EP1744997A1 - Composite hydroxylapatite-m tal et proc d de fabrication dudit composite - Google Patents

Composite hydroxylapatite-m tal et proc d de fabrication dudit composite

Info

Publication number
EP1744997A1
EP1744997A1 EP04804140A EP04804140A EP1744997A1 EP 1744997 A1 EP1744997 A1 EP 1744997A1 EP 04804140 A EP04804140 A EP 04804140A EP 04804140 A EP04804140 A EP 04804140A EP 1744997 A1 EP1744997 A1 EP 1744997A1
Authority
EP
European Patent Office
Prior art keywords
hydroxyapatite
metal
hydroxylapatite
composite material
metal composite
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Withdrawn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
EP04804140A
Other languages
German (de)
English (en)
Inventor
Jianmin Institut für Physikalische und Theo SHI
Ulrich Bismayer
Arndt Klocke
Bogdan Palosz
Stanislaw Gierlotka
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.)
Universitatsklinikum Hamburg Eppendorf
Universitaet Hamburg
Instytut Wysokich Cisnien of PAN
Original Assignee
Universitatsklinikum Hamburg Eppendorf
Universitaet Hamburg
Instytut Wysokich Cisnien of PAN
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 Universitatsklinikum Hamburg Eppendorf, Universitaet Hamburg, Instytut Wysokich Cisnien of PAN filed Critical Universitatsklinikum Hamburg Eppendorf
Publication of EP1744997A1 publication Critical patent/EP1744997A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/42—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
    • A61L27/425—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix of phosphorus containing material, e.g. apatite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/50—Preparations specially adapted for dental root treatment
    • A61K6/58—Preparations specially adapted for dental root treatment specially adapted for dental implants
    • 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
    • A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
    • A61K6/838—Phosphorus compounds, e.g. apatite
    • 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
    • A61K6/844—Noble metals
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C04B35/645—Pressure sintering

Definitions

  • the invention relates to a hydroxyapatite-metal composite and a method for its production.
  • Metals and ceramics have been used for many years as a replacement for hard, usually human body tissue. Materials that are used for implantation in the human body to replace damaged or diseased tissue must be biocompatible and have suitable mechanical properties.
  • the use of metal and bio-inert ceramics for biomedical applications encounters many problems due to their high modulus of elasticity (compared to that of bone) or the formation of a non-adherent fibrous capsule (the resulting movement of which can impair the functionality of the implant) (L.L. Hench, 1998; M. Long et al. 1998)). Even bioactive ceramics are limited in their usability due to their limited mechanical properties (W. Suchanek et al. 1998).
  • biomaterials based on hydroxyapatite have been developed in recent years using particles, whiskers and long fibers as reinforcements to improve their mechanical reliability (W. Bonefield et al. 1981).
  • metal particles are a preferred reinforcement for hydroxylapatite based composites (C. Chu et al. 2002, X. Zhang et at. 1997; J. Choi et at. 1998).
  • it did not have a significant stiffening effect reported.
  • the reactivity of some metals, such as Ti promotes the decomposition of hydroxyapatite in tricalcium phosphate during sintering (CQ Ning et at. 2002).
  • No. 4,708,652 describes an apatite composite ceramic which has a crosslinked fluorapatide structure and at least partially crystallized, biologically active glass.
  • the ceramic is obtained by reaction sintering a powdery mixture of hydroxyapatite and biologically active glass, which contains fluoride ionides, at a temperature of 700 to 1000 ° C.
  • the composite ceramic obtained in this way should have a high mechanical strength and good biological compatibility.
  • the elasticity property of such a composite ceramic is essentially based on the presence of the glass. Furthermore, jumps cannot be completely prevented.
  • JP 11240782 discloses a process for producing a metal-impregnated hydroxyapatite which is said to have high mechanical strength.
  • a densely sintered hydroxyapatite is first pre-sintered and placed with the metal in a heat and pressure-resistant vessel.
  • the hydroxyapatite and the metal are heated under vacuum to a temperature which is above the melting point of the metal.
  • the metal is then pressurized so that the metal penetrates into the hydroxylapatite.
  • no cross-linked material is obtained by this process.
  • JP 2000095577 describes a method for producing a hydroxyapatite-metal composite material which is said to have good mechanical strength, high stability in water and high compatibility with the human body.
  • This procedure includes the Sintering of the hydroxyapatite at 700 to 1300 ° C and the connection of the thus treated hydroxyapatite with a metal such as titanium by means of discharge plasma sintering at about 600 ° C.
  • no crosslinked material is obtained by this process either.
  • the object of the invention is to eliminate the disadvantages of the prior art.
  • a hydroxyapatite-metal composite material that has a high mechanical strength and a high biocompatibility should be specified.
  • a method for producing the hydroxyapatite-metal composite material and the use thereof are to be specified.
  • a hydroxylapatite metal composite is provided, which by
  • step (b) pre-pressing the mixture obtained in step (a) into a green compact and (c) Sintering the green compact obtained in step (b) at a pressure of 1.4 to 7.7 GPa and a temperature of 500 to 900 ° C
  • the invention is based on the knowledge that the mechanical strength and the elasticity properties of hydroxyapatite-metal composite material can be significantly improved if a metallic network that surrounds the ceramic grains is formed in the composite material.
  • the hydroxylapatite-metal composite according to the invention accordingly has a high mechanical strength in comparison to the prior art and a lower modulus of elasticity in comparison with the composite materials of the prior art, as a result of which its biocompatibility can be significantly improved. It has a homogeneous micro structure. The occurrence of jumps is better prevented due to these properties.
  • the metal can be titanium, a noble metal such as gold or silver, or a mixture of these metals.
  • a preferred metal is titanium.
  • a hydroxyapatite powder is first provided, the particle size of the hydroxyapatite powder being in the micrometer or nanometer range. This hydroxyapatite powder is then mixed thoroughly with a metal powder, the particle size of which is also in the micrometer or nanometer range, and the powder mixture is pre-pressed in a vacuum. The pre-pressed green compact obtained in this way was sintered under high pressure and at high temperature for one to three minutes, which leads to the infiltration of the metal and the production of crosslinked material. The pressure for sintering is between 1, 4 and 7.7 GPa.
  • the temperature during sintering is 500 to 900 ° C.
  • the choice of a sintering time of one to three minutes prevents the decomposition of the hydroxyapatite during the sintering. It also enables rapid production of the hydroxyapatite metal [composite material according to the invention.
  • the method according to the invention enables the production of a hydroxyapatite-metal composite material with a cross-linked metal structure by infiltrating the metal into the ceramic powder by means of high pressure and high temperature.
  • the hydroxylapatite-metal composite according to the invention can be used to replace and repair hard organic tissue even in stressed areas. It is preferably used as an implant, in particular as a dental implant or as a bone implant.
  • An example of a dental implant is an artificial tooth root.
  • An example of a bone implant is an artificial bone.
  • the hydroxyapatite-metal composite material can be used as a replacement for the tooth crown in part or in whole, since the material can also be used in the mouth as a filler and for the production of dental prosthetic work (dentures) in addition to the implant application.
  • Fig. 1 shows a device for performing the invention
  • FIG. 5 X-ray diffraction diagrams of the embodiments shown in Figs. 2 to 4 as well
  • Fig. 6 infrared absorption spectra of the embodiments shown in Figs. 2 to 4.
  • the device 1 shown in FIG. 1 was used to produce the hydroxyapatite-metal composites according to the invention.
  • the device is a high pressure / high temperature cell.
  • This device 1 consists of two opposing stamps 2, between which boron nitride pressure transmitters 3 are inserted.
  • the device has a graphite heater 4 and a CaC0 3 container 5.
  • the mixture 6 of hydroxyapatite powder and metal powder is introduced into the device 1 between the stamp 2 and the boron nitride pressure transmitter 3.
  • the predetermined pressure is exerted on the mixture via the stamp 2.
  • Hydroxyapatite powder (Plasma Biotal Limited, UK) with an average particle size of 5.30 ⁇ m and titanium powder with an average particle size of 28.90 ⁇ m were mixed together. The mixture was then placed in hexane and thoroughly in a pot mill for 30 minutes mixed. The resulting mixture was dried in vacuo using a dryer at 110 ° C to remove the hexane remaining in the mixture.
  • step (a) The mixture obtained in step (a) was placed in a printing machine and pressed into a green compact under a pressure of 20 MPa and vacuum.
  • step (b) The green compact obtained in step (b) was sintered in the high pressure / high temperature cell at a pressure of 2.5 GPa at 900 ° C. for 2 minutes.
  • FIG. 2 shows a scanning electron micrograph of the hydroxylapatite-titanium composite thus obtained, the hydroxylapatite phase appearing white, while the titanium phase appears black.
  • This image clearly shows the three-dimensional network structure of the composite material, which brings about an improvement in the tensile and compressive strength of the hydroxylapatite-titanium composite material compared to the previously known materials.
  • the X-ray diffraction diagram (labeled HA / Ti in FIG. 5) and the infrared absorption spectrum (labeled HA / Ti in FIG. 6) show that the hydroxylapatite-titanium composite according to the invention does not decompose during manufacture.
  • the volume ratio of hydroxyapatite to titanium in the composite was 1: 1.
  • Example 1 The procedure described in Example 1 was repeated, except that gold was used instead of titanium, which had an average particle size of 28.9 ⁇ m, and that the sintering in step (c) was carried out at a temperature of 700 ° C.
  • the volume ratio of hydroxyapatite to gold in the composite was 1: 1.
  • Fig. 3 shows a scanning electron micrograph of the hydroxylapatite-gold composite thus obtained
  • Hydroxyapatite phase appears white, while the gold phase appears black.
  • This image clearly shows the three-dimensional network structure of the composite material, which brings about an improvement in the tensile and compressive strength of the hydroxylapatite-gold composite material compared to the previously known materials.
  • the X-ray diffraction diagram (labeled HA / Au in FIG. 5) and the infrared absorption spectrum (labeled HA / Au in FIG. 6) show that the hydroxylapatite-gold composite according to the invention does not decompose during manufacture.
  • Example 1 The procedure described in Example 1 was repeated, except that silver, which had a particle size of 10.00 ⁇ m, was used instead of titanium and that the sintering in step (c) was carried out at a temperature of 800 ° C.
  • the volume ratio of hydroxyapatite to silver in the composite was 1: 1.
  • Fig. 4 shows a scanning electron micrograph of the thus obtained hydroxyapatite-silver composite, the Hydroxyapatite phase appears white, while the silver phase appears black.
  • This image clearly shows the three-dimensional network structure of the composite material, which improves the tensile and compressive strength of the hydroxyapatite-silver composite material compared to the previously known materials.
  • the X-ray diffraction diagram (labeled HA / Ag in FIG. 5) and the infrared absorption spectrum (labeled HA / Ag in FIG. 6) show that the hydroxylapatite-silver composite according to the invention does not decompose during manufacture.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Engineering & Computer Science (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Dermatology (AREA)
  • Medicinal Chemistry (AREA)
  • Transplantation (AREA)
  • Composite Materials (AREA)
  • Materials For Medical Uses (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

Composite hydroxylapatite-métal et procédé de fabrication dudit composite qui consiste (a) à produire un mélange constitué d'hydroxylapatite en poudre et de métal en poudre, (b) à précomprimer le mélange obtenu à l'étape (a) pour obtenir un produit vert et (c) à fritter le produit vert obtenu à l'étape (b) à une pression de 1,4 à 7,7 GPa et à une température de 500 à 900 DEG C.
EP04804140A 2003-12-23 2004-12-21 Composite hydroxylapatite-m tal et proc d de fabrication dudit composite Withdrawn EP1744997A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10360813A DE10360813A1 (de) 2003-12-23 2003-12-23 Hydroxylapatit-Metall-Verbundwerkstoff und ein Verfahren zu dessen Herstellung
PCT/EP2004/014543 WO2005063651A1 (fr) 2003-12-23 2004-12-21 Composite hydroxylapatite-métal et procédé de fabrication dudit composite

Publications (1)

Publication Number Publication Date
EP1744997A1 true EP1744997A1 (fr) 2007-01-24

Family

ID=34706505

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04804140A Withdrawn EP1744997A1 (fr) 2003-12-23 2004-12-21 Composite hydroxylapatite-m tal et proc d de fabrication dudit composite

Country Status (4)

Country Link
US (1) US20080015100A1 (fr)
EP (1) EP1744997A1 (fr)
DE (1) DE10360813A1 (fr)
WO (1) WO2005063651A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004060745A1 (de) * 2004-11-01 2006-05-04 Universität Hamburg Hydroxylapatit-Werkstoff und ein Verfahren zu dessen Herstellung
US20100185299A1 (en) * 2006-11-27 2010-07-22 Berthold Nies Bone Implant, and Set for the Production of Bone Implants

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2857621C2 (fr) * 1978-06-23 1988-03-31 Battelle-Institut Ev, 6000 Frankfurt, De
DE2827529C2 (de) * 1978-06-23 1982-09-30 Battelle-Institut E.V., 6000 Frankfurt Implantierbarer Knochenersatzwerkstoff bestehend aus einem Metallkern und aus bioaktiven, gesinterten Calciumphosphat-Keramik-Partikeln und ein Verfahren zu seiner Herstellung
DE2928007A1 (de) * 1979-07-11 1981-01-15 Riess Guido Dr Knochen-implantatkoerper fuer prothesen und knochenverbindungsstuecke sowie verfahren zu seiner herstellung
DE3615732A1 (de) * 1986-05-09 1987-11-12 Leitz Ernst Gmbh Kompositwerkstoff fuer prothetische zwecke, verfahren zu dessen herstellung sowie verwendung des kompositwerkstoffs bzw. anwendung des herstellungsverfahrens zur beschichtung von prothesen
JP2000095577A (ja) * 1998-09-24 2000-04-04 Asahi Optical Co Ltd ハイドロキシアパタイト−金属複合体の製造方法およびハイドロキシアパタイト−金属複合体
SE513036C2 (sv) * 1998-10-02 2000-06-26 Doxa Certex Ab Sätt att framställa förbättrade biofunktionella kompositmaterial baserade på apatit genom att minimera oönskade reaktioner vid materialens framställning
JP4148599B2 (ja) * 1999-07-01 2008-09-10 Ｈｏｙａ株式会社 多孔質リン酸カルシウム系化合物／金属複合焼結体及びその製造方法
JP2001259017A (ja) * 2000-03-19 2001-09-25 Fumio Watari 生体材料用リン酸カルシウム−チタン系複合材料およびその製造方法
SE520731C2 (sv) * 2001-12-28 2003-08-19 Nobel Biocare Ab Anordning applicerbar i anslutning till ben och/eller vävnad i människokropp samt metod och användning härför

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005063651A1 *

Also Published As

Publication number Publication date
US20080015100A1 (en) 2008-01-17
DE10360813A1 (de) 2005-07-28
WO2005063651A1 (fr) 2005-07-14

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