CN108543109B - Low-abrasion dual-antibacterial titanium-based nanocomposite bone implant and forming method thereof - Google Patents

Low-abrasion dual-antibacterial titanium-based nanocomposite bone implant and forming method thereof Download PDF

Info

Publication number
CN108543109B
CN108543109B CN201810203105.5A CN201810203105A CN108543109B CN 108543109 B CN108543109 B CN 108543109B CN 201810203105 A CN201810203105 A CN 201810203105A CN 108543109 B CN108543109 B CN 108543109B
Authority
CN
China
Prior art keywords
titanium
bone implant
antibacterial
titanium alloy
low
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.)
Active
Application number
CN201810203105.5A
Other languages
Chinese (zh)
Other versions
CN108543109A (en
Inventor
夏木建
李年莲
林岳宾
刘爱辉
丁红燕
陈中
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.)
Huaiyin Institute of Technology
Original Assignee
Huaiyin Institute of Technology
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 Huaiyin Institute of Technology filed Critical Huaiyin Institute of Technology
Priority to CN201810203105.5A priority Critical patent/CN108543109B/en
Publication of CN108543109A publication Critical patent/CN108543109A/en
Application granted granted Critical
Publication of CN108543109B publication Critical patent/CN108543109B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • A61L27/025—Other specific inorganic materials not covered by A61L27/04 - A61L27/12
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/20—Direct sintering or melting
    • 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
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/06—Titanium or titanium alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—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
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/30—Process control
    • B22F10/32—Process control of the atmosphere, e.g. composition or pressure in a building chamber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/30—Process control
    • B22F10/34—Process control of powder characteristics, e.g. density, oxidation or flowability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • A61L2300/104—Silver, e.g. silver sulfadiazine
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
    • 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
    • A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/30—Process control
    • B22F10/36—Process control of energy beam parameters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/30—Process control
    • B22F10/36—Process control of energy beam parameters
    • B22F10/366—Scanning parameters, e.g. hatch distance or scanning strategy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Medicinal Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dermatology (AREA)
  • Public Health (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Biomedical Technology (AREA)
  • Molecular Biology (AREA)
  • Prostheses (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention discloses a low-abrasion dual-antibacterial titanium-based nanocomposite bone implant and a forming method thereof, wherein the titanium-based nanocomposite bone implant is a dual-phase antibacterial nano silver and titanium dioxide ceramic reinforced titanium alloy bone implant generated in situ; the titanium-based nano composite material bone implant has excellent lasting antibacterial function and wear resistance. The forming method comprises the following steps: (1) acquiring a bone implant three-dimensional model; (2) carrying out vacuum drying treatment on the micron silver oxide particles, then carrying out wet ball milling mixing on the micron silver oxide particles and medical spherical titanium alloy powder, and drying the mixture to obtain dry micron silver oxide-titanium alloy composite material powder; (3) under the protection of high-purity argon, nano silver particles and titanium dioxide are formed in situ by a laser additive manufacturing process and dispersed in the titanium alloy bone implant, so that the integrated precise manufacturing of the complex structure, the nano composite material and the dual antibacterial function of the high-performance titanium-based nano composite material bone implant is realized.

Description

Low-abrasion dual-antibacterial titanium-based nanocomposite bone implant and forming method thereof
Technical Field
The invention relates to a composite material bone implant and a forming method thereof, in particular to a low-abrasion dual-antibacterial titanium-based nano composite material bone implant and a forming method thereof.
Background
Titanium and titanium alloys are widely used in the field of surgical implants because of their good biocompatibility and biomechanical properties, and in particular, novel low-modulus beta-type titanium alloys developed in recent years, such as Ti-13Nb-13Zr alloy developed by Smith & Nephew Riehards, added with non-toxic elements Nb and Zr, and have an elastic modulus close to that of human bones. Although titanium alloys have significant advantages in the field of artificial bone implants, the problems of low activity, insufficient safety and the like still exist. Particularly, titanium alloy belongs to inert materials, has no antibacterial property, and is easy to be infected by bacteria to influence the combination with bone tissues although aseptic operation is adopted in the implantation process and the titanium alloy is matched with antibiotics.
At present, firstly, an antibacterial coating is deposited on the surface of a titanium alloy implant by a surface modification method to improve the antibacterial capability of the implant; and secondly, forming the titanium-copper antibacterial implant by adopting a hot-pressing sintering or laser 3D printing method. These measures improve the antibacterial effect of the titanium alloy bone implant to a certain extent, but have the following disadvantages: (1) the bonding strength of the antibacterial coating and the titanium alloy matrix is limited, the bone implant is often interacted with surrounding soft/hard tissues in the service process under the complex physiological condition of a human body, particularly the interaction stress action is often generated between a hip joint and a knee joint which are highly loaded and human bones, so that the antibacterial coating is easy to lose efficacy, and the condition of a patient is further worsened; (2) bacteriostatic copper Cu certified by the United states environmental protection agency+"is biased to the bacteriostatic performance and has not ideal antibacterial effect.
On the other hand, the titanium alloy bone implant has insufficient wear resistance, and the factors of corrosion and abrasion in the internal service process of a human body cause the dissolution of harmful metal elements in a metal material in the human body, so that the allergy, inflammatory reaction, local necrosis and even canceration of tissues around the metal implant are caused. Currently, the main approaches to improve the wear resistance of titanium alloy bone implants are: obtaining a high-wear-resistance ceramic film on the surface of the titanium alloy based on a material surface modification technology; secondly, the ceramic reinforced titanium-based composite material is prepared by processes of vacuum casting, powder sintering and the like so as to improve the wear resistance of the ceramic reinforced titanium-based composite material. Through a series of clinical experiments, the measures have certain defects, which are specifically shown as follows: (1) the ceramic membrane has high hardness and large brittleness, so that the wear resistance of the titanium alloy can be obviously improved, but the physical property mismatch of the ceramic and the titanium alloy substrate often causes weak bonding strength of the ceramic membrane and the substrate, and the ceramic membrane is easy to crack or even crack under the action of impact load or point contact stress in the service process, and finally fails; (2) for the ceramic reinforced titanium-based composite material, the interface wetting property is poor due to the difference of physical properties of the ceramic and the titanium alloy matrix, and in the process of rubbing with human bones, ceramic particles are separated from the titanium alloy matrix under the action of friction force and easily infect tissues around an implant, so that the infection phenomenon is particularly obvious in a corrosive and wear environment.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a low-abrasion double-antibacterial titanium-based nano composite material bone implant and a forming method thereof aiming at the problems of the existing titanium-based bone implant.
The technical scheme is as follows: the low-abrasion double-antibacterial titanium-based nano composite material bone implant is a two-phase antibacterial nano silver and titanium dioxide ceramic reinforced titanium alloy bone implant generated in situ.
Preferably, the nano silver particles and the nano titanium dioxide ceramic are obtained by in-situ reaction of titanium alloy powder and micro silver oxide particles under the action of a high-energy laser beam, and the in-situ reaction process comprises the following steps: 2Ag2O+Ti→TiO2+4 Ag; wherein the mass of the micron silver oxide particles accounts for 1-10% of the total mass of the micron silver oxide particles and the titanium alloy powder.
The invention relates to a forming method of a low-abrasion double-antibacterial titanium-based nanocomposite bone implant, which comprises the following steps:
(1) acquiring a bone implant three-dimensional model, and carrying out layered slicing processing on the three-dimensional model;
(2) carrying out vacuum drying treatment on the micron silver oxide particles, carrying out wet ball milling mixing on the dried micron silver oxide particles and titanium alloy powder, and then drying to obtain uniformly mixed dry micron silver oxide-titanium alloy composite material powder;
(3) under the protection atmosphere of high-purity argon, dispersing the dried micron silver oxide-titanium alloy composite powder in-situ formed nano silver particles and nano titanium dioxide ceramic into the titanium alloy bone implant through a laser additive manufacturing process to obtain the low-abrasion dual-antibacterial titanium-based nano composite bone implant.
In the step (2), the vacuum drying process preferably includes: the vacuum drying temperature is 60-80 ℃, and the drying time is 5-10 h.
In the forming raw material, the mass of the dried micron silver oxide particles accounts for 1-10% of the total mass of the titanium alloy particles and the dried micron silver oxide particles. Wherein the titanium alloy powder is medical spherical titanium alloy powder, which can be medical pure titanium, Ti-Nb-Zr alloy or Ti-Ta alloy. Further, the particle size of the titanium alloy powder is 10-60 mu m, and the purity is 99.5%; the average grain diameter of the micron silver oxide particles is 15-40 mu m, and the purity is 99.9%.
Preferably, in the step (2), the dried micron silver oxide particles and the titanium alloy powder are placed in a ball milling tank, and wet ball milling and mixing are carried out by using a high-energy ball milling process, wherein the conditions of the high-energy ball milling process are as follows: the revolution speed is 100-250 rpm, and the rotation speed of the ball milling pot is 200-500 rpm.
In the step (3), the dry micron silver oxide-titanium alloy composite powder can be placed in a powder bin of laser additive manufacturing equipment, a mechanical pump is started to vacuumize a forming cavity, when the pressure in the cavity is lower than 0.05Pa, high-purity argon is introduced into the cavity, the laser additive manufacturing process conditions are set, and the low-abrasion double-antibacterial titanium-based nano composite bone implant is precisely formed.
Preferably, the laser additive manufacturing process conditions are as follows: the energy density of the high-energy laser beam body is 30-150J/m3And adopting a fault orthogonal scanning strategy.
The invention principle is as follows: based on the thermodynamic characteristics of the in-situ reaction of titanium and silver oxide and the excellent antibacterial function of the nano-silver particles, the invention adopts the laser additive manufacturing technology to generate the nano-scale silver and nano-titanium dioxide particles with double-phase antibacterial property by the in-situ reaction of 2Ag2O + Ti → TiO2+4Ag, thereby greatly enhancing the antibacterial property of the titanium alloy bone implant; moreover, based on the dependence relationship between the antibacterial ability of the nano-silver and the titanium dioxide particles and the sizes of the nano-silver and the titanium dioxide particles, the controllable growth of the in-situ nano-particles can be realized by changing the parameters of the laser additive manufacturing process, so that the regulation and control of the antibacterial function are realized; in addition, based on the physical property characteristic of low melting point of the silver oxide, the silver oxide with micron scale is completely melted under the action of high-energy laser beam, the nano titanium dioxide ceramic generated by the in-situ reaction with titanium has good interface bonding strength with the titanium alloy matrix, and the nano titanium dioxide ceramic is dispersed in the titanium alloy matrix, so that the wear resistance of the titanium alloy implant under the physiological condition of a human body is enhanced.
Has the advantages that: compared with the prior art, the invention has the beneficial effects that: (1) the titanium-based nano composite material bone implant is dispersed with in-situ synthesized two-phase antibacterial nano silver and titanium dioxide particles, and has excellent lasting antibacterial function and prolonged service life compared with a single antibacterial titanium alloy bone implant; (2) the nano titanium dioxide ceramic generated in situ is dispersed in the titanium alloy bone implant, so that the strength of the titanium alloy bone implant can be further improved, the corrosive wear rate is reduced, the service performance of the titanium alloy bone implant is excellent, and the titanium alloy bone implant has a good market prospect; (3) the invention adopts an advanced laser additive manufacturing process, realizes the integrated precise manufacturing of the complex structure, the nano composite material and the dual antibacterial function of the high-performance titanium-based nano composite material bone implant, has simple forming process, does not need subsequent complex process, greatly improves the manufacturing efficiency, and avoids the economic cost and the external bacteria invasion caused by multiple processes; in addition, the controllable growth of the in-situ nano particles can be realized by changing the parameters of the laser additive manufacturing process, so that the regulation and control of the antibacterial function are realized.
Drawings
FIG. 1 is a microstructural view of a low-wear dual antimicrobial titanium-based nanocomposite bone implant formed in accordance with example 1;
FIG. 2 is a friction coefficient of a low wear dual antimicrobial titanium-based nanocomposite bone implant formed in accordance with example 2 in simulated body fluid;
FIG. 3 is a graph of the wear rate of low-wear dual antimicrobial titanium-based nanocomposite bone implants formed in examples 1-6 in simulated body fluids.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
The low-abrasion double-antibacterial titanium-based nano composite material bone implant is a titanium alloy bone implant, and the inside of the bone implant contains nano silver and titanium dioxide double-phase particles with antibacterial performance; wherein, the nano silver particles and the nano titanium dioxide ceramics are formed and dispersed in the titanium alloy bone implant in an in-situ synthesis mode.
The nano silver particles and the nano titanium dioxide ceramic can be obtained by the in-situ reaction of titanium alloy powder and micro silver oxide particles under the action of a high-energy laser beam, and the in-situ reaction process comprises the following steps: 2Ag2O+Ti→TiO2+4 Ag; in the raw materials, the mass of the micron silver oxide particles accounts for 1-10% of the total mass of the micron silver oxide particles and the titanium alloy powder.
Thermodynamic and kinetic conditions (2 Ag) based on in-situ generation of nano-scale silver and titanium dioxide dual-phase antibacterial particles2O+Ti→TiO2+4Ag), according to the service function requirements of the titanium alloy artificial bone implant such as low abrasion and high antibacterial property in human body and the manufacturing requirements of precise formation of the bone implant, the invention realizes the integrated precise manufacturing of the complex structure, the nano composite material and the dual antibacterial function of the high-performance titanium-based nano composite material bone implant by means of the laser additive manufacturing technology.
Example 1
(1) Scanning a bone model of a diseased part of a patient through an electronic computed tomography scanner to obtain a spatial three-dimensional model, repairing the defective part by using topology optimization software to generate a complete bone implant model, and carrying out layered slicing on the model;
(2) implanting the micron silver oxide particles into a vacuum drying furnace, setting the drying temperature to be 70 ℃ and the drying time to be 5h, and removing the moisture adsorbed on the surfaces of the particles;
(3) weighing dried micron silver oxide particles and medical spherical titanium alloy powder according to the mass fraction ratio of the micron silver oxide particles of 1%, placing the mixture into a ball milling tank, wherein the average particle size of the silver oxide is 15 microns, the purity is 99.9%, the spherical titanium alloy is medical pure titanium, the particle size is 10-60 microns, the purity is 99.5%, adding not less than 200ml of absolute ethyl alcohol into the ball milling tank, performing wet ball milling mixing on the weighed powder by using a high-energy ball milling process, drying, the revolution speed is 200rpm, and the autorotation speed of the ball milling tank is 400rpm, so as to obtain uniformly mixed dried micron silver oxide-titanium alloy composite powder;
(4) placing dry micron silver oxide-titanium alloy composite material powder in a powder bin of laser additive manufacturing equipment, starting a mechanical pump to vacuumize a forming cavity, introducing high-purity argon into the cavity when the pressure in the cavity is lower than 0.05Pa, and setting the energy density of a high-energy laser beam body to be 30J/m3And precisely forming the low-abrasion nano-silver and titanium dioxide double-antibacterial titanium-based nano-composite material bone implant by adopting a fault orthogonal scanning strategy.
The microstructure of the low-abrasion dual-antibacterial titanium-based nanocomposite bone implant formed by the implementation is shown in fig. 1, and it can be seen that the formed nano silver particles with the antibacterial function and the nano carbon dioxide ceramic are dispersed in the titanium alloy bone implant in situ, and the interface of the nano titanium dioxide particles and the titanium alloy matrix has no obvious defect and is well combined.
The low-abrasion dual-antibacterial titanium-based nanocomposite bone implant formed in the embodiment is subjected to an antibacterial performance test, staphylococcus aureus is selected as a test object, the antibacterial performance of the artificial hip joint is detected according to QB/T2591-2003 'antibacterial plastic-antibacterial performance test method and antibacterial effect', the result shows that after 24 hours of the test, the antibacterial rate of the titanium alloy hip joint on the staphylococcus aureus reaches 99.8%, the antibacterial rate of the titanium alloy hip joint after 96 hours of the test still reaches 99.6%, and the titanium alloy hip joint has good lasting antibacterial performance.
Example 2
A low wear dual antimicrobial titanium-based nanocomposite bone implant was prepared with reference to the forming method of example 1, except that: the titanium alloy adopted in the step (3) of the embodiment is Ti-Ta alloy, and the average grain diameter of silver oxide is 40 μm; the energy density of the high-energy laser beam body in the step (4) is 150J/m3。
The low-abrasion dual-antibacterial titanium-based nanocomposite bone implant formed in the embodiment is subjected to an antibacterial performance test, staphylococcus aureus is selected as a test object, the antibacterial performance of the artificial hip joint is detected according to QB/T2591-2003 'antibacterial plastic-antibacterial performance test method and antibacterial effect', the result shows that after 24 hours of the test, the antibacterial rate of the titanium alloy hip joint on the staphylococcus aureus reaches 99.5%, the antibacterial rate of the titanium alloy hip joint after 96 hours of the test still reaches 99.4%, and the titanium alloy hip joint has good lasting antibacterial performance.
The low-wear dual antibacterial titanium-based nanocomposite bone implant formed in the embodiment was subjected to a wear resistance test, as shown in fig. 2, it can be seen that the friction coefficient of the low-wear dual antibacterial titanium-based nanocomposite bone implant in a simulated body fluid is only 0.05, and the friction coefficient has no fluctuation, indicating that the friction process is relatively stable.
Example 3
A low wear dual antimicrobial titanium-based nanocomposite bone implant was prepared with reference to the forming method of example 2, except that: in the step (3) of this example, the mass fraction of the micron silver oxide is 5%, the average particle size of the silver oxide is 15 μm, and the titanium alloy used is Ti-Nb-Zr alloy.
The low-abrasion dual-antibacterial titanium-based nanocomposite bone implant formed in the embodiment is subjected to an antibacterial performance test, staphylococcus aureus is selected as a test object, the antibacterial performance of the artificial hip joint is detected according to QB/T2591-2003 'antibacterial plastic-antibacterial performance test method and antibacterial effect', the result shows that after 24 hours of the test, the antibacterial rate of the titanium alloy hip joint on the staphylococcus aureus reaches 99.9%, the antibacterial rate of the titanium alloy hip joint after 96 hours of the test still reaches 99.8%, and the titanium alloy hip joint has good lasting antibacterial performance.
Example 4
A low wear dual antimicrobial titanium-based nanocomposite bone implant was prepared with reference to the forming method of example 3, except that: the titanium alloy adopted in the step (3) of the embodiment is medical pure titanium, and the average grain size of silver oxide is 40 μm; the energy density of the high-energy laser beam body in the step (4) is 90J/m3。
The low-abrasion dual-antibacterial titanium-based nanocomposite bone implant formed in the embodiment is subjected to an antibacterial performance test, staphylococcus aureus is selected as a test object, the antibacterial performance of the artificial hip joint is detected according to QB/T2591-2003 'antibacterial plastic-antibacterial performance test method and antibacterial effect', the result shows that after 24 hours of the test, the antibacterial rate of the titanium alloy hip joint on the staphylococcus aureus reaches 99.9%, the antibacterial rate of the titanium alloy hip joint after 96 hours of the test still reaches 99.7%, and the titanium alloy hip joint has good lasting antibacterial performance.
Example 5
A low wear dual antimicrobial titanium-based nanocomposite bone implant was prepared with reference to the forming method of example 4, except that: in the step (3) of this embodiment, the titanium alloy is Ti — Ta alloy, the average particle size of silver oxide is 15 μm, and the mass fraction of micron silver oxide is 10%.
The low-abrasion dual-antibacterial titanium-based nanocomposite bone implant formed in the embodiment is subjected to an antibacterial performance test, staphylococcus aureus is selected as a test object, the antibacterial performance of the artificial hip joint is detected according to QB/T2591-2003 'antibacterial plastic-antibacterial performance test method and antibacterial effect', the result shows that after 24 hours of the test, the antibacterial rate of the titanium alloy hip joint on the staphylococcus aureus reaches 99.9%, the antibacterial rate of the titanium alloy hip joint after 96 hours of the test still reaches 99.8%, and the titanium alloy hip joint has good lasting antibacterial performance.
Example 6
A low wear dual antimicrobial titanium-based nanocomposite bone implant was prepared with reference to the forming method of example 5, except that: the titanium alloy used in step (3) of this example is a Ti-Nb-Zr alloy, and the average particle size of silver oxide is 40 μm; the energy density of the high-energy laser beam body in the step (4) is 120J/m3。
The low-abrasion dual-antibacterial titanium-based nanocomposite bone implant formed in the embodiment is subjected to an antibacterial performance test, staphylococcus aureus is selected as a test object, the antibacterial performance of the artificial hip joint is detected according to QB/T2591-2003 'antibacterial plastic-antibacterial performance test method and antibacterial effect', the result shows that after 24 hours of the test, the antibacterial rate of the titanium alloy hip joint on the staphylococcus aureus reaches 99.7%, the antibacterial rate of the titanium alloy hip joint after 96 hours of the test still reaches 99.4%, and the titanium alloy hip joint has good lasting antibacterial performance.
The low-wear dual-antibacterial titanium-based nanocomposite bone implant formed in the embodiments 1 to 6 is subjected to 24-hour and 96-hour antibacterial experiments by taking staphylococcus aureus as a test object, and the results show that the bacteriostasis rate of the titanium alloy hip joint to the staphylococcus aureus after 24 hours is higher than 99.5%, and the bacteriostasis rate of the titanium alloy hip joint to the staphylococcus aureus after 96 hours is higher than 99.4%.
the wear resistance of the low-wear dual antibacterial titanium-based nanocomposite bone implant formed in examples 1-6 in simulated body fluid is shown in fig. 3, and it can be seen that the wear rates of the low-wear dual antibacterial titanium-based nanocomposite bone implant formed in the above examples are all lower than 4.5 × 10-5mm3N · m; therefore, the low-wear dual-antibacterial titanium-based nanocomposite bone implant formed under different forming processes has good antibacterial durability and good corrosion and abrasion resistance, and the performance test result shows that the low-wear dual-antibacterial titanium-based nanocomposite bone implant provided by the invention has excellent comprehensive service performance.

Claims (8)

1. A low-abrasion dual antibacterial titanium-based nanocomposite bone implant is characterized in that the titanium-based nanocomposite bone implant is a biphase antibacterial nano silver and titanium dioxide ceramic reinforced titanium alloy bone implant generated in situ;
the method of forming the titanium-based nanocomposite bone implant comprises the steps of:
(1) acquiring a bone implant three-dimensional model, and performing repair and layered slicing on the three-dimensional model;
(2) carrying out vacuum drying treatment on the micron silver oxide particles, carrying out wet ball milling mixing on the dried micron silver oxide particles and titanium alloy powder, and then drying to obtain uniformly mixed dry micron silver oxide-titanium alloy composite material powder;
(3) under the protection atmosphere of high-purity argon, dispersing the dried micron silver oxide-titanium alloy composite powder in-situ formed nano silver particles and nano titanium dioxide ceramic into the titanium alloy bone implant through a laser additive manufacturing process to obtain the low-abrasion dual-antibacterial titanium-based nano composite bone implant.
2. The low-wear dual antibacterial titanium-based nanocomposite bone implant according to claim 1, wherein in step (2), the vacuum drying process conditions are: the vacuum drying temperature is 60-80 ℃, and the drying time is 5-10 h.
3. The low-wear dual antibacterial titanium-based nanocomposite bone implant according to claim 1, wherein in step (2), the mass of the dry micro silver oxide particles is 1 to 10% of the total mass of the dry micro silver oxide particles and the titanium alloy powder.
4. The low-wear dual antibacterial titanium-based nanocomposite bone implant according to claim 1, wherein in step (2), the dried micron silver oxide particles and titanium alloy powder are placed in a ball milling tank and wet ball milled and mixed using a high energy ball milling process, the conditions of the high energy ball milling process being: the revolution speed is 100-250 rpm, and the rotation speed of the ball milling pot is 200-500 rpm.
5. The low-wear dual antibacterial titanium-based nanocomposite bone implant according to claim 1, wherein in step (2), the titanium alloy powder is a medical spherical titanium alloy powder, and the medical spherical titanium alloy is medical pure titanium, a Ti-Nb-Zr alloy, or a Ti-Ta alloy.
6. The low-wear dual antibacterial titanium-based nanocomposite bone implant according to claim 1, wherein in step (2), the titanium alloy powder has a particle size of 10 to 60 μm and a purity of 99.5%; the average particle size of the micron silver oxide particles is 15-40 mu m, and the purity is 99.9%.
7. The low-abrasion dual-antibacterial titanium-based nanocomposite bone implant according to claim 1, wherein in the step (3), the dry micro silver oxide-titanium alloy composite powder is placed in a powder bin of a laser additive manufacturing device, a mechanical pump is started to vacuumize a forming cavity, when the pressure in the cavity is lower than 0.05Pa, high-purity argon gas is introduced into the cavity, the laser additive manufacturing process conditions are set, and the low-abrasion dual-antibacterial titanium-based nanocomposite bone implant is precisely formed.
8. The low-wear dual antibacterial titanium-based nanocomposite bone implant according to claim 1, wherein in step (3), the laser additive manufacturing process conditions are: the energy density of the high-energy laser beam body is 30-150J/m3And adopting a fault orthogonal scanning strategy.
CN201810203105.5A 2018-03-13 2018-03-13 Low-abrasion dual-antibacterial titanium-based nanocomposite bone implant and forming method thereof Active CN108543109B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810203105.5A CN108543109B (en) 2018-03-13 2018-03-13 Low-abrasion dual-antibacterial titanium-based nanocomposite bone implant and forming method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810203105.5A CN108543109B (en) 2018-03-13 2018-03-13 Low-abrasion dual-antibacterial titanium-based nanocomposite bone implant and forming method thereof

Publications (2)

Publication Number Publication Date
CN108543109A CN108543109A (en) 2018-09-18
CN108543109B true CN108543109B (en) 2020-09-18

Family

ID=63516066

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810203105.5A Active CN108543109B (en) 2018-03-13 2018-03-13 Low-abrasion dual-antibacterial titanium-based nanocomposite bone implant and forming method thereof

Country Status (1)

Country Link
CN (1) CN108543109B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110039041A (en) * 2019-04-22 2019-07-23 依波精品（深圳）有限公司 Antibacterial stainless steel composite powder, antibacterial stainless steel and preparation method thereof
PL239585B1 (en) 2019-06-25 2021-12-20 Politechnika Slaska Im Wincent Method of obtaining porous antibacterial coatings on the surface of titanium and its alloys
PL239584B1 (en) 2019-06-25 2021-12-20 Politechnika Slaska Im Wincent Method of obtaining porous antibacterial coatings on the surface of titanium and its alloys
CN111922340B (en) * 2020-06-30 2021-05-25 吉林大学 Method for preparing medical titanium alloy material by laser sintering

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU3709100A (en) * 1999-02-26 2000-09-14 Advanced Cardiovascular Systems Inc. Composite super elastic/shape memory alloy and malleable alloy stent
CN102758202B (en) * 2012-08-11 2014-05-07 西北有色金属研究院 Method for preparing biomedical titanium and titanium alloy surface antibacterial coatings
CN105435305B (en) * 2015-12-17 2019-02-26 西南交通大学 A kind of POROUS TITANIUM composite material and preparation method
CN106745237A (en) * 2016-12-30 2017-05-31 尹宗杰 A kind of layer type casting moulding Graphene non-metallic metal composite and preparation method
CN107130138B (en) * 2017-05-19 2018-09-04 淮阴工学院 The method of medical high abrasion titanium alloy composite material and 3D printing gradient in-situ nano complex phase anti-attrition medical titanium alloy

Also Published As

Publication number Publication date
CN108543109A (en) 2018-09-18

Similar Documents

Publication Publication Date Title
CN108543109B (en) Low-abrasion dual-antibacterial titanium-based nanocomposite bone implant and forming method thereof
Sharifianjazi et al. Hydroxyapatite consolidated by zirconia: applications for dental implant
Ullah et al. Mechanical, biological, and antibacterial characteristics of plasma-sprayed (Sr, Zn) substituted hydroxyapatite coating
CN107952962B (en) A kind of functionally gradient biomimetic features titanium alloy artificial implant and its manufacturing process
CN108705092B (en) 3D printing in-situ rare earth doped titanium-based composite material active bone implant and forming method
Avila et al. Additive manufacturing of titanium and titanium alloys for biomedical applications
CN107904424A (en) A kind of preparation method of the medical porous Ti Cu alloys of biologically active antimicrobial form
US20110195378A1 (en) Composite Bio-Ceramic Dental Implant and Fabricating Method Thereof
US20130150227A1 (en) Composite Bio-Ceramic Dental Implant and Fabricating Method Thereof
Feng et al. Toughening and strengthening mechanisms of porous akermanite scaffolds reinforced with nano-titania
Bakhsheshi-Rad et al. Synthesis and in-vitro characterization of biodegradable porous magnesium-based scaffolds containing silver for bone tissue engineering
CN104195367B (en) A kind of preparation method of low elastic modulus bio-medical TiNbSn-HA composite
Wang et al. A trilogy antimicrobial strategy for multiple infections of orthopedic implants throughout their life cycle
Zhang et al. Effect of surface treatments on the surface morphology, corrosion property, and antibacterial property of Ti–10Cu sintered alloy
Müller et al. In vitro apatite formation on chemically treated (P/M) Ti–13Nb–13Zr
Pandey et al. Progress on medical implant: a review and prospects
Raj et al. Fracture resistant, antibiofilm adherent, self-assembled PMMA/ZnO nanoformulations for biomedical applications: physico-chemical and biological perspectives of nano reinforcement
CN109055814A (en) A kind of preparation method of medical antibacterial titanium alloy
CN104152840A (en) Method for preparing TiO2/Ta2O5 composite coating with special micro nano structure
CN108380890A (en) A kind of low-elasticity-modulus titanium zirconium dentistry implant material and preparation method thereof
Yang et al. Copper-doped mesoporous bioactive glass endows magnesium-based scaffold with antibacterial activity and corrosion resistance
CN112620626B (en) Forming method of bone induction type titanium alloy bone implant with high antibacterial property
CN112063886B (en) Magnesium-containing biological beta titanium alloy with micro/nano pores and preparation method thereof
KR101134977B1 (en) Implant surface treatment method and implant treated by the method
Ou et al. Microstructure, mechanical properties and osseointegration ability of Ta–20Zr alloy used as dental implant material

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
GR01 Patent grant
GR01 Patent grant