WO2005107830A1 - Implants medicaux a couche superficielle multielement de type vitroceramique - Google Patents

Implants medicaux a couche superficielle multielement de type vitroceramique Download PDF

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Publication number
WO2005107830A1
WO2005107830A1 PCT/EP2005/004862 EP2005004862W WO2005107830A1 WO 2005107830 A1 WO2005107830 A1 WO 2005107830A1 EP 2005004862 W EP2005004862 W EP 2005004862W WO 2005107830 A1 WO2005107830 A1 WO 2005107830A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
implant
elements
implant according
chemical
Prior art date
Application number
PCT/EP2005/004862
Other languages
German (de)
English (en)
Inventor
Günter Marx
Joachim Schreckenbach
Hans-Ludwig Graf
Volkhard-Hagen Clostermann
Original Assignee
Heraeus Kulzer Gmbh
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 Heraeus Kulzer Gmbh filed Critical Heraeus Kulzer Gmbh
Publication of WO2005107830A1 publication Critical patent/WO2005107830A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/0007—Compositions for glass with special properties for biologically-compatible glass
    • 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
    • A61L27/025—Other specific inorganic materials not covered by A61L27/04 - A61L27/12
    • 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
    • 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
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
    • C03C3/247—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus

Definitions

  • the invention relates to medical or veterinary implants with a glass-ceramic-like multi-element surface layer, in particular dental implants made of titanium or titanium-based alloys, which are suitable for implantation in bones, and a method for producing the surface-coated implants.
  • the surface of implants should not only be biocompatible, it should also promote healing if possible.
  • a very common implant material is titanium.
  • titanium Currently, a large part of the commercially available implant systems are based on titanium materials.
  • An essential property of titanium is its "passivation" through an oxide layer - analogous to aluminum. If titanium with its superficial oxide layer is brought into contact with living body tissue, the organism does not recognize the titanium oxide layer as a foreign body. There is therefore no defense reaction aimed at isolating and rejecting the "foreign body” from the perspective of the organism.
  • WO 02/07792 A2 lists surface modifications, for example by amino, amide or carboxyl groups, in order to improve the osteointegration properties of Ti implants.
  • bioactive surface layers on titanium implants can be obtained by means of electrolytes containing ethylenediaminetetraacetic acid. Due to the use of organic compounds described in these patent applications, a possible unwanted chemical change of these compounds during the manufacture or storage of the implants must be considered.
  • WO 00/72776 discusses porous oxide layer structures on Ti implants that do not contain any organic components, but also do not have any compound that increases the biocompatibility, such as Ca phosphates, as they are e.g. in U.S. Patent 6,596,338 B2.
  • a combination of organic active ingredients with calcium phosphate materials is disclosed in DE 10113,108 A1.
  • the purpose of the surface treatment is to improve the healing behavior through different morphology of the titanium surfaces.
  • the object of the present invention was to coat or modify surfaces of metal implants in such a way that a broad spectrum of inorganic-chemical compounds and structures creates optimized conditions for the complex reactions at the interface of the implant with the biological system and thus to improve the Implants with regard to their biocompatibility and the healing behavior towards them.
  • the layers preferably contain the elements Ca and Mg in a ratio of 10.2> Ca / Mg> 0.08 and the elements F and K, Na in a ratio of F / K, Na> 1.5.
  • the task is thus solved by medical implants with a glass-ceramic-like multi-element surface layer, which contains compounds of the elements Ca, Mg, Ti, F, P, O, K and / or Na, which, due to their phase composition and chemical composition, have different energetic states take in.
  • the subject of the invention takes into account the different reaction types and requirements for surface reactivity depending on the respective integration stage of the implant in the biological matrix.
  • the layer according to the invention contains a mixture of condensed, solid phases of oxides, phosphates and fluorides of the elements Ti, Ca, Mg, which are present in a kinetically unstable and X-ray amorphous state characterized by increased reactivity.
  • the layer preferably contains the elements Ca and Mg in the ratio
  • phases are generally understood to mean uniform regions of particles with the same properties. For example, one speaks of glass phases with irregular particle arrangements. In contrast to this, crystalline phases characterize defined, regular particle arrangements, for example for TiO 2 arrangements in the rutile or anatase lattice. The phase inventory of an element therefore affects its energetic state.
  • different energetic states is to be understood as a sum parameter (eg binding, dissociation, surface energy) which results from the different chemical composition, eg the different forms of connection - eg fluorides, oxides, hydroxides, differently condensed phosphates - and from the amorphous or nano- to microcrystalline phases of these compounds (phase inventory) as well as from the surface morphology of the layer
  • connection - eg fluorides, oxides, hydroxides, differently condensed phosphates - and from the amorphous or nano- to microcrystalline phases of these compounds (phase inventory) as well as from the surface morphology of the layer
  • binding energy states are known for example for Ti and P in the layers according to the invention.
  • energetic states are meant especially surface and binding energies which have different values depending on the order status of the particles and spatial dimension of the phases or type of chemical binding.
  • the energy difference of the Ti 2p electrons in TiO and TiO 2 is due to about 3-4 eV of the different Ti-O bonds.
  • the present case involves glass-ceramic-like structures (phases) with different order states and different spatial dimensions, as well as the bond energies between different bond combinations and bonds compared to single crystals (these have a clearly defined structure and chemical composition), there is a broadened spectrum of energetic states for these glass-ceramic layer structures.
  • the amorphous states present in the coatings according to the invention have been demonstrated in investigations by means of X-ray and electron diffraction. Characteristically, they are also present in glass-ceramic-like states in which crystallites are only partially formed.
  • porous morphology of these implant layers has a positive synergistic effect to support the chemical / structural layer structure.
  • These pore structures come about through an electrochemical-plasma chemical coating process, which leads to a partial melting of the glass-ceramic-like surface, the simultaneously electrolytically and thermally formed gases oxygen and water vapor at the moment the plastic-deformability of this glass-ceramic-like multi-element surface layer causes its pore structure.
  • complex reactions between the electrolyte components and the anode materials take place during the electrochemical plasma chemical processes, which lead to glass-ceramic-like, firmly adhering layers on the Ti implant materials functioning as anode.
  • the electrolytes for the plasma-chemical electrochemical coatings consist of phosphoric acid solutions of Ca or Mg hydrogen phosphates, the alkaline earth metal salts being expediently added at most until the saturation limit of the respective electrolyte system is reached.
  • the layers are subsequently conditioned in aqueous KF and / or NaF electrolytes.
  • alkali fluoride microcrystallites form on the surface of the layer, the ions of which can be very easily mobilized in the initial phase of the implantation.
  • the layer according to the invention is distinguished by the fact that, with regard to its chemical structure, the formation of a concentration gradient is achieved, so that a high concentration of differently bound fluorides exists in the area near the surface, which is replaced by oxides and condensed phosphates in the inner layer areas with increasing distance from the layer surface ,
  • 0.2 mol of calcium dihydrogen phosphate and 0.2 mol of magnesium hydrogen phosphate are dissolved in phosphoric acid solution (pH ⁇ 2.3).
  • the electrochemical-plasma chemical oxidation of a Ti dental implant with a total surface area of 3.7 cm 2 is carried out in this electrolyte at electrolyte temperatures between 18 ° C. and 35 ° C. in such a way that plasma discharges occur on the implant surface for 60 s.
  • the implant is then rinsed in dist. Water.
  • the implant is fluoridated in a 15% KF solution for 1 h.
  • the final rinse is carried out in a water / propanol mixture 1: 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Veterinary Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • Medicinal Chemistry (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Dermatology (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Materials For Medical Uses (AREA)

Abstract

L'invention concerne des implants médicaux pourvus de couches superficielles multiéléments de type vitrocéramiques. Selon ladite invention, ces couches contiennent des composés des éléments Ca, Mg, Ti, F, P, O, K et/ou Na, lesquels éléments présentent des états énergétiques différents selon leur état de phase et leur composition chimique.
PCT/EP2005/004862 2004-05-05 2005-05-04 Implants medicaux a couche superficielle multielement de type vitroceramique WO2005107830A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004022768.3 2004-05-05
DE200410022768 DE102004022768A1 (de) 2004-05-05 2004-05-05 Medizinische Implantate mit glaskeramikartiger Multielement-Oberflächenschicht

Publications (1)

Publication Number Publication Date
WO2005107830A1 true WO2005107830A1 (fr) 2005-11-17

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2005/004862 WO2005107830A1 (fr) 2004-05-05 2005-05-04 Implants medicaux a couche superficielle multielement de type vitroceramique

Country Status (2)

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DE (1) DE102004022768A1 (fr)
WO (1) WO2005107830A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009016554A1 (de) 2009-02-19 2010-09-09 Heraeus Kulzer Gmbh Medizinisches Implantat mit einer Oberflächenschicht und Verfahren zur Herstellung der Implantatoberfläche

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4917702A (en) * 1984-09-10 1990-04-17 Hans Scheicher Bone replacement material on the basis of carbonate and alkali containing calciumphosphate apatites
US5039546A (en) * 1990-02-05 1991-08-13 Harvey Chung Fluoride treatment of hydroxyapatite coated metal implants
DD210607B5 (de) * 1982-10-13 1994-04-14 Hans-Ludwig Dr Med Graf Beschichtetes Implantat
EP1266874A1 (fr) * 2001-06-15 2002-12-18 Bundesanstalt Für Materialforschung Und -Prufung (Bam) Matière vitreuse-cristalline de faible solubilité et son procédé de réalisation

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63102762A (ja) * 1986-10-20 1988-05-07 丸野　重雄 生体適合性複合体及びその製法
US5478237A (en) * 1992-02-14 1995-12-26 Nikon Corporation Implant and method of making the same
CA2073781A1 (fr) * 1992-07-13 1994-01-14 Morteza Shirkhanzadeh Procede de formation de revetements bioactifs composes sur les implants
US6139585A (en) * 1998-03-11 2000-10-31 Depuy Orthopaedics, Inc. Bioactive ceramic coating and method
EP1275442A1 (fr) * 2001-07-13 2003-01-15 Stichting voor de Technische Wetenschappen Revêtement par pulvérisation électrostatique de couches biocompatibles sur des substrats métalliques
CN100515504C (zh) * 2001-10-12 2009-07-22 美国英佛曼公司 涂层,涂布体及其制造方法
GB0126467D0 (en) * 2001-11-03 2002-01-02 Accentus Plc Deposition of coatings on substrates
JP2003235954A (ja) * 2002-02-20 2003-08-26 Toshihiro Kasuga 骨伝導性生体材料及びその製造方法
FR2842750B1 (fr) * 2002-07-26 2004-10-08 Toulouse Inst Nat Polytech Procede permettant de recouvrir a basse temperature des surfaces par des phosphates apatitiques nanocristallins, a partir d'une suspension aqueuse de phosphate amorphe

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD210607B5 (de) * 1982-10-13 1994-04-14 Hans-Ludwig Dr Med Graf Beschichtetes Implantat
US4917702A (en) * 1984-09-10 1990-04-17 Hans Scheicher Bone replacement material on the basis of carbonate and alkali containing calciumphosphate apatites
US5039546A (en) * 1990-02-05 1991-08-13 Harvey Chung Fluoride treatment of hydroxyapatite coated metal implants
EP1266874A1 (fr) * 2001-06-15 2002-12-18 Bundesanstalt Für Materialforschung Und -Prufung (Bam) Matière vitreuse-cristalline de faible solubilité et son procédé de réalisation

Also Published As

Publication number Publication date
DE102004022768A1 (de) 2005-12-08

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