CN113430330A - Preparation method of zirconia solid electrolyte tube and oxygen determination probe - Google Patents
Preparation method of zirconia solid electrolyte tube and oxygen determination probe Download PDFInfo
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- CN113430330A CN113430330A CN202110697416.3A CN202110697416A CN113430330A CN 113430330 A CN113430330 A CN 113430330A CN 202110697416 A CN202110697416 A CN 202110697416A CN 113430330 A CN113430330 A CN 113430330A
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- zirconia
- solid electrolyte
- mass
- tube
- electrolyte tube
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 122
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 43
- 239000001301 oxygen Substances 0.000 title claims abstract description 43
- 239000000523 sample Substances 0.000 title claims abstract description 32
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 38
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims abstract description 34
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 19
- 239000011780 sodium chloride Substances 0.000 claims abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 16
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000008247 solid mixture Substances 0.000 claims abstract description 15
- 238000012545 processing Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 28
- 238000001746 injection moulding Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 238000005259 measurement Methods 0.000 abstract description 7
- 150000003839 salts Chemical class 0.000 abstract description 4
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000004018 waxing Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910002085 magnesia-stabilized zirconia Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/28—Manufacture of steel in the converter
- C21C5/42—Constructional features of converters
- C21C5/46—Details or accessories
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/411—Cells and probes with solid electrolytes for investigating or analysing of liquid metals
- G01N27/4112—Composition or fabrication of the solid electrolyte
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/10—Reduction of greenhouse gas [GHG] emissions
- Y02P10/134—Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen
Abstract
The invention discloses a preparation method of a zirconia solid electrolyte tube and an oxygen determination probe, comprising the following steps: heating a first mass of sodium chloride crystals to a molten state; adding a second mass of magnesium oxide and a third mass of barium carbonate to the sodium chloride in the molten state, mixing, and obtaining a solid mixture after cooling; and processing the solid mixture into a zirconia tube for an oxygen determination probe. According to the embodiment of the invention, magnesium oxide and barium carbonate are subjected to molten salt catalytic reaction, so that the density of the prepared zirconia electrolyte tube is close to the theoretical density, and the measurement requirement of ultra-low oxygen aluminum determination is met.
Description
Technical Field
The invention relates to the field of sensing equipment, in particular to a preparation method of a zirconia solid electrolyte tube and an oxygen determination probe.
Background
Under the measurement conditions of medium-high oxygen (more than 10ppm) and common low oxygen (5-10 ppm) contents, the requirements of a zirconium oxide solid electrolyte tube for an oxygen determination probe are mainly reflected on the improvement of density (the density can reach about 95%), however, when the acid-soluble aluminum is measured through the oxygen probe at the ultra-low oxygen content (0-5 ppm), two factors of physical oxygen permeation and electrochemical oxygen permeation exist, the stability and the accuracy of an oxygen potential value in the measurement process of an oxygen battery can be influenced, and the final acid-soluble aluminum data is unstable and the deviation of a test value is large.
The oxygen probe prepared by the prior technical scheme basically meets the existing requirements on the oxygen probe, but the accuracy and the stability of the measurement of the acid-dissolved aluminum corresponding to the ultra-low oxygen content are not completely met all the time.
Disclosure of Invention
The embodiment of the invention provides a preparation method of a zirconia solid electrolyte tube and an oxygen determination probe, which are used for solving the problems of physical oxygen permeation and chemical oxygen permeation of the zirconia solid electrolyte tube in the prior art, realizing that the density of the prepared zirconia solid electrolyte tube is close to the theoretical density, and meeting the measurement requirement of ultra-low oxygen aluminum determination.
The embodiment of the disclosure provides a preparation method of a zirconia solid electrolyte tube, which comprises the following steps:
heating a first mass of sodium chloride crystals to a molten state;
adding a second mass of magnesium oxide and a third mass of barium carbonate to the sodium chloride in the molten state, mixing, and obtaining a solid mixture after cooling;
and processing the solid mixture into a zirconia tube for an oxygen determination probe.
In one embodiment, the purity of the sodium chloride crystals ranges from [ 99%, 100% ].
In one embodiment, the magnesium oxide has a particle size in the range of [50nm, 150nm ].
In one embodiment, the ratio of the second mass to the first mass ranges from [ 0.64%, 0.92% ].
In one embodiment, the barium carbonate has a purity range that satisfies [ 99.5%, 100% ].
In one embodiment, the ratio of the third mass to the first mass is in a range of [ 2.5%, 5% ].
In one embodiment, the processing of the solid mixture into a zirconia tube for a fixed oxygen probe comprises:
and processing the solid mixture into a zirconia tube for the oxygen determination probe by an injection molding process.
The embodiment of the disclosure also provides an oxygen determination probe, which comprises a shell and a zirconia tube manufactured by the preparation method of the zirconia solid electrolyte tube; the zirconia tube includes opposing first and second ends; the first end of the zirconia tube is embedded in the shell, and the second end of the zirconia tube extends out of the shell; the second end is used as a detection part of the oxygen determination probe to be contacted with molten steel to be detected.
According to the embodiment of the invention, magnesium oxide and barium carbonate are subjected to molten salt catalytic reaction, so that the density of the prepared zirconia electrolyte tube is close to the theoretical density, and the measurement requirement of ultra-low oxygen aluminum determination is met.
The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
fig. 1 is a basic flow chart of a method for manufacturing a zirconia solid electrolyte tube according to an embodiment of the present disclosure;
fig. 2 is a schematic structural diagram of a probe according to an embodiment of the present disclosure.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
The existing zirconia solid electrolyte tube for the oxygen determination probe is mostly realized by adopting a mode of codoping magnesia or a plurality of oxides, for example, a magnesia stabilized zirconia tube is adopted by imports of Germany Heley, American Minkou and the like, and domestic manufacturers generally adopt the procedures of firstly preparing precursor powder by adopting magnesia or magnesia and other oxides by a coprecipitation method, then combining a hot injection mode, discharging glue, sintering and the like to complete the manufacture of the zirconia solid electrolyte tube.
The stable zirconia powder formed by the coprecipitation method cannot ensure that the stabilizer is not lost completely in the coprecipitation process, so that the stability of the doped content batch is insufficient, the performance of the finished zirconia solid electrolyte tube is unstable, and the stability and the reproducibility of the oxygen determination probe are poor. In addition, the stabilizer formed in the way has a large amount of residues at the crystal boundary position in the high-temperature firing process, and is not effectively embedded on the original lattice position, so that the electronic conductance ratio of the electrolyte at high temperature is too high, and the obvious electrochemical oxygen permeation problem exists.
The embodiment of the present disclosure provides a method for preparing a zirconia solid electrolyte tube, and as shown in fig. 1, the method for preparing a zirconia solid electrolyte tube starts with step S101, and a first mass of sodium chloride crystals is heated to a molten state. After the sodium chloride crystal is heated to the molten state, step S102 is performed, and the second mass of magnesium oxide and the third mass of barium carbonate are added to the sodium chloride in the molten state and mixed. The specific mixing method may be stirring during the process of adding magnesium oxide and barium carbonate to the sodium chloride in a molten state, thereby achieving uniform mixing of magnesium oxide and barium carbonate. Then, S103, cooling to obtain a solid mixture. It may be cooled to room temperature or a specified temperature, thereby obtaining a solid mixture, which may be a cake. And finally S104, processing the solid mixture into a zirconia tube for the oxygen determination probe. The magnesium oxide and the barium carbonate are subjected to molten salt catalytic reaction, so that the compactness of the zirconia solid electrolyte tube is close to the theoretical density, and the electronic conductance of the zirconia solid electrolyte tube is controlled to be below 0.1% at high temperature, thereby meeting the measurement requirement of the ultra-low oxygen fixed aluminum.
In one embodiment, the purity of the sodium chloride crystals ranges from [ 99%, 100% ]. In one embodiment, the magnesium oxide has a particle size in the range of [50nm, 150nm ]. In one embodiment, the barium carbonate has a purity range that satisfies [ 99.5%, 100% ]. Specifically, high-purity sodium chloride crystals can be used for heating, and nano-scale magnesium oxide and reagent-grade barium carbonate are used for mixing, so that the compactness of the prepared zirconia solid electrolyte tube can be further improved to be close to the theoretical density.
In one embodiment, the ratio of the second mass to the first mass ranges from [ 0.64%, 0.92% ]. In one embodiment, the ratio of the third mass to the first mass is in a range of [ 2.5%, 5% ]. Specifically, the corresponding mass ratio can be adjusted according to the requirements of the prepared zirconia tube.
In one embodiment, the processing of the solid mixture into a zirconia tube for a fixed oxygen probe comprises: and processing the solid mixture into a zirconia tube for the oxygen determination probe by an injection molding process. Specifically, before the injection molding process, the obtained block mixture can be dissolved and washed in deionized water, repeated for several times, and then dried. And then based on the dried blocky mixture, completing the procedures of injection molding, pre-burning and de-waxing, high-temperature burning and the like according to an injection molding process to obtain the zirconia tube for the oxygen determination probe.
The following embodiment also provides an embodiment of a method for preparing a zirconia solid electrolyte tube:
case one
The first step is as follows: weighing 1000 g of high-purity sodium chloride crystals (the content is 99%), heating to 830 ℃, and keeping a molten state;
the second step is that: slowly adding 6.4 g of nano-scale magnesium oxide (with the particle size of 50nm) and 25 g of reagent-grade barium carbonate (with the content of 99.5%) into the molten liquid, fully stirring and mixing, and then cooling to form a block-shaped object;
the third step: dissolving and cleaning the mixture in deionized water, repeating the dissolving and cleaning for 6 times, and then drying;
the fourth step: according to the injection molding process, the procedures of injection molding, pre-burning and de-waxing, high-temperature sintering and the like are completed, and the zirconia tube for the oxygen determination probe is obtained.
Case two
The first step is as follows: weighing 1000 g of high-purity sodium chloride crystals (the content is 99.5 percent), heating to 850 ℃, and keeping a molten state;
the second step is that: slowly adding 9.2 g of nano-scale magnesium oxide (particle size 150nm) and 50 g of reagent-grade barium carbonate (content 99.9%) into the molten liquid, fully stirring and mixing, and cooling to form a block;
the third step: dissolving and cleaning the mixture in deionized water, repeating the dissolving and cleaning for 5 times, and then drying;
the fourth step: according to the injection molding process, the procedures of injection molding, pre-burning and de-waxing, high-temperature sintering and the like are completed, and the zirconia tube for the oxygen determination probe is obtained.
Case three
The first step is as follows: weighing 1000 g of high-purity sodium chloride crystals (the content is 99.3 percent), heating to 900 ℃, and keeping the sodium chloride crystals in a molten state;
the second step is that: slowly adding 7.5 g of nano-scale magnesium oxide (with the particle size of 100nm) and 40 g of reagent-grade barium carbonate (with the content of 99.9%) into the molten liquid, fully stirring and mixing, and then cooling to form a block-shaped object;
the third step: dissolving and cleaning the mixture in deionized water, repeating the dissolving and cleaning for 6 times, and then drying;
the fourth step: according to the injection molding process, the procedures of injection molding, pre-burning and de-waxing, high-temperature sintering and the like are completed, and the zirconia tube for the oxygen determination probe is obtained.
Performance index of zirconia solid electrolyte tube
The preparation method disclosed in this example uses sodium chloride as flux, and realizes the binding state of the stabilizer and zirconia at molecular level by molten salt method. By introducing barium carbonate as a catalyst and a fluxing agent, the compactness of the zirconia solid electrolyte tube reaches 100%, the stabilizing agent is completely embedded in crystal lattices, no residue is left at the crystal boundaries basically, the high-temperature electronic conductance ratio is controlled below 0.1%, and the high-temperature ionic conductivity is very stable.
The embodiment of the present disclosure further provides an oxygen determination probe, as shown in fig. 2, including a housing and a zirconia tube manufactured by the method for manufacturing a zirconia solid electrolyte tube; the zirconia tube includes opposing first and second ends; the first end of the zirconia tube is embedded in the shell, and the second end of the zirconia tube extends out of the shell; the second end is used as a detection part of the oxygen determination probe to be contacted with molten steel to be detected.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
The above-mentioned serial numbers of the embodiments of the present invention are merely for description and do not represent the merits of the embodiments.
While the present invention has been described with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, which are illustrative and not restrictive, and it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. A method for preparing a zirconia solid electrolyte tube, comprising:
heating a first mass of sodium chloride crystals to a molten state;
adding a second mass of magnesium oxide and a third mass of barium carbonate to the sodium chloride in the molten state, mixing, and obtaining a solid mixture after cooling;
and processing the solid mixture into a zirconia tube for an oxygen determination probe.
2. The method for producing a zirconia solid electrolyte tube according to claim 1, wherein the purity of the sodium chloride crystal is in a range of [ 99%, 100% ].
3. The method for producing a zirconia solid electrolyte tube according to claim 1, wherein the magnesia has a particle size in a range of [50nm, 150nm ].
4. The method of producing a zirconia solid electrolyte tube according to claim 3, wherein a ratio range of the second mass to the first mass satisfies [ 0.64%, 0.92% ].
5. The method of preparing a zirconia solid electrolyte tube according to claim 1, wherein the barium carbonate has a purity in a range of [ 99.5%, 100% ].
6. The method of producing a zirconia solid electrolyte tube according to claim 5,
the ratio range of the third mass to the first mass satisfies [ 2.5%, 5% ].
7. The method of manufacturing a zirconia solid electrolyte tube according to claim 1, wherein the processing the solid mixture into a zirconia tube for an oxygen determination probe comprises:
and processing the solid mixture into a zirconia tube for the oxygen determination probe by an injection molding process.
8. An oxygen determination probe comprising a case and a zirconia tube produced by the method for producing a zirconia solid electrolyte tube according to any one of claims 1 to 7;
the zirconia tube includes opposing first and second ends;
the first end of the zirconia tube is embedded in the shell, and the second end of the zirconia tube extends out of the shell;
the second end is used as a detection part of the oxygen determination probe to be contacted with molten steel to be detected.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110697416.3A CN113430330A (en) | 2021-06-23 | 2021-06-23 | Preparation method of zirconia solid electrolyte tube and oxygen determination probe |
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| CN202110697416.3A CN113430330A (en) | 2021-06-23 | 2021-06-23 | Preparation method of zirconia solid electrolyte tube and oxygen determination probe |
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|---|---|---|---|---|
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| CN108706631A (en) * | 2018-08-08 | 2018-10-26 | 景德镇陶瓷大学 | A kind of preparation method of rectangular patch monoclinic zirconia |
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| CN110600778A (en) * | 2018-06-12 | 2019-12-20 | 阜阳师范学院 | MgO and Y2O3Double-doped ZrO2-alkali metal salt complex and process for producing the same |
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2021
- 2021-06-23 CN CN202110697416.3A patent/CN113430330A/en active Pending
Patent Citations (6)
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|---|---|---|---|---|
| CN1031098A (en) * | 1987-07-07 | 1989-02-15 | 首都钢铁公司 | Coating for tubular zirconium-oxide electrode |
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| CN108706631A (en) * | 2018-08-08 | 2018-10-26 | 景德镇陶瓷大学 | A kind of preparation method of rectangular patch monoclinic zirconia |
| CN109437296A (en) * | 2018-12-06 | 2019-03-08 | 洛阳理工学院 | A kind of method that molten-salt growth method prepares tetragonal phase zirconia nanorod |
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Application publication date: 20210924 |
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