CN106456839A - Method for the surface treatment of a biocorrodable implant - Google Patents

Method for the surface treatment of a biocorrodable implant Download PDF

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Publication number
CN106456839A
CN106456839A CN201580021762.2A CN201580021762A CN106456839A CN 106456839 A CN106456839 A CN 106456839A CN 201580021762 A CN201580021762 A CN 201580021762A CN 106456839 A CN106456839 A CN 106456839A
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Prior art keywords
implantation body
polarization
pulse
weight
percentage
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Inventor
福尔克马·诺伊贝尔特
福尔克马-迪尔克·诺伊贝尔特
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Poly Entelikesi Co Ltd
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Poly Entelikesi Co Ltd
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    • 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

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Epidemiology (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Transplantation (AREA)
  • Surgery (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Medicinal Chemistry (AREA)
  • Dermatology (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Vascular Medicine (AREA)
  • Orthopedic Medicine & Surgery (AREA)
  • Automation & Control Theory (AREA)
  • Neurology (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Biomedical Technology (AREA)
  • Medical Informatics (AREA)
  • Molecular Biology (AREA)
  • Mechanical Engineering (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Materials For Medical Uses (AREA)
  • Prostheses (AREA)
  • Dental Preparations (AREA)

Abstract

The invention discloses a method for the surface treatment of a biocorrodable implant. The subject of the present invention is a method for the surface treatment of a biocorrodable implant by means of electrochemical reactions, comprising the steps of: a) providing an implant of a biocorrodable magnesium alloy; b) introducing the implant into an electrolyte with a pH of 9-13; c) electrochemically treating the surface of the implant, wherein the implant serves as the working electrode and there is also a counterelectrode, and wherein the working electrode is alternately polarized cathodically and anodically, the current density being set to -0.1 to -7 mA/cm2 for the cathodic polarization and to 0.1 to 2 mA/cm2 for the anodic polarization. A corresponding implant is also the subject of the invention.

Description

A kind of method on the surface processing biodegradable implantation body
Technical field
The present invention relates to a kind of surface processing biodegradable implantation body by alternate negative electrode and anode polarization Method and corresponding implantation body.
The effect of implantation body is to support or substitutes bodily fuctions, and obtains in Medical Technology in different forms Application.Except the implantation body for fixing organization, Ink vessel transfusing implantation body, artificial tooth implantation body, beyond the implantation body of joint, for processing The implantation body of bone injury, such as screw, nail, plate, or also find application for substituting the implantation body of bone.
Background technology
Now, the implantation body's great majority for bone are made of titanium.Although with other can compared with the implantation body of life-time service, The implantation body being made of titanium has the good compatibility with human body（Biocompatibility）, people always attempting continue improve this Plant the compatibility.Often carry out coating in implant surface, for improving biocompatibility.
In implant surface coating the disadvantage is that, just little at last coating also can change the geometry of implantation body. Additionally, the fastness of coating is not optimal.
DE 195 04 386 C2 discloses a kind of method manufacturing gradient coating in metal implants body surface face, described coating By phosphoric acid calcium phase and metal-oxide phase, described implantation body is preferably made from titanium.In the matrix electrode being made up of metal implants body And one in the electrochemical effect that formed of back electrode, micro- acid to neutral containing calcium ion and phosphorus aqueous acid as electrolysis Liquid, the matrix electrode alternant polarization being made up of implantation body is anode and negative electrode.Firm by forming one in implant surface Calcium phosphate, can make bone grow well in implantation body.
DE 100 29 520 A1 describes in implant surface coating thus improving Integrated implant.Implantation body is in an electrolyzer In, containing calcium ion, polarized in phosphate ion, and the electrolyte containing collagen.In this process, implant surface Form a collagen layer mineralizing.
In general, implantation body, especially cardiovascular and orthopaedics implantation body only need to temporarily retain in vivo.By can not The implantation body that degradable material is made must be removed by further surgery.Therefore, Biodegradable material obtains in implantation body To utilization.Biodegradation refers to material and is gradually degraded in body itself medium.Can be to biodegradable material in fall Control in solution preocess is favourable.
However, the degraded of biodegradable implantation body at least should not be completely prevented, because final be desirable that After regular hour, plantation physical ability is dissolved in vivo.It is more the speed of degraded to be controlled, thus according to Need, the degraded of implantation body can be made to be delayed by.
In order to improve corrosion resistance, as used in permanent implant, etch resistant layer can be plated on implantation body.
Representative has been DE 103 57 281 this public announcement of a patent application of the A1. degradable being made up of magnesium material Pan straddle, this rack surface has the coating delaying to degrade.Without the implantation body containing mixed oxide layer for the coating Surface is converted into mixed fluoride nitride layer.Complete to plate in the fluorine-containing medium that electrolyte can be contained or not contain by immersion Layer.
Content of the invention
The task of the present invention is to provide the method that another kind is processed to biodegradable implant surface, by this Method can make the different needs of the velocity adaptive of implantation body's degraded.
The solution of this task is the method for the biodegradable implant surface of process in claim 1.
The method on the surface processing biodegradable implantation body by electro-chemical reaction of the present invention comprises the following steps:
A) provide a kind of implantation body being made up of biodegradable magnesium alloy,
B) above-mentioned implantation body is put in electrolyte between 9 to 13 for the pH value,
C) implant surface is carried out with electrification process, wherein this implantation body is as working electrode, and there is a back of the body electricity simultaneously Pole, wherein, described working electrode alternant polarization is negative electrode and anode, and wherein, electric current density during cathodic polarization is adjusted to -0.1 To -75mA/cm2, electric current density during anode polarization is adjusted to 0.1 to 25mA/cm2.
One magnesium hydride layer is formed by the method for the present invention, this magnesium hydride layer is from implant surface toward plantation bulk-growth.Hydrogen Ion negative electrode from electrolyte deposits, and is planted in implant surface.
The metal hydride layer being formed can be described as growing into plantation in vivo from implant surface.So, the method for the present invention This have the advantage that, implantation body does not have the change of geometrical aspects, because metal hydride layer is to implantation body's growth inside.
The implantation body of indication of the present invention is the artificial material planted in vivo.Because implantation body employs biodegradable Alloy, so the material being used gradually is degraded in the medium of itself in vivo.Implantation body is in whole or in part by can be biological The alloy of degraded is made.According to demand, implantation body can meet different targets and function, for example, interface screw, screw, use In plate and the screw of fixing bone, store implantation body, articular prosthesis, pan straddle and lower jaw and the dental implant of medicine. These are simply illustrated, and do not represent implantation body's classification that whole present invention can comprise.
By described hydride coatings, the speed that is corroded of implantation body is reduced.The speed that is corroded of hydride coatings is compared not There is the speed that is corroded of the material of hydride coatings relatively low.As long as implant surface has the hydride coatings of a closing, implantation body The speed that is corroded is determined by the corrosion reaction of magnesium hydride.Once this hydride coatings is consumed by corrosion, implantation body is corroded Speed is the speed that is corroded of the biodegradable magnesium alloy of implantation body itself.After hydride coatings are consumed to by corrosion, Described alloy is degraded by corrosion, such as surface treated implantation body.By hydride coatings, it is rotten that implantation body has two benches Erosion process.
Preferably, the method for the present invention is carried out as follows:
One by biodegradable metal alloy, preferably biodegradable magnesium alloy, the implantation body made, for example One forcing screw, is through on platinum filament.Then, the surface of screw is immersed in aqueous citric acid solution, and the concentration of this solution is preferably 1-10%, starts 1 to 10 second.Afterwards, sample cleans in deionized water, preferably 5 to the 30 seconds time.
In further process, described screw is fixed on nonmetal sample frame.Platinum filament is drawn out of.It is fixed on sample It is to prevent screw landing on frame.Or, described screw may be inserted in the plate with hole, and wherein, the two ends of screw are not subject to Constraint, for being connected with such as clamp afterwards.
Screw and clip contact, are conductively connected for setting up.Described clamp is preferably connected to the outside two ends of screw.
If using the implantation body of very little, the such as screw of very little or pin, do not use clamp because now with folder Clipper joint is unrealistic.It is more biased towards in using exquisite metal grill, screw and pin are placed on grid.Can be built by grid Vertical being conductively connected with implantation body.Also it is partial to when being started using aqueous citric acid solution and being cleaned with water and use grid.
Then, implantation body is placed in electrolyte.Described electrolyte has alkaline ph values, and pH value is between 9 to 13, excellent Elect as between 9 to 10.Further preferably, electrolyte contains 0.01M NaOH and 0.2M Na2SO4.
Magnesium hydride layer is formed under alkaline ph values.When pH value is less than 9, magnesium material will be corroded because of its basic character.
By positive pulse, implant surface is carried out afterwards.In this process, implantation body is as working electrode.Simultaneously There is a back electrode.This back electrode is preferably made up of a noncorroding metal material, such as platinum, chrome-nickel steel etc..As electrolyzer Preferably glass container.
When cleaning surface, preferably use 15mA/cm2bis 35mA/cm2Positive pulse, the pulse duration be 0.1 to 0.5 second.The total time of pulse is 5 to 40 minutes.Especially preferably using 25mA/cm2Pulse, the pulse duration is 0.2 second, total time was 20 minutes.
Then, alternately implantation body is hydrogenated by multiple positive negative pulse stuffing.The process of the present invention is partial to, described work The multiple alternant polarization of electrode is negative electrode and anode, and by cathodic polarization, deposition is terminated by cathodic polarization for polarization.
In a preferred enforcement example, electric current density during cathodic polarization is adjusted to -35 to -55mA/cm2, anode pole Electric current density during change is adjusted to 5 to 25mA/cm2.
Preferably, the electric current density of a pulse during anode polarization step and its total time are than the anode polarization step carrying out before The electric current density of pulse when rapid and its total time are low.
The polarisation steps of indication of the present invention refer to there is certain electric current density and the positive pulse of persistent period or negative pulse Process.
Further preferably, pulse duration during cathodic polarization is 0.40 to 2.5 second, pulse persistance during anode polarization Time is 0.10 to 0.50 second.
One in the present invention is preferable to carry out in example, during cathodic polarization step the total time of pulse 5 to 90 minutes it Between, during anode polarization step, the total time of pulse is between 1 to 20 minute.
Another in the present invention is preferable to carry out in example, and total time of all negative electrodes and anodic pulse is 20 to 300 Between minute, preferably between 120 to 240 minutes, especially preferably 195 minutes.
One in the present invention is preferable to carry out in example, and the process of the present invention is made up of 5 alternate polarisation steps:
1. polarisation steps:Cathodic polarization (negative pulse)
Electric current density:- 0.1 to -75mA/cm2
Pulse duration:0.50 to 2.5 second
Total time 60 minutes (3.6ks)
2. polarisation steps:Anode polarization (positive pulse)
Electric current density:+ 0.1 to+25mA/cm2
Pulse duration:0.20 to 0.5 second
Total time 10 minutes (0.6ks)
3. polarisation steps:Cathodic polarization (negative pulse)
Electric current density:- 0.1 to -75mA/cm2
Pulse duration:0.50 to 2.5 second
Total time 60 minutes (3.6ks)
4. polarisation steps:Anode polarization (positive pulse)
Electric current density:+ 0.1 to+15mA/cm2
Pulse duration:0.20 to 0.5 second
Total time 5 minutes (0.3ks)
5. polarisation steps:Cathodic polarization (negative pulse)
Electric current density:- 0.1 to -75mA/cm2
Pulse duration:0.50 to 2.5 second
Total time 60 minutes (3.6ks)
It is an advantage of the present invention that deposition velocity reaches 5 to 8nm/h.
The deposition velocity of indication of the present invention refers to hydride coatings from implant surface to the speed of plantation tumor growth.
After negative electrode and anode alternant polarization, implantation body is taken out from electrolyte, and deionized water cleaning 30 To 60 seconds.Implantation body is passivated in thermal current, and preferably the temperature of thermal current is 60 DEG C, and passivation time is 10 to 100 seconds.Make With before, implantation body is sealed by packaging, it is to avoid oxidation.
One magnesium hydride layer is formed in implant surface by the method for the present invention, this magnesium hydride layer improves the anti-of implantation body Corrosivity.If using higher than electric current used in the present invention, hydride coatings can be formed faster in unified time section.But It is that the growth of this faster hydride is usually associated with the different intrusion thickness of hydride coatings, thus leading to uneven table Face and unbalanced extent of corrosion.In a magnesium hydride layer not in uneven thickness, the little part of thickness is big with respect to thickness Part be quickly corroded.If consumption is corroded completely in the subregion in hydride layer, and other parts do not have, permissible Causing corrosion speed increases astatically, because in these regions, does not have hydride corrosion to occur, but only to implantation body originally The corrosion of stature material.Implantation body is unevenly degraded, and may lose its stability.
The parameter of the present invention of foregoing description can obtain optimal surface in suitable use time.
The growth of hydride occurs in cathodic polarization step.Between the length in pulse duration only has to hydride growth The impact connecing.Except electro-chemical reaction, the major function of pulse is, the hydrogen (H that will generate2) equably discharge in short interval To working electrode.Hydrogen gas bubbles can slow down in the attachment on electrode or interrupt the generation of hydride at this.Because, extreme In the case of, raw material（Working electrode）And be not in contact between electrolyte.
In pulse step, all there is between pulse and pulse brief interval.Between between " having electricity " and " not having electricity " Have a rest should long enough so that hydrogen gas bubbles can leave working electrode.
Especially rectangular impulse current is favourable to the present invention, because it is provided that time enough makes hydrogen gas bubbles leave electrode. The rectangular impulse current of indication of the present invention is that have precipitous rise and fall and there is the electric current of stabilization sub stage centre.Pulse persistance Time is constant.When pulse within a time period is too short too many, interval is too short, thus leading to a large amount of hydrogen gas bubbles to be attached to work On electrode.
One in the present invention is preferable to carry out in example, the interval between two pulses at least 0.1 second.
Implantation body（Working electrode）Geometry the preferable pulse duration is also had an impact.One smooth uniform Surface is conducive to hydrogen gas bubbles landing.At this moment, the pulse duration can shorten.There is the sample of uneven surface, or spiral shell Stricture of vagina, as electrode, such as when using very little implantation body, hydrogen gas bubbles need more for such as screw-like implantation body, or protection support lattice Many time leaves electrode.
So, the pulse duration can adjust according to the geometry of implantation body.When too many hydrogen gas is had on electrode During bubble, the burst length is extended.
Method parameter can be made by this method to adapt to different implantation body's sizes and geometry.Furthermore, it is possible to Adjust the speed of implantation body's degraded according to demand.When needing fast degradation, the total time of pulse, i.e. each cathodic polarization step Time, be shortened, so that the hydride coatings generating go deep into degree reducing, the thickness of generation reduces.On the contrary, when pulse is total Between increase when, hydride coatings go deep into degree and thickness all increases.
Another of the present invention is implemented in example, and the implantation body being provided is made up of a biodegradable magnesium alloy, and The content of magnesium at least 50%. especially preferably following component:
- rare earth metal component, percentage by weight is 2.5 to 5%,
- yttrium, percentage by weight is 1.5 to 5%,
- zirconium, percentage by weight is 0.1 to 2.5%,
- zinc, percentage by weight is 0.01 to 0.8%,
- and unavoidable impurity, the percentage by weight of the total content of the impurity that may contain is less than 1%, the weight of aluminum Percentage ratio is less than 0.5%, preferably smaller than 0.1%,
- remaining be magnesium, with above-mentioned each composition altogether add up percentage by weight be 100%.
Preferably, described implantation body is made up of Biodegradable magnesium alloys in whole or in part.
Advantageous is the implantation body containing anti-corrosion coating being made up of the method for the present invention.
The outside hydride layer of the method according to the invention generation is contained on the surface of described implantation body, and this hydride layer has anti-corruption Corrosion.Be preferably, the thickness of described erosion-resisting hydride coatings is at least 10nm, preferably at least 15nm, be particularly preferably to Few 20nm.
Another of the present invention is implemented in example, and the implantation body being provided is made up of a biodegradable magnesium alloy, and The content of magnesium at least makes implantation body biodegradable magnesium alloy described in 50%. contains following composition:
- rare earth metal component, percentage by weight is 2.5 to 5%,
- yttrium, percentage by weight is 1.5 to 5%,
- zirconium, percentage by weight is 0.1 to 2.5%,
- zinc, percentage by weight is 0.01 to 0.8%,
- and unavoidable impurity, the percentage by weight of the total content of the impurity that may contain is less than 1%, the weight of aluminum Percentage ratio is less than 0.5%, preferably smaller than 0.1%,
- remaining be magnesium, with above-mentioned each composition altogether add up percentage by weight be 100%.
Because it contains very low, the almost content of negligible aluminum, described Biodegradable magnesium alloys are adapted for use with Implantation body in human medical, because the material of insalubrity that aluminum is well recognized as, is such as conducive to cancer or Alzheimer The formation of disease.
Preferably, described implantation body is made up of Biodegradable magnesium alloys in whole or in part.
The present invention will be further illustrated by example is implemented as follows.
Implement example:
Process of the present invention uses the round bar being made up of magnesium alloy ZfW 102PM F.
Magnesium alloy ZfW 102PM F contains rare earth metal（Including neodymium）Percentage by weight 4.05%, the percentage by weight of neodymium is 2.35%, the percentage by weight of yttrium is 1.56%, and the percentage by weight of zirconium is 0.78%, and the percentage by weight of zinc is 0.4%, the weight of aluminum Amount percentage ratio is 0.0032%.Remaining is magnesium, and altogether adding up percentage by weight with above-mentioned each composition is 100%.
Described round bar is one a diameter of 6 millimeters, and length is 3 centimetres of cylinder.This cylinder is as working electrode.Back of the body electricity Pole is a platinum electrode containing titanium core, a diameter of 6 millimeters, and length is 7 centimetres.
Use 500 milliliters of glass beaker as electrolyzer.Electrolyte contains 0.01M NaOH and 0.2M Na2SO4, and its pH value is 9.4.Process is carried out at 24 DEG C.
Using 25mA/cm when being carried out to surface2Positive pulse, the pulse duration is 0.20 second, and total time is 20 Minute.
Next, being hydrogenated to circle bar by repeatedly replacing positive negative pulse stuffing conversion.The process of the present invention is alternate by 5 Polarisation steps form:
1. polarisation steps:Cathodic polarization (negative pulse)
Electric current density:-50mA/cm2
Pulse duration:0.50 second
Total time 60 minutes (3.6ks)
2. polarisation steps:Anode polarization (positive pulse)
Electric current density:+20mA/cm2
Pulse duration:0.20 second
Total time 10 minutes (0.6ks)
3. polarisation steps:Cathodic polarization (negative pulse)
Electric current density:-50mA/cm2
Pulse duration:0.50 second
Total time 60 minutes (3.6ks)
4. polarisation steps:Anode polarization (positive pulse)
Electric current density:+10mA/cm2
Pulse duration:0.20 second
Total time 5 minutes (0.3ks)
5. polarisation steps:Cathodic polarization (negative pulse)
Electric current density:-50mA/cm2
Pulse duration:0.50 second
Total time 60 minutes (3.6ks)
After altogether 195 minutes, thickness reaches 18nm.
The result processing passes through roentgen's diffractometry（RDA）, secondary ion mass spectrometry (SIMS) and determine spontaneous corrosion Current potential is determined.As a comparison, using a living round bar being made up of magnesium alloy ZfW 102PM F, this circle bar Do not processed by the method for the present invention.
Brief description of drawingsfig
Result is shown in Fig. 1 to 4.
Fig. 1 shows by roentgen's diffractometry（RDA）The hydride coatings detecting.
Fig. 2 shows the hydride coatings detecting by secondary ion mass spectrometry (SIMS).
Fig. 3 shows the determination to spontaneous potential.
Fig. 4 is shown in the corrosion rate in Lactated Ringer'S Solution.
Describe in detail
Pass through roentgen's diffractometry according to the round bar that the present invention implements example 1 process to be detected.Fig. 1 shows in material Each phase.Magnesium hydride phase (MgH2) appearance demonstrate the hydride coatings generating by the process of the present invention.
Pass through SIMS according to the round bar that the present invention implements example 1 process to be detected.Fig. 2 shows according to hydrion in material In deep degree and the hydride coatings that formed prove.
The round bar being processed according to present invention enforcement example 1 and the spontaneous potential of not processed round bar are true Fixed.Fig. 3 shows, the round bar processing（H-EIR, H electrification induced reaction）There is 1680mV just with respect to untreated round bar Corrosion potential.
Round bar and the corrosion rate implementing the round bar that example 1 was processed according to the present invention that Fig. 4 display processing is crossed.Detection It is in the 37 DEG C Lactated Ringer'S Solutions close with human body（125–134mmol/l Na+,4,0–5,4mmol/l K+,0,9–2, 0mmol/l Ca2+,106–117mmol/l Cl-, 25 31mmol/l lactates-）.Ringer's solution and blood plasma and extracellular fluid Constituent is very close.Result shows, the round bar processing has relatively low corrosion rate with respect to untreated round bar.Example As undressed round bar, is 0.415mm/ in 432 hours corrosion rates afterwards, in 624 hours corrosion rates afterwards For 0.339mm/.It is 0.224mm/ according to the round bar that present invention enforcement example 1 was processed in 432 hours corrosion rates afterwards Year, it is 0.153mm/ in 624 hours corrosion rates afterwards（Fig. 4）.
The biodegradable implantation body that the method according to the invention is processed, the degradation speed being delayed by because of it, in plantation After entering human body, it is relatively free of the same implantation body of processed constituent, there is the longer life-span.By the present invention's Method can make the degradation speed of internal implantation body adapt to its different application target and the necessary time of staying.If planted Implant is necessary to stop in vivo longer time, and the material of itself cannot allow it reach the required time of staying, can Improve its corrosion resistance to carry out to implantation body processing by the method for the present invention.The corrosion resistance that improve can also improve plantation The stability of body, because corrosion is accompanied by implantation body's mass loss.When implantation body degrades very much in vivo soon, bone is having Implantation body is replaced less than time enough length in implantation body and with sclerotin in the case of a little.Therefore, the selection of corrosion resistance is depended on Situation in implantation body position in vivo and patient.For auld crowd, because its hyperostosis grows slow, need Will be using the biodegradable implantation body with altitude delay degradation speed.Contrary, if simply needing to make in bone Use less implantation body, this implantation body does not result in very big machinery burden, it is possible to use have the plantation of relatively thin hydride coatings Body.

Claims (10)

1. a kind of method on the surface processing biodegradable implantation body by electro-chemical reaction, the method comprises the following steps:
A) provide a kind of implantation body being made up of biodegradable magnesium alloy,
B) above-mentioned implantation body is put in electrolyte between 9 to 13 for the pH value,
C) implant surface is carried out with electrification process, wherein this implantation body is as working electrode, and there is a back electrode simultaneously, its In, described working electrode alternant polarization be negative electrode and anode, wherein, electric current density during cathodic polarization be adjusted to -0.1 to - 75mA/cm2, electric current density during anode polarization is adjusted to 0.1 to 25mA/cm2.
2. the method in claim 1, it is characterised in that the multiple alternant polarization of described working electrode is negative electrode and anode, polarizes By cathodic polarization, deposition is terminated by cathodic polarization.
3. the method in claim 1 or 2 is it is characterised in that the electric current density of pulse during an anode polarization step and its total Time is lower than the electric current density of the pulse during anode polarization step carrying out before and its total time.
4. the method in any of the above-described claim is it is characterised in that pulse duration during cathodic polarization is 0.40 to 2.5 Second, pulse duration during anode polarization is 0.10 to 0.50 second.
5. the method in any of the above-described claim it is characterised in that during cathodic polarization step the total time of pulse at 5 to 90 points Between clock, during anode polarization step, the total time of pulse is between 1 to 20 minute.
6. the method in any of the above-described claim it is characterised in that the total time of all pulses between 20 to 300 minutes.
7. the method in any of the above-described claim is it is characterised in that implant surface forms hydride coatings, this hydride coatings Thickness be at least 10nm, preferably at least 15nm.
8. the implantation body with anticorrosion coating being obtained according to the method in claim 1 to 7.
9. the implantation body in claim 8, the thickness of the anticorrosion hydride of this implant surface is at least 10nm, preferably at least It is 15nm.
10. the implantation body in claim 8 or 9 is it is characterised in that described biodegradable magnesium alloy contains
- rare earth metal component, percentage by weight is 2.5 to 5%,
- yttrium, percentage by weight is 1.5 to 5%,
- zirconium, percentage by weight is 0.1 to 2.5%,
- zinc, percentage by weight is 0.01 to 0.8%,
- and unavoidable impurity, the percentage by weight of the total content of the impurity that may contain is less than 1%, the weight hundred of aluminum Divide ratio less than 0.5%,
- remaining be magnesium, with above-mentioned each composition altogether add up percentage by weight be 100%.
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