CN107140977B - Preparation method of barium-doped lanthanum chromate coated yttrium stabilized zirconia negative temperature coefficient thermosensitive composite ceramic material - Google Patents
Preparation method of barium-doped lanthanum chromate coated yttrium stabilized zirconia negative temperature coefficient thermosensitive composite ceramic material Download PDFInfo
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Abstract
The invention relates to a preparation method of a barium-doped lanthanum chromate coated yttrium stabilized zirconia negative temperature coefficient thermal sensitive composite ceramic material, wherein the inner core of the method is a high-resistance phase Yttrium Stabilized Zirconia (YSZ) material with high resistance value, the outer shell is a low-resistance phase LaBaCrO material with low resistivity and low thermal sensitive constant, and the core and the shell are respectively coated with zirconium oxychloride octahydrate, yttrium nitrate hexahydrate and ammonia water; lanthanum sesquioxide, chromium sesquioxide and barium carbonate are taken as raw materials, and the LaBaCrO-YSZ coated thermal sensitive ceramic with the material constant B can be obtained by grinding, calcining, grinding, composite briquetting forming, cold isostatic pressing forming and high-temperature sintering‑75℃/‑50℃The range of (1700-3500) × (1 ± 2%) K, and the range of the resistance value at-50 ℃ is (15-3132) × (1 ± 2%) Ω. The barium-doped lanthanum chromate coated yttria-stabilized zirconia thermal sensitive ceramic material prepared by the method has the characteristics of negative temperature coefficient, stable electrical property and better consistency, and is suitable for manufacturing a thermal resistor in a wide temperature zone environment at medium and low temperature.
Description
Technical Field
The invention relates to a preparation method of a barium-doped lanthanum chromate coated yttrium stabilized zirconia negative temperature coefficient composite material, wherein the thermal sensitive ceramic material has obvious negative temperature coefficient characteristics within the temperature range of-196-50 ℃, is a novel ceramic material suitable for manufacturing a wide-temperature-range thermistor at medium and low temperature, has the characteristic of regulating the resistance value of the thermistor within a wide range, and belongs to the field of semiconductor sensors.
Background
The sensitive material and the element are one of three major pillars of the electronic information industry determined by the state, are considered to be electronic technical products with the greatest development prospect, and the development of the sensitive element plays a very important role in improving the international position of the electronic industry in China. The thermistor has the characteristics of good reliability, high sensitivity, low price and the like, and is widely applied to temperature sensing and control of electric appliances and industrial equipment in daily life. The main applications of NTC thermistors include: suppressing surge current, temperature compensation, temperature measurement and control. In order to meet the application requirements of wide temperature range measurement in the aviation industry and daily life, the wide temperature range thermistor material becomes a new development trend and a research hotspot in the field of NTC thermistors.
LaCrO3Has the advantages of high melting point (2400 ℃), chemical corrosion resistance and the like, and is widely used in the fields of refractory materials, heating materials, fuel cells and the like. By Ba2+Doping of ions, adjusting LaCrO3The resistivity p and the thermal constant B thereof, a ceramic material with low p and low B can be obtained; YSZ has the characteristics of stable chemical property, corrosion resistance, high resistance and the like.
According to the invention, the LaBaCrO material of the low resistance phase is coated with the Yttrium Stabilized Zirconia (YSZ) of the high resistance phase for the first time to obtain the LaBaCrO-YSZ composite phase thermosensitive material system, the resistance value of the material can be adjusted in a wider range, the influence on the B value of the material is smaller, and the obtained composite thermosensitive resistance material system is suitable for manufacturing the thermosensitive resistor applied to the wide temperature zone environment at the medium and low temperature.
Disclosure of Invention
The invention aims to provide a preparation method of a barium-doped lanthanum chromate coated yttrium-stabilized zirconia negative temperature coefficient thermosensitive composite ceramic material, wherein the inner core of the method is high-resistance phase yttrium-stabilized zirconia (YSZ) material, wherein the outer shell is low-resistivity phase LaBaCrO material with low resistivity and low thermal sensitive constant, and the core and the shell are respectively coated with zirconium oxychloride octahydrate, yttrium nitrate hexahydrate and ammonia water; lanthanum sesquioxide, chromium sesquioxide and barium carbonate are taken as raw materials, and the LaBaCrO-YSZ coated thermal sensitive ceramic with the material constant B can be obtained by grinding, calcining, grinding, composite briquetting forming, cold isostatic pressing forming and high-temperature sintering-75℃/-50℃The range of (1700-3500) × (1 ± 2%) K, and the range of the resistance value at-50 ℃ is (15-3132) × (1 ± 2%) Ω. The barium-doped lanthanum chromate coated yttria-stabilized zirconia thermal sensitive ceramic resistor prepared by the method has the characteristics of negative temperature coefficient, stable electrical property of a material system and better consistency, and is suitable for manufacturing a thermal sensitive resistor used in a wide temperature zone environment at medium and low temperature.
The invention relates to a preparation method of a barium-doped lanthanum chromate coated yttrium stabilized zirconia negative temperature coefficient thermal sensitive composite ceramic material, wherein the material structure involved in the method consists of an inner core yttrium stabilized zirconia (1) and an outer shell LaBaCrO (2), and the specific operation is carried out according to the following steps:
a. the raw material La is added2O3、BaCO3And Cr2O3Accurately weighing the materials according to the molar ratio of La, Ba and Cr which is 30-50:1-30:40-50, and putting the materials into an agate mortar for grinding for 5-8 hours to obtain a uniformly mixed powder material;
b. calcining the powder material obtained in the step a at the temperature of 1200-1400 ℃ for 5-8h, and grinding for 6-10h again to obtain barium-doped lanthanum chromate powder (2);
c. raw material ZrOCl2·8H2O and Y (NO)3)3·6H2Accurately weighing O according to the mol ratio of Zr to Y of 84-96:4-16, and respectively adding the weighed O into deionized water to prepare 0.2-0.5mol/L solution for later use;
d. accurately measuring strong ammonia water, and dissolving the strong ammonia water in deionized water to prepare a solution of 10-12mol/L for later use;
e. mixing the two solutions obtained in the step c, then dropwise adding into the ammonia water prepared in the step d while stirring until white floccules are completely separated out, washing, filtering, and drying at the temperature of 70-80 ℃ to obtain powder;
f. calcining the powder obtained in the step e at the temperature of 600-900 ℃ for 4-6h, and grinding for 6-10h again to obtain yttrium-stabilized zirconia powder;
g. f, mixing the powder material obtained in the step f at a ratio of 3-6Kg/cm2Pressing into blocks under the pressure of the pressure, and maintaining the pressure for 1min to obtain a nuclear yttrium stabilized zirconia (1) wafer green compact with the diameter of 2-15 mm;
h. g, placing the green body of the nuclear yttrium-stabilized zirconia (1) obtained in the step g into the lanthanum chromate powder (2) obtained in the step b, and controlling the volume to be 30-60Kg/cm2Pressing and molding under the pressure of the pressure, maintaining the pressure for 1-3min to obtain a wafer green compact with the diameter of 5-20mm, performing cold isostatic pressing on the molded block material, maintaining the pressure for 1-4min at the pressure of 200-400MPa, and sintering the block material at the temperature of 1400-1700 ℃ for 4-7h to obtain the barium-doped lanthanum chromate coated yttrium stabilized zirconia thermal sensitive ceramic material;
i. and (5) coating silver paste electrodes on the front and back surfaces of the thermosensitive ceramic material obtained in the step h, and sintering and infiltrating at the temperature of 850 ℃ for 2h to obtain the barium-doped lanthanum chromate coated yttrium stabilized zirconia negative temperature coefficient thermosensitive composite ceramic material.
The invention relates to a preparation method of a barium-doped lanthanum chromate coated yttrium stabilized zirconia negative temperature coefficient thermosensitive composite ceramic material. The Yttrium Stabilized Zirconia (YSZ) powder is prepared by respectively mixing ZrOCl2·8H2O and Y (NO)3)3·6H2Hydrolyzing O to 0.2-0.5mol/L solution with equal molar concentration, then mixing the two solutions, taking ammonia water with the molar concentration of 10-12mol/L as a precipitator to ensure that white floccule of the mixed solution is completely precipitated, and washing, drying and calcining to obtain YSZ powder; preparation of LaBaCrO powder with La2O3、Cr2O3And BaCO3Mixing, grinding, calcining and grinding the raw materials to obtain LaBaCrO powder. Briquetting YSZ powder, coating LaBaCrO powder, briquetting, and coolingIsostatic pressing to obtain green body, and final high temperature sintering. And coating silver paste electrodes to obtain a resistance wafer, wherein the ceramic resistance belongs to one expression form of composite ceramic. Its material constant B-75℃/-50℃The range is (1700-3500) × (1 + -2%) K, and the resistance value range is (15-3132) × (1 + -2%) omega at-50 ℃. The barium-doped lanthanum chromate-coated yttrium-stabilized zirconia thermal sensitive composite ceramic material prepared by the method has the characteristics of high resistance and low negative temperature coefficient of B, and the ceramic resistor has stable electrical property and better consistency, is suitable for measuring a wide temperature zone at medium and low temperature, and provides a novel preparation method for the preparation of the negative temperature coefficient thermal sensitive ceramic material.
The LaBaCrO-YSZ thermal sensitive ceramic is prepared in a physical coating mode, and the innovation points of the LaBaCrO-YSZ thermal sensitive ceramic mainly comprise the following two aspects.
(1) The physical coating mode is applied to research of NTC thermal sensitive ceramic materials for the first time, and the resistance value is adjusted in a wider range by taking high-resistance phase Yttrium Stabilized Zirconia (YSZ) as a core and low-resistance low-B LaBaCrO as a shell.
(2) The thermal sensitive ceramic has the characteristics of stable chemical property and electrical property, corrosion resistance and the like, and can be applied to the measurement of a wide temperature range from liquid nitrogen to 50 ℃.
Drawings
FIG. 1 is a schematic view of a composite ceramic structure according to the present invention;
FIG. 2 is an X-ray diffraction pattern of the present invention wherein (a) Yttrium Stabilized Zirconia (YSZ); (b) LaBaCrO; (c) composite ceramic material LaBaCrO-YSZ;
FIG. 3 is a scanning electron microscope image of the junction of the composite ceramic material of the present invention.
Detailed Description
Example 1
a. The raw material La is added2O3、BaCO3And Cr2O3Calculating the mass of the required raw materials according to the molar ratio of La, Ba and Cr which is 30:30:40, accurately weighing, and grinding in an agate mortar for 8 hours to obtain a uniformly mixed powder material;
b. calcining the powder material obtained in the step a at the temperature of 1400 ℃ for 5h, and grinding for 6h again to obtain barium-doped lanthanum chromate powder LaBaCrO 2;
c. raw material ZrOCl2·8H2O and Y (NO)3)3·6H2Calculating the mass of the required raw materials according to the molar ratio Zr to Y of 84 to 16, accurately weighing, and respectively adding the raw materials into deionized water to prepare 0.5mol/L solution for later use;
d. accurately measuring strong ammonia water, and dissolving the strong ammonia water in deionized water to prepare a solution of 12mol/L for later use;
e. mixing the two solutions obtained in the step c, then dropwise adding the ammonia water solution prepared in the step d while stirring until white floccules are completely separated out, washing, filtering, and drying at the temperature of 70 ℃ to obtain powder;
f. calcining the powder obtained in the step e at the temperature of 600 ℃ for 6h, and grinding for 6h again to obtain yttrium-stabilized zirconia powder;
g. f, mixing the powder material obtained in the step f at a ratio of 3Kg/cm2Pressing into a block under the pressure of the pressure, and maintaining the pressure for 1min to obtain a yttrium-stabilized zirconia 1 wafer green body with the diameter of 2 mm;
h. g, placing the yttrium-stabilized zirconia 1 green compact obtained in the step g into the barium-doped lanthanum chromate powder LaBaCrO2 obtained in the step b, and controlling the volume to be 30Kg/cm2Pressing the mixture into a block under the pressure of the pressure, keeping the pressure for 1min to obtain a wafer green body with the diameter of 5mm, carrying out cold isostatic pressing on the formed block material, keeping the pressure for 4min under the pressure of 200MPa, and sintering the block material at the temperature of 1400 ℃ for 7h to obtain the barium-doped lanthanum chromate coated yttrium-stabilized zirconia thermal sensitive ceramic material;
i. and (5) coating silver paste electrodes on the front and back surfaces of the thermosensitive ceramic material obtained in the step h, and sintering and infiltrating at the temperature of 850 ℃ for 2h to obtain the barium-doped lanthanum chromate coated yttrium stabilized zirconia negative temperature coefficient thermosensitive composite ceramic material.
The thermistor material obtained by the method has a resistance of 15.0 x (1 + -2%) omega at a temperature of-50 deg.C and a material constant of B-75℃/-50℃＝1700×(1±2％)K。
Example 2
a. The raw material La is added2O3、BaCO3And Cr2O3Calculating the mass of the required raw materials according to the molar ratio of La, Ba and Cr which is 37:20:43, accurately weighing, and putting the raw materials into an agate mortar for grinding for 7 hours to obtain a uniformly mixed powder material;
b. calcining the powder obtained in the step a at the temperature of 1350 ℃ for 6h, and grinding for 7h again to obtain barium-doped lanthanum chromate powder LaBaCrO 2;
c. raw material ZrOCl2·8H2O and Y (NO)3)3·6H2Calculating the mass of the required raw materials according to the molar ratio of Zr to Y of 88 to 12, accurately weighing, and respectively adding the raw materials into deionized water to prepare 0.4mol/L solution for later use;
d. accurately measuring strong ammonia water, and dissolving the strong ammonia water in deionized water to prepare 11mol/L solution for later use;
e. mixing the two solutions obtained in the step c, then dropwise adding the ammonia water prepared in the step d while stirring until white floccules are completely separated out, washing, filtering, and drying at the temperature of 75 ℃ to obtain powder;
f. calcining the powder obtained in the step e at the temperature of 700 ℃ for 5 hours, and grinding for 7 hours again to obtain yttrium-stabilized zirconia powder;
g. f, mixing the powder material obtained in the step f at a ratio of 4Kg/cm2Pressing into a block under the pressure of the pressure, and maintaining the pressure for 1min to obtain a yttrium-stabilized zirconia 1 wafer green body with the diameter of 5 mm;
h. putting the yttrium stabilized zirconia 1 green compact obtained in the step g into the barium doped lanthanum chromate LaBaCrO2 obtained in the step b, and controlling the volume to be 40Kg/cm2Pressing the raw materials into a block under the pressure of the raw materials, keeping the pressure for 2.5min to obtain a wafer green body with the diameter of 10mm, carrying out cold isostatic pressing on the formed block material, keeping the pressure for 3min under the pressure of 270MPa, and sintering the block material at the temperature of 1500 ℃ for 6h to obtain the barium-doped lanthanum chromate coated yttrium-stabilized zirconia thermal sensitive ceramic material;
i. and (5) coating silver paste electrodes on the front and back surfaces of the thermosensitive ceramic material obtained in the step h, and sintering and infiltrating at the temperature of 850 ℃ for 2h to obtain the barium-doped lanthanum chromate coated yttrium stabilized zirconia negative temperature coefficient thermosensitive composite ceramic material.
The thermistor material obtained by the method has a resistance of 245.0 x (1 + -2%) omega at a temperature of-50 deg.C and a material constant of B-75℃/-50℃＝2010×(1±2％)K。
Example 3
a. The raw material La is added2O3、BaCO3And Cr2O3Calculating the mass of the required raw materials according to the molar ratio of La, Ba and Cr which is 42 to 12 to 46, accurately weighing, and putting the raw materials into an agate mortar for grinding for 6 hours to obtain a uniformly mixed powder material;
b. calcining the powder obtained in the step a at 1300 ℃ for 7h, and grinding for 8.5h again to obtain barium-doped lanthanum chromate powder LaBaCrO 2;
c. raw material ZrOCl2·8H2O and Y (NO)3)3·6H2Calculating the mass of the required raw materials according to the molar ratio of Zr to Y of 92 to 8, and respectively adding the raw materials into deionized water to prepare 0.3mol/L solution for later use;
d. accurately measuring strong ammonia water, and dissolving the strong ammonia water in deionized water to prepare 11mol/L solution for later use;
e. mixing the two solutions obtained in the step c, then dropwise adding the ammonia water prepared in the step d while stirring until white floccules are completely separated out, washing, filtering, and drying at the temperature of 80 ℃ to obtain powder;
f. calcining the powder obtained in the step e at the temperature of 800 ℃ for 4.5h, and grinding for 8.5h again to obtain yttrium-stabilized zirconia powder;
g. f, mixing the powder material obtained in the step f at a ratio of 5Kg/cm2Pressing into a block under the pressure of the pressure, and maintaining the pressure for 1min to obtain a yttrium-stabilized zirconia 1 wafer green body with the diameter of 10 mm;
h. putting the yttrium stabilized zirconia 1 green compact obtained in the step g into the barium doped lanthanum chromate LaBaCrO2 obtained in the step b, and controlling the weight of the barium doped lanthanum chromate LaBaCrO2 to be 50Kg/cm2Pressing the mixture into a block under the pressure of the pressure for 2.5min to obtain a wafer green compact with the diameter of 15mm, carrying out cold isostatic pressing on the formed block material, keeping the pressure for 2min at the pressure of 320MPa, and sintering the block material at 1600 ℃ for 5h to obtain the barium-doped lanthanum chromate coated yttrium-stabilized zirconia thermal sensitive materialA ceramic material;
i. and (5) coating silver paste electrodes on the front and back surfaces of the thermosensitive ceramic material obtained in the step h, and sintering and infiltrating at the temperature of 850 ℃ for 2h to obtain the barium-doped lanthanum chromate coated yttrium stabilized zirconia negative temperature coefficient thermosensitive composite ceramic material.
The thermistor material obtained by the method has resistance of 1968.0 x (1 + -2%) omega at-50 deg.C, and material constant of B-75℃/-50℃＝2860×(1±2％)K。
Example 4
a. The raw material La is added2O3、BaCO3And Cr2O3Calculating the mass of the required raw materials according to the molar ratio of La to Cr of 49:1:50, accurately weighing, and grinding in an agate mortar for 5 hours to obtain a uniformly mixed powder material;
b. calcining the powder obtained in the step a at 1200 ℃ for 8h, and grinding for 10h again to obtain barium-doped lanthanum chromate LaBaCrO 2;
c. raw material ZrOCl2·8H2O and Y (NO)3)3·6H2Calculating the mass of the required raw materials according to the molar ratio Zr to Y of 96 to 4, and respectively adding the raw materials into deionized water to prepare 0.2mol/L solution for later use;
d. accurately measuring strong ammonia water, and dissolving the strong ammonia water in deionized water to prepare a solution of 10mol/L for later use;
e. mixing the two solutions obtained in the step c, then dropwise adding the two solutions into the ammonia water prepared in the step d while stirring until white floccules are completely separated out, washing, filtering, and drying at the temperature of 80 ℃ to obtain powder;
f. calcining the powder obtained in the step e at the temperature of 900 ℃ for 4h, and grinding for 10h again to obtain yttrium-stabilized zirconia powder;
g. f, mixing the powder material obtained in the step f at the ratio of 6Kg/cm2Pressing into a block under the pressure of the pressure, and maintaining the pressure for 1min to obtain a yttrium-stabilized zirconia 1 wafer green body with the diameter of 15 mm;
h. g, placing the yttrium-stabilized zirconia 1 green compact obtained in the step g into the barium-doped lanthanum chromate powder LaBaCrO2 obtained in the step b, and controlling the volume to be 60Kg/cm2Pressing the raw materials into blocks, keeping the pressure for 3min to obtain wafer green bodies with the diameter of 20mm, carrying out cold isostatic pressing on the formed block materials, keeping the pressure for 1min at the pressure of 400MPa, and sintering the block materials at 1700 ℃ for 4h to obtain the lanthanum chromate coated yttrium-stabilized zirconia thermal sensitive ceramic material;
i. and (5) coating silver paste electrodes on the front and back surfaces of the thermosensitive ceramic material obtained in the step h, and carrying out sintering infiltration for 2h at the temperature of 850 ℃ to obtain the lanthanum chromate coated yttrium stabilized zirconia negative temperature coefficient thermosensitive composite ceramic material.
The thermistor material obtained by the method has resistance of 3132.0 x (1 + -2%) omega at-50 deg.C, and material constant of B-75℃/-50℃＝3500×(1±2％)K。
Claims (1)
1. A preparation method of a barium-doped lanthanum chromate coated yttrium stabilized zirconia negative temperature coefficient thermosensitive composite ceramic material is characterized in that a material structure related in the method consists of an inner core yttrium stabilized zirconia (1) and an outer shell barium-doped lanthanum chromate (2), and the specific operation is carried out according to the following steps:
a. the raw material La is added2O3、BaCO3And Cr2O3Accurately weighing the materials according to the molar ratio of La to Ba to Cr =30-50:1-30:40-50, and grinding the materials in an agate mortar for 5-8h to obtain a uniformly mixed powder material;
b. calcining the powder material obtained in the step a at the temperature of 1200-1400 ℃ for 5-8h, and grinding for 6-10h again to obtain barium-doped lanthanum chromate powder (2);
c. raw material ZrOCl2·8H2O and Y (NO)3)3·6H2Accurately weighing O according to the mol ratio of Zr to Y =84-96 to 4-16, and respectively adding the weighed O into deionized water to prepare 0.2-0.5mol/L solution for later use;
d. accurately measuring strong ammonia water, and dissolving the strong ammonia water in deionized water to prepare a solution of 10-12mol/L for later use;
e. mixing the two solutions obtained in the step c, then dropwise adding into the ammonia water prepared in the step d while stirring until white floccules are completely separated out, washing, filtering, and drying at the temperature of 70-80 ℃ to obtain powder;
f. calcining the powder obtained in the step e at the temperature of 600-900 ℃ for 4-6h, and grinding for 6-10h again to obtain yttrium-stabilized zirconia powder;
g. f, mixing the powder material obtained in the step f at a ratio of 3-6Kg/cm2Pressing into blocks under the pressure of the pressure, and maintaining the pressure for 1min to obtain yttrium-stabilized zirconia (1) wafer green bodies with the diameter of 2-15 mm;
h. g, placing the yttrium stabilized zirconia (1) green compact obtained in the step (g) into the lanthanum chromate powder (2) obtained in the step (b) at the rate of 30-60Kg/cm2Pressing and molding under the pressure of the pressure, maintaining the pressure for 1-3min to obtain a wafer green compact with the diameter of 5-20mm, performing cold isostatic pressing on the molded block material, maintaining the pressure for 1-4min at the pressure of 200-400MPa, and sintering the block material at the temperature of 1400-1700 ℃ for 4-7h to obtain the barium-doped lanthanum chromate coated yttrium stabilized zirconia thermal sensitive ceramic material;
i. and (5) coating silver paste electrodes on the front and back surfaces of the thermosensitive ceramic material obtained in the step h, and sintering and infiltrating at the temperature of 850 ℃ for 2h to obtain the barium-doped lanthanum chromate coated yttrium stabilized zirconia negative temperature coefficient thermosensitive composite ceramic material.
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| CN101882490A (en) * | 2010-03-25 | 2010-11-10 | 中国科学院新疆理化技术研究所 | Rare earth oxide doped negative temperature coefficient thermistor material |
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| CN101882490A (en) * | 2010-03-25 | 2010-11-10 | 中国科学院新疆理化技术研究所 | Rare earth oxide doped negative temperature coefficient thermistor material |
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