CN118619693A - Rare earth doped zirconia pressure transmission medium and preparation method and application thereof - Google Patents
Rare earth doped zirconia pressure transmission medium and preparation method and application thereof Download PDFInfo
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 459
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 125
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 125
- 230000005540 biological transmission Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 146
- 239000000843 powder Substances 0.000 claims abstract description 113
- 239000002245 particle Substances 0.000 claims abstract description 82
- 238000002156 mixing Methods 0.000 claims abstract description 79
- 239000000919 ceramic Substances 0.000 claims abstract description 73
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 23
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000007873 sieving Methods 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 48
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 48
- 238000000465 moulding Methods 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 26
- 238000003825 pressing Methods 0.000 claims description 17
- 238000009413 insulation Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 3
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 3
- 238000004321 preservation Methods 0.000 abstract description 16
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 71
- 238000002474 experimental method Methods 0.000 description 26
- 239000011812 mixed powder Substances 0.000 description 24
- 238000001132 ultrasonic dispersion Methods 0.000 description 21
- 239000000292 calcium oxide Substances 0.000 description 20
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 20
- 238000005303 weighing Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 238000011068 loading method Methods 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 229910052709 silver Inorganic materials 0.000 description 9
- 239000004332 silver Substances 0.000 description 9
- 229910010293 ceramic material Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 238000004806 packaging method and process Methods 0.000 description 7
- 230000000630 rising effect Effects 0.000 description 7
- 238000011049 filling Methods 0.000 description 6
- 238000000748 compression moulding Methods 0.000 description 5
- 229910052903 pyrophyllite Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000012774 insulation material Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000010729 system oil Substances 0.000 description 3
- 230000027311 M phase Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 239000003921 oil Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002468 ceramisation Methods 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 230000002441 reversible effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a rare earth doped zirconia pressure transmission medium, a preparation method and application thereof, wherein the preparation method comprises the steps of firstly uniformly mixing yttrium oxide, zirconia powder and cerium oxide powder to obtain rare earth co-doped zirconia powder; compacting rare earth co-doped zirconia powder to obtain a first rare earth co-doped zirconia blank; then sintering the pressed first rare earth co-doped zirconia blank to obtain a primary sintering product; crushing, grinding and sieving the primary sintering product to obtain rare earth co-doped zirconia particles with different particle sizes; then adding rare earth co-doped zirconia particles with different particle sizes into a forming die to be pressed and formed to obtain a second rare earth co-doped zirconia blank; and sintering the pressed second rare earth co-doped zirconia blank to obtain the rare earth co-doped zirconia ceramic. The zirconia ceramic with high heat preservation performance and pressure transmission performance is prepared by doping the yttrium oxide and the cerium oxide into the zirconia and optimizing the preparation process.
Description
Technical Field
The invention belongs to the field of ceramic materials, relates to zirconia ceramics, and particularly relates to a rare earth doped zirconia pressure transmission medium, a preparation method and application thereof.
Background
The zirconia ceramic has the advantages of high toughness, high bending strength, high wear resistance, excellent heat insulation performance, thermal expansion coefficient close to that of steel and the like, so that the zirconia ceramic is widely applied to the field of structural ceramics: in addition, due to the excellent high temperature resistance, the heat-resistant material can be used as an induction heating pipe, a refractory material and a heating element; zirconium oxide, which has a relatively high melting point (about 2700 ℃ under normal pressure) and excellent heat insulation performance, is often used as a heat insulation material under high temperature and high pressure conditions; however, pure zirconia has a reversible phase change from monoclinic phase (m) to tetragonal phase (t) at 1170 ℃, namely m-phase ZrO 2 is converted into t-phase ZrO 2 in a temperature range above 1170 ℃, and at the same time, t-phase ZrO 2 is converted back into m-phase in a low-temperature state, and the phase change is accompanied by 5% of volume change, so that the cracking of the material is easy to cause, and the zirconia ceramic is limited to be used as a thermal insulation material under a high-temperature condition.
At present, in order to solve the problem of phase change volume change cracking of zirconia at high temperature, calcium oxide, magnesium oxide and the like are generally added into zirconia ceramic as stabilizers, so that the zirconia sintered at high temperature is stabilized in tetragonal phase (t) and cubic phase (c), and phase change does not occur in the heating process, thereby improving the stability of the material. Along with the increasing demand for heat insulation performance, zirconia with lower heat conductivity and more excellent heat insulation performance becomes an important development direction, and rare earth doping becomes an important method.
Meanwhile, zirconia is used as an important heat-insulating material and has wide application in the field of high-temperature high-pressure experiments, and the preparation of the zirconia material with both high heat-insulating performance and excellent pressure transmission performance is important for the high-temperature high-pressure experiments. Zirconium oxide is commonly used in the current high-temperature high-pressure experiments: the Japanese imported zirconia and domestic CaO stabilize the zirconia. Japanese zirconia is high in cost, and domestic CaO stabilized zirconia is serious in ceramization in the use process, and high in structural strength, so that on one hand, processing is difficult, and on the other hand, in a high-pressure experiment, pressure loading consumption is high, and the achievable cavity pressure is low. The method disclosed by the invention is used for preparing the rare earth co-doped zirconia material by doping yttrium oxide and cerium oxide so as to meet the performance requirements of the zirconia ceramic material on temperature isolation and pressure conduction in high-temperature and high-pressure experiments.
Disclosure of Invention
In high temperature and high pressure experiments, a heat insulating material with better heat insulating performance is required to realize higher temperature in the cavity. At present, domestic zirconia is usually used as calcium oxide stabilized zirconia in high-temperature and high-pressure experiments, but the two problems of low pressure conduction efficiency and low temperature generation efficiency are faced when the calcium oxide stabilized zirconia is used as a heat-insulating pressure-transmitting medium for high-temperature and high-pressure experiments, so that the maximum temperature and pressure conditions which can be achieved in the high-temperature and high-pressure experiments are limited. Aiming at the technical problems, the invention provides a rare earth doped zirconia pressure transmission medium and a preparation method thereof, and the rare earth doping is used for enhancing the phonon scattering of zirconia ceramics so as to improve the heat preservation performance; meanwhile, the rare earth zirconia ceramics with different grain diameters are adopted to be proportioned, so that the strength and compactness of the rare earth zirconia ceramics are improved, the prepared rare earth zirconia ceramics have the optimal compression ratio in the high-temperature high-pressure experimental pressurizing process, the consumption of pressure by a sealing edge is reduced, more pressure is conducted to a sample cavity, and the pressure in the cavity is improved.
Another object of the invention is to provide the use of the rare earth doped zirconia pressure transmission medium described above.
In order to achieve the above purpose, the present invention is realized by adopting the following technical scheme.
The invention provides a preparation method of a rare earth doped zirconia pressure transmission medium, which comprises the following steps:
(1) Mixing material
Firstly, uniformly mixing yttrium oxide and zirconium oxide powder to obtain yttrium oxide doped zirconium oxide powder; uniformly mixing the yttrium oxide doped zirconia powder and the cerium oxide powder to obtain rare earth co-doped zirconia powder; the yttrium oxide powder accounts for 3-12% of the mass of the yttrium oxide doped zirconium oxide powder; the cerium oxide powder accounts for 10-50% of the rare earth co-doped zirconium oxide powder in mass percent;
(2) Primary sintering
Compacting rare earth co-doped zirconia powder under the condition of 40-80 MPa to obtain a first rare earth co-doped zirconia blank; then sintering the pressed first rare earth co-doped zirconia blank for 2-10 hours at 1200-1500 ℃ to obtain a primary sintered product;
(3) Molding and sintering
Crushing, grinding and sieving the primary sintering product to obtain rare earth co-doped zirconia particles with different particle sizes; uniformly mixing rare earth co-doped zirconia particles with different particle sizes, and then adding the mixture into a forming die; then pressing and forming under 300-500 MPa to obtain a second rare earth co-doped zirconia blank; and sintering the pressed second rare earth co-doped zirconia blank for 2-10 hours at 1100-1600 ℃ to obtain the rare earth co-doped zirconia ceramic.
In the step (1), the particle size of the yttrium oxide powder is 50nm-500nm; the particle size of the cerium oxide powder is 50nm-500nm; the mixing time of the yttrium oxide and the zirconium oxide powder is 4-12 hours; the mixing time of the zirconia powder doped with the yttrium oxide and the cerium oxide is 4-12 h.
In the step (2), the sintering heating rate is 100 ℃/h to 300 ℃/h; cooling to below 100 ℃ after sintering, wherein the cooling rate is 100 ℃/h-200 ℃/h.
In the step (3), the particle sizes of the rare earth co-doped zirconia with different particle sizes comprise 20-50 meshes, 50-100 meshes and more than 100 meshes. The rare earth co-doped zirconia particles with different particle sizes are prepared from the following components in percentage by mass: 20 mesh-50 mesh: 50 mesh-100 mesh: more than 100 meshes of = (7-4): (2-4): (1-2) and mixing uniformly for 4-12 h; then adding the mixture into a forming die for press forming. In the sintering process of the pressed second rare earth co-doped zirconia blank, the sintering heating rate is 100 ℃/h to 300 ℃/h; cooling to below 100 ℃ after sintering, wherein the cooling rate is 100 ℃/h-200 ℃/h.
The invention also provides the rare earth doped zirconia pressure transmission medium prepared by the method.
The invention also provides application of the rare earth doped zirconia pressure transmission medium, which is used as a heat preservation pressure transmission medium.
The zirconia ceramic with high heat preservation performance and pressure transmission performance is prepared by doping the yttrium oxide and the cerium oxide into the zirconia; compared with the prior art, the invention has the following beneficial effects:
1) The invention utilizes yttrium and cerium to replace zirconium atoms in the zirconia crystal lattice to form solid solution, and generates point defects with different types and mechanisms in the zirconia, wherein the point defects mainly exist in the form of oxygen vacancies; the oxygen vacancy defects can cause phonon scattering, so that phonon heat transmission is reduced, and the rare earth co-doped zirconia has lower heat conductivity coefficient, namely, compared with the traditional domestic zirconia, the rare earth co-doped zirconia realizes higher cavity temperature under the same heating power loading; the zirconia has better thermal stability due to the doping of the cerium oxide and the yttrium oxide multi-element rare earth stabilizer; therefore, the rare earth zirconia prepared by the method has better heat preservation performance and thermal stability;
2) The invention uses mixed grain size rare earth co-doped zirconia grains for proportioning, and the gaps among the zirconia grains with large grain size are filled by zirconia grains with smaller grain size, so that the prepared oxidation ditch ceramic material has higher density; the bonding and growth among zirconia ceramic grains are controlled through the regulation and control of the sintering temperature, the ceramic degree is reduced, the prepared zirconia ceramic assembly has good rheological property in the pressure loading process, and the consumption of loading pressure in zirconia is reduced; the proper compactness enables the zirconia and the pyrophyllite compression ratio to form good matching in a high-temperature high-pressure experiment, and the pressure of a sample cavity can be maximally close to the calibration pressure of a pyrophyllite solid block; thereby obtaining higher pressure conditions in high temperature and high pressure experiments.
Drawings
FIG. 1 is an XRD analysis of 25% CeO 2 -8Y stabilized zirconia prepared in example 3;
FIG. 2 is a SEM analysis of 25% CeO 2 -8Y stabilized zirconia prepared in example 3;
FIG. 3 is an image of a different zirconia ceramic;
FIG. 4 is a high temperature, high pressure test assembly; wherein, the sample comprises 1-zirconia ceramic, a 2-graphite layer, a 3-sample cavity, a 4-steel plug and 5-pyrophyllite;
FIG. 5 is the results of temperature testing of various zirconia ceramic cavities prepared in example 4, comparative example 1 and comparative example 2;
FIG. 6 is a graph showing the results of temperature testing of different zirconia ceramic chambers prepared in examples 1-4;
FIG. 7 shows the silver melting point temperature test results of domestic CaO stabilized zirconia ceramics under different system oil pressure loads in standard pressure by silver melting point method;
FIG. 8 shows the results of silver melting point temperature test under oil pressure loading of different system pressures in the 25% CeO 2 -8Y stabilized zirconia ceramic silver melting point method prepared in example 3;
fig. 9 is the results of internal pressure testing of different zirconia ceramic cavities prepared in example 3 and comparative example 1.
Detailed Description
The following description of the embodiments of the present invention will be made more fully hereinafter with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the invention, are within the scope of the invention.
According to the invention, rare earth oxides with different proportions are doped in zirconia, and meanwhile, different particle sizes are used for proportioning, so that the zirconia ceramic material with excellent heat conduction performance and improved pressure transmission performance is prepared, and the zirconia ceramic material is suitable for being used as a heat-preservation pressure transmission medium in high-temperature high-pressure experiments to realize higher temperature and pressure experimental conditions. And measuring the temperature of the sample center under the same power by a high-temperature high-pressure generating device (a hexahedral top hinge press), and further obtaining the thermal insulation performance comparison of the zirconium oxide under different doping proportions. And the silver melting point method is used for calibrating the pressure in the high-temperature high-pressure experimental cavity, so that the pressure transmission performance difference between the zirconia prepared by different methods and the traditional domestic zirconia is obtained.
The zirconia used in examples 1-7 and comparative example 1 below was domestic zirconia, and was purchased from microphone.
Example 1
The example provides a method for preparing 0% CeO 2 -8Y stabilized zirconia, comprising the following steps:
(1) Mixing material
Respectively carrying out ultrasonic dispersion on yttrium oxide and zirconium oxide powder with particle diameters of 50nm obtained by market purchase by using an ultrasonic generator, setting the ultrasonic dispersion time to be 10min, and obtaining nano yttrium oxide and nano zirconium oxide powder after the ultrasonic dispersion is finished; weighing 16g of yttrium oxide and 184g of zirconium oxide with the particle size of 50nm according to the mass fraction ratio of 8:92 to prepare mixed powder; packaging the mixed powder, and then placing the packaged mixed powder into a mixer for mixing, wherein the mixing time is set to be 12 hours; after the completion of the mixing, a uniformly mixed 8% yttria-doped zirconia powder was obtained, which was designated as 8Y zirconia powder.
(2) Primary sintering
And (3) loading 100g of 8Y zirconia powder by using a die with the side length of 48mm and 48mm, and pressing the 8Y zirconia powder into a block by using a four-column press with the set pressure of 60MPa to obtain a first rare earth co-doped zirconia blank.
Placing the pressed first rare earth co-doped zirconia blank into a muffle furnace for primary sintering, and setting the sintering temperature to 1250 ℃; heating up to 1250 ℃ at a sintering heating rate of 200 ℃/h, then preserving heat and sintering for 2h, and then cooling to below 100 ℃ according to a cooling rate of 200 ℃/h; after primary sintering, an initial sintered product was obtained, which was designated as 8Y stabilized zirconia.
(3) Molding and sintering
Crushing the 8Y stabilized zirconia blocks after primary sintering, and sieving and screening by using 100-mesh, 50-mesh and 20-mesh screens to obtain 8Y stabilized zirconia particles with the particle sizes of 20-50-mesh, 50-100-mesh and more than 100-mesh.
Stabilizing zirconia particles with different particle diameters of 8Y according to a mass ratio of 20-50 meshes: 50-100 mesh: mixing in a mixer for 12h in a mixing time period of more than 100 meshes=7:2:1; then, 10g was weighed and put into a molding die, and molding and pressing (dimensions: inner diameter 12mm, outer diameter 18.2mm, height 12 mm) were performed under a pressure of 400MPa of actual pressure using a four-column press.
Placing the rare earth co-doped zirconia into a muffle furnace for molding and sintering after compression molding, and setting the sintering temperature to 1450 ℃; the sintering temperature rising rate is 300 ℃/h, the heat preservation and sintering are carried out for 4h after the temperature rises to the sintering temperature of 1450 ℃, and then the temperature is reduced to below 100 ℃ according to the temperature reducing rate of 200 ℃/h.
Obtaining rare earth co-doped zirconia ceramics after sintering is completed, and marking the rare earth co-doped zirconia ceramics as 8Y stabilized zirconia ceramics; and then the material is processed into a required shape by using an engraving machine or a lathe, so that the material can be used for high-temperature and high-pressure experiments.
Example 2
The embodiment provides a preparation method of 10% CeO 2 -8Y stabilized zirconia, which comprises the following steps:
(1) Mixing material
Respectively carrying out ultrasonic dispersion on yttrium oxide and zirconium oxide powder with particle diameters of 50nm obtained by market purchase by using an ultrasonic generator, setting the ultrasonic dispersion time to be 10min, and obtaining nano yttrium oxide and nano zirconium oxide powder after the ultrasonic dispersion is finished; weighing 16g of yttrium oxide and 184g of zirconium oxide with the particle size of 50nm according to the mass fraction ratio of 8:92 to prepare mixed powder; packaging the mixed powder, and then placing the packaged mixed powder into a mixer for mixing, wherein the mixing time is set to be 12 hours; after the completion of the mixing, a uniformly mixed 8% yttria-doped zirconia powder was obtained, which was designated as 8Y zirconia powder.
Then weighing 20g of cerium oxide powder and 180g of 8Y zirconium oxide powder according to the mass fraction ratio of 10:90 to prepare rare earth co-doped zirconium oxide powder; putting the mixed rare earth co-doped zirconia powder into a mixer for mixing, and setting the mixing time to be 12 hours; and obtaining the uniformly mixed rare earth co-doped zirconia powder after the mixing is completed.
(2) Primary sintering
And (3) filling 100g of rare earth co-doped zirconia powder into a die with the side length of 48mm or 48mm, setting the pressure to be 60MPa by using a four-column press, and pressing the rare earth co-doped zirconia powder into a block to obtain a first rare earth co-doped zirconia blank.
Placing the pressed first rare earth co-doped zirconia blank into a muffle furnace for primary sintering, and setting the sintering temperature to 1250 ℃; heating up to 1250 ℃ at a sintering heating rate of 200 ℃/h, then preserving heat and sintering for 2h, and then cooling to below 100 ℃ according to a cooling rate of 200 ℃/h; and obtaining an initial sintering product after primary sintering, namely 10% CeO 2 -8Y stabilized zirconia.
(3) Molding and sintering
Crushing the 10% CeO 2 -8Y stabilized zirconia blocks after primary sintering, and sieving and screening by using 100-mesh, 50-mesh and 20-mesh screens to obtain 10% CeO2-8Y stabilized zirconia particles with the particle sizes of 20-50-mesh, 50-100-mesh and more than 100-mesh.
The CeO 2 -8Y stabilized zirconia particles with different particle diameters are mixed according to the mass ratio of 20-50 meshes: 50-100 mesh: mixing in a mixer for 12h in a mixing time period of more than 100 meshes=7:2:1; then, 10g was weighed and put into a molding die, and molding and pressing (dimensions: inner diameter 12mm, outer diameter 18.2mm, height 12 mm) were performed under a pressure of 400MPa of actual pressure using a four-column press.
Placing 10% CeO 2 -8Y stabilized zirconia into a muffle furnace for molding and sintering, and setting the sintering temperature to 1450 ℃; the sintering temperature rising rate is 300 ℃/h, the heat preservation and sintering are carried out for 4h after the temperature rises to the sintering temperature of 1450 ℃, and then the temperature is reduced to below 100 ℃ according to the temperature reducing rate of 200 ℃/h.
After sintering, obtaining rare earth co-doped zirconia ceramic, namely 10% CeO 2 -8Y stabilized zirconia ceramic; and then the material is processed into a required shape by using an engraving machine or a lathe, so that the material can be used for high-temperature and high-pressure experiments.
Example 3
The example provides a method for preparing 25% CeO 2 -8Y stabilized zirconia, comprising the following steps:
(1) Mixing material
Respectively carrying out ultrasonic dispersion on yttrium oxide and zirconium oxide powder with particle diameters of 50nm obtained by market purchase by using an ultrasonic generator, setting the ultrasonic dispersion time to be 10min, and obtaining nano yttrium oxide and nano zirconium oxide powder after the ultrasonic dispersion is finished; weighing 16g of yttrium oxide and 184g of zirconium oxide with the particle size of 50nm according to the mass fraction ratio of 8:92 to prepare mixed powder; packaging the mixed powder, and then placing the packaged mixed powder into a mixer for mixing, wherein the mixing time is set to be 12 hours; after the completion of the mixing, a uniformly mixed 8% yttria-doped zirconia powder was obtained, which was designated as 8Y zirconia powder.
Weighing 50g of cerium oxide powder and 150g of 8Y zirconium oxide powder according to the mass fraction ratio of 25:75, and preparing rare earth co-doped zirconium oxide powder; putting the mixed rare earth co-doped zirconia powder into a mixer for mixing, and setting the mixing time to be 12 hours; and obtaining the uniformly mixed rare earth co-doped zirconia powder after the mixing is completed.
(2) Primary sintering
And (3) filling 100g of rare earth co-doped zirconia powder into a die with the side length of 48mm or 48mm, setting the pressure to be 60MPa by using a four-column press, and pressing the rare earth co-doped zirconia powder into a block to obtain a first rare earth co-doped zirconia blank.
Placing the pressed first rare earth co-doped zirconia blank into a muffle furnace for primary sintering, and setting the sintering temperature to 1250 ℃; heating up to 1250 ℃ at a sintering heating rate of 200 ℃/h, then preserving heat and sintering for 2h, and then cooling to below 100 ℃ according to a cooling rate of 200 ℃/h; after primary sintering, an initial sintered product is obtained, which is marked as 25% CeO 2 -8Y stabilized zirconia.
(3) Molding and sintering
Crushing the primary sintered 25% CeO 2 -8Y stabilized zirconia blocks, and sieving with 100 mesh, 50 mesh and 20 mesh sieve to obtain 25% CeO2-8Y stabilized zirconia particles with particle diameters of 20-50 mesh, 50-100 mesh and more than 100 mesh.
The stable zirconia particles with different particle diameters of 25 percent CeO 2 -8Y are mixed according to the mass ratio of 20-50 meshes: 50-100 mesh: mixing in a mixer for 12h in a mixing time period of more than 100 meshes=7:2:1; then, 10g was weighed and put into a molding die, and molding and pressing (dimensions: inner diameter 12mm, outer diameter 18.2mm, height 12 mm) were performed under a pressure of 400MPa of actual pressure using a four-column press.
Placing 25% CeO 2 -8Y stabilized zirconia into a muffle furnace for molding and sintering, and setting the sintering temperature to 1450 ℃; the sintering temperature rising rate is 300 ℃/h, the heat preservation and sintering are carried out for 4h after the temperature rises to the sintering temperature of 1450 ℃, and then the temperature is reduced to below 100 ℃ according to the temperature reducing rate of 200 ℃/h.
After sintering, obtaining rare earth co-doped zirconia ceramic, namely 25% CeO 2 -8Y stabilized zirconia ceramic; and then the material is processed into a required shape by using an engraving machine or a lathe, so that the material can be used for high-temperature and high-pressure experiments.
Example 4
The example provides a method for preparing 50% CeO 2 -8Y stabilized zirconia, comprising the following steps:
(1) Mixing material
Respectively carrying out ultrasonic dispersion on yttrium oxide and zirconium oxide powder with particle diameters of 50nm obtained by market purchase by using an ultrasonic generator, setting the ultrasonic dispersion time to be 10min, and obtaining nano yttrium oxide and nano zirconium oxide powder after the ultrasonic dispersion is finished; weighing 16g of yttrium oxide and 184g of zirconium oxide with the particle size of 50nm according to the mass fraction ratio of 8:92 to prepare mixed powder; packaging the mixed powder, and then placing the packaged mixed powder into a mixer for mixing, wherein the mixing time is set to be 12 hours; after the completion of the mixing, a uniformly mixed 8% yttria-doped zirconia powder was obtained, which was designated as 8Y zirconia powder.
Weighing 100g of cerium oxide powder and 100g of 8Y zirconium oxide powder according to the mass fraction ratio of 50:50, and preparing rare earth co-doped zirconium oxide powder; putting the mixed rare earth co-doped zirconia powder into a mixer for mixing, and setting the mixing time to be 12 hours; and obtaining the uniformly mixed rare earth co-doped zirconia powder after the mixing is completed.
(2) Primary sintering
And (3) filling 100g of rare earth co-doped zirconia powder into a die with the side length of 48mm or 48mm, setting the pressure to be 60MPa by using a four-column press, and pressing the rare earth co-doped zirconia powder into a block to obtain a first rare earth co-doped zirconia blank.
Placing the pressed first rare earth co-doped zirconia blank into a muffle furnace for primary sintering, and setting the sintering temperature to 1250 ℃; heating up to 1250 ℃ at a sintering heating rate of 200 ℃/h, then preserving heat and sintering for 2h, and then cooling to below 100 ℃ according to a cooling rate of 200 ℃/h; after primary sintering, an initial sintered product is obtained, which is marked as 50% CeO 2 -8Y stabilized zirconia.
(3) Molding and sintering
Crushing the primary sintered 50% CeO 2 -8Y stabilized zirconia blocks, and sieving with 100 mesh, 50 mesh and 20 mesh sieve to obtain 50% CeO 2 -8Y stabilized zirconia particles with particle diameters of 20-50 mesh, 50-100 mesh and more than 100 mesh.
The stable zirconia particles with different particle diameters of 50 percent CeO 2 -8Y are mixed according to the mass ratio of 20-50 meshes: 50-100 mesh: mixing in a mixer for 12h in a mixing time period of more than 100 meshes=7:2:1; then, 10g was weighed and put into a molding die, and molding and pressing (dimensions: inner diameter 12mm, outer diameter 18.2mm, height 12 mm) were performed under a pressure of 400MPa of actual pressure using a four-column press.
Placing 50% CeO 2 -8Y stabilized zirconia into a muffle furnace for molding and sintering, and setting the sintering temperature to 1450 ℃; the sintering temperature rising rate is 300 ℃/h, the heat preservation and sintering are carried out for 4h after the temperature rises to the sintering temperature of 1450 ℃, and then the temperature is reduced to below 100 ℃ according to the temperature reducing rate of 200 ℃/h.
After sintering, obtaining rare earth co-doped zirconia ceramic, namely 50% CeO 2 -8Y stabilized zirconia ceramic; and then the material is processed into a required shape by using an engraving machine or a lathe, so that the material can be used for high-temperature and high-pressure experiments.
Example 5
The present example provides a method for preparing 50% CeO 2 -3Y stabilized zirconia, comprising the steps of:
(1) Mixing material
Respectively carrying out ultrasonic dispersion on yttrium oxide and zirconium oxide powder with particle sizes of 200nm obtained by market purchase by using an ultrasonic generator, setting the ultrasonic dispersion time to be 10min, and obtaining nano yttrium oxide and nano zirconium oxide powder after the ultrasonic dispersion is finished; weighing 15g of yttrium oxide and 485g of zirconium oxide with the particle size of 200nm according to the mass fraction ratio of 3:97 to prepare mixed powder; packaging the mixed powder, and then placing the packaged mixed powder into a mixer for mixing, wherein the mixing time is set to be 8 hours; after the completion of the mixing, a uniformly mixed yttria-doped zirconia powder of 3% was obtained, which was designated as 3Y zirconia powder.
Weighing 100g of cerium oxide powder and 100g of 3Y zirconium oxide powder according to the mass fraction ratio of 50:50, and preparing rare earth co-doped zirconium oxide powder; putting the mixed rare earth co-doped zirconia powder into a mixer for mixing, and setting the mixing time to be 8 hours; and obtaining the uniformly mixed rare earth co-doped zirconia powder after the mixing is completed.
(2) Primary sintering
And (3) filling 100g of rare earth co-doped zirconia powder into a die with the side length of 48mm or 48mm, setting the pressure to 80MPa by using a four-column press, and pressing the rare earth co-doped zirconia powder into a block to obtain a first rare earth co-doped zirconia blank.
Placing the pressed first rare earth co-doped zirconia blank into a muffle furnace for primary sintering, and setting the sintering temperature to be 1500 ℃; heating up to 1500 ℃ at a sintering heating rate of 300 ℃/h, then preserving heat and sintering for 2h, and then cooling to below 100 ℃ according to a cooling rate of 200 ℃/h; after primary sintering, an initial sintered product is obtained, which is marked as 50% CeO 2 -3Y stabilized zirconia.
(3) Molding and sintering
Crushing the primary sintered 50% CeO 2 -3Y stabilized zirconia blocks, and sieving with 100 mesh, 50 mesh and 20 mesh sieve to obtain 50% CeO 2 -3Y stabilized zirconia particles with particle diameters of 20-50 mesh, 50-100 mesh and more than 100 mesh.
The stable zirconia particles with different particle diameters of 50 percent CeO 2 -3Y are mixed according to the mass ratio of 20-50 meshes: 50-100 mesh: mixing in a mixer for 8h in a mixing time period of more than 100 meshes=6:3:1; then, 10g was weighed and put into a molding die, and molding and pressing (dimensions: inner diameter 12mm, outer diameter 18.2mm, height 12 mm) were performed under a pressure of 500MPa of actual pressure using a four-column press.
After compression molding, placing 50% CeO 2 -3Y stabilized zirconia into a muffle furnace for molding and sintering, and setting the sintering temperature to 1600 ℃; the sintering temperature rising rate is 300 ℃/h, the heat preservation and sintering are carried out for 2h after the temperature rises to 1600 ℃, and then the temperature is reduced to below 100 ℃ according to the temperature reducing rate of 200 ℃/h.
After sintering, obtaining rare earth co-doped zirconia ceramic, namely 50% CeO 2 -3Y stabilized zirconia ceramic; and then the material is processed into a required shape by using an engraving machine or a lathe, so that the material can be used for high-temperature and high-pressure experiments.
Example 6
The embodiment provides a preparation method of 50% CeO 2 -12Y stabilized zirconia, which comprises the following steps:
(1) Mixing material
Respectively carrying out ultrasonic dispersion on yttrium oxide and zirconium oxide powder with particle sizes of 500nm obtained by market purchase by using an ultrasonic generator, setting the ultrasonic dispersion time to be 10min, and obtaining nano yttrium oxide and nano zirconium oxide powder after the ultrasonic dispersion is finished; weighing 24g of yttrium oxide and 176g of zirconium oxide with the particle size of 200nm and zirconium oxide with the particle size of 500nm according to the mass fraction ratio of 12:88 to prepare mixed powder; packaging the mixed powder, and then placing the packaged mixed powder into a mixer for mixing, wherein the mixing time is set to be 4 hours; after the completion of the mixing, a uniformly mixed zirconia powder doped with 12% yttria was obtained, which was designated as 12Y zirconia powder.
Weighing 100g of cerium oxide powder and 100g of 12Y zirconium oxide powder with the particle size of 500nm according to the mass fraction ratio of 50:50, and preparing rare earth co-doped zirconium oxide powder; putting the mixed rare earth co-doped zirconia powder into a mixer for mixing, and setting the mixing time to be 4 hours; and obtaining the uniformly mixed rare earth co-doped zirconia powder after the mixing is completed.
(2) Primary sintering
And (3) filling 100g of rare earth co-doped zirconia powder into a die with the side length of 48mm or 48mm, setting the pressure to 40MPa by using a four-column press, and pressing the rare earth co-doped zirconia powder into a block to obtain a first rare earth co-doped zirconia blank.
Placing the pressed first rare earth co-doped zirconia blank into a muffle furnace for primary sintering, and setting the sintering temperature to 1200 ℃; heating up to 1200 ℃ at a sintering heating rate of 100 ℃/h, then preserving heat and sintering for 10h, and then cooling to below 100 ℃ according to a cooling rate of 100 ℃/h; after primary sintering, an initial sintered product is obtained, which is marked as 50% CeO 2 -12Y stabilized zirconia.
(3) Molding and sintering
Crushing the primary sintered 50% CeO 2 -12Y stabilized zirconia blocks, and sieving with 100 mesh, 50 mesh and 20 mesh sieve to obtain 50% CeO 2 -12Y stabilized zirconia particles with particle size of 20-50 mesh, 50-100 mesh and more than 100 mesh.
The stable zirconia particles with different particle diameters of 50 percent CeO 2 -12Y are mixed according to the mass ratio of 20-50 meshes: 50-100 mesh: mixing in a mixer for 4h in a mixing time of more than 100 meshes=5:3:2; then, 10g was weighed and put into a molding die, and molding and pressing (dimensions: inner diameter 12mm, outer diameter 18.2mm, height 12 mm) were performed under a pressure of 300MPa of actual pressure using a four-column press.
After compression molding, placing 50% CeO 2 -12Y stabilized zirconia into a muffle furnace for molding and sintering, and setting the sintering temperature to 1100 ℃; the sintering temperature rise rate is 100 ℃/h, the heat preservation and sintering are carried out for 10h after the temperature is raised to 1100 ℃, and then the temperature is reduced to be lower than 100 ℃ according to the temperature reduction rate of 100 ℃/h.
Obtaining rare earth co-doped zirconia ceramics after sintering, namely 50% CeO 2 -12Y stabilized zirconia ceramics; and then the material is processed into a required shape by using an engraving machine or a lathe, so that the material can be used for high-temperature and high-pressure experiments.
Example 7
The example provides a method for preparing 25% CeO 2 -8Y stabilized zirconia, comprising the following steps:
(1) Mixing material
Respectively carrying out ultrasonic dispersion on yttrium oxide and zirconium oxide powder with particle sizes of 100nm obtained by market purchase by using an ultrasonic generator, setting the ultrasonic dispersion time to be 10min, and obtaining nano yttrium oxide and nano zirconium oxide powder after the ultrasonic dispersion is finished; weighing 16g of yttrium oxide and 184g of zirconium oxide with the particle size of 100nm according to the mass fraction ratio of 8:92 to prepare mixed powder; packaging the mixed powder, and then placing the packaged mixed powder into a mixer for mixing, wherein the mixing time is set to be 8 hours; after the completion of the mixing, a uniformly mixed 8% yttria-doped zirconia powder was obtained, which was designated as 8Y zirconia powder.
Weighing 50g of cerium oxide powder and 150g of 8Y zirconium oxide powder according to the mass fraction ratio of 25:75 to prepare rare earth co-doped zirconium oxide powder; putting the mixed rare earth co-doped zirconia powder into a mixer for mixing, and setting the mixing time to be 8 hours; and obtaining the uniformly mixed rare earth co-doped zirconia powder after the mixing is completed.
(2) Primary sintering
And (3) filling 100g of rare earth co-doped zirconia powder into a die with the side length of 48mm or 48mm, setting the pressure to be 60MPa by using a four-column press, and pressing the rare earth co-doped zirconia powder into a block to obtain a first rare earth co-doped zirconia blank.
Placing the pressed first rare earth co-doped zirconia blank into a muffle furnace for primary sintering, and setting the sintering temperature to 1200 ℃; heating up to 1200 ℃ at a sintering heating rate of 100 ℃/h, then preserving heat and sintering for 8h, and then cooling to below 100 ℃ according to a cooling rate of 100 ℃/h; after primary sintering, an initial sintered product is obtained, which is marked as 25% CeO 2 -8Y stabilized zirconia.
(3) Molding and sintering
Crushing the primary sintered 25% CeO 2 -8Y stabilized zirconia blocks, and sieving with 100 mesh, 50 mesh and 20 mesh sieve to obtain 25% CeO 2 -8Y stabilized zirconia particles with particle size of 20-50 mesh, 50-100 mesh and more than 100 mesh.
The stable zirconia particles with different particle diameters of 25 percent CeO 2 -8Y are mixed according to the mass ratio of 20-50 meshes: 50-100 mesh: mixing in a mixer for 8h in a mixing time period of more than 100 meshes = 4:4:2; then, 10g was weighed and put into a molding die, and molding and pressing (dimensions: inner diameter 12mm, outer diameter 18.2mm, height 12 mm) were performed under a pressure of 400MPa of actual pressure using a four-column press.
Placing 25% CeO 2 -8Y stabilized zirconia into a muffle furnace for molding and sintering, and setting the sintering temperature to 1400 ℃; the sintering temperature rise rate is 200 ℃/h, the heat preservation and sintering are carried out for 6h after the temperature is raised to the sintering temperature of 1400 ℃, and then the temperature is reduced to be below 100 ℃ according to the temperature reduction rate of 100 ℃/h.
After sintering, obtaining rare earth co-doped zirconia ceramic, namely 25% CeO 2 -8Y stabilized zirconia ceramic; and then the material is processed into a required shape by using an engraving machine or a lathe, so that the material can be used for high-temperature and high-pressure experiments.
Comparative example 1
The comparative example provides a method for preparing domestic CaO-stabilized zirconia, comprising the following steps:
(1) Mixing material
Weighing 500nm zirconium oxide and 500nm calcium oxide powder purchased in the market according to the mass ratio of 10:1, preparing mixed powder, and placing the mixed powder into a mixer for mixing, wherein the mixing time is set to be 12 hours. After the step is completed, the uniformly mixed zirconia mixed powder doped with 10% of calcium oxide is obtained and is marked as domestic CaO stabilized zirconia powder.
(2) Primary sintering
100G of domestic CaO-stabilized zirconia powder is filled into a die with the side length of 48mm by 48mm, and the domestic CaO-stabilized zirconia powder is pressed into a block by using a four-column press with the pressure set to be 60 MPa.
Placing the pressed powder block into a muffle furnace for primary sintering, and setting the sintering temperature to 1500 ℃; heating up to 1500 ℃ at a sintering heating rate of 200 ℃/h, then preserving heat and sintering for 2h, and then cooling to below 100 ℃ according to a cooling rate of 200 ℃/h; and obtaining an initial sintering product after primary sintering, and marking the initial sintering product as domestic CaO stabilized zirconia.
(3) Molding and sintering
Crushing the domestic CaO-stabilized zirconia blocks after primary sintering, and sieving the crushed blocks by using a 100-mesh screen to obtain the calcium oxide stabilized zirconia particles with the particle size of less than 100 meshes.
10G of domestic CaO stabilized zirconia granules are weighed and placed into a forming die, and are formed and pressed under the condition of actual pressure of 400MPa by using a four-column press (the dimensions are that the inner diameter is 12mm, the outer diameter is 18.2mm and the height is 12 mm).
After compression molding, the domestic CaO stabilized zirconia is put into a muffle furnace for molding and sintering, and the sintering temperature is set at 1450 ℃; the sintering temperature rising rate is 300 ℃/h, the heat preservation and sintering are carried out for 4h after the temperature rises to the sintering temperature of 1450 ℃, and then the temperature is reduced to below 100 ℃ according to the temperature reducing rate of 200 ℃/h.
After sintering, the domestic CaO stabilized zirconia ceramics are obtained, and then are processed into the required shape by using an engraving machine or a lathe, thus being used for high-temperature and high-pressure experiments.
Comparative example 2
The comparative example provides a method for preparing Japanese zirconia, comprising the following steps:
(1) Primary sintering
100G of Japanese zirconia powder (purchased from Wo Genrui. Mu.m, particle size: 10 μm) was charged using a 48 mm-48 mm side mold, and the Japanese zirconia powder was pressed into a block using a four-column press with a set pressure of 60 MPa.
Placing the pressed Japanese zirconia block into a muffle furnace for primary sintering, and setting the sintering temperature to be 1500 ℃; heating up to 1500 ℃ at a sintering heating rate of 200 ℃/h, then preserving heat and sintering for 2h, and then cooling to below 100 ℃ according to a cooling rate of 200 ℃/h; after the primary sintering, an initial sintered product was obtained, which was designated as Japanese zirconia.
(2) Molding and sintering
Crushing the primarily sintered Japanese zirconia blocks, and sieving the crushed Japanese zirconia blocks by using a 100-mesh sieve to obtain Japanese zirconia particles with the particle size of more than 100 meshes.
10G of Japanese zirconia pellets were weighed into a molding die and molded under a pressure of 400MPa as an actual pressure (dimensions: inside diameter 12mm, outside diameter 18.2mm, height 12 mm) using a four-column press.
Placing the Japanese zirconia into a muffle furnace for molding and sintering after compression molding, and setting the sintering temperature to 1450 ℃; the sintering temperature rising rate is 300 ℃/h, the heat preservation and sintering are carried out for 4h after the temperature rises to the sintering temperature of 1450 ℃, and then the temperature is reduced to below 100 ℃ according to the temperature reducing rate of 200 ℃/h.
After sintering, the Japanese zirconia ceramic is obtained, and then is processed into a required shape by using an engraving machine or a lathe, so that the Japanese zirconia ceramic can be used for high-temperature and high-pressure experiments.
Characterization of ceramic Structure
XRD analysis is carried out on 25% CeO 2 -8Y stabilized zirconia prepared in example 3, the analysis result is shown in figure 1, and it can be seen from the figure that 25% CeO 2 -8Y stabilized zirconia is prepared, the stabilized zirconia is c-phase (cubic phase), and the stable zirconia has better thermal stability at high temperature. .
SEM analysis is carried out on the 25% CeO 2 -8Y stabilized zirconia prepared in the embodiment 3, and the analysis result is shown in figure 2, and the figure shows that the zirconia ceramic material prepared by the method adopts different particle size mixing ratios for initial powder, and the large particle size zirconia and the small particle size zirconia are uniformly distributed through electron microscope observation, and gaps among the large particle sizes are filled and compacted by the small particle size zirconia, so that the compactness of the prepared zirconia ceramic is higher.
Images of 25% CeO 2 -8Y stabilized zirconia, domestic CaO stabilized zirconia ceramics, and Japanese zirconia ceramics prepared in example 3 were collected as shown in FIG. 3. From the graph, domestic zirconia is stabilized by using CaO as a stabilizer, and the prepared ceramic material is white; the rare earth zirconia prepared by the method of the invention is doped by rare earth oxide cerium oxide, cerium oxide powder is yellowish, and the prepared zirconia ceramic is also yellowish; the Japanese zirconia is yellow.
Density measurements were performed on the ceramic samples prepared in examples 1-4, comparative example 1 and comparative example 2, and the results are shown in Table 1.
TABLE 1 ceramic density
As can be seen from Table 1, the rare earth co-doped zirconia ceramics prepared by the method of the invention have higher density.
(II) characterization of ceramic thermal insulation Properties
Here, the high temperature and high pressure generating device (hexahedral top hinge press) measures the temperature of the sample center under the same power, and then obtains the thermal insulation performance comparison of zirconia under different doping ratios. Fig. 4 shows high-temperature high-pressure experimental assembly, a graphite layer 2 is arranged in a zirconia ceramic 1, a h-BN layer (hexagonal-boron nitride) is arranged between the graphite layer 2 and a sample cavity 3, the sample cavity is filled with samples according to experimental requirements, steel plugs 4 are loaded at two ends of the zirconia ceramic 1, and the periphery of the zirconia ceramic 1 is sealed by pyrophyllite 5.
The experimental process is as follows: pressing graphite powder to diameterThe block with the height H=8.0 mm is put into a sample cavity and assembled according to the previous high-temperature high-pressure experiment assembly; punching the high-temperature high-pressure experimental assembly, wrapping the thermocouple by using an alumina ceramic tube, penetrating the thermocouple from the hole, enabling the node of the thermocouple to be positioned at the center of the sample cavity, applying 5.5GPa pressure to the experimental assembly through the high-temperature high-pressure generating device, and testing the center temperature of the sample cavity under the condition. And acquiring thermoelectric potential signals of the thermocouples through a multichannel recorder, and converting the thermoelectric potential signals into corresponding temperature data, so that the temperature in the cavity is obtained.
The changes in the internal pairs of zirconia ceramic cavities prepared in example 4, comparative example 1 and comparative example 2 with heating power are shown in fig. 5. As can be seen from the graph, the efficiency of the generation of the temperature was improved by about 15.2% and 9.3% respectively (50% CeO 2 -8Y stabilized zirconia ceramic cavity temperature: 2164 ℃ C., japanese zirconia ceramic cavity temperature: 1878 ℃ C., domestic CaO temperature: zirconia ceramic cavity temperature: 1980 ℃ C.) at the same heating power as compared with Japanese zirconia and domestic CaO stabilized zirconia.
The change in the internal pair of zirconia ceramic cavities prepared in examples 1 to 4 with heating power is shown in fig. 6. It can be seen from the graph that at the same heating power (greater than 2.0 Kw), the temperature in the zirconia ceramic cavity gradually increases with the increase of the cerium oxide, and the temperature in the zirconia ceramic cavity is highest in the stable zirconia ceramic cavity of 50% CeO 2 -8Y in the measurement range. Therefore, the cerium oxide doping effectively improves the temperature generation efficiency and the heat preservation performance of the zirconium oxide.
The cerium atoms replace zirconium atoms in the zirconia crystal lattice during doping, and the radius of the cerium atoms is larger than that of the zirconium atoms, so that phonon scattering is aggravated and heat conduction is inhibited under a high-temperature environment, and the zirconia has better heat insulation performance. Compared with the traditional zirconia heat insulation material, the invention can improve the temperature generation efficiency of the high-temperature high-pressure cavity by 15% under the same power.
(III) characterization of ceramic pressure transmission performance
The high temperature and high pressure generating device used for the test was as described above. The pressure calibration is carried out by adopting a silver melting point method by using a hexahedral top hinge press.
The principle of calibrating cavity pressure is carried out by using a silver melting point method: silver has different melting points under different pressures and increases with increasing pressure. Thus, the corresponding chamber temperature at this time can be obtained by measuring the melting point of silver under this condition in turn.
The specific method comprises the following steps:
2.0g of sample (Ag) was weighed, and a mold with a diameter of 8.0mm was used to perform pre-press molding under the condition of 10MPa oil pressure (sample pressure: 438 MPa) of a jack, and the molding size was: diameter of High h=4.0 mm, pre-compaction: 9.94g/cm 3, theoretical density 10.5g/cm 3, pre-compaction: 94.73%.
And placing the formed Ag sample into a sample cavity, assembling according to the high-temperature high-pressure experiment assembly, punching by using a bench drill, and inserting a thermocouple.
And setting pressure and temperature process curves after the assembly is completed, carrying out experiments, starting heating after the pressure reaches the set values of 30MPa, 40MPa and 50MPa and is kept stable, and opening a multichannel recorder (setting the type of a thermocouple to be W), and recording temperature data.
The Ag melting point test results are shown in FIG. 7 and FIG. 8 for 25% CeO 2 -8Y stabilized zirconia ceramics and the CaO stabilized zirconia ceramics commonly used in domestic high temperature and high pressure experiments at present. The Ag sites were then converted to the corresponding cavity internal pressures, and the results are shown in fig. 9 and table 2.
The internal pressure of the cavity taking domestic zirconia as a pressure transmission medium is measured under the loading of 30MPa, 40MPa and 50MPa of different system oil pressures: 2.7GPa, 3.5GPa and 4.2GPa, the rare earth zirconia prepared in the embodiment 3 of the invention is used as the pressure in the pressure transmission medium cavity, and the pressure is as follows: 3.3GPa, 4.4GPa, 5.1GPa. The highest pressure is improved by about 0.9GPa, and the pressure transmission performance is improved by 21.4%. Compared with the conventional domestic calcium oxide stabilized zirconia material, the pressure generating efficiency of the invention is higher, namely the pressure in the cavity is obviously improved under the same system oil pressure loading condition. Therefore, compared with the conventional domestic CaO-stabilized zirconia used in high-temperature and high-pressure experiments in China, the rare earth co-doped zirconia ceramic prepared by the invention has more excellent pressure transmission performance.
TABLE 2 comparison of rare earth doped zirconia and domestic zirconia pressure generation efficiencies
Therefore, the rare earth co-doped zirconia particles with mixed grain sizes are used for proportioning, and gaps among zirconia particles with large grain sizes are filled with zirconia particles with smaller grain sizes, so that the prepared oxidation ditch ceramic material has higher density; and the bonding and growth among zirconia ceramic grains are controlled through the regulation and control of the sintering temperature, so that the ceramic degree is reduced, the prepared zirconia ceramic assembly has better rheological property in the pressure loading process, and the consumption of loading pressure in zirconia is reduced. Moreover, the rare earth zirconia ceramics with different grain sizes are adopted to improve the strength and compactness of the rare earth zirconia ceramics, so that the high-temperature and high-pressure test assembly assembled by the rare earth zirconia ceramics has the optimal compression ratio in the high-temperature and high-pressure test pressurizing process, the consumption of the sealing edge on the pressure is reduced, the pressure is more conducted to the sample cavity, and the pressure in the cavity is improved.
Those of ordinary skill in the art will recognize that the embodiments herein are intended to assist the reader in understanding the principles of the invention and should be understood that the scope of the invention is not limited to such specific statements and embodiments. Those of ordinary skill in the art can make various other specific modifications and combinations from the teachings of the present disclosure without departing from the spirit thereof, and such modifications and combinations remain within the scope of the present disclosure.
Claims (9)
1. The preparation method of the rare earth doped zirconia pressure transmission medium is characterized by comprising the following steps of:
(1) Mixing material
Firstly, uniformly mixing yttrium oxide and zirconium oxide powder to obtain yttrium oxide doped zirconium oxide powder; uniformly mixing the yttrium oxide doped zirconia powder and the cerium oxide powder to obtain rare earth co-doped zirconia powder; the yttrium oxide powder accounts for 3-12% of the mass of the yttrium oxide doped zirconium oxide powder; the cerium oxide powder accounts for 10-50% of the rare earth co-doped zirconium oxide powder in mass percent;
(2) Primary sintering
Compacting rare earth co-doped zirconia powder under the condition of 40-80 MPa to obtain a first rare earth co-doped zirconia blank; then sintering the pressed first rare earth co-doped zirconia blank for 2-10 hours at 1200-1500 ℃ to obtain a primary sintered product;
(3) Molding and sintering
Crushing, grinding and sieving the primary sintering product to obtain rare earth co-doped zirconia particles with different particle sizes; uniformly mixing rare earth co-doped zirconia particles with different particle sizes, and then adding the mixture into a forming die; then pressing and forming under 300-500 MPa to obtain a second rare earth co-doped zirconia blank; and sintering the pressed second rare earth co-doped zirconia blank for 2-10 hours at 1100-1600 ℃ to obtain the rare earth co-doped zirconia ceramic.
2. The method for preparing a rare earth doped zirconia pressure transmission medium according to claim 1, wherein the particle size of the yttria powder is 50nm-500nm; the particle size of the cerium oxide powder is 50nm-500nm.
3. The method for preparing a rare earth doped zirconia pressure transmission medium according to claim 1 or 2, wherein the mixing time of the yttria and zirconia powder is 4-12 h; the mixing time of the zirconia powder doped with the yttrium oxide and the cerium oxide is 4-12 h.
4. The method for preparing a rare earth doped zirconia pressure transmission medium according to claim 1, wherein in the step (2), the sintering heating rate is 100 ℃/h to 300 ℃/h; cooling to below 100 ℃ after sintering, wherein the cooling rate is 100 ℃/h-200 ℃/h.
5. The method for preparing a rare earth doped zirconia pressure transmission medium according to claim 1, wherein in the step (3), the particle sizes of the rare earth co-doped zirconia with different particle sizes comprise 20-50 mesh, 50-100 mesh and more than 100 mesh.
6. The method for preparing rare earth doped zirconia pressure transmission medium according to claim 5, wherein the rare earth co-doped zirconia particles with different particle diameters are prepared according to the mass ratio: 20 mesh-50 mesh: 50 mesh-100 mesh: mixing more than 100 meshes = (7-4): (2-4): (1-2) uniformly.
7. The method for preparing a rare earth doped zirconia pressure transmission medium according to claim 1, 5 or 6, wherein in the step (3), the sintering temperature rise rate is 100 ℃/h to 300 ℃/h; cooling to below 100 ℃ after sintering, wherein the cooling rate is 100 ℃/h-200 ℃/h.
8. A rare earth doped zirconia pressure transmission medium prepared by the method of any one of claims 1 to 7.
9. The use of the rare earth doped zirconia pressure transmission medium according to claim 8, as a thermal insulation pressure transmission medium.
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