CN106278221A - Thermistor material and its preparation method and application - Google Patents
Thermistor material and its preparation method and application Download PDFInfo
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- CN106278221A CN106278221A CN201610592786.XA CN201610592786A CN106278221A CN 106278221 A CN106278221 A CN 106278221A CN 201610592786 A CN201610592786 A CN 201610592786A CN 106278221 A CN106278221 A CN 106278221A
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- C04B35/2633—Compositions containing one or more ferrites of the group comprising manganese, zinc, nickel, copper or cobalt and one or more ferrites of the group comprising rare earth metals, alkali metals, alkaline earth metals or lead containing barium, strontium or calcium
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Abstract
The invention discloses a kind of thermistor material and its preparation method and application, its chemical general formula is LaxSr1‑xCoyFe1‑yO3, wherein, 0.5 ＜ x < 1,0 ＜ y < 1.Four kinds of metallic elements form La Sr Co Fe O system with O.The molal quantity sum of two kinds of elements of La Yu Sr is 1:1 with the ratio of the molal quantity sum of two kinds of elements of Co Yu Fe, and, the ratio that ratio shared in thermistor material for 0.5 ＜ x < 1, La element is shared in thermistor material more than Sr element.Through experimental test, this thermistor material better crystallinity degree, B value is relatively low, resistivity is less.Can be applicable to low temperature, high frequency, the temperature damping of the specific occasion such as high-power compensate.
Description
Technical field
The present invention relates to resistance material technical field, especially relate to a kind of thermistor material and preparation method thereof and answer
With.
Background technology
Thermal resistor is the sensitive unit that a class is temperature sensitive, show different resistance values at different temperature
Part, is divided into positive temperature coefficient thermistor (PTC) and negative temperature coefficient thermistor (NTC) according to temperature coefficient difference.
Wherein negative temperature coefficient thermistor (NTC) is the semi-conducting material that a quasi-resistance value reduces with temperature increase, has survey
Temperature, temperature control, temperature-compensating, suppression surge etc. act on.
NTC thermistor material is usually the spinel-type solid solution of transition metal oxide composition.Typically there is one
Or two kinds of metallic elements form crystal structure with oxygen.But, the temperature-sensitive constant (B value) of traditional NTC thermistor material is general
At 2000K～6000K, resistivity is typically at 2 more than Ω cm.B value is higher, resistivity is relatively big, be not suitable for low temperature, high frequency,
The temperature damping of the specific occasion such as high-power compensates.
Summary of the invention
Based on this, it is necessary to provide a kind of thermistor material that B value is relatively low, resistivity is less and preparation method thereof and answer
With.
A kind of thermistor material, it is characterised in that the chemical general formula of described thermistor material is LaxSr1-xCoyFe1- yO3, wherein, 0.5 ＜ x < 1,0 ＜ y < 1.
In one embodiment, 0.6≤x≤0.9,0.4≤y≤0.8.
In one embodiment, described thermistor material the temperature-sensitive constant of the resistor prepared be 100K～
2000K, described thermistor material the resistivity of the resistor prepared is 0.005 Ω cm～2 Ω cm.
The preparation method of above-mentioned thermistor material, comprises the following steps:
By containing La compound, containing Sr compound, the chemistry of pressing thermistor material containing Co compound and the compound Han Fe
Stoichiometry in formula is mixed to form mix, and wherein, the chemical general formula of described thermistor material is LaxSr1- xCoyFe1-yO3, 0.5 ＜ x < 1,0 ＜ y < 1；
Carry out ball milling after adding ball-milling medium and mill ball in described mix, obtain the first powder；
Described first powder is carried out pre-burning, obtains Preburning material；
Carry out ball milling again after adding ball-milling medium and mill ball in described Preburning material, obtain the second powder；And
Described second powder is sintered, obtains described thermistor material.
In one embodiment, described is La containing La compound2O3, described is Sr containing Sr compound2CO3, described containing Co
Compound is Co3O4, described is Fe containing Fe compound2O3。
In one embodiment, the behaviour of ball milling is carried out after adding ball-milling medium and mill ball in described mix
In work, described ball-milling medium is 0.8～1.5:1 with the mass ratio of described mix, described mill ball and described mix
Mass ratio be 2～8:1, the rotating speed of ball milling is 200r/min～300r/min, and Ball-milling Time is 2h～12h.
In one embodiment, ball milling is carried out again after adding ball-milling medium and mill ball in described Preburning material
In operation, described ball-milling medium is 0.8～1.5:1 with the mass ratio of described Preburning material, described mill ball and described Preburning material
Mass ratio is 2～8:1, and the rotating speed of ball milling is 200r/min～400r/min, and Ball-milling Time is 10h～24h.
In one embodiment, described first powder is carried out the operation of pre-burning particularly as follows: put by described first powder
In agglomerating plant, with the heating rate of 1 DEG C/min～10 DEG C/min from room temperature to 900 DEG C～1100 DEG C, at 900 DEG C～
At 1100 DEG C, temperature retention time is 2h～12h；
The operation being sintered described second powder is particularly as follows: be placed in described second powder in agglomerating plant, with 0.5
DEG C/heating rate of min～5 DEG C/min from room temperature to 1200 DEG C～1300 DEG C, at 1200 DEG C～1300 DEG C during insulation
Between be 2h～24h.
In one embodiment, described ball-milling medium is dehydrated alcohol or deionized water, and described mill ball is zirconium oxide
Ball.
The application in resistor and sensor of the above-mentioned thermistor material.
Above-mentioned thermistor material, chemical general formula is LaxSr1-xCoyFe1-yO3, wherein, 0.5 ＜ x < 1,0 ＜ y < 1.This heat
Quick resistance material includes four kinds of metallic element La (lanthanum), Sr (strontium), Co (cobalt) and Fe (ferrum), four kinds of metallic elements and O (oxygen) group
Become La-Sr-Co-Fe-O system.The molal quantity sum of the molal quantity sum of two kinds of elements of La Yu Sr and two kinds of elements of Co Yu Fe
Ratio is 1:1, and, ratio shared in thermistor material for 0.5 ＜ x < 1, La element is more than Sr element at critesistor
Ratio shared in material.Through experimental test, the thermistor material better crystallinity degree of this La-Sr-Co-Fe-O system, B value exists
100K～2000K, electrical resistivity range is 0.005 Ω cm～2 Ω cm, and B value is relatively low, resistivity is less.Can be applicable to low
Temperature, high frequency, the temperature damping of the specific occasion such as high-power compensate.
Accompanying drawing explanation
Fig. 1 is the flow chart of the preparation method of the thermistor material of an embodiment；
Fig. 2 is the XRD spectra of the thermistor material that embodiment 1 prepares；
Fig. 3 is the resistance v. temperature characteristic curve of the thermistor material that embodiment 1 prepares；
Fig. 4 is the XRD spectra of the thermistor material that embodiment 2 prepares；
Fig. 5 is the resistance v. temperature characteristic curve of the thermistor material that embodiment 2 prepares；
Fig. 6 is the XRD spectra of the thermistor material that embodiment 3 prepares；
Fig. 7 is the resistance v. temperature characteristic curve of the thermistor material that embodiment 3 prepares.
Detailed description of the invention
Mainly in combination with accompanying drawing and specific embodiment, thermistor material and its preparation method and application is made into one below
Step detailed description.
The thermistor material of one embodiment, its chemical general formula is LaxSr1-xCoyFe1-yO3, wherein, 0.5 ＜ x < 1,0
＜ y < 1.
The thermistor material of present embodiment includes four kinds of metallic element La (lanthanum), Sr (strontium), Co (cobalt) and Fe (ferrum),
Four kinds of metallic elements form La-Sr-Co-Fe-O system with O (oxygen).The molal quantity sum of two kinds of elements of La Yu Sr and Co Yu Fe two
The ratio of the molal quantity sum planting element is 1:1.Further, shared in thermistor material for 0.5 ＜ x < 1, La element ratio
More than the ratio that Sr element is shared in thermistor material.
Wherein, x and y can be expressed as the mol ratio of each element.Further, 0.6≤x≤0.9,0.4≤y≤0.8.
Concrete, above-mentioned thermistor material the temperature-sensitive constant of the resistor prepared is 100K～2000K, by above-mentioned heat
The resistivity of resistor prepared by quick resistance material is 0.005 Ω cm～2 Ω cm.
Further, in-60 DEG C～120 DEG C of temperature ranges, the heat of resistor prepared by above-mentioned thermistor material
Quick constant is 100K～1000K, above-mentioned thermistor material the resistivity of the resistor prepared is 0.005 Ω cm～0.07
Ω·cm。
Four kinds of metallic elements (La, Sr, Co and Fe) of above-mentioned thermistor material are respectively selected from lanthanide series, alkaline earth gold
Genus, transition metal and transition metal.The molal quantity sum of two kinds of elements of La Yu Sr and two kinds of elements of Co Yu Fe
The ratio of molal quantity sum is 1:1.Through experimental test, the crystal structure of the thermistor material of this combination is relatively tight, diffraction
Peak is sharp-pointed, better crystallinity degree.The resistance value of this thermistor material increases with temperature and reduces, and has negative temperature coefficient thermistor power
The characteristic of resistance device (NTC).Its B value is at 100K～2000K, and electrical resistivity range is 0.005 Ω cm～2 Ω cm, B value is relatively low,
Resistivity is less.Can be applicable to low temperature, high frequency, the temperature damping of the specific occasion such as high-power compensate, and can be applicable in half-breadth
The fields such as warm area thermometric.
As it is shown in figure 1, the preparation method of the thermistor material of an embodiment, comprise the following steps S110～S150.
S110, by containing La compound, containing Sr compound, press thermistor material containing Co compound and the compound Han Fe
Stoichiometry in chemical general formula is mixed to form mix.
Wherein, the chemical general formula of thermistor material is LaxSr1-xCoyFe1-yO3, 0 ＜ x < 1,0 ＜ y < 1.
Further, 0.6≤x≤0.9,0.4≤y≤0.8.La compound will be contained, containing Sr compound, containing Co compound
And containing Fe compound according to the stoichiometry mix homogeneously in chemical general formula.
Concrete, it is La containing La compound2O3(lanthanum sesquioxide), is Sr containing Sr compound2CO3(strontium carbonate), containing Coization
Compound is Co3O4(Cobalto-cobaltic oxide), is Fe containing Fe compound2O3(iron sesquioxide).Wherein, Sr2CO3(strontium carbonate) is through pre-
The SrO (strontium oxide) being decomposed into after burning operation and CO2(carbon dioxide).These several compounds contain La (lanthanum), Sr respectively
(strontium), Co (cobalt) and Fe (ferrum) element, the thermistor material obtained through the operation such as ball milling and sintering after mixing contains only La-
Sr-Co-Fe-O system, will not introduce other impurity.Certainly, in other embodiments, containing La compound, containing Sr compound,
Containing Co compound and the compound that also can also is that other containing Fe compound, such as, can also be La containing La compound2
(CO3)3(lanthanum carbonate) etc., can be SrO (strontium oxide) etc. containing Sr compound, containing Co compound can with CoO (cobalt black) etc.,
Can be FeO (ferrous oxide) etc. containing Fe compound.
Carry out ball milling after S120, the mix obtained in S110 add ball-milling medium and mill ball, obtain the
One powder.
In S110, the mix obtained after each material mixing is generally powder or graininess, adds abrasive media
Grind again and can increase the dispersion effect of powder.Concrete, ball-milling medium is dehydrated alcohol or deionized water, and mill ball is zirconium oxide
Ball.The diameter of zirconia ball can be typically 1mm～about 10mm.Ball milling rear oxidation zirconium ball is recyclable to be reused.
Concrete, carry out in the operation of ball milling after adding ball-milling medium and mill ball in mix, ball-milling medium
Being 0.8～1.5:1 with the mass ratio of mix, mill ball is 2～8:1 with the mass ratio of mix, and the rotating speed of ball milling is
200r/min's (rev/min)～300r/min (rev/min), Ball-milling Time is 2h (hour)～12h (hour).Through ball milling
After can by containing La compound, containing Sr compound, containing Co compound and containing Fe compound composition mix fully mix.
Further, also include carrying out drying to remove ball-milling medium by the first powder obtained after ball milling.The most permissible
Under the temperature conditions of 60 DEG C～100 DEG C, the first powder is dried.By first under the temperature conditions of 85 DEG C in present embodiment
Powder is dried.
Further, also pre-burning operation is carried out again, to remove some grains after the first powder after drying can be sieved
The powder that footpath is excessive or too small, improves the uniformity of final thermistor material.
Each material is mixed by the way of ball milling in the way of solid state reaction by present embodiment, will compare traditional solution
The mode of method mixing, the mixed powder that solid state reaction obtains is more beneficial for being formed the crystal of better crystallinity degree in sintering.
S130, the first powder obtained in S120 is carried out pre-burning, obtain Preburning material.
To the first powder pre-burning obtained after ball milling so that the first powder is pre-formed crystalline structure.
Concrete, the first powder is carried out the operation of pre-burning particularly as follows: be placed in agglomerating plant by the first powder, with 1 DEG C/
The heating rate of min～10 DEG C/min is from room temperature to 900 DEG C～1100 DEG C, and at 900 DEG C～1100 DEG C, temperature retention time is
2h～12h.
S140, in the Preburning material that S130 obtains, add ball-milling medium and mill ball after carry out ball milling again, obtain the
Two powders.
Concrete, ball-milling medium is dehydrated alcohol or deionized water, and mill ball is zirconia ball.The diameter one of zirconia ball
As can be 5mm～about 10mm.Ball milling rear oxidation zirconium ball is recyclable to be reused.
Concrete, carry out again in the operation of ball milling after adding ball-milling medium and mill ball in Preburning material, ball milling is situated between
Matter is 0.8～1.5:1 with the mass ratio of Preburning material, and mill ball is 2～8:1 with the mass ratio of Preburning material, and the rotating speed of ball milling is
200r/min's～400r/min, Ball-milling Time is 10h～24h.
First powder pre-burning is terminated laggard row ball milling again so that the material forming crystal structure after pre-burning mixes again
Even, improve the mixing uniformity of each component further, ball milling forms new less crystal structure again.
Further, also include carrying out drying to remove ball-milling medium by the second powder obtained after ball milling again.Such as
Under the temperature conditions of 60 DEG C～100 DEG C, the second powder can be dried.Will under the temperature conditions of 85 DEG C in present embodiment
Second powder is dried.
Further, also the powder after drying can be sieved, the powder excessive or too small to remove some particle diameters, carry
The uniformity of high final thermistor material.The size of screen cloth can be 80 mesh mesh screen to 120 mesh.
S150, the second powder obtained in S140 is sintered, obtains thermistor material.
To the second powder sintering so that powder forms more stable crystalline structure.
Concrete, the operation being sintered the second powder is particularly as follows: be placed in the second powder in agglomerating plant, with 0.5
DEG C/heating rate of min～5 DEG C/min from room temperature to 1200 DEG C～1300 DEG C, at 1200 DEG C～1300 DEG C during insulation
Between be 2h～24h.
Concrete, the second powder pressing can be become cylindric part before sintering, then be sintered i.e. can get resistance porcelain
Body.Upper and lower surface at resistance porcelain body can prepare silver electrode by modes such as silk screen printing silver slurries, through 800 after printing silver slurry
DEG C burning infiltration 5min～30min, can carry out resistance-temperature characteristics test.
First powder pre-burning terminates laggard row ball milling again so that the material forming crystal structure after pre-burning mixes again
Even, improve the mixing uniformity of each component further, ball milling can form new less crystal structure again.By ball milling again
After the second powder of obtaining be sintered, promote the compactness of five kinds of crystal structure of element of La, Sr, Co, Fe and O further,
Making the thermistor material better crystallinity degree of La-Sr-Co-Fe-O system, performance is more excellent.And between crystal grain, arrange that more compact can
Can be to cause the reason that B value is relatively low, resistivity is less.
The preparation method of above-mentioned thermistor material, will contain La compound, containing Sr compound, containing Co compound and containing Fe
Compound mixes, and carries out ball milling, pre-burning, again ball milling and the operation of sintering successively.Carry out under solid phase conditions during reaction,
The impurity minimally controlling other introduces.The Preburning material obtained after first powder pre-burning carries out ball milling again so that pre-
The material forming crystal structure after burning mixes again, improves the mixing uniformity of each component further, and ball milling is formed again
New less crystal structure.The second powder that ball milling obtains again is sintered operation, can promote La, Sr, Co, Fe further
And the compactness of five kinds of crystal structure of element of O so that the thermistor material better crystallinity degree of La-Sr-Co-Fe-O system, property
Can be more excellent.The crystal structure of the thermistor material that this method prepares is relatively tight, diffraction maximum is sharp-pointed, better crystallinity degree.B value
At 100K～2000K, electrical resistivity range is 0.005 Ω cm～2 Ω cm, and B value is relatively low, resistivity is less.Can be applicable to
Low temperature, high frequency, the temperature damping of the specific occasion such as high-power compensate, and can be applicable in fields such as half-breadth warm area thermometrics.
The thermistor material of the present invention can be applicable in the field such as resistor and sensor.By thermistor material system
Resistor and sensor, B value is relatively low, resistivity is less, thus can be used for low temperature, high frequency, the specific occasion such as high-power
Temperature damping compensates.
It it is below specific embodiment part.
If no special instructions, the experimental technique of unreceipted actual conditions, generally according to normal condition for following example.Each reality
Execute the B value obtained in example to be calculated by equation below:
B=T1T2Ln(RT1/RT2)/(T2-T1),
Wherein T1And T2Represent the triumphant formula temperature value (K) two temperature specified, RT1Represent temperature T1Time zero energy electricity
Resistance, RT2Represent temperature T2Time zero-power resistance.
Embodiment 1
Preparation La0.8Sr0.2Co0.4Fe0.6O3Porcelain body
According to chemical general formula La0.8Sr0.2Co0.4Fe0.6O3Stoichiometric proportion weigh lanthanum sesquioxide, strontium carbonate, four oxygen
Change three cobalts, iron sesquioxide carries out dispensing.Raw material after weighing is put in ball grinder, adds dehydrated alcohol and is situated between as ball milling
Matter, zirconia ball is as mill ball, and wherein the quality of dehydrated alcohol is 1 times of mix, and the quality of zirconia ball is mixing
5 times of dispensing quality, ball milling mixing 6h, rotating speed is 250r/min.By the slurry after ball milling under the conditions of 85 DEG C by dehydrated alcohol
Carrying out pre-burning, calcined temperature 1100 DEG C after drying, heating rate is 2 DEG C/min, is incubated 12h, obtains Preburning material.In Preburning material
Again add dehydrated alcohol as ball-milling medium, and add zirconia ball and carry out ball milling again as mill ball.The most anhydrous second
The quality of alcohol is 1 times of Preburning material, and the quality of zirconia ball is 5 times of Preburning material quality, ball milling 12h, rotating speed 250r/min.Will
Dehydrated alcohol is dried under the conditions of 85 DEG C by the slurry after ball milling again.Then the drying material after ball milling again is pressed into cylinder
Body, the heating rate of 1 DEG C/min to 1200 DEG C insulation 3h, i.e. can get formula is La0.8Sr0.2Co0.4Fe0.6O3NTC temperature-sensitive
Resistance porcelain body.Then the upper and lower surface at porcelain body prepares silver electrode by the way of silk screen printing silver is starched, and after printing, silver slurry is through 800
DEG C burning infiltration 30min, last test resistance-temperature characteristics.
Refer to Fig. 2, the La that embodiment 1 prepares0.8Sr0.2Co0.4Fe0.6O3The XRD spectra of porcelain body.Can from Fig. 2
Going out this porcelain body is perovskite structure, and diffraction maximum is sharp-pointed, and degree of crystallinity is preferable.Refer to Fig. 3, La0.8Sr0.2Co0.4Fe0.6O3Porcelain body electricity
Resistance-temperature characteristics.As can be seen from Figure 3 the room temperature resistivity of this material is 0.03 Ω cm, is calculated B25/85
Value is 880K.La is described0.8Sr0.2Co0.4Fe0.6O3The resistivity of porcelain body is less, and B value is less.
Embodiment 2
Preparation La0.8Sr0.2Co0.7Fe0.3O3Porcelain body
According to chemical general formula La0.8Sr0.2Co0.7Fe0.3O3Stoichiometric proportion weigh lanthanum sesquioxide, strontium carbonate, four oxygen
Change three cobalts, iron sesquioxide carries out dispensing.Raw material after weighing is put in ball grinder, adds dehydrated alcohol and is situated between as ball milling
Matter, adds zirconia ball as mill ball, and wherein the quality of dehydrated alcohol is 1 times of mix, and the quality of zirconia ball is
5 times of mix quality, carry out ball milling mixing 6h, rotating speed 250r/min.Nothing will be dried under the conditions of 85 DEG C of slurry after ball milling
Carrying out pre-burning, calcined temperature 1100 DEG C after water-ethanol, heating rate is 2 DEG C/min, is incubated 12h.Preburning material is again with anhydrous second
Alcohol, as ball-milling medium, adds zirconia ball again as mill ball, and wherein the quality of dehydrated alcohol is 1 times of raw material, oxidation
The quality of zirconium ball is 5 times of raw materials quality, carries out ball milling 12h, rotating speed 250r/min.Slurry after ball milling is dried nothing at 85 DEG C
Water-ethanol.Then the drying material after ball milling again is pressed into cylinder, the heating rate of 1 DEG C/min to 1200 DEG C insulation 3h,
I.e. can get formula is La0.8Sr0.2Co0.7Fe0.3O3NTC thermistor porcelain body.Then the upper and lower surface at porcelain body passes through silk
The mode of wire mark brush silver slurry prepares silver electrode, and after printing, silver slurry is through 800 DEG C of burning infiltration 30min, last test resistance-temperature characteristics.
Refer to Fig. 4, the La that embodiment 2 prepares0.8Sr0.2Co0.7Fe0.3O3The XRD figure of porcelain body.As can be seen from Figure 4
This porcelain body is perovskite structure, and diffraction maximum is sharp-pointed, and degree of crystallinity is preferable.Refer to Fig. 5, La0.8Sr0.2Co0.7Fe0.3O3The electricity of porcelain body
Resistance-temperature characteristics.From figure 5 it can be seen that the room temperature resistivity of this material is 0.02 Ω cm, it is calculated B25/85
Value is 780K.La is described0.8Sr0.2Co0.7Fe0.3O3The resistivity of porcelain body is less, and B value is less.
Embodiment 3
Preparation La0.7Sr0.3Co0.8Fe0.2O3Porcelain body.
According to chemical general formula La0.7Sr0.3Co0.8Fe0.2O3Stoichiometric proportion weigh lanthanum sesquioxide, strontium carbonate, four oxygen
Change three cobalts, iron sesquioxide carries out dispensing.Raw material after weighing is put in ball grinder, using dehydrated alcohol as ball-milling medium,
Adding zirconia ball as mill ball, wherein the quality of dehydrated alcohol is 0.8 times of mix, and the quality of zirconia ball is mixed
Close dispensing quality 6 times, carry out ball milling mixing 8h, rotating speed 248r/min.After 85 DEG C of slurry after ball milling is dried dehydrated alcohol
Carry out pre-burning, calcined temperature 1000 DEG C, 5 DEG C/min of heating rate, be incubated 11h.Preburning material is again with dehydrated alcohol and zirconium oxide
Ball carries out ball milling as medium, and wherein the quality of dehydrated alcohol is 0.8 times of raw material, and the quality of zirconia ball is raw materials quality
6 times, carry out ball milling 12h, rotating speed 248r/min.Slurry after ball milling is dried dehydrated alcohol at 85 degrees Celsius；Then by ball milling
After drying material be pressed into cylinder, the heating rate of 1 DEG C/min to 1250 DEG C insulation 3h, i.e. can get formula is
La0.7Sr0.3Co0.8Fe0.2O3NTC thermistor porcelain body；Then the side starched by silk screen printing silver in the upper and lower surface of porcelain body
Formula prepares silver electrode, and after printing, silver slurry is through 800 DEG C of burning infiltration 30min, last test resistance-temperature characteristics.Refer to Fig. 6, implement
The La that example 3 obtains0.7Sr0.3Co0.8Fe0.2O3The XRD figure of porcelain body.As can be seen from Figure 6 this porcelain body is perovskite structure, diffraction maximum
Sharply, degree of crystallinity is preferable.Refer to Fig. 7, La0.7Sr0.3Co0.8Fe0.2O3The resistance-temperature characteristics curve of porcelain body.Can from Fig. 7
To find out, the room temperature resistivity of this material is 0.007 Ω cm, is calculated B25/85 value for 200K.Explanation
La0.7Sr0.3Co0.8Fe0.2O3The resistivity of porcelain body is less, and B value is less.
Embodiment 4
Preparation La0.6Sr0.4Co0.1Fe0.9O3Porcelain body
According to chemical general formula La0.6Sr0.4Co0.1Fe0.9O3Stoichiometric proportion weigh lanthanum sesquioxide, strontium carbonate, four oxygen
Change three cobalts, iron sesquioxide carries out dispensing.Raw material after weighing is put in ball grinder, adds deionized water and is situated between as ball milling
Matter, zirconia ball is as mill ball, and wherein the quality of deionized water is 1.5 times of mix, and the quality of zirconia ball is mixed
Close dispensing quality 8 times, ball milling mixing 2h (hour), rotating speed is 200r/min (rev/min).By the slurry after ball milling at 85 DEG C
Under the conditions of by deionized water dry after carry out pre-burning, calcined temperature 1100 DEG C, heating rate is 10 DEG C/min, be incubated 12h, obtain
Preburning material.In Preburning material, again add deionized water as ball-milling medium, and add zirconia ball and carry out again as mill ball
Secondary ball milling.Wherein the quality of deionized water is 1.5 times of Preburning material, and the quality of zirconia ball is 8 times of Preburning material quality, ball milling
10h, rotating speed 200r/min.Deionized water is dried under the conditions of 85 DEG C by the slurry after ball milling again.Then by ball milling again
After drying material be pressed into cylinder, the heating rate of 1 DEG C/min to 1300 DEG C insulation 3h, i.e. can get formula is
La0.6Sr0.4Co0.1Fe0.9O3NTC thermistor porcelain body.Then the side starched by silk screen printing silver in the upper and lower surface of porcelain body
Formula prepares silver electrode, and after printing, silver slurry is through 800 DEG C of burning infiltration 30min, last test resistance-temperature characteristics.
La after tested0.6Sr0.4Co0.1Fe0.9O3The room temperature resistivity of porcelain body is 2 Ω cm, and B25/85 value is 1800K.Say
Bright La0.6Sr0.4Co0.1Fe0.9O3The resistivity of porcelain body is less, and B value is less.
Embodiment 5
Preparation La0.9Sr0.1Co0.8Fe0.2O3Porcelain body
According to chemical general formula La0.9Sr0.1Co0.8Fe0.2O3Stoichiometric proportion weigh lanthanum sesquioxide, strontium carbonate, four oxygen
Change three cobalts, iron sesquioxide carries out dispensing.Raw material after weighing is put in ball grinder, adds dehydrated alcohol and is situated between as ball milling
Matter, zirconia ball is as mill ball, and wherein the quality of dehydrated alcohol is 0.8 times of mix, and the quality of zirconia ball is mixed
Close dispensing quality 2 times, ball milling mixing 12h (hour), rotating speed is 300r/min (rev/min).By the slurry after ball milling 85
Carrying out pre-burning, calcined temperature 900 DEG C after being dried by dehydrated alcohol under the conditions of DEG C, heating rate is 1 DEG C/min, is incubated 12h, obtains
Preburning material.In Preburning material, again add deionized water as ball-milling medium, and add zirconia ball and carry out again as mill ball
Secondary ball milling.Wherein the quality of deionized water is 0.8 times of Preburning material, and the quality of zirconia ball is 10 times of Preburning material quality, ball
Mill 24h, rotating speed 400r/min.Deionized water is dried under the conditions of 85 DEG C by the slurry after ball milling again.Then by ball again
Drying material after mill is pressed into cylinder, and the heating rate of 0.5 DEG C/min to 1200 DEG C insulation 3h, i.e. can get formula is
La0.9Sr0.1Co0.8Fe0.2O3NTC thermistor porcelain body.Then the side starched by silk screen printing silver in the upper and lower surface of porcelain body
Formula prepares silver electrode, and after printing, silver slurry is through 800 DEG C of burning infiltration 30min, last test resistance-temperature characteristics.
La after tested0.9Sr0.1Co0.8Fe0.2O3The room temperature resistivity of porcelain body is 1.5 Ω cm, and B25/85 value is 2000K.
La is described0.9Sr0.1Co0.8Fe0.2O3The resistivity of porcelain body is less, and B value is less.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more concrete and detailed, but also
Therefore the restriction to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that, for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement, these broadly fall into the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a thermistor material, it is characterised in that the chemical general formula of described thermistor material is LaxSr1-xCoyFe1- yO3, wherein, 0.5 ＜ x < 1,0 ＜ y < 1.
Thermistor material the most according to claim 1, it is characterised in that 0.6≤x≤0.9,0.4≤y≤0.8.
Thermistor material the most according to claim 1, it is characterised in that the resistance prepared by described thermistor material
The temperature-sensitive constant of device is 100K～2000K, described thermistor material the resistivity of the resistor prepared is 0.005 Ω cm
～2 Ω cm.
4. such as the preparation method of thermistor material of any one of claims 1 to 3, it is characterised in that comprise the following steps:
By containing La compound, containing Sr compound, the chemical general formula of pressing thermistor material containing Co compound and the compound Han Fe
In stoichiometry be mixed to form mix, wherein, the chemical general formula of described thermistor material is LaxSr1-xCoyFe1- yO3, 0.5 ＜ x < 1,0 ＜ y < 1；
Carry out ball milling after adding ball-milling medium and mill ball in described mix, obtain the first powder；
Described first powder is carried out pre-burning, obtains Preburning material；
Carry out ball milling again after adding ball-milling medium and mill ball in described Preburning material, obtain the second powder；And
Described second powder is sintered, obtains described thermistor material.
The preparation method of thermistor material the most according to claim 4, it is characterised in that described containing La compound be
La2O3, described is Sr containing Sr compound2CO3, described is Co containing Co compound3O4, described is Fe containing Fe compound2O3。
The preparation method of thermistor material the most according to claim 4, it is characterised in that add in described mix
Carrying out in the operation of ball milling after entering ball-milling medium and mill ball, described ball-milling medium with the mass ratio of described mix is
0.8～1.5:1, the mass ratio of described mill ball and described mix is 2～8:1, the rotating speed of ball milling be 200r/min～
300r/min's, Ball-milling Time is 2h～12h.
The preparation method of thermistor material the most according to claim 4, it is characterised in that add in described Preburning material
Carrying out again in the operation of ball milling after ball-milling medium and mill ball, described ball-milling medium with the mass ratio of described Preburning material is
0.8～1.5:1, described mill ball is 2～8:1 with the mass ratio of described Preburning material, and the rotating speed of ball milling is 200r/min～400r/
Min's, Ball-milling Time is 10h～24h.
The preparation method of thermistor material the most according to claim 4, it is characterised in that described first powder is carried out
The operation of pre-burning particularly as follows: described first powder is placed in agglomerating plant, with the heating rate of 1 DEG C/min～10 DEG C/min from
Room temperature is to 900 DEG C～1100 DEG C, and at 900 DEG C～1100 DEG C, temperature retention time is 2h～12h；
The operation that described second powder is sintered particularly as follows: described second powder is placed in agglomerating plant, with 0.5 DEG C/
The heating rate of min～5 DEG C/min is from room temperature to 1200 DEG C～1300 DEG C, and at 1200 DEG C～1300 DEG C, temperature retention time is
2h～24h.
The preparation method of thermistor material the most according to claim 4, it is characterised in that described ball-milling medium is anhydrous
Ethanol or deionized water, described mill ball is zirconia ball.
10. the described thermistor material of any one of claims 1 to 3 application in resistor and sensor.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108627080A (en) * | 2017-03-20 | 2018-10-09 | 上海敏传智能科技有限公司 | A kind of strain transducer and strain transducer composite material of included temperature compensation function |
| CN109060160A (en) * | 2018-06-25 | 2018-12-21 | 泗阳君子兰激光科技发展有限公司 | High voltage bearing temperature sensor |
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