CN114099777A - Multi-layer active coating for orthopedic implant and preparation method thereof - Google Patents

Multi-layer active coating for orthopedic implant and preparation method thereof Download PDF

Info

Publication number
CN114099777A
CN114099777A CN202111408288.2A CN202111408288A CN114099777A CN 114099777 A CN114099777 A CN 114099777A CN 202111408288 A CN202111408288 A CN 202111408288A CN 114099777 A CN114099777 A CN 114099777A
Authority
CN
China
Prior art keywords
layer
orthopedic implant
coating
bionic
tantalum metal
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.)
Pending
Application number
CN202111408288.2A
Other languages
Chinese (zh)
Inventor
陈光英
宋坤
王国华
刘江
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.)
Hunan Printer Medical Devices Co ltd
Original Assignee
Hunan Printer Medical Devices Co ltd
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 Hunan Printer Medical Devices Co ltd filed Critical Hunan Printer Medical Devices Co ltd
Priority to CN202111408288.2A priority Critical patent/CN114099777A/en
Publication of CN114099777A publication Critical patent/CN114099777A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • A61L27/28Materials 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
    • A61L27/50Materials 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
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54Biologically active materials, e.g. therapeutic substances
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61L27/56Porous materials, e.g. foams or sponges
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14Metallic material, boron or silicon
    • C23C14/16Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34Sputtering
    • C23C14/35Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • 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
    • A61L2300/20Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
    • A61L2300/252Polypeptides, proteins, e.g. glycoproteins, lipoproteins, cytokines
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404Biocides, antimicrobial agents, antiseptic agents
    • A61L2300/406Antibiotics
    • 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
    • A61L2300/41Anti-inflammatory agents, e.g. NSAIDs
    • 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
    • A61L2300/414Growth factors
    • 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
    • A61L2300/60Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/606Coatings
    • 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
    • A61L2430/24Materials or treatment for tissue regeneration for joint reconstruction
    • 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
    • A61L2430/38Materials or treatment for tissue regeneration for reconstruction of the spine, vertebrae or intervertebral discs

Abstract

The invention relates to the technical field of biomedical materials, in particular to an orthopedic implant multilayer active coating and a preparation method thereof. The coating comprises a basic strengthening layer, a bionic layer and an active functional layer; the basic strengthening layer is a tantalum metal layer; the bionic layer is a calcium phosphate or hydroxyapatite coating; the active functional layer is a coating comprising one or more of bone morphogenetic proteins, bone growth factors or antibiotics. The inside tantalum metal layer forms compact coating on orthopedic implant substrate surface as strengthening layer and the inside strengthening layer and the bionical layer in bionical layer, and intensity is high, is difficult for the fracture to drop, and bionical layer surface adheres to has biological function molecule and medicine, can promote the growth of bone tissue, and the inflammatory reaction is avoided to antibiotic medicine.

Description

Multi-layer active coating for orthopedic implant and preparation method thereof
Technical Field
The invention relates to the technical field of biomedical materials, in particular to an orthopedic implant multilayer active coating and a preparation method thereof.
Background
Currently, most of common orthopedic implantation instruments such as acetabular cups, intervertebral fusion devices, joint prostheses, bone plates, dental implants and the like need to bear certain mechanical support performance as bone implantation instruments, and therefore the orthopedic implantation instruments have appropriate load capacity, corrosion resistance and wear resistance. Once the bone implant prosthesis collapses, wears and corrodes on the surface in the later period, the patient needs secondary operation treatment, such as revision operations of hip joint and knee joint, revision operations of intervertebral fusion cage and the like, the operation pain is brought to the patient, and the economic pressure of treatment of the patient is increased.
The existing acetabulum cup is usually prepared from materials such as titanium alloy, tantalum metal, cobalt-chromium alloy, ultra-high molecular weight polyethylene and the like, an intervertebral fusion device is mostly prepared from materials such as titanium alloy, PEEK, bovine bone and the like, bovine bone prosthesis has the problems of rejection, infection, poor activity and the like, although the titanium alloy intervertebral fusion device can maintain intervertebral stability, the titanium alloy intervertebral fusion device is difficult to realize bone conduction and bone growth induction and realizes connection growth with host bone, so that the fusion effect is poor, although the elastic modulus of the PEEK material is close to human bone, the surface hydrophilic groups are few, a space cannot be provided for cell adhesion, the PEEK material has biological inertia, and the bone integration capability is still insufficient. The existing partial orthopedic implants adopt hydroxyapatite coatings to provide titanium alloy bone fusion performance, but titanium alloy particles generated by long-term bearing abrasion of the orthopedic implants still exist, and the abrasion particles around the prosthesis can cause inflammation, which is one of the main reasons of failure of prosthesis replacement operation and revision of the operation. At present, a hydroxyapatite coating is prepared on the surface of an orthopedic implant, but plasma spraying requires high temperature conditions and easily causes the blockage of a porous structure, so that the implant cannot exert the performance of guiding bone ingrowth by the porous structure.
Disclosure of Invention
The invention aims to solve the technical problems that the existing metal orthopedic implant instrument is easy to wear, has poor particle and corrosion resistance, has poor porous structure aging caused by difficult modification of porous implant apatite, and has poor fusion effect between the implant and host bone caused by insufficient biocompatibility.
In view of the above, the embodiment of the present invention provides a multi-layer active coating for an orthopedic implant, which is applied to a metal bone implant, and the coating comprises a basal strengthening layer, a bionic layer and an active functional layer;
the basic strengthening layer is a tantalum metal layer;
the bionic layer is a calcium phosphate or hydroxyapatite coating;
the active functional layer is a coating comprising one or more of bone morphogenetic proteins, bone growth factors or antibiotics.
Further, the metal bone implant is any one of an intervertebral fusion device with a porous structure, an acetabular cup, an artificial vertebral body and a filling block, and the material of the metal bone implant is one of TC4 titanium alloy, pure titanium and cobalt-chromium alloy.
Further, the thickness of the tantalum metal layer is 10-40 μm.
Further, the antibiotic is one or more of gentamicin, vancomycin and clindamycin.
Based on the same inventive concept, the embodiment of the invention also provides a preparation method of the multi-layer active coating of the orthopedic implant, which comprises the following steps:
performing sand blasting treatment and cleaning on the orthopedic implant to obtain a pretreated orthopedic implant;
preparing a tantalum metal layer by adopting a magnetron sputtering spraying method to the pretreated orthopedic implant to obtain a tantalum metal layer orthopedic implant;
activating the tantalum metal layer orthopedic implant by alkali, and introducing a bionic layer by a sol-gel method, plasma spraying, electrochemical deposition or a bionic deposition method to obtain a bionic-tantalum metal orthopedic implant;
and introducing the bionic-tantalum metal orthopedic implant into an active functional layer by adopting a spraying method or a dipping method to obtain the multi-layer active coating of the orthopedic implant.
Further, the magnetron sputtering spraying method specifically comprises the following steps:
the protective gas of the cavity of the magnetron sputtering spraying instrument is high-purity argon with the purity of 99.99 percent, the negative voltage of the cathode is between 260 and 330V, and when the sputtering cavity is vacuumized to be less than 2 x 10 < -3 > Pa, the argon is filled to 2 to 5 Pa; the target base spacing was 20 mm.
Further, the alkali adopted by the tantalum metal layer orthopedic implant through the alkali activation process is sodium hydroxide or alkaline dopamine.
Further, the step of introducing the bionic-tantalum metal orthopedic implant into an active functional layer by adopting a spraying method or a dipping method to obtain a multi-layer active coating of the orthopedic implant specifically comprises the following steps:
preparing an active functional layer solution: adding bone morphogenetic protein or bone growth factor into distilled water to prepare 5-10mg/mL biomacromolecule solution or suspension; adding antibiotics into distilled water to prepare 1-3mg/mL antibiotic water solution;
and mixing the biomacromolecule solution or suspension with an antibiotic aqueous solution, and introducing an active functional layer into the bionic-tantalum metal orthopedic implant by adopting a spraying method or a dipping method.
Has the advantages that:
(1) the composite coating is arranged on the surface of the orthopedic implant, and specifically comprises a tantalum metal layer, a bionic calcium phosphate or hydroxyapatite coating and an active functional layer, wherein the tantalum metal improves the wear resistance and corrosion resistance of the implant, the bionic layer effectively improves the bone fusion capability of the orthopedic metal implant, and biological functional molecules and drugs are attached to the surface of the bionic layer, so that the growth of bone tissues can be promoted, and the antibiotic drugs avoid inflammatory reaction.
(2) The preparation process of the composite coating is simple, and only one layer of the outer surface of the tantalum coating is needed; the preparation of the calcium phosphate or the hydroxyapatite adopts a bionic method to prepare the calcium phosphate or the hydroxyapatite, so that a uniform bionic layer can be formed in a complex porous structure, the inner pores of the implant with the porous structure can not be blocked, and the problems of high-temperature energy consumption and hydroxyapatite cracking are avoided; the inner strengthening layer and the bionic layer form a compact coating on the surface of the orthopedic implant substrate, and the coating has high strength and is not easy to crack and fall off.
Drawings
FIG. 1 is a schematic structural diagram of a composite coating for orthopedic implants according to an embodiment of the present invention.
Description of reference numerals:
1. an orthopedic implant; 2. a tantalum metal layer; 3. a biomimetic layer; 4. and an active functional layer.
Detailed Description
In order to more clearly illustrate the technical content of the present invention, the detailed description is given herein with reference to specific examples and drawings, and it is obvious that the examples are only preferred embodiments of the technical solution, and other technical solutions that can be obviously derived by those skilled in the art from the technical content disclosed still belong to the protection scope of the present invention.
In the embodiment of the invention, the chemical reagents used are all analytical grade reagents, and are obtained by purchasing or preparing by an existing method.
In the embodiment of the invention, the multilayer active coating is mainly applied to an orthopedic implant 1, which specifically comprises any one of a fusion device, an acetabular cup, an artificial vertebral body and a filling block, wherein the orthopedic implant material is one of TC4 titanium alloy, pure titanium and cobalt-chromium alloy. The method mainly adopts an additive manufacturing mode, comprises a selective laser melting manufacturing process and an electron beam selective melting technology, and the orthopedic implant is of a porous structure. The multilayer active coating comprises a tantalum metal layer 2, a bionic layer 3 and an active functional layer 4, wherein the bionic layer 3 is a calcium phosphate or hydroxyapatite coating, the active functional layer 4 contains active factors such as bone morphogenetic protein, bone growth factors, antibiotics and the like, and the antibiotics comprise one or more of gentamicin, vancomycin and clindamycin; the multilayer active coating realizes the organic combination of the mechanical property, the biocompatibility and the bone ingrowth property of the coating.
In the embodiment of the invention, the preparation method of the multi-layer active coating of the orthopedic implant specifically comprises the following steps: cleaning an orthopedic implant, installing a magnetron sputtering instrument, adjusting parameters of the magnetron sputtering instrument, vacuumizing and flushing argon, carrying out magnetron sputtering spraying, generating a calcium phosphate (hydroxyapatite) bionic coating, and preparing a functional coating by a dip coating method. The method for preparing the tantalum metal coating by the magnetron sputtering spraying comprises the steps that a cavity protective gas of a magnetron sputtering spraying instrument is high-purity argon with the purity of 99.99 percent, the negative voltage of a cathode is between 260 and 330V, and when a sputtering cavity is vacuumized to be less than 2 x 10-3Pa, argon is filled to 2-5 Pa; the target base spacing was 20 mm.
Example 1
Cleaning the orthopedic implant: cleaning the orthopedic implant after sand blasting, removing oil stains on the surface by using acetone, and performing ultrasonic cleaning by using ethanol as a cleaning agent;
preparing the tantalum metal layer orthopedic implant: installation of a magnetron sputtering spraying instrument: installing the ultrasonically cleaned orthopedic implant and the tantalum metal target material into an instrument cavity; adjusting the position of the orthopedic implant, clamping the orthopedic implant by using a clamp, and adjusting the parameters of a magnetron sputtering spraying instrument: the power supply voltage of the target is 600V, the target material is metal tantalum with the thickness of 400 x 200 x 4mm, and the protective gas is high-purity argon with the purity of 99.99 percent; vacuumizing the sputtering cavity to less than 2 x 10-3Pa, and filling argon to 2-5 Pa; the distance between the target bases is 20 mm; the negative voltage 260-320V is applied to the cathode, Ar ions accelerate to fly to the cathode target under the action of an electric field and bombard the surface of the target at high energy, so that the target is sputtered to impact the surface of the orthopedic implant and is deposited; magnetron sputtering the orthopedic implant for 30-120min, wherein the tantalum coating on the surface of the orthopedic implant is between 3.6-14.4 mu m. In the magnetron sputtering process, when the sputtering distance and the sputtering current are fixed, the thickness of the tantalum coating layer and positive ions (Ar) bombarding the target are constant+) The amount is in direct proportion, the current 5A bombards 100min tantalum coating with the thickness of 12 μm, and the coating is taken out and cooled to 15-25 ℃ after sputtering.
Preparing the bionic-tantalum metal orthopedic implant: preparing a calcium phosphate coating by adopting an immersion method, based on a heterogeneous nucleation principle, immersing the tantalum metal layer orthopedic implant into 0.5M NaOH aqueous solution, immersing for 24h at 60 ℃ for surface activation, taking out, cleaning with deionized water, preparing supersaturated calcium phosphate solution 1L, immersing the activated tantalum metal layer orthopedic implant in saturated calcium phosphate solution in a constant temperature oscillator at 37 ℃ for 2h to generate an amorphous calcium phosphate film, taking out the bone implant with a plurality of layers of active coatings, and naturally drying.
Preparation of the multi-layer active coating of the orthopedic implant: preparing a 1mg/mL gentamicin aqueous solution, dissolving the water-soluble gene recombinant bone morphogenetic protein into an 8mg/mL bone growth factor solution or suspension by using distilled water, and mixing the gentamicin solution and the bone growth factor solution or suspension according to the ratio of 1: 1, spraying the mixed fusion to a bone implant with a multilayer active coating by using an ultrasonic spraying instrument, and airing the bone implant at room temperature to obtain the bone implant with the multilayer active coating.
Example 2
Cleaning the orthopedic implant: cleaning the orthopedic implant after sand blasting, removing oil stains on the surface by using acetone, and performing ultrasonic cleaning by using ethanol as a cleaning agent;
preparing the tantalum metal layer orthopedic implant: installation of a magnetron sputtering spraying instrument: installing the ultrasonically cleaned orthopedic implant and the tantalum metal target material into an instrument cavity; adjusting the position of the orthopedic implant, clamping the orthopedic implant by using a clamp, and adjusting the parameters of a magnetron sputtering spraying instrument: the power supply voltage of the target is 600V, the target material is metal tantalum with the thickness of 400 x 200 x 4mm, and the protective gas is high-purity argon with the purity of 99.99 percent; vacuumizing the sputtering cavity to less than 2 x 10-3Pa, and filling argon to 2-5 Pa; the distance between the target bases is 20 mm; the negative voltage 260-320V is applied to the cathode, Ar ions accelerate to fly to the cathode target under the action of an electric field and bombard the surface of the target at high energy, so that the target is sputtered to impact the surface of the orthopedic implant and is deposited; magnetron sputtering the orthopedic implant for 30-120min, wherein the tantalum coating on the surface of the orthopedic implant is 10-40 mu m. In the magnetron sputtering process, when the sputtering distance and the sputtering current are fixed, the thickness of the tantalum coating layer and positive ions (Ar) bombarding the target are constant+) The amount is in direct proportion, the current 5A bombards for 60min, the thickness of the tantalum coating is 7.2 mu m, and the tantalum coating is taken out and cooled to 15-25 ℃ after sputtering is finished.
Preparing the bionic-tantalum metal orthopedic implant: preparing a hydroxyapatite coating by adopting a bionic deposition method, placing the tantalum metal layer orthopedic implant in an alkaline dopamine solution in a constant-temperature shaking table for 24 hours, taking out the alkaline dopamine solution, cleaning the alkaline dopamine solution by using deionized water, wherein the concentration of the dopamine solution is 10mmol/L, a pH regulator is a Tris-HCl solution, the pH value is regulated to 8.5, and the temperature of the constant-temperature shaking table is 37 ℃. Placing the cleaned tantalum-coated orthopedic implant in simulated body fluid in a constant-temperature shaking table for 3d, taking out the orthopedic implant, and cleaning the orthopedic implant by using deionized water, wherein the simulated body fluid is 1.5SBF, and the temperature of the constant-temperature shaking table is 37 ℃. activation-OH is a necessary condition for forming a biomimetic layer, and an alkaline heat treatment method is commonly used to treat various metals to form active-OH on the surface thereof.
Preparation of the multi-layer active coating of the orthopedic implant: preparing a 1mg/mL gentamicin aqueous solution, dissolving the water-soluble gene recombinant bone morphogenetic protein into an 8mg/mL bone growth factor solution or suspension by using distilled water, and mixing the gentamicin solution and the bone growth factor solution or suspension according to the ratio of 1: 1, soaking the bone implant with the multilayer active coating in the mixed solution for 2 hours, taking out, and airing at room temperature to obtain the bone implant with the multilayer active coating.
The bone implant coating prepared by the technical scheme of the invention is mainly used for metal porous bone implants, in particular porous titanium bone implant products. The titanium alloy bone implant is easy to wear to generate particles to cause inflammation, the strengthening layer of the coating is strengthened by adopting a tantalum metal coating to improve the wear resistance of the implant, the tantalum coating is prepared by adopting a magnetron sputtering technology, the thickness is only 3.4-14.4 mu m, the porosity of porous tantalum is generally 500 mu m in 200-materials, and the coating thickness can be controlled by magnetron sputtering time; the bionic coating is prepared by adopting a calcium phosphate supersaturated solution or a bionic method, the coating is thin and cannot block pores, the biomineralization performance on the surface of the implant is greatly improved, the hydrophilic performance is improved, and the attachment growth of osteoblasts is facilitated; the outermost coating contains bone growth factors and anti-inflammatory drugs, can realize antibacterial and anti-inflammatory effects after implantation, and simultaneously promotes bone growth into porous gaps to accelerate the healing rate of patients.
The above-mentioned embodiments are only preferred embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical scope of the present invention, and equivalents and modifications of the technical solutions and concepts of the present invention should be covered by the scope of the present invention.

Claims (8)

1. The multi-layer active coating for the orthopedic implant is applied to the metal bone implant and is characterized by comprising a basal strengthening layer, a bionic layer and an active functional layer;
the basic strengthening layer is a tantalum metal layer;
the bionic layer is a calcium phosphate or hydroxyapatite coating;
the active functional layer is a coating comprising one or more of bone morphogenetic proteins, bone growth factors or antibiotics.
2. The multi-layer active coating for orthopedic implants according to claim 1, wherein the metal bone implant is any one of porous structured intervertebral cage, acetabular cup, artificial vertebral body and filling block, and the material of the metal bone implant is one of TC4 titanium alloy, pure titanium and cobalt chromium alloy.
3. The orthopedic implant multilayer active coating of claim 1, wherein the tantalum metal layer has a thickness of 10-40 μ ι η.
4. The orthopedic implant multilayer active coating of claim 1, wherein the antibiotic is one or more of gentamicin, vancomycin, clindamycin.
5. The preparation method of the multi-layer active coating for the orthopedic implant is characterized by specifically comprising the following steps of:
performing sand blasting treatment and cleaning on the orthopedic implant to obtain a pretreated orthopedic implant;
preparing a tantalum metal layer by adopting a magnetron sputtering spraying method to the pretreated orthopedic implant to obtain a tantalum metal layer orthopedic implant;
activating the tantalum metal layer orthopedic implant by alkali, and introducing a bionic layer by a sol-gel method, plasma spraying, electrochemical deposition or a bionic deposition method to obtain a bionic-tantalum metal orthopedic implant;
and introducing the bionic-tantalum metal orthopedic implant into an active functional layer by adopting a spraying method or a dipping method to obtain the multi-layer active coating of the orthopedic implant.
6. The method for preparing the multilayer active coating for the orthopedic implant according to claim 5, wherein the magnetron sputtering spraying method comprises the following steps:
the protective gas of the cavity of the magnetron sputtering spraying instrument is high-purity argon with the purity of 99.99 percent, the negative voltage of the cathode is between 260 and 330V, and the sputtering cavity is vacuumized to be less than 2 x 10-3When Pa, filling argon to 2-5 Pa; the target base spacing was 20 mm.
7. The method for preparing the multi-layer active coating of the orthopedic implant according to claim 5, wherein the alkali used in the alkali activation process of the tantalum metal layer orthopedic implant is sodium hydroxide or alkaline dopamine.
8. The preparation method of the multi-layer active coating of the orthopedic implant according to claim 5, wherein the step of introducing the biomimetic-tantalum metal orthopedic implant into the active functional layer by adopting a spraying method or a dipping method to obtain the multi-layer active coating of the orthopedic implant specifically comprises the following steps:
preparing an active functional layer solution: adding bone morphogenetic protein or bone growth factor into distilled water to prepare 5-10mg/mL biomacromolecule solution or suspension; adding antibiotics into distilled water to prepare 1-3mg/mL antibiotic water solution;
and mixing the biomacromolecule solution or suspension with an antibiotic aqueous solution, and introducing an active functional layer into the bionic-tantalum metal orthopedic implant by adopting a spraying method or a dipping method.
CN202111408288.2A 2021-11-19 2021-11-19 Multi-layer active coating for orthopedic implant and preparation method thereof Pending CN114099777A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111408288.2A CN114099777A (en) 2021-11-19 2021-11-19 Multi-layer active coating for orthopedic implant and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111408288.2A CN114099777A (en) 2021-11-19 2021-11-19 Multi-layer active coating for orthopedic implant and preparation method thereof

Publications (1)

Publication Number Publication Date
CN114099777A true CN114099777A (en) 2022-03-01

Family

ID=80372403

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111408288.2A Pending CN114099777A (en) 2021-11-19 2021-11-19 Multi-layer active coating for orthopedic implant and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114099777A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115120783A (en) * 2022-06-29 2022-09-30 湖南华翔医疗科技有限公司 Porous titanium-based antibacterial active material, and preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101984939A (en) * 2010-12-16 2011-03-16 西安福安创意咨询有限责任公司 Design method of artificial elbow joint prosthesis with tantalum coating
CN103041449A (en) * 2012-12-19 2013-04-17 北京固圣生物科技有限公司 Composite bioactivity functional coating
CN103451602A (en) * 2012-05-28 2013-12-18 江苏创英医疗器械有限公司 Surface treatment process of bioactive metallic titanium implant having multistage micro-pit structure
JP2017093995A (en) * 2015-11-27 2017-06-01 HOYA Technosurgical株式会社 Method for producing composite body, and composite body
CN110115777A (en) * 2019-05-29 2019-08-13 扬州大学 The preparation method for having the titanium alloy material of good biocompatibility and bacteria resistance function coating
CN113289057A (en) * 2021-05-19 2021-08-24 北京爱康宜诚医疗器材有限公司 Tantalum-coated orthopedic implant material, preparation method thereof and orthopedic implant
CN214285311U (en) * 2020-12-09 2021-09-28 湖南普林特医疗器械有限公司 Low-elasticity-modulus acetabulum outer cup

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101984939A (en) * 2010-12-16 2011-03-16 西安福安创意咨询有限责任公司 Design method of artificial elbow joint prosthesis with tantalum coating
CN103451602A (en) * 2012-05-28 2013-12-18 江苏创英医疗器械有限公司 Surface treatment process of bioactive metallic titanium implant having multistage micro-pit structure
CN103041449A (en) * 2012-12-19 2013-04-17 北京固圣生物科技有限公司 Composite bioactivity functional coating
JP2017093995A (en) * 2015-11-27 2017-06-01 HOYA Technosurgical株式会社 Method for producing composite body, and composite body
CN110115777A (en) * 2019-05-29 2019-08-13 扬州大学 The preparation method for having the titanium alloy material of good biocompatibility and bacteria resistance function coating
CN214285311U (en) * 2020-12-09 2021-09-28 湖南普林特医疗器械有限公司 Low-elasticity-modulus acetabulum outer cup
CN113289057A (en) * 2021-05-19 2021-08-24 北京爱康宜诚医疗器材有限公司 Tantalum-coated orthopedic implant material, preparation method thereof and orthopedic implant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
黄利平等: "真空等离子喷涂HA/Ta复合涂层", 《热喷涂技术》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115120783A (en) * 2022-06-29 2022-09-30 湖南华翔医疗科技有限公司 Porous titanium-based antibacterial active material, and preparation method and application thereof

Similar Documents

Publication Publication Date Title
Ran et al. Osteogenesis of 3D printed porous Ti6Al4V implants with different pore sizes
Montazerian et al. Bioceramic coatings on metallic implants: An overview
Zhu et al. Advances in implant surface modifications to improve osseointegration
Spriano et al. A critical review of multifunctional titanium surfaces: New frontiers for improving osseointegration and host response, avoiding bacteria contamination
Duan et al. Surface modifications of bone implants through wet chemistry
Neacşu et al. Inorganic micro-and nanostructured implants for tissue engineering
Han et al. Surface modification techniques of titanium and titanium alloys for biomedical orthopaedics applications: A review
US6461385B1 (en) Method and apparatus for augmenting osteointegration of prosthetic implant devices
EP2014319A1 (en) A bone tissue implant comprising strontium ions
US20080269910A1 (en) Medical prosthetic devices having improved biocompatibility
CA2685878A1 (en) Coating of implants with hyaluronic acid solution
Oshida et al. Biocompatible coatings for metallic biomaterials
Anil et al. Bone response to calcium phosphate coatings for dental implants
Shi et al. Surface modification on biodegradable zinc alloys
CN114099777A (en) Multi-layer active coating for orthopedic implant and preparation method thereof
Layrolle 1.112-Calcium Phosphate Coatings
WO2002017820A1 (en) Porous attachment material for cells
CN1282489C (en) Boneoid apatite bio-active gradient coated artificial joint material and preparing process thereof
KR101822255B1 (en) A method for preparation of a metallic implant comprising biocompatable fluoride ceramic coating
RU2765921C1 (en) Method for manufacturing a dental implant using a composite nanocoating
Victoria Cabanas Bioceramic coatings for medical implants
Iqbal et al. Coating of hydroxyapatite and substituted apatite on dental and orthopedic implants
Cosma et al. Surface treatments applied on titanium implants
De Groot et al. Biomimetic coatings on orthopedic implants: a review
EP3195825A1 (en) Dental implant

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20220301

RJ01 Rejection of invention patent application after publication