CN102249649A - Thermal sensitive ceramic and preparation method thereof - Google Patents
Thermal sensitive ceramic and preparation method thereof Download PDFInfo
- Publication number
- CN102249649A CN102249649A CN2011101074916A CN201110107491A CN102249649A CN 102249649 A CN102249649 A CN 102249649A CN 2011101074916 A CN2011101074916 A CN 2011101074916A CN 201110107491 A CN201110107491 A CN 201110107491A CN 102249649 A CN102249649 A CN 102249649A
- Authority
- CN
- China
- Prior art keywords
- preparation
- thermal sensitive
- acetate
- powder
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a thermal sensitive ceramic and a preparation method thereof. In the ceramic, the molar ratio of manganese element to cobalt element to nickel element is (35-37): (15-17): (6-10). The preparation method comprises the following steps: adding acetates containing the manganese element, cobalt element and nickel element to a solution of water and acetic acid in a proportion and then stirring so as to obtain sol, wherein the acetates comprise manganese acetate, nickel acetate and cobalt acetate; ageing at constant temperature so as to obtain wet gel; then drying at constant temperature so as to obtain dried gel; grinding so as to obtain powders, and presintering the powder so as to obtain black powder; carrying out grinding and ball milling on the black powder, drying, adding an adhesive, and then sieving so as to obtain the required thermal sensitive ceramic powder; carrying out compression moulding on the thermal sensitive ceramic powder so as to obtain green bodies; and embedding the green bodies in aluminum oxide powder, and sintering in a high temperature electric resistance furnace so as to prepare the required thermal sensitive ceramic. The thermal sensitive ceramic is especially suitable for various high-sensitivity negative-temperature-coefficient thermal sensitive resistances and multilayer type thermal sensitive resistances.
Description
Technical field
The present invention relates to the thermistor material field, specifically is a kind of thermal sensitive ceramics and preparation method thereof.
Background technology
Negative temperature coefficient (NTC) thermistor because highly sensitive, reliability is high and cheap, and is widely used in the temperature sensing of household electrical appliance, automobile and the equipment of industrial product and control etc.The trend of electronic devices and components chip type/microminiaturization also expands to sensor field, and chip type and filming thermistor are complied with this trend, obtain great development in the nineties.At present, the tempo of chip type thermistor is considerably beyond traditional discrete thermistor, and since nineteen ninety, the ratio of Japanese chip type thermistor is to be higher than 20% speed increase every year.
The sintering temperature that the present Mn-Co-Ni-O that adopts conventional solid-state method to prepare is the NTC thermal sensitive ceramics is up to 1200～1250 ℃, and the cost costliness, electric property consistence poor (the resistivity consistence is up to ± 2%, and the consistence of B value is up to ± 1%).Realize that thermistor chipization (especially multilayer sheet type) just needs to reduce below the sintering temperature to 1100 ℃ of thermal sensitive ceramics, if adopt the thermal sensitive ceramics of solid-phase synthesis preparation to reduce sintering temperature then can cause that density is low, sensitivity is low wait not enough.These deficiencies have brought very big obstruction all for the development of highly sensitive chip type thermistor and application.Therefore, how preparing the thermal sensitive ceramics of highly sensitive (high B value) under sintering temperature and low, is gordian technique.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of thermal sensitive ceramics and preparation method thereof is provided, the thermal sensitive ceramics that the inventive method is prepared is to fire to form under lower sintering temperature, and possesses the characteristics of highly sensitive (high B value).
The present invention is achieved by the following technical solutions:
A kind of thermal sensitive ceramics, the molar ratio of manganese element, cobalt element, nickel element is in the described pottery: (35～37): (15～17): (6～10).
The molar ratio of manganese element, cobalt element, nickel element is in the described pottery: (35～37): 17: (6～8).
A kind of preparation method of thermal sensitive ceramics comprises the steps:
(1) earlier with water and anhydrous acetic acid be 1: 1 mixed by volume, the molar ratio according to manganese element, cobalt element, nickel element is (35～37) again: (15～17): the ratio that (6～10) are converted into manganous acetate, nickelous acetate, cobaltous acetate joins in the solution of above-mentioned water and acetate and is configured to acetate solution;
(2) above-mentioned acetate solution stirring is obtained colloidal sol, the ageing under constant temperature of this colloidal sol is obtained wet gel, then this wet gel drying under constant temperature is obtained xerogel;
(3) above-mentioned xerogel grinding is obtained powder,, obtain the black powder this powder pre-burning, behind this black powder grinding, ball milling, oven dry, and add tackiness agent, and sieve, can obtain the powder of required thermal sensitive ceramics;
(4) after the powder compression moulding with above-mentioned thermal sensitive ceramics, obtain giving birth to embryo, above-mentioned living embryo is imbedded in the aluminium sesquioxide powder, sintering in high-temperature electric resistance furnace can make required thermal sensitive ceramics.
In the described step (1), the acetate solution of configuration also needs further to handle: after the volumetric molar concentration of this solution is controlled to be 0.2mol/L, add methyl ethyl diketone again, the add-on of described methyl ethyl diketone is 1/30 of an acetate solution volume.
In the described step (2), the temperature of preparation colloidal sol is 80 ℃, and churning time is 48 hours, and stirring velocity is greater than 500r/min, and the temperature of preparation wet gel is 60 ℃, and digestion time is 72 hours, and the temperature of preparation xerogel is 120 ℃, and be 5 hours time of drying.
Also adopt ultrasonic wave to carry out one time ultra-sonic dispersion every 12 hours described in the step (2) in the preparation process of colloidal sol and wet gel, each ultra-sonic dispersion time is 30 minutes.
Calcined temperature is 750 ℃ in the described step (3), and the pre-burning time is 2 hours.
Tackiness agent in the described step (3) is that mass concentration is 5% polyvinyl alcohol solution, and its add-on is 8～10% of a black powder quality.
Sintering temperature described in the described step (4) is 950 ℃～1050 ℃, and sintering time is 3 hours.
Living embryo in the described step (4) after the compression moulding also needs further to handle: carry out isostatic cool pressing under 250MPa, the dwell time is 10 minutes, puts into electric furnace then and removes above-mentioned tackiness agent.
Compared with prior art, the present invention has following advantage and beneficial effect:
The present invention adopts sol-gel technology, the powder granule of the preparation thermal sensitive ceramics that obtains thin (Nano grade), uniform particles, good dispersity, therefore, under lower sintering temperature (950～1050 ℃), can obtain highly sensitive thermal sensitive ceramics (B value for about 4000K), and its electric property high conformity (the resistivity consistence is less than ± 0.9%, the consistence of B value is less than ± 0.5%), be suitable for various types of high-sensitivity measurement thermistors and multilayer sheet type thermistor.
Embodiment
Below in conjunction with specific embodiment the present invention is done further concrete detailed description the in detail, but embodiments of the present invention are not limited thereto, the processing parameter for not indicating especially can carry out with reference to routine techniques.
Embodiment 1
Adopt following steps preparation technology:
(1) the used acetate raw material of preparation thermal sensitive ceramics of the present invention: the molar percentage that contains manganese element, cobalt element, nickel element in manganous acetate, nickelous acetate, the cobaltous acetate is: 37: 17: 6, this molar ratio is converted into required acetate raw material is respectively: manganous acetate 613.01g, nickelous acetate 285.96g and cobaltous acetate 101.03g.
(2) water (500ml) and anhydrous acetic acid (500ml) mixing are made into acetic acid solution, the method of employing water-bath is controlled at 80 ℃ with the temperature of above-mentioned acetic acid solution, again load weighted acetate raw material is slowly added and be made into acetate solution in the acetic acid solution, the volumetric molar concentration of regulating above-mentioned acetate solution is 0.2mol/L, adds the hydrolysis rate that methyl ethyl diketone is controlled acetate by 1/30 of liquor capacity then;
(3) acetate solution that above-mentioned steps is obtained obtains colloidal sol after stirring 48 hours under 80 ℃, and magnetic agitation speed is put into thermostat container greater than 500r/min with this colloidal sol, and 60 ℃ of ageings obtained wet gel in 72 hours.At whipping process and colloidal sol agglomeration traits appears in ageing process for fear of solution, adopted ultrasonic wave that colloidal sol is carried out ultra-sonic dispersion 30min (ultrasonic 10 times altogether) every 12 hours, the wet gel that obtains is put into loft drier, and drying temperature is 120 ℃, obtains xerogel.Powder after the xerogel grinding 750 ℃ of following pre-burnings, is incubated 2 hours, obtains the black powder of high reactivity, nano particle.
(4) with after the grinding of black powder, by the black powder: water: ethanol: the weight ratio between the abrading-ball is 1: 0.8: 0.8: 2 mix, and ball milling is after 2 hours, oven dry, add mass concentration then and be 5% polyvinyl alcohol solution 34g, obtain the powder that granularity is 200 purpose thermal sensitive ceramicses by sieving.
(5) powder of above-mentioned thermal sensitive ceramics carries out isostatic cool pressing after pre-molding is made a living embryo, in electric furnace, remove above-mentioned tackiness agent then after, the sample that obtains is imbedded Al
2O
3In the powder, sintering in high-temperature electric resistance furnace can obtain required thermal sensitive ceramics then, and sintering temperature curve is:
Room temperature～550 ℃, 3 ℃/min of temperature rise rate;
550 ℃, insulation 60min;
550 ℃～1020 ℃, 4 ℃/min of temperature rise rate;
1020 ℃, insulation 180min;
1020 ℃～200 ℃, lower the temperature with stove.
(5) the above-mentioned thermal sensitive ceramics sheet that sinters into is measured its physical parameter, result such as following table:
(6) adopt weight percent be 75% Ag slurry at the thermal sensitive ceramics sheet two sides of sintering gained printed electrode, at 550 ℃ of reduction 30min down, make thermal sensitive ceramics specimen chip.The lead-in wire of then 100 chips being burn-on places 25 ± 0.1 ℃ and 50 ± 0.1 ℃ of thermostat containers to measure its resistance value, i.e. R respectively
25And R
50, and calculated resistance rate ρ
25And B
25/50Value.Its result such as following table:
Embodiment 2:
Adopt following steps preparation technology:
(1) the used acetate raw material of preparation thermal sensitive ceramics of the present invention: the molar percentage that contains manganese element, cobalt element, nickel element in manganous acetate, nickelous acetate, the cobaltous acetate is: 36: 17: 7, this molar ratio is converted into required acetate raw material is respectively: manganous acetate 596.28g, nickelous acetate 285.89g and cobaltous acetate 117.83g.
(2) sintering temperature curve in the high-temperature electric resistance furnace is:
Room temperature～550 ℃, 3 ℃/min of temperature rise rate;
550 ℃, insulation 60min;
550 ℃～980 ℃, 4 ℃/min of temperature rise rate;
980 ℃, insulation 180min;
980 ℃～200 ℃, lower the temperature with stove.
Other step is pressed the technology of embodiment 1 and is made sample.
The sample test result is as follows:
Physical property:
Electrology characteristic:
Embodiment 3:
Adopt following steps preparation technology:
(1) the used acetate raw material of preparation thermal sensitive ceramics of the present invention: the molar percentage that contains manganese element, cobalt element, nickel element in manganous acetate, nickelous acetate, the cobaltous acetate is: 35: 17: 8, this molar ratio is converted into required acetate raw material is respectively: manganous acetate 579.56g, nickelous acetate 285.81g and cobaltous acetate 134.63g.
(2) sintering temperature curve in the high-temperature electric resistance furnace is:
Room temperature～550 ℃, 3 ℃/min of temperature rise rate;
550 ℃, insulation 60min;
550 ℃～950 ℃, 4 ℃/min of temperature rise rate;
950 ℃, insulation 180min;
950 ℃～200 ℃, lower the temperature with stove.
Other step is pressed the technology of embodiment 1 and is made sample.
The sample test result is as follows:
Physical property:
Electrology characteristic:
Embodiment 4:
Sintering temperature curve changes into:
Room temperature～550 ℃, 3 ℃/min of temperature rise rate;
550 ℃, insulation 60min;
550 ℃～1050 ℃, 4 ℃/min of temperature rise rate;
1050 ℃, insulation 180min;
1050 ℃～200 ℃, lower the temperature with stove.
Other step is pressed the technology of case study on implementation 1 and is made sample.
The sample test result is as follows:
Physical property:
Electrology characteristic:
The result of embodiment 1～4 shows, the resistivity at room temperature of the prepared thermal sensitive ceramics that goes out of composition of raw materials provided by the invention and preparation method is about 1100 Ω cm, the B value is about 4000K, the resistivity consistence is less than ± 0.9%, the consistence of B value is less than ± 0.5%, be very ideal sintering temperature and low, high B value, the conforming thermal sensitive ceramic material of high electric property, be particularly suitable for various types of highly sensitive negative tempperature coefficient thermistors and multilayer sheet type thermistor.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a thermal sensitive ceramics is characterized in that, the molar ratio of manganese element, cobalt element, nickel element is in the described pottery: (35～37): (15～17): (6～10).
2. pottery according to claim 1 is characterized in that, the molar ratio of manganese element, cobalt element, nickel element is in the described pottery: (35～37): 17: (6～8).
3. the preparation method of a thermal sensitive ceramics is characterized in that, comprises the steps:
(1) earlier with water and anhydrous acetic acid be 1: 1 mixed by volume, the molar ratio according to manganese element, cobalt element, nickel element is (35～37) again: (15～17): the ratio that (6～10) are converted into manganous acetate, nickelous acetate, cobaltous acetate joins in the solution of above-mentioned water and acetate and is configured to acetate solution;
(2) above-mentioned acetate solution stirring is obtained colloidal sol, the ageing under constant temperature of this colloidal sol is obtained wet gel, then this wet gel drying under constant temperature is obtained xerogel;
(3) above-mentioned xerogel grinding is obtained powder,, obtain the black powder this powder pre-burning, behind this black powder grinding, ball milling, oven dry, and add tackiness agent, and sieve, can obtain the powder of required thermal sensitive ceramics;
(4) after the powder compression moulding with above-mentioned thermal sensitive ceramics, obtain giving birth to embryo, above-mentioned living embryo is imbedded in the aluminium sesquioxide powder, sintering in high-temperature electric resistance furnace can make required thermal sensitive ceramics.
4. preparation method according to claim 3, it is characterized in that, in the described step (1), the acetate solution of configuration also needs further to handle: after the volumetric molar concentration of this solution is controlled to be 0.2mol/L, add methyl ethyl diketone again, the add-on of described methyl ethyl diketone is 1/30 of an acetate solution volume.
5. preparation method according to claim 3, it is characterized in that, in the described step (2), the temperature of preparation colloidal sol is 80 ℃, and churning time is 48 hours, and stirring velocity is greater than 500r/min, the temperature of preparation wet gel is 60 ℃, digestion time is 72 hours, and the temperature of preparation xerogel is 120 ℃, and be 5 hours time of drying.
6. according to claim 3 or 5 described preparation methods, it is characterized in that, also adopt ultrasonic wave to carry out one time ultra-sonic dispersion every 12 hours described in the step (2) in the preparation process of colloidal sol and wet gel, each ultra-sonic dispersion time is 30 minutes.
7. preparation method according to claim 3 is characterized in that, calcined temperature is 750 ℃ in the described step (3), and the pre-burning time is 2 hours.
8. preparation method according to claim 3 is characterized in that, the tackiness agent in the described step (3) is that mass concentration is 5% polyvinyl alcohol solution, and its add-on is 8～10% of a black powder quality.
9. preparation method according to claim 3 is characterized in that, sintering temperature described in the described step (4) is 950 ℃～1050 ℃, and sintering time is 3 hours.
10. preparation method according to claim 3 is characterized in that, the living embryo in the described step (4) after the compression moulding also needs further to handle: carry out isostatic cool pressing under 250MPa, the dwell time is 10 minutes, puts into electric furnace then and removes above-mentioned tackiness agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101074916A CN102249649A (en) | 2011-04-28 | 2011-04-28 | Thermal sensitive ceramic and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101074916A CN102249649A (en) | 2011-04-28 | 2011-04-28 | Thermal sensitive ceramic and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102249649A true CN102249649A (en) | 2011-11-23 |
Family
ID=44977272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101074916A Pending CN102249649A (en) | 2011-04-28 | 2011-04-28 | Thermal sensitive ceramic and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102249649A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102650037A (en) * | 2012-05-09 | 2012-08-29 | 中国科学院上海技术物理研究所 | Method for manufacturing magnetron sputtering target material of Mn-Co-Ni-O thin film |
| CN102732848A (en) * | 2012-06-25 | 2012-10-17 | 中国科学院上海技术物理研究所 | Method for preparing single oriented manganese cobalt nickel oxygen film by magnetron sputtering |
| CN105139990A (en) * | 2015-08-28 | 2015-12-09 | 南京先正电子有限公司 | Small-sized thermistor sintering method |
| CN106977180A (en) * | 2017-05-11 | 2017-07-25 | 句容市博远电子有限公司 | The preparation method of block NTC thermistor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1908229A (en) * | 2006-08-17 | 2007-02-07 | 中国科学院上海技术物理研究所 | Preparation method of manganese-cobalt-nickel thin film heat-sensitive material |
| CN101108773A (en) * | 2006-07-20 | 2008-01-23 | 西北工业大学 | NTC heat-sensitive semiconductive ceramic capable of low-temperature melting and method of manufacturing the same |
| CN101719404A (en) * | 2009-12-28 | 2010-06-02 | 中国科学院新疆理化技术研究所 | Ternary-system chip negative temperature coefficient thermal resistor |
-
2011
- 2011-04-28 CN CN2011101074916A patent/CN102249649A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101108773A (en) * | 2006-07-20 | 2008-01-23 | 西北工业大学 | NTC heat-sensitive semiconductive ceramic capable of low-temperature melting and method of manufacturing the same |
| CN1908229A (en) * | 2006-08-17 | 2007-02-07 | 中国科学院上海技术物理研究所 | Preparation method of manganese-cobalt-nickel thin film heat-sensitive material |
| CN101719404A (en) * | 2009-12-28 | 2010-06-02 | 中国科学院新疆理化技术研究所 | Ternary-system chip negative temperature coefficient thermal resistor |
Non-Patent Citations (1)
| Title |
|---|
| J.L.MATIN DE VIDALES ET.AL.: "Preparation and characterization of spinel-type Mn-Ni-Co-O negative temperature coefficient ceramic thermistors", 《JOURNAL OF MATERIALS SCIENCE》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102650037A (en) * | 2012-05-09 | 2012-08-29 | 中国科学院上海技术物理研究所 | Method for manufacturing magnetron sputtering target material of Mn-Co-Ni-O thin film |
| CN102732848A (en) * | 2012-06-25 | 2012-10-17 | 中国科学院上海技术物理研究所 | Method for preparing single oriented manganese cobalt nickel oxygen film by magnetron sputtering |
| CN102732848B (en) * | 2012-06-25 | 2014-07-30 | 中国科学院上海技术物理研究所 | Method for preparing single oriented manganese cobalt nickel oxygen film by magnetron sputtering |
| CN105139990A (en) * | 2015-08-28 | 2015-12-09 | 南京先正电子有限公司 | Small-sized thermistor sintering method |
| CN106977180A (en) * | 2017-05-11 | 2017-07-25 | 句容市博远电子有限公司 | The preparation method of block NTC thermistor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107474312B (en) | The preparation method of ceramic filled polytetrafluoroethylglass microwave composite medium substrate | |
| CN102249649A (en) | Thermal sensitive ceramic and preparation method thereof | |
| CN104944933B (en) | The high frequency transformer preparation method of inductance value high magnetic conductivity ferrite magnetic core high | |
| CN102627446B (en) | Method for preparing negative temperature coefficient (NTC) thermistor and NTC thermistor chip manufactured by same | |
| JP2023514317A (en) | Method for preparing spherical silica powder filler, powder filler obtained thereby and use thereof | |
| CN105330277B (en) | Negative tempperature coefficient thermistor raw material composition and application | |
| CN103354142B (en) | Motor protection negative temperature coefficient NTC themistor and manufacture method thereof | |
| CN106882963A (en) | A kind of method that CaCu 3 Ti 4 O is prepared based on sol-gal process | |
| CN108863346A (en) | A kind of NTC thermal sensitive ceramic material and the preparation method and application thereof of novel high B value | |
| Tian et al. | Phase evolutions and electric properties of BaTiO 3 ceramics by a low-temperature sintering process | |
| CN108610042A (en) | Dielectric material and preparation method thereof with the high insulation characterisitic of huge dielectric constant | |
| CN108546115A (en) | A kind of barium phthalate base low-loss huge dielectric constant dielectric substance and preparation method thereof | |
| CN104311004B (en) | PTC ceramic material and method for improving resistance temperature stability below curie point of PTC ceramic material | |
| Guo et al. | Electrical conductivity & temperature sensitivity of ceramics based on NiO simple oxides for NTC applications | |
| CN102627445A (en) | composition for preparing negative temperature coefficient (NTC) thermistor chip and NTC thermistor made by using composition | |
| CN102924064B (en) | Wide-temperature range NTC thermosensitive ceramic material and preparation method thereof | |
| CN101717241A (en) | Low-temperature sintering NTC oxide heat sensitive material and preparation method thereof | |
| CN100415414C (en) | High precision thermosensitive resistor nanometer powder production method | |
| CN103449801B (en) | Preparation method of high-TCR (temperature coefficient of resistance) polycrystalline ceramic | |
| CN104692800A (en) | Temperature-stable lead-free giant dielectric constant ceramic material | |
| CN101423645A (en) | Dielectric composite material and preparation method thereof | |
| CN107817277A (en) | The preparation method of new high selectivity acetone gas sensor | |
| CN102627444A (en) | Combination for preparing negative temperature coefficient (NTC) thermistor chip and NTC thermistor made by using combination | |
| CN107365153A (en) | A kind of high-performance NTC thermal sensitive ceramic materials and preparation method and application | |
| CN107903042A (en) | A kind of preparation method of NTC thermistor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20111123 |
|
| RJ01 | Rejection of invention patent application after publication |