CN117164355A - Zirconia ceramics containing a glassy phase - Google Patents
Zirconia ceramics containing a glassy phase Download PDFInfo
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- CN117164355A CN117164355A CN202310834530.5A CN202310834530A CN117164355A CN 117164355 A CN117164355 A CN 117164355A CN 202310834530 A CN202310834530 A CN 202310834530A CN 117164355 A CN117164355 A CN 117164355A
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 249
- 239000000919 ceramic Substances 0.000 title claims abstract description 57
- 239000011521 glass Substances 0.000 claims abstract description 101
- 239000013078 crystal Substances 0.000 claims abstract description 25
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 11
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 4
- 239000007943 implant Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 16
- 210000003127 knee Anatomy 0.000 claims description 4
- 238000011540 hip replacement Methods 0.000 claims description 3
- 238000013150 knee replacement Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 description 56
- 238000010335 hydrothermal treatment Methods 0.000 description 43
- 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 40
- 238000002156 mixing Methods 0.000 description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 238000001035 drying Methods 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- 238000013001 point bending Methods 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 15
- 238000001816 cooling Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 238000003825 pressing Methods 0.000 description 12
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 9
- 239000006063 cullet Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 238000000498 ball milling Methods 0.000 description 4
- 238000005204 segregation Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 210000001624 hip Anatomy 0.000 description 2
- 210000004394 hip joint Anatomy 0.000 description 2
- 210000000629 knee joint Anatomy 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 230000009466 transformation Effects 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
- 208000012659 Joint disease Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 210000003423 ankle Anatomy 0.000 description 1
- 210000000544 articulatio talocruralis Anatomy 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 210000001513 elbow Anatomy 0.000 description 1
- 210000002310 elbow joint Anatomy 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding 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
- 230000002401 inhibitory effect Effects 0.000 description 1
- 210000001503 joint Anatomy 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 210000000707 wrist Anatomy 0.000 description 1
- 210000003857 wrist joint Anatomy 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
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
The application relates to a zirconia ceramic containing a glass phase, which consists of 1.0 to 5.5wt% of YASZ glass phase and the balance of 3Y-TZP crystal phase, wherein the YASZ glass phase is positioned between crystal grains of the 3Y-TZP crystal phase, and the YASZ glass phase consists of 15 to 35wt% of Y 2 O 3 、10‑30wt％Al 2 O 3 、35～55wt％SiO 2 And 4-10wt% ZrO 2 And the dihedral angle formed between the YASZ glass phase and the 3Y-TZP crystal phase is 62-85 deg. The application also relates to bone implant prostheses made from zirconia ceramics containing a glassy phase.
Description
Technical Field
The present application relates to a zirconia ceramic containing a glass phase, and further relates to a bone implant prosthesis prepared from the zirconia ceramic containing a glass phase.
Background
Replacement of damaged joints (including hip, knee, elbow, wrist or ankle) with artificial prostheses has become the first choice for clinical treatment of joint disease. Currently, the prostheses clinically used to replace a damaged hip or knee are metal-to-polyethylene, metal-to-metal, ceramic-to-polyethylene, and ceramic-to-ceramic. Among them, ceramic-to-polyethylene type and ceramic-to-ceramic type are increasingly commonly used due to significantly reduced wear amount. The ceramic materials used are mainly alumina ceramic, zirconia ceramic and alumina-zirconia composite ceramic.
Zirconia ceramics have three crystalline phases: monoclinic, tetragonal and cubic phases. When the tetragonal phase is converted to 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.
With the development of technology, it has further been found that Y 2 O 3 The tetragonal zirconia ceramics used as the stabilizer can spontaneously change into monoclinic phase under the hydrothermal environment of 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 3-5% volume change accompanying the phase transformation. This phenomenon limits the further use of tetragonal zirconia ceramics.
In order to solve the problem, the application creatively introduces a glass phase containing yttrium (Y) element into the tetragonal zirconia ceramics, and obviously reduces the depletion of Y ions in the zirconia grains after sintering by inhibiting the segregation of Y ions to the grain boundaries of the zirconia grains in the sintering process, thereby reducing the spontaneous phase transition (tetragonal phase is converted into monoclinic phase) of the zirconia ceramics in the hydrothermal environment and improving the long-term service performance of the zirconia ceramics.
Disclosure of Invention
In the present application, "YASZ glass" means Y 2 O 3 -Al 2 O 3 -SiO 2 -ZrO 2 Glass.
In the present application, "3Y-TZP" means that the composition contains 2.0 to 3.5mol%, preferably 2.5 to 3.2mol%, more preferably 3.0mol% of Y 2 O 3 Tetragonal phase zirconia of (a).
The present application relates to a zirconia ceramic containing a glass phase, which is composed of a YASZ glass phase and a balance of a 3Y-TZP crystal phase, the YASZ glass phase being located between crystal grains of the 3Y-TZP crystal phase, and a dihedral angle formed between the YASZ glass phase and the 3Y-TZP crystal phase being 62 to 90 °.
According to embodiments of the present application, the YASZ vitreous phase content of the zirconia ceramic may be 1.0-5.5 wt.%, 1.5-5.0 wt.%, 1.5-4.5 wt.%, 2.0-4.0 wt.%, 2.0-3.5 wt.%, 3.0-3.2 wt.%, 2.0-2.5 wt.%, or 2.2-2.5 wt.%.
According to an embodiment of the present application, the dihedral angle formed between the YASZ glass phase and the 3Y-TZP crystal phase is 62 to 90 °, preferably 62 to 85 °, more preferably 65 to 80 °, further preferably 65 to 75 °, still more preferably 65 to 70 °, most preferably 65 to 68 °.
According to an embodiment of the application, the YASZ vitreous phase consists of 15 to 35wt% Y 2 O 3 、10-30wt％Al 2 O 3 、35～55wt％SiO 2 And 4-10wt% ZrO 2 Composed preferably of 28 to 35wt% Y 2 O 3 、10-20wt％Al 2 O 3 、40～55wt％SiO 2 And 4-10wt% ZrO 2 It further preferably consists of 30 to 35wt% of Y 2 O 3 、10-20wt％Al 2 O 3 、45～50wt％SiO 2 And 4-10wt% ZrO 2 And most preferably consists of 30 to 32wt% Y 2 O 3 、10-20wt％Al 2 O 3 、45～50wt％SiO 2 And 4-10wt% ZrO 2 Composition is prepared.
According to the zirconia ceramics containing a glass phase of the present application, the grain size of the 3Y-TZP crystal phase is 1.0. Mu.m, preferably 0.6. Mu.m, most preferably 0.4. Mu.m.
The application also relates to bone implant prostheses made from zirconia ceramics containing a vitreous phase, including hip joint prostheses, knee joint prostheses, elbow joint prostheses, wrist joint prostheses, ankle joint prostheses, and the like.
The zirconia ceramics containing a vitreous phase of the present application can also be used for other industrial applications.
In nature, hafnium (Hf) and zirconium are present in solid solution and are difficult to separate, so in the present application, "oxygenZirconium (ZrO) 2 ) "contains less than or equal to 5wt% hafnium oxide.
In the present application, "hydrothermal treatment" means exposure to water vapor in an autoclave at a temperature of 134.+ -. 2 ℃ and a pressure of 0.2MPa, and can be seen in particular in section 4.8 of ISO 13356.
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. The sample size was 10 mm. Times.10 mm. Times.2 mm. The results of the test refer to the average content of 5 samples.
In the present application, room temperature means-20℃to 40 ℃.
In the present application, the flexural strength means four-point flexural strength, and the test bars have dimensions of 3mm×4mm×45mm. The test results refer to the average strength of 12 bars.
In the present application, the dihedral angle between the glass phase and the crystal phase is observed using a high resolution transmission electron microscope.
Detailed Description
The present application is further specifically illustrated by the following examples, but the present application is not limited to these examples.
In the examples, the 3Y-TZP powder used was one containing 3mol% of Y 2 O 3 The tetragonal zirconia powder is purchased from Hebei Hengbo new materials science and technology Co., ltd.
Example 1 preparation of zirconia ceramic 1
500g of 3Y-TZP powder is dried and pressed at 100MPa, then the temperature is raised from room temperature to 1500 ℃ at the speed of 20 ℃/h, the temperature is kept for 3 hours, and the powder is cooled to the room temperature along with a furnace.
The obtained sintered body was processed into 12 four-point flexural strength bars and 10 XRD blocks. Wherein 5 XRD samples were subjected to hydrothermal treatment for 10 hours.
Through testing, the four-point bending strength is 1020MPa, the phase composition before the hydrothermal treatment is monoclinic phase content of 0.5vol%, the rest is tetragonal phase, the monoclinic phase content after the hydrothermal treatment for 10 hours is 25.4vol%, and the rest is tetragonal phase.
EXAMPLE 2 preparation of zirconia ceramic 2
Chemically pure Y 2 O 3 Powder, al 2 O 3 Powder, siO 2 Powder and ZrO 2 Mixing the powder together according to the weight ratio of 30:14:50:6, adding absolute ethyl alcohol, uniformly mixing on a ball mill, pouring out, drying, placing into a platinum crucible, placing into a glass melting furnace, melting for 2 hours at 1550 ℃, directly taking out, and pouring into deionized water to obtain glass cullet. Ball milling the glass powder into glass powder.
Mixing 3Y-TZP powder and glass powder according to the weight ratio of 98.8:1.2, adding absolute ethyl alcohol, uniformly mixing on a ball mill, pouring out, drying, dry-pressing at 100MPa for molding, then heating from room temperature to 1500 ℃ at the speed of 20 ℃/h, preserving heat for 3 hours, and cooling to room temperature along with a furnace.
The sintered body was processed into 12 four-point flexural strength bars and 10 XRD blocks. Wherein 5 XRD samples were subjected to hydrothermal treatment for 10 hours.
Through testing, the four-point bending strength is 963MPa; the dihedral angle between the zirconia grains and the glass phase was 68 °; the composition of the crystalline phase before the hydrothermal treatment was 0.5vol% monoclinic zirconia, the balance being tetragonal zirconia, the monoclinic zirconia content after 10 hours of the hydrothermal treatment was 7.2vol%, and the balance being tetragonal zirconia.
EXAMPLE 3 preparation of zirconia ceramic 3
Mixing 3Y-TZP powder and the glass powder prepared in the example 2 according to the weight ratio of 98.2:1.8, adding absolute ethyl alcohol, uniformly mixing on a ball mill, pouring out, drying, dry-pressing at 100MPa, then heating from room temperature to 1500 ℃ at the speed of 20 ℃/h, preserving heat for 3 hours, and cooling to room temperature along with a furnace.
The sintered body was processed into 12 four-point flexural strength bars and 10 XRD blocks. Wherein 5 XRD samples were subjected to hydrothermal treatment for 10 hours.
Through testing, the four-point bending strength is 950MPa; the dihedral angle between the zirconia grains and the glass phase was 68 °; the composition of the crystalline phase before the hydrothermal treatment was 0.5vol% monoclinic zirconia, the balance being tetragonal zirconia, the monoclinic zirconia content after 10 hours of the hydrothermal treatment was 6.5vol%, and the balance being tetragonal zirconia.
EXAMPLE 4 preparation of zirconia ceramic 4
Mixing 3Y-TZP powder and the glass powder prepared in the example 2 according to the weight ratio of 98.0:2.0, adding absolute ethyl alcohol, uniformly mixing on a ball mill, pouring out, drying, dry-pressing at 100MPa, then heating from room temperature to 1500 ℃ at the speed of 20 ℃/h, preserving heat for 3 hours, and cooling to room temperature along with a furnace.
The sintered body was processed into 12 four-point flexural strength bars and 10 XRD blocks. Wherein 5 XRD samples were subjected to hydrothermal treatment for 10 hours.
Through testing, the four-point bending strength is 941MPa; the dihedral angle between the zirconia grains and the glass phase was 68 °; the composition of the crystalline phase before the hydrothermal treatment was 0.5vol% monoclinic zirconia, the balance being tetragonal zirconia, the monoclinic zirconia content after 10 hours of the hydrothermal treatment was 3.0vol%, and the balance being tetragonal zirconia.
EXAMPLE 5 preparation of zirconia ceramic 5
Mixing 3Y-TZP powder and the glass powder prepared in the example 2 according to the weight ratio of 97.8:2.2, adding absolute ethyl alcohol, uniformly mixing on a ball mill, pouring out, drying, dry-pressing at 100MPa, then heating from room temperature to 1500 ℃ at the speed of 20 ℃/h, preserving heat for 3 hours, and cooling to room temperature along with a furnace.
The sintered body was processed into 12 four-point flexural strength bars and 10 XRD blocks. Wherein 5 XRD samples were subjected to hydrothermal treatment for 10 hours.
Through testing, the four-point bending strength is 940MPa; the dihedral angle between the zirconia grains and the glass phase was 68 °; the composition of the crystalline phase before the hydrothermal treatment was 0.5vol% monoclinic zirconia, the balance being tetragonal zirconia, and the monoclinic zirconia after 10 hours of the hydrothermal treatment was 2.5vol%, the balance being tetragonal zirconia.
EXAMPLE 6 preparation of zirconia ceramic 6
Mixing 3Y-TZP powder and the glass powder prepared in the example 2 according to the weight ratio of 97.5:2.5, adding absolute ethyl alcohol, uniformly mixing on a ball mill, pouring out, drying, dry-pressing at 100MPa, then heating from room temperature to 1500 ℃ at the speed of 20 ℃/h, preserving heat for 3 hours, and cooling to room temperature along with a furnace.
The sintered body was processed into 12 four-point flexural strength bars and 10 XRD blocks. Wherein 5 XRD samples were subjected to hydrothermal treatment for 10 hours.
Through testing, the four-point bending strength is 935MPa; the dihedral angle between the zirconia grains and the glass phase was 68 °; the composition of the crystalline phase before the hydrothermal treatment was 0.5vol% monoclinic zirconia, the balance being tetragonal zirconia, and the monoclinic zirconia after 10 hours of the hydrothermal treatment was 2.4vol%, the balance being tetragonal zirconia.
EXAMPLE 7 preparation of zirconia ceramic 7
Mixing 3Y-TZP powder and the glass powder prepared in the example 2 according to the weight ratio of 97.0:3.0, adding absolute ethyl alcohol, uniformly mixing on a ball mill, pouring out, drying, dry-pressing at 100MPa, then heating from room temperature to 1500 ℃ at the speed of 20 ℃/h, preserving heat for 3 hours, and cooling to room temperature along with a furnace.
The sintered body was processed into 12 four-point flexural strength bars and 10 XRD blocks. Wherein 5 XRD samples were subjected to hydrothermal treatment for 10 hours.
Through testing, the four-point bending strength is 882MPa; the dihedral angle between the zirconia grains and the glass phase was 68 °; the composition of the crystalline phase before the hydrothermal treatment was 0.5vol% monoclinic zirconia, the balance being tetragonal zirconia, and the monoclinic zirconia after 10 hours of the hydrothermal treatment was 2.4vol%, the balance being tetragonal zirconia.
EXAMPLE 8 preparation of zirconia ceramic 8
Mixing 3Y-TZP powder and glass powder 1 prepared in example 2 according to the weight ratio of 96.5:3.5, adding absolute ethyl alcohol, uniformly mixing on a ball mill, pouring out, drying, dry-pressing at 100MPa, then heating from room temperature to 1500 ℃ at the speed of 20 ℃/h, preserving heat for 3 hours, and cooling to room temperature along with a furnace.
The sintered body was processed into 12 four-point flexural strength bars and 10 XRD blocks. Wherein 5 XRD samples were subjected to hydrothermal treatment for 10 hours.
Through testing, the four-point bending strength is 821MPa; the dihedral angle between the zirconia grains and the glass phase was 68 °; the composition of the crystalline phase before the hydrothermal treatment was 0.5vol% monoclinic zirconia, the balance being tetragonal zirconia, and the monoclinic zirconia after 10 hours of the hydrothermal treatment was 2.4vol%, the balance being tetragonal zirconia.
EXAMPLE 9 preparation of zirconia ceramic 9
Mixing 3Y-TZP powder and the glass powder prepared in the example 2 according to the weight ratio of 95.0:5.0, adding absolute ethyl alcohol, uniformly mixing on a ball mill, pouring out, drying, dry-pressing at 100MPa, then heating from room temperature to 1500 ℃ at the speed of 20 ℃/h, preserving heat for 3 hours, and cooling to room temperature along with a furnace.
The sintered body was processed into 12 four-point flexural strength bars and 10 XRD blocks. Wherein 5 XRD samples were subjected to hydrothermal treatment for 10 hours.
Through testing, the four-point bending strength is 734MPa; the dihedral angle between the zirconia grains and the glass phase was 68 °; the composition of the crystalline phase before the hydrothermal treatment was 0.5vol% monoclinic zirconia, the balance being tetragonal zirconia, and the monoclinic zirconia after 10 hours of the hydrothermal treatment was 2.5vol%, the balance being tetragonal zirconia.
EXAMPLE 10 preparation of zirconia ceramic 10
Chemically pure Y 2 O 3 Powder, al 2 O 3 Powder, siO 2 Powder and ZrO 2 Mixing the powder together according to the weight ratio of 32:15:45:8, adding absolute ethyl alcohol, uniformly mixing on a ball mill, pouring out, drying, placing into a platinum crucible, placing into a glass melting furnace, melting for 2 hours at 1550 ℃, directly taking out, and pouring into deionized water to obtain glass cullet. The glass cullet was ball milled to glass frit 1.
Mixing 3Y-TZP powder and glass powder according to the weight ratio of 97.8:2.2, adding absolute ethyl alcohol, uniformly mixing on a ball mill, pouring out, drying, dry-pressing at 100MPa for molding, then heating from room temperature to 1500 ℃ at the speed of 20 ℃/h, preserving heat for 3 hours, and cooling to room temperature along with a furnace.
The sintered body was processed into 12 four-point flexural strength bars and 10 XRD blocks. Wherein 5 XRD samples were subjected to hydrothermal treatment for 10 hours.
Through testing, the four-point bending strength is 940MPa; the dihedral angle between the zirconia grains and the glass phase was 65 °; the composition of the crystalline phase before the hydrothermal treatment was 0.5vol% monoclinic zirconia, the balance being tetragonal zirconia, and the monoclinic zirconia after 10 hours of the hydrothermal treatment was 2.5vol%, the balance being tetragonal zirconia.
EXAMPLE 11 preparation of zirconia ceramic 11
Chemically pure Y 2 O 3 Powder, al 2 O 3 Powder, siO 2 Powder and ZrO 2 Mixing the powder together according to the weight ratio of 35:22:35:8, adding absolute ethyl alcohol, uniformly mixing on a ball mill, pouring out, drying, placing into a platinum crucible, placing into a glass melting furnace, melting for 2 hours at 1550 ℃, directly taking out, and pouring into deionized water to obtain glass cullet. Ball milling the glass powder into glass powder.
Mixing 3Y-TZP powder and glass powder according to the weight ratio of 97.5:2.5, adding absolute ethyl alcohol, uniformly mixing on a ball mill, pouring out, drying, dry-pressing at 100MPa for molding, then heating from room temperature to 1500 ℃ at the speed of 20 ℃/h, preserving heat for 3 hours, and cooling to room temperature along with a furnace.
The sintered body was processed into 12 four-point flexural strength bars and 10 XRD blocks. Wherein 5 XRD samples were subjected to hydrothermal treatment for 10 hours.
Through testing, the four-point bending strength is 782MPa; the dihedral angle between the zirconia grains and the glass phase is 45 °; the composition of the crystalline phase before the hydrothermal treatment was 0.5vol% monoclinic zirconia, the balance being tetragonal zirconia, and the monoclinic zirconia after 10 hours of the hydrothermal treatment was 2.5vol%, the balance being tetragonal zirconia.
EXAMPLE 12 preparation of zirconia ceramics 12
Chemically pure Y 2 O 3 Powder, al 2 O 3 Powder, siO 2 Powder and ZrO 2 Mixing the powder together according to the weight ratio of 15:27:50:8, adding absolute ethyl alcohol, uniformly mixing on a ball mill, pouring out, drying, placing into a platinum crucible, placing into a glass melting furnace, melting for 2 hours at 1550 ℃, directly taking out, and pouring into deionized water to obtain glass cullet. Ball milling the glass powder into glass powder.
Mixing 3Y-TZP powder and glass powder according to the weight ratio of 97.5:2.5, adding absolute ethyl alcohol, uniformly mixing on a ball mill, pouring out, drying, dry-pressing at 100MPa for molding, then heating from room temperature to 1500 ℃ at the speed of 20 ℃/h, preserving heat for 3 hours, and cooling to room temperature along with a furnace.
The sintered body was processed into 12 four-point flexural strength bars and 10 XRD blocks. Wherein 5 XRD samples were subjected to hydrothermal treatment for 10 hours.
Through testing, the four-point bending strength is 940MPa; the dihedral angle between the zirconia grains and the glass phase is 70 °; the composition of the crystalline phase before the hydrothermal treatment was 0.5vol% monoclinic zirconia, the balance being tetragonal zirconia, the monoclinic zirconia content after 10 hours of the hydrothermal treatment was 8.9vol%, and the balance being tetragonal zirconia.
EXAMPLE 13 preparation of zirconia ceramics 13
Chemically pure Y 2 O 3 Powder, al 2 O 3 Powder, siO 2 Powder and ZrO 2 Mixing the powder together according to the weight ratio of 30:10:54:6, adding absolute ethyl alcohol, uniformly mixing on a ball mill, pouring out, drying, placing into a platinum crucible, placing into a glass melting furnace, melting for 2 hours at 1550 ℃, directly taking out, and pouring into deionized water to obtain glass cullet. Ball milling the glass powder into glass powder.
Mixing 3Y-TZP powder and glass powder according to the weight ratio of 97.5:2.5, adding absolute ethyl alcohol, uniformly mixing on a ball mill, pouring out, drying, dry-pressing at 100MPa for molding, then heating from room temperature to 1500 ℃ at the speed of 20 ℃/h, preserving heat for 3 hours, and cooling to room temperature along with a furnace.
The sintered body was processed into 12 four-point flexural strength bars and 10 XRD blocks. Wherein 5 XRD samples were subjected to hydrothermal treatment for 10 hours.
Through testing, the four-point bending strength is 936MPa; the dihedral angle between the zirconia grains and the glass phase was 85 °; the composition of the crystalline phase before the hydrothermal treatment was 0.5vol% monoclinic zirconia, the balance being tetragonal zirconia, and the monoclinic zirconia after 10 hours of the hydrothermal treatment was 12.5vol%, the balance being tetragonal zirconia.
The results of the above examples are summarized in the following table.
It is found from examples 2 to 13 that, after adding the glass containing the Y element to the tetragonal zirconia ceramics, a glass phase was formed between the zirconia grains. Because the content of the Y element in the glass is high, the segregation of Y ions in the zirconia grains to the grain boundary in the sintering process is inhibited, so that the depletion of Y ions in the zirconia grains is avoided. The depletion of Y ions in zirconia grains is a main reason for spontaneous conversion of tetragonal phase into monoclinic phase in hydrothermal treatment. Therefore, after adding the glass phase containing Y ions, the ability to resist the hydrothermal treatment is improved.
As shown in example 12, if the content of Y element in the glass phase is too low, the effect of suppressing the segregation of Y ions is reduced, and the hydrothermal aging resistance of the whole is still insufficient.
If the glass phase content is too small, as shown in examples 2 and 3, a part of the zirconia grains do not have glass phase between them, and there is still Y ion segregation in the zirconia grains, so that the monoclinic phase content after the hydrothermal treatment is high. If the glass phase content is too high, as shown in example 9, a glass communication network is formed, resulting in a decrease in four-point flexural strength.
In addition, as shown in example 11, when the dihedral angle between the glass phase and the crystal phase is too low, a glass communication network is also easily formed, resulting in a decrease in four-point bending strength of the entire material. As shown in example 13, when the dihedral angle between the glass phase and the crystalline phase is too large, the glass phase is unevenly distributed among the grains, resulting in a lack of glass phase in some regions where the zirconia grains are still depleted in Y ions, so that the hydrothermal aging resistance of the whole is still remarkably insufficient.
Therefore, examples 4 to 6 are preferable from the viewpoint of the combination of the hydrothermal aging resistance and the four-point bending strength.
EXAMPLE 14 preparation of zirconia-based ceramic femoral head for hip replacement
In examples 1 to 13, a rubber mold having a femoral head shape for hip replacement was used in dry press molding. Thus, after sintering, a spherical zirconia ceramic sintered body containing a glass phase was obtained. The spherical sintered body is ground to prepare the hip joint ceramic femoral head prosthesis.
EXAMPLE 15 preparation of zirconia-based ceramic prosthesis for knee replacement
In examples 1-13 above, a rubber mold in the shape of a knee prosthesis tibial tray was used in dry compression molding. Thus, a zirconia ceramic sintered body containing a glass phase in the shape of a tibial plateau tray is obtained after sintering. The zirconia ceramic prosthesis for knee joint replacement is prepared through grinding.
Claims (9)
1. Zirconia ceramic containing glass phase, which consists of 1.0 to 5.5wt% of YASZ glass phase and the balance of 3Y-TZP crystal phase, wherein the YASZ glass phase is positioned between crystal grains of the 3Y-TZP crystal phase, and the YASZ glass phase consists of 15 to 35wt% of Y 2 O 3 、10-30wt％Al 2 O 3 、35～55wt％SiO 2 And 4-10wt% ZrO 2 And the dihedral angle formed between the YASZ glass phase and the 3Y-TZP crystal phase is 62-85 deg.
2. The zirconia ceramic of claim 1 containing a glass phase, said YASZ glass phase being present in an amount of from 2.0 to 3.5% by weight and said YASZ glass phase consisting of from 28 to 35% by weight of Y 2 O 3 、10-20wt％Al 2 O 3 、40～55wt％SiO 2 And 4-10wt% ZrO 2 Composition, and the dihedral angle formed between the YASZ glass phase and the 3Y-TZP crystal phase is65～80°。
3. The zirconia ceramic of claim 2 containing a glass phase, said YASZ glass phase being present in an amount of 2.0 to 3.0% by weight, said YASZ glass phase consisting of 30 to 35% by weight of Y 2 O 3 、10-20wt％Al 2 O 3 、45～50wt％SiO 2 And 4-10wt% ZrO 2 And a dihedral angle formed between the YASZ glass phase and the 3Y-TZP crystal phase is 65 to 75 degrees.
4. The zirconia ceramic of claim 3 comprising a glass phase, said YASZ glass phase being present in an amount of from 2.0 to 2.5% by weight and said YASZ glass phase consisting of from 30 to 32% by weight of Y 2 O 3 、10-20wt％Al 2 O 3 、45～50wt％SiO 2 And 4-10wt% ZrO 2 And a dihedral angle formed between the YASZ glass phase and the 3Y-TZP crystal phase is 65 to 70 degrees.
5. The zirconia ceramic of claim 4 containing a glass phase, said YASZ glass phase being present in an amount of 2.2 to 2.5% by weight and said YASZ glass phase consisting of 30 to 32% by weight of Y 2 O 3 、10-20wt％Al 2 O 3 、45～50wt％SiO 2 And 4-10wt% ZrO 2 And a dihedral angle formed between the YASZ glass phase and the 3Y-TZP crystal phase is 65 to 70 degrees.
6. The zirconia ceramic containing a glass phase according to any one of claims 1 to 5, wherein the grain size of the 3Y-TZP crystal phase is 1.0 μm or less.
7. The zirconia ceramic containing a glass phase according to claim 6, wherein the grain size of the 3Y-TZP crystal phase is 0.6 μm or less.
8. The zirconia ceramic containing a glass phase according to claim 7, wherein the grain size of the 3Y-TZP crystal phase is 0.4 μm or less.
9. A bone implant prosthesis made using the vitreous phase containing zirconia ceramic of any one of claims 1 to 8, comprising an artificial femoral head and liner for hip replacement and a knee prosthesis for knee replacement.
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