CN110423112A - A kind of warm area and the adjustable double-perovskite phase composite thermistor material of B value and preparation method thereof - Google Patents

A kind of warm area and the adjustable double-perovskite phase composite thermistor material of B value and preparation method thereof Download PDF

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CN110423112A
CN110423112A CN201910728850.6A CN201910728850A CN110423112A CN 110423112 A CN110423112 A CN 110423112A CN 201910728850 A CN201910728850 A CN 201910728850A CN 110423112 A CN110423112 A CN 110423112A
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warm area
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CN110423112B (en
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张惠敏
桑旭
常爱民
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention discloses a kind of warm areas and the adjustable double-perovskite phase composite thermistor material of B value and preparation method thereof, the resistance material using titanium, lanthanum, the oxide of manganese and barium, strontium, calcium carbonate as raw material, it is prepared using solid phase method, prepare two kinds of perovskite structure powder body materials respectively first, powder is made by calcining respectively, bipolar mixture grinding, molding, sintering.The composite thermistor material of the present invention compared with current material, being overregulated X, Y, chemical general formula molar ratio and sintering temperature can be accurately adjusted B value, thermometric section and its resistivity of material system, unit for electrical property parameters are as follows: B25/50=4422.910K-2527.529K, ρ25℃=26.02M Ω .cm-234 Ω .cm, adjusting warm area range is -100 DEG C -550 DEG C.The material solves B value and is difficult to adjust within 30K；Measurement warm area is difficult to dramatically change；Material it is less reproducible；The problems such as manganese ion is unevenly distributed in lattice.The material has excellent linear relationship, can be applied to thermometric and inhibits surge field.

Description

A kind of warm area and the adjustable double-perovskite phase composite thermistor material of B value and its system Preparation Method
Technical field
The present invention relates to a kind of warm areas and the adjustable double-perovskite phase composite thermistor material of B value and preparation method thereof. The new material is related to semiconductor carriers transmission field, is applied to thermometric, inhibits the fields such as surge.
Background technique
NTC thermistor can be roughly divided into two types structure by prolonged research and development, i.e., spinel structure with Perovskite structure.For spinelle configuration, Co-Mn-Ni-O is most commonly seen material system, however since manganese ion exists Valence distribution is uneven in Spinel.The regulation of B value is difficult to reach in the NTC temperature element of same material on the market at present Within 30K, generally for same material system by the modification scope of doping B value generally in 50K or more.Most of producers in order to Can cross keep the adjusting more refinement of B value most take following three kinds of methods: (1) change material system；(2) strict control produces Each of link；(3) relevant parameter is searched out by batch preparation.These three methods improve NTC thermistor Production cost.It is found through experiments that wherein still there is part manganese under high temperature sintering for the thermistor containing manganese element simultaneously Be precipitated, in order to solve this problem we chooses first fusing point it is higher be not easily decomposed, the oxide of the moisture absorption or volatilization is as being sintered Manganese element oxide is mixed the precipitation in agglutinant to inhibit manganese element by agent.
It is well known that perovskite structure is more more stable than spinel structure, crystal structure void is less.Perovskite structure Stability not only can (wherein barium strontium titanate and lanthanum manganate mix the drift of calcium double-perovskite phase composite materials resistance from resistance fluctuating Shifting rate is up to 6/10000ths) obtain, can also from Alexandra Navrotsky article (Chemistry of Materials, 1998,10 [10] 2787-2793) the tolerance factor this concept for being proposed show that he points out when the tolerance factor Perovskite structure is more stable when closer to 1.Single-phase La0.8Ca0.2MnO3The tolerance factor is 1.07, and molar percentage is respectively 0.125 and 0.875 La0.8Ca0.2MnO3And Ba0.5Sr0.5TiO3The tolerance factor is 1.05 after mutually compound, and double-perovskite is mutually compound For the tolerance factor afterwards than single Perovskite Phase tolerance factor closer to 1, this shows the mutually compound material that can be improved of double-perovskite Stability.It is higher compared to Perovskite Phase and Spinel stable composition.Double-perovskite phase composite materials, which have, simultaneously makes temperature Degree measurement range broaden this characteristic, lanthanum manganate room temperature resistance is only tens ohm, and warm area is relatively narrow to be of limited application, by with With high dielectric constant and room temperature resistivity, barium strontium titanate (its forbidden bandwidth range is 3.2eV-3.4eV) two-phase is compound Lanthanum manganate warm area can be substantially widened, its application in field of temperature measurement is extended.It is former using structure additive effect and seepage flow simultaneously Reason, realizes the compound of material property, and the electrology characteristic using two kinds of different materials in composite ceramic material is learnt from other's strong points to offset one's weaknesses, and reaches single The promotion of the repeatability of the intense adjustment and material of the unobtainable thermometric section of one material and B value.For double-perovskite Mutually compound NTC thermistor is strictly comparing 2 angles θ in existing PDF card after calcining, can accurately control and mutually tie Structure improves the repeatability of component.
Summary of the invention
Present invention aims at provide a kind of warm area and the adjustable double-perovskite phase composite thermistor material of B value, the material Material is by BaCO3、SrCO3、La2O3、TiO2、CaCO3And MnO2For raw material, double-perovskite phase composite thermistor material is synthesized, Its chemical general formula molar ratio are as follows: Ba1-XSrXTiO3:La1-YCaYMnO3=0.9:0.1-0.1:0.9, wherein 0.1≤X≤0.9, 0.1≤Y≤0.9, it is adjustable double by the resulting warm area of the preparation flows such as ball milling, calcining, compound, molding, high temperature sintering and B value The compound NTC thermistor of Perovskite Phase.Warm area and the adjustable double-perovskite of B value of the present invention are mutually compound compared with current material Thermistor material, overregulated X, Y, chemical general formula molar ratio and sintering temperature can be accurately adjusted material system B value, Thermometric section and its resistivity, unit for electrical property parameters are as follows: B25/50=4422.910K-2527.529K, ρ25℃=26.02M Ω .cm-234 Ω .cm, it is -100 DEG C -550 DEG C that warm area range, which is adjusted,.The material system solves B value and is difficult to adjust within 30K Section；Measurement warm area is difficult to dramatically change；Material it is less reproducible；The problems such as manganese ion is unevenly distributed in lattice.According to this Material has excellent linear relationship, can be applied to thermometric and inhibits surge field.
A kind of warm area of the present invention and the adjustable double-perovskite phase composite thermistor material of B value, the material be by BaCO3、SrCO3、La2O3、TiO2、CaCO3And MnO2For raw material, double-perovskite phase composite thermistor material, chemistry are synthesized General formula molar ratio are as follows: Ba1-XSrXTiO3:La1-YCaYMnO3=0.9:0.1-0.1:0.9, wherein 0.1≤X≤0.9,0.1≤Y≤ 0.9。
The preparation method of the warm area and the adjustable double-perovskite phase composite thermistor material of B value, follows these steps It carries out:
A, powder matches: according to chemical general formula molar ratio: Ba1-XSrXTiO3:La1-YCaYMnO3=0.9:0.1-0.1: 0.9, wherein 0.1≤X≤0.9,0.1≤Y≤0.9, by BaCO3-SrCO3-TiO2With La2O3-CaCO3-MnO2Respectively according to member Plain Ba-Sr-Ti and La-Ca-Mn molar ratio is weighed, and is respectively implanted in polytetrafluoroethyltank tank, and control agate ball, divides powder Powder dehydrated alcohol and acetone mixing mass ratio are 1-4:1:1, carry out 8h-12h ball milling, dry at 100 DEG C -150 DEG C of Yu Wendu, Obtain BaCO3-SrCO3-TiO2Mixed powder and La2O3-CaCO3-MnO2Mixed powder, wherein dispersing agent dehydrated alcohol and acetone Mixed volume ratio is 1:9-9:1；
B, it calcines: by BaCO obtained in step a3-SrCO3-TiO2Mixed powder and La2O3-CaCO3-MnO2Mixed powder Body is respectively placed in 800 DEG C -1000 DEG C of temperature, calcines 1-4h at 900 DEG C -1100 DEG C of temperature, obtain Ba1-XSrXTiO3With La1- YCaYMnO3Powder；
C, mixed grinding: by the calcined powder Ba of step b1-XSrXTiO3With La1-YCaYMnO3According to chemical general formula mole Regulated and controled than 0.9:0.1-0.1:0.9, progress two-phase is compound and the poly-vinyl alcohol solution of 0.5-5%wt grinding 2-5h is added；
D, it forms: powder of the step c after compound is formed after isostatic cool pressing 75s-110s under 150-220MP；
E, it is sintered: the merging of step d formed blocks is contained into MnO, Mn2O3、Mn3O4、MnO2Middle one kind or four kinds of Al2O3Or ZrO2In powder, it is sintered 2-6h at Yu Wendu 1200-1400 DEG C, obtains warm area and the mutually compound temperature-sensitive of the adjustable double-perovskite of B value Resistance material.
A kind of warm area of the present invention has with the adjustable double-perovskite phase composite thermistor material of B value, the material Following characteristics:
When X, Y, chemical general formula molar ratio are a certain determining value, by the adjusting to sintering temperature, current chemistry can be made The B value of formula, thermometric warm area change.75 DEG C of sintering temperature are improved for same chemical formula and its proportion, B value can be made to improve 200K。
The invention has the advantages that mutually compound can be unevenly distributed in lattice structure to avoid manganese ion of double-perovskite improves crystal knot The stability of structure, while B value adjustable range can be made in 30K or less.Barium strontium titanate and the compound of lanthanum manganate have widened lanthanum manganate The warm area of base phase NTC thermistor makes up to -100 DEG C -550 DEG C of temperature.By adjusting chemical general formula molar ratio are as follows: Ba1- XSrXTiO3: La1-YCaYMnO3=0.9:0.1-0.1:0.9, wherein the relevant parameter of 0.1≤X≤0.9,0.1≤Y≤0.9 makes to test Precision is minimized, and directly reduces production cost.The repeatability for also substantially increasing material simultaneously, solves phase structure It is difficult to control this problem.
Detailed description of the invention
Fig. 1 is the resistivity of 5-8 of the embodiment of the present invention and the relational graph of temperature, wherein S1、S2、S3、S4Respectively with chemical formula 0.875Ba0.5Sr0.5TiO3-0.125La0.8Ca0.2MnO3、0.75Ba0.5Sr0.5TiO3-0.25La0.8Ca0.2MnO3、 0.625Ba0.5Sr0.5TiO3-0.375La0.8Ca0.2MnO3、0.5Ba0.5Sr0.5TiO3-0.5La0.8Ca0.2MnO3It corresponds.
Specific embodiment
Invention is further described in detail with reference to embodiments.Without departing from the principle of the present invention, still Several improvement can be so made, these improvement are considered as protection scope of the present invention.
Embodiment 1
A, powder matches: according to chemical general formula 0.9Ba0.9Sr0.1TiO3-0.1La0.1Ca0.9MnO3Molar ratio 0.9:0.1, X =0.1, Y=0.9:
By BaCO3-SrCO3-TiO2With La2O3-CaCO3-MnO2Respectively according to element B a-Sr-Ti and La-Ca-Mn moles Than being weighed, it is respectively implanted in polytetrafluoroethyltank tank, control agate ball, powder, dispersing agent dehydrated alcohol mix matter with acetone Amount carries out 8h ball milling, drying at 100 DEG C of Yu Wendu obtains BaCO than being 1:1:13-SrCO3-TiO2Mixed powder and La2O3- CaCO3-MnO2Mixed powder, wherein dispersing agent dehydrated alcohol and acetone mixed volume ratio are 1:9；
B, it calcines: by BaCO obtained in step a3-SrCO3-TiO2Mixed powder and La2O3-CaCO3-MnO2Mixed powder Body is respectively placed in 800 DEG C of temperature, calcines 1h at 900 DEG C of temperature, obtain 0.9Ba0.9Sr0.1TiO3-0.1La0.1Ca0.9MnO3Powder Body；
C, mixed grinding: by the calcined powder 0.9Ba of step b0.9Sr0.1TiO3-0.1La0.1Ca0.9MnO3According to chemistry General formula molar ratio 0.9:0.1 is regulated and controled, and progress two-phase is compound and the poly-vinyl alcohol solution of 0.5%wt grinding 2h is added；
D, it forms: powder of the step c after compound is formed after isostatic cool pressing 110s under 150MP；
E, it is sintered: step d formed blocks is placed in the Al containing MnO2O3In powder, it is sintered 2h at 1200 DEG C of Yu Wendu, is obtained To warm area and the adjustable double-perovskite phase composite thermistor material of B value；
Electrode preparation: silver paste is coated on warm area and the adjustable double-perovskite phase composite thermistor material positive and negative two of B value Face is placed in bell-type furnace and is sintered 60min at 800 DEG C of temperature；By the double-perovskite phase negative temperature coefficient heat by electrode preparation Quick resistance material carries out electrical performance testing, as a result are as follows: B25/50=4282.860K, ρ25℃=17.48M Ω .cm.
Embodiment 2
A, powder matches: according to chemical general formula 0.8Ba0.9Sr0.1TiO3-0.2La0.1Ca0.9MnO3Molar ratio 0.8:0.2, X =0.1, Y=0.9:
By BaCO3-SrCO3-TiO2With La2O3-CaCO3-MnO2Respectively according to element B a-Sr-Ti and La-Ca-Mn moles Than being weighed, it is respectively implanted in polytetrafluoroethyltank tank, control agate ball, powder, dispersing agent dehydrated alcohol mix matter with acetone Amount carries out 8h ball milling, drying at 100 DEG C of Yu Wendu obtains BaCO than being 2:1:13-SrCO3-TiO2Mixed powder and La2O3- CaCO3-MnO2Mixed powder, wherein dispersing agent dehydrated alcohol and acetone mixed volume ratio are 2:8；
B, it calcines: by BaCO obtained in step a3-SrCO3-TiO2Mixed powder and La2O3-CaCO3-MnO2Mixed powder Body is respectively placed in 800 DEG C of temperature, calcines 2h at 900 DEG C of temperature, obtain 0.8Ba0.9Sr0.1TiO3-0.2La0.1Ca0.9MnO3Powder Body；
C, mixed grinding: by the calcined powder 0.8Ba of step b0.9Sr0.1TiO3-0.2La0.1Ca0.9MnO3According to chemistry General formula molar ratio 0.8:0.2 is regulated and controled, and progress two-phase is compound and the poly-vinyl alcohol solution of 1%wt grinding 3h is added；
D, it forms: powder of the step c after compound is formed after isostatic cool pressing 90s under 180MP；
E, it is sintered: the merging of step d formed blocks is contained into MnO and MnO2ZrO2In powder, it is sintered at 1200 DEG C of Yu Wendu 4h obtains warm area and the adjustable double-perovskite phase composite thermistor material of B value；
Electrode preparation: silver paste is coated on warm area and the adjustable double-perovskite phase composite thermistor material positive and negative two of B value Face is placed in bell-type furnace and is sintered 60min at 800 DEG C of temperature；By the double-perovskite phase negative temperature coefficient heat by electrode preparation Quick resistance material carries out electrical performance testing, as a result are as follows: B25/50=4079.289K, ρ25℃=365.69K Ω .cm.
Embodiment 3
A, powder matches: according to chemical general formula 0.7Ba0.9Sr0.1TiO3-0.3La0.1Ca0.9MnO3Molar ratio 0.7:0.3, X =0.1, Y=0.9:
By BaCO3-SrCO3-TiO2With La2O3-CaCO3-MnO2Respectively according to element B a-Sr-Ti and La-Ca-Mn moles Than being weighed, it is respectively implanted in polytetrafluoroethyltank tank, control agate ball, powder, dispersing agent dehydrated alcohol mix matter with acetone Amount carries out 8.5h ball milling, drying at 110 DEG C of Yu Wendu obtains BaCO than being 3:1:13-SrCO3-TiO2Mixed powder and La2O3- CaCO3-MnO2Mixed powder, wherein dispersing agent dehydrated alcohol and acetone mixed volume ratio are 3:7；
B, it calcines: by BaCO obtained in step a3-SrCO3-TiO2Mixed powder and La2O3-CaCO3-MnO2Mixed powder Body is respectively placed in 800 DEG C of temperature, calcines 4h at 900 DEG C of temperature, obtain 0.7Ba0.9Sr0.1TiO3-0.3La0.1Ca0.9MnO3Powder Body；
C, mixed grinding: by the calcined powder 0.7Ba of step b0.9Sr0.1TiO3-0.3La0.1Ca0.9MnO3According to chemistry General formula molar ratio 0.7:0.3 is regulated and controled, and progress two-phase is compound and the poly-vinyl alcohol solution of 2%wt grinding 4h is added；
D, it forms: powder of the step c after compound is formed after isostatic cool pressing 80s under 160MP；
E, it is sintered: the merging of step d formed blocks is contained into MnO, Mn2O3And Mn3O4ZrO2In powder, 1200 DEG C of Yu Wendu Lower sintering 5h obtains warm area and the adjustable double-perovskite phase composite thermistor material of B value；
Electrode preparation: silver paste is coated on warm area and the adjustable double-perovskite phase composite thermistor material positive and negative two of B value Face is placed in bell-type furnace and is sintered 60min at 800 DEG C of temperature；By the double-perovskite phase negative temperature coefficient heat by electrode preparation Quick resistance material carries out electrical performance testing, as a result are as follows: B25/50=3222.495K, ρ25℃=4.85K Ω .cm.
Embodiment 4
A, powder matches: according to chemical general formula 0.6Ba0.9Sr0.1TiO3-0.4La0.1Ca0.9MnO3Molar ratio 0.6:0.4, X =0.1, Y=0.9:
By BaCO3-SrCO3-TiO2With La2O3-CaCO3-MnO2Respectively according to element B a-Sr-Ti and La-Ca-Mn moles Than being weighed, it is respectively implanted in polytetrafluoroethyltank tank, control agate ball, powder, dispersing agent dehydrated alcohol mix matter with acetone Amount carries out 9h ball milling, drying at 110 DEG C of Yu Wendu obtains BaCO than being 4:1:13-SrCO3-TiO2Mixed powder and La2O3- CaCO3-MnO2Mixed powder, wherein dispersing agent dehydrated alcohol and acetone mixed volume ratio are 4:6；
B, it calcines: by BaCO obtained in step a3-SrCO3-TiO2Mixed powder and La2O3-CaCO3-MnO2Mixed powder Body is respectively placed in 850 DEG C of temperature, calcines 3h at 950 DEG C of temperature, obtain 0.6Ba0.9Sr0.1TiO3-0.4La0.1Ca0.9MnO3Powder Body；
C, mixed grinding: by the calcined powder 0.6Ba of step b0.9Sr0.1TiO3-0.4La0.1Ca0.9MnO3According to chemistry General formula molar ratio 0.6:0.4 is regulated and controled, and progress two-phase is compound and the poly-vinyl alcohol solution of 5%wt grinding 5h is added；
D, it forms: powder of the step c after compound is formed after isostatic cool pressing 75s under 220MP；
E, it is sintered: the merging of step d formed blocks is contained into MnO, Mn2O3、Mn3O4And MnO2Al2O3In powder, Yu Wendu It is sintered 6h at 1200 DEG C, obtains warm area and the adjustable double-perovskite phase composite thermistor material of B value.
Electrode preparation: silver paste is coated on warm area and the adjustable double-perovskite phase composite thermistor material positive and negative two of B value Face is placed in bell-type furnace and is sintered 60min at 800 DEG C of temperature；By the double-perovskite phase negative temperature coefficient heat by electrode preparation Quick resistance material carries out electrical performance testing, as a result are as follows: B25/50=2593.082K, ρ25℃=382.1 Ω .cm.
Embodiment 5
A, powder matches: according to chemical general formula 0.875Ba0.5Sr0.5TiO3-0.125La0.8Ca0.2MnO3Molar ratio 0.875: 0.125, X=0.5, Y=0.2:
By BaCO3-SrCO3-TiO2With La2O3-CaCO3-MnO2Respectively according to element B a-Sr-Ti and La-Ca-Mn moles Than being weighed, it is respectively implanted in polytetrafluoroethyltank tank, control agate ball, powder, dispersing agent dehydrated alcohol mix matter with acetone Amount carries out 9.5h ball milling, drying at 125 DEG C of Yu Wendu obtains BaCO than being 1:1:13-SrCO3-TiO2Mixed powder and La2O3- CaCO3-MnO2Mixed powder, wherein dispersing agent dehydrated alcohol and acetone mixed volume ratio are 5:5；
B, it calcines: by BaCO obtained in step a3-SrCO3-TiO2Mixed powder and La2O3-CaCO3-MnO2Mixed powder Body is respectively placed in 850 DEG C of temperature, calcines 1.5h at 950 DEG C of temperature, obtain 0.875Ba0.5Sr0.5TiO3- 0.125La0.8Ca0.2MnO3Powder；
C, mixed grinding: by the calcined powder 0.875Ba of step b0.5Sr0.5TiO3-0.125La0.8Ca0.2MnO3According to Chemical general formula molar ratio 0.875:0.125 is regulated and controled, and progress two-phase is compound and the grinding of the poly-vinyl alcohol solution of 0.5%wt is added 5h；
D, it forms: powder of the step c after compound is formed after isostatic cool pressing 85s under 170MP；
E, it is sintered: the merging of step d formed blocks is contained into Mn2O3And MnO2ZrO2In powder, burnt at 1300 DEG C of Yu Wendu 2h is tied, warm area and the adjustable double-perovskite phase composite thermistor material of B value are obtained；
Electrode preparation: silver paste is coated on warm area and the adjustable double-perovskite phase composite thermistor material positive and negative two of B value Face is placed in bell-type furnace and is sintered 10min at 800 DEG C of temperature；By the double-perovskite phase negative temperature coefficient heat by electrode preparation Quick resistance material carries out electrical performance testing, result B25/50=4388.716K, ρ25℃=26.02M Ω .cm.
Embodiment 6
A, powder matches: according to chemical general formula 0.75Ba0.5Sr0.5TiO3-0.25La0.8Ca0.2MnO3Molar ratio 0.75: 0.25, X=0.5, Y=0.2:
By BaCO3-SrCO3-TiO2With La2O3-CaCO3-MnO2Respectively according to element B a-Sr-Ti and La-Ca-Mn moles Than being weighed, it is respectively implanted in polytetrafluoroethyltank tank, control agate ball, powder, dispersing agent dehydrated alcohol mix matter with acetone Amount carries out 10h ball milling, drying at 125 DEG C of Yu Wendu obtains BaCO than being 1.5:1:13-SrCO3-TiO2Mixed powder and La2O3-CaCO3-MnO2Mixed powder, wherein dispersing agent dehydrated alcohol and acetone mixed volume ratio are 5:5；
B, it calcines: by BaCO obtained in step a3-SrCO3-TiO2Mixed powder and La2O3-CaCO3-MnO2Mixed powder Body is respectively placed in 900 DEG C of temperature, calcines 2.5h at 1000 DEG C of temperature, obtain 0.75Ba0.5Sr0.5TiO3- 0.25La0.8Ca0.2MnO3Powder；
C, mixed grinding: by the calcined powder 0.75Ba of step b0.5Sr0.5TiO3-0.25La0.8Ca0.2MnO3According to change It learns general formula molar ratio 0.75:0.25 to be regulated and controled, progress two-phase is compound and the poly-vinyl alcohol solution of 1.5%wt grinding 3h is added；
D, it forms: powder of the step c after compound is formed after isostatic cool pressing 90s under 180MP；
E, it is sintered: the merging of step d formed blocks is contained into MnO, Mn2O3And MnO2ZrO2In powder, 1300 DEG C of Yu Wendu Lower sintering 3h obtains warm area and the adjustable double-perovskite phase composite thermistor material of B value.
Electrode preparation: silver paste is coated on warm area and the adjustable double-perovskite phase composite thermistor material positive and negative two of B value Face is placed in bell-type furnace and is sintered 30min at 830 DEG C of temperature；By the double-perovskite phase negative temperature coefficient heat by electrode preparation Quick resistance material carries out electrical performance testing, as a result are as follows: B25/50=4086.1858K, ρ25℃=303.53K Ω .cm.
Embodiment 7
A, powder matches: according to chemical general formula 0.625Ba0.5Sr0.5TiO3-0.375La0.8Ca0.2MnO3Molar ratio 0.625: 0.375, X=0.5, Y=0.2:
By BaCO3-SrCO3-TiO2With La2O3-CaCO3-MnO2Respectively according to element B a-Sr-Ti and La-Ca-Mn moles Than being weighed, it is respectively implanted in polytetrafluoroethyltank tank, control agate ball, powder, dispersing agent dehydrated alcohol mix matter with acetone Amount carries out 10.5h ball milling, drying at 130 DEG C of Yu Wendu obtains BaCO than being 2.5:1:13-SrCO3-TiO2Mixed powder and La2O3-CaCO3-MnO2Mixed powder, wherein dispersing agent dehydrated alcohol and acetone mixed volume ratio are 6:4；
B, it calcines: by BaCO obtained in step a3-SrCO3-TiO2Mixed powder and La2O3-CaCO3-MnO2Mixed powder Body is respectively placed in 900 DEG C of temperature, calcines 3.5h at 1000 DEG C of temperature, obtain 0.625Ba0.5Sr0.5TiO3- 0.375La0.8Ca0.2MnO3Powder；
C, mixed grinding: by the calcined powder 0.625Ba of step b0.5Sr0.5TiO3-0.375La0.8Ca0.2MnO3According to Chemical general formula molar ratio 0.625:0.375 is regulated and controled, and progress two-phase is compound and the grinding of the poly-vinyl alcohol solution of 5%wt is added 5h；
D, it forms: powder of the step c after compound is formed after isostatic cool pressing 110s under 220MP；
E, it is sintered: the merging of step d formed blocks is contained into Mn2O3、Mn3O4And MnO2Al2O3In powder, Yu Wendu 1300 It is sintered 5h at DEG C, obtains warm area and the adjustable double-perovskite phase composite thermistor material of B value.
Electrode preparation: silver paste is coated on warm area and the adjustable double-perovskite phase composite thermistor material positive and negative two of B value Face is placed in bell-type furnace and is sintered 10min at 860 DEG C of temperature；By the double-perovskite phase negative temperature coefficient heat by electrode preparation Quick resistance material carries out electrical performance testing, as a result are as follows: B25/50=3223.042K, ρ25℃=3.21K Ω .cm.
Embodiment 8
A, powder matches: according to chemical general formula 0.5Ba0.5Sr0.5TiO3-0.5La0.8Ca0.2MnO3Molar ratio 0.5:0.5, X =0.5, Y=0.2:
By BaCO3-SrCO3-TiO2With La2O3-CaCO3-MnO2Respectively according to element B a-Sr-Ti and La-Ca-Mn moles Than being weighed, it is respectively implanted in polytetrafluoroethyltank tank, control agate ball, powder, dispersing agent dehydrated alcohol mix matter with acetone Amount carries out 10.5h ball milling, drying at 130 DEG C of Yu Wendu obtains BaCO than being 3.5:1:13-SrCO3-TiO2Mixed powder and La2O3-CaCO3-MnO2Mixed powder, wherein dispersing agent dehydrated alcohol and acetone mixed volume ratio are 6:4；
B, it calcines: by BaCO obtained in step a3-SrCO3-TiO2Mixed powder and La2O3-CaCO3-MnO2Mixed powder Body is respectively placed in 950 DEG C of temperature, calcines 4h at 1050 DEG C of temperature, obtain 0.5Ba0.5Sr0.5TiO3-0.5La0.8Ca0.2MnO3Powder Body；
C, mixed grinding: by the calcined powder 0.5Ba of step b0.5Sr0.5TiO3-0.5La0.8Ca0.2MnO3According to chemistry General formula molar ratio 0.5:0.5 is regulated and controled, and progress two-phase is compound and the poly-vinyl alcohol solution of 2.5%wt grinding 2.5h is added；
D, it forms: powder of the step c after compound is formed after isostatic cool pressing 95s under 190MP；
E, it is sintered: the merging of step d formed blocks is contained into MnO2Al2O3In powder, it is sintered 6h at 1300 DEG C of Yu Wendu, Obtain warm area and the adjustable double-perovskite phase composite thermistor material of B value.
Electrode preparation: silver paste is coated on warm area and the adjustable double-perovskite phase composite thermistor material positive and negative two of B value Face is placed in bell-type furnace and is sintered 60min at 800 DEG C of temperature；By the double-perovskite phase negative temperature coefficient heat by electrode preparation Quick resistance material carries out electrical performance testing, as a result are as follows: B25/50=2627.124K, ρ25℃=286.2 Ω .cm.
Embodiment 9
A, powder matches: according to chemical general formula 0.4Ba0.1Sr0.9TiO3-0.6La0.9Ca0.1MnO3Molar ratio 0.4:0.6, X =0.9, Y=0.1:
By BaCO3-SrCO3-TiO2With La2O3-CaCO3-MnO2Respectively according to element B a-Sr-Ti and La-Ca-Mn moles Than being weighed, it is respectively implanted in polytetrafluoroethyltank tank, control agate ball, powder, dispersing agent dehydrated alcohol mix matter with acetone Amount carries out 11h ball milling, drying at 140 DEG C of Yu Wendu obtains BaCO than being 4:1:13-SrCO3-TiO2Mixed powder and La2O3- CaCO3-MnO2Mixed powder, wherein dispersing agent dehydrated alcohol and acetone mixed volume ratio are 7:3；
B, it calcines: by BaCO obtained in step a3-SrCO3-TiO2Mixed powder and La2O3-CaCO3-MnO2Mixed powder Body is respectively placed in 950 DEG C of temperature, calcines 1h at 1050 DEG C of temperature, obtain 0.4Ba0.1Sr0.9TiO3-0.6La0.9Ca0.1MnO3Powder Body；
C, mixed grinding: by the calcined powder 0.4Ba of step b0.1Sr0.9TiO3-0.6La0.9Ca0.1MnO3According to chemistry General formula molar ratio 0.4:0.6 is regulated and controled, and progress two-phase is compound and the poly-vinyl alcohol solution of 0.5%wt grinding 2h is added；
D, it forms: powder of the step c after compound is formed after isostatic cool pressing 105s under 200MP；
E, it is sintered: the merging of step d formed blocks is contained into Mn2O3And Mn3O4Al2O3In powder, at 1400 DEG C of Yu Wendu It is sintered 2h, obtains warm area and the adjustable double-perovskite phase composite thermistor material of B value.
Electrode preparation: silver paste is coated on warm area and the adjustable double-perovskite phase composite thermistor material positive and negative two of B value Face is placed in bell-type furnace and is sintered 60min at 830 DEG C of temperature；By the double-perovskite phase negative temperature coefficient heat by electrode preparation Quick resistance material carries out electrical performance testing, as a result are as follows: B25/50=4422.910K, ρ25℃=20.92M Ω .cm.
Embodiment 10
A, powder matches: according to chemical general formula 0.3Ba0.1Sr0.9TiO3-0.7La0.9Ca0.1MnO3Molar ratio: 0.3:0.7, X =0.9, Y=0.1:
By BaCO3-SrCO3-TiO2With La2O3-CaCO3-MnO2Respectively according to element B a-Sr-Ti and La-Ca-Mn moles Than being weighed, it is respectively implanted in polytetrafluoroethyltank tank, control agate ball, powder, dispersing agent dehydrated alcohol mix matter with acetone Amount carries out 11.5h ball milling, drying at 150 DEG C of Yu Wendu obtains BaCO than being 2.5:1:13-SrCO3-TiO2Mixed powder and La2O3-CaCO3-MnO2Mixed powder, wherein dispersing agent dehydrated alcohol and acetone mixed volume ratio are 7:3；
B, it calcines: by BaCO obtained in step a3-SrCO3-TiO2Mixed powder and La2O3-CaCO3-MnO2Mixed powder Body is respectively placed in 1000 DEG C of temperature, calcines 2h at 1100 DEG C of temperature, obtain 0.3Ba0.1Sr0.9TiO3-0.7La0.9Ca0.1MnO3Powder Body；
C, mixed grinding: by the calcined powder 0.3Ba of step b0.1Sr0.9TiO3-0.7La0.9Ca0.1MnO3According to chemistry General formula molar ratio 0.3:0.7 is regulated and controled, and progress two-phase is compound and the poly-vinyl alcohol solution of 2%wt grinding 3h is added；
D, it forms: powder of the step c after compound is formed after isostatic cool pressing 105s under 210MP；
E, it is sintered: the merging of step d formed blocks is contained into MnO, Mn3O4And MnO2Al2O3In powder, 1400 DEG C of Yu Wendu Lower sintering 3h obtains warm area and the adjustable double-perovskite phase composite thermistor material of B value；
Electrode preparation: silver paste is coated on warm area and the adjustable double-perovskite phase composite thermistor material positive and negative two of B value Face is placed in bell-type furnace and is sintered 20min at 800 DEG C of temperature；By the double-perovskite phase negative temperature coefficient heat by electrode preparation Quick resistance material carries out electrical performance testing, as a result are as follows: B25/50=4377.288K, ρ25℃=602.83K Ω .cm.
Embodiment 11
A, powder matches: according to chemical general formula 0.2Ba0.1Sr0.9TiO3-0.8La0.9Ca0.1MnO3Molar ratio 0.2:0.8, X =0.9, Y=0.1:
By BaCO3-SrCO3-TiO2With La2O3-CaCO3-MnO2Respectively according to element B a-Sr-Ti and La-Ca-Mn moles Than being weighed, it is respectively implanted in polytetrafluoroethyltank tank, control agate ball, powder, dispersing agent dehydrated alcohol mix matter with acetone Amount carries out 12h ball milling, drying at 100 DEG C of Yu Wendu obtains BaCO than being 1.5:1:13-SrCO3-TiO2Mixed powder and La2O3-CaCO3-MnO2Mixed powder, wherein dispersing agent dehydrated alcohol and acetone mixed volume ratio are 8:2；
B, it calcines: by BaCO obtained in step a3-SrCO3-TiO2Mixed powder and La2O3-CaCO3-MnO2Mixed powder Body is respectively placed in 1000 DEG C of temperature, calcines 3h at 1100 DEG C of temperature, obtain 0.2Ba0.1Sr0.9TiO3-0.8La0.9Ca0.1MnO3Powder Body；
C, mixed grinding: by the calcined powder 0.2Ba of step b0.1Sr0.9TiO3-0.8La0.9Ca0.1MnO3According to chemistry General formula molar ratio 0.2:0.8 is regulated and controled, and progress two-phase is compound and the poly-vinyl alcohol solution of 4.5%wt grinding 3h is added；
D, it forms: powder of the step c after compound is formed after isostatic cool pressing 75s under 150MP；
E, it is sintered: the merging of step d formed blocks is contained into MnO, Mn2O3、Mn3O4And MnO2ZrO2In powder, Yu Wendu It is sintered 4h at 1400 DEG C, obtains warm area and the adjustable double-perovskite phase composite thermistor material of B value.
Electrode preparation: silver paste is coated on warm area and the adjustable double-perovskite phase composite thermistor material positive and negative two of B value Face is placed in bell-type furnace and is sintered 15min at 860 DEG C, by the double-perovskite phase negative temperature coefficient thermistor power by electrode preparation It hinders material and carries out electrical performance testing, obtain following parameter B25/50=3700.293K, ρ25℃=5.50K Ω .cm.
Embodiment 12
A, powder matches: according to chemical general formula 0.1Ba0.1Sr0.9TiO3-0.9La0.9Ca0.1MnO3Molar ratio 0.1:0.9.X =0.9, Y=0.1:
By BaCO3-SrCO3-TiO2With La2O3-CaCO3-MnO2Respectively according to element B a-Sr-Ti and La-Ca-Mn moles Than being weighed, it is respectively implanted in polytetrafluoroethyltank tank, control agate ball, powder, dispersing agent dehydrated alcohol mix matter with acetone Amount carries out 12h ball milling, drying at 150 DEG C of Yu Wendu obtains BaCO than being 1:1:13-SrCO3-TiO2Mixed powder and La2O3- CaCO3-MnO2Mixed powder, wherein dispersing agent dehydrated alcohol and acetone mixed volume ratio are 9:1；
B, it calcines: by BaCO obtained in step a3-SrCO3-TiO2Mixed powder and La2O3-CaCO3-MnO2Mixed powder Body is respectively placed in 1000 DEG C of temperature, calcines 4h at 1100 DEG C of temperature, obtain 0.1Ba0.1Sr0.9TiO3-0.9La0.9Ca0.1MnO3Powder Body；
C, mixed grinding: by the calcined powder 0.1Ba of step b0.1Sr0.9TiO3-0.9La0.9Ca0.1MnO3According to chemistry General formula molar ratio 0.1:0.9 is regulated and controled, and progress two-phase is compound and the poly-vinyl alcohol solution of 5%wt grinding 5h is added；
D, it forms: powder of the step c after compound is formed after isostatic cool pressing 110s under 220MP；
E, it is sintered: the merging of step d formed blocks is contained into Mn2O3ZrO2In powder, it is sintered 6h at 1400 DEG C of Yu Wendu, Obtain warm area and the adjustable double-perovskite phase composite thermistor material of B value.
Electrode preparation: silver paste is coated on warm area and the adjustable double-perovskite phase composite thermistor material positive and negative two of B value Face is placed in bell-type furnace and is sintered 10min at 860 DEG C, by the double-perovskite phase negative temperature coefficient thermistor power by electrode preparation It hinders material and carries out electrical performance testing, obtain following parameter B25/50=2527.529K, ρ25℃=234 Ω .cm.
The picture of any one warm area that embodiment 1-12 is obtained and the adjustable double-perovskite phase composite thermistor material of B value Structure is Perovskite Phase, and all potsherd microscopic appearances all show good compactness, preferable at porcelain, and test warm area is adjustable And B value is controllable, specific manifestation are as follows: Fig. 1 is embodiment 5-8 by resistance test and the obtained relationship of formula calculating Figure can substantially judge thermometric section within the scope of -100 DEG C -550 DEG C according to relation curve on the way using extrapolation.

Claims (2)

1. a kind of warm area and the adjustable double-perovskite phase composite thermistor material of B value, it is characterised in that the material is by BaCO3、 SrCO3、La2O3、TiO2、CaCO3And MnO2For raw material, double-perovskite phase composite thermistor material is synthesized, chemical general formula rubs That ratio are as follows: Ba1-XSrXTiO3:La1-YCaYMnO3=0.9:0.1-0.1:0.9, wherein 0.1≤X≤0.9,0.1≤Y≤0.9.
2. the preparation method of warm area according to claim 1 and the adjustable double-perovskite phase composite thermistor material of B value, It is characterized in that following these steps to carry out:
A, powder matches: according to chemical general formula molar ratio: Ba1-XSrXTiO3:La1-YCaYMnO3=0.9:0.1-0.1:0.9, wherein 0.1≤X≤0.9,0.1≤Y≤0.9, by BaCO3-SrCO3-TiO2With La2O3-CaCO3-MnO2Respectively according to element B a-Sr- Ti is weighed with La-Ca-Mn molar ratio, is respectively implanted in polytetrafluoroethyltank tank, and control agate ball, powder, dispersing agent are anhydrous Ethyl alcohol and acetone mixing mass ratio are 1-4:1:1, carry out 8h-12h ball milling, and drying at 100 DEG C -150 DEG C of Yu Wendu obtains BaCO3-SrCO3-TiO2Mixed powder and La2O3-CaCO3-MnO2Mixed powder, wherein dispersing agent dehydrated alcohol is mixed with acetone Volume ratio is 1:9-9:1；
B, it calcines: by BaCO obtained in step a3-SrCO3-TiO2Mixed powder and La2O3-CaCO3-MnO2Mixed powder, point It is not placed in 800 DEG C -1000 DEG C of temperature, calcines 1-4h at 900 DEG C -1100 DEG C of temperature, obtains Ba1-XSrXTiO3With La1-YCaYMnO3 Powder；
C, mixed grinding: by the calcined powder Ba of step b1-XSrXTiO3With La1-YCaYMnO3According to chemical general formula molar ratio 0.9:0.1-0.1:0.9 is regulated and controled, and progress two-phase is compound and the poly-vinyl alcohol solution of 0.5-5%wt grinding 2-5h is added；
D, it forms: powder of the step c after compound is formed after isostatic cool pressing 75s-110s under 150-220MP；
E, it is sintered: the merging of step d formed blocks is contained into MnO, Mn2O3、Mn3O4、MnO2Middle one kind or four kinds of Al2O3Or ZrO2 In powder, it is sintered 2-6h at Yu Wendu 1200-1400 DEG C, obtains warm area and the adjustable double-perovskite phase composite thermistor of B value Material.
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