DE102004021739B4 - Metal implant with surface coating - Google Patents

Metal implant with surface coating Download PDF

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Publication number
DE102004021739B4
DE102004021739B4 DE200410021739 DE102004021739A DE102004021739B4 DE 102004021739 B4 DE102004021739 B4 DE 102004021739B4 DE 200410021739 DE200410021739 DE 200410021739 DE 102004021739 A DE102004021739 A DE 102004021739A DE 102004021739 B4 DE102004021739 B4 DE 102004021739B4
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Prior art keywords
metal implant
selenium
layer
metal
implant according
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Expired - Fee Related
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DE200410021739
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German (de)
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DE102004021739A1 (en
Inventor
Günter Prof. Dr. Marx
Joachim Schreckenbach
Alexandra Voigt
Hans-Ludwig Prof. Dr. Med. Dent. Graf
Volkhard-Hagen Clostermann
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GRAF, HANS-LUDWIG, PROF. DR., 04451 BORSDORF, DE
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Heraeus Kulzer GmbH
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    • 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
    • A61F2/30767Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
    • 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
    • A61L27/04Metals or alloys
    • A61L27/06Titanium or titanium alloys
    • 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
    • A61L27/28Materials for coating prostheses
    • A61L27/30Inorganic materials
    • 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
    • A61L27/28Materials for coating prostheses
    • A61L27/30Inorganic materials
    • A61L27/32Phosphorus-containing materials, e.g. apatite
    • 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
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54Biologically active materials, e.g. therapeutic substances
    • 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
    • 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
    • A61F2310/00023Titanium or titanium-based alloys, e.g. Ti-Ni alloys
    • 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
    • A61F2310/00389The prosthesis being coated or covered with a particular material
    • A61F2310/00592Coating or prosthesis-covering structure made of ceramics or of ceramic-like compounds
    • A61F2310/00796Coating or prosthesis-covering structure made of a phosphorus-containing compound, e.g. hydroxy(l)apatite
    • 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404Biocides, antimicrobial agents, antiseptic agents

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Transplantation (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Dermatology (AREA)
  • Epidemiology (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Biomedical Technology (AREA)
  • Vascular Medicine (AREA)
  • Molecular Biology (AREA)
  • Orthopedic Medicine & Surgery (AREA)
  • Cardiology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Materials For Medical Uses (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)

Abstract

Medizinisches Metallimplantat mit biokompatibler, poröser Oberflächenschicht, dadurch gekennzeichnet, dass die Schicht durch elektrochemisch-plasmachemische anodische Oxidation erhalten wird und Selen enthält.medical Metal implant with biocompatible, porous surface layer, characterized that the layer by electrochemical-plasmachemic anodic Oxidation is obtained and contains selenium.

Description

Die Erfindung betrifft oberflächenbeschichtete medizinische Metallimplantate, besonders aus Titan oder Titanbasislegierungen, geeignet für die Implantation in Knochen, sowie die Herstellung der beschichteten Metallimplantate.The The invention relates to surface-coated medical metal implants, in particular of titanium or titanium-based alloys, suitable for the implantation in bone, as well as the production of the coated ones Metal implants.

Selen besitzt im menschlichen Organismus eine essentielle Rolle für das Immunsystem. Es liegt dabei in einer Vielzahl von Proteinen vor. Das Spurenelement ist unter anderem Bestandteil des antioxidativ wirkenden Enzyms Glutathionperoxidase, welches den Schutzmechanismus gegen freie Radikale durch das Selen aktiviert. Auch die Aktivität eines Schilddrüsenhormones ist durch gezielte Selenaufnahme beeinflussbar. Das Element ist hierbei im Selenocystein gebunden.selenium has an essential role for the immune system in the human organism. It is present in a variety of proteins. The trace element is part of the antioxidant enzyme Glutathione peroxidase, which is the protective mechanism against free Radicals activated by the selenium. Also the activity of a thyroid Hormones is influenced by specific selenium intake. The element is bound in selenocysteine.

Neben der Stärkung des Immunsystems besitzt Selen eine entzündungshemmende Wirkung. Entsprechende Anwendungen werden in der Krebstherapie beschrieben und zur Heilung genutzt. Die tägliche Selenaufnahmedosis sollte zwischen 70 und 400 μg/Tag liegen, da sonst Mangelerscheinungen oder Selenosen folgen.Next the strengthening In the immune system selenium has an anti-inflammatory effect. Appropriate Applications are described in cancer therapy and for healing used. The daily Selenaufnahmedosis should be between 70 and 400 micrograms / day, otherwise deficiency symptoms or Selenoses follow.

Die antiseptische bzw. entzündungshemmende Wirkung von Selenverbindungen wird als „anti-fouling agent" in WO 00/016624 A1 bei medizinischen Implantanten beschrieben. Dabei wird die Selenverbindung aber erst kurz vor der Anwendung durch Tränken aufgebracht. Ein weiterer Einsatz selenhaltiger Implantatmaterialien für subkutane Implantate auf der Basis von Gläsern geschmolzener Natriumoxid-Kaliumoxid-Zinkoxid-Selenoxid-Mischungen findet sich in AU 556909 B2 . Es finden sich im Stand der Technik jedoch keine Hinweise auf poröse, biokompatible Oberflächenschichten, welche gezielt Se-Anteile aufwiesen.The antiseptic or anti-inflammatory action of selenium compounds is described as an "anti-fouling agent" in medical implants in WO 00/016624 A1, but the selenium compound is applied only shortly before application by impregnation the base of glasses of molten sodium oxide-potassium oxide-zinc oxide-selenium oxide mixtures can be found in AU 556909 B2 , However, there are no indications in the prior art of porous, biocompatible surface layers which have specific Se contents.

Nach WO 02/078759 A1 können poröse Oberflächenschichten auf Ti-Implantaten mittels Ethylendiamintetraessigsäure-haltigen Elektrolyten erhalten werden.To WO 02/078759 A1 can porous surface layers on Ti implants using ethylenediaminetetraacetic acid-containing Electrolytes are obtained.

In WO 00/72776 A1 werden poröse Oxidschichtstrukturen auf Ti-Implantaten diskutiert, die keine Selen-Komponenten enthalten, aber auch keine die Biokompatibilität steigernden Verbindungen wie beispielsweise Ca-Phosphate aufweisen, wie sie in US-Patent 6,596,338 B2 aufgeführt werden.In WO 00/72776 A1 become porous Oxide layer structures discussed on Ti implants that do not contain selenium components but also biocompatibility-enhancing compounds such as For example, have Ca phosphates, as described in US Patent 6,596,338 B2 listed become.

Der vorliegenden Erfindung lag die Aufgabe zugrunde, Oberflächen von Metallimplantaten derart zu beschichten bzw. zu modifizieren, dass biokompatible poröse Oberflächen mit biologisch wirksamen Selenkomponenten entstehen und eine Verbesserung der antiseptischen bzw. entzündungshemmenden Wirkung der Metallimplantate erreicht wird.Of the Present invention was based on the object surfaces of To coat or modify metal implants such that biocompatible porous surfaces with biologically active selenium components and an improvement the antiseptic or anti-inflammatory Effect of metal implants is achieved.

Erfindungsgemäß wird auf das Metallimplantatmaterial eine poröse selenhaltige Schicht aus bio-kompatiblem Material mit Hilfe elektrochemisch-plasmachemische Oxidation aufgebracht. Die erfindungsgemäße Schicht enthält im allgemeinen bis zu 1,1% Se. Das Selen wird in die Schichtmatrix eingelagert. Bevorzugt werden als biokompatible Schichten poröse, Ca-phosphathaltige Schichten eingesetzt,
d.h. es werden Ca-phosphathaltige Schichten mittels plasmachemisch-elektrochemischer anodischer Oxidation von Titanimplantaten in selenhaltigen Elektrolytsystemen erzeugt. Dabei ist der Konzentrationsbereich der darin enthaltenen Selenverbindungen so zu wählen, dass keine verstärkte Selenabscheidung auf der Kathodenoberfläche auftritt, sondern eine Einlagerung des Selens in die Schicht erfolgt.
According to the invention, a porous selenium-containing layer of bio-compatible material is applied to the metal implant material with the aid of electrochemical-plasmachemical oxidation. The layer of the invention generally contains up to 1.1% Se. The selenium is incorporated in the layer matrix. Preference is given to using porous, calcium phosphate-containing layers as biocompatible layers,
ie Ca-phosphate-containing layers are produced by means of plasma-chemical-electrochemical anodic oxidation of titanium implants in selenium-containing electrolyte systems. In this case, the concentration range of the selenium compounds contained therein should be chosen so that no increased selenium deposition on the cathode surface occurs, but a storage of selenium in the layer takes place.

Die so gebildete selenhaltige Schicht ist porös und zeigt eine stark strukturierte Oberfläche. Die auf dem Ti-Substrat fest haftende Schicht verfügt über ein Porensystem, welches nicht untereinander vernetzt ist, sondern aus isolierten geschlossenen bzw. zur Oberfläche geöffneten Poren mit einem mittlerem Porendurchmesser von 1–2 μm besteht.The thus formed selenium-containing layer is porous and shows a highly structured Surface. The firmly adhering to the Ti substrate layer has a Pore system, which is not networked with each other, but out isolated closed or open to the surface pores with a middle Pore diameter of 1-2 microns.

Neben dem Einsatz von Kalziumdihydrogenphospat-Grundelektrolyten, können auch Schwefel- oder Phosphorsäurelösungen als Grundelektrolyt dienen. Die selenhaltige Verbindung wird im Grundelektrolyten gelöst und das Metallimplantat darin bei hohen Spannungen einer elektrochemisch-plasmachemischen Oxidation unterworfen.Next The use of calcium dihydrogen phosphate base electrolytes may also Sulfuric or phosphoric acid solutions as Serve basic electrolyte. The selenium-containing compound is in the base electrolyte solved and the metal implant therein at high voltages of an electrochemical-plasma-chemical Subjected to oxidation.

Der Selenanteil bewirkt eine langsame Freisetzung des Selens. Die mikrobizide Wirkung macht erfindungsgemäß beschichtete Metallimplantate insbesondere für Risikopatientengruppen geeignet.Of the Selenium causes a slow release of selenium. The microbicides Effect makes coated according to the invention Metal implants in particular for Risk patient groups suitable.

Die Erfindung wird an nachstehendem Ausführungsbeispiel beschrieben.The Invention will be described in the following embodiment.

Beispiel:Example:

30 g/l Kalziumdihydrogenphospat und 0,8 g/l Natriumselenat werden in wässriger Lösung aufgelöst. In diesem Elektrolyten wird die elektrochemisch-plasmachemische Oxidation eines Ti-Dental-implantates mit einer Gesamtoberfläche von 2,5 cm2 bei Elektrolyttemperaturen zwischen 18°C–35°C so durchgeführt, dass 130 s an der Metallimplantatoberfläche Plasmaentladungen auftreten. Das Anodenpotential liegt dabei im Bereich von 165 V.30 g / l calcium dihydrogen phosphate and 0.8 g / l sodium selenate are dissolved in aqueous solution. In this electrolyte, the electrochemical-plasmachemic oxidation of a Ti-dental implant with a total surface area of 2.5 cm 2 at electrolyte temperatures between 18 ° C-35 ° C is performed so that 130 s on the metal implant surface plasma discharges occur. The anode potential is in the range of 165 V.

Anschließend erfolgt die Spülung des Metallimplantates in dest. Wasser. Die Abschlußspülung erfolgt in einem Wasser/Propanol Gemisch 1:1.Then done the conditioner of the metal implant in dest. Water. The final rinse takes place in a water / propanol mixture 1: 1.

Claims (7)

Medizinisches Metallimplantat mit biokompatibler, poröser Oberflächenschicht, dadurch gekennzeichnet, dass die Schicht durch elektrochemisch-plasmachemische anodische Oxidation erhalten wird und Selen enthält.Medical metal implant with biocompatible, porous surface layer, characterized in that the layer is obtained by electrochemical-plasmachemic anodic oxidation and contains selenium. Metallimplantat nach Anspruch 1, dadurch gekennzeichnet, dass das Metallimplantat aus Titan oder dessen Legierungen ist.Metal implant according to claim 1, characterized in that the metal implant is made of titanium or its alloys. Metallimplantat nach Anspruch 1 oder 2, gekennzeichnet dadurch, dass die Schicht Calciumphosphat enthält.Metal implant according to claim 1 or 2, characterized in that the layer contains calcium phosphate. Metallimplantat nach einem der vorstehenden Ansprüche, gekennzeichnet dadurch, dass die Oberflächenschicht 0,01–1,1% Selen enthält.Metal implant according to one of the preceding claims in that the surface layer 0.01 to 1.1% Contains selenium. Verfahren zur Herstellung eines Metallimplantats nach einem der vorstehenden Ansprüche 1 bis 4, dadurch gekennzeichnet, dass man ein medizinisches Metallimplantat nach Anspruch 1 – in einem selenhaltigen Calciumdihydrogenphospat-Grundelektrolyten – elektrochemisch-plasmachemisch anodisch oxidiert.Method for producing a metal implant according to one of the preceding claims 1 to 4, characterized that a medical metal implant according to claim 1 - in one selenium-containing calcium dihydrogen phosphate base electrolyte - electrochemical-plasma-chemical anodized. Verfahren nach Anspruch 5, gekennzeichnet dadurch, dass dem Grundelektrolyten Selen in Form von Alkaliselenaten in Konzentrationen von 0,1–1,5% zugesetzt wird.Method according to claim 5, characterized in that that the base electrolyte contains selenium in the form of alkali metal selenates in Concentrations of 0.1-1.5% added becomes. Verfahren nach Anspruch 5, gekennzeichnet dadurch, dass der Grundelektrolyt schwefel- und/oder phosphorsauer ist.Method according to claim 5, characterized in that that the base electrolyte is sulfur and / or phosphoric acid.
DE200410021739 2004-04-30 2004-04-30 Metal implant with surface coating Expired - Fee Related DE102004021739B4 (en)

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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090220566A1 (en) * 2006-02-01 2009-09-03 Jake Barralet Bioimplants for use in tissue growth
DE102006025682A1 (en) 2006-06-01 2007-12-06 Linde Ag Production of a medical implant for joints comprises coating the implant with a particulate material by cold gas spraying
ES2435433T3 (en) * 2006-12-21 2013-12-19 Thommen Medical Ag Bioactive Implant Coating
DE102007032686A1 (en) * 2007-07-13 2009-01-15 Biotronik Vi Patent Ag Stent with a coating
DE102007042451A1 (en) * 2007-09-06 2009-03-12 Biotronik Vi Patent Ag Stent with a body made of a biocorrodible alloy
DE102009016554A1 (en) 2009-02-19 2010-09-09 Heraeus Kulzer Gmbh Medical implant i.e. dental implant, for implanting in human body, has metallic body comprising surface layer which contains calcium and/or phosphorus, where zirconium and/or zirconium dioxide are stored in surface layer
ES2399261B1 (en) * 2011-09-13 2013-10-18 Universidad De Vigo SYNTHETIC COATING OF BONE IMPLANT.

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0987031A1 (en) * 1998-09-15 2000-03-22 Isotis B.V. Method for coating medical implants
DE10227935A1 (en) * 2002-06-21 2004-01-15 Heraeus Kulzer Gmbh & Co. Kg Antibiotic coating of porous bodies and process for their production and use
EP1407764A1 (en) * 1998-04-17 2004-04-14 PSIMEDICA Limited Implants for administering substances and methods of producing implants

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1407764A1 (en) * 1998-04-17 2004-04-14 PSIMEDICA Limited Implants for administering substances and methods of producing implants
EP1071398B1 (en) * 1998-04-17 2004-05-26 PSIMEDICA Limited Implants for administering substances and methods of producing implants
EP0987031A1 (en) * 1998-09-15 2000-03-22 Isotis B.V. Method for coating medical implants
DE10227935A1 (en) * 2002-06-21 2004-01-15 Heraeus Kulzer Gmbh & Co. Kg Antibiotic coating of porous bodies and process for their production and use

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Effective date: 20111101