CN116621573A - Spinel type thermistor material for measuring temperature in high-temperature wide temperature area and preparation method thereof - Google Patents

Spinel type thermistor material for measuring temperature in high-temperature wide temperature area and preparation method thereof Download PDF

Info

Publication number
CN116621573A
CN116621573A CN202310589422.6A CN202310589422A CN116621573A CN 116621573 A CN116621573 A CN 116621573A CN 202310589422 A CN202310589422 A CN 202310589422A CN 116621573 A CN116621573 A CN 116621573A
Authority
CN
China
Prior art keywords
temperature
equal
ceramic block
spinel
powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310589422.6A
Other languages
Chinese (zh)
Inventor
张博
咸越
刘亚飞
常爱民
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xinjiang Technical Institute of Physics and Chemistry of CAS
Original Assignee
Xinjiang Technical Institute of Physics and Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xinjiang Technical Institute of Physics and Chemistry of CAS filed Critical Xinjiang Technical Institute of Physics and Chemistry of CAS
Priority to CN202310589422.6A priority Critical patent/CN116621573A/en
Publication of CN116621573A publication Critical patent/CN116621573A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/04—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient
    • H01C7/042—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having negative temperature coefficient mainly consisting of inorganic non-metallic substances
    • H01C7/043—Oxides or oxidic compounds
    • H01C7/046—Iron oxides or ferrites
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
    • C04B35/2608—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
    • C04B35/2625—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 magnesium
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
    • C04B35/443—Magnesium aluminate spinel
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
    • C04B41/5122—Pd or Pt
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/88—Metals
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
    • G01K7/16—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements
    • G01K7/22—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using resistive elements the element being a non-linear resistance, e.g. thermistor
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • C04B2235/3267—MnO2
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
    • C04B2235/3274—Ferrites
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention relates to a spinel type thermistor material for measuring temperature in a high-temperature wide-temperature area and a preparation method thereof, wherein the thermistor material takes analytically pure magnesium oxide, aluminum oxide, manganese dioxide and ferric oxide as raw materials, and the chemical composition of Mg can be obtained through the steps of mixing grinding, presintering, cold isostatic pressing, high-temperature sintering, electrode coating and the like x Mn 1‑x Al 2x Fe 2(1‑x) O 4 Wherein x is more than or equal to 0.2 and less than or equal to 0.8,the ceramic crystal structure is spinel structure, and the material constant can be regulated and controlled in different solid solution ratiosB 150℃/600℃ =4383K-7609K, resistivity at 150 ℃ is 2.6x10 7 Ω.cm‑2.25×10 3 Ω.cm,lnρAnd 1000-TThe linear fitting Pearson's r coefficients of the high-temperature heat-sensitive resistor are all greater than or equal to 99.76%, and the high-temperature heat-sensitive resistor has obvious negative temperature coefficient characteristics in a wide temperature range of 0-600 ℃.

Description

Spinel type thermistor material for measuring temperature in high-temperature wide temperature area and preparation method thereof
Technical Field
The invention relates to a spinel type thermistor material for measuring temperature in a high-temperature wide temperature area and a preparation method thereof, wherein the thermistor material has obvious negative temperature coefficient characteristics in the temperature range of 0-600 ℃, and the coefficients of lnρ and 1000/T of linear fitting Pearson's r are more than or equal to 99.76%, so that the spinel type thermistor material is suitable for manufacturing a thermistor in the high-temperature wide temperature area.
Background
The negative temperature coefficient thermal sensitive ceramic material has unique advantages over the traditional temperature sensor in the aspects of high precision, quick response, low cost, small volume and the like, so that the negative temperature coefficient thermal sensitive ceramic material is expected to become an ideal material for accurate temperature measurement. The structural general formula of the spinel thermosensitive material is AB 2 O 4 . Conventional spinel structures such as Li-Mn-O, ni-Mn-O, mn-Co-Ni-O, etc., are usually used under low temperature conditions. Because the spinel type NTC thermal sensitive ceramic material has the advantages of relatively mature process, wide application, better compatibility with devices and the like, researchers mainly develop the research of the novel spinel type NTC thermal sensitive resistor through doping modification means, and the spinel material is expected to be applied in the high-temperature field.
Magnesia-alumina spinel (MgAl) 2 O 4 ) Has the characteristics of high temperature stability and wide band gap. It is widely used in refractory materials, catalysts and humidity sensors in various industries. The elements of the AB position of the magnesia-alumina spinel structure are all easily substituted, so that it is advantageous that distinct properties can be obtained by substituting different elements. Although the production process of spinel thermal ceramics is mature, its development is still limited due to its own drawbacks. There are currently two main problems. The single-component magnesia-alumina spinel is an insulator and has poor conductivity. The resistivity of the magnesia-alumina spinel is 10 even at high temperature 6 Omega cm or above. The sintering temperature of the ceramic is high due to the poor sintering activity of the powder, and is usually 1600 ℃ and above. In order to solve the two problems, researchers have studied the novel spinel NTC thermistors mainly by doping modification and composite modification methods, and generally doping a variable element at the B site of spinel. However, these methods do not significantly reduce the thermal constant (B value) of the material and increase the difficulty of preparation. Therefore, new material modification methods are necessary.
Spinel manganese ferrite (MnFe) 2 O 4 ) Is usually of inverse spinel or semi-inverse spinel structure, with MgAl 2 O 4 The same belongs to Fd-3m space group, and can form stable solid solution with the space group. The conductive material has better conductivity due to the inclusion of two valence-variable elements of Mn and Fe. Meanwhile, the sintering temperature of the spinel manganese ferrite is low, so that the preparation difficulty can be reduced to a certain extent.
The invention synthesizes Mg which can be used in the range of 0-600 ℃ based on the characteristics of two solid solution units x Mn 1- x Al 2x Fe 2(1-x) O 4 Spinel type high-temperature heat-sensitive resistor material. The test shows that the ceramic has good negative temperature coefficient thermal sensitivity, and the content of the valence-variable ions can be regulated and controlled by configuring different solid solution ratios, so that the high-temperature stability and the electric transport property of the ceramic can be directly influenced. The solid solution material obtained by solid solution modification has MgAl 2 O 4 And MnFe 2 O 4 The characteristics of the two solid solution units, namely high temperature stability and reduced resistance, are that the chemical formula is Mg x Mn 1-x Al 2x Fe 2(1-x) O 4 The spinel ceramic composition is suitable as a heat-sensitive material due to its high temperature stability and multivalent state of valence-changing elements.
Disclosure of Invention
The invention aims to provide a spinel type thermistor material for measuring temperature in a high-temperature wide-temperature area and a preparation method thereof, wherein the thermistor material takes magnesium oxide, aluminum oxide, manganese dioxide and ferric oxide as raw materials, and the chemical composition of Mg is obtained through the steps of mixing grinding, presintering, cold isostatic pressing, high-temperature sintering, electrode coating and the like x Mn 1-x Al 2x Fe 2(1-x) O 4 Wherein x is more than or equal to 0.2 and less than or equal to 0.8, the crystal structure is spinel structure, and the material constant is B 150℃/500℃ =4383K-7609K, resistivity at 150 ℃ is 2.6x10 7 Ω.cm-2.25×10 3 The coefficients of omega cm, ln rho and linear fitting Pearson's r of 1000/T are more than or equal to 99.76%, so that the spinel type thermistor material is suitable for manufacturing the thermistor in a high-temperature wide-temperature area.
The invention relates to a spinel type thermistor material for measuring temperature in a high-temperature wide-temperature area, which takes magnesium oxide, aluminum oxide, manganese dioxide and ferric oxide as raw materials, and has the chemical composition of Mg x Mn 1-x Al 2x Fe 2(1-x) O 4 Wherein x is more than or equal to 0.2 and less than or equal to 0.8, and the crystal structure of the resistance material is spinel structure. The specific operation is carried out according to the following steps:
a. according to Mg x Mn 1-x Al 2x Fe 2(1-x) O 4 The molar ratio of x is more than or equal to 0.2 and less than or equal to 0.8, the raw materials of magnesium oxide, aluminum oxide, manganese dioxide and ferric oxide are respectively weighed, put into an agate mortar for mixed grinding for 8-10h, then calcined for 2-3h at the temperature of 1100-1200 ℃ and ground for 6-8h again, thus obtaining single-phase Mg x Mn 1-x Al 2x Fe 2(1-x) O 4 Powder;
b. the powder material obtained in the step a is mixed with 10Kg/cm to 25Kg/cm 2 Briquetting for 10-30 seconds, cold isostatic pressing, maintaining the pressure at 200-350MPa for 2-5 min, and sintering at 1300-1400 deg.C for 0.5-6 hr to obtain Mg x Mn 1-x Al 2x Fe 2(1-x) O 4 A disk-shaped high-density ceramic block material;
c. coating the front and back surfaces of the wafer-shaped high-density ceramic block material sintered in the step B with platinum slurry electrodes, and then preserving the temperature at 900 ℃ for 30 minutes to obtain the ceramic block material with the temperature range of 0-600 ℃ and the material constant of B 150℃/500℃ =4383K-7609K, resistivity at 150 ℃ is 2.60×10 7 Ω.cm-2.25×10 3 Linear fitting Pearson's r coefficients of Ω, cm, ln ρ and 1000/T are all 99.76% or more in the high temperature wide temperature rangeSpinel thermistor materials.
The preparation method of the spinel type thermistor material for measuring the temperature in the high-temperature wide temperature area comprises the following steps:
a. according to Mg x Mn 1-x Al 2x Fe 2(1-x) O 4 The molar ratio of x is more than or equal to 0.2 and less than or equal to 0.8, the raw materials of magnesium oxide, aluminum oxide, manganese dioxide and ferric oxide are respectively weighed, put into an agate mortar for mixed grinding for 8-10h, then calcined for 2-3h at the temperature of 1100-1200 ℃ and ground for 6-8h again, thus obtaining single-phase Mg x Mn 1-x Al 2x Fe 2(1-x) O 4 Powder;
b. the powder material obtained in the step a is mixed with 10Kg/cm to 25Kg/cm 2 Briquetting for 10-30 seconds, cold isostatic pressing, maintaining the pressure at 200-350MPa for 2-5 min, and sintering at 1300-1400 deg.C for 0.5-6 hr to obtain Mg x Mn 1-x Al 2x Fe 2(1-x) O 4 A disk-shaped high-density ceramic block material;
c. coating the front and back surfaces of the wafer-shaped high-density ceramic block material sintered in the step B with platinum slurry electrodes, and then preserving the temperature at 900 ℃ for 30 minutes to obtain the ceramic block material with the temperature range of 0-600 ℃ and the material constant of B 150℃/500℃ =4383K-7609K, resistivity at 150 ℃ is 2.60×10 7 Ω.cm-2.25×10 3 And the coefficients of omega cm, ln rho and 1000/T of linear fit Pearson's r are more than or equal to 99.76% of spinel type thermistor materials in a high-temperature wide-temperature area.
The spinel type thermistor material for measuring the temperature in a high-temperature wide temperature area is prepared by taking magnesium oxide, aluminum oxide, manganese dioxide and ferric oxide as raw materials, mixing, grinding, calcining, cold isostatic pressing, sintering at high temperature and electrode coating. The method realizes the preparation of the single spinel high-temperature thermistor under normal pressure, and the process has low equipment requirement and simple operation process, and can realize mass production. The chemical composition system is Mg x Mn 1-x Al 2x Fe 2(1-x) O 4 Wherein x is more than or equal to 0.2 and less than or equal to 0.8. General purpose medicineThe solid solution proportion is adjusted to adjust the electrical property of the system thermistor material, and the high-temperature wide-temperature area thermistor with adjustable electrical property is manufactured.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
1)Mg x Mn 1-x Al 2x Fe 2(1-x) O 4 the temperature measuring range of the spinel type thermosensitive ceramic is raised to a high temperature area, so that the temperature measurement in a high temperature wide temperature area can be realized;
2) The preparation method realizes the preparation of the single spinel high-temperature thermistor under normal pressure, has low equipment requirement and simple operation process, and can realize mass production;
3) The constant of the thermistor material is B 150℃/500℃ =4383K-7609K, and the range can be regulated by changing the solid solution ratio, and the resistivity of the material at 150 ℃ is 2.6x10 7 Ω.cm-2.25×10 3 The linear fitting Pearson's r coefficients of Ω, cm, ln rho and 1000/T are more than or equal to 99.76%, the resistance drift rate is less than 2.24% after 1000 hours of aging at 1000 ℃, and the linear fitting Pearson has the advantages of stable performance, high accuracy, high sensitivity, good consistency and the like, and specific performance parameters are shown in Table 1;
TABLE 1
Drawings
FIG. 1 is an X-ray diffraction pattern of a thermistor material (uncoated platinum paste electrode) of the present invention.
FIG. 2 is a graph showing the thermal resistance characteristics of the thermistor ceramics according to the present invention.
Detailed Description
Example 1 (x=0.8)
a. According to Mg 0.8 Mn 0.2 Al 1.6 Fe 0.4 O 4 Respectively weighing raw materials of magnesium oxide, aluminum oxide, manganese dioxide and ferric oxide, mixing and grinding for 10 hours in an agate mortar, calcining for 3 hours at 1200 ℃ and grinding for 8 hours again to obtain the dispersionSingle-phase Mg 0.8 Mn 0.2 Al 1.6 Fe 0.4 O 4 Powder;
b. the powder material obtained in the step a is mixed with 10Kg/cm 2 Briquetting for 30 seconds, cold isostatic pressing the formed block material, maintaining the pressure at 200MPa for 2 minutes, and sintering at 1400 ℃ for 6 hours to obtain a round-plate-shaped high-density ceramic block material;
c. coating the positive and negative sides of the material sintered in the step B with platinum slurry electrodes, and then continuously annealing at 900 ℃ for 30 minutes to obtain the material with the temperature range of 0-600 ℃ and the material constant of B 150℃/550℃ =7609K, a resistivity of 2.60×10 at 150 ℃ 7 Linear fitting Pearson's r coefficient of 99.99% for Ω cm, ln ρ and 1000/T;
after aging for 1000 hours at 1000 ℃, the absolute value of the resistance deviation is less than 1.95%.
Example 2 (x=0.6)
a. According to Mg 0.6 Mn 0.4 Al 1.2 Fe 0.8 O 4 Respectively weighing raw materials of magnesium oxide, aluminum oxide, manganese dioxide and ferric oxide, mixing and grinding for 8 hours in an agate mortar, calcining for 3 hours at 1200 ℃ and grinding for 6 hours again to obtain dispersed single-phase Mg 0.6 Mn 0.4 Al 1.2 Fe 0.8 O 4 Powder;
b. the powder material obtained in the step a is processed by 15Kg/cm 2 Briquetting for 20 seconds, cold isostatic pressing the formed block material, maintaining the pressure at 250MPa for 3 minutes, and sintering at 1350 ℃ for 5 hours to obtain a round-plate-shaped high-density ceramic block material;
c. coating the positive and negative sides of the material sintered in the step B with platinum slurry electrodes, and then continuously annealing at 900 ℃ for 30 minutes to obtain the material with the temperature range of 0-600 ℃ and the material constant of B 150℃/550℃ = 6543K, a temperature of 150 ℃ resistivity of 5.68×10 5 Spinel type thermistor material with linear fitting Pearson's r coefficient of 99.96% for omega cm, ln rho and 1000/T in high-temperature wide-temperature area；
After aging for 1000 hours at 1000 ℃, the absolute value of the resistance deviation is less than 2.03%.
Example 3 (x=0.5)
a. According to Mg 0.5 Mn 0.5 AlFeO 4 Respectively weighing raw materials of magnesium oxide, aluminum oxide, manganese dioxide and ferric oxide, mixing and grinding for 9 hours in an agate mortar, calcining for 2 hours at 1100 ℃ and grinding for 7 hours again to obtain dispersed single-phase Mg 0.5 Mn 0.5 AlFeO 4 Powder;
b. the powder material obtained in the step a is processed by 20Kg/cm 2 Briquetting for 20 seconds, cold isostatic pressing the formed block material, maintaining the pressure at 300MPa for 2 minutes, and sintering at 1300 ℃ for 6 hours to obtain a round-plate-shaped high-density ceramic block material;
c. coating the positive and negative sides of the material sintered in the step B with platinum slurry electrodes, and then continuously annealing at 900 ℃ for 30 minutes to obtain the material with the temperature range of 0-600 ℃ and the material constant of B 150℃/550℃ =6357K, a temperature of 150 ℃ resistivity of 3.29×10 4 A spinel thermistor material with the coefficient of linear fit Pearson's r of omega cm, ln rho and 1000/T being 99.98% in a high-temperature wide-temperature area;
after aging for 1000 hours at 1000 ℃, the absolute value of the resistance deviation is less than 1.99%.
Example 4 (x=0.4)
a. According to Mg 0.4 Mn 0.6 Al 0.8 Fe 1.2 O 4 Respectively weighing raw materials of magnesium oxide, aluminum oxide, manganese dioxide and ferric oxide, mixing and grinding for 9 hours in an agate mortar, calcining for 2 hours at 1150 ℃ and grinding for 7 hours again to obtain dispersed single-phase Mg 0.4 Mn 0.6 Al 0.8 Fe 1.2 O 4 Powder;
b. the powder material obtained in the step a is mixed with 25Kg/cm 2 Briquetting for 10 seconds, cold isostatic pressing, holding pressure at 350MPa for 4 min, and sintering at 1400 deg.C4 hours to obtain a round-plate-shaped high-density ceramic block material;
c. coating the positive and negative sides of the material sintered in the step B with platinum slurry electrodes, and then continuously annealing at 900 ℃ for 30 minutes to obtain the material with the temperature range of 0-600 ℃ and the material constant of B 150℃/550℃ =4826k, a temperature of 150 ℃ resistivity of 1.35×10 4 A spinel thermistor material with the coefficient of linear fit Pearson's r of omega cm, ln rho and 1000/T being 99.92% in a high-temperature wide-temperature area;
after aging for 1000 hours at 1000 ℃, the absolute value of the resistance deviation is less than 2.21%.
Example 5 (x=0.2)
a. According to Mg 0.2 Mn 0.8 Al 0.4 Fe 1.6 O 4 Respectively weighing raw materials of magnesium oxide, aluminum oxide, manganese dioxide and ferric oxide, mixing and grinding for 8 hours in an agate mortar, calcining for 2 hours at 1100 ℃ and grinding for 6 hours again to obtain dispersed single-phase Mg 0.2 Mn 0.8 Al 0.4 Fe 1.6 O 4 Powder;
b. the powder material obtained in the step a is mixed with 10Kg/cm 2 Briquetting for 10 seconds, cold isostatic pressing the formed block material, maintaining the pressure for 5 minutes under 200MPa, and sintering at 1370 ℃ for 0.5 hours to obtain a disc-shaped high-density ceramic block material;
c. coating the positive and negative sides of the material sintered in the step B with platinum slurry electrodes, and then continuously annealing at 900 ℃ for 30 minutes to obtain the material with the temperature range of 0-600 ℃ and the material constant of B 150℃/550℃ 4383K, a resistivity of 2.25X10 at 150 ℃ 3 Linear fitting Pearson's r coefficient of 99.76% for linear fitting of Ω cm, ln ρ and 1000/T;
after aging for 1000 hours at 1000 ℃, the absolute value of the resistance deviation is less than 2.24%.
The foregoing is merely a specific embodiment of the present invention, but the design concept of the present invention is not limited thereto.

Claims (2)

1. A spinel type thermistor material for measuring temperature in high-temperature wide-temperature area is characterized in that the thermistor material takes magnesium oxide, aluminum oxide, manganese dioxide and ferric oxide as raw materials, and has the chemical composition of Mg x Mn 1-x Al 2x Fe 2(1-x) O 4 Wherein x is more than or equal to 0.2 and less than or equal to 0.8, and the crystal structure of the resistance material is spinel structure. The specific operation is carried out according to the following steps:
a. according to Mg x Mn 1-x Al 2x Fe 2(1-x) O 4 The molar ratio of x is more than or equal to 0.2 and less than or equal to 0.8, the raw materials of magnesium oxide, aluminum oxide, manganese dioxide and ferric oxide are respectively weighed, put into an agate mortar for mixed grinding of 8-10h, then calcined at the temperature of 1100-1200 ℃ for 2-3h, and ground again for 6-8h, thus obtaining single-phase Mg x Mn 1-x Al 2x Fe 2(1-x) O 4 Powder;
b. the powder material obtained in the step a is mixed with the powder material of 10 to 25Kg/cm 2 Briquetting for 10-30 seconds, cold isostatic pressing, maintaining the pressure at 200-350MPa for 2-5 min, and sintering at 1300-1400 deg.C for 0.5-6 hr to obtain Mg x Mn 1-x Al 2x Fe 2(1-x) O 4 A disk-shaped high-density ceramic block material;
c. coating the front and back surfaces of the wafer-shaped high-density ceramic block material sintered in the step b with platinum slurry electrodes, and then preserving the temperature at 900 ℃ for 30 minutes to obtain the ceramic block material with the temperature range of 0-600 ℃ and the material constant ofB 150℃/500℃ =4383K-7609K, resistivity at 150 ℃ is 2.60×10 7 Ω.cm-2.25×10 3 Ω.cm, lnρAnd 1000-TAnd the coefficient of the linear fit Pearson's r is more than or equal to 99.76 percent.
2. The preparation method of the spinel type thermistor material for measuring the temperature in a high-temperature wide temperature area is characterized by comprising the following steps of:
a. according to Mg x Mn 1-x Al 2x Fe 2(1-x) O 4 ，0.2≤x≤0.8, respectively weighing raw materials of magnesium oxide, aluminum oxide, manganese dioxide and ferric oxide, mixing and grinding in an agate mortar for 8-10h, calcining at 1100-1200 ℃ for 2-3h, and grinding again for 6-8h to obtain single-phase Mg x Mn 1-x Al 2x Fe 2(1-x) O 4 Powder;
b. the powder material obtained in the step a is mixed with the powder material of 10 to 25Kg/cm 2 Briquetting for 10-30 seconds, cold isostatic pressing, maintaining the pressure at 200-350MPa for 2-5 min, and sintering at 1300-1400 deg.C for 0.5-6 hr to obtain Mg x Mn 1-x Al 2x Fe 2(1-x) O 4 A disk-shaped high-density ceramic block material;
c. coating the front and back surfaces of the wafer-shaped high-density ceramic block material sintered in the step b with platinum slurry electrodes, and then preserving the temperature at 900 ℃ for 30 minutes to obtain the ceramic block material with the temperature range of 0-600 ℃ and the material constant ofB 150℃/500℃ =4383K-7609K, resistivity at 150 ℃ is 2.60×10 7 Ω.cm-2.25×10 3 Ω.cm, lnρAnd 1000-TAnd the coefficient of the linear fit Pearson's r is more than or equal to 99.76 percent.
CN202310589422.6A 2023-05-24 2023-05-24 Spinel type thermistor material for measuring temperature in high-temperature wide temperature area and preparation method thereof Pending CN116621573A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310589422.6A CN116621573A (en) 2023-05-24 2023-05-24 Spinel type thermistor material for measuring temperature in high-temperature wide temperature area and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310589422.6A CN116621573A (en) 2023-05-24 2023-05-24 Spinel type thermistor material for measuring temperature in high-temperature wide temperature area and preparation method thereof

Publications (1)

Publication Number Publication Date
CN116621573A true CN116621573A (en) 2023-08-22

Family

ID=87616577

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310589422.6A Pending CN116621573A (en) 2023-05-24 2023-05-24 Spinel type thermistor material for measuring temperature in high-temperature wide temperature area and preparation method thereof

Country Status (1)

Country Link
CN (1) CN116621573A (en)

Similar Documents

Publication Publication Date Title
CN107324799B (en) Perovskite-like high-temperature thermistor material and preparation method thereof
CN110903087B (en) Low-B high-resistance wide-temperature-zone high-temperature thermistor material and preparation method and application thereof
WO2019096335A1 (en) Composite thermistor material, and preparation method therefor and application thereof
CN108439982B (en) Axial composite negative temperature coefficient thermal sensitive ceramic material and preparation method thereof
CN105967656B (en) Novel NTC thermistor material based on nickel oxide
CN110550947A (en) yttrium and zirconium co-doped wide-temperature-zone high-temperature thermistor material and preparation method thereof
CN111620689A (en) Perovskite-like high-temperature thermistor material with different A-site elements and preparation method thereof
CN115093224A (en) Preparation method and application of pyrochlore phase high-entropy ceramic
CN102964119A (en) Low-temperature-sintered BiFeO3-based high-performance negative-temperature-coefficient thermosensitive ceramic material and preparation method thereof
CN104692802B (en) A kind of warm area thermistor material wide of yttria doping and preparation method thereof
CN108585854B (en) Iron-doped perovskite type negative temperature coefficient thermosensitive ceramic material and preparation thereof
CN116621573A (en) Spinel type thermistor material for measuring temperature in high-temperature wide temperature area and preparation method thereof
CN112830770B (en) High-temperature composite thermistor material and preparation method thereof
CN113979728A (en) Preparation method of double perovskite type and yttrium oxide compounded negative temperature coefficient thermistor material
CN101402523A (en) Complex-phase NTC thermal sensitive ceramic and method of manufacturing the same
CN113956038A (en) Cerium-doped perovskite type high-temperature thermal sensitive ceramic resistor material and preparation method thereof
CN112759391A (en) Ytterbium-doped NTC (negative temperature coefficient) type high-temperature thermistor ceramic material as well as preparation method and application thereof
CN112851335A (en) Perovskite-like base composite high-temperature thermistor material and preparation method thereof
JPH0541304A (en) Metallic oxide group thermistor material
CN108863350B (en) Bismuth titanate-based perovskite phase thermal sensitive ceramic composite material and preparation method and application thereof
CN114956789B (en) Linear wide-temperature-area high-temperature-sensitive resistor material and preparation method thereof
CN115872741A (en) High-stability thermistor material suitable for temperature measurement in high-temperature wide-temperature region and preparation method thereof
CN108439970B (en) Rare earth doped perovskite type NTC composite thermosensitive ceramic material and preparation method thereof
CN109265159A (en) A kind of high-performance novel NTC thermistor material based on zinc oxide
CN109796203A (en) A kind of zno-based negative temperature coefficient heat-sensitive resistance material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination