DE102004021739A1 - Implant with improved antiseptic and antiinflammatory effects has surface layers containing selenium and can be produced electrochemically - Google Patents

Implant with improved antiseptic and antiinflammatory effects has surface layers containing selenium and can be produced electrochemically Download PDF

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Publication number
DE102004021739A1
DE102004021739A1 DE200410021739 DE102004021739A DE102004021739A1 DE 102004021739 A1 DE102004021739 A1 DE 102004021739A1 DE 200410021739 DE200410021739 DE 200410021739 DE 102004021739 A DE102004021739 A DE 102004021739A DE 102004021739 A1 DE102004021739 A1 DE 102004021739A1
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selenium
implant
surface layers
layers containing
containing selenium
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DE200410021739
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German (de)
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DE102004021739B4 (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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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS 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
    • A61F2/00—Filters 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
    • A61F2/02—Prostheses implantable into the body
    • A61F2/30—Joints
    • A61F2/30767—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
    • 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
    • A61L27/04—Metals or alloys
    • A61L27/06—Titanium or titanium 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
    • A61L27/28—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
    • A61L27/32—Phosphorus-containing materials, e.g. apatite
    • 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
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS 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
    • A61F2/00—Filters 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
    • A61F2/02—Prostheses implantable into the body
    • A61F2/30—Joints
    • A61F2/3094—Designing or manufacturing processes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS 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
    • A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00005—The prosthesis being constructed from a particular material
    • A61F2310/00011—Metals or alloys
    • A61F2310/00023—Titanium or titanium-based alloys, e.g. Ti-Ni alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS 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
    • A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00389—The prosthesis being coated or covered with a particular material
    • A61F2310/00592—Coating or prosthesis-covering structure made of ceramics or of ceramic-like compounds
    • A61F2310/00796—Coating or prosthesis-covering structure made of a phosphorus-containing compound, e.g. hydroxy(l)apatite
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • 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
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents

Abstract

Medicinal implants have biocompatible, porous surface layers containing selenium. An independent claim is also included for production of certain of the implants by electrochemically-plasmachemically anodically oxidizing an implant in a selenium-containing potassium dihydrogen phosphate electrolyte.

Description

Die Erfindung betrifft oberflächenbeschichtete medizinische Implantate, besonders aus Titan oder Titanbasislegierungen, geeignet für die Implantation in Knochen, sowie die Herstellung der beschichteten Implantate.The The invention relates to surface-coated Medical implants, in particular of titanium or titanium-based alloys, suitable for the implantation in bone, as well as the production of the coated ones 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 "antifouling agent" in WO 2000 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. Es finden sich im Stand der Technik jedoch keine Hinweise auf poröse, biokompatible Oberflächenschichten, welche gezielt Se-Anteile aufwiesen.The antiseptic or anti-inflammatory Effect of selenium compounds is described as "antifouling agent" in WO 2000 016624 A1 in medical Implantants described. But the selenium compound only becomes just before use by watering applied. Another use of selenium-containing implant materials for subcutaneous Implants based on glasses molten sodium oxide-potassium oxide-zinc oxide-selenium oxide mixtures is found in AU 556909. However, it can be found in the prior art no evidence of porous, biocompatible surface layers, which had targeted Se shares.

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 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 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 Implantate 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 implants is achieved.

Erfindungsgemäß wird auf das Implantatmaterial eine poröse selenhaltige Schicht aus biokompatiblem Material aufgebracht. Die erfindungsgemäße Schicht enthält im allgemeinen bis zu 1,1 % Se. Das Selen wird in die Schichtmatrix eingelagert, zweckmäßig mit Hilfe plasmachemisch-elektrochemischer Reaktionen. Bevorzugt werden als biokompatible Schichten poröse, Ca-phosphathaltige Schichten eingesetzt.According to the invention the implant material is a porous one selenium-containing layer of biocompatible material applied. The inventive layer contains generally up to 1.1% Se. The selenium gets into the layer matrix stored, convenient with Help of plasmachemic-electrochemical reactions. To be favoured as biocompatible layers porous, Ca phosphate-containing layers used.

In einer bevorzugten Ausführungsform der Erfindung 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.In a preferred embodiment Ca phosphate-containing layers of the invention by means of plasmachemisch-electrochemical anodic oxidation of titanium implants in selenium-containing electrolyte systems generated. The concentration range of the contained therein To choose selenium compounds so that no reinforced Selenium deposition occurs on the cathode surface, but a storage of selenium into the layer.

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 Implantat 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 implant therein electrochemically at high voltages subjected to plasma-chemical oxidation.

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

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

30g/l Kalziumdihydrogenphospat und 0,8g/l Natriumselenat werden in wässriger Lösung aufgelöst. In diesem Elektrolyt wird die elektrochemisch-plasmachemische Oxidation eines Ti-Dentalimplantates mit einer Gesamtoberfläche von 2,5 cm2 bei Elektrolyttemperaturen zwischen 18°C–35°C so durchgeführt, dass 130 s an der Implantatoberfläche 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 occur at the implant surface plasma discharges. The anode potential is in the range of 165 V.

Anschließend erfolgt die Spülung des Implantates in dest. Wasser. Die Abschlussspülung erfolgt in eine Wasser/Propanol Gemisch 1:1.Then done the conditioner of the implant in dist. Water. The final rinse takes place in a water / propanol Mixture 1: 1.

Claims (7)

Medizinisches Implantat mit biokompatibler, poröser Oberflächenschicht, dadurch gekennzeichnet, dass die Schicht Selen enthält.Medical implant with biocompatible, porous surface layer, characterized in that the layer contains selenium. Implantat nach Anspruch 1, dadurch gekennzeichnet, dass das Implantat aus Titan oder dessen Legierungen ist.Implant according to claim 1, characterized in that that the implant is made of titanium or its alloys. Implantat nach Anspruch 1 oder 2, gekennzeichnet dadurch, dass die Schicht Calciumphosphat enthält.Implant according to claim 1 or 2, characterized in that the layer contains calcium phosphate. Implantat nach einem der vorstehenden Ansprüche, gekennzeichnet dadurch, dass die Oberflächenschicht 0,01 – 1,1 % Selen enthält.Implant according to one of the preceding claims in that the surface layer 0.01 - 1.1 Contains% selenium. Verfahren zur Herstellung eines Implantats nach einem der vorstehenden Ansprüche 2 bis 4, dadurch gekennzeichnet, dass man ein medizinisches Implantat nach Anspruch 2 – in einem selenhaltigen Kalziumdihydrogenphospat-Grundelektrolyten – elektrochemisch-plasmachemisch anodisch oxidiert.Process for producing an implant after a of the preceding claims 2 to 4, characterized in that one is a medical implant according to claim 2 - in a 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% is added. 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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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1864686A1 (en) 2006-06-01 2007-12-12 Linde Aktiengesellschaft Process for the manufacture of medical implantes by cold gas spraying
EP1991284A1 (en) * 2006-02-01 2008-11-19 Jake Barralet Bioimplants for use in tissue growth
DE102007032686A1 (en) * 2007-07-13 2009-01-15 Biotronik Vi Patent Ag Stent with a coating
EP2033669A2 (en) * 2007-09-06 2009-03-11 BIOTRONIK VI Patent AG Stent with a base body made of a biocorrodible alloy
WO2008074175A3 (en) * 2006-12-21 2009-03-26 Thommen Medical Ag Bioactive implant coating
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
ES2399261A1 (en) * 2011-09-13 2013-03-27 Universidad De Vigo Synthetic coating of bone implant. (Machine-translation by Google Translate, not legally binding)

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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

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1991284A1 (en) * 2006-02-01 2008-11-19 Jake Barralet Bioimplants for use in tissue growth
EP1991284A4 (en) * 2006-02-01 2012-07-04 Jake Barralet Bioimplants for use in tissue growth
EP1864686A1 (en) 2006-06-01 2007-12-12 Linde Aktiengesellschaft Process for the manufacture of medical implantes by cold gas spraying
WO2008074175A3 (en) * 2006-12-21 2009-03-26 Thommen Medical Ag Bioactive implant coating
DE102007032686A1 (en) * 2007-07-13 2009-01-15 Biotronik Vi Patent Ag Stent with a coating
EP2033669A2 (en) * 2007-09-06 2009-03-11 BIOTRONIK VI Patent AG Stent with a base body made of a biocorrodible alloy
DE102007042451A1 (en) * 2007-09-06 2009-03-12 Biotronik Vi Patent Ag Stent with a body made of a biocorrodible alloy
EP2033669A3 (en) * 2007-09-06 2013-06-05 Biotronik VI Patent AG Stent with a base 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
ES2399261A1 (en) * 2011-09-13 2013-03-27 Universidad De Vigo Synthetic coating of bone implant. (Machine-translation by Google Translate, not legally binding)

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