CN103073267A - NTC (negative temperature coefficient) thermal-sensitive material with low resistivity and high B-value and preparation method thereof - Google Patents
NTC (negative temperature coefficient) thermal-sensitive material with low resistivity and high B-value and preparation method thereof Download PDFInfo
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- CN103073267A CN103073267A CN2012105708493A CN201210570849A CN103073267A CN 103073267 A CN103073267 A CN 103073267A CN 2012105708493 A CN2012105708493 A CN 2012105708493A CN 201210570849 A CN201210570849 A CN 201210570849A CN 103073267 A CN103073267 A CN 103073267A
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Abstract
The invention relates to the field of thermal-sensitive materials, specifically discloses an NTC (negative temperature coefficient) thermal-sensitive material with low resistivity and high B-value and a preparation method thereof. The NTC thermal-sensitive material with low resistivity and high B-value employs Mn-Co-Al oxides as main components, and is characterized in that the material is prepared by mixing low-valent metal particles Nb2O5 and high-stable impurities TiO2 and ZrO into the main components, wherein the main components comprises Mn3O4, Co3O4 and Al2O3 in the weight ratio of (50-60): (40-55): (2-10). The material provided by the invention has the characteristics of low resistivity and high B-value, is the important material required by temperature sensors, and is good in consistency, repeatability and stability.
Description
(1) technical field
The present invention relates to the thermo-sensitive material field, particularly a kind of low-resistivity, high B-value negative temperature coefficient thermo-sensitive material and preparation method thereof.
(2) background technology
Temperature survey, temperature control, temperature compensation and circuit overcurrent protection that the element of low-resistivity, high B-value negative temperature coefficient thermo-sensitive material preparation and sensor are widely used for various fields.But the low-resistivity because Present Domestic is correlated with outward, high B value product, MEMS digital sensor precision is on the low side relatively, and the lower cost materials that therefore can make more high-precision low-resistivity/high B value becomes the target of whole world pursuit of the same trade.
Initial negative tempperature coefficient thermistor usually adopt from transition metal Mn, Co, Ni, Fe, Cu, oxide compound choose 3 ~ 4 kinds as main formula, mix simultaneously some high prices or at a low price other metallization oxide compound and some rare earth elements, the resistivity of material is from several ohmcms, to several kilohms centimetres, and B value (material coefficient) is in 1000 ~ 4300K scope; The normal resistance of the thermistor made from these materials is that hundreds of ohm is to hundreds of thousands of ohm, up to now, this serial formula materials scheme does not also have a kind of manufacture method of low-resistance/high B-value negative temperature coefficient thermo-sensitive material of desirable realization high precision, high consistence and interchangeability.
(3) summary of the invention
The present invention is in order to remedy the deficiencies in the prior art, and low-resistivity, high B-value negative temperature coefficient thermo-sensitive material of a kind of high precision, high consistence and interchangeability, high stability and preparation method thereof are provided.
The present invention is achieved through the following technical solutions:
A kind of low-resistivity, high B-value negative temperature coefficient thermo-sensitive material, with Mn-Co-Al be oxide compound as main formula, it is characterized in that: in main formula, mix at a low price metallics Nb
2O
5With high stable impurity TiO
2Make with ZrO, wherein, main formula is that weight ratio is the Mn of 50 ~ 60:40 ~ 55:2 ~ 10
3O
4, Co
3O
4And Al
2O
3, the addition of high stable impurity is 0.5 ~ 10% of main formula weight.
The preparation method of low-resistivity of the present invention, high B-value negative temperature coefficient thermo-sensitive material, key step is: after main formula Mn-Co-Al is to mix low price metallics and high stable impurity in the oxide compound it is carried out 8 ~ 12 hours ball milling, after 100 ~ 150 ℃ of oven dry, add tackiness agent and cause 80 ~ 200 purpose particles, and make the shaping disk, sintering is 2.5 ~ 6 hours under 1200 ~ 1340 ℃ of high temperature, and at last printing obtains finished product.
The present invention is metallics Nb at a low price
2O
5Mix and reduce material resistance in the prescription, and mix high stable impurity TiO
2, the ZrO material, changed carrier concentration, improved thermal excitation efficient, and the invariant energy level position, therefore the material B value obtains to promote, and material structure thermal distortion effect also weakens simultaneously, thereby has improved stability of material, the resistivity of material in the time of 25 ℃ is 200 ~ 800 Ω cm, and the B value of 25 ~ 50 ℃ of warm areas is 3300 ~ 5000K.
More excellent scheme of the present invention is:
During described ball milling, the weight proportion of ball milling material, water and ball is 1:1.1 ~ 1.4:1.5 ~ 2.
Described tackiness agent is that mass concentration is 10 ~ 20% polyvinyl alcohol solution, and its consumption is 20 ~ 30% of main formula weight.
The diameter of described shaping disk is 5cm, and shaping density is 2.4 ~ 3.6g/cm
3
Described sintering process is during by room temperature ~ 500 ℃, temperature rise rate is 0.5 ℃/min, then constant temperature is 2 hours, continue afterwards to be warming up to 800 ℃, temperature rise rate is 0.8 ℃/min, and then constant temperature is 2 hours, again be warming up to sintering temperature, temperature rise rate is 6 ℃/min, and constant temperature is 2.5 ~ 6 hours on sintering temperature, lowers the temperature with stove at last.
During described printing, reduce slurry under 750 ~ 850 ℃ silver slurry reduction temperature, the recovery time is 25 ~ 35min.
Prescription in the technique of the present invention, sintering, printing are critical process; Prescription has determined material behavior, and sintering, printing then are the assurances that realizes this characteristic.
The present invention for Cu, Fe etc., adds the additive that contains Nb, Ti, Zr oxide compound with Al, and resistivity and B value are compensated, and can realize the various parameters that temperature sensor is required.
Material of the present invention has low-resistivity/high B value characteristics, it is the required important materials of temperature sensor, has preferably consistence, repeated and stable, this material is particularly suitable for making the temperature compensating element of automotive electronics sensor special heat-sensitive resistance, various semiconducter device, wide warm area thermometric and special sensor.
(4) embodiment
Embodiment 1:
(1) prescription: with Mn
3O
4, Co
3O
4, Al
2O
3Be raw material, purity is technical grade, gets Mn
3O
4: Co
3O
4: Al
2O
3=50:40:10(%wt)+the 6%(additive)=53:40:7(% wt)+the 6%(additive)=56:40:4(% wt)+6% (additive)=58:40:2(% wt)+6% (additive); Additive: Nb
2O
5: TiO
2: ZrO=60:30:10%wt, 8 hours ball millings;
(2) with aforementioned proportion formulation material ball milling 10 hours, material: water: ball=1.0:1.2:1.5;
(3) granulation: adding concentration is 10% PVA sol solution 25%wt in powder, and the 80-200 mesh sieve is crossed in manual granulation;
(4) be shaped: use 20Mpa pressure, shaping Ф 5.4(mm) * the base sheet of 1.2mm, pressed density is 3.2g/cm
3
(5) the base sheet that is shaped is packed in the ceramic alms bowl under 1250 ℃ of high temperature sintering 3 hours.Sintering curre is:
Room temperature ~ 500 ℃ temperature rise rate is 0.5 ℃/min,
500 ℃ ~ 500 ℃ constant temperature 2 hours,
500 ℃ ~ 800 ℃ temperature rise rates are 0.8 ℃/min,
800 ℃ ~ 800 ℃ constant temperature 2 hours,
800 ℃ ~ 1250 ℃ temperature rise rates are 6 ℃/min,
1250 ℃ ~ 1250 ℃ constant temperature 3.5 hours,
Then with the stove cooling, below 200 ℃, come out of the stove;
(6) print electrode 830 ℃ of reduction 30min;
(7) R of sample is measured in test in 25 ℃ ± 0.01 ℃ thermostatic oil bath
25And R
50Value and calculate ρ
25And B
25/
50Its result such as following table
(with 100 chip statistics)
The result shows, along with Al
2O
3The minimizing of amount, resistance descend, and B value also has decline, the homogeneity of resistance value and B value even identical with the Mn-Co-Al based material.
Embodiment 2:
Main formula is got MnO
2: Co
3O
4, Al
2O
3=56:40:4%wt, the amount of additive is taken as respectively 1.0,3.0,5.0,7.0,10.0,12.0%wt, is made into the sample of Ф 10 by the technique of embodiment 1, its test result such as following table (with 100 chips statistics)
The result shows, along with the increase of additive capacity, resistance descends, and B value is obviously decline also.When the consumption of additive reached 12%, resistance was 147 Ω, and the B value only is 4030K, and the dispersion of material becomes large.
Embodiment 3:
Prescription is got MnO
2: Co
3O
4, Al
2O
3=53:40:7%wt, the amount of additive is that the technique of 6%wt ［ by embodiment 1 ］ is made Ф 10 base sheets, gets different sintering temperature sintering, the measuring result of sample such as following table (with 100 chip statistics)
The result shows, sintering temperature is lower than 1230 ℃, is higher than 1270 ℃, and the sample consistence degenerates, so optimum temps is 1230-1270 ℃, if the amount of prescription Al increases, sintering temperature raises, and same Al amount reduces, and sintering temperature contains corresponding reduction.
Material prescription of the present invention and technology of preparing can be produced in batches, the required various parameters of performance satisfied temperature sensor of material, this material have low-resistivity/high B value characteristics, are the required important materials of temperature sensor, have preferably consistence, repeated and stable.
Claims (7)
1. a low-resistivity, high B-value negative temperature coefficient thermo-sensitive material, with Mn-Co-Al be oxide compound as main formula, it is characterized in that: in main formula, mix at a low price metallics Nb
2O
5With high stable impurity TiO
2Make with ZrO, wherein, main formula is that weight ratio is the Mn of 50 ~ 60:40 ~ 55:2 ~ 10
3O
4, Co
3O
4And Al
2O
3, the addition of high stable impurity is 0.5 ~ 10% of main formula weight.
2. the preparation method of low-resistivity according to claim 1, high B-value negative temperature coefficient thermo-sensitive material, it is characterized in that: after main formula Mn-Co-Al is to mix low price metallics and high stable impurity in the oxide compound, it is carried out 8 ~ 12 hours ball milling, after 100 ~ 150 ℃ of oven dry, add tackiness agent and cause 80 ~ 200 purpose particles, and make the shaping disk, sintering is 2.5 ~ 6 hours under 1200 ~ 1340 ℃ of high temperature, and at last printing obtains finished product.
3. the preparation method of low-resistivity according to claim 2, high B-value negative temperature coefficient thermo-sensitive material, it is characterized in that: during described ball milling, the weight proportion of ball milling material, water and ball is 1:1.1 ~ 1.4:1.5 ~ 2.
4. the preparation method of low-resistivity according to claim 2, high B-value negative temperature coefficient thermo-sensitive material, it is characterized in that: described tackiness agent is that mass concentration is 10 ~ 20% polyvinyl alcohol solution, and its consumption is 20 ~ 30% of main formula weight.
5. the preparation method of low-resistivity according to claim 2, high B-value negative temperature coefficient thermo-sensitive material, it is characterized in that: the diameter of described shaping disk is 5cm, shaping density is 2.4 ~ 3.6g/cm
3
6. the preparation method of low-resistivity according to claim 2, high B-value negative temperature coefficient thermo-sensitive material, it is characterized in that: described sintering process is for by room temperature ~ 500 ℃ the time, temperature rise rate is 0.5 ℃/min, and then constant temperature is 2 hours, continues afterwards to be warming up to 800 ℃, temperature rise rate is 0.8 ℃/min, then constant temperature is 2 hours, again is warming up to sintering temperature, and temperature rise rate is 6 ℃/min, constant temperature is 2.5 ~ 6 hours on sintering temperature, lowers the temperature with stove at last.
7. the preparation method of low-resistivity according to claim 2, high B-value negative temperature coefficient thermo-sensitive material is characterized in that: during described printing, reduce slurry under 750 ~ 850 ℃ silver slurry reduction temperature, the recovery time is 25 ~ 35min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664141A (en) * | 2013-12-19 | 2014-03-26 | 深圳顺络电子股份有限公司 | Negative temperature coefficient thermistor chip, thermistor and preparation method of chip |
| CN107140965A (en) * | 2017-04-25 | 2017-09-08 | 山东中厦电子科技有限公司 | A kind of high resistivity, low B value negative temperature coefficient thermo-sensitive materials and preparation method thereof |
| CN108727068A (en) * | 2018-07-03 | 2018-11-02 | 句容市博远电子有限公司 | A kind of preparation method of thin slice NTC thermistor |
| CN111116173A (en) * | 2019-12-16 | 2020-05-08 | 深圳顺络电子股份有限公司 | Low-temperature sintered NTC thermistor ceramic material and preparation method thereof |
| CN113674938A (en) * | 2021-08-06 | 2021-11-19 | 开特电子云梦有限公司 | Thermistor, chip material and preparation method thereof |
| CN115862979A (en) * | 2023-01-09 | 2023-03-28 | 山东中厦电子科技有限公司 | Square sheet resistor for temperature sensor and preparation method thereof |
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| CN102219479A (en) * | 2011-04-21 | 2011-10-19 | 西安交通大学 | Negative temperature coefficient (NTC) material utilized at high temperature and preparation method thereof |
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| CN101127266A (en) * | 2007-09-12 | 2008-02-20 | 山东中厦电子科技有限公司 | High evenness negative temperature coefficient heat-sensitive resistance material and its preparation method |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664141A (en) * | 2013-12-19 | 2014-03-26 | 深圳顺络电子股份有限公司 | Negative temperature coefficient thermistor chip, thermistor and preparation method of chip |
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| CN107140965A (en) * | 2017-04-25 | 2017-09-08 | 山东中厦电子科技有限公司 | A kind of high resistivity, low B value negative temperature coefficient thermo-sensitive materials and preparation method thereof |
| CN107140965B (en) * | 2017-04-25 | 2020-05-08 | 山东中厦电子科技有限公司 | Negative temperature coefficient thermosensitive material with high resistivity and low B value and preparation method thereof |
| CN108727068A (en) * | 2018-07-03 | 2018-11-02 | 句容市博远电子有限公司 | A kind of preparation method of thin slice NTC thermistor |
| CN108727068B (en) * | 2018-07-03 | 2021-04-13 | 句容市博远电子有限公司 | Preparation method of thin NTC thermistor |
| CN111116173A (en) * | 2019-12-16 | 2020-05-08 | 深圳顺络电子股份有限公司 | Low-temperature sintered NTC thermistor ceramic material and preparation method thereof |
| CN113674938A (en) * | 2021-08-06 | 2021-11-19 | 开特电子云梦有限公司 | Thermistor, chip material and preparation method thereof |
| CN115862979A (en) * | 2023-01-09 | 2023-03-28 | 山东中厦电子科技有限公司 | Square sheet resistor for temperature sensor and preparation method thereof |
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Effective date of registration: 20190121 Address after: 274 000 Lanzhou Road, Wanfu Office, Heze High-tech Zone, Shandong Province, 369 (in Zhongxia Electronic College) Patentee after: Shandong Moxin New Material Technology Co., Ltd. Address before: 274000 Lanzhou Road 369, Mudan District, Heze City, Shandong Province Patentee before: Shandong Zhongxia Electronics Technology Co., Ltd. |