CN116606133A - Preparation method of zirconia ceramic with glass permeation layer on surface - Google Patents
Preparation method of zirconia ceramic with glass permeation layer on surface Download PDFInfo
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- CN116606133A CN116606133A CN202310344355.1A CN202310344355A CN116606133A CN 116606133 A CN116606133 A CN 116606133A CN 202310344355 A CN202310344355 A CN 202310344355A CN 116606133 A CN116606133 A CN 116606133A
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 283
- 239000000919 ceramic Substances 0.000 title claims abstract description 114
- 239000011521 glass Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 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 claims abstract description 50
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 14
- -1 lanthanum-aluminum-silicon-boron Chemical compound 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims abstract description 9
- 238000000465 moulding Methods 0.000 claims abstract description 8
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003825 pressing Methods 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 238000009694 cold isostatic pressing Methods 0.000 claims 1
- 238000000748 compression moulding Methods 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 49
- 238000002441 X-ray diffraction Methods 0.000 description 19
- 230000009466 transformation Effects 0.000 description 16
- 230000008859 change Effects 0.000 description 15
- 230000007704 transition Effects 0.000 description 10
- 238000004626 scanning electron microscopy Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 244000137852 Petrea volubilis Species 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 230000002269 spontaneous effect Effects 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000462 isostatic pressing Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000006063 cullet Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 210000004394 hip joint Anatomy 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting 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
- 235000011837 pasties Nutrition 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
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- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
The application provides a preparation method of zirconia ceramic with a glass permeation layer on the surface, which comprises the following steps: pressing and molding zirconia powder containing 2.0-4.0 mol% of yttrium oxide to prepare a green body; placing the green body into a sintering furnace in air atmosphere or vacuum atmosphere, and sintering for 1-20 hours at 1350-1500 ℃ to obtain tetragonal zirconia ceramics with the density of more than or equal to 98% of theoretical density; carrying out hydrothermal treatment on tetragonal zirconia ceramics for more than or equal to 30 hours; preparing lanthanum-aluminum-silicon-boron glass powder into powder slurry by using water, and uniformly coating the powder slurry on the surface of the zirconia ceramic subjected to the hydrothermal treatment; and (3) putting the zirconia ceramic coated with the glass powder slurry into a sintering furnace, and preserving the temperature for 1-4 hours at 1100-1170 ℃ to obtain the zirconia ceramic with the glass permeation layer on the surface. The zirconia ceramic has a completely compact surface, and effectively cuts off the way of external moisture entering the interior of the zirconia ceramic, so that the zirconia ceramic with the glass permeation layer on the surface and extremely excellent durability in a hydrothermal environment is obtained.
Description
Technical Field
The application relates to the field of zirconia ceramics, in particular to a preparation method of zirconia ceramics with glass permeation layers on the surfaces.
Background
Zirconia ceramics have three crystalline phases: monoclinic, tetragonal and cubic phases. When the tetragonal phase is converted into the monoclinic phase, not only energy consumption but also volume expansion of 3 to 5% is accompanied. The volume expansion results in the generation of compressive stress. The synergistic effect of the energy consumption and the formation of the compressive stress effectively blocks the expansion of cracks, thereby obviously improving the fracture toughness of the zirconia ceramics and leading the tetragonal zirconia ceramics to obtain the reputation of ceramic steel.
Pure zirconia exists as a monoclinic phase at 1170 ℃ or below, as a tetragonal phase at 1170-2370 ℃ and as a cubic phase at above 2370 ℃. Therefore, in order to obtain tetragonal zirconia ceramics at room temperature, a stabilizer is often added to the zirconia ceramics so that the tetragonal phase can be maintained to room temperature. Common stabilizers are Y 2 O 3 、CeO 2 MgO, etc. Wherein Y is 2 O 3 The stabilized tetragonal zirconia ceramics (hereinafter referred to as "Y-TZ") have been most widely used because of their extremely high fracture strength and fracture toughness.
With the development of technology, it has further been found that the existing Y-TZ tetragonal zirconia ceramics spontaneously transform into monoclinic phase in a hydrothermal environment at 100-400 ℃. This spontaneous phase transformation not only causes submicron cracks to occur in the zirconia ceramic, but also causes a change in the surface roughness of the zirconia ceramic due to a 3 to 5% volume change accompanying the phase transformation. This phenomenon limits the further use of 3Y-TZ tetragonal zirconia ceramics.
In order to solve this problem, researchers represented by CeramTec, germany, developed alumina-zirconia ceramics in which zirconia was used as a minor component in an amount of about 15wt% not only utilized the advantage of phase transition toughening thereof, but also utilized the pinning effect of the major component, alumina matrix, to prevent spontaneous phase transition of zirconia in a hydrothermal environment. This idea achieves a certain effect, but practical experience shows that spontaneous phase transition of zirconia still exists.
CN115304371a is a solution proposed by the present inventors, and glass infiltration is performed on the surface of the sintered dense zirconia ceramic, so that the glass can enter into grain boundaries, cracks or pores of the ceramic surface, thereby preventing water molecules from entering into the interior of the ceramic through these surface defects. Thus, the spontaneous phase transition of the zirconia ceramic can be effectively delayed, and no new monoclinic phase is generated after the hydrothermal treatment for 20 hours. However, when water molecules contact the surface grains for a sufficient period of time, phase transformation of the surface grains is still induced, such as a new monoclinic phase formation after 30 hours of hydrothermal treatment. This phase transformation causes cracks to form along which water molecules penetrate into the ceramic interior and contact the internal grains, causing these internal grains to also undergo a phase transformation in succession.
In order to overcome the defects, the application develops a new way, and creatively places the sintered compact tetragonal zirconia ceramic in the hydrothermal environment for a certain time by utilizing the characteristics that the tetragonal phase-to-monoclinic phase transformation of the tetragonal phase zirconia ceramic in the hydrothermal environment can be balanced, so that the surface is fully transformed from the tetragonal phase to the monoclinic phase, and after the transformation is finished, glass is permeated into cracks formed by the transformation, so that the completely compact surface is formed. In the subsequent formal use process, on one hand, as the surface is subjected to hydrothermal treatment, the transformation from the tetragonal phase to the monoclinic phase is saturated, so that the transformation from the tetragonal phase to the monoclinic phase can not occur any more, and cracks can not be formed any more; on the other hand, the completely dense surface cuts off the way of water entering the inside of the zirconia ceramic, prevents the inside of the zirconia ceramic from undergoing phase change when the zirconia ceramic is used in a hydrothermal environment, and thus obtains the zirconia ceramic with a glass permeation layer on the surface, which has extremely excellent durability in the hydrothermal environment.
Disclosure of Invention
The technical problems to be solved are as follows: the application aims to provide a preparation method of zirconia ceramic with a glass permeation layer on the surface, which is characterized in that the zirconia ceramic is placed in a hydrothermal environment for a period of time, so that the surface of the zirconia ceramic is fully transformed from tetragonal phase to monoclinic phase, and after the phase transformation is finished, glass is permeated into cracks formed by the phase transformation, so that a completely compact surface is formed, and the zirconia ceramic has extremely excellent hydrothermal aging phase transformation resistance.
The technical scheme is as follows: a preparation method of zirconia ceramic with a glass permeation layer on the surface comprises the following steps:
(1) Pressing and molding zirconia powder containing 2.0-4.0 mol% of yttrium oxide to prepare a green body;
(2) Placing the green body into a sintering furnace in air atmosphere or vacuum atmosphere, and sintering for 1-20 hours at 1350-1500 ℃ to obtain tetragonal zirconia ceramics with the density of more than or equal to 98% of theoretical density;
(3) Carrying out hydrothermal treatment on tetragonal zirconia ceramics for more than or equal to 30 hours;
(4) Preparing lanthanum-aluminum-silicon-boron glass powder into powder slurry by using water, and uniformly coating the powder slurry on the surface of the zirconia ceramic subjected to the hydrothermal treatment;
(5) And (3) putting the zirconia ceramic coated with the glass powder slurry into a sintering furnace, and preserving the temperature for 1-4 hours at 1100-1170 ℃ to obtain the zirconia ceramic with the glass permeation layer on the surface.
Further, the press molding in the step (1) is cold isostatic molding under a pressure of 150 to 250 MPa.
Further, in the step (1), the press molding is performed under a pressure of 30-100 MPa, and then the cold isostatic molding is performed under a pressure of 150-250 MPa.
Further, the hydrothermal treatment time in the step (3) is 30 to 60 hours, preferably 30 to 40 hours.
Further, the content of yttrium oxide in the step (1) is 3.0mol%.
Further, the zirconia powder in the step (1) further contains 0.15 to 0.35wt% of alumina.
Further, the zirconia powder in the step (1) further contains 0.20 to 0.25wt% of alumina.
Further, the lanthanum-aluminum-silicon-boron glass in the step (4) contains 40wt% of La 2 O 3 、18wt％Al 2 O 3 、20wt％SiO 2 、19wt％B 2 O 3 And the balance of CaO.
Furthermore, the zirconia ceramic prepared by the preparation method has the glass permeation layer on the surface.
The beneficial effects are that: the application has the following advantages:
1. the application creatively places the sintered compact tetragonal zirconia ceramic in the hydrothermal environment for a certain time by utilizing the characteristic that the tetragonal phase to monoclinic phase transformation balance of the tetragonal phase zirconia ceramic in the hydrothermal environment, so that the surface is fully transformed from tetragonal phase to monoclinic phase, and glass is permeated into cracks formed by phase transformation after the phase transformation is completed, thereby the zirconia ceramic forms a completely compact surface.
2. The zirconia ceramic with the glass permeation layer has a completely compact surface, can effectively cut off the way of external moisture entering the interior of the zirconia ceramic, and prevents the interior of the zirconia ceramic from undergoing phase change when the zirconia ceramic is used in a hydrothermal environment, so that the zirconia ceramic with the glass permeation layer on the surface and extremely excellent durability in the hydrothermal environment is obtained.
The zirconia ceramics of the present application can be used for semiconductor, medical and other industrial applications.
In nature, hafnium (Hf) and zirconium are present in the form of solid solutions, which are difficult to separate, so in the present application, "zirconium oxide (ZrO 2 ) "contains less than or equal to 5wt% hafnium oxide.
In the present application, "hydrothermal treatment" means exposure to steam in an autoclave at a temperature of 134 ℃ and a pressure of 0.2 MPa. In the present application, "vol%" means a volume percentage, "wt%" means a mass percentage, and "mol%" means a mole percentage.
In the present application, X-ray diffraction analysis (abbreviated as "XRD", cukα,30KV,15 mA) was used to determine the crystalline phase content. Thus, the obtained crystal phase content refers to the crystal phase content in the surface layer penetrated by X-rays in XRD analysis.
In the present application, room temperature means-20℃to 40 ℃.
In the present application, the density of the zirconia ceramic is measured by the drainage method specified in GB/T25995.
Detailed Description
The application is further described below with reference to the following examples, which are illustrative of the application and are not intended to limit the application thereto:
example 1 preparation of zirconia ceramics and hydrothermal treatment
400 g of commercially available tetragonal zirconia granulated powder containing 3mol% of yttrium oxide and having an average particle size of 50 μm was dry-pressed under a pressure of 50MPa to form a powder, and then heated to 1400℃at a rate of 2℃per minute in a high-temperature furnace in an air atmosphere and kept at that temperature for 2 hours. After cooling to 600 ℃ at a rate of 2 ℃/min and furnace cooling to room temperature, zirconia ceramic with a density of 98.5% of theoretical density is obtained, numbered ZR-01. The ceramic block ZR-01 was cut into 20 sample blocks having a length of 10mm, a width of 10mm and a height of 10 mm. 1 sample block was randomly taken out, and the crystal phase composition of the zirconia ceramic was analyzed by X-ray diffraction, and it was found that the zirconia ceramic contained 99.2vol% of tetragonal phase zirconia and 0.8vol% of monoclinic phase zirconia; the zirconia ceramic ZR-01 was analyzed under SEM (scanning electron microscope) to have a grain size of 0.35. Mu.m.
3 sample blocks are randomly taken out, and after hydrothermal treatment for 20 hours at the temperature of 134 ℃ under the pressure of 0.2MPa, XRD and SEM analysis show that the thickness of the surface phase-change layer is 8 microns, and the monoclinic phase and tetragonal phase zirconia contents in the surface phase-change layer are 18.2vol% and 81.8vol% respectively.
3 sample blocks are randomly taken out, and after hydrothermal treatment for 30 hours at the temperature of 134 ℃ under the pressure of 0.2MPa, XRD and SEM analysis show that the thickness of the surface phase-change layer is 12 microns, and the monoclinic phase and tetragonal phase zirconia contents in the surface phase-change layer are 27.2vol% and 72.8vol% respectively.
3 sample blocks are randomly taken out, and after hydrothermal treatment for 40 hours at 134 ℃ of water vapor under the pressure of 0.2MPa, XRD and SEM analysis show that the thickness of the surface phase-change layer is 16 microns, and the monoclinic phase and tetragonal phase zirconia contents in the surface phase-change layer are 27.2vol% and 72.8vol% respectively.
This shows that after the zirconia ceramic ZR-01 is subjected to hydrothermal treatment for 30 hours at 134 ℃ and under the pressure of 0.2MPa, the phase transition can continue to go deep inside the ceramic, but the hydrothermal phase transition of the surface layer reaches saturation, and the tetragonal phase and monoclinic phase contents are not changed any more.
Example 2 preparation of zirconia ceramics and hydrothermal treatment
400 g of commercial tetragonal zirconia granulated powder containing 3mol% of yttrium oxide and having an average particle size of 50 microns is taken, subjected to dry pressing under 50MPa pressure, subjected to isostatic pressing under 190MPa pressure, and then heated to 1500 ℃ at a rate of 2 ℃/min in a high-temperature furnace in an air atmosphere and kept for 5 hours. After cooling to 600 ℃ at a rate of 2 ℃/min and furnace cooling to room temperature, a dense zirconia ceramic with a density of 99.0% of theoretical density was obtained, numbered ZR-02.
The ceramic block ZR-02 was cut into 20 sample blocks having a length of 10mm, a width of 10mm and a height of 10 mm.
1 sample block was randomly taken out, and the crystal phase composition of the zirconia ceramic was analyzed by X-ray diffraction, and it was found that the zirconia ceramic contained 93.2vol% of tetragonal phase zirconia and 6.8vol% of monoclinic phase zirconia; the zirconia ceramic ZR-02 had a grain size of 0.55 μm as analyzed under SEM (scanning electron microscope).
3 sample blocks are randomly taken out, and after hydrothermal treatment for 20 hours at the temperature of 134 ℃ of water vapor under the pressure of 0.2MPa, the surface phase-change layer thickness is found to be 14 microns through XRD and SEM analysis, and the monoclinic phase and tetragonal phase zirconia content in the surface phase-change layer zirconia is respectively 26.8vol% and 73.2vol%.
3 sample blocks are randomly taken out, and after hydrothermal treatment for 30 hours at 134 ℃ of water vapor under the pressure of 0.2MPa, XRD and SEM analysis show that the thickness of the surface phase-change layer is 20 microns, and the monoclinic phase and tetragonal phase zirconia contents in the zirconia of the surface phase-change layer are 34.6vol% and 65.4vol% respectively.
3 sample blocks are randomly taken out, and after hydrothermal treatment for 40 hours at 134 ℃ of water vapor under the pressure of 0.2MPa, XRD and SEM analysis show that the thickness of the surface phase-change layer is 25 microns, and the monoclinic phase and tetragonal phase zirconia contents in the zirconia of the surface phase-change layer are 34.6vol% and 65.4vol% respectively.
This shows that after the zirconia ceramic ZR-02 is subjected to hydrothermal treatment at 134 ℃ and a pressure of 0.2MPa for 30 hours, the phase transition continues deep inside the ceramic, but the hydrothermal phase transition of the surface layer reaches saturation, and the tetragonal phase and monoclinic phase contents are not changed any more.
EXAMPLE 3 preparation of zirconia ceramics and hydrothermal treatment
Commercially available 0.25w containing 3mol% yttriat％Al 2 O 3 400 g of tetragonal zirconia granulated powder with the average granularity of 60 microns is subjected to dry pressing under the pressure of 50MPa, isostatic pressing under the pressure of 180MPa, and then is heated to 1350 ℃ at the speed of 2 ℃/min in a high-temperature furnace in air atmosphere and is kept for 10 hours. After cooling to 600 ℃ at a rate of 2 ℃/min and furnace cooling to room temperature, a dense zirconia ceramic with a density of 99.7% of theoretical density is obtained, numbered ZR-03.
The ceramic block ZR-03 was cut into 20 sample blocks having a length of 10mm, a width of 10mm and a height of 10 mm.
1 sample was randomly taken out, and the crystal phase composition of the zirconia ceramic was analyzed by X-ray diffraction, and it was found that the zirconia ceramic contained 100vol% of tetragonal phase; the zirconia ceramic ZR-03 had a grain size of 0.28 μm as analyzed under SEM (scanning electron microscope).
3 sample blocks are randomly taken out, and after hydrothermal treatment for 20 hours at the temperature of 134 ℃ of water vapor under the pressure of 0.2MPa, XRD and SEM analysis show that the thickness of the surface phase-change layer is 6 microns, and the content of monoclinic phase zirconia and tetragonal phase zirconia in the surface phase-change layer is 14.2vol% and 85.8vol% respectively.
3 sample blocks are randomly taken out, and after hydrothermal treatment for 30 hours at 134 ℃ of water vapor under the pressure of 0.2MPa, XRD and SEM analysis show that the thickness of the surface phase-change layer is 10 microns, and the content of monoclinic phase zirconia and tetragonal phase zirconia in the surface phase-change layer is 24.7vol% and 75.3vol% respectively.
3 sample blocks are randomly taken out, and after hydrothermal treatment for 40 hours at 134 ℃ of water vapor under the pressure of 0.2MPa, the surface phase-change layer thickness is found to be 14 microns through XRD and SEM analysis, and the monoclinic phase and tetragonal phase zirconia contents in the surface phase-change layer zirconia are 24.7vol% and 75.3vol% respectively.
This shows that after the zirconia ceramic ZR-03 is subjected to hydrothermal treatment for 30 hours at 134 ℃ and under the pressure of 0.2MPa, the phase transition can continue to go deep inside the ceramic, but the hydrothermal phase transition of the surface layer reaches saturation, and the tetragonal phase and monoclinic phase contents are not changed any more.
EXAMPLE 4 preparation of lanthanum-boron-silicon-aluminum glass frit
Lanthanum oxide La of chemical purity 2 O 3 Alumina Al 2 O 3 Silicon oxide SiO 2 Boron oxide B 2 O 3 And adding a proper amount of absolute ethyl alcohol into the calcium oxide CaO powder according to the mass ratio of 40:18:20:19:3, ball-milling for 4 hours, and then putting the mixture into a baking oven at 100 ℃ for baking. And (3) placing the dried powder into a platinum crucible, melting for 3 hours in a sintering furnace at 1400 ℃, and then taking out at high temperature and directly pouring into deionized water to obtain glass cullet. Putting the glass powder into an agate ball milling tank, adopting zirconia to grind balls, adding a proper amount of absolute ethyl alcohol, ball milling for 24 hours, pouring into a porcelain plate, and drying in a 100 ℃ oven to obtain lanthanum-boron-silicon-aluminum glass powder.
EXAMPLE 5 preparation of glass-infiltrated zirconia ceramic
10 cut zirconia ceramic ZR-01 blocks prepared in example 1 were placed in an autoclave at a temperature of 134℃and a pressure of 0.2MPa and subjected to hydrothermal treatment for 30 hours.
100 g of the lanthanum-boron-silicon-aluminum glass powder prepared in example 4 was taken, a proper amount of deionized water was added, the mixture was prepared into a paste, the paste was uniformly coated on all surfaces of 10 sample pieces by a brush, the glass paste-coated sample pieces were placed in a sintering furnace, heated to 1120℃at a rate of 5℃per minute, kept for 2 hours, and then cooled to room temperature at a rate of 5℃per minute. And taking out the sample block, and lightly polishing the surface glass layer by using 800-mesh sand paper to obtain the glass-infiltrated zirconia ceramic sample block with the number of ZR-01G.
3 ZR-01G coupons were randomly removed and the grain size and glass phase distribution was observed using back scattered electrons in a Scanning Electron Microscope (SEM). The thickness of the phase-change layer is found to be unchanged and is 12 microns; the glass not only fully penetrates into the surface phase-change layer of the zirconia ceramic, but also enters into a thickness area of 5 microns below the phase-change layer, and cracks formed by the previous phase change are filled with the glass phase. XRD analysis of the phase structure showed that the relative amounts of monoclinic and tetragonal zirconia remained unchanged, at 27.2 and 72.8vol%, respectively, as before glass infiltration.
3 ZR-01G samples were randomly taken out, subjected to a hydrothermal treatment at 134℃for 60 hours under a pressure of 0.2MPa, then subjected to XRD analysis of the phase structure, and the microstructure was observed under SEM, and it was found that the original surface phase-change layer had no change in thickness, was still 12 μm, and no new cracks were formed, and that the monoclinic phase and tetragonal phase zirconia contents had no change from those before the hydrothermal treatment, respectively, of 27.2vol% and 72.8vol%.
It can be seen that the zirconia ceramic ZR-01G with the surface glass-permeation layer of the present application does not undergo a hydrothermal aging phase change after a hydrothermal treatment for up to 60 hours.
EXAMPLE 6 preparation of glass-infiltrated zirconia ceramic
10 cut zirconia ceramic ZR-02 sample blocks prepared in example 2 were placed in an autoclave at a temperature of 134℃and a pressure of 0.2MPa, and subjected to hydrothermal treatment for 30 hours.
100 g of the lanthanum-boron-silicon-aluminum glass powder prepared in example 4 was taken, a proper amount of deionized water was added, the mixture was prepared into a paste, the paste was uniformly coated on all surfaces of 10 sample pieces by a brush, the glass paste-coated sample pieces were placed in a sintering furnace, heated to 1120℃at a rate of 5℃per minute, kept for 3 hours, and then cooled to room temperature at a rate of 5℃per minute. And taking out the sample strip, and lightly polishing off the glass layer on the surface by using 800-mesh sand paper to obtain a glass-infiltrated zirconia ceramic sample block with the number of ZR-02G.
3 ZR-02G coupons were randomly removed and the grain size and glass phase distribution was observed using back scattered electrons in a Scanning Electron Microscope (SEM). The thickness of the phase-change layer is found to be unchanged and still 20 microns; the glass not only fully penetrates into the surface phase-change layer of the zirconia ceramic, but also enters into the thickness area of 4 microns below the phase-change layer, and cracks formed by the previous phase change are filled with the glass phase. XRD analysis of the phase structure showed that the relative amounts of monoclinic and tetragonal zirconia remained unchanged, at 34.6% and 65.4% by volume, respectively. 3 ZR-02G coupons were randomly removed, hydrothermally treated with 0.2MPa pressure at 134℃for 60 hours, then XRD analyzed for phase structure, and the microstructure was observed under SEM. The original surface phase change layer was found to have no change in thickness, still 20 microns, nor was there any new crack formation, and the relative amounts of monoclinic and tetragonal zirconia had not changed from that before this hydrothermal treatment, 34.6 and 65.4vol%, respectively.
It can be seen that the zirconia ceramic with the surface glass-permeated layer of the present application does not undergo a hydrothermal aging phase change after the hydrothermal treatment for up to 60 hours.
EXAMPLE 7 preparation of glass-infiltrated zirconia ceramic
10 cut zirconia ceramic ZR-03 blocks prepared in example 3 were placed in an autoclave at a temperature of 134℃and a pressure of 0.2MPa, and subjected to hydrothermal treatment for 30 hours.
100 g of the lanthanum-boron-silicon-aluminum glass powder prepared in example 4 was taken, a proper amount of deionized water was added, the mixture was prepared into a paste, the paste was uniformly coated on all surfaces of 10 sample pieces by a brush, the glass paste-coated sample pieces were placed in a sintering furnace, heated to 1120℃at a rate of 5℃per minute, kept for 4 hours, and then cooled to room temperature at a rate of 5℃per minute. And taking out the sample strip, and lightly polishing off the glass layer on the surface by using 800-mesh sand paper to obtain a glass-infiltrated zirconia ceramic sample block with the number of ZR-03G.
2 were randomly removed and the grain size and glass phase distribution were observed using back scattered electrons in a Scanning Electron Microscope (SEM). The thickness of the phase-change layer is found to be unchanged and still 10 microns; the glass not only fully penetrates into the surface phase-change layer of the zirconia ceramic, but also enters into a thickness area of 2 microns below the phase-change layer, and cracks formed by the previous phase change are filled with the glass phase. XRD analysis of the phase structure showed that the relative amounts of monoclinic and tetragonal zirconia remained unchanged, at 24.7% and 75.3% by volume, respectively.
3 ZR-03G samples were randomly taken out, subjected to a hydrothermal treatment at 134℃for 60 hours under a pressure of 0.2MPa, then subjected to XRD analysis of the phase structure, and the microstructure was observed under SEM, and it was found that the thickness of the original surface phase-change layer was not changed, still 10. Mu.m, and no new cracks were formed, and the relative contents of monoclinic phase and tetragonal phase zirconia were not changed as compared with those before the hydrothermal treatment, and were 24.7vol% and 75.3vol%, respectively.
It can be seen that the zirconia ceramic ZR-03G with the surface glass-permeated layer of the present application does not undergo a hydrothermal aging phase change after a hydrothermal treatment for up to 60 hours.
The test results of the above examples are summarized in the following table.
EXAMPLE 8 preparation of zirconia ceramic femoral head prosthesis with glass infiltration layer
The process of example 3 was used to prepare a zirconia ceramic femoral head prosthesis for hip joint replacement, the internal taper hole and the external spherical surface of the femoral head prosthesis were ground to final dimensions, 10 g of the lanthanum-boron-silicon-aluminum glass powder prepared in example 4 was added, a proper amount of deionized water was prepared to be pasty, the surface of the internal taper hole of the femoral head prosthesis was uniformly coated with the glass paste by a brush, the femoral head prosthesis coated with the glass paste was placed in a sintering furnace, heated to 1120 ℃ at a rate of 5 ℃/min, heat-preserved for 4 hours, and then cooled to room temperature at a rate of 5 ℃/min. And taking out the femoral head prosthesis. And lightly polishing the glass layer on the surface of the inner taper hole by using 800-mesh sand paper to obtain the glass-infiltrated zirconia ceramic femoral head prosthesis. After the zirconia ceramic femoral head prosthesis with the surface glass permeation layer is implanted into a human body, the zirconia ceramic femoral head prosthesis with the surface glass permeation layer can reasonably predict that the aging phase change can not occur, and has the service life of more than 30 years.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the application.
Claims (8)
1. A preparation method of zirconia ceramic with a glass permeation layer on the surface is characterized by comprising the following steps: the method comprises the following steps:
(1) Pressing and molding zirconia powder containing 2.0-4.0 mol% of yttrium oxide to prepare a green body;
(2) Placing the green body into a sintering furnace in air atmosphere or vacuum atmosphere, and sintering for 1-20 hours at 1350-1500 ℃ to obtain tetragonal zirconia ceramics with the density of more than or equal to 98% of theoretical density;
(3) Carrying out hydrothermal treatment on tetragonal zirconia ceramics for more than or equal to 30 hours;
(4) Preparing lanthanum-aluminum-silicon-boron glass powder into powder slurry by using water, and uniformly coating the powder slurry on the surface of the zirconia ceramic subjected to the hydrothermal treatment;
(5) And (3) putting the zirconia ceramic coated with the glass powder slurry into a sintering furnace, and preserving the temperature for 1-4 hours at 1100-1170 ℃ to obtain the zirconia ceramic with the glass permeation layer on the surface.
2. The method for producing a zirconia ceramic having a glass-permeated layer on the surface thereof according to claim 1, wherein: and (3) performing compression molding in the step (1) to obtain cold isostatic molding under the pressure of 150-250 MPa.
3. The method for producing a zirconia ceramic having a glass-permeated layer on the surface thereof according to claim 1, wherein: and (3) in the step (1), the dry pressing is carried out under the pressure of 30-100 MPa, and then the cold isostatic pressing is carried out under the pressure of 150-250 MPa.
4. The method for producing a zirconia ceramic having a glass-permeated layer on the surface thereof according to claim 1, wherein: the hydrothermal treatment time in the step (3) is 30-40 hours.
5. The method for producing a zirconia ceramic having a glass-permeated layer on the surface thereof according to claim 1, wherein: the content of yttrium oxide in the step (1) is 3.0mol%.
6. The method for producing a zirconia ceramic having a glass-permeated layer on the surface thereof according to claim 1, wherein: the zirconia powder in the step (1) also contains 0.15-0.35 wt% of alumina.
7. An oxidation process according to claim 1, wherein the glass is impregnated with a glassThe preparation method of the zirconium ceramic is characterized by comprising the following steps: the lanthanum-aluminum-silicon-boron glass in the step (4) contains 40 weight percent of La 2 O 3 、18wt％Al 2 O 3 、20wt％SiO 2 、19wt％B 2 O 3 And the balance of CaO.
8. Zirconia ceramic having a glass-permeated layer on the surface thereof prepared by the preparation method according to any one of claims 1 to 7.
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| CN1931760A (en) * | 2005-09-14 | 2007-03-21 | 中国科学院过程工程研究所 | Glass permeated zirconia ceramic dental material and its prepn process |
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| US20220133601A1 (en) * | 2019-03-04 | 2022-05-05 | 3M Innovative Properties Company | Process for Producing a Colored Dental Zirconia Article |
| CN115304371A (en) * | 2021-05-07 | 2022-11-08 | 苏州宸泰医疗器械有限公司 | Glass-infiltrated zirconia ceramic and preparation method thereof |
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| CN1931760A (en) * | 2005-09-14 | 2007-03-21 | 中国科学院过程工程研究所 | Glass permeated zirconia ceramic dental material and its prepn process |
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| CN111801067A (en) * | 2018-02-28 | 2020-10-20 | 3M创新有限公司 | Kit and method for rapid firing of porous zirconia articles in combination with surface treatment agent comprising glass powder |
| US20220133601A1 (en) * | 2019-03-04 | 2022-05-05 | 3M Innovative Properties Company | Process for Producing a Colored Dental Zirconia Article |
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