CN108546114A - A kind of width warm area negative temperature coefficient thermal-sensitive ceramic material and preparation method thereof - Google Patents

A kind of width warm area negative temperature coefficient thermal-sensitive ceramic material and preparation method thereof Download PDF

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CN108546114A
CN108546114A CN201810346749.XA CN201810346749A CN108546114A CN 108546114 A CN108546114 A CN 108546114A CN 201810346749 A CN201810346749 A CN 201810346749A CN 108546114 A CN108546114 A CN 108546114A
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CN108546114B (en
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傅邱云
周东祥
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Huazhong University of Science and Technology
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Abstract

Raw material composition the invention discloses a kind of wide warm area negative temperature coefficient thermal-sensitive ceramic material and preparation method thereof, wherein negative temperature coefficient thermal-sensitive ceramic material includes BaTiO3、TiO2、M1O、M2O、M3O、M4O and M5O, M1For at least one kind of element in Sm, Nd, Y, La and Nb；M2For at least two kinds of elements in Si, Al and Ti；M3For the combination of at least one kind of element and Ca elements in Sr and Pb；M4For at least one kind of element in Sb and Bi；M5For at least one kind of element in Na, K and Li.The present invention passes through the constituent to ceramic material key, the corresponding overall flow technique of preparation method, the conditional parameter of each reaction step are improved and further preferably, by being doped modification to barium titanate-based semiconductor thermal sensitive ceramics, barium phthalate base can be obtained, measure warm area up to 300 degree or more of wide range NTC thermosensitive ceramic material.

Description

A kind of width warm area negative temperature coefficient thermal-sensitive ceramic material and preparation method thereof
Technical field
The invention belongs to ceramic material technical fields, more particularly, to a kind of wide warm area negative temperature coefficient heat-sensitive Ceramic material and preparation method thereof, especially a kind of BaTiO3Based negative temperature coefficient (NTC) thermal sensitive ceramic material and its preparation side Method.
Background technology
Typical NTC thermal sensitive ceramicses be mostly using transition metal oxides such as manganese, cobalt, nickel as the semiconductor ceramic material of base, Its main feature is that the resistivity of material rises and exponentially type decline with environment temperature, it is special to generate negative resistance temperature (NTC) Property.All kinds of temperature sensors are can be made into using this kind of ceramic material, there is a system such as of simple structure and low cost and safe and reliable Row advantage and be widely used in various household electrical appliance, automotive electronics, automatically control and the fields such as electronic equipment, have very high Practical value and economic value.
It is sufficiently complex as the conductive mechanism of the semiconductor heat sensitive ceramic material of base using transition metal oxides such as Manganese, cobalt, nickel, It is generally acknowledged that belong to polaron conduction, and since (Metal-vacancy, ion appraise at the current rate different kinds of ions defect in multicomponent material system Deng) presence, the determinant of conductivity is complicated and changeable, but the following mathematic(al) representation that can usually apply greatly is retouched It states：
In formula：ΔHfTo ionize defect activation energy, Δ HmFor carrier mobility activation energy.Δ H under normal circumstancesf、ΔHmAll Parameter related with temperature, only error allow narrow temperature within the scope of just can approximation regard constant as, at this time (1) Formula can be reduced to：
You Yu using the transition metal oxides such as Manganese, cobalt, nickel as the B values correlation of the NTC semiconductor heat sensitive ceramic materials of base because Element is more, causes to be prepared into that measuring temperature range is very wide, and the temperature sensor that required precision is very high, can only divide warm area The sensor of different materials proportioning is prepared to realize that wide warm area accurately measures.Meanwhile such semiconductor ceramic material is technically very Difficulty prepare low-resistivity, high B values and high resistivity, low B values thermo-sensitive material, thus limit its application field and measure model It encloses.
Transform (2) can obtain：
Material B values, wherein R can be acquired using formula (3)1Be corresponding temperature be T1Resistance value when (such as 25 DEG C), R2It is corresponding Temperature is T2Resistance value when (such as 85 DEG C).T1、T2Also it can be determined according to the measuring temperature range of element.
On the other hand, it is well known that by the semiconductive ceramic of base of barium titanate be a kind of typical positive temperature coefficient (PTC) Thermo-sensitive material, its main feature is that (curie point or switch temperature point) its resistivity will be violent when temperature rise is to a certain specific temperature Increase several orders of magnitude, PTC effects as switch occurs, and resistance varies with temperature very little, room temperature to Curie before curie point Temperature range resistance change rate is not more than 1 order of magnitude.Use the PTC effects of this material as heater its heating power almost Do not change with the variation of applied voltage, thus has the function of automatic constant-temperature.Meanwhile using material more than Curie temperature Ptc characteristics can also be prepared into temperature-sensing element, but this temperature-sensitive element measurement warm area is very narrow (generally room temperature is to 100 DEG C), It is of limited application, only measures in vehicle water temp and be applied with a small number of fields such as control aspect.
The present invention uses defect chemistry and material semiconductor technology, is doped modification to barium titanate ceramics, substantially carries High material Curie temperature carrier concentration below to improve the NTC effects of material and reduce PTC effects, while passing through residence In the mobile realization width warm area put measure.
Invention content
For the disadvantages described above or Improvement requirement of the prior art, the purpose of the present invention is to provide a kind of wide warm area negative temperatures Coefficient thermosensitive ceramics material and preparation method thereof, wherein passing through constituent to ceramic material key (including specific ingredient Type and the proportioning etc. between them), the overall flow technique of corresponding preparation method, the conditional parameter of each reaction step are (such as Temperature control of reaction etc.) it is improved and further preferably, is changed by being doped to barium titanate-based semiconductor thermal sensitive ceramics Property, barium phthalate base can be obtained, measure warm area up to 300 degree or more of wide range NTC thermosensitive ceramic material, especially Ke Zhen Dui Manganese, The shortcomings that cobalt, nickel transition metal oxide semiconductor thermal sensitive ceramics, realizes low-resistivity, high B values and high resistivity, low B values The preparation of thermo-sensitive material.Novel barium phthalate base NTC semiconductor thermal sensitive ceramicses in the present invention are a kind of measurement warm areas up to 300 degree Above wide range NTC thermosensitive ceramic material, not only measurement range is wide for the material system, but also the linearity (under single logarithmic coordinates) Good, measuring accuracy height；Material average grain size small (being less than 1 micron), ceramic multicrystal body densification, reliability are high simultaneously.
To achieve the above object, according to one aspect of the present invention, a kind of negative temperature coefficient thermal-sensitive ceramic material is provided, It is characterized in that, the raw material composition of the negative temperature coefficient thermosensitive ceramics includes BaTiO3、TiO2、M1O、M2O、M3O、M4O and M5O, and BaTiO3、TiO2、M1O、M2O、M3O、M4O and M5The molar ratio of O meets (1-x-y)：(x+y)：v：w：x：y： Y, wherein v=0.1~0.5, w=1.0~5.0, x=0~40.0, y=0.1~10.0；Each raw material correspond pass System is shown below：
(1-x-y)BaTiO3+(x+y)TiO2+vM1O+wM2O+xM3O+y(M4O+M5O)；
In addition, the M1For at least one kind of element in Sm, Nd, Y, La and Nb；
The M2For at least two kinds of elements in Si, Al and Ti；
The M3For the combination of at least one kind of element and Ca elements in Sr and Pb；
The M4For at least one kind of element in Sb and Bi；
The M5For at least one kind of element in Na, K and Li.
As present invention further optimization, the M2In, the sum of Si, Al or both elements (Si+Al) are with Ti's Molar ratio is 2: 1；
The M3In, the molar ratio of the sum of Sr elements, Pb elements or both elements (Sr+Pb) and Ca elements is 3：1.
It is another aspect of this invention to provide that the present invention provides the preparation sides of above-mentioned negative temperature coefficient thermal-sensitive ceramic material Method, which is characterized in that include the following steps：
(1) NTC powder body materials are prepared：
By BaTiO3、TiO2、M1O、M2O、M3O、M4O、M5The target molar ratio of O matches BaTiO3Source power, the sources Ti powder End, M1Source power, M2Source power, M3Source power, M4Source power and M5Source power is mixed to get mixed powder；Then, by the mixing Powder presses (0.4~0.7) with premixed liquid: the weight ratio of (0.6~0.3) carries out ball milling mixing, and the premixed liquid is by organic list Body, crosslinking agent and water press 10：(0.5~1)：100 weight ratio mixed preparing；Ball milling slurry is placed in container after ball milling, Catalyst and initiator is added, standing makes the ball milling slurry be frozen into colloid；Then, colloid is dried into back glue, then Calcining obtains NTC powder body materials；
(2) NTC thermal sensitive ceramicses are prepared：
Adhesive is added in the NTC powder body materials obtained to the step (1) to be granulated, is then molded and 1250 It is sintered at a high temperature of DEG C -1350 DEG C, you can obtain NTC thermal sensitive ceramicses.
It is described to be sintered at a high temperature of 1250 DEG C -1350 DEG C in the step (2) as present invention further optimization, Specifically first 400 DEG C~500 DEG C are warming up to the heating rate of 150 DEG C/h~200 DEG C/h and keep the temperature at least half an hour；Then again First be warming up to 800 DEG C~1000 DEG C with 150 DEG C/h~250 DEG C/h rates and keep the temperature at least half an hour, then again with 300 DEG C/h~ The sintering temperature that the rate of 350 DEG C/h is warming up to 1250 DEG C~1350 DEG C is sintered, again with 200 after the completion of sintering processes DEG C/cooling of the rate of temperature fall of h~300 DEG C/h.
As present invention further optimization, the time being sintered under 1250 DEG C~1350 DEG C of sintering temperature It is 1~3 hour.
As present invention further optimization, in the step (1), the Ti source powers are TiO2Powder, the M1Source powder End is M1Oxide powder, M2Source power is M2Oxide powder, M3Source power is M3Oxide powder or carbonate powder End, M4Source power is M4Oxide powder, M5Source power is M5Oxide powder or carbonate powder；Described in mixing is constituted The grain size of the various source powers of mixed powder is respectively less than 500 nanometers.
As present invention further optimization, in the step (1), the additive amount of the catalyst and the initiator is equal Meet respectively per 1~5ml of 100ml ball milling slurries.
As present invention further optimization, in the step (1), the drying is dried at 100 DEG C；It is described Dumping be at 600 DEG C dumping (1~3) hour；The calcining is to keep the temperature (1~3) hour at 750~950 DEG C.
As present invention further optimization, in the step (1), the organic monomer is acrylamide (AM), described Crosslinking agent is methylene-bisacrylamide (MBAM), and the catalyst is tetramethylethylenediamine (TEMD), and the initiator is matter Measure the ammonium persulfate (APS) of percentage concentration 10%.
Contemplated above technical scheme through the invention, compared with prior art, by barium titanate-based semiconductor heat Quick ceramics carry out specific composition ingredient and the doping vario-property of proportioning, can obtain following advantageous effect：
1, novel barium phthalate base NTC thermal sensitive ceramic materials of the present invention have measurement wide temperature region, measurement accurate and steady The advantages that fixed high, while macroscopical electric property of material includes：Warm area, normal temperature resistance, material B values etc. is measured to be easy to pass through material Formula is adjusted.For example, when x is 20, y is 5, the measurement warm area of material is -60~180 DEG C, and normal temperature resistance is 100k Ω, Material B values are 2000；When x is 30, y is 0.5, the measurement warm area of material is -50~250 DEG C, and normal temperature resistance is 500 Ω, material Expect that B values are 600 etc..
For the present invention by being doped modification to barium titanate-based semiconductor thermal sensitive ceramics, what is obtained has special component composition Ceramic material can be further used as negative temperature coefficient thermal-sensitive ceramic material application.In doping is at being grouped as, M1In The elements such as Sm, Nd, Y, the La contained are mixed as semiconductor transformation element, and resistivity of material can be adjusted and control, with suitable Thermometric demand for different occasions；M2In the elements such as Si, Al, Ti for containing can control semiconductive ceramic crystallite dimension and Density；M3In the elements such as Ca, Sr, Pb for containing can adjust the measuring temperature range of temperature element；M4In Sb, Bi etc. for containing Element can adjust the material B values of semiconductor ceramic material；M5In the Na, K, the Li et al. element that contain can also adjust semiconductor pottery The material B values of ceramic material.The whole synthesis of these doping components is exactly utilized to act on so that barium phthalate base NTC temperature-sensitives obtained Ceramic material has the characteristics that measure wide temperature region, measures accurate and stablize high.
2, conventional solid-state method prepares thermal sensitive ceramic powder, generally all must be added to deionization in material ball milling mixing technique If water, containing the element that Na, K etc. are soluble easily in water in component, will cause easily as blending agent in subsequent dehydration It is dissolved in the loss of water element (such as Na, K), leads to stoichiometric ratio mismatch.To solve problems, the present invention proposes to use solid phase Gel method prepares powder technology, solves the losing issue of the element soluble easily in water such as Na, K contained in component, it is therefore prevented that chemistry Metering has ensured material property than mismatch.
3, bond material formula designs, and proposes that the sintering process using rapidly heating and cooling prepares thermal sensitive ceramics, rapidly rises to Liquid additive during sintering temperature makes material form quickly forms liquid phase, is wrapped in grain surface and forms layer protecting film, has Effect prevents element evaporation.Fast cooling can inhibit the growth of PTC effects, effectively improve NTC effects.
4, gel calcination temperature is low, can avoid sub- crystalline substance and grows up and reunite, maintains high activity, while largely lowering The volatilization of Pb, Bi plasma.
5, NTC thermal sensitive ceramicses crystallite dimension produced by the present invention is tiny, and close to nanoscale, porcelain body is fine and close, it can be ensured that material High reliability and the long-life.
Description of the drawings
Fig. 1 is the powder preparation flow figure of the present invention.
Fig. 2 is the sintering process figure of the present invention.
Fig. 3 is each sample resistance temperature characteristics figure of 1~6 gained of the embodiment of the present invention.
Fig. 4 is the typical microstructure figure that the present invention implements sample 6.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below It does not constitute a conflict with each other and can be combined with each other.
The wide range NTC thermosensitive ceramic material of the present invention, raw material group become：
(1-x-y)BaTiO3+(x+y)TiO2+vM1O+wM2O+xM3O+y(M4O+M5O)(I)
In formula (I), v=0.1~0.5；W=1.0~5.0；X=0~40.0；Y=0.1~10.0；Correspond to molar ratio Content.
M in ingredient1For at least one kind of element such as Sm, Nd, Y, La, Nb；M2For at least two kinds of elements such as Si, Al, Ti, wherein Si Or the molar ratio of the sum of Al or both elements (Si+Al) and Ti are 2: 1, that is, the molar ratio of Si and Ti be 2: 1 or Al with The molar ratio of Ti is 2: 1, or the molar ratio of (Si+Al) and Ti are 2: 1；M3For Ca, Sr, Pb etc., at least Ca and Sr, Pb The molar ratio of a kind of element combinations, wherein Ca and Pb or Sr or Ca and (Pb+Sr) are 1: 3, that is, molar ratio Ca：Pb=1：3, or Molar ratio Ca：Sr=1：3 or molar ratio Ca: (Pb+Sr)=1: 3；M4For at least one kind of element such as Sb, Bi；M5For Na, K, Li et al. At least one kind of element.Initial feed is all made of the associated metal oxide such as Y that purity is 99.8% or more2O3、Sm2O3、TiO2、 Bi2O3Deng；Or carbonate such as CaCO3、SrCO3Equal raw material；Barium titanate directly uses the BaTiO that purity is more than 99.8%3Powder Body.The grain size of various material powders can be required to be less than 800 nanometers simultaneously.
M1In the elements such as Sm, Nd, Y, La for containing be to be mixed as semiconductor transformation element, the purpose is to be adjustment and control Prepared material resistivity, with the thermometric demand suitable for different occasions；
M2In the elements such as Si, Al, Ti for containing be semiconductive ceramic in order to control crystallite dimension and density；
M3In the elements such as Ca, Sr, Pb for containing be to adjust the measuring temperature range of temperature element；
M4In the elements such as Sb, Bi for containing be the material B values for adjusting semiconductor ceramic material；
M5In the Na, K, the Li et al. element that contain be the material B values for adjusting semiconductor ceramic material.
Negative temperature coefficient thermal-sensitive ceramic material in the present invention is by the raw material by formula (I) composition and ratio, after calcining Form single perovskite structure, the NTC thermal sensitive ceramicses being especially sintered at a high temperature of 1250 DEG C -1350 DEG C (member Part).
Semiconductor N TC thermal sensitive ceramic material preparation methods of the present invention further relate to specific charge ratio, Yi Jigu Phase gel method prepares nano-powder and the rapidly proprietary technology of preparing such as heating and cooling firing process.It is specifically described as follows：
1, solid phase gel method prepares nano-powder
It is matched by formula (I) and carries out dispensing：
(1-x-y)BaTiO3+(x+y)TiO2+vM1O+wM2O+xM3O+y(M4O+M5O)(I)
Wherein：V=0.1~0.5；W=1.0~5.0；X=0~40.0；Y=0.1~10.0；Percentage is corresponded to contain Amount；
Due to, containing the ingredient that Na, K etc. are soluble easily in water, being synthesized according to conventional solid-state method, due to usually all using in component The method of press filtration sends moisture, is bound to cause the loss of the elemental compositions such as Na, the K for being dissolved in water, causes stoichiometric ratio mismatch.But If using solution phase sol-gel method (such as CN101830698B), it is necessary to first by material (such as SiO not soluble in water2) be prepared into it is molten It can then be increased substantially in water such as citric acid salt, manufacturing cost, the present invention proposes to prepare powder using solid phase gel method thus Body technique, detailed process are as shown in Figure 1.
Specifically it may include following steps：
Premixed liquid is prepared first, according to organic monomer: crosslinking agent: water=10: (0.5~1): 100 mass ratio carries out pre- The preparation of mixed liquid, as shown in Figure 1.After the completion of prepared by premixed liquid, will be matched by formula (I) load weighted mixed powder and premixed liquid into Row ball milling mixing, powder: premixed liquid=(0.4~0.7):(0.6~0.3), the ratio are mass ratio, and Ball-milling Time is 1~3 small When；
Secondly, after ball milling, ball milling slurry is placed in container, catalyst is added while stirring, catalyst adds After adding, continue to stir slurry and initiator solution is added dropwise, need to use catalyst and each 1~5ml of initiator left per 100ml slurries It is right.It is stood after dripping off, slurry can be frozen into colloid；
Cured colloid is put into baking oven at 100 DEG C dry by third step；
4th step is calcined, and colloid dumping (1~3) hour at 600 DEG C, is burnt at 750~950 DEG C later, heat preservation (1 ~3) hour can obtain NTC powder body materials.
Organic monomer can be acrylamide (AM) in the premixed liquid, and crosslinking agent can be methylene-bisacrylamide (MBAM)。
The catalyst can be tetramethylethylenediamine (TEMD), and initiator can be the ammonium sulfate (APS) of over-richness 10%, match Method processed is to carry out weighing mixing in mass ratio, APS: H2O=1: 9.
2, NTC thermal sensitive ceramicses are prepared
By gained powder be added adhesive be granulated, it is dry-pressing formed after be sintered 1~3 hour at 1250 DEG C -1350 DEG C of high temperature, It can be obtained NTC sensitive ceramic resistors.
Contain the Volatile Elements such as a large amount of Na, K, Bi, Sb, Pb in being formed due to material, it is necessary to use special agglomerant Skill, the present invention propose to use sintering process as shown in Figure 2.
Can be specifically that the first heating rate with 150 DEG C/h~200 DEG C/h is warming up to 400 DEG C~500 DEG C and keeps the temperature at least Half an hour, it is therefore an objective to exclude the organic matter in green body (such as the adhesive being added in being molded)；Then again first with 150 DEG C/h~250 DEG C/h rates are warming up to 800 DEG C~1000 DEG C and keep the temperature at least half an hour, then again with the rate liter of 300 DEG C/h~350 DEG C/h The sintering temperature of temperature to 1250 DEG C~1350 DEG C is sintered, and sintering temperature is rapidly risen to from (800 DEG C -1000 DEG C) (1250 DEG C -1350 DEG C) are to prevent the volatilization of Volatile Elements, principle from being：Rapidly rising to sintering temperature can be such that material forms In liquid additive quickly form liquid phase, be wrapped in grain surface formed layer protecting film, element evaporation can be effectively prevent. The purpose of (800 DEG C -1000 DEG C) temperature section heat preservation half an hour is to be equivalent to midway to make sintering furnace more effectively be rapidly heated Rest, in case reinforcing.It is cooled to room temperature again with the rate of temperature fall of 200 DEG C/h~300 DEG C/h after the completion of sintering processes, fast cooling It is to effectively improve NTC effects to inhibit the generation of PTC effects.
In the present invention 1~6 embodiment below, raw materials used is barium titanate (BaTiO3), calcium carbonate (CaCO3), carbon Sour sodium (Na2CO3), titanium dioxide (TiO2), yttria (Y2O3), silica (SiO2), bismuth oxide (Bi2O3) etc., purity It is all higher than 99.8%；Organic monomer used is acrylamide (AM), and crosslinking agent is methylene-bisacrylamide (MBAM)；Catalyst For tetramethylethylenediamine (TEMD), initiator is the ammonium persulfate (APS) of concentration 10%.
Sample is listed in when associated electrical performance in table 1 and Fig. 3.
1 each embodiment material prescription table of table
Sintering process shown in table 2 and Fig. 2 is respectively adopted in 1~6 embodiment, and material B values sintering result is also shown in Table 2 below, electricity Resistance temperature characteristics is shown in attached drawing 3.Fig. 4 is the ceramic material micro-structure diagram of embodiment 6.
Table 2：Each embodiment sintering process and material B values are sintered result table
Other than the organic monomer used in above-described embodiment, the present invention can also use other collosol and gels with organic Monomer, and corresponding catalyst, initiator etc..
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to The limitation present invention, all within the spirits and principles of the present invention made by all any modification, equivalent and improvement etc., should all include Within protection scope of the present invention.

Claims (9)

1. a kind of negative temperature coefficient thermal-sensitive ceramic material, which is characterized in that the raw material of the negative temperature coefficient thermosensitive ceramics form Including BaTiO3、TiO2、M1O、M2O、M3O、M4O and M5O, and BaTiO3、TiO2、M1O、M2O、M3O、M4O and M5O Molar ratio meet (1-x-y)：(x+y)：v：w：x：y：Y, wherein v=0.1~0.5, w=1.0~5.0, x=0~40.0, y =0.1~10.0；The relationship that corresponds of each raw material is shown below：
(1-x-y)BaTiO3+(x+y)TiO2+vM1O+wM2O+xM3O+y(M4O+M5O)；
In addition, the M1For at least one kind of element in Sm, Nd, Y, La and Nb；
The M2For at least two kinds of elements in Si, Al and Ti；
The M3For the combination of at least one kind of element and Ca elements in Sr and Pb；
The M4For at least one kind of element in Sb and Bi；
The M5For at least one kind of element in Na, K and Li.
2. negative temperature coefficient thermal-sensitive ceramic material as described in claim 1, which is characterized in that the M2In, Si, Al or this two The molar ratio of the sum of kind element (Si+Al) and Ti are 2: 1；
The M3In, the molar ratio of the sum of Sr elements, Pb elements or both elements (Sr+Pb) and Ca elements is 3：1.
3. the method for preparing negative temperature coefficient thermal-sensitive ceramic material as claimed in claim 1 or 2, which is characterized in that including following Step：
(1) NTC powder body materials are prepared：
By BaTiO3、TiO2、M1O、M2O、M3O、M4O、M5The target molar ratio of O matches BaTiO3Source power, Ti source powers, M1Source power, M2Source power, M3Source power, M4Source power and M5Source power is mixed to get mixed powder；Then, by the mixed powder Body presses (0.4~0.7) with premixed liquid：The weight ratio of (0.6~0.3) carries out ball milling mixing, the premixed liquid be by organic monomer, Crosslinking agent presses 10 with water：(0.5~1)：100 weight ratio mixed preparing；Ball milling slurry is placed in container after ball milling, is added Catalyst and initiator, standing make the ball milling slurry be frozen into colloid；Then, colloid is dried into back glue, then calcined Obtain NTC powder body materials；
(2) NTC thermal sensitive ceramicses are prepared：
In the NTC powder body materials obtained to the step (1) be added adhesive be granulated, then molding and 1250 DEG C- It is sintered at a high temperature of 1350 DEG C, you can obtain NTC thermal sensitive ceramicses.
4. preparation method as claimed in claim 3, which is characterized in that described at 1250 DEG C -1350 DEG C in the step (2) It is sintered, is specifically first warming up to 400 DEG C~500 DEG C with the heating rate of 150 DEG C/h~200 DEG C/h and is kept the temperature to not a half under high temperature Hour；Then 800 DEG C~1000 DEG C first are warming up to 150 DEG C/h~250 DEG C/h rates again and keep the temperature at least half an hour, then again It is warming up to 1250 DEG C~1350 DEG C of sintering temperature with the rate of 300 DEG C/h~350 DEG C/h to be sintered, sintering processes are complete Cheng Houzai is cooled down with the rate of temperature fall of 200 DEG C/h~300 DEG C/h.
5. preparation method as claimed in claim 3, which is characterized in that be sintered under 1250 DEG C~1350 DEG C of sintering temperature The time of processing is 1~3 hour.
6. preparation method as claimed in claim 3, which is characterized in that in the step (1), the Ti source powers are TiO2Powder, The M1Source power is M1Oxide powder, M2Source power is M2Oxide powder, M3Source power is M3Oxide powder Or carbonate powder, M4Source power is M4Oxide powder, M5Source power is M5Oxide powder or carbonate powder；It is mixed The grain size for closing the various source powers for constituting the mixed powder is respectively less than 500 nanometers.
7. preparation method as claimed in claim 3, which is characterized in that in the step (1), the catalyst and the initiator Additive amount respectively meet per 100ml ball milling slurries 1~5ml.
8. preparation method as claimed in claim 3, which is characterized in that in the step (1), the drying be at 100 DEG C into Row drying；The dumping be at 600 DEG C dumping (1~3) hour；The calcining is that heat preservation (1~3) is small at 750~950 DEG C When.
9. preparation method as claimed in claim 3, which is characterized in that in the step (1), the organic monomer is preferably propylene Amide (AM), the crosslinking agent are preferably methylene-bisacrylamide (MBAM), and the catalyst is preferably tetramethylethylenediamine (TEMD), the initiator is preferably the ammonium persulfate (APS) of mass percentage concentration 10%.
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CN114315344A (en) * 2021-12-09 2022-04-12 太原师范学院 Negative temperature coefficient ceramic dielectric 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
CN116283274A (en) * 2023-03-06 2023-06-23 肇庆市金龙宝电子有限公司 NTC thermistor material based on rare earth element and preparation method thereof

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110423112A (en) * 2019-08-08 2019-11-08 中国科学院新疆理化技术研究所 A kind of warm area and the adjustable double-perovskite phase composite thermistor material of B value and preparation method thereof
CN110423112B (en) * 2019-08-08 2022-01-18 中国科学院新疆理化技术研究所 Double-perovskite phase composite thermistor material with adjustable temperature zone and B value 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
CN114315344A (en) * 2021-12-09 2022-04-12 太原师范学院 Negative temperature coefficient ceramic dielectric material and preparation method thereof
CN116283274A (en) * 2023-03-06 2023-06-23 肇庆市金龙宝电子有限公司 NTC thermistor material based on rare earth element and preparation method thereof
CN116283274B (en) * 2023-03-06 2024-04-16 肇庆市金龙宝电子有限公司 NTC thermistor material based on rare earth element and preparation method thereof

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