EP1276517A2 - Composant biomedical en zircone dopee a l'yttrium - Google Patents

Composant biomedical en zircone dopee a l'yttrium

Info

Publication number
EP1276517A2
EP1276517A2 EP01929718A EP01929718A EP1276517A2 EP 1276517 A2 EP1276517 A2 EP 1276517A2 EP 01929718 A EP01929718 A EP 01929718A EP 01929718 A EP01929718 A EP 01929718A EP 1276517 A2 EP1276517 A2 EP 1276517A2
Authority
EP
European Patent Office
Prior art keywords
zirconia
component
ceramic
component according
yttrium oxide
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.)
Withdrawn
Application number
EP01929718A
Other languages
German (de)
English (en)
French (fr)
Inventor
Bernard Cales
Laurence Blaise
Franceline Villermaux
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saint Gobain Ceramiques Avancees Desmarquest SAS
Original Assignee
Saint Gobain Ceramiques Avancees Desmarquest SAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Saint Gobain Ceramiques Avancees Desmarquest SAS filed Critical Saint Gobain Ceramiques Avancees Desmarquest SAS
Publication of EP1276517A2 publication Critical patent/EP1276517A2/fr
Withdrawn legal-status Critical Current

Links

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/10Ceramics or glasses
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2/32Joints for the hip
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48Shaped 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
    • C04B35/486Fine ceramics
    • C04B35/488Composites
    • C04B35/4885Composites with aluminium oxide
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    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64Burning or sintering processes
    • C04B35/645Pressure sintering
    • C04B35/6455Hot isostatic pressing
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2/3094Designing or manufacturing processes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2/32Joints for the hip
    • A61F2/34Acetabular cups
    • AHUMAN NECESSITIES
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    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2/32Joints for the hip
    • A61F2/36Femoral heads ; Femoral endoprostheses
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2/38Joints for elbows or knees
    • A61F2/3859Femoral components
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2/38Joints for elbows or knees
    • A61F2/389Tibial components
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2/44Joints for the spine, e.g. vertebrae, spinal discs
    • A61F2/442Intervertebral or spinal discs, e.g. resilient
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2002/30001Additional features of subject-matter classified in A61F2/28, A61F2/30 and subgroups thereof
    • A61F2002/30316The prosthesis having different structural features at different locations within the same prosthesis; Connections between prosthetic parts; Special structural features of bone or joint prostheses not otherwise provided for
    • A61F2002/30329Connections or couplings between prosthetic parts, e.g. between modular parts; Connecting elements
    • A61F2002/30331Connections or couplings between prosthetic parts, e.g. between modular parts; Connecting elements made by longitudinally pushing a protrusion into a complementarily-shaped recess, e.g. held by friction fit
    • A61F2002/30332Conically- or frustoconically-shaped protrusion and recess
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2/3094Designing or manufacturing processes
    • A61F2002/30968Sintering
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2/32Joints for the hip
    • A61F2/36Femoral heads ; Femoral endoprostheses
    • A61F2/3609Femoral heads or necks; Connections of endoprosthetic heads or necks to endoprosthetic femoral shafts
    • A61F2002/3611Heads or epiphyseal parts of femur
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2/32Joints for the hip
    • A61F2/36Femoral heads ; Femoral endoprostheses
    • A61F2/3609Femoral heads or necks; Connections of endoprosthetic heads or necks to endoprosthetic femoral shafts
    • A61F2002/3625Necks
    • A61F2002/3631Necks with an integral complete or partial peripheral collar or bearing shoulder at its base
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/30Joints
    • A61F2/32Joints for the hip
    • A61F2/36Femoral heads ; Femoral endoprostheses
    • A61F2/3609Femoral heads or necks; Connections of endoprosthetic heads or necks to endoprosthetic femoral shafts
    • A61F2002/365Connections of heads to necks
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2220/00Fixations or connections for prostheses classified in groups A61F2/00 - A61F2/26 or A61F2/82 or A61F9/00 or A61F11/00 or subgroups thereof
    • A61F2220/0025Connections or couplings between prosthetic parts, e.g. between modular parts; Connecting elements
    • A61F2220/0033Connections or couplings between prosthetic parts, e.g. between modular parts; Connecting elements made by longitudinally pushing a protrusion into a complementary-shaped recess, e.g. held by friction fit
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2310/00Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00005The prosthesis being constructed from a particular material
    • A61F2310/00011Metals or alloys
    • AHUMAN NECESSITIES
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    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2310/00Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00005The prosthesis being constructed from a particular material
    • A61F2310/00179Ceramics or ceramic-like structures
    • A61F2310/00185Ceramics or ceramic-like structures based on metal oxides
    • A61F2310/00239Ceramics or ceramic-like structures based on metal oxides containing zirconia or zirconium oxide ZrO2
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    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225Yttrium oxide or oxide-forming salts thereof
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    • C04B2235/5418Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
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    • C04B2235/963Surface properties, e.g. surface roughness

Definitions

  • Partially stabilized zirconia and more particularly tetragonal zirconia stabilized with yttrium oxide has been successfully used as a material for biomedical prostheses (see in particular Piconi C , Maccauro G: Zirconia as a ceramic biomaterial. Biomaterials 20: 1-25, 1999; or Cales B, Stefani Y: Yttria-Stabilized Zirconia for Improved Orthocher Prostheses.
  • Wise DL Trantolo DJ, Altobelli DE, et al (eds ).
  • Biomedical components are also known in YTZP zirconia manufactured by densification of green parts, themselves made from zirconia particles containing a deposit of yttrium oxide (W. Burger, HG Richter, C. Piconi et al .. In Andersson ⁇ H, Happonen RP, Yli-Urpo A (eds. Bioceramics 7. Oxford, Butterworth-Heinemann 389-394, - 1994).
  • the addition of yttrium oxide is done by depositing yttrium oxide around the zirconia particles, unlike other powders for which the zirconia-yttrium oxide mixture is obtained by co- precipitation.
  • this method of preparation does not make it possible to obtain sufficient homogeneity of the distribution of yttrium oxide in the sintered zirconia part, since yttrium oxide is mainly concentrated on the surface of the zirconia particles.
  • the object of the invention is to overcome the drawbacks of known solutions, that is to say a subject of a YTZP zirconia material having a high resistance to LTD degradation, having a density close to the theoretical density, and good homogeneity. of the distribution of yttrium oxide.
  • a zirconia material doped with yttrium oxide in particular a YTZP zirconia, having a high resistance to LTD degradation can be obtained: using a doped zirconia powder , with yttrium oxide obtained by co-precipitation, by adding a small amount of alumina powder (for example between approximately 0.05% and 1% by weight), - by producing a green part from the powder mixture, by sintering the green part without pressure, and by subjecting the sintered part to a complementary densification step by hot isostatic compression (HIP).
  • a doped zirconia powder with yttrium oxide obtained by co-precipitation
  • alumina powder for example between approximately 0.05% and 1% by weight
  • the resulting ceramic part has greater resistance to degradation (LTD) than the ceramics obtained according to the traditional methods described above.
  • co-precipitated powders of zirconia and yttrium oxide are used with a homogeneous distribution of yttrium oxide in the zirconia.
  • addition of a small amount of alumina in the green part has the effect of modifying the microstructure of the sintered ceramic part and thus increasing its resistance to degradation ( LTD).
  • LTD resistance to degradation
  • a biomedical component consisting of a ceramic.
  • tetragonal zirconia doped with yttrium oxide comprising at least 90 mol% of zirconia and at least 2.1 mol% of yttrium oxide Y2O3, between 0.01% and 1% by weight of alumina AI2O3, this zirconia having a density of at least 99% of the theoretical density, an average grain size, measured by the linear interception method, not more than 1 ⁇ m and a homogeneous distribution of yttrium oxide.
  • this zirconia is stabilized in tetragonal form by 2.5% to 3.5% by moles of yttrium oxide Y2O3.
  • the YTZP zirconia ceramic of the present invention is characterized by high resistance to degradation (LTD).
  • LTD resistance to degradation
  • this ceramic has a rate of monoclinic phase on the surface of less than 10% by volume (advantageously less than 8% by volume, preferably less than 5% by volume) after 5 cycles of exposure to water vapor at 134 ° C under 2 bar pressure and for 20 hours, for a total exposure of 100 hours.
  • the ceramic contains between 96.5% and 97.5% by mole of zirconia, - the alumina content is between 0.05% and 0.15% by weight, the ceramic has a density of at least 99.5% of the theoretical density, the ceramic has a surface having a roughness Ra of less than 10 nm, the average grain size is less than 0.5 microns.
  • the aforementioned component is advantageously a hip prosthesis head, an insert for an acetabular cup, a tibial plate, a femoral component of knee prosthesis, an intervertebral disc or a component for dental prosthesis.
  • FIG. 1 is a graph showing the evolution of the phase content monoclinic according to the duration of autoclave treatment (in h at 134 ° C under 2 bars) of femoral heads manufactured with a conventional zirconia and with zirconia according to the invention
  • FIG. 2 is an example of a biomedical component, within a hip prosthesis.
  • the monoclinic phase content on the surface of the zirconia ceramic is defined as the monoclinic phase content measured by X-ray diffraction (CuK ⁇ line, penetration depth of 5 nm); the surface roughness Ra is measured by optical interferometry; the yttrium oxide content of the YTZP zirconia is defined in mole% and is calculated only on the basis of the molar fractions of yttrium oxide relative to the sum of zirconia + hafnium oxide (impurity) + d oxide 'yttrium.
  • the zirconia content is considered to include conventional contamination with hafnium oxide (in an amount up to 5%).
  • a preferred method for preparing the YTZP zirconia of the present invention consists in mixing a co-precipitated submicron powder of zirconia, containing 3 mol% of yttrium oxide, to 0.01% by weight of size alumina powder 0.45 ⁇ m on average, pressing the powder mixture by cold isostatic compression between 50 and 400 MPa and machining at the raw state to obtain a raw biomedical component. Once the green component has been produced, it is then sintered between approximately 1300 ° C. and 1500 ° C. for approximately 1 to 4 hours to reach a density of at least 95% of the theoretical density.
  • the sintered part is then subjected to hot isostatic compression (HIP) in an inert gas, such as argon, between approximately 1300 ° C. and 1500 ° C. for 0.5 to 4 hours to reach a density of at least 99.9% of theoretical density.
  • HIP treatment can possibly induce a more or less pronounced blackening of the zirconia ceramic due to the loss of oxygen.
  • the return to stoichiometry and to the desired classic white-cream color is advantageously achieved by annealing at a temperature of 900 ° C. to 1200 ° C. for 2 to 5 hours.
  • the densified component then possibly undergoes final machining in order to have the required geometry.
  • the following steps of the process should preferably be carried out: optimization of the composition, with a content of oxide of yttrium greater than 2.1 mol%, advantageously between 2.5% and 3.5% and preferably between 2.9% and 3.2 mol%, more preferably approximately 3 mol%. sintering at the lowest possible temperature to ensure at least 95% of the theoretical density, for example in the range 1400 ° C - 1450 ° C.
  • the biomedical component has a surface with a roughness less than Ra ⁇ 10 nm and more preferably less than Ra ⁇ 5 nm.
  • the YTZP ceramic having a high resistance to degradation has a low porosity, less than 0.4% by volume, and preferably less than 0.1% by volume.
  • the transformation of the grains of tetragonal zirconia into grains of monoclinic zirconia occurs initially preferably in the vicinity of the porosities present on the surface of the ceramic. So the elimination of porosity tends to decrease the transformation of zirconia into the monoclinic phase.
  • the porosity present in a pressureless sintered YTZP zirconia (which usually has a porosity of at least 1.5% by volume) can be removed by hot isostatic compression (HIP) of this sintered material up to 'to obtain the maximum density.
  • HIP hot isostatic compression
  • the average grain size of the YTZP zirconia is less than 0.5 ⁇ m.
  • the smaller grain size of this ceramic provides the grains with even better resistance to low temperature degradation (LTD).
  • the average grain size of the YTZP zirconia ceramic is in the range 0.30 to 0.45 ⁇ m. In this size range, the grains are small enough to resist degradation at low temperatures, but not too small to eliminate the capacity to transform the tetragonal phase into the monoclinic phase which gives the ceramic its great mechanical properties.
  • effective grain size measurements G
  • average linear intercept size measurements L
  • the biomedical component in zirconia YTZP preferably contains at least 90 mol% of zirconia (including the amount of hafnium oxide). More preferably, it contains 96.5% to 97.5% in moles of zirconia.
  • the YTZP zirconia is stabilized by yttrium oxide at the concentration of 2.5 to 3.5 mol% (percentage based on the zirconia + hafnium oxide fraction), and more preferably from 2.9 to 3.1% by moles.
  • the zirconia in the sintered biomedical component typically comprises at least 95% by volume of tetragonal phase, and preferably at least 99% by volume.
  • the YTZP zirconia contains approximately 0.05% to 1% by weight of alumina, more preferably between 0.05% to 0.15% by weight.
  • the YTZP zirconia grains preferably have an average size of less than 0.5 ⁇ m (Scanning Electron Microscopy, ASTM 112/82), preferably between 0.30 and 0.45 ⁇ m.
  • the alumina grains in the YTZP ceramic have an average size of less than 1 ⁇ m, preferably between 0.3 and 0.8 ⁇ m.
  • the density of the material must be between 99 and 100% of the theoretical density.
  • the open porosity must be less than 0.1% by volume.
  • the biomedical component in YTZP zirconia advantageously has, in the volume, a 4-point flexural strength of at least 1300 MPa and is typically between 1300 MPa and 2000 MPa.
  • the elastic modulus is less than 230 Gpa, and preferably between 200 and 230 GPa.
  • the YTZP zirconia biomedical component typically has a toughness (measured according to the Chantikul formula) of at least 5 MPa m 1/2 and preferably between 5 and 10 MPa m 1/2 .
  • the initial monoclinic phase content on the surface of a YTZP zirconia biomedical component produced according to the process of the present invention is preferably less than 5% by volume and preferably less than 2% by volume.
  • the zirconia ceramic according to the present invention can be evaluated for its resistance to low temperature degradation (LTD) by exposing a polished sample to 5 cycles of 134 ° C. under 2 bar of steam for 20 hours.
  • LTD low temperature degradation
  • the content of monoclinic phase on the polished surface after the test is less than 10% by volume, preferably less than 8% and more preferably less than 5%.
  • the low monoclinic phase content on the surface of the aged material indicates that this YTZP zirconia ceramic is better for resistance to degradation at low temperature and advantageous for application as a biomedical component.
  • a femoral head for hip prosthesis was produced from a co-precipitated submicron powder of zirconia containing 3 mol% of yttrium oxide and comprising an addition of 0.24% by weight of a
  • This part was then polished until a surface with a roughness Ra of less than 5 nm ( ⁇ 0.005 ⁇ m) was obtained.
  • the resistance to aging was evaluated by measuring the monoclinic phase content on the surface of the part by X-ray diffraction, after treatment in an autoclave at
  • the aforementioned femoral head is for example part of the hip prosthesis shown in FIG. 2, cooperating with a femur 1 by a rod 2, and with the pelvic bone 15.
  • a first part 3 of the femoral rod 2 is implanted in the femur 1.
  • the second part of the femoral stem 2 has the shape of a truncated cone 4 which cooperates with a ceramic head according to the invention 5.
  • the recess that this head has has approximately the same angle at the top as the cone 4 and is adjusted by force thereon.
  • the conical wall 6 of the femoral head 5 defined by the frustoconical recess is in contact over most of its length with the surface 7 of the truncated cone 4.
  • a reserve 8 between the truncated cone 4 and the apex 16 of the conical recess of the femoral head is also shown.
  • the junction 12 between the top 16 of the conical recess and the conical wall 6 can be formed in certain realizations by a cylinder with connecting radii or by a recess.
  • an acetabular cup 13 having an insert insert made of YTZP zirconia ceramic 14 which is held by conical fixation in a metal support 17, is adapted in the pelvic bone 15.
  • the YTZP 5 zirconia ceramic head is positioned in the zirconia ceramic insert 14 of the acetabular cup 13 to form the hip joint.
  • the zirconia component YTZP according to the present invention can be used in any part of the body where alumina, zirconia ceramics or alumina-zirconia composites (ZTA) are usually used.
  • ZTA alumina-zirconia composites
  • These applications include: the heads of hip prostheses, such as the configurations presented in US Patents 5,181,929; US no. 4,964,869 and US no. 5,972,033, - monolithic acetabular cups, modular acetabular cups for conical fixing in a metal support (metal-back), such as the configurations shown in US patents no. 5,879,397; US No. 5,609,647 and US No.
  • an acetabular cup intended to receive a hip prosthesis head having a substantially spherical convex external surface
  • the cup comprising: a ceramic zirconia component YTZP of the present invention having a surface essentially spherical concave for receiving and allowing the rotation of the convex spherical surface of the hip prosthesis head, and a metal support in which the acetabular cup is fixed, preferably by tight adjustment, either i) directly inside support metal, or ii) by means of a plastic insert, itself fixed by a tight fit in the metal support.
  • an acetabular cup insert made of YTZP zirconia intended to receive a hip prosthesis head having a substantially spherical convex external surface
  • the insert comprising: a surface essentially spherical concave making it possible to receive and allow the rotation of the convex spherical surface of the hip prosthesis head, and - an external surface with an appropriate shape, preferably comprising a frustoconical shape, for fixing in the metal support.
  • a YTZP zirconia hip prosthesis head comprising: a substantially spherical convex external surface, and a conically shaped recess extending towards the inside from the outside diameter of the head, said recess having a suitable shape to allow attachment to the metal cone of a femoral prosthesis rod by contact between the wall of the recess and the first part of the metal cone.
  • a prosthesis in particular a hip prosthesis, comprising: an essentially spherical ceramic head made of YTZP zirconia according to the present invention, and an acetabular cup having a concave surface essentially spherical made of zirconia YTZP according to the present invention and making it possible to receive and allow the rotation of the convex spherical surface of the hip prosthesis head (this case corresponds to that of FIG. 2).
  • a dental prosthesis component with the ceramic according to the invention.

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EP01929718A 2000-04-27 2001-04-26 Composant biomedical en zircone dopee a l'yttrium Withdrawn EP1276517A2 (fr)

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