CN113929456B - Preparation method of zirconia-based high-temperature humidity sensor material - Google Patents

Preparation method of zirconia-based high-temperature humidity sensor material Download PDF

Info

Publication number
CN113929456B
CN113929456B CN202111111072.XA CN202111111072A CN113929456B CN 113929456 B CN113929456 B CN 113929456B CN 202111111072 A CN202111111072 A CN 202111111072A CN 113929456 B CN113929456 B CN 113929456B
Authority
CN
China
Prior art keywords
zirconia
powder
parts
humidity sensor
mixed 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.)
Active
Application number
CN202111111072.XA
Other languages
Chinese (zh)
Other versions
CN113929456A (en
Inventor
冯江涛
蒲健
池波
王杰
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.)
Changzhou Lambda Electronic Ltd
Original Assignee
Changzhou Lambda Electronic Ltd
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 Changzhou Lambda Electronic Ltd filed Critical Changzhou Lambda Electronic Ltd
Priority to CN202111111072.XA priority Critical patent/CN113929456B/en
Publication of CN113929456A publication Critical patent/CN113929456A/en
Application granted granted Critical
Publication of CN113929456B publication Critical patent/CN113929456B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/486—Fine ceramics
    • C04B35/488—Composites
    • C04B35/4885—Composites with aluminium oxide
    • 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
    • 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
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/638—Removal 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
    • 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
    • C04B35/64—Burning or sintering processes
    • 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
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6565—Cooling rate
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/668—Pressureless sintering
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention relates to the field of a sensor preparation method, in particular to a preparation method of a zirconia-based high-temperature humidity sensor material. The method comprises the following steps: A. mixing zirconia powder and alumina powder according to a certain proportion to form mixed powder; B. uniformly mixing the mixed powder, a solvent and a dispersing agent to form a biscuit material; C. and finally, preparing the biscuit material into a zirconia ceramic plate. According to the invention, the crystal grain refinement of the zirconia-based material is realized by the ceramic sintering process through the zirconia powder and the alumina powder according to the proportion, so that the aging phenomenon of the high-temperature ceramic humidity sensor caused by thermal hydrolysis is solved. The invention relieves the common pyrohydrolysis phenomenon of the high-temperature ceramic humidity sensor, thereby improving the service life and the reliability of the device.

Description

Preparation method of zirconia-based high-temperature humidity sensor material
Technical Field
The invention relates to the field of a sensor preparation method, in particular to a preparation method of a zirconia-based high-temperature humidity sensor material.
Background
Atmospheric humidity is an important physical parameter, and has wide application in the fields of industrial and agricultural production, environmental protection, transportation and the like, for example, a large number of sensors are needed in grain tobacco storage and semiconductor processing workshops to monitor the humidity in the environment. The detection principle of the humidity sensor is that the resistance or the capacitance of a sensitive device changes along with the amount of the water layer adsorbed on the surface of the porous material, so that the corresponding relation between the resistance and the capacitance is established. The polymer-based humidity sensor can be divided into two categories, namely a polymer and a porous ceramic according to a material system, has the advantages of quick response and high precision, but has short service life and cannot be applied to high-temperature or high-pollution environments, so the porous ceramic-based humidity sensor becomes the mainstream of development, has the advantages of wide humidity range, quick response speed, strong pollution resistance and the like, and needs to be improved in the aspects of stability, consistency, reliability and the like of devices. The porous ceramic-based humidity sensor can be divided into three types of thin film, thick film and block according to the structure,all can be used in high temperature state, for example, a zirconia-based sensor can measure 600 o And C, atmospheric humidity. The high-temperature humidity sensor is also an important part for controlling the combustion of the automobile engine, and the air-fuel ratio of the engine is automatically adjusted by detecting the humidity of air entering the engine, so that the dual purposes of improving the combustion efficiency of the engine and reducing the emission of pollutants are finally achieved.
In the use process of the ceramic humidity sensor, various pollutants such as organic steam, dust, oil stain, harmful gas and the like are inevitably influenced, especially organic matters (alcohol, acetone and the like) containing hydroxyl and carboxyl are adsorbed on the surface interface of the sensitive device, so that the area for effectively adsorbing water molecules is greatly reduced, and the poisoning and passivation effects of the sensor are generated. Therefore, the humidity sensor is aged in a long-term use process, the measurement standard of the humidity sensor continuously drifts to a high resistance value, and the humidity sensitivity is continuously reduced. The humidity sensor element is usually cleaned by heating at high temperature to overcome aging and improve long-term stability, and the aim of high-temperature regeneration is to keep the humidity resistance of the sensor unchanged during long-term use. The ceramic humidity sensor needs to be heated to 800 deg.C o The cleaning of the surface of the porous ceramic can be realized, the complexity of the service of the device is increased by the heating and cleaning process, and meanwhile, the risk of the thermal hydrolysis damage of the ceramic material can be increased by repeated heating and cooling in a humidity environment. Researchers generally believe that the aging phenomenon of the humidity sensor is mainly due to the contamination of the surface and interface of the sensitive element, so that the humidity resistance and humidity resistance of the sensitive element are affected. Different from the corresponding relation between the detected atmospheric humidity and the resistance, the novel humidity sensor can avoid the influence of pollutants on the resistance signal of the sensitive element, the guiding idea is to electrolyze water in the atmosphere into hydrogen ions and oxygen ions, wherein the oxygen ions are led out through an oxygen pump on a zirconia electrolyte layer, the quantity of the oxygen ions can be known by calculating the current of the oxygen pump, and then the water content in the atmosphere can be known, as shown in figure 1. In order to increase the ion conductivity of the zirconia electrolyte layer, it is necessary to heat the zirconia to 600 f o C to 1000 o C, so this type of humidity sensor will have built-in heating electronicsAnd (4) a way. When water vapor in the air enters the porous ceramic electrode and is adsorbed on the surface of the hydrophilic electrode to complete the electrolytic process, the novel ceramic humidity sensor does not need to be heated and cleaned, the long-term stability of the sensor is greatly improved, and the drift amount of an electric signal is reduced.
Pure zirconium oxide (ZrO) 2 ) There are three crystal structures: monoclinic (M), tetragonal (T) and cubic (C) crystal forms. The crystal form changes are as follows:
Figure DEST_PATH_IMAGE001
the phase changes can cause a large volume effect, for example, when the material is heated, a monoclinic phase is changed into a tetragonal phase, and the volume is shrunk by 7-9%; during cooling, the expansion effect is opposite to the former. In addition, the thermal conductivity coefficient of the zirconia material is small, and the thermal expansion coefficient is large, so that the pure zirconia has extremely poor thermal shock resistance and cannot be directly used. On the other hand, the oxygen ion conductivity of the zirconia is very low, and oxygen vacancy can be obviously increased by doping rare earth elements, so that the oxygen ion conductivity is improved. For both reasons, stabilization of pure zirconia is desirable. Common zirconia stabilizers are primarily rare earth or alkaline earth oxides (e.g., Y) 2 O 3 、 MgO、 CaO、CeO 2 Etc.) at high temperature, the cations of the stabilizers have certain solubility in zirconium oxide, can replace zirconium ions in the zirconium oxide to form a replacement type solid solution, and hinder the transformation from a cubic crystal form to a monoclinic crystal form, so that the C-ZrO2 is metastable to room temperature. From the viewpoint of ionic conductivity, the most widely used YSZ (yttria-stabilized zirconia) is taken as an example, and the amount of Y dopant required for achieving full stabilization is 8 to 9 mol% 2 O 3 At 1000 o The conductivity of the alloy is up to 0.1S cm at C -1 . YSZ has high stability in a redox atmosphere, but lowering the operating temperature will cause the oxygen ion conduction activation energy and conductivity of the YSZ electrolyte to drop rapidly.
However, the tetragonal YSZ ceramic is at high temperature (>250 o C) The phase change of T phase to M phase can occur under the humid environmentDue to the difference of lattice constants of the two ceramic products, the ceramic product has a volume expansion effect in the phase change process, so that microcracks appear on the surface of the YSZ ceramic and rapid reduction of mechanical properties is brought, and the phenomenon of thermal hydrolysis and pulverization of the ceramic occurs under severe conditions, as shown in FIG. 2. The problem of performance stability generated in the service process of the YSZ ceramic with the square structure is reported in oxygen sensors and dental materials. Comprehensively considering the mechanical property and oxygen ion conductivity of YSZ material, Y is generally selected as YSZ for high-temperature ceramic humidity sensor 2 O 3 The doping amount is about 5 mol%, the crystal form of the crystal is mainly a tetragonal phase (T phase), and therefore, the problem of performance stability reduction caused by thermal hydrolysis exists in a high-temperature and humid service environment. The pyrohydrolysis phenomenon of the zirconia-based material is closely related to the induction action of water molecules. It is generally believed that for semi-stable tetragonal YSZ, water molecules will interact with Y in the zirconia 2 O 3 Reaction to form Y (OH) 3 Thereby depleting Y present as a stabilizer 2 O 3 The metastable-state zirconia tetragonal-phase structure is caused to perform phase transformation to a stable-state monoclinic structure, and on the other hand, water molecules adsorbed on the surface of the zirconia are dissociated to form Zr-OH bonds and cause the stress concentration of the surface lattice of the zirconia, so that the destabilization phase transformation of the tetragonal-phase zirconia is caused. The aging phenomenon of the material caused by the high-temperature pyrohydrolysis of the zirconia can be relieved by technical approaches such as refining the grain size, changing the stabilizer or applying surface compressive stress, but the problem is not well solved because the high-temperature ceramic humidity sensor needs to meet the use requirements in various aspects of temperature, humidity and mechanical property.
Disclosure of Invention
The invention provides a preparation method of a zirconia-based high-temperature humidity sensor material, aiming at overcoming the defect that the existing sensor can not meet the requirements of temperature, humidity and mechanical property at the same time.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for preparing a zirconia-based high-temperature humidity sensor material comprises the following steps:
A. mixing zirconia powder and alumina powder according to a certain proportion to form mixed powder;
B. uniformly mixing the mixed powder, a solvent and a dispersing agent to form a biscuit material;
C. and finally, preparing the biscuit material into a zirconia ceramic plate.
According to another embodiment of the present invention, further comprising a method of preparing the zirconia ceramic plate, the method comprises:
preparing the biscuit material into a flat-plate biscuit by a ceramic tape casting process; heating to 300 deg.C in a degreasing furnace o C, the rate of temperature rise is 2 o C/min; is at a pressure of 5 DEG in a high-temperature furnace under non-pressure condition o C/min heating to 1400- o C, preserving heat for 5-10 min and sintering at high temperature; from high temperatures to faster than 20 deg.C o The cooling rate of C/min is reduced to 1000- o And C, preserving the heat for 300-600min, and naturally cooling to obtain the zirconia ceramic.
According to another embodiment of the invention, the mixed powder further comprises the following components in parts by weight: 10-20 parts of zirconia powder and 1 part of alumina powder;
the biscuit material comprises the following components in parts by weight: 100-150 parts of mixed powder, 10-50 parts of solvent and 1-2 parts of dispersant.
According to another embodiment of the invention, the coating further comprises 15 parts of zirconia powder and 1 part of alumina powder;
100 parts of mixed powder, 50 parts of solvent and 1 part of dispersant.
According to another embodiment of the present invention, the zirconia powder is 5 mol% yttria-stabilized zirconia powder.
According to another embodiment of the present invention, it is further comprised that the solvent is alcohol.
According to another embodiment of the invention, it is further comprised that the dispersant is herring oil.
According to another embodiment of the invention, the mixed powder, the solvent and the dispersant are uniformly mixed by a high-speed ball mill.
The invention has the beneficial effects that the grain refinement of the zirconia-based material is realized by the ceramic sintering process through the zirconia powder and the alumina powder according to the proportion, thereby solving the aging phenomenon of the high-temperature ceramic humidity sensor caused by thermal hydrolysis. The invention relieves the common pyrohydrolysis phenomenon of the high-temperature ceramic humidity sensor, thereby prolonging the service life and improving the reliability of the device.
Drawings
The present invention will be further described with reference to the accompanying drawings and examples.
FIG. 1 is a schematic thermal hydrolysis diagram of a zirconia electrolyte material of the present invention;
FIG. 2 is a grain refinement of the zirconia matrix of the present invention;
FIG. 3 is a graph of the relationship between the critical grain size value and thermal hydrolysis of a zirconia matrix of the present invention;
Detailed Description
FIG. 1 is a schematic illustration of the pyrohydrolysis of a zirconia electrolyte material of the present invention; FIG. 2 is a grain refinement diagram of a zirconia matrix of the present invention; FIG. 3 is a graph of the relationship between the critical grain size value and thermal hydrolysis of a zirconia matrix of the present invention;
referring to the attached figures 1, 2 and 3, a method for preparing a zirconia-based high temperature humidity sensor material comprises the following steps:
A. mixing 10-20 parts of zirconia powder and 1 part of alumina powder according to a certain proportion to form mixed powder; the zirconia powder is 5 mol percent yttria-stabilized zirconia powder.
B. And uniformly mixing 100-150 parts of mixed powder, 10-50 parts of solvent and 1-2 parts of dispersing agent by a high-speed ball mill to form the biscuit material. The solvent is alcohol. The dispersant is herring oil.
C. And finally, preparing the biscuit material into a zirconia ceramic plate.
The preparation method of the zirconia ceramic plate comprises the following steps:
preparing the biscuit material into a flat-plate biscuit by a ceramic tape casting process; heating to 300 deg.C in a degreasing furnace o C, the rate of temperature rise is 2 o C/min; at a high temperature furnace under a pressureless condition of 5 o C/min heating to 1400- o C, keeping the temperature for 5-10 min for raisingCarrying out warm sintering; from high temperatures to faster than 20 deg.C o Cooling to 1000- o And C, preserving the heat for 300-600min, and naturally cooling to obtain the zirconia ceramic.
The specific embodiment is as follows:
A. mixing 15 parts of zirconia powder and 1 part of alumina powder according to a certain proportion to form mixed powder; the zirconia powder is 5 mol percent yttria-stabilized zirconia powder.
B. And uniformly mixing 100 parts of the mixed powder, 50 parts of the solvent and 1 part of the dispersant by a high-speed ball mill to form the biscuit material. The solvent is alcohol. The dispersant is herring oil.
C. And finally, preparing the biscuit material into a zirconia ceramic plate.
The preparation method of the zirconia ceramic plate comprises the following steps:
preparing the biscuit material into a flat-plate biscuit by a ceramic tape casting process; heating to 300 deg.C in a degreasing furnace oC The temperature rise rate is 2 o C/min; is at a pressure of 5 DEG in a high-temperature furnace under non-pressure condition o C/min heating to 1450 o C, preserving heat for 10 min and carrying out high-temperature sintering; from high temperatures to faster than 20 deg.C o Cooling to 1200 deg.C/min o And C, preserving the heat for 600min, and naturally cooling to obtain the zirconia ceramic.
Compared with the traditional sintering method, the technology for high-temperature short-time heating, low-temperature long-time heat preservation has the advantages of short sintering time of the zirconia electrolyte layer, fine crystal grains, compact structure and the like.
From the thermodynamic theory, it is known that when the grain size of zirconia is refined to a critical value, the aging phenomenon of zirconia in a high-temperature and humid environment can be effectively inhibited. In the above process route of component design and sintering, a proper amount of alumina powder is added to the semi-stable zirconia (5YSZ), and the sintering process is optimized, so that the structural densification and grain refinement of the zirconia layer of the high-temperature ceramic humidity sensor can be realized. The grain size of the zirconia ceramic layer of the traditional sensor is in a coarse grain state, the 5YSZ ceramic-based device has the phenomenon that the material is pulverized due to thermal hydrolysis in the working temperature high-temperature humidity environment, the grain size is reduced to 1/4-1/5, and the 5YSZ ceramic-based device keeps complete structure under the same experimental condition and has no sign of crack generation. This demonstrates that the problem of thermal hydrolysis of the zirconia material can be effectively suppressed below the critical grain size.

Claims (6)

1. A method for preparing a zirconia-based high-temperature humidity sensor material is characterized by comprising the following steps:
A. mixing zirconia powder and alumina powder according to a certain proportion to form mixed powder;
B. uniformly mixing the mixed powder, a solvent and a dispersing agent to form a biscuit material;
C. finally, preparing the biscuit material into a zirconia ceramic plate;
the preparation method of the zirconia ceramic plate comprises the following steps:
preparing the biscuit material into a flat-plate biscuit by a ceramic tape casting process; heating to 300 deg.C in a degreasing furnace o C, the rate of temperature rise is 2 o C/min; at a high temperature furnace under a pressureless condition of 5 o C/min heating to 1400- o C, preserving heat for 5-10 min and sintering at high temperature; from high temperatures to faster than 20 deg.C o Cooling to 1000- o C, preserving the heat for 300-;
the mixed powder comprises the following components in parts by weight: 10-20 parts of zirconium oxide powder and 1 part of aluminum oxide powder;
the biscuit material comprises the following components in parts by weight: 100 portions of mixed powder, 150 portions of solvent, 10 to 50 portions of dispersant and 1 to 2 portions of dispersant.
2. The method for preparing a zirconia-based high temperature and humidity sensor material according to claim 1, wherein the mixed powder comprises the following components in parts by weight: 15 parts of zirconium oxide powder and 1 part of aluminum oxide powder;
the embryo material comprises the following components in parts by weight: 100 parts of mixed powder, 50 parts of solvent and 1 part of dispersant.
3. The method according to claim 1, wherein the zirconia powder is 5 mol% yttria-stabilized zirconia powder.
4. The method according to claim 1, wherein the solvent is alcohol.
5. The method of claim 1, wherein the dispersion agent is menhaden oil.
6. The method for preparing a zirconia-based high temperature humidity sensor material according to claim 1, wherein the mixed powder, the solvent and the dispersant are uniformly mixed by a high speed ball mill.
CN202111111072.XA 2021-09-23 2021-09-23 Preparation method of zirconia-based high-temperature humidity sensor material Active CN113929456B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111111072.XA CN113929456B (en) 2021-09-23 2021-09-23 Preparation method of zirconia-based high-temperature humidity sensor material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111111072.XA CN113929456B (en) 2021-09-23 2021-09-23 Preparation method of zirconia-based high-temperature humidity sensor material

Publications (2)

Publication Number Publication Date
CN113929456A CN113929456A (en) 2022-01-14
CN113929456B true CN113929456B (en) 2022-09-30

Family

ID=79276475

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111111072.XA Active CN113929456B (en) 2021-09-23 2021-09-23 Preparation method of zirconia-based high-temperature humidity sensor material

Country Status (1)

Country Link
CN (1) CN113929456B (en)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1259080A (en) * 1985-09-06 1989-09-05 Nobuo Kimura High density alumina zirconia ceramics and a process for production thereof
CN101357845A (en) * 2008-09-11 2009-02-04 西北有色金属研究院 Stable tetragonal zirconia ceramics material of manganese oxide and method of preparing the same
CN103698358B (en) * 2012-09-27 2015-11-18 中国科学院金属研究所 A kind of preparation method of porous ceramics alumina type humidity sensor
CN104891969A (en) * 2015-05-26 2015-09-09 苏州工业园区传世汽车电子有限公司 Preparation method of zirconium oxide ceramic for oxygen sensor
CN104944945B (en) * 2015-06-20 2018-02-27 宁波博莱特光电科技股份有限公司 A kind of preparation method of anti-aging ceramic lock pin based on zirconium oxide
CN105272224A (en) * 2015-10-21 2016-01-27 上海大学 Preparation method of Al2O3 doped Mg-PSZ (magnesia partially stabilized zirconia) ceramic
CN110540426B (en) * 2019-10-11 2022-04-08 石家庄高新区亿成科技有限公司 Zirconia-based biological ceramic material and preparation method and application thereof
CN112062558B (en) * 2020-08-03 2021-06-29 山东金三河新材料科技有限公司 Preparation method of zirconia ceramic

Also Published As

Publication number Publication date
CN113929456A (en) 2022-01-14

Similar Documents

Publication Publication Date Title
Dudek Ceramic oxide electrolytes based on CeO2—preparation, properties and possibility of application to electrochemical devices
CN103011811B (en) Method for preparing high temperature NTC (Negative Temperature Coefficient) thermistor material
Dueker et al. Ceramic aspects of the bosch lambda-sensor
CN103529107B (en) Limited current type oxygen sensor and manufacturing method thereof
CN104597095A (en) Co3V2O8 sensing electrode and three-dimensional three-phase boundary-based YSZ electrode mixed potential NO2 sensor and preparation method thereof
Künstler et al. Synthesis, structure and electrochemical properties of In-doped BaCeO3
Tan et al. Electronic conductivity of a ZrO2 thin film as an oxygen sensor
CN113929456B (en) Preparation method of zirconia-based high-temperature humidity sensor material
CN102376378B (en) Heating electrode paste, heating electrode and planar oxygen sensor comprising heating electrode
CN104819998A (en) Impedance spectroscopy type NOx (Nitric Oxide) sensor and preparation method of solid electrolyte material thereof
US4792752A (en) Sensor for measuring partial pressures of gases
Aktas et al. Electrical Conductivity of Er 2 O 3-Doped c-ZrO 2 Ceramics
Kim et al. Effect of ZnO and TiO2 doping on the sintering behavior of Y2O3 ceramics
Tikhonov et al. Preparation and properties of ceramic composites with oxygen ionic conductivity in the ZrO 2-CeO 2-Al 2 O 3 and ZrO 2-Sc 2 O 3-Al 2 O 3 systems
Subbarao Oxygen sensors
RU2379670C1 (en) Electrochemical element and method of its manufacturing
CN110391455B (en) Yttrium-stabilized zirconium dioxide-low-melting-point glass powder compound and preparation method thereof
An et al. Effect of heat treatment on structure and properties of MgO-PSZ electrolyte
Feng et al. Insight into the thermal hydrolysis behaviors of 5Y-TZP based oxygen sensor: Effect of grain size dependent TM phase transformation and residual stress
Fonseca et al. Impedance spectroscopy study of the sintering of yttria-stabilized zirconia/magnesia composites
Aktaş Microstructure, mechanical and electrical properties of CuO doped 8YSZ
Tekeli et al. Microstructural and electrical conductivity properties of cubic zirconia doped with various amount of titania
Chen et al. Gas sensing properties of asymmetrically reduced Na1/2Bi1/2TiO3–based ceramics
JPH06283310A (en) Temperature sensor
Wu et al. Electrical behavior of ZrO 2-MgO-Y 2 O 3 solid electrolyte

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
GR01 Patent grant
GR01 Patent grant