CN108744058A - A kind of degradable synthetism stick implantation instrument and preparation method thereof - Google Patents

A kind of degradable synthetism stick implantation instrument and preparation method thereof Download PDF

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Publication number
CN108744058A
CN108744058A CN201810681147.XA CN201810681147A CN108744058A CN 108744058 A CN108744058 A CN 108744058A CN 201810681147 A CN201810681147 A CN 201810681147A CN 108744058 A CN108744058 A CN 108744058A
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Prior art keywords
synthetism
stick
degradable
equal
implantation instrument
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CN201810681147.XA
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CN108744058B (en
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李扬德
李卫荣
滑有录
刘芳菲
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Dongguan Magnesium Medical Equipment Co ltd
Dongguan Eontec Co Ltd
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Dongguan City Meian Magnesium Industry Technology Co Ltd
Dongguan Eontec Co Ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/04Metals or alloys
    • A61L27/047Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28Materials for coating prostheses
    • A61L27/30Inorganic materials
    • A61L27/306Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28Materials for coating prostheses
    • A61L27/30Inorganic materials
    • A61L27/32Phosphorus-containing materials, e.g. apatite
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54Biologically active materials, e.g. therapeutic substances
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C23/00Alloys based on magnesium
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02Anodisation
    • C25D11/024Anodisation under pulsed or modulated current or potential
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02Anodisation
    • C25D11/026Anodisation with spark discharge
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02Anodisation
    • C25D11/30Anodisation of magnesium or alloys based thereon
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • A61L2300/104Silver, e.g. silver sulfadiazine
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/112Phosphorus-containing compounds, e.g. phosphates, phosphonates
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/412Tissue-regenerating or healing or proliferative agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/02Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Abstract

The present invention provides a kind of degradable synthetism stick implantation instruments, including degradable medical synthetism stick and the coating for being compound in Medical bone stick surface;The Medical bone stick is pure magnesium material or magnesium alloy materials, and the magnesium alloy materials include:The Mg of the Sr and surplus of Fe more than 0 and less than or equal to 0.5wt%, the Zn more than 0 and less than or equal to 1wt%, the Mn more than 0 and less than or equal to 0.6wt%, Cu, 0.8wt% more than 0 and less than or equal to 0.05wt%;The coating is Ca-P-Ag coatings.Present invention also provides the preparation methods of degradable synthetism stick implantation instrument.Material of main part of the application by using pure magnesium material or magnesium alloy materials as degradable synthetism stick implantation instrument, and pass through the Ca-P-Ag coating compound in bulk material surface, degradable synthetism stick implantation instrument is set to can induce new Bone Ingrowth, reconstruction of bone tissue achievees the purpose that repairing bone defect.

Description

A kind of degradable synthetism stick implantation instrument and preparation method thereof
Technical field
The present invention relates to medical bio implantation field of material technology more particularly to a kind of degradable synthetism stick implantation instrument and Preparation method.
Background technology
Bio-medical material is for its disease damage tissue, organ or increasing is diagnosed, treated, repaired or replaced to organism Into the material of its function;It is the basis for studying artificial organs and medical instrument, it has also become the important branch of current material subject, It has become scientists from all over the world especially with booming and important breakthrough, the bio-medical material of biotechnology and competitively grinds The hot spot studied carefully and developed.
Bio-medical material can be divided into the bonemuscle systems repair materials such as bone, tooth, joint, tendon by purposes, skin, The soft-tissue materials such as breast, esophagus, respiratory tract, bladder, the cardiovascular systems commons such as heart valve film, blood vessel, cardiovascular interpolation pipe Material, membrane for purifying blood and seperation film, gas-selectively are through medical film materials, tissue adhesive and seams such as film, contact lens Wire material, drug release carrier material, clinical diagnosis and biosensor material, dental material etc..In above-mentioned bio-medical material In material, bonemuscle system repair materials are the materials of commonplace application, and especially bone implantation instrument is in such biology doctor It is used widely in material.
Biomedical metallic material is used as the metal or alloy of bio-medical material, also known as surgery metal material or doctor It is a kind of inert material with metal material.Main problem in medical metal material application be corrosion due to physiological environment and Caused by metal ion to surrounding tissue spread and be implanted into material self property regression, the former may lead to toxic side effect, after Person frequently results in the failure of implantation.Synthetism biomedical metallic material is used to connect the both ends of knochenbruch, or is implanted into Bone defect part;To achieve the goals above, it is desirable to provide a kind of new medical is implanted into material for synthetism, reaches reparation bone The purpose of defect.
Invention content
Present invention solves the technical problem that being to provide a kind of degradable synthetism stick implantation instrument, which plants Enter instrument can reconstruction of bone tissue, achieve the purpose that repair bone injury.
In view of this, this application provides a kind of degradable synthetism stick implantation instrument, including degradable medical synthetism stick with It is compound in the coating on the degradable medical synthetism stick surface;
The degradable medical synthetism stick is pure magnesium material or magnesium alloy materials, and the magnesium alloy materials include:More than 0 And less than or equal to the Fe of the 0.5wt%, Zn more than 0 and less than or equal to 1wt%, the Mn more than 0 and less than or equal to 0.6wt%, big In the 0 and Mg of the Sr and surplus of Cu, 0.8wt% less than or equal to 0.05wt%;
The coating is Ca-P-Ag coatings.
Preferably, the degradable medical synthetism stick includes coaxially connected pedestal and cylinder, and the diameter of the pedestal is big In the diameter of the cylinder, and the bottom center setting of the pedestal is fluted.
Preferably, the ratio of the diameter of the diameter of the pedestal and the cylinder is 4:3~2:1, the height of the pedestal Ratio with the height of the cylinder is (0.8~2):1.
Preferably, the ratio of the length of the diameter of the pedestal and the groove is 1:(0.4~0.8), the pedestal The ratio of height and the height of the groove is (3~8):1.
Preferably, in the Ca-P-Ag coatings, the content of Ag is no more than 0.1wt%, and surplus is Ca and P.
Preferably, the mass ratio of the Ca and P is 5:3.
Preferably, the thickness of the Ca-P-Ag coatings is more than 0 and is less than or equal to 0.5mm.
Present invention also provides the preparation methods of the degradable synthetism stick implantation instrument, include the following steps:
Ca-P-Ag coatings are grown in degradable medical synthetism stick surface in situ using micro-arc oxidation process;
The degradable medical synthetism stick is pure magnesium material or magnesium alloy materials, and the magnesium alloy materials include:More than 0 And less than or equal to the Fe of the 0.5wt%, Zn more than 0 and less than or equal to 1wt%, the Mn more than 0 and less than or equal to 0.6wt%, big In the 0 and Mg of the Sr and surplus of Cu, 0.8wt% less than or equal to 0.05wt%;
The coating is Ca-P-Ag coatings.
Preferably, the electrolyte in the micro-arc oxidation process is made of following compositions:Sodium metasilicate, the 50wt% of 40wt% Nanometer hydroxyapatite powder, the sodium fluoride of 5wt%, the glycerine of >=2wt%, the sodium hydroxide of 2wt% ,≤1wt% receive Rice Ag powder and 2000mL deionized waters.
Preferably, the constant voltage of the differential arc oxidation is 250~400V;Pulse frequency is 300~400Hz;Duty ratio It is 10~15%, 20~30min of oxidization time.
This application provides a kind of degradable synthetism stick implantation instruments, by degradable medical synthetism stick and are compound in described The coating on degradable medical synthetism stick surface forms, wherein degradable medical synthetism stick is pure magnesium material or magnesium alloy materials, institute It is Ca-P-Ag coatings to state coating.Degradable synthetism stick implantation instrument provided by the present application is used to connect both ends or the implantation of knochenbruch Bone defect part, due to main part degradable medical synthetism stick be pure magnesium material or magnesium alloy materials, then degrade after magnesium from Son induces new Bone Ingrowth, reconstruction of bone tissue to repair bone injury;Further, be conducive to health and life due to being added The Ca-P-Ag coatings of class bone composition are contained on essential trace element-iron, zinc, manganese, copper, strontium and surface so that bone tissue has good Good regeneration function effect.
Description of the drawings
Fig. 1 is the photo in kind of degradable synthetism stick implantation instrument provided by the invention;
Fig. 2 is the sectional view of degradable synthetism stick implantation instrument provided by the invention;
Fig. 3 is the 3 months HE stained photographs in magnesium alloy synthetism stick implanted femur distal end that the embodiment of the present invention 1 provides;
Fig. 4 is the 3 months HE stained photographs in magnesium alloy synthetism stick implanted femur distal end that the embodiment of the present invention 2 provides;
Fig. 5 is the 3 months HE stained photographs in magnesium alloy synthetism stick implanted femur distal end that the embodiment of the present invention 3 provides.
Specific implementation mode
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still It should be appreciated that these descriptions are only the feature and advantage further illustrated the present invention, rather than to the claims in the present invention Limitation.
In order to match the specific requirement of different implant sites, especially stress size, Bone density and implantation environment Influence, this application provides a kind of degradable synthetism stick implantation instrument, this kind of degradable synthetism stick implantation instrument can induce new Bone Ingrowth, reconstruction of bone tissue, repairing bone defect.Specifically, the embodiment of the invention discloses a kind of degradable synthetism stick implanting devices Tool, including degradable medical synthetism stick and the coating for being compound in the degradable medical synthetism stick surface;
The Medical bone stick is pure magnesium material or magnesium alloy materials, and the magnesium alloy materials include:More than 0 and it is less than Zn equal to the Fe of 0.5wt%, more than 0 and less than or equal to 1wt%, the Mn more than 0 and less than or equal to 0.6wt%, it is more than 0 and small In the Sr of Cu, 0.8wt% equal to 0.05wt% and the Mg of surplus;
The coating is Ca-P-Ag coatings.
Degradable synthetism stick implantation instrument provided by the present application is by Medical bone stick and is compound in the Medical bone stick table The coating in face forms;Specifically, the Medical bone stick is pure magnesium material or magnesium alloy materials, for pure magnesium material, it can pass through Magnesium ion after degradation induces new Bone Ingrowth;Further, due to implant site difference, the size withstood forces and implantation Partial bone tissue microenvironment is different, and herein described degradable medical synthetism stick can also be magnesium alloy materials, the magnesium alloy Material specifically includes:Fe more than 0 and less than or equal to 0.5wt%, the Zn more than 0 and less than or equal to 1wt%, more than 0 and it is less than The Mg of the Sr and surplus of Mn equal to 0.6wt%, Cu, 0.8wt% more than 0 and less than or equal to 0.05wt%;Due to adding Iron, zinc, manganese, copper and this kind of essential trace element for being conducive to health and life of strontium, make bone tissue have good regeneration Function;Above-mentioned trace element can improve the intensity of Medical bone stick simultaneously, make have suitable degradation rate in degradation process, with Match the knitting required time.In a particular embodiment, the content of the Fe is 0.08~0.40wt%, and the Zn's contains Amount is 0.15~0.80wt%, and the content of the Mn is 0.12~0.54wt%, the content of the Cu is 0.012~ 0.039wt%.The content of described Fe, Zn, Mn, Cu and Sr exceed above range, then degradable synthetism stick implantation instrument biofacies Capacitive is poor.
The both ends of detachment bone, herein described degradable medical synthetism are connected for the ease of degradable synthetism stick implantation instrument Stick includes coaxially connected pedestal and cylinder, and the diameter of the pedestal is more than the diameter of the cylinder, and the bottom of the pedestal Center setting is fluted.Specifically, Fig. 1 is the photo in kind of degradable synthetism stick implantation instrument provided by the invention, figure a) is It is b) reality of degradable synthetism stick implantation instrument composite coating that degradable synthetism stick implantation instrument, which does not have cated photo in kind, figure, Object photo;Fig. 2 is the sectional view of degradable synthetism stick implantation instrument provided by the invention.For this kind of Medical bone stick its pedestal Diameter and the cylinder diameter ratio be 4:3~2:1, the ratio of the height of the height of the pedestal and the cylinder is (0.8~2):1;The ratio of the length of the diameter of the pedestal and the groove is 1:(0.4~0.8), the height of the pedestal Ratio with the height of the groove is (3~8):1.In actual application, can be adjusted according to specific application environment can The size of degradation Medical bone stick.
According to the present invention, the degradable medical synthetism stick surface recombination has Ca-P-Ag coatings, the coating have antibacterial, The effect of class bone, in favor of the regeneration of bone tissue.Specifically, the Ca-P-Ag coatings are the calcium phosphorus compositions formed containing class bone With the nanometer Ag coating of antibacterial functions;Wherein the content of Ag is no more than 0.1wt%, and surplus is Ca and P, more specifically, the Ca Mass ratio with P is 5:3.The thickness of the Ca-P-Ag coatings is more than 0 and is less than or equal to 0.5mm.
Present invention also provides the preparation methods of the degradable synthetism stick implantation instrument, include the following steps:
Ca-P-Ag coatings are grown in degradable medical synthetism stick surface in situ using micro-arc oxidation process;
The degradable medical synthetism stick is pure magnesium material or magnesium alloy materials, and the magnesium alloy materials include:More than 0 And less than or equal to the Fe of the 0.5wt%, Zn more than 0 and less than or equal to 1wt%, the Mn more than 0 and less than or equal to 0.6wt%, big In the 0 and Mg of the Sr and surplus of Cu, 0.8wt% less than or equal to 0.05wt%;
The coating is Ca-P-Ag coatings.
During preparing degradable synthetism stick implantation instrument, the application is by micro-arc oxidation process in Medical bone stick Surface is prepared for Ca-P-Ag coatings;The Medical bone stick is prepared according to method well known to those skilled in the art, to this this Shen It please be not particularly limited.The micro-arc oxidation process is a kind of technique well known to those skilled in the art, is in alloy table The TRANSIENT HIGH TEMPERATURE high pressure effect that face is generated by arc discharge, growth in situ go out the ceramic membrane based on substrate metal oxide Layer;The technical process of the differential arc oxidation is carried out according to mode well known to those skilled in the art, to concrete operations flow The application is without particularly illustrating.In this application, Ca-P-Ag coatings in order to obtain, the electricity in the micro-arc oxidation process Solution liquid is made of following compositions:The sodium metasilicate of 40wt%, the nanometer hydroxyapatite powder of 50wt%, 5wt% sodium fluoride, >= The glycerine of 2wt%, the sodium hydroxide of 2wt%, the nanometer Ag powder of≤1wt% and 2000mL deionized waters.The differential arc oxidation 250~400V of constant voltage;300~400Hz of pulse frequency;Duty ratio 10~15%, 20~30min of oxidization time.This Shen Micro-arc oxidation process please be use in degradable medical synthetism stick surface recombination Ca-P-Ag coatings, so that coating is in degradable medical Synthetism stick surface forms the coating combined closely.
In order to match the micro- of the specific requirement of different implant sites, especially stress size and Bone density and implantation Environment, final purpose are that the healing of bone tissue and the degradation speed of magnesium alloy is made to match.Therefore, provided by the present application degradable Synthetism stick implantation instrument further adds polynary trace alloying element in vivo on the basis of high purity magnesium and magnesium alloy has been prepared, The bone implant material that connects that its element is formed with content is prepared when different has different mechanical property and degradation rate, to expire The functional requirement of foot difference implant site.
For a further understanding of the present invention, with reference to embodiment to degradable synthetism stick implantation instrument provided by the invention It is described in detail, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Medical bone stick as shown in Figure 2 is provided, which is 8mm, height h by coaxially connected diameter D0For 10mm Pedestal and diameter d be 4mm, height h1It is formed for the cylinder of 6mm, the length W of the groove in base bottom center is 6mm, height h2 For 3mm;Simultaneously the synthetism stick be magnesium alloy materials, by the Mn of Zn, 0.6wt% of Fe, 0.6wt% of 0.1wt%, The Sr of Cu, 0.8wt% of 0.02wt% and the Mg of surplus are formed;
Ca-P-Ag coatings are grown in Medical bone stick surface in situ using micro-arc oxidation process, obtain degradable magnesium alloy Synthetism stick implantation instrument;The electrolyte of micro-arc oxidation process specifically comprises sodium metasilicate 40wt%+ nanometer hydroxyapatite powder Nanometer Ag powder+deionized water of last 50wt%+ sodium fluorides 5wt%+ glycerine 2wt%+ sodium hydroxides 2wt%+1wt% 2000mL, technological parameter are specially constant voltage 300V;Pulse frequency 350Hz;Duty ratio 12%, oxidization time 25min.
Degradable magnesium alloy synthetism stick implantation instrument manufactured in the present embodiment is detected, magnesium alloy synthetism stick implantation instrument is measured Tensile strength 210MPa, nonproportional cyclic straining 140MPa, elongation 8.6%, degradation rate≤0.3mm/year.
Fig. 3 is the 3 months HE stained photographs in magnesium alloy synthetism stick implantation instrument implanted femur manufactured in the present embodiment distal end, The effect for repairing bone tissue is as shown in the figure:Wherein purple is new bone tissue, and blue is osteogenic tissue, and white is fibr tissue.
Embodiment 2
Medical bone stick as shown in Figure 2 is provided, which is 6mm, height h by coaxially connected diameter D0For 8mm Pedestal and diameter d be 3mm, height h1It is formed for the cylinder of 4mm, the length W of the groove in base bottom center is 4mm, height h2 For 2mm;Simultaneously the synthetism stick be magnesium alloy materials, by the Mn of Zn, 0.4wt% of Fe, 0.8wt% of 0.4wt%, The Sr of Cu, 0.8wt% of 0.03wt% and the Mg of surplus are formed;
Ca-P-Ag coatings are grown in Medical bone stick surface in situ using micro-arc oxidation process, obtain degradable magnesium alloy Synthetism stick implantation instrument;The electrolyte of micro-arc oxidation process specifically comprises sodium metasilicate 50wt%+ nano HA powder 40wt%+ Nanometer Ag powder+deionized water 2000mL of sodium fluoride 5wt%+ glycerine 2wt%+ sodium hydroxides 2wt%+1wt%, technological parameter Specially constant voltage 400V;Pulse frequency 250Hz;Duty ratio 10%, oxidization time 20min.
Degradable magnesium alloy synthetism stick implantation instrument manufactured in the present embodiment is detected, magnesium alloy synthetism stick implantation instrument is measured Tensile strength 180MPa, nonproportional cyclic straining 120MPa, elongation 10.2%, degradation rate≤0.15mm/year.
Fig. 4 is the 3 months HE stained photographs in magnesium alloy synthetism stick implantation instrument implanted femur manufactured in the present embodiment distal end, The effect for repairing bone tissue is as shown in the figure:Wherein purple is new bone tissue, and kermesinus is osteogenic tissue, and white is fibr tissue.
Embodiment 3
Medical bone stick as shown in Figure 2 is provided, which is 4mm, height h by coaxially connected diameter D0For 6mm Pedestal and diameter d be 4mm, height h1It is formed for the cylinder of 5mm, the length W of the groove in base bottom center is 3mm, height h2 For 2mm;Simultaneously the synthetism stick be magnesium alloy materials, by the Mn of Zn, 0.1wt% of Fe, 0.2wt% of 0.1wt%, The Sr of Cu, 0.8wt% of 0.01wt% and the Mg of surplus are formed;
Ca-P-Ag coatings are grown in Medical bone stick surface in situ using micro-arc oxidation process, obtain degradable magnesium alloy Synthetism stick implantation instrument;The electrolyte of micro-arc oxidation process specifically comprises sodium metasilicate 30wt%+ nanometer hydroxyapatite powder Last 60wt%+ sodium fluorides 5wt%+ glycerine 2wt%+ sodium hydroxides 2wt%+ nanometer Ag powder 1wt%+ deionized water 2000mL, Technological parameter is specially constant voltage 200V;Pulse frequency 200Hz;Duty ratio 12%, oxidization time 30min.
Degradable magnesium alloy synthetism stick implantation instrument manufactured in the present embodiment is detected, magnesium alloy synthetism stick implantation instrument is measured Tensile strength 230MPa, nonproportional cyclic straining 140MPa, elongation 7.2%, degradation rate≤0.2mm/year.
Fig. 5 is the 3 months HE stained photographs in magnesium alloy synthetism stick implantation instrument implanted femur manufactured in the present embodiment distal end, The effect for repairing bone tissue is as shown in the figure:Wherein purple is new bone tissue, and kermesinus is osteogenic tissue, and white is fibr tissue.
The explanation of above example is only intended to facilitate the understanding of the method and its core concept of the invention.It should be pointed out that pair For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out Some improvements and modifications, these improvement and modification are also fallen within the protection scope of the claims of the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, as defined herein General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one The widest range caused.

Claims (10)

1. a kind of degradable synthetism stick implantation instrument, including degradable medical synthetism stick and it is compound in the degradable medical synthetism The coating on stick surface;
The degradable medical synthetism stick is pure magnesium material or magnesium alloy materials, and the magnesium alloy materials include:It is more than 0 and small In equal to 0.5wt% Fe, more than 0 and less than or equal to 1wt% Zn, more than 0 and less than or equal to 0.6wt% Mn, be more than 0 and The Sr of Cu, 0.8wt% less than or equal to 0.05wt% and the Mg of surplus;
The coating is Ca-P-Ag coatings.
2. degradable synthetism stick implantation instrument according to claim 1, which is characterized in that the degradable medical synthetism stick Including coaxially connected pedestal and cylinder, the diameter of the pedestal is more than the diameter of the cylinder, and in the bottom of the pedestal Centre setting is fluted.
3. degradable synthetism stick implantation instrument according to claim 2, which is characterized in that the diameter of the pedestal with it is described The ratio of the diameter of cylinder is 4:3~2:1, the ratio of the height of the height of the pedestal and the cylinder is (0.8~2):1.
4. degradable synthetism stick implantation instrument according to claim 2 or 3, which is characterized in that the diameter of the pedestal with The ratio of the length of the groove is 1:The ratio of the height of (0.4~0.8), the height of the pedestal and the groove be (3~ 8):1。
5. degradable synthetism stick implantation instrument according to claim 1, which is characterized in that in the Ca-P-Ag coatings, Ag Content be no more than 0.1wt%, surplus be Ca and P.
6. degradable synthetism stick implantation instrument according to claim 1, which is characterized in that the quality of the Ca and the P Than being 5:3.
7. degradable synthetism stick implantation instrument according to claim 1, which is characterized in that the thickness of the Ca-P-Ag coatings Degree is more than 0 and is less than or equal to 0.5mm.
8. the preparation method of degradable synthetism stick implantation instrument described in claim 1, includes the following steps:
Ca-P-Ag coatings are grown in degradable medical synthetism stick surface in situ using micro-arc oxidation process;
The degradable medical synthetism stick is pure magnesium material or magnesium alloy materials, and the magnesium alloy materials include:It is more than 0 and small In equal to 0.5wt% Fe, more than 0 and less than or equal to 1wt% Zn, more than 0 and less than or equal to 0.6wt% Mn, be more than 0 and The Sr of Cu, 0.8wt% less than or equal to 0.05wt% and the Mg of surplus;
The coating is Ca-P-Ag coatings.
9. preparation method according to claim 8, which is characterized in that the electrolyte in the micro-arc oxidation process is by following At being grouped as:The sodium metasilicate of 40wt%, the nanometer hydroxyapatite powder of 50wt%, the sodium fluoride of 5wt%, >=2wt% it is sweet Oil, the sodium hydroxide of 2wt%, the nanometer Ag powder of≤1wt% and 2000mL deionized waters.
10. preparation method according to claim 8 or claim 9, which is characterized in that the constant voltage of the differential arc oxidation is 250 ~400V;Pulse frequency is 300~400Hz;Duty ratio is 10~15%, 20~30min of oxidization time.
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