-800(PEG-800 in molar ratio) add in the mixture of gained, continue grinding 4 hours, make it occur green viscous thing that solid state reaction becomes uniform color;
After the dope obtained being placed in the dehydration of temperature 100 DEG C of baking ovens, pulverize, be and then placed in temperature 400 DEG C of clock hood type furnaces and decompose 6 hours, after having decomposed, powder body material to be placed in 700 DEG C of clock hood type furnaces pre-burning 4 hours;
Then carry out pre-molding, isostatic pressed, sinter 2 hours temperature 1220 DEG C, negative tempperature coefficient thermistor stupalith can be obtained;
By the negative tempperature coefficient thermistor stupalith obtained, through ordinary method section, be coated with electrode, scribing, welding lead and encapsulation, the NTC thermistor element B made
25/50=4160 × (1 ± 0.5%) K, resistance value R
25 DEG Cabout 20.5 k Ω
,yield rate in 1% is 75%, and the yield rate within 3% reaches 85%.This product can be applied to electromagnetic oven, electric pressure cooking saucepan, electric cooker, electric oven, sterilizing-cabinet, water dispenser, microwave oven, and the temperature of the household appliance technical field such as Electric heating range controls and temperature detection.
Embodiment 3
Manganese in molar ratio: nickel: magnesium: aluminium=2.5:1.4:2:0.1 takes four water manganous acetates, six water nickelous nitrates, magnesium nitrate hexahydrate and nine water aluminum nitrates and prepares burden, mixed grinding 2 hours in planetary ball mill;
5:0.2 is by ammonium citrate and surfactant polyethylene-800(PEG-800 in molar ratio) add in the mixture of gained, continue grinding 6 hours, make it occur green viscous thing that solid state reaction becomes uniform color;
After the dope obtained being placed in the dehydration of temperature 100 DEG C of baking ovens, pulverize, be and then placed in temperature 450 DEG C of clock hood type furnaces and decompose 5 hours, after having decomposed, powder body material to be placed in 750 DEG C of clock hood type furnaces pre-burning 3 hours;
Then carry out pre-molding, isostatic pressed, sinter 4 hours temperature 1150 DEG C, negative tempperature coefficient thermistor stupalith can be obtained;
By the negative tempperature coefficient thermistor stupalith obtained, through ordinary method section, be coated with electrode, scribing, welding lead and encapsulation, the NTC thermistor element B made
25/50=4200 × (1 ± 0.5%) K, resistance value R
25 DEG C=32 k Ω; The yield rate of resistance value in 1% is 80%, and the yield rate within 3% reaches 95%.This product can be applied to electromagnetic oven, electric pressure cooking saucepan, electric cooker, electric oven, sterilizing-cabinet, water dispenser, microwave oven, and the temperature of the household appliance technical field such as Electric heating range controls and temperature detection.
Embodiment 4
Manganese in molar ratio: nickel: magnesium: aluminium=2.8:1.5:1.6:0.1 takes four water manganous acetates, six water nickelous nitrates, magnesium nitrate hexahydrate, nine water aluminum nitrates, prepares burden, mixed grinding 2 hours in planetary ball mill;
5:0.2 is by ammonium citrate and surfactant polyethylene-800(PEG-800 in molar ratio) add in the mixture of gained, continue grinding 7 hours, make it occur green viscous thing that solid state reaction becomes uniform color;
After the dope obtained being placed in the dehydration of temperature 100 DEG C of baking ovens, pulverize, be and then placed in temperature 450 DEG C of clock hood type furnaces and decompose 5 hours, after having decomposed, powder body material to be placed in 750 DEG C of clock hood type furnaces pre-burning 3 hours;
Then carry out pre-molding, isostatic pressed, sinter 4 hours temperature 1150 DEG C, negative tempperature coefficient thermistor stupalith can be obtained;
By the negative tempperature coefficient thermistor stupalith obtained, through ordinary method section, be coated with electrode, scribing, welding lead and encapsulation, the NTC thermistor element B made
25/50=4300 × (1 ± 0.5%) K, resistance value R
25 DEG C=40 k Ω, the yield rate of resistance value in 1% is 75%, and the yield rate within 3% reaches 92%.This product can be applied to electromagnetic oven, electric pressure cooking saucepan, electric cooker, electric oven, sterilizing-cabinet, water dispenser, microwave oven, and the temperature of the household appliance technical field such as Electric heating range controls and temperature detection.
Claims (1)
1. two step solid state reactions prepare a method for negative temperature coefficient thermal-sensitive ceramic material, and it is characterized in that employing two step solid state reaction, concrete operations follow these steps to carry out:
A, in molar ratio manganese: nickel: magnesium: aluminium=2-3.1: 1.4-2.5: 1.4-2: 0.1 takes raw material four water manganous acetate, six water nickelous nitrates, magnesium nitrate hexahydrate and nine water aluminum nitrates, mixed grinding 2 hours in planetary ball mill;
Ammonium citrate and surfactant polyethylene-800 add in the mixture that step a obtains by b, in molar ratio 5:0.2, continue grinding 4-8 hour, make it occur green viscous thing that solid state reaction becomes uniform color;
C, the dope obtained in step b is placed in temperature 100 DEG C of baking ovens dehydrations after, pulverize, be and then placed in temperature 400-500 DEG C of clock hood type furnace and decompose 3-6 hour, after having decomposed, powder body material is placed in pre-burning 2-4 hour in temperature 700-850 DEG C of clock hood type furnace;
D, then carry out pre-molding, isostatic pressed, at temperature 1100-1220 DEG C of sintering 2-5 hour, negative tempperature coefficient thermistor stupalith can be obtained.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105810377A (en) * | 2016-05-24 | 2016-07-27 | 怀远县金浩电子科技有限公司 | Liquid-phase preparation method of thermistor powder material |
| CN108329015A (en) * | 2016-05-06 | 2018-07-27 | 中南大学 | A kind of doping vario-property nickel oxide-base NTC thermistor material and preparation method thereof |
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| CN1457061A (en) * | 2003-06-05 | 2003-11-19 | 宁波科联电子有限公司 | MOS thermistor producing method |
| CN1461064A (en) * | 2003-06-19 | 2003-12-10 | 南京大学 | Method for preparing lithium manganese oxide by using low-heat solid phase reaction |
| CN104362329A (en) * | 2014-09-18 | 2015-02-18 | 长沙矿冶研究院有限责任公司 | Method for preparing lithium-rich manganese-based layered lithium battery cathode material based on efficient solid-phase chemical complexation reaction |
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Patent Citations (3)
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|---|---|---|---|---|
| CN1457061A (en) * | 2003-06-05 | 2003-11-19 | 宁波科联电子有限公司 | MOS thermistor producing method |
| CN1461064A (en) * | 2003-06-19 | 2003-12-10 | 南京大学 | Method for preparing lithium manganese oxide by using low-heat solid phase reaction |
| CN104362329A (en) * | 2014-09-18 | 2015-02-18 | 长沙矿冶研究院有限责任公司 | Method for preparing lithium-rich manganese-based layered lithium battery cathode material based on efficient solid-phase chemical complexation reaction |
Non-Patent Citations (1)
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| 王忠兵 等: ""掺杂对Ni-Mn-O系NTC热敏陶瓷及其电学性能的影响"", 《硅酸盐学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108329015A (en) * | 2016-05-06 | 2018-07-27 | 中南大学 | A kind of doping vario-property nickel oxide-base NTC thermistor material and preparation method thereof |
| CN108329015B (en) * | 2016-05-06 | 2021-02-05 | 中南大学 | Doped modified nickel oxide-based NTC (negative temperature coefficient) thermistor material and preparation method thereof |
| CN105810377A (en) * | 2016-05-24 | 2016-07-27 | 怀远县金浩电子科技有限公司 | Liquid-phase preparation method of thermistor powder material |
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