WO2009103775A2 - Procédés et compositions pour créer par enduction un composite atomique de céramiques enduites de titane - Google Patents

Procédés et compositions pour créer par enduction un composite atomique de céramiques enduites de titane Download PDF

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WO2009103775A2
WO2009103775A2 PCT/EP2009/051999 EP2009051999W WO2009103775A2 WO 2009103775 A2 WO2009103775 A2 WO 2009103775A2 EP 2009051999 W EP2009051999 W EP 2009051999W WO 2009103775 A2 WO2009103775 A2 WO 2009103775A2
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titanium
ceramic
titanium compound
layer
plasma
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PCT/EP2009/051999
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WO2009103775A3 (fr
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Sorin Lenz
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Sorin Lenz
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Priority claimed from EP08151711A external-priority patent/EP2018879B1/fr
Application filed by Sorin Lenz filed Critical Sorin Lenz
Priority to US12/918,791 priority Critical patent/US8507049B2/en
Publication of WO2009103775A2 publication Critical patent/WO2009103775A2/fr
Publication of WO2009103775A3 publication Critical patent/WO2009103775A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
    • C04B41/90—Coating or impregnation for obtaining at least two superposed coatings having different compositions at least one coating being a metal
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/20—Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
    • A61K6/807—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising magnesium oxide
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
    • A61K6/816—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising titanium oxide
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
    • A61K6/818—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising zirconium oxide
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
    • A61K6/82—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising hafnium oxide
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
    • A61K6/822—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising rare earth metal oxides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
    • A61K6/824—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising transition metal oxides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/84—Preparations for artificial teeth, for filling teeth or for capping teeth comprising metals or alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/10—Ceramics or glasses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
    • A61C8/00—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools
    • A61C8/0012—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the material or composition, e.g. ceramics, surface layer, metal alloy
    • A61C8/0013—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the material or composition, e.g. ceramics, surface layer, metal alloy with a surface layer, coating
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00836—Uses not provided for elsewhere in C04B2111/00 for medical or dental applications

Definitions

  • This invention is in the field of ceramics and ceramic production.
  • the invention is in particular in the field of ceramics with titanium surface layers.
  • Such ceramics with one or more titanium surface layers according to the invention may be used as dental implants comprising for example an anchoring part for anchoring within the bone and comprising a mounting part for receiving an element to be attached, such as an abutment or a crown, a bridge or a prosthesis construction.
  • the invention also relates to other applications of the ceramic titanium combination, such as its use in the field of ammunition or projectiles.
  • Dental implants have been successfully used since more than 10 years.
  • the major part of the dental implants currently used consist of titanium, since titanium has a sufficiently low elastic modulus and also has a relatively large strength.
  • a safe integral osteogenesis can be reached when the surface is suitably treated (e.g. roughened by sand blasting).
  • the titanium implants after reaching a primary stability by screwing into the bone, safely ossify within a healing time of about 3 to 4 months so that a permanent bond between the anchoring part screwed into the bone and the bone is guaranteed.
  • two-part implants are utilized. Basically, there are to possibiiities for this end:
  • the anchoring part of the implant is embedded until the bone ridge so that the mucoperiost cover can be sewn above the implant.
  • a drawback is the necessary secondary operation at the end of the primary healing phase for allowing a subsequent application of a mounting part and thereon the desired prosthesis or crown.
  • the anchoring part of the implant can be sunk in up to about 3-5 mm above the bone ridge at mucosal level, thus avoiding a secondary operation.
  • the wound edges can be directly adapted to the implant neck portion, thereby effecting a primary soft tissue closure to the implant.
  • Ceramic abutments offer particular advantages during the subsequent matching of the supra-construction, such as bridges or crowns, to the abutment. They can be simply ground and allow to build constructions using prior art processes known to the dentist. Ceramic abutments offer particular advantages due to the fact that their color can be closely matched to the natural tooth color. Lately also abutments of zirconia have been developed which offer a particularly high strength.
  • Such a system consisting of two-part impiants having an anchoring part and a mounting part, an abutment and a prosthesis applied thereon offers a good matching to the geometric situation for different indications, however, generally the multitude of the components used is detrimentai for the mechanical stability of the total system. Also each further bonding leads to possible starting points for bacteria which may cause parodontitis or gingivitis with the gap.
  • zirconia ceramics have become available that have an extremely high strength, in particular when the shaped bodies are prepared by hot isostatic pressing or by subsequent hot isostatic densifying.
  • Such a zirconia ceramic which may roughly comprise 92.1-93.5 wt-% ZrO 2 , 4.5-5.5 wt. ⁇ % Y 2 O 3 and 3.8-2.2 wt-% HfO 2 is for instance known from U.S. Pat. No. 6,165,925.
  • zirconia ceramic as a material for making the anchoring part of an implant seems not possible, since a sufficient mechanica! stability of a zirconia ceramic is necessary, this requiring a highly dense preparation, practically without any porosity to be measured, this simultaneously leading to a clean cut extremely hard surface.
  • the present invention solves the problems outlined above by providing for a method which leads to an extreme bonding strength between a given ceramic unit and its titanium layer.
  • the present invention relates to a method for the coating of a surface of a ceramic basic body with a titanium compound, comprising the steps of (i) providing a preformed ceramic material; (ii) at least one step of surface activation of said ceramic material using a plasma for plasma-chemical surface preparation wherein the plasma comprises high-energy ions; (iii) at least one step of applying a titanium compound bonding layer to said ceramic material by plasma-supported coating wherein the plasma-supported coating is performed in an pulsed and/or non-pulsed fashion; (iv) at least one step of applying a functional titanium compound layer by pulsed plasma-supported coating.
  • the invention also relates to novel compositions as well as uses of the novel compositions.
  • Fig. 3 Scanning electron micrograph (20 ⁇ m) of surface.
  • Fig. 4 Scanning electron micrograph of the ceramic-titanium interface of a titanium- coated ceramic basic body (20 ⁇ m)
  • Fig. 5 Scanning electron micrograph of the fracture surface of the ceramic-titanium interface of a titanium-coated ceramic basic body (20 ⁇ m)
  • Fig. 6 Scanning electron micrograph of the fracture surface of the ceramic-titanium interface of a titanium-coated ceramic basic body (5 ⁇ m)
  • Fig. 7 Dispersive X-ray spectroscopy of the ceramic-titanium interface.
  • FIG. 8 Schematic drawing of implant - abutment (7).
  • (1 ) is the zircon body; (2) is the zircon face without coating; (3) is the titanium face (cover with titanium intraossar); (4) tissue; (5) bone; (6) bone at border of implant entry point
  • Fig. 9 is the same as Fig. 8 but a one piece implant. Schematic drawing of implant - abutment. (1 ) is the zirconium body; (2) is the zirconium face without coating; (3) is the titanium face (cover with titanium intraossar)
  • FIG. 10 Two piece implant with abutment, other than Fig. 8 and 9. Schematic drawing of implant - abutment.
  • (1 ) is the zirconium body; (2) is the zirconium face without coating; (3) is the titanium face (cover with titanium)
  • Fig, 11 Example of an artificial hip joint.
  • (1 ) is the zirconium body; (2) is the zirconium face without coating; (3) is the titanium face (cover with titanium intraossar); (4) tissue; (5) bone; (6) bone at border of implant entry point; 7,8 artificial hip; (7) femur; (8) pelvic bone.
  • Fig. 13 Scanning electron micrograph of the ceramic-titanium interface of a titanium- coated ceramic basic body (1 ⁇ m) (1) is the zircon body; (3) is the titanium face; (9) is the atomic bonding of between layers of Ti and ceramics body; (10) is the surface Fig. 14 Scanning electron micrograph of the ceramic-titanium interface of a titanium- coated ceramic basic body (200nm), Enlargement of Fig. 13 (1) is the zircon body(3) is the titanium face; (9) is the atomic bonding of between layers of Ti and ceramics body; The Distance from Pa1 to PaR1 is 140,5nm
  • Fig. 15 Scanning electron micrograph of the ceramic-titanium interface of a titanium- coated ceramic basic body (3 ⁇ m); (1 ) is the zircon body; (3) is the titanium face; (9) is the atomic bonding of between layers of Ti and ceramics body; (a) is zircon- concentration (b) is Ti-concentration; (c) is O 2 -concentration; The overlap of the Zircon- and Ti-concentration in the area of interconnection of titanium face and zircon body demonstrates atomic bonding. Concentration of the respective elements has been determined using Energy Dispersive X-ray (EDX)analysis.
  • EDX Energy Dispersive X-ray
  • the present invention relates to a method for the coating of a surface of a ceramic basic body with a titanium compound, comprising the steps of (i) providing a preformed ceramic material; (ii) at least one step of surface activation of said ceramic material using a plasma for piasma-chemical surface preparation wherein the plasma comprises high-energy ions; (iii) at least one step of applying a titanium compound bonding layer to said ceramic material by plasma-supported coating wherein the plasma-supported coating is performed in pulsed and/or non-pulsed fashion; (iv) at least one step of applying a functional titanium compound layer by pulsed plasma-supported coating.
  • High-energy ions in the context of the present invention are ions having energies in the range of from 1 MeV to 2.3 MeV.
  • the surface activation step (ii) is performed under an inert gas atmosphere.
  • the inert gas is a noble gas; most preferably the noble gas is selected from the group of argon, xenon and krypton.
  • the high- energy ions are titanium ions.
  • Step (ii) is preferably an ion implantation of titanium ions into the ceramics surface.
  • the implantation dose is from about 10 15 to 10 16 ions per cm 2 .
  • step (H) etching of the surface takes place at an etching speed of preferably between 5 and 32 nm/min.
  • step (iii) may take place at temperatures of from 50 to 300 0 C.
  • Step ⁇ iii) may be performed at a partial pressure of from about 10" 5 mbar to about 1 mbar, preferably of from 10" 5 mbar to 10' 3 mbar.
  • the ions implanted in step (ii) are substantially not melt away during steps (iii) and (iv).
  • the coating method according to the present invention leads to titanium coatings that adhere very tightly to the ceramic basic body. At the Interface of the ceramic body and the titanium compound bonding layer, a composite is formed at atomic level between the ceramic basic body and the titanium compound layer.
  • the properties of the resulting titanium compound bonding layer can be adjusted.
  • Alternating pulsed and non-pulsed schemes may in some embodiments be used.
  • Preferably, oniy pulsed plasma supported coating is used in step (iii). Variation of the energy used during the plasma-supported coating steps, e.g. by varying the applied voltage or the pulsing scheme, results in a variation of the physical properties of the titanium compound layers.
  • the titanium compound bonding layer mediates the adherence of the titanium functional layer to the ceramic basic body and thereby provides a good interlocking between the ceramic material of the ceramic basic body and the functional titanium compound layer.
  • the titanium compound bonding layer and the titanium compound functional layer may gradually merge at their interface.
  • titanium compound functional layer titanium compound functional layer
  • functional titanium compound layer titanium compound-coated surface layer
  • the titanium compound bonding layer has a thickness of from 1 nm to 4 ⁇ m, from 1 nm to 3 ⁇ m, from 1 nm to 2 ⁇ m, from 1 nm to 1 ⁇ m, from 10 nm to 3 ⁇ m, from 100 nm to 3 ⁇ m, preferably from 4 nm to 3 ⁇ m, more preferably of from 1 ⁇ m to 100 ⁇ m, most preferably of from 5 ⁇ m to 18 ⁇ m.
  • the functional titanium compound layer has a thickness of from 0.1 ⁇ m to 200 ⁇ m, 0.1 ⁇ m to 100 ⁇ m, 0.1 ⁇ m to 50 ⁇ m, more preferably from 0.1 ⁇ m to 20 ⁇ m, more preferably from 0.1 ⁇ m to 15 ⁇ m, even more preferably from 0,1 ⁇ m to 10 ⁇ m, most preferably of from 5 ⁇ m to 18 ⁇ m.
  • one or more of the steps of the method are controlled by means of programmable logical control (PLC).
  • PLC programmable logical control
  • MFC mass flow control
  • the titanium compound according to the present invention is (elementary) titanium, titanium dioxide, titanium nitride, or a titanium alloy.
  • the titanium compound may in some embodiments be a compound of titanium with elements of the 14 th (e.g. C, Si, Ge, Sn, Pb), 15th ( e .g. N, P, As, Sb, Bi) or 16th ( e . g . o, S, Se, Te, Po) group of the periodic table.
  • the titanium compound is elementary titanium. Therefore, titanium compound (bonding and functional) layers relate e.g. to titanium layers, titanium dioxide layers, titanium nitride layers or titanium alloy layers, preferably titanium layers. Also mixtures of different titanium compounds may be used.
  • the surface of the functional titanium compound layer is nitrated. This results in a hardening of the surface of the functional titanium compound layer. Nitration can for example be achieved by a step of plasma-supported thermo-chemical nitration. This is preferred for hard coatings.
  • the surface of said preformed ceramic material is only partially coated with a titanium compound coating.
  • the method additionally comprises a step of applying a microporous titanium compound layer. This results in an enlargement of surface area.
  • the titanium compound is biocompatible.
  • the functional titanium compound layer is biocompatible. This enables the use of compositions prepared by the methods according to the present invention in medicinal contexts.
  • the ceramic material according to the present invention may comprise zirconium dioxide (zirconia), aluminium oxide (alumina), titanium dioxide (titania), silicon nitride, yttrium oxide, hafnium oxide, silicon oxide (silica), magnesium oxide
  • the ceramic material is zirconium oxide or comprises zirconium oxide. Zirconium oxide has a white colour and therefore is preferred for the use in dental contexts.
  • the preformed ceramic materia! provided in step (i) is preformed before sintering, i.e. green ceramic material is preformed and then sintered,
  • Green ceramic material in the context of the present invention relates to unsintered ceramic material.
  • the titanium compound coating described herein is performed on sintered ceramic material, i.e. steps (ii) to (iv) of the method of the present invention are performed on a sintered preformed ceramic material.
  • the ceramic material is preformed before sintering, i.e. the green ceramic material is shaped and preformed.
  • This has the advantage that green ceramic material is relatively soft and easy to shape as compared to the relatively hard ceramic material after sintering.
  • One advantage of the method according to the present invention is thus the possibility to produce individualized (customized) implants at comparably low costs, e.g. shaping the implants using 3D reconstruction techniques to resemble the anatomical structures to be replaced.
  • the green ceramic material can be pressed or may for example be shaped by lathing, milling, drilling or cutting, it is known to a skilled person, that lathing, milling, drilling and cutting machines may be operated manually or under computer numerical control (CNC).
  • CNC computer numerical control
  • the preformed ceramic material can be mechanically or physically treated before or after sintering, e.g. for surface enlargement.
  • such mechanical or physical treatment is performed on the green ceramic material, i.e. before sintering.
  • Mechanical treatment in the context of the present invention comprises inter alia grinding.
  • Physical treatment comprises in the context of the present invention inter alia the treatment by a sandbiaster, a laser beam or a high pressure water jet.
  • the sintered ceramic material may also be chemically treated, e.g. chemically treated by an acid or a mixture of acids.
  • an acid or acid mixture may be selected from the group consisting of phosphoric acid, sulphuric acid, hydrochloric acid, hydrofluoric acid, nitric acid, nitric acid/hydrochloric acid mixture or hydrochloric acid/sulphuric acid mixture.
  • the method additionally comprises the step of increasing to surface area of said functional titanium compound layer by chemically, mechanically or physically treating the functional titanium compound layer.
  • An enlarged surface can improve for example the osseo-integration when titanium-coated ceramic materia! is used in medicinal contexts, e.g. as an implant.
  • the method comprises a step of coating the titanium compound-coated surface layer ⁇ i.e. the functional titanium compound layer) with an additional layer of a biocompatible materia! and/or an additional bioactive surface layer.
  • the biocompatible material is in a preferred embodiment selected from the group consisting of hydroxylapatite and tricalciumphosphate and the bioactive surface layer comprises a composition selected from the group of antibiotic, growth factor, peptide, fibronectin and anti-inflammator.
  • Hydroxyiapatite and tricalciumphosphate are osseoactive, i.e. they mediate and/or facilitate osseointegration.
  • the antibiotic in the context of the present invention can for example be selected from the group of Amikacin, Gentamicin, Kanamycin, Neomycin, Netilmicin, Paromomycin, Streptomycin, Tobramycin, Cephalosporins, Fluoroquinolone antibiotics, Azithromycin, Erythromycin, Clarithromycin, Dirithromycin, Roxithromycin, Telithromycin, Penicillins, Ampicillin, Sulfonamides, Tetracycline antibiotics, Clindamycin, Metronidazole, and Vancomycin.
  • the growth factors in the context of the present invention can for example be selected from the group of Transforming growth factor beta (TGF- ⁇ ) t Granulocyte- colony stimulating factor (G-CSF), Granulocyte-macrophage colony stimulating factor (GM-CSF), Nerve growth factor (NGF), Neurotrophins, Platelet-derived growth factor (PDGF), Erythropoietin (EPO), Thrombopoietin (TPO) 5 Myostatin
  • TGF- ⁇ Transforming growth factor beta
  • G-CSF Granulocyte- colony stimulating factor
  • GM-CSF Granulocyte-macrophage colony stimulating factor
  • NGF Nerve growth factor
  • Neurotrophins Neurotrophins
  • PDGF Platelet-derived growth factor
  • EPO Erythropoietin
  • TPO Thrombopoietin 5 Myostatin
  • GDF-8 Growth differentiation factor-9
  • GDF9 Acidic fibroblast growth factor (aFGF or FGF-1 )
  • EGF Epidermal growth factor
  • HGF Hepatocyte growth factor
  • IGFs Insulin-like growth factors
  • BMPs Bone Morphogenetic Proteins
  • the anti-inflammator in the context of the present invention can for example be selected from the group of glucocorticoids, corticosteroids and non-steroidal antiinflammatory drugs (e.g. ibuprofen, aspirin and naproxen).
  • non-steroidal antiinflammatory drugs e.g. ibuprofen, aspirin and naproxen.
  • a peptide can for example be a bioactive peptide such as RGD.
  • said bioactive surface layer comprises osseous stem ceils or chondral stem cells or a mixture thereof. These stem cells improve osseointegration of the titanium-coated ceramic materials according to the present invention.
  • the present invention also relates to the use of the above described methods for the preparation of a medicinal implant.
  • Medical in the context of the present invention relates to the fields of human medicine, dentistry, veterinary medicine and dental veterinary medicine. Therefore, medicinal impiants also comprise e.g. implants and dental implants for humans and animals.
  • the medicinal implants are in preferred embodiments of the invention selected from the group consisting of dental implant, hip implant, epithesis, artificial joint and prosthesis.
  • a medicinal implant in the context of the present invention is a medicinal device prepared to replace and act as a missing biologicai structure in a human or animal body.
  • a prosthesis is an artificial extension that replaces a missing (e.g. because of a disease, an accident or an amputation) body part, whereas an epithesis has primarily a cosmetic function (e.g. as an artificial eye or ear).
  • Medicinal implants and in particular prostheses can be used to replace bioiogicai structures, such as bones or part of bones, in nearly ail parts of the body, e.g. scull, teeth, (upper and lower) arm, elbow, (upper and lower) leg, hip, toes, fingers, knee, spine, joints and the like.
  • hearing aids artificial limbs, replacement joints and hair prostheses (wigs) are medicinal implants in the context of the present invention. Also implants for the anchoring of other implants such as protheses, epitheses and wigs are within the scope of the invention. In very particular embodiments, hearing aids may be integrated into other implants.
  • Implants and dental implants are in some embodiments of the present invention multi- or single-part implants.
  • only the part(s) of the medicinal implant, and dental implant in particular, that has/have contact with a bone is titanium compound-coated.
  • the dental implant is in a particular embodiment a one-piece implant or a two-piece implant.
  • the dental implant may comprise a screw thread.
  • the dental implant comprises an anchoring part for anchoring said implant in the bone and a mounting part for receiving a prosthetic superstructure, wherein only the anchoring part is coated with the biocompatible titanium compound, in one particular embodiment of a two-piece dental implant, the surface area on one part (e.g. on the abutment) which makes contact to the other part (i.e. a "plug-and-socket connection" between implant and abutment), is titanium-coated.
  • no screw connection is necessary between the two parts because a good fitting accuracy can be reached, resulting in a high stability of the connection.
  • the implant is an artificial joint and the preformed ceramic material is monolithic.
  • at least one part of the artificial joint is titanium compound coated.
  • a pair of two parts which can slide relative to each other is present.
  • the surface of only one part is titanium-compound coated.
  • the surface of both parts is coated or at least coated in part.
  • a "ball-and-socket" artificial hip joint i.e. an artificial hip replacement
  • only the part of the surface of the joint implant which makes contact to the ball of the joint is coated or vice versa.
  • titanium cup which is present in some state-of-the-art hip replacements, can be omitted according to the present invention.
  • one or both blocks may be titanium coated according to the present invention.
  • a ceramic implant makes contact to another part that is made of other materials such as polyethylene, only the area that is involved in the contact is coated with a biocompatible titanium layer.
  • the biocompatible titanium coating on parts of artificial joints, particularly hip joints, can avoid squeaking or other unwanted noises which may occur during movement of these joints.
  • the coating of the sphere in the artificial hip joint may be used to reduce squeaking noises and the titanium coating serves as a lubricant.
  • the implant is a muitipart-implant, e.g. a two-part-implant (such as a "plug- and-socket connection" in an artificial hip joint)
  • a two-part-implant such as a "plug- and-socket connection" in an artificial hip joint
  • only one part e.g. the part inserted into the sphere in an artificial hip joint
  • a biocompatible titanium compound layer e.g. the part inserted into the sphere in an artificial hip joint
  • plug connections are concerned, only the plug in one part is coated and the borehole in another part is not coated.
  • An example for such an embodiment is an artificial hip joint.
  • Such a titanium compound coated ceramic projectile has a hard ceramic body and a relatively soft titanium compound surface. This allows a better penetration of the target.
  • the titanium layer serves as a lubricant.
  • the projectile is e.g. a munitions projectile.
  • the term "projectile” herein also refers to all kinds of ballistic bodies, e.g. rockets, grenades, munitions for firearms, crossbows and the like.
  • the present invention also relates to a composition
  • a composition comprising a ceramic material coated with a titanium compound, obtainable with any of the methods described herein.
  • Such a composition may in some embodiments also comprise an additional layer of diamond-like carbon (DLC).
  • DLC is an amorphous hard carbon.
  • the composition may comprise one or more additional metal coating layers such as gold, silver, platinum, aluminium, copper, iron, nickel, tin, tantalum, zinc and/or chromium and/or alloys such as steel or bronze.
  • a ceramic composition comprising a ceramic part and at least a first biocompatible titanium compound layer, wherein said titanium compound layer has a thickness of from 0.1 to 1 mm, preferably 0.1 to 100 ⁇ m, more preferably of from 0.5 to 50 ⁇ m, and wherein the bonding strength between the ceramic part and said at least first titanium layer when measured by applying a load at a stretching speed of 1 mm/minute until the test piece is broken, is above 100 MPa, preferably above 200 MPa, more preferably above 700 MPa, even more preferably above 900 MPa, most preferably above 1200 MPa.
  • the titanium layer breaks under these conditions only upon breakage of the ceramic part.
  • a homogenous film of pure titanium was used as specified in the description.
  • the body is made of ceramic.
  • the film on top is pure titanium with a thickness of 6- 16 ⁇ m.
  • One of the prototypes was used for analysing the break point as well as the flaking properties of the layer.
  • the layers were analysed using the scanning electron microscopy.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Ceramic Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Epidemiology (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Dermatology (AREA)
  • Transplantation (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Physical Vapour Deposition (AREA)
  • Chemical Vapour Deposition (AREA)
  • Materials For Medical Uses (AREA)
  • Prostheses (AREA)

Abstract

La présente invention concerne un procédé permettant d'enduire d'un composé au titane une surface d'un corps de base en céramique. Ce procédé comporte les opérations suivantes: (i) mise à disposition d'un matériau en céramique préformée; (ii) au moins une opération d'activation de surface de la céramique considérée en utilisant un plasma de façon à préparer chimiquement la surface au moyen du plasma, lequel plasma comprend des ions de hautes énergies; (iii) au moins une opération consistant à enduire d'une couche de liaison en composé au titane le matériau de céramique considéré, l'enduction sous plasma se faisant en mode pulsé et/ou en mode non pulsé; (iv) au moins une opération consistant à appliquer une couche fonctionnelle de composé au titane sous plasma pulsé. L'invention concerne également de nouvelles compositions ainsi que des utilisations de ces nouvelles compositions.
PCT/EP2009/051999 2007-07-25 2009-02-19 Procédés et compositions pour créer par enduction un composite atomique de céramiques enduites de titane WO2009103775A2 (fr)

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EP08151711.2 2008-02-20
EP08151711A EP2018879B1 (fr) 2007-07-25 2008-02-20 Utilisation du procédé de création d'un composite atomique de céramiques revêtues de titane

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012068239A1 (fr) 2010-11-17 2012-05-24 Zimmer, Inc. Implants monoblocs en céramique à surfaces de fixation ostéo-intégrées
WO2013034583A1 (fr) 2011-09-06 2013-03-14 Vita Zahnfabrik H. Rauter Gmbh & Co. Kg Procédé pour la préparation d'implants en céramique à des fins médicales

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Publication number Priority date Publication date Assignee Title
JPS6421054A (en) * 1987-07-14 1989-01-24 Furukawa Electric Co Ltd Film forming method
EP0606566A1 (fr) * 1992-12-07 1994-07-20 Nobelpharma AB Méthode de préparation des surfaces de corps d'implantation
US20010036530A1 (en) * 2000-03-27 2001-11-01 Kyocera Corporation Biomedical implant material and method of producing the same
US20030175444A1 (en) * 1999-12-23 2003-09-18 Nan Huang Method for forming a tioss(2-x) film on a material surface by using plasma immersion ion implantation and the use thereof
US20050106534A1 (en) * 2001-11-30 2005-05-19 Michael Gahlert Ceramic dental implant

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6421054A (en) * 1987-07-14 1989-01-24 Furukawa Electric Co Ltd Film forming method
EP0606566A1 (fr) * 1992-12-07 1994-07-20 Nobelpharma AB Méthode de préparation des surfaces de corps d'implantation
US20030175444A1 (en) * 1999-12-23 2003-09-18 Nan Huang Method for forming a tioss(2-x) film on a material surface by using plasma immersion ion implantation and the use thereof
US20010036530A1 (en) * 2000-03-27 2001-11-01 Kyocera Corporation Biomedical implant material and method of producing the same
US20050106534A1 (en) * 2001-11-30 2005-05-19 Michael Gahlert Ceramic dental implant

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012068239A1 (fr) 2010-11-17 2012-05-24 Zimmer, Inc. Implants monoblocs en céramique à surfaces de fixation ostéo-intégrées
US9248020B2 (en) 2010-11-17 2016-02-02 Zimmer, Inc. Ceramic monoblock implants with osseointegration fixation surfaces
WO2013034583A1 (fr) 2011-09-06 2013-03-14 Vita Zahnfabrik H. Rauter Gmbh & Co. Kg Procédé pour la préparation d'implants en céramique à des fins médicales
KR20140056249A (ko) * 2011-09-06 2014-05-09 비타 찬파브릭 하. 라우터 게엠베하 & 코.카게 의료용 세라믹 임플란트 제조 방법
US9241795B2 (en) 2011-09-06 2016-01-26 Vita Zahnfabrik H. Rauter Gmbh & Co. Process for preparing ceramic implants for medical purposes
KR102005950B1 (ko) 2011-09-06 2019-08-01 비타 찬파브릭 하. 라우터 게엠베하 & 코.카게 의료용 세라믹 임플란트 제조 방법

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