CN104193331B - Bone implants prosthese zirconia base composite ceramics and bone prepared therefrom implants prosthese - Google Patents
Bone implants prosthese zirconia base composite ceramics and bone prepared therefrom implants prosthese Download PDFInfo
- Publication number
- CN104193331B CN104193331B CN201410382009.3A CN201410382009A CN104193331B CN 104193331 B CN104193331 B CN 104193331B CN 201410382009 A CN201410382009 A CN 201410382009A CN 104193331 B CN104193331 B CN 104193331B
- Authority
- CN
- China
- Prior art keywords
- prosthese
- composite ceramics
- bone
- zro
- implants
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000002131 composite material Substances 0.000 title claims abstract description 87
- 239000000919 ceramic Substances 0.000 title claims abstract description 76
- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 21
- 239000007943 implant Substances 0.000 title claims abstract description 18
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 53
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 45
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 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 33
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 30
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 30
- 239000013078 crystal Substances 0.000 claims abstract description 14
- 239000003381 stabilizer Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000008187 granular material Substances 0.000 claims description 26
- 238000010335 hydrothermal treatment Methods 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 238000000975 co-precipitation Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 6
- 239000003595 mist Substances 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 238000005056 compaction Methods 0.000 claims description 4
- 210000000629 knee joint Anatomy 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 238000011540 hip replacement Methods 0.000 claims description 3
- 210000003127 knee Anatomy 0.000 claims description 3
- 229910009523 YCl3 Inorganic materials 0.000 claims 1
- 229910006251 ZrOCl2.8H2O Inorganic materials 0.000 claims 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- 210000001694 thigh bone Anatomy 0.000 claims 1
- 238000002513 implantation Methods 0.000 abstract description 2
- 238000005452 bending Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000003825 pressing Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 238000007656 fracture toughness test Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000007689 inspection Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000013001 point bending Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 210000004394 hip joint Anatomy 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 210000003797 carpal joint Anatomy 0.000 description 2
- 210000002310 elbow joint Anatomy 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 208000012659 Joint disease Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- VCRLKNZXFXIDSC-UHFFFAOYSA-N aluminum oxygen(2-) zirconium(4+) Chemical compound [O--].[O--].[Al+3].[Zr+4] VCRLKNZXFXIDSC-UHFFFAOYSA-N 0.000 description 1
- 210000003423 ankle Anatomy 0.000 description 1
- 210000000544 articulatio talocruralis Anatomy 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 210000001624 hip Anatomy 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Materials For Medical Uses (AREA)
Abstract
The present invention relates to bone and implant prosthese zirconia base composite ceramics and bone prepared therefrom implantation prosthese.Described bone implants the chemical composition of prosthese zirconia base composite ceramics by the ZrO of 93.00-95.40wt%2, 4.50-6.00wt% Y2O3, 0.05-0.50wt%Al2O3, 0.05～0.50wt%Nb2O5Composition, wherein Y2O3、Al2O3And Nb2O5It is ZrO2Stabilizer；With, described composite ceramics is made up of the tetragonal phase zirconium oxide of 90～100vol% and the monoclinic phase zirconium oxide of 0～10vol% at the crystal phase structure of room temperature.
Description
Technical field
The present invention relates to bone and implant prosthese zirconia base composite ceramics, implant prosthese further to the bone prepared by this zirconia base composite ceramics.
Background technology
Adopt artificial prosthesis to replace impaired joint (including hip joint, knee joint, elbow joint, carpal joint or ankle joint) and have become as the primary selection of clinical treatment joint disease.At present, it is used for clinically replacing impaired hip joint or kneed artificial prosthesis has metal pair polyethylene, metal to metal type and pottery to polyethylene and ceramic-on-ceramic type.Wherein, polyethylene and ceramic-on-ceramic type are obtained more and more common application due to significantly reduced wear extent by pottery.The ceramic material adopted is mainly aluminium oxide ceramics, zirconia ceramics and aluminium oxide-zirconium oxide composite ceramics.
Zirconia ceramics has three kinds of crystalline phases: monoclinic phase, Tetragonal and Emission in Cubic.When tetragonal phase converting is monoclinic phase, not only along with the consumption of energy, and along with the volumetric expansion of 3-5%.Volumetric expansion can cause the generation of compressive stress.The synergism of this energy expenditure and formation compressive stress, hinders the extension of crackle, effectively thus significantly improving the fracture toughness of zirconia ceramics so that tetragonal phase zirconium oxide pottery obtains the good reputation of " Ceramo-steel ".
Exist with monoclinic phase when pure zirconium oxide is below 1170 DEG C, exist with Tetragonal form when 1170～2370 DEG C, exist with Emission in Cubic form during higher than 2370 DEG C.So, people, in order to obtain tetragonal phase zirconium oxide pottery in room temperature, often add stabilizer so that Tetragonal can remain to room temperature in zirconia ceramics.Common stabilizer has Y2O3、CeO2, MgO etc..
Along with the development of science and technology, people, it has furthermore been found that existing tetragonal phase zirconium oxide pottery is under the thermal and hydric environment of 100～400 DEG C, can spontaneously be transformed into monoclinic phase.This spontaneous phase transformation not only results in there is submicron crackle in zirconia ceramics, and due to the change in volume of the adjoint 3-5% of phase transformation, can cause that the surface roughness of zirconia ceramics changes.This phenomenon limits the further application of tetragonal phase zirconium oxide pottery.
In order to solve this problem, the present invention creatively adopts combining and the content of various stabilizers in conservative control combination of plurality of stable agent, considerably reduce the zirconia ceramics spontaneous phase transformation (tetragonal phase converting is monoclinic phase) under thermal and hydric environment, thus significantly improving the Long-Term Properties of zirconia ceramics.
Summary of the invention
The present invention relates to bone and implant prosthese zirconia base composite ceramics, the chemical composition of described composite ceramics is by the ZrO of 93.00-95.40wt%2, 4.50-6.00wt% Y2O3, 0.05-0.50wt%Al2O3, 0.05～0.50wt%Nb2O5Composition, wherein Y2O3、Al2O3And Nb2O5It is ZrO2Stabilizer；With, described composite ceramics is made up of the tetragonal phase zirconium oxide of 90～100vol% and the monoclinic phase zirconium oxide of 0～10vol% at the crystal phase structure of room temperature.
According to embodiment of the present invention, the bone of the present invention implants prosthese grain size≤0.5 micron of zirconia base composite ceramics, it is preferable that≤0.4 micron.
The invention further relates to the preparation method that bone implants prosthese zirconia base composite ceramics, including: 1) adopt coprecipitation to prepare ZrO2With the composite powder of stabilizer, powder size is less than 100 nanometers, it is preferable that less than 60 nanometers；2) by 1) in the composite powder that obtains carry out pelletize, obtain the powder that granularity is 50-100 micron；3) by 2) in the powder that obtains suppress under the uniaxial pressure of 20-100MPa, obtain a base substrate；4) by 3) in molded body cold isostatic compaction under 200-280MPa pressure of obtaining, obtain secondary base substrate；5) by 4) in secondary base substrate after cold isostatic compaction put in the sintering furnace of air atmosphere, sinter 1-5 hour at 1350-1500 DEG C.
The invention still further relates to and implanted bone implantation prosthese prepared by prosthese zirconia base composite ceramics by bone, including hip prosthesis, knee-joint prosthesis, elbow joint prosthese, carpal joint prosthese and ankle prosthesis etc..
The zirconia base composite ceramics of the present invention can be used for other industrial use.
In nature, hafnium (Hf) and zr element are to exist with the form of solid solution, it is difficult to separate, so in this application, and " zirconium oxide (ZrO2) " in containing≤5wt% hafnium oxide.
In this application, " hydrothermal treatment consists " refers to and is exposed in steam under the temperature of 134 ± 2 DEG C, the pressure of 0.2MPa in autoclave, specifically may refer to the 4.8th trifle of ISO13356.
In this application, " vol% " refers to percent by volume, and " wt% " refers to mass percent.
In this application, X-ray diffraction analysis (referred to as " XRD ", Cuk α, 30KV, 15mA) is adopted to determine crystal content.So, the crystal content obtained refers to the crystal content in the top layer that in XRD analysis, X ray penetrates.
In this application, room temperature refers to-20 DEG C～40 DEG C.
Detailed description of the invention
Specifically set forth the present invention by following example further, but the invention is not restricted to these embodiments.
Embodiment 1a prepares ZrO2/Y2O3/Al2O3/Nb2O5Composite granule
ZrO2/Y2O3/Al2O3/Nb2O5Composite granule adopts coprecipitation to prepare.Specifically, by the ZrOCl of concentration 15wt%2.8H2O aqueous solution, concentration are the YCl of 20wt%3Solution, concentration are the AlCl of 25wt%3Solution and concentration are the (NH of 50wt%4)3[NbO(C2O4)3].2H2O solution, according to ZrO2∶Y2O3∶Al2O3∶Nb2O5The ratio that mass ratio is 94.60: 4.80: 0.50: 0.10 mixing.Heating is to 75 DEG C, and being added dropwise over ammonia under being stirred continuously to pH is 8.5, generates white colloidal precipitation.Filter out white colloidal precipitate, do not measure chloride ion with inspection in deionized water wash to filtrate.After 50 DEG C of vacuum dryings, calcine 2 hours with the ramp of 100 DEG C/h to 800 DEG C.Namely the ZrO that particle mean size is 20 nanometers is obtained2-Y2O3-Al2O3-Nb2O5Composite granule.
Embodiment 1b prepares ZrO2/Y2O3/Al2O3/Nb2O5Composite granule
ZrO2/Y2O3/Al2O3/Nb2O5Composite granule adopts coprecipitation to prepare.Specifically, by the ZrOCl of concentration 15wt%2.8H2O aqueous solution, concentration are the YCl of 20wt%3Solution, concentration are the AlCl of 25wt%3Solution and concentration are the (NH of 50wt%4)3[NbO(C2O4)3].2H2O solution, according to ZrO2∶Y2O3∶Al2O3∶Nb2O5The ratio that mass ratio is 94.20: 5.20: 0.40: 0.20 mixing.Heating is to 75 DEG C, and being added dropwise over ammonia under being stirred continuously to pH is 8.5, generates white colloidal precipitation.Filter out white colloidal precipitate, do not measure chloride ion with inspection in deionized water wash to filtrate.After 50 DEG C of vacuum dryings, calcine 2 hours with the ramp of 100 DEG C/h to 800 DEG C.Namely the ZrO that particle mean size is 20 nanometers is obtained2-Y2O3-Al2O3-Nb2O5Composite granule.
Embodiment 1c prepares ZrO2/Y2O3/Al2O3/Nb2O5Composite granule
ZrO2/Y2O3/Al2O3/Nb2O5Composite granule adopts coprecipitation to prepare.Specifically, by the ZrOCl of concentration 15wt%2.8H2O aqueous solution, concentration are the YCl of 20wt%3Solution, concentration are the AlCl of 25wt%3Solution and concentration are the (NH of 50wt%4)3[NbO(C2O4)3].2H2O solution, according to ZrO2∶Y2O3∶Al2O3∶Nb2O5The ratio that mass ratio is 93.90: 5.50: 0.30: 0.30 mixing.Heating is to 75 DEG C, and being added dropwise over ammonia under being stirred continuously to pH is 8.5, generates white colloidal precipitation.Filter out white colloidal precipitate, do not measure chloride ion with inspection in deionized water wash to filtrate.After 50 DEG C of vacuum dryings, calcine 2 hours with the ramp of 100 DEG C/h to 800 DEG C.Namely the ZrO that particle mean size is 20 nanometers is obtained2-Y2O3-Al2O3-Nb2O5Composite granule.
Embodiment 1d prepares ZrO2/Y2O3/Al2O3/Nb2O5Composite granule
ZrO2/Y2O3/Al2O3/Nb2O5Composite granule adopts coprecipitation to prepare.Specifically, by the ZrOCl of concentration 15wt%2.8H2O aqueous solution, concentration are the YCl of 20wt%3Solution, concentration are the AlCl of 25wt%3Solution and concentration are the (NH of 50wt%4)3[NbO(C2O4)3].2H2O solution, according to ZrO2∶Y2O3∶Al2O3∶Nb2O5The ratio that mass ratio is 93.86: 5.52: 0.17: 0.45 mixing.Heating is to 75 DEG C, and being added dropwise over ammonia under being stirred continuously to pH is 8.5, generates white colloidal precipitation.Filter out white colloidal precipitate, do not measure chloride ion with inspection in deionized water wash to filtrate.After 50 DEG C of vacuum dryings, calcine 2 hours with the ramp of 100 DEG C/h to 800 DEG C.Namely the ZrO that particle mean size is 20 nanometers is obtained2-Y2O3-Al2O3-Nb2O5Composite granule.
Embodiment 1e prepares ZrO2/Y2O3/Al2O3/Nb2O5Composite granule
ZrO2/Y2O3/Al2O3/Nb2O5Composite granule adopts coprecipitation to prepare.Specifically, by the ZrOCl of concentration 15wt%2.8H2O aqueous solution, concentration are the YCl of 20wt%3Solution, concentration are the AlCl of 25wt%3Solution and concentration are the (NH of 50wt%4)3[NbO(C2O4)3].2H2O solution, according to ZrO2∶Y2O3∶Al2O3∶Nb2O5The ratio that mass ratio is 93.87: 5.52: 0.13: 0.48 mixing.Heating is to 75 DEG C, and being added dropwise over ammonia under being stirred continuously to pH is 8.5, generates white colloidal precipitation.Filter out white colloidal precipitate, do not measure chloride ion with inspection in deionized water wash to filtrate.After 50 DEG C of vacuum dryings, calcine 2 hours with the ramp of 100 DEG C/h to 800 DEG C.Namely the ZrO that particle mean size is 20 nanometers is obtained2-Y2O3-Al2O3-Nb2O5Composite granule.
Embodiment 2a prepares ZrO2-Y2O3-Al2O3-Nb2O5Composite ceramics
ZrO prepared by embodiment 1a2/Y2O3/Al2O3/Nb2O5Composite granule carries out mist projection granulating, it is thus achieved that granularity is the granule of 60 microns.Then through dry-pressing formed under 50MPa pressure, then after the quiet molding such as 300MPa is cold, then with the ramp of 3 DEG C/minute to 1400 DEG C and be incubated 2 hours in the high temperature furnace of air atmosphere.It is cooled to 300 DEG C with the speed of 1 DEG C/minute and after stove is as cold as room temperature, obtains ZrO2-Y2O3-Al2O3-Nb2O5Composite ceramics.
The crystal structure of this composite ceramics of X-ray diffraction analysis is the monoclinic phase zirconium oxide of the tetragonal phase zirconium oxide of 95.2vol% and 4.8vol%, and the grain size analyzing this composite ceramics under SEM (scanning electron microscope) is 0.35 μm.Carry out four point bending strength and fracture toughness test at mechanics machine, bending strength is 1150MPa, and fracture toughness is 10.8MPa.m1/2.
This composite ceramics is through the pressure of 0.2MPa after 134 DEG C of hydrothermal treatment consists of steam 5 hours, and its bending strength is 1100MPa, and fracture toughness is 10.0MPa.m1/2, and monoclinic phase zirconia content is 12.4vol%, and tetragonal phase zirconium oxide content is 87.6vol%.
This composite ceramics is through the pressure of 0.2MPa after 134 DEG C of hydrothermal treatment consists of steam 10 hours, and its bending strength is 1050MPa, and fracture toughness is 9.2MPa.m1/2, and monoclinic phase zirconia content is 17.6vol%, and tetragonal phase zirconium oxide content is 82.4vol%.
This composite ceramics is through the pressure of 0.2MPa after 134 DEG C of hydrothermal treatment consists of steam 20 hours, and its bending strength is 1000MPa, and fracture toughness is 8.7MPa.m1/2, and monoclinic phase zirconia content is 20.9vol%, and tetragonal phase zirconium oxide content is 79.1vol%.
Embodiment 2b prepares ZrO2-Y2O3-Al2O3-Nb2O5Composite ceramics
ZrO prepared by embodiment 1b2/Y2O3/Al2O3/Nb2O5Composite granule carries out mist projection granulating, it is thus achieved that granularity is the granule of 60 microns.Then through dry-pressing formed under 50MPa pressure, then after the quiet molding such as 300MPa is cold, then with the ramp of 3 DEG C/minute to 1400 DEG C and be incubated 2 hours in the high temperature furnace of air atmosphere.It is cooled to 300 DEG C with the speed of 1 DEG C/minute and after stove is as cold as room temperature, obtains ZrO2-Y2O3-Al2O3-Nb2O5Composite ceramics
The crystal structure of this composite ceramics of X-ray diffraction analysis is the monoclinic phase zirconium oxide of the tetragonal phase zirconium oxide of 96.3vol% and 3.7vol%, and the grain size at this composite ceramics of sem analysis is 0.35 μm.Carry out four point bending strength and fracture toughness test at mechanics machine, bending strength is 1155MPa, and fracture toughness is 11.0MPa.m1/2.
This composite ceramics is through the pressure of 0.2MPa after 134 DEG C of hydrothermal treatment consists of steam 5 hours, and its bending strength is 1120MPa, and fracture toughness is 10.4MPa.m1/2, and monoclinic phase zirconia content is 9.5vol%, and tetragonal phase zirconium oxide content is 90.5vol%.
This composite ceramics is through the pressure of 0.2MPa after 134 DEG C of hydrothermal treatment consists of steam 10 hours, and its bending strength is 1080MPa, and fracture toughness is 9.9MPa.m1/2, and monoclinic phase zirconia content is 13.1vol%, and tetragonal phase zirconium oxide content is 86.9vol%.
This composite ceramics is through the pressure of 0.2MPa after 134 DEG C of hydrothermal treatment consists of steam 20 hours, and its bending strength is 1065MPa, and fracture toughness is 9.6MPa.m1/2, and monoclinic phase zirconia content is 14.8vol%, and tetragonal phase zirconium oxide content is 9.5vol%.
Embodiment 2c prepares ZrO2-Y2O3-Al2O3-Nb2O5Composite ceramics
ZrO prepared by embodiment 1c2/Y2O3/Al2O3/Nb2O5Composite granule carries out mist projection granulating, it is thus achieved that granularity is the granule of 60 microns.Then through dry-pressing formed under 50MPa pressure, then after the quiet molding such as 300MPa is cold, then with the ramp of 3 DEG C/minute to 1400 DEG C and be incubated 2 hours in the high temperature furnace of air atmosphere.It is cooled to 300 DEG C with the speed of 1 DEG C/minute and after stove is as cold as room temperature, obtains ZrO2-Y2O3-Al2O3-Nb2O5Composite ceramics
The crystal structure of this composite ceramics of X-ray diffraction analysis is the monoclinic phase zirconium oxide of the tetragonal phase zirconium oxide of 98.0vol% and 2.0vol%, and the grain size at this composite ceramics of sem analysis is 0.35 μm.Carry out four point bending strength and fracture toughness test at mechanics machine, bending strength is 1158MPa, and fracture toughness is 11.5MPa.m1/2.
This composite ceramics is through the pressure of 0.2MPa after 134 DEG C of hydrothermal treatment consists of steam 5 hours, and its bending strength is 1150MPa, and fracture toughness is 10.8MPa.m1/2, and monoclinic phase zirconia content is 4.9vol%, and tetragonal phase zirconium oxide content is 95.1vol%.
This composite ceramics is through the pressure of 0.2MPa after 134 DEG C of hydrothermal treatment consists of steam 10 hours, and its bending strength is 1128MPa, and fracture toughness is 10.4MPa.m1/2, and monoclinic phase zirconia content is 6.8vol%, and tetragonal phase zirconium oxide content is 93.2vol%.
This composite ceramics is through the pressure of 0.2MPa after 134 DEG C of hydrothermal treatment consists of steam 20 hours, and its bending strength is 1125MPa, and fracture toughness is 10.2MPa.m1/2, and monoclinic phase zirconia content is 7.7vol%, and tetragonal phase zirconium oxide content is 92.3vol%.
Embodiment 2d prepares ZrO2-Y2O3-Al2O3-Nb2O5Composite ceramics
ZrO prepared by embodiment 1d2/Y2O3/Al2O3/Nb2O5Composite granule carries out mist projection granulating, it is thus achieved that granularity is the granule of 60 microns.Then through dry-pressing formed under 50MPa pressure, then after the quiet molding such as 300MPa is cold, then with the ramp of 3 DEG C/minute to 1400 DEG C and be incubated 2 hours in the high temperature furnace of air atmosphere.It is cooled to 300 DEG C with the speed of 1 DEG C/minute and after stove is as cold as room temperature, obtains ZrO2-Y2O3-Al2O3-Nb2O5Composite ceramics.
The crystal structure of this composite ceramics of X-ray diffraction analysis is the tetragonal phase zirconium oxide of 100vol%, and the grain size at this composite ceramics of sem analysis is 0.35 μm.Carry out four point bending strength and fracture toughness test at mechanics machine, bending strength is 1160MPa, and fracture toughness is 11.8MPa.m1/2.
This composite ceramics is through the pressure of 0.2MPa after 134 DEG C of hydrothermal treatment consists of steam 5 hours, and its bending strength is 1160MPa, and fracture toughness is 11.8MPa.m1/2, and monoclinic phase zirconia content is 0vol%, and tetragonal phase zirconium oxide is 100vol%.
This composite ceramics is through the pressure of 0.2MPa after 134 DEG C of hydrothermal treatment consists of steam 10 hours, and its bending strength is 1160MPa, and fracture toughness is 11.8MPa.m1/2, and monoclinic phase zirconia content is 0vol%, and tetragonal phase zirconium oxide content is 100vol%.
This composite ceramics is through the pressure of 0.2MPa after 134 DEG C of hydrothermal treatment consists of steam 20 hours, and its bending strength is 1160MPa, and fracture toughness is 11.7MPa.m1/2, and monoclinic phase zirconia content is 0.9vol%, and tetragonal phase zirconium oxide content is 99.1vol%.
Embodiment 2e prepares ZrO2-Y2O3-Al2O3-Nb2O5Composite ceramics
ZrO prepared by embodiment 1e2/Y2O3/Al2O3/Nb2O5Composite granule carries out mist projection granulating, it is thus achieved that granularity is the granule of 60 microns.Then through dry-pressing formed under 50MPa pressure, then after the quiet molding such as 300MPa is cold, then with the ramp of 3 DEG C/minute to 1400 DEG C and be incubated 2 hours in the high temperature furnace of air atmosphere.It is cooled to 300 DEG C with the speed of 1 DEG C/minute and after stove is as cold as room temperature, obtains ZrO2-Y2O3-Al2O3-Nb2O5Composite ceramics
The crystal structure of this composite ceramics of X-ray diffraction analysis is the tetragonal phase zirconium oxide of 100vol%, and the grain size at this composite ceramics of sem analysis is 0.35 μm.Carry out four point bending strength and fracture toughness test at mechanics machine, bending strength is 1160MPa, and fracture toughness is 11.8MPa.m1/2.
This composite ceramics is through the pressure of 0.2MPa after 134 DEG C of hydrothermal treatment consists of steam 5 hours, and its bending strength is 1160MPa, and fracture toughness is 11.8MPa.m1/2, and crystal structure is the tetragonal phase zirconium oxide of 100vol%.
This composite ceramics is through the pressure of 0.2MPa after 134 DEG C of hydrothermal treatment consists of steam 10 hours, and its bending strength is 1160MPa, and fracture toughness is 11.8MPa.m1/2, and crystal structure is the tetragonal phase zirconium oxide of 100vol%.
This composite ceramics through the pressure of 0.2MPa after 134 DEG C of hydrothermal treatment consists of steam 20 hours, its bending strength is 1160MPa, fracture toughness is 11.7MPa.m1/2, and crystal structure is monoclinic phase zirconia content is 0.5vol%, and tetragonal phase zirconium oxide content is 99.5vol%.
The capital preparation of embodiment 3 hip replacement zirconia-based ceramics
In above-described embodiment 2a-2e, when dry-pressing formed, adopt the rubber mold of hip replacement femoral head shape.Thus obtaining spherical zirconia base composite ceramics sintered body after sintering.Hip joint composite ceramics femoral head prosthesis is prepared in this ground processing of spherical sintered body.
The preparation of zirconia-based ceramics prosthese of embodiment 4 knee prosthesis
In examples detailed above 2a-2e, when dry-pressing formed, adopt the rubber mold of knee-joint prosthesis tibial plateau holder shape.Thus obtaining the zirconia base composite ceramics sintered body of tibial plateau holder shape after sintering.Knee prosthesis zirconia base composite ceramics prosthese is prepared in ground processing.
Claims (6)
1. bone implants prosthese zirconia base composite ceramics, and the chemical composition of described composite ceramics is by the ZrO of 93.30-94.55wt%2, 5.00-6.00wt% Y2O3, 0.10-0.20wt%Al2O3, 0.35～0.50wt%Nb2O5Composition, wherein Y2O3、Al2O3And Nb2O5It is ZrO2Stabilizer；With, described composite ceramics is made up of the tetragonal phase zirconium oxide of 98～100vol% and the monoclinic phase zirconium oxide of 0～2vol% at the crystal phase structure of room temperature；And, wherein said composite ceramics hydrothermal treatment consists 20 hours, it is changed into monoclinic phase zirconium oxide less than the tetragonal phase zirconium oxide equal to 1vol%.
2. the bone of claim 1 implants prosthese zirconia base composite ceramics, wherein ZrO2∶Y2O3∶Al2O3∶Nb2O5Mass ratio be 93.86: 5.52: 0.17: 0.45.
3. the bone of claim 1 implants prosthese zirconia base composite ceramics, wherein ZrO2∶Y2O3∶Al2O3∶Nb2O5Mass ratio be 93.87: 5.52: 0.13: 0.48.
4. the bone of claim 1 implants prosthese zirconia base composite ceramics, and its grain size is less than 0.5 micron.
5. bone arbitrary for manufacturing claims 1-4 implants the method for prosthese zirconia base composite ceramics, including: 1) by ZrOCl2.8H2O aqueous solution, YCl3Aqueous solution, AlCl3Aqueous solution and (NH4)3[NbO(C2O4)3].2H2O aqueous solution, according to required ZrO2: Y2O3: Al2O3: Nb2O5Mass ratio mixes, and obtains ZrO by coprecipitation2/Y2O3/Al2O3/Nb2O5Composite granule, powder size is less than 100 nanometers；2) by 1) in the composite powder that obtains carry out mist projection granulating, obtain the powder that granularity is 50-100 micron；3) by 2) in the powder that obtains after pelletize suppress under the uniaxial pressure of 20-100MPa, obtain a base substrate；4) by 3) in molded body cold isostatic compaction under 200-300MPa pressure of obtaining, obtain secondary base substrate；5) by 4) in secondary base substrate after cold isostatic compaction put in the sintering furnace of air atmosphere, sinter 1-5 hour at 1350-1500 DEG C.
6. bone prepared by prosthese zirconia base composite ceramics implants prosthese to utilize arbitrary for claim 1-4 bone to implant, including hip replacement artificial thigh bone and liner and knee prosthesis knee-joint prosthesis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410382009.3A CN104193331B (en) | 2014-07-30 | 2014-07-30 | Bone implants prosthese zirconia base composite ceramics and bone prepared therefrom implants prosthese |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410382009.3A CN104193331B (en) | 2014-07-30 | 2014-07-30 | Bone implants prosthese zirconia base composite ceramics and bone prepared therefrom implants prosthese |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104193331A CN104193331A (en) | 2014-12-10 |
| CN104193331B true CN104193331B (en) | 2016-07-06 |
Family
ID=52078747
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410382009.3A Active CN104193331B (en) | 2014-07-30 | 2014-07-30 | Bone implants prosthese zirconia base composite ceramics and bone prepared therefrom implants prosthese |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104193331B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106938931A (en) * | 2017-03-13 | 2017-07-11 | 南京云启金锐新材料有限公司 | High purity high dense yttrium stable zirconium oxide ceramics and preparation method thereof |
| CN110256042A (en) * | 2019-06-26 | 2019-09-20 | 福建省德化县邦威陶瓷有限公司 | The anti-folding heatproof and shockproof ceramic blank of one kind, anti-folding heatproof and shockproof ceramic product and preparation method thereof |
| JP6912689B1 (en) * | 2019-12-26 | 2021-08-04 | クラレノリタケデンタル株式会社 | Method for producing processable zirconia composite sintered body, raw material composition of processable zirconia composite sintered body, and processable zirconia composite calcined product |
| CN115304370A (en) * | 2021-05-07 | 2022-11-08 | 苏州宸泰医疗器械有限公司 | Zirconia-yttrium aluminum garnet composite ceramic and bone implant prosthesis prepared from same |
| CN113321505A (en) * | 2021-08-03 | 2021-08-31 | 中南大学湘雅医院 | Zirconia-based ceramic material and preparation method thereof |
| CN116370701A (en) * | 2023-04-12 | 2023-07-04 | 西北工业大学 | Impact-resistant extremely-small curved surface bone scaffold capable of promoting bone differentiation and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044024B (en) * | 2012-12-11 | 2015-08-19 | 北京固圣生物科技有限公司 | Bone implanting prosthetic zirconia base composite ceramics and bone implanting prosthetic prepared therefrom |
| CN103550069B (en) * | 2013-10-30 | 2015-04-22 | 西安博科新材料科技有限责任公司 | Zirconia ceramic material applied to dental restoration and preparation method of zirconia ceramic material |
-
2014
- 2014-07-30 CN CN201410382009.3A patent/CN104193331B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104193331A (en) | 2014-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104193331B (en) | Bone implants prosthese zirconia base composite ceramics and bone prepared therefrom implants prosthese | |
| Nevarez-Rascon et al. | On the wide range of mechanical properties of ZTA and ATZ based dental ceramic composites by varying the Al2O3 and ZrO2 content | |
| CN103044024B (en) | Bone implanting prosthetic zirconia base composite ceramics and bone implanting prosthetic prepared therefrom | |
| KR101639708B1 (en) | Machinable zirconia | |
| JP6637956B2 (en) | Sintered ceramic material, powder composition for obtaining sintered ceramic material, method for producing the same, and ceramic component | |
| Sung et al. | Preparation of hydroxyapatite/zirconia bioceramic nanocomposites for orthopaedic and dental prosthesis applications | |
| JP2018165243A (en) | Zirconia sintered body, and composition and calcined body of zirconia | |
| JP2008050247A (en) | Sintered zirconia having high strength and process for production thereof | |
| CN108439979A (en) | For dental applications, CeO2Stable ZrO2Ceramics | |
| JP2013514104A (en) | Ceramic composite material mainly composed of aluminum oxide and zirconium oxide | |
| JP2010524834A (en) | Sintered compact | |
| Wang et al. | Fabrication of highly translucent yttria-stabilized zirconia ceramics using stereolithography-based additive manufacturing | |
| Kwon et al. | Evaluation of mechanical properties of dental zirconia in different milling conditions and sintering temperatures | |
| Grech et al. | Optimization of two-step sintering conditions of zirconia blanks for dental restorations | |
| JP2002362972A (en) | Zirconia ceramics for living organism and method of manufacturing for the same | |
| CN109467441A (en) | The preparation method of bio-medical silicon nitride compositions and silicon nitride ceramics | |
| Ai et al. | Microstructure and properties of Al2O3-ZrO2 ceramics prepared by microwave sintering | |
| Mansur et al. | Zirconia-calcium phosphate composites for bone replacement | |
| Kim et al. | Effect of solid loading on the sintered properties of 3 mol% yttria-stabilized tetragonal zirconia polycrystals (3Y-TZP) ceramics via slip casting | |
| JP2005131082A (en) | Living body member and artificial joint using the same | |
| Gunduz et al. | Effect of yttria-doping on mechanical properties of bovine hydroxyapatite (BHA) | |
| Amat et al. | Influence of Presintering Parameters on the Mechanical Properties of Presintered Dental Zirconia Block | |
| CN115304370A (en) | Zirconia-yttrium aluminum garnet composite ceramic and bone implant prosthesis prepared from same | |
| Parvin | Structural and mechanical properties of Al2O3-ZrO2 dental bioceramics | |
| CN116785498A (en) | Zirconia ceramic bone implant prosthesis and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C53 | Correction of patent of invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Cao Xiaogang Inventor after: Tian Jiemo Inventor after: Zhang Lin Inventor after: Yin Feng Inventor before: Cao Xiaogang Inventor before: Tian Jiemo Inventor before: Zhang Lin |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: CAO XIAOGANG TIAN JIEMO ZHANG LIN TO: CAO XIAOGANG TIAN JIEMO ZHANG LIN YIN FENG |
|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PP01 | Preservation of patent right | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20200605 Granted publication date: 20160706 |
|
| PD01 | Discharge of preservation of patent | ||
| PD01 | Discharge of preservation of patent |
Date of cancellation: 20201106 Granted publication date: 20160706 |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210322 Address after: 400000 6-1, unit 1, building 7, No.2, Aoyun Road, Jiulongpo District, Chongqing Patentee after: Zheng Bin Address before: 100094 door 2, building 1, 103 Beiqing Road, Haidian District, Beijing Patentee before: BEIJING GUSHENG BIOTECHNOLOGY Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220402 Address after: 215000 room 510-c18, building 2, No. 8, Jinfeng Road, science and Technology City, high tech Zone, Suzhou, Jiangsu Province Patentee after: Suzhou chentai Medical Instrument Co.,Ltd. Address before: 400000 6-1, unit 1, building 7, No.2, Aoyun Road, Jiulongpo District, Chongqing Patentee before: Zheng Bin |