CN107140977A - The preparation method of barium doping Lanthanum Chromite Yttrium coated stable zirconium oxide negative temperature coefficient heat-sensitive composite ceramic material - Google Patents

The preparation method of barium doping Lanthanum Chromite Yttrium coated stable zirconium oxide negative temperature coefficient heat-sensitive composite ceramic material Download PDF

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CN107140977A
CN107140977A CN201710350950.0A CN201710350950A CN107140977A CN 107140977 A CN107140977 A CN 107140977A CN 201710350950 A CN201710350950 A CN 201710350950A CN 107140977 A CN107140977 A CN 107140977A
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zirconium oxide
yttrium
stable zirconium
lanthanum chromite
temperature
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CN107140977B (en
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张惠敏
陈明星
刘婷
姜辉
常爱民
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Abstract

The present invention relates to a kind of preparation method of barium doping Lanthanum Chromite Yttrium coated stable zirconium oxide negative temperature coefficient heat-sensitive composite ceramic material, this method inner core is the high resistant phase yttrium stable zirconium oxide with high resistance（YSZ）Material, external shell is the low-resistance phase LaBaCrO materials with low-resistivity and the quick constant of low-heat, and core and shell are respectively by with six hydrates, the ammoniacal liquor of eight hydrates of zirconium oxychloride, yttrium nitrate；Lanthanum sesquioxide, chrome green and barium carbonate are raw material, by grinding, calcining, grinding, composite compact shaping, cold isostatic compaction, high temperature sintering, you can obtain the thermal sensitive ceramics of LaBaCrO YSZ clad structures, its material constant B‑75℃/‑50℃Scope be (1,700 3500) × (1 ± 2%) K, the scope of temperature 50 C resistance value is (15 3132) × (1 ± 2%) Ω.The Lanthanum Chromite cladding yttria-stabilized zirconia thermal sensitive ceramic material of the barium doping prepared using the present invention has negative temperature coefficient feature, and electric performance stablity, uniformity preferably, is adapted in manufacture the thermal resistor in wide warm area environment under low temperature.

Description

Barium doping Lanthanum Chromite Yttrium coated stable zirconium oxide negative temperature coefficient heat-sensitive composite ceramics material The preparation method of material
Technical field
The present invention relates to a kind of preparation side of barium doping Lanthanum Chromite Yttrium coated stable zirconium oxide composite material with negative temperature coefficient Method, the thermal sensitive ceramic material has obvious negative temperature coefficient feature in -196-50 DEG C of temperature ranges, is that one kind is applied to system The new ceramic material of wide warm area thermal resistor under low temperature is made, the clad structure has in regulated in wider range temperature-sensitive electricity The feature of resistance is hindered, belongs to semiconductor transducer field.
Background technology
Sensitive material is one of national three big pillars of electronics and information industry determined with component, has been considered as most Electronic technology product with development prospect, to lifting China electronics industry, status has act foot light to development Sensitive Apparatus in the world The effect of weight.Thermistor has good reliability, sensitivity height, lower-price characteristic, has been widely used in daily life The TEMP and control of electrical appliance and industrial equipment.The application of NTC thermistor mainly includes：Suppress surge current, temperature Compensation, therm-param method.The wide warm area application demand of measurement to meet aircraft industry and daily life, wide warm area temperature-sensitive electricity Hinder material has turned into the new development trend in NTC thermistor field and study hotspot.
LaCrO3With very high fusing point (2400 DEG C), and with the good characteristics such as resistant to chemical etching, have been widely used for The fields such as refractory material, heating material and fuel cell.Pass through Ba2+The doping of ion, adjusts LaCrO3Electricalresistivityρ and its heat Quick constant B, can obtain the ceramic material with low ρ and low B；YSZ has the features such as stable, the corrosion-resistant, high value of chemical property.
First passage of the present invention coats the LaBaCrO materials of low-resistance phase the yttrium stable zirconium oxide (YSZ) of high resistant phase, obtains LaBaCrO-YSZ compound phase thermo-sensitive material systems, resistance value that can be in regulated in wider range material and the B values influence on material It is smaller, the thermistor of composite thermistor material system wide warm area environmental applications under low temperature manufacture of acquisition.
The content of the invention
It is an object of the present invention to provide a kind of barium doping Lanthanum Chromite Yttrium coated stable zirconium oxide negative temperature coefficient heat-sensitive is answered The preparation method of ceramic material is closed, this method inner core is high resistant phase yttrium stable zirconium oxide (YSZ) material with high resistance, External shell is the low-resistance phase LaBaCrO materials with low-resistivity and the quick constant of low-heat, and core and shell are respectively by with zirconium oxychloride Eight hydrates, six hydrates, the ammoniacal liquor of yttrium nitrate；Lanthanum sesquioxide, chrome green and barium carbonate are raw material, are passed through Grinding, calcining, grinding, composite compact shaping, cold isostatic compaction, high temperature sintering, you can obtain LaBaCrO-YSZ clad structures Thermal sensitive ceramics, its material constant B-75℃/-50℃Scope be (1700-3500) × (1 ± 2%) K, -50 DEG C of resistance values of temperature Scope is (15-3132) × (1 ± 2%) Ω.The Lanthanum Chromite cladding stabilized with yttrium oxide oxidation of the barium doping prepared using the present invention Zirconium sensitive ceramic resistor has a negative temperature coefficient feature, material system electric performance stablity, and preferably, suitable manufacture is used for uniformity The thermal resistor used under low temperature in wide warm area environment.
A kind of barium doping Lanthanum Chromite Yttrium coated stable zirconium oxide negative temperature coefficient heat-sensitive composite ceramics material of the present invention The material structure being related in the preparation method of material, this method is made up of kernel yttrium stable zirconium oxide (1) and shell LaBaCrO (2), Concrete operations follow these steps to carry out：
A, by raw material La2O3、BaCO3And Cr2O3, La in molar ratio:Ba:Cr=30-50:1-30:40-50 precises, Agate mortar grinding 5-8h is placed in, well mixed powder body material is obtained；
B, by the powder body material obtained in step a in 1200-1400 DEG C of temperature calcining 5-8h, regrind 6-10h, obtain The Lanthanum Chromite Powders (2) of barium doping；
C, by raw material ZrOCl2·8H2O and Y (NO3)3·6H2O Zr in molar ratio:Y=84-96:4-16 precises, point 0.2-0.5mol/L solution Jia Ru not be configured in deionized water, it is standby；
D, concentrated ammonia liquor is accurately measured, then concentrated ammonia liquor is dissolved in deionized water, be configured to 10-12mol/L solution, it is standby With；
E, two kinds of solution obtained by step c are mixed, then instilled dropwise in the ammoniacal liquor of step d configurations, in drop Stirring, separates out, is washed, filtered completely to White Flocculus, and in 70-80 DEG C of drying of temperature, obtains powder；
F, by the powder obtained in step e in 600-900 DEG C of temperature calcining 4-6h, regrind 6-10h, obtain yttrium stable The powder of zirconium oxide；
G, the powder body material for obtaining step f are with 3-6Kg/cm2Pressure carry out compound stalk forming, pressurize 1min obtains straight Footpath is 2-15mm core yttrium stable zirconium oxide (1) disk green compact；
H, core yttrium stable zirconium oxide (1) green compact that step g is obtained are placed in the Lanthanum Chromite Powders (2) obtained in step b, With 30-60Kg/cm2Pressure carry out compound stalk forming, pressurize 1-3min obtains a diameter of 5-20mm disk green compact, will be molded Block materials carry out isostatic cool pressing, pressure be 200-400MPa under pressurize 1-4min, after by block materials in temperature 1400- 1700 DEG C of sintering 4-7h, you can obtain barium doping Lanthanum Chromite Yttrium coated stable zirconium oxide thermal sensitive ceramic material；
I, the thermal sensitive ceramic material tow sides for obtaining step h coat ag paste electrode, in burning infiltration 2h at 850 DEG C of temperature, Obtain the negative temperature coefficient heat-sensitive composite ceramic material of barium doping Lanthanum Chromite Yttrium coated stable zirconium oxide.
Barium doping Lanthanum Chromite Yttrium coated stable zirconium oxide negative temperature coefficient heat-sensitive composite ceramic material of the present invention Preparation method, the preparation of this method inner core yttrium stable zirconium oxide (YSZ) uses coprecipitation, external shell LaBaCrO preparation Using oxide solid phase method.Prepared by yttrium stable zirconium oxide (YSZ) powder is respectively by ZrOCl2·8H2O and Y (NO3)3·6H2O water Solve as the solution of 0.2-0.5mol/L equimolar concentrations, then mix two kinds of solution, with molar concentration 10-12mol/L's Ammoniacal liquor is precipitating reagent, the White Flocculus of mixed solution is precipitated complete, YSZ is can obtain being washed, being dried and being calcined Powder；LaBaCrO powders are prepared with La2O3、Cr2O3And BaCO3For raw material, mixed, ground, being calcined, ground obtain again LaBaCrO powders.YSZ powders are subjected to compound stalk forming, LaBaCrO powders is then coated and carries out compound stalk forming again, then will The block of composite molding carries out cold isostatic compaction, obtains green compact, finally carries out high temperature sintering to green compact.In coating ag paste electrode Resistance disk is obtained, the ceramic resistor belongs to a kind of form of expression of composite ceramics.Its material constant B-75℃/-50℃Scope is (1700-3500) × (1 ± 2%) K, -50 DEG C of resistance value scopes of temperature are (15-3132) × (1 ± 2%) Ω.Using the present invention The Lanthanum Chromite Yttrium coated stable zirconium oxide temperature-sensitive composite ceramic material of the barium doping of preparation, is presented high resistant, low B negative temperature coefficient Characteristic, the electric performance stablity of the ceramic resistor, uniformity is preferable, it is adaptable to which the measurement of the wide warm area under middle low temperature, is negative temperature The preparation of coefficient thermosensitive ceramics material provides a kind of novel preparation method.
The form that the present invention is coated using a kind of physics has carried out LaBaCrO-YSZ thermal sensitive ceramicses, and its innovative point mainly has Below two aspect.
(1) physics cladding form is applied in the research of NTC thermal sensitive ceramic materials first, aoxidized so that the yttrium of high resistant phase is stable Zirconium (YSZ) is core, and the low B of low-resistance LaBaCrO is shell, realizes regulation of the resistance value in relative broad range.
(2) characteristic such as thermal sensitive ceramics of the invention has chemical property and electrical properties are stable, corrosion-resistant, and can answer Wide warm area for measuring liquid nitrogen to 50 DEG C.
Brief description of the drawings
Fig. 1 is composite ceramic structures schematic diagram of the invention；
Fig. 2 is X ray diffracting spectrum of the invention, wherein (a) yttrium stable zirconium oxide (YSZ)；(b)LaBaCrO；(c) it is multiple Close ceramic material LaBaCrO-YSZ；
Fig. 3 is scanning electron microscope (SEM) photograph at the composite ceramic material border of the present invention.
Embodiment
Embodiment 1
A, by raw material La2O3、BaCO3And Cr2O3, La in molar ratio:Ba:Cr=30:30:40 calculate the matter of required raw material Measure and precise, be placed in agate mortar grinding 8h, obtain well mixed powder body material；
B, by the powder body material obtained in step a in 1400 DEG C of temperature calcining 5h, regrinding 6h is to obtain what barium adulterated Lanthanum Chromite Powders LaBaCrO 2；
C, by raw material ZrOCl2·8H2O and Y (NO3)3·6H2O Zr in molar ratio:Y=84:16 calculate required raw material Quality and precise, are separately added into the solution that 0.5mol/L is configured in deionized water, standby；
D, concentrated ammonia liquor is accurately measured, then concentrated ammonia liquor is dissolved in deionized water, be configured to 12mol/L solution, it is standby；
E, two kinds of solution obtained by c are mixed, the ammonia spirit of step d configurations is then instilled dropwise, is stirred in drop Mix, separated out completely to White Flocculus, washed, filtered, and in temperature 70 C drying, obtain powder；
F, by the powder obtained in step e in 600 DEG C of temperature calcining 6h, regrinding 6h is to obtain yttrium stable zirconium oxide Powder；
G, the powder body material for obtaining step f are with 3Kg/cm2Pressure carry out compound stalk forming, pressurize 1min obtains diameter For the 2mm disk green compact of yttrium stable zirconium oxide 1；
H, the powder that the green compact of yttrium stable zirconium oxide 1 that step g is obtained are placed in the barium doping Lanthanum Chromite obtained in step b In LaBaCrO2, with 30Kg/cm2Pressure carry out compound stalk forming, pressurize 1min obtains a diameter of 5mm disk green compact, will be into The block materials of type carry out isostatic cool pressing, the pressurize 4min in the case where pressure is 200MPa, after by block materials in 1400 DEG C of burnings of temperature Tie 7h, you can obtain barium doping Lanthanum Chromite Yttrium coated stable zirconium oxide thermal sensitive ceramic material；
I, the thermal sensitive ceramic material tow sides for obtaining step h coat ag paste electrode, in burning infiltration 2h at 850 DEG C of temperature, Obtain the negative temperature coefficient heat-sensitive composite ceramic material of barium doping Lanthanum Chromite Yttrium coated stable zirconium oxide.
The thermistor material obtained by this method is that resistance is 15.0 × (1 ± 2%) Ω, material at -50 DEG C in temperature Material constant is B-75℃/-50℃=1700 × (1 ± 2%) K.
Embodiment 2
A, by raw material La2O3、BaCO3And Cr2O3, La in molar ratio:Ba:Cr=37:20:43 calculate the matter of required raw material Measure and precise, be placed in agate mortar grinding 7h, obtain well mixed powder body material；
B, by the powder obtained in step a in 1350 DEG C of temperature calcining 6h, regrinding 7h is the chromic acid for obtaining barium doping Lanthanum powder LaBaCrO 2；
C, by raw material ZrOCl2·8H2O and Y (NO3)3·6H2O Zr in molar ratio:Y=88:12 calculate required raw material Quality and precise, are separately added into the solution that 0.4mol/L is configured in deionized water, standby；
D, concentrated ammonia liquor is accurately measured, then concentrated ammonia liquor is dissolved in deionized water, be configured to 11mol/L solution, it is standby；
E, two kinds of solution obtained by c are mixed, the ammoniacal liquor of step d configurations is then instilled dropwise, is stirred in drop, extremely White Flocculus is separated out completely, is washed, filtered, and in 75 DEG C of drying of temperature, obtains powder；
F, by the powder obtained in step e in 700 DEG C of temperature calcining 5h, regrinding 7h is to obtain yttrium stable zirconium oxide Powder；
G, the powder body material for obtaining step f are with 4Kg/cm2Pressure carry out compound stalk forming, pressurize 1min obtains diameter For the 5mm disk green compact of yttrium stable zirconium oxide 1；
H, the powder that the green compact of yttrium stable zirconium oxide 1 that step g is obtained are placed in the barium doping Lanthanum Chromite obtained in step b In LaBaCrO2, with 40Kg/cm2Pressure carry out compound stalk forming, pressurize 2.5min obtains a diameter of 10mm disk green compact, The block materials of shaping are subjected to isostatic cool pressing, the pressurize 3min in the case where pressure is 270MPa, after by block materials in temperature 1500 DEG C sintering 6h, you can barium doping Lanthanum Chromite Yttrium coated stable zirconium oxide thermal sensitive ceramic material；
I, the thermal sensitive ceramic material tow sides for obtaining step h coat ag paste electrode, in burning infiltration 2h at 850 DEG C of temperature, Obtain the negative temperature coefficient heat-sensitive composite ceramic material of barium doping Lanthanum Chromite Yttrium coated stable zirconium oxide.
The thermistor material obtained by this method is that resistance is 245.0 × (1 ± 2%) Ω, material at -50 DEG C in temperature Material constant is B-75℃/-50℃=2010 × (1 ± 2%) K.
Embodiment 3
A, by raw material La2O3、BaCO3And Cr2O3, La in molar ratio:Ba:Cr=42:12:46 calculate the matter of required raw material Measure and precise, be placed in agate mortar grinding 6h, obtain well mixed powder body material；
B, by the powder obtained in step a in 1300 DEG C of temperature calcining 7h, regrinding 8.5h is the chromium for obtaining barium doping Sour lanthanum powder LaBaCrO 2；
C, by raw material ZrOCl2·8H2O and Y (NO3)3·6H2O Zr in molar ratio:Y=92:8 calculate the matter of required raw material Amount, is separately added into the solution that 0.3mol/L is configured in deionized water, standby；
D, concentrated ammonia liquor is accurately measured, then concentrated ammonia liquor is dissolved in deionized water, be configured to 11mol/L solution, it is standby；
E, two kinds of solution obtained by c are mixed, the ammoniacal liquor of step d configurations is then instilled dropwise, is stirred in drop, extremely White Flocculus is separated out completely, is washed, filtered, and in 80 DEG C of drying of temperature, obtains powder；
F, by the powder obtained in step e in 800 DEG C of temperature calcining 4.5h, regrinding 8.5h is to obtain the stable oxidation of yttrium The powder of zirconium；
G, the powder body material for obtaining step f are with 5Kg/cm2Pressure carry out compound stalk forming, pressurize 1min obtains diameter For the 10mm disk green compact of yttrium stable zirconium oxide 1；
H, the powder that the green compact of yttrium stable zirconium oxide 1 that step g is obtained are placed in the barium doping Lanthanum Chromite obtained in step b In LaBaCrO2, with 50Kg/cm2Pressure carry out compound stalk forming, pressurize 2.5min obtains a diameter of 15mm disk green compact, The block materials of shaping are subjected to isostatic cool pressing, the pressurize 2min in the case where pressure is 320MPa, after by block materials in 1600 DEG C of burnings Tie 5h, you can obtain barium doping Lanthanum Chromite Yttrium coated stable zirconium oxide thermal sensitive ceramic material；
I, the thermal sensitive ceramic material tow sides for obtaining step h coat ag paste electrode, in burning infiltration 2h at 850 DEG C of temperature, Obtain the negative temperature coefficient heat-sensitive composite ceramic material of barium doping Lanthanum Chromite Yttrium coated stable zirconium oxide.
The thermistor material obtained by this method is that resistance is 1968.0 × (1 ± 2%) Ω at -50 DEG C in temperature, Material constant is B-75℃/-50℃=2860 × (1 ± 2%) K.
Embodiment 4
A, by raw material La2O3、BaCO3And Cr2O3, La in molar ratio:Cr=49:1:50 calculate the quality of required raw material simultaneously Precise, is placed in agate mortar grinding 5h, obtains well mixed powder body material；
B, by the powder obtained in step a in 1200 DEG C of temperature calcining 8h, regrinding 10h is the chromic acid for obtaining barium doping Lanthanum powder LaBaCrO 2；
C, by raw material ZrOCl2·8H2O and Y (NO3)3·6H2O Zr in molar ratio:Y=96:4 calculate the matter of required raw material Amount, is separately added into the solution that 0.2mol/L is configured in deionized water, standby；
D, concentrated ammonia liquor is accurately measured, then concentrated ammonia liquor is dissolved in deionized water, be configured to 10mol/L solution, it is standby；
E, two kinds of solution obtained by c are mixed, then instill in the ammoniacal liquor of step d configurations, stirred in drop dropwise, Separated out completely to White Flocculus, washed, filtered, and in 80 DEG C of drying of temperature, obtain powder；
F, by the powder obtained in step e in 900 DEG C of temperature calcining 4h, regrinding 10h is to obtain yttrium stable zirconium oxide Powder；
G, the powder body material for obtaining step f are with 6Kg/cm2Pressure carry out compound stalk forming, pressurize 1min obtains diameter For the 15mm disk green compact of yttrium stable zirconium oxide 1；
H, the powder that the green compact of yttrium stable zirconium oxide 1 that step g is obtained are placed in the barium doping Lanthanum Chromite obtained in step b In LaBaCrO2, with 60Kg/cm2Pressure carry out compound stalk forming, pressurize 3min obtains a diameter of 20mm disk green compact, will The block materials of shaping carry out isostatic cool pressing, the pressurize 1min in the case where pressure is 400MPa, after by block materials in 1700 DEG C of sintering 4h, you can obtain Lanthanum Chromite Yttrium coated stable zirconium oxide thermal sensitive ceramic material；
I, the thermal sensitive ceramic material tow sides for obtaining step h coat ag paste electrode, in burning infiltration 2h at 850 DEG C of temperature, Obtain the negative temperature coefficient heat-sensitive composite ceramic material of Lanthanum Chromite Yttrium coated stable zirconium oxide.
The thermistor material obtained by this method is that resistance is 3132.0 × (1 ± 2%) Ω at -50 DEG C in temperature, Material constant is B-75℃/-50℃=3500 × (1 ± 2%) K.

Claims (1)

  1. The preparation method of Lanthanum Chromite Yttrium coated stable zirconium oxide negative temperature coefficient heat-sensitive composite ceramic material 1. a kind of barium adulterates, its It is characterised by the material structure being related in this method by kernel yttrium stable zirconium oxide（1）With shell LaBaCrO（2）Composition, specifically Operation follows these steps to carry out：
    A, by raw material La2O3、BaCO3And Cr2O3, La in molar ratio:Ba:Cr =30-50:1-30:40-50 precises, are placed in Agate mortar grinds 5-8h, obtains well mixed powder body material；
    B, by the powder body material obtained in step a in 1200-1400 DEG C of temperature calcining 5-8h, regrind 6-10h, obtain barium and mix Miscellaneous Lanthanum Chromite Powders（2）；
    C, by raw material ZrOCl2·8H2O and Y (NO3)3·6H2O Zr in molar ratio:Y=84-96:4-16 precises, are separately added into 0.2-0.5mol/L solution is configured in deionized water, it is standby；
    D, concentrated ammonia liquor is accurately measured, then concentrated ammonia liquor is dissolved in deionized water, be configured to 10-12mol/L solution, it is standby；
    E, two kinds of solution obtained by step c are mixed, then instill in the ammoniacal liquor of step d configurations, stirred in drop dropwise, Separated out completely to White Flocculus, washed, filtered, and in 70-80 DEG C of drying of temperature, obtain powder；
    F, by the powder obtained in step e in 600-900 DEG C of temperature calcining 4-6h, regrind 6-10h, obtain the stable oxidation of yttrium The powder of zirconium；
    G, the powder body material for obtaining step f are with 3-6Kg/cm2Pressure carry out compound stalk forming, pressurize 1min obtains a diameter of 2- 15mm core yttrium stable zirconium oxide（1）Disk green compact；
    H, the core yttrium stable zirconium oxide for obtaining step g（1）Green compact are placed in the Lanthanum Chromite Powders obtained in step b（2）In, with 30-60Kg/cm2Pressure carry out compound stalk forming, pressurize 1-3min obtains a diameter of 5-20mm disk green compact, by shaping Block materials carry out isostatic cool pressing, pressure be 200-400MPa under pressurize 1-4min, after by block materials in temperature 1400- 1700 DEG C of sintering 4-7h, you can obtain barium doping Lanthanum Chromite Yttrium coated stable zirconium oxide thermal sensitive ceramic material；
    I, the thermal sensitive ceramic material tow sides for obtaining step h coat ag paste electrode, in burning infiltration 2h at 850 DEG C of temperature, produce To the negative temperature coefficient heat-sensitive composite ceramic material of barium doping Lanthanum Chromite Yttrium coated stable zirconium oxide.
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