EP3134563A1 - Procédé de traitement de la surface d'un implant biocorrodable - Google Patents

Procédé de traitement de la surface d'un implant biocorrodable

Info

Publication number
EP3134563A1
EP3134563A1 EP15726055.5A EP15726055A EP3134563A1 EP 3134563 A1 EP3134563 A1 EP 3134563A1 EP 15726055 A EP15726055 A EP 15726055A EP 3134563 A1 EP3134563 A1 EP 3134563A1
Authority
EP
European Patent Office
Prior art keywords
implant
polarization
content
corrosion
weight
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Withdrawn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
EP15726055.5A
Other languages
German (de)
English (en)
Inventor
Volkmar-Dirk Neubert
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.)
Syntellix AG
Original Assignee
Syntellix AG
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 Syntellix AG filed Critical Syntellix AG
Publication of EP3134563A1 publication Critical patent/EP3134563A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
    • A61B17/56—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor
    • A61B17/58—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor for osteosynthesis, e.g. bone plates, screws, setting implements or the like
    • A61B17/68—Internal fixation devices, including fasteners and spinal fixators, even if a part thereof projects from the skin
    • A61B17/84—Fasteners therefor or fasteners being internal fixation devices
    • A61B17/86—Pins or screws or threaded wires; nuts therefor
    • A61B17/866—Material or manufacture
    • 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
    • A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • 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
    • 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
    • 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
    • A61L27/58—Materials at least partially resorbable by the body
    • 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
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/02—Inorganic materials
    • A61L31/022—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
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/08—Materials for coatings
    • A61L31/082—Inorganic materials
    • A61L31/088—Other specific inorganic materials not covered by A61L31/084 or A61L31/086
    • 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
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified 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
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/148—Materials at least partially resorbable by the body
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • C25D9/12—Electrolytic coating other than with metals with inorganic materials by cathodic processes on light metals
    • 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
    • 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
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
    • 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
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
    • 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
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses
    • 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
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/24—Materials or treatment for tissue regeneration for joint reconstruction

Definitions

  • the present invention relates to a method for surface treatment of a biocorrodible implant by means of alternating cathodic and anodic polarization and a corresponding implant.
  • Implants have the task of supporting or replacing body functions and have found application in various applications in medical technology.
  • endovascular implants In addition to implants for attachment of tissues, endovascular implants, dental prosthesis implants, joint replacement implants also find implants for the treatment of bone damage, such as screws, nails, plates, or as a bone substitute application.
  • Implants used on the bone are nowadays mostly made of titanium. Despite the relatively good biocompatibility of titanium implants compared to other permanent implants, efforts are being made to further improve them. Often, coatings are applied to the implant surface to improve biocompatibility.
  • a disadvantage of applying layers to the implant surface is on the one hand a geometry change of the implant, even with small layer thicknesses.
  • the adhesion of the applied layers is usually not optimal.
  • DE 195 04 386 C2 discloses a method for producing a graded coating of calcium phosphate phases and metal oxide phases on metallic implants, preferably of titanium.
  • an aqueous solution with calcium and phosphate ions in the weakly acidic to neutral range is used as the electrolyte and the substrate electrode formed by the implant is alternately anodically and cathodically polarized. Due to the solid incorporation of calcium phosphate phases into the implant Surface is achieved a good growth of the bone to the implant.
  • DE 100 29 520 A1 describes a coating for a metallic implant surface for improving osteointegration.
  • the implant is cathodically polarized in an electrolytic cell in a calcium, phosphate and collagen-containing electrolyte.
  • the method forms a mineralized collagen layer on the implant surface.
  • Implants made of a permanent material must then be removed by another operation. For this reason biocorrodible materials are used for implants. Under biocorrosion in the present case, the gradual degradation of the material is understood due to the body's own media. Even with biocorrodible materials influencing the corrosion process is advantageous.
  • DE 103 57 281 A1 discloses a degradable stent made of a magnesium material which is provided with a coating which retards the degradation.
  • the uncoated implant surface which has a natural mixed oxide layer, is converted into a mixed fluoride layer.
  • the coating can be done by dipping in fluoride-containing media with or without electrolytic support.
  • the object of the present invention was to provide an alternative method for surface treatment of a biocorrodible implant, whereby the degradation rate of the implant can be adjusted as needed.
  • the object is achieved by the method according to the invention for the surface treatment of a biocorrodible implant according to claim 1.
  • the method according to the invention for the surface treatment of a biocorrodible implant by means of electrochemical reactions comprises the steps of: a) providing an implant of a biocorrodible magnesium alloy;
  • the implant serves as a working electrode and further a counter electrode is present, and
  • the working electrode is alternately cathodically and anodically polarized, wherein the current density in the cathodic polarization to -0.1 to -75 mA / cm 2 and the current density in the anodic polarization to 0.1 to 25 mA / cm 2 is set.
  • the inventive method results in a magnesium hydride layer that grows from the implant surface into the implant. Hydrogen ions are cathodically deposited from the electrolyte and implanted in the implant surface.
  • a metal hydride layer is formed which, starting from the implant surface, virtually grows into the implant.
  • the method has the advantage that no geometry change takes place on the implant, since the metal hydride layer grows into the implant.
  • an implant is to be understood as meaning an artificial material implanted in the body. Due to the use of a biocorrodible alloy for the implant body, the material used is gradually degraded by the body's own media. It is envisaged that the implant, in whole or in part, consists of a biocorrodible alloy.
  • the implants can fulfill different purposes and functions as required, such as interference screws, screws and plates for fixation of bones, implants as a drug depot, joint prostheses, stents, jaw and dental implants. The list is only an example and by no means exhaustive.
  • the hydride layer slows down the corrosion of the implant.
  • the corrosion rate of the hydride layer is lower than that of the actual material without hydride layer.
  • the corrosion rate of the implant is thus determined by the corrosion reaction of the magnesium hydride.
  • the rate of corrosion of the implant corresponds to the rate of corrosion of the actual biocorrodible magnesium alloy.
  • the alloy is thus degraded by corrosion as further as would be the case with an untreated implant. Due to the formation of the hydride layer, a two-stage corrosion behavior is present.
  • the process according to the invention is carried out as follows:
  • An implant for example a compression screw made of a biocorrodible metal alloy, preferably a biocorrodible magnesium alloy, is threaded onto a platinum wire. Subsequently, the surface of the screw is activated by a bath in aqueous citric acid solution, preferably a 1 -10% solution, for 1 to 10 seconds. Subsequently, the specimen is rinsed in deionized water, preferably for about 5 to 30 seconds. For further treatment, the screw is fixed on a non-metallic slide. The platinum wire is pulled out afterwards. Notches in the slide prevent later slippage of the screw. Alternatively, the screw can be inserted through a plate with a hole, whereby the ends of the screw are free, in order to later make contact eg with clamps.
  • the screw is contacted with terminals to make conductive contact.
  • the clamps are preferably attached to the outer ends of the screw.
  • the electrolyte has a basic pH of from pH 9 to pH 13, preferably from pH 9 to pH 10. It is further preferred that the electrolyte contains 0.01 M NaOH and 0.2 M Na 2 SO 4 .
  • the basic pH enables the formation of the magnesium hydride layer. At a pH below pH 9, the magnesium material would corrode due to its base character.
  • the implant forms the working electrode. Furthermore, in the arrangement, a counter electrode is present.
  • the counterelectrode preferably consists of a corrosion-resistant metallic material, for example of platinum, chromium-nickel steel, etc. Glass vessels are preferably used as electrolysis cell.
  • a positive pulse of 15 mA / cm 2 to 35 mA / cm 2 is preferred for a pulse length (pulse duration) of 0.10 s to 0.50 s (seconds) and a total duration of the pulses of a total of 5 min 40 min. Particularly preferred is a positive pulse of 25 mA / cm 2 with a pulse length of 0.20 s and a total duration of 20 min.
  • the hydrogenation of the implant is carried out by alternating negative and positive pulse changes.
  • the working electrode is repeatedly alternately cathodically and anodically polarized, starting with a cathodic polarization and terminating the deposition with a cathodic polarization.
  • the current density in the cathodic polarization is adjusted to -35 to -55 mA / cm 2 and the current density in the anodic polarization to 5 to 25 mA / cm 2 .
  • the current density and the total duration of the pulses are lower in an anodic polarization step than in a previous anodic polarization step.
  • a polarization step is to be understood as a sequence of positive or negative pulses of a specific current density and pulse length.
  • the pulse length in the cathodic polarization 0.40 s to 2.5 s and in the anodic polarization 0.10 s to 0.50 s.
  • the total duration of the pulses in a cathodic polarization step is 5 minutes to 90 minutes and the total duration of the pulses in an anodic polarization step is 1 minute to 20 minutes.
  • the total duration of all pulses of the cathodic and anodic polarization steps is 20 minutes to 300 minutes, preferably 1 minute to 240 minutes, particularly preferably 195 minutes.
  • the method according to the invention consists of an alternating sequence of five polarization steps:
  • Polarization step cathodic polarization (negative pulse)
  • Pulse length 0.50 to 2.5 s
  • Pulse length 0.20 to 0.5 s
  • Polarization step cathodic polarization (negative pulse)
  • Pulse length 0.50 to 2.5 s
  • Polarization step anodic polarization (positive pulse)
  • Pulse length 0.20 to 0.5 s
  • Polarization step cathodic polarization (negative pulse)
  • Pulse length 0.50 to 2.5 s
  • the term deposition rate is to be understood as the growth of the metal hydride layer from the implant surface into the implant.
  • the implant is removed from the electrolyte and rinsed with deionized water for about 30 to 60 seconds.
  • the implant is introduced into a stream of hot air, preferably at a temperature of 60 ° C. for 10 to 100 seconds.
  • the implant is preferably packaged airtight to prevent oxidation.
  • a magnesium hydride layer is formed on the implant surface, which increases the corrosion resistance of the implant.
  • higher current intensities than those specified for the method according to the invention can lead to a faster formation of the hydride layer in a defined time interval.
  • the faster growth of the hydride layer which results in a different penetration depth of the hydride layer, can lead to an inhomogeneous surface and thus uneven corrosion.
  • thinner layer regions are completely degraded faster than thicker regions.
  • magnesium hydride layer is already degraded in some areas, but not yet in others, it can lead to a sudden increase in the corrosion rate, since in these places no more hydride corrosion takes place, but the corrosion of the actual material.
  • the implant is thus degraded unevenly and can lose its stability. The parameters described lead to an optimal surface with a reasonable amount of time.
  • the growth of the hydride layer occurs during the cathodic polarization steps. Longer or shorter pulse lengths only have an indirect influence on the growth of the hydride layer.
  • the impulse serves above all to release the hydrogen (H2) formed at the working electrode uniformly and at short intervals. Additions of hydrogen bubbles can lead to slowing down or interrupting the formation of the hydride layer at this point, since in extreme cases no contact between material (working electrode) and electrolyte takes place more.
  • a rectangular pulse current in the sense of the present invention is to be understood as meaning a current with a steep rise and drop and a constant plateau located therebetween. The same applies to the pulse length. With short and many pulses in a time interval, the rest phase is too short and there is a strong hydrogen gas accumulation in the form of bubbles at the working electrode.
  • the geometry of the implant also has an influence on the optimal pulse length.
  • a smooth or uniform surface promotes the bubbling of the hydrogen bubbles.
  • the pulse length can be shortened. Samples with uneven surfaces or threads, such as screw-type implants, or a support grid as an electrode used on small implants will cause the hydrogen bubbles to take more time to bead off.
  • the pulse length is adjustable depending on the geometry of the implant. If too many hydrogen bubbles are accumulated on the working electrode, the pulse length is extended.
  • the individual process parameters can be adapted to different implant sizes and geometries.
  • the degradation speed of the implant can be adjusted as needed. If a rapid degradation is desired, the total duration of the pulses, ie the duration of the respective cathodic polarization step, is reduced in order to limit the formation of the hydride layer to a low penetration depth and thus a small layer thickness. With a longer total duration of the pulses, however, the penetration depth and thus the layer thickness is increased.
  • the implant provided consists of a biocorrodible magnesium alloy which has a magnesium content of at least 50%.
  • a biocorrodible magnesium alloy which has a magnesium content of at least 50%.
  • Particularly preferred is the following composition:
  • the total content of possible impurities being less than 1% by weight and the aluminum content being less than 0.5% by weight, preferably less than 0.1% by weight.
  • the implant consists in whole or in part of a biocorrodible magnesium alloy.
  • the surface of the implant has a hydrogenated outer layer, which increases the corrosion resistance.
  • the corrosion-inhibiting hydride layer has a layer thickness of at least 10 nm, preferably at least 15 nm, particularly preferably 20 nm.
  • the provided implant made of a biocorrodible magnesium alloy has a magnesium content of at least 50%.
  • the biocorrodible magnesium alloy from which the implant is made preferably contains the following composition:
  • the total content of possible impurities being less than 1% by weight and the aluminum content being less than 0.5% by weight, preferably less than 0.1% by weight.
  • the biocorrodible magnesium alloy is suitable for the use of implants in human medicine, because aluminum putatively attributed to harmful properties, such as the promotion of Alzheimer's or cancer.
  • the implant consists in whole or in part of a biocorrodible magnesium alloy.
  • a round material of the magnesium alloy ZfW 102 PM F is treated by the method according to the invention.
  • the magnesium alloy ZfW 102 PM F consists of a rare earth metal content (including neodymium) of 4.05 wt.%, The neodymium content corresponds to 2.35 wt.%, An yttrium content of 1. 56 wt. a zirconium content of 0.78 wt .-%, a zinc content of 0.4 wt .-%, an aluminum content of 0.0032 wt .-%. The remainder to 100% by weight is magnesium.
  • the round material is a solid cylinder with a diameter of 6 mm and a length of 3 cm. This solid cylinder acts as a working electrode.
  • the counter electrode used is a platinum electrode with titanium core with a diameter of 6 mm and a length of 7 cm.
  • electrolysis cell As electrolysis cell, a 500 ml beaker is used.
  • the electrolyte consists of 0.01 M NaOH and 0.2 M Na2SO4 and has a pH of 9.4. The process is carried out at 24 ° C.
  • a positive pulse of 25 mA / cm 2 is used with a pulse length of 0.20 s and a total duration of 20 min.
  • Polarization step cathodic polarization (negative pulse)
  • Polarization step cathodic polarization (negative pulse)
  • Polarization step anodic polarization (positive pulse)
  • Polarization step cathodic polarization (negative pulse)
  • the treatment success is determined by means of X-ray diffractometry (RDA), secondary mass spectrometry (SIMS) and determination of the free corrosion potential.
  • RDA X-ray diffractometry
  • SIMS secondary mass spectrometry
  • determination of the free corrosion potential As a comparison serves an identical round material of the magnesium alloy ZfW 102 PM F, which was not treated with the inventive method.
  • RDA X-ray diffractometry
  • Fig. 4 shows the corrosion rate in a Ringer's lactate solution.
  • a round piece which was treated according to the inventive method according to Example 1, was examined by means of X-ray diffractometry.
  • Fig. 1 the phases located in the material are shown.
  • the occurrence of magnesium hydride phases (MgH2) is evidence of the hydride layer formed by the process of the present invention.
  • the free corrosion potential was determined by a round piece treated according to the inventive method according to Example 1 and an untreated round piece.
  • Fig. 3 shows that the treated Round piece (H-EIR, H electrochemical induced reaction) with 1 680 mV has a more positive corrosion potential than the untreated round piece.
  • FIG. 4 shows the corrosion rate of an untreated round piece and a round piece which has been treated according to the inventive method according to exemplary embodiment 1.
  • the corrosion rate under body-like conditions was determined in each case at 37 ° C. in a Ringer's lactate solution (125-134 mmol / l Na + , 4.0-5.4 mmol / l K + , 0.9-2.0 mmol / l Ca 2+ , 106-1 17 mmol / l CI " , 25-31 mmol / l lactate " ).
  • a Ringer's solution has a similar composition as the blood plasma and the extracellular fluid. It turns out that the treated round piece has a lower corrosion rate than the untreated round piece.
  • the untreated round piece has a corrosion rate of 0.415 mm / year after 432 h and a corrosion rate of 0.399 mm / year after 624 h
  • the round piece treated according to the inventive method according to Example 1 has a corrosion rate of 0.244 mm after 432 h / Year and after 624 h a corrosion rate of 0.153 mm / year (see Fig. 4).
  • a biocorrodible implant which is treated with the method according to the invention, thus has a longer life after implantation into the human body due to a delayed degradation rate than an untreated implant of identical construction.
  • the rate of degradation can be increased.
  • An increased corrosion resistance also gives the implant increased stability, since corrosion is associated with loss of mass of the implant. If the implant breaks down too quickly in the body, the bone may not have enough time to grow into the implant and replace the material with bone material.

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Abstract

L'invention concerne un procédé de traitement de la surface d'un implant biocorrodable à l'aide de réactions électrochimiques. Ledit procédé comprend les étapes consistant à : a) fournir un implant composé d'un alliage de magnésium biocorrodable ; b) introduire l'implant dans un électrolyte présentant un pH de pH9-13 ; c) mettre en œuvre le traitement électrochimique de la surface de l'implant, l'implant servant d'électrode de travail et une contre-électrode étant en outre présente. L'électrode de travail effectue alternativement une polarisation cathodique et une polarisation anodique, la densité de travail étant réglée sur -0,1 bis -7 m A/cm2 pour la polarisation cathodique et la densité de travail étant réglée sur 0,1 bis 2 mA/cm2 pour la polarisation anodique. L'invention concerne en outre un implant correspondant.
EP15726055.5A 2014-04-23 2015-05-21 Procédé de traitement de la surface d'un implant biocorrodable Withdrawn EP3134563A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201410105732 DE102014105732B3 (de) 2014-04-23 2014-04-23 Verfahren zur Oberflächenbehandlung eines biokorrodierbaren Implantats und nach dem Verfahren erhaltenes Implantat
PCT/EP2015/061210 WO2015162306A1 (fr) 2014-04-23 2015-05-21 Procédé de traitement de la surface d'un implant biocorrodable

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JP (1) JP2017519538A (fr)
KR (1) KR20170023799A (fr)
CN (1) CN106456839A (fr)
AU (1) AU2015250774A1 (fr)
BR (1) BR112016024664A2 (fr)
CA (1) CA2946676A1 (fr)
DE (1) DE102014105732B3 (fr)
IL (1) IL248450A0 (fr)
RU (1) RU2016144709A (fr)
SG (1) SG11201608850RA (fr)
WO (1) WO2015162306A1 (fr)

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DE102016119234A1 (de) * 2016-10-10 2018-04-12 Syntellix Ag Schraubenantrieb mit integrierter Drehmomentsicherung
CN108553187A (zh) * 2018-05-16 2018-09-21 广州市健齿生物科技有限公司 一种内部组合生物可降解镁合金的多孔牙种植体及制造方法
CN114571015B (zh) * 2022-03-17 2023-08-11 江苏江航智飞机发动机部件研究院有限公司 一种钛铝合金脊髓固定钉精密电解加工方法

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DE19504386C2 (de) * 1995-02-10 1997-08-28 Univ Dresden Tech Verfahren zur Herstellung einer gradierten Beschichtung aus Calciumphosphatphasen und Metalloxidphasen auf metallischen Implantaten
DE10029520A1 (de) * 2000-06-21 2002-01-17 Merck Patent Gmbh Beschichtung für metallische Implantatmaterialien
DE10357281A1 (de) * 2003-12-05 2005-07-14 Hassel, Thomas, Dipl.-Ing. Gefäßstütze
US20080097577A1 (en) * 2006-10-20 2008-04-24 Boston Scientific Scimed, Inc. Medical device hydrogen surface treatment by electrochemical reduction
CN100998893B (zh) * 2006-12-26 2010-05-12 重庆大学 生物可降解稀土镁合金材料
DE102008054920A1 (de) * 2008-12-18 2010-07-01 Biotronik Vi Patent Ag Implantat sowie Verfahren zur Herstellung einer Schichtstruktur
DE102010027532B8 (de) * 2010-07-16 2014-09-18 Aap Biomaterials Gmbh Verfahren zur PEO-Beschichtung
WO2013024124A1 (fr) * 2011-08-15 2013-02-21 Meko Laserstrahl-Materialbearbeitungen E.K. Alliage de magnésium et endoprothèses résorbables contenant cet alliage

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KR20170023799A (ko) 2017-03-06
DE102014105732B3 (de) 2015-04-09
CN106456839A (zh) 2017-02-22
IL248450A0 (en) 2016-11-30
WO2015162306A1 (fr) 2015-10-29
BR112016024664A2 (pt) 2018-06-19
WO2015162306A8 (fr) 2015-12-17
CA2946676A1 (fr) 2015-10-29
SG11201608850RA (en) 2016-12-29
AU2015250774A1 (en) 2016-12-01
RU2016144709A (ru) 2018-05-23
JP2017519538A (ja) 2017-07-20

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