CN111956862A - Preparation method of graphene oxide composite titanium-based medical material - Google Patents

Preparation method of graphene oxide composite titanium-based medical material Download PDF

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CN111956862A
CN111956862A CN202010964853.2A CN202010964853A CN111956862A CN 111956862 A CN111956862 A CN 111956862A CN 202010964853 A CN202010964853 A CN 202010964853A CN 111956862 A CN111956862 A CN 111956862A
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graphene oxide
titanium
powder
medical material
micro
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刘汉源
余森
胡锐
申琦
刘少辉
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Northwestern Polytechnical University
Northwest Institute for Non Ferrous Metal Research
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Northwestern Polytechnical University
Northwest Institute for Non Ferrous Metal Research
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    • 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
    • A61L27/02—Inorganic materials
    • A61L27/08—Carbon ; Graphite
    • 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
    • A61L27/56—Porous materials, e.g. foams or sponges
    • 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
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • 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
    • B33Y80/00—Products made by additive manufacturing
    • 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

Abstract

The invention discloses a preparation method of a graphene oxide composite titanium-based medical material, which comprises the following steps: firstly, putting graphene oxide into deionized water or ethanol, performing ultrasonic treatment, and then freeze-drying to obtain graphene oxide powder; secondly, ball-milling the graphene oxide powder and the titanium-based powder to obtain mixed powder; thirdly, 3D printing is carried out on the mixed powder to obtain the porous composite material; fourthly, stress relief annealing is carried out on the porous composite material; fifthly, preparing micro-nano holes on the surface of the porous composite material to obtain the graphene oxide composite titanium-based medical material. According to the invention, the graphene oxide is introduced, so that the graphene oxide composite titanium-based medical material has excellent mechanical properties, and the graphene oxide composite titanium-based medical material and surrounding bone tissues can quickly form good bony combination by preparing the micro-nano holes, so that the applicability of the graphene oxide composite titanium-based medical material is improved.

Description

Preparation method of graphene oxide composite titanium-based medical material
Technical Field
The invention belongs to the technical field of medical titanium and titanium alloy materials, and particularly relates to a preparation method of a graphene oxide composite titanium-based medical material.
Background
Titanium and titanium alloy are preferred materials for medical appliance products for replacing or repairing hard tissues such as artificial joints, bone wound products, artificial dental implants and the like due to excellent biocompatibility, corrosion resistance and good comprehensive mechanical properties, particularly lower elastic modulus compared with stainless steel and cobalt-chromium alloy. However, the elasticity modulus (about 110GPa) of pure titanium and TC4 which are commonly used clinically is still obviously higher than that of human bone tissues (10-30GPa), and the stress shielding effect is caused. Meanwhile, titanium and titanium alloy are biological inert materials, the combination with the bone is mechanical locking rather than osseous combination, and a fiber layer lacking blood vessels is easily formed at an implant/bone combination interface, so that a series of complications such as implant infection, looseness and the like are caused. In addition, titanium and titanium alloys do not have antibacterial ability, and are liable to cause adhesion of bacteria, causing infection of the implant, and resulting in implant failure.
The graphene oxide is a derivative obtained by chemically modifying graphene through an oxygen-containing functional group, has excellent physical and chemical properties of graphene, can provide a large surface area, promotes stem cell proliferation and osteogenic differentiation within a certain concentration range, and has unique biocompatibility and antibacterial performance. The graphene oxide can improve the strength of the titanium and the titanium alloy, further improve the corrosion resistance of the titanium and the titanium alloy, and enhance the biological activity of the titanium and the titanium alloy, thereby achieving multiple purposes. So the application in biomedicine provides wide prospect.
The metal 3D printing technology is a novel rapid prototyping preparation technology gradually accumulated from line to surface and from surface to body, and compared with the traditional processing technology, the 3D printing technology has the characteristics of no mould, compact rapid prototyping or porous complex structure. The elastic modulus of the composite material can be reduced through 3D printing, and the composite material has bioactivity and antibacterial property. There is therefore a need for a medical material which bonds well to bone and has good mechanical properties.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a graphene oxide composite titanium-based medical material aiming at the defects of the prior art. According to the method, a 3D printing technology is fully utilized, the biological corrosion resistance and the comprehensive mechanical property of the titanium base and the biological compatibility and the antibacterial property of the graphene oxide are combined, meanwhile, the biological activity of the composite material is further increased by preparing the micro-nano structure on the surface of the composite material, and the prepared composite material has the comprehensive mechanical property, the biological activity and the antibacterial property and is applied to the fields of orthopedics and the like.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a preparation method of a graphene oxide composite titanium-based medical material is characterized by comprising the following steps:
step one, placing graphene oxide into deionized water or ethanol, performing ultrasonic treatment to obtain a graphene oxide solution, and then performing freeze drying on the graphene oxide solution to obtain graphene oxide powder;
step two, putting the graphene oxide powder and the titanium-based powder obtained in the step one into a vacuum ball-milling tank for ball-milling to obtain mixed powder; the titanium-based powder is titanium powder or titanium alloy powder;
step three, loading the mixed powder obtained in the step two into a 3D printer for 3D printing to obtain a porous composite material;
step four, stress relief annealing is carried out on the porous composite material obtained in the step three;
step five, preparing micro-nano holes on the surface of the porous composite material subjected to stress relief annealing in the step four to obtain the graphene oxide composite titanium-based medical material; the method for preparing the micro-nano holes is a dealloying method or a micro-arc oxidation method.
The method comprises the steps of firstly carrying out ultrasonic dispersion on graphene oxide in deionized water or ethanol, wherein the graphene oxide is floccule, and plays a role in emulsification and dispersion after ultrasonic is added, the flocculent graphene oxide can also play a role in particle refinement in the process, the flocculent graphene oxide is dispersed into particles, so that the subsequent mixing of the graphene oxide powder and the titanium-based powder is more uniform, a graphene oxide solution is obtained, then the graphene oxide solution is freeze-dried, the graphene oxide solution is quickly frozen at a low temperature, frozen water molecules are directly sublimated into water vapor and escape under a proper vacuum environment, the solutions such as water or ethanol are more quickly volatilized, the production efficiency is improved, the graphene oxide powder and the titanium-based powder are fully mixed by ball milling, and the fluidity of the mixed powder is ensured, the preparation method is favorable for the 3D printing, the antibacterial effect of the graphene oxide composite titanium-based medical material is enhanced by introducing the graphene oxide, the mechanical strength and the wear resistance are simultaneously improved, the porous composite material with a porous structure prepared by the 3D printing is adopted, the aim of metallurgy is achieved by spreading powder layer by layer and then melting and solidifying the powder layer by layer, the elastic modulus of the graphene oxide composite titanium-based medical material is reduced, the workpiece can crack, deform or change the size due to the residual stress, a part of the residual stress reserved by the porous composite material after the 3D printing process is removed by stress relief annealing, the metal chemical activity of the porous composite material is improved, the phenomena of intergranular corrosion crack, influence on the service performance of the material and premature failure of the workpiece under the action of the residual tensile stress are avoided, and the micro-nano holes are prepared on the surface of the porous composite material after the stress relief annealing, the porous structure is prepared by 3D printing, and micro-nano holes are prepared on the secondary surface of the porous composite material, which is equivalent to holes with various dimensions and is beneficial to transportation of nutrient substances in bones and growth of cells at all levels of the graphene oxide composite medical titanium-based material.
The preparation method of the graphene oxide composite titanium-based medical material is characterized in that the freeze drying conditions in the step one are as follows: the vacuum degree is 1 Pa-10 Pa, and the temperature is-30 ℃ to-50 ℃. According to the invention, through controlling the freeze-drying process parameters, the graphene oxide solution is quickly frozen at a low temperature, then the frozen water molecules are directly sublimated to form water vapor and escape in a proper vacuum environment, the solutions such as water or ethanol are more quickly volatilized, the time is saved, the water or ethanol in the graphene oxide solution is firstly sublimated after being solidified, the energy consumption is not wasted due to too low temperature, and the oxidation and pollution of the graphene oxide are avoided under the vacuum condition.
The preparation method of the graphene oxide composite titanium-based medical material is characterized in that in the second step, the titanium alloy powder is TLM titanium alloy powder or TC4ELI titanium alloy powder, the particle size of the titanium-based powder is 15-40 mu m, and liquid nitrogen is introduced around the vacuum ball-milling tank for cooling. The invention enlarges the application range of the graphene oxide composite titanium-based medical material by controlling the type of the titanium-based powder, ensures that the graphene oxide composite titanium-based medical material can be used in various application environments, improves the applicability of the graphene oxide composite titanium-based medical material, improves the fluidity of mixed powder by controlling the particle size of the titanium-based powder, theoretically, the smaller the particle size is, the better the fluidity of the mixed powder is, the finer the product tissue is, the better the performance is, but the particle size cannot be infinitely small due to the technology and the cost, the excellent fluidity of the mixed powder can be controlled to be 15-40 mu m, the preparation cost can be reduced, the ball milling process can generate heat, the temperature of a ball milling tank is reduced by introducing liquid nitrogen, the oxidation and deformation of spherical powder caused by friction heat of the mixed powder are reduced, and then the mobility of the mixed powder and the quality stability of the finished product in the 3D printing process are improved.
The preparation method of the graphene oxide composite titanium-based medical material is characterized in that the mass fraction of the graphene oxide powder in the mixed powder in the second step is 0.1-10%. According to the invention, by controlling the mass fraction of the graphene oxide powder, the graphene oxide composite titanium-based medical material is ensured to have optimal properties, the defects of formation of more reinforcing phases caused by excessive graphene oxide, reduction of the molding and overall service life are avoided, cytotoxicity is caused by excessive graphene oxide, the biomedical application is not facilitated, and the defect of limited reinforcing effect caused by too little graphene oxide is avoided.
The preparation method of the graphene oxide composite titanium-based medical material is characterized in that the porosity of the porous composite material in the third step is 30% -80%. According to the invention, the porosity of the porous composite material is controlled, so that the graphene oxide composite titanium-based medical material is ensured to have corresponding porosity at the same time, the porosity of the graphene oxide composite titanium-based medical material is reasonably designed according to different use positions and different stress, the elastic modulus of the graphene oxide composite titanium-based medical material is reduced to match with bones, the biocompatibility of the graphene oxide composite titanium-based medical material is increased, the graphene oxide composite titanium-based medical material is ensured to be well combined with the bones, the applicability of the graphene oxide composite titanium-based medical material is enhanced, and the graphene oxide composite titanium-based medical material is ensured to have proper strength and elastic modulus.
The preparation method of the graphene oxide composite titanium-based medical material is characterized in that when the titanium-based powder in the second step is titanium powder, the method for preparing the micro-nano holes in the fifth step is a micro-arc oxidation method, and the process of the micro-arc oxidation method is as follows: in a mixed aqueous solution, controlling the voltage of micro-arc oxidation to be 300-350V, the duty ratio to be 15-20% and the frequency to be 80-100 Hz, and carrying out micro-arc oxidation on the porous composite material subjected to stress relief annealing for 3-8 min, wherein the mixed solution contains calcium phosphate with the concentration of 7-9 mol/L and NaOH with the concentration of 3-5 mol/L. When the titanium-based powder is titanium powder, micro-nano holes are prepared on the surface of the porous composite material subjected to stress relief annealing by adopting a micro-arc oxidation method, calcium and phosphorus in the solution can be deposited on the surface of the porous composite material subjected to stress relief annealing to form a porous calcium and phosphorus containing micro-arc oxidation coating under a high-pressure environment provided by micro-arc oxidation, the thickness of the coating is controlled by controlling the duty ratio, frequency and time of the micro-arc oxidation method, the formed porous calcium and phosphorus containing coating is favorable for cell adhesion, and calcium and phosphorus elements contained in the coating can promote osteogenesis.
The preparation method of the graphene oxide composite titanium-based medical material is characterized in that when the titanium alloy powder is TLM titanium alloy powder, the method for preparing the micro-nano holes in the fifth step is a dealloying method, and the dealloying method comprises the following steps: in a mixed acid solution, a constant potential rectifier is adopted to apply a voltage of 5V-20V, dealloying is carried out on the porous composite material after the stress relief annealing for 20 min-60 min, and the mixed acid solution contains 0.5-2% of NaF and 8-12% of HNO by mass3. When the titanium alloy powder is TLM titanium alloy powder, micro-nano holes are prepared on the surface of the porous composite material subjected to stress relief annealing by a dealloying method, under the condition that a constant potential instrument applies voltage, the porous composite material subjected to stress relief annealing is in a mixed acid solution, fluorine ions provided by NaF break through an original oxide film layer on the surface of the porous composite material subjected to stress relief annealing, so that alloy elements in the porous composite material subjected to stress relief annealing are selectively dissolved out under the action of acid ions, a nano-scale porous structure is formed on the surface of the porous composite material subjected to stress relief annealing, the bonding force between the graphene oxide composite titanium alloy medical material and a substrate is enhanced, the nano-scale porous structure simulates a bone tissue structure, the biocompatibility of the graphene oxide composite titanium alloy medical material is improved, and the voltage and time are controlled and addedThe flow of ions in the solution is accelerated, so that the dealloying process is accelerated, and the aperture of the nano-scale porous structure is controlled.
The preparation method of the graphene oxide composite titanium-based medical material is characterized in that when the titanium alloy powder is TC4ELI titanium alloy powder, the method for preparing the micro-nano holes in the fifth step is a dealloying method, and the dealloying method comprises the following steps: in NaOH solution, a constant potential rectifier is adopted to apply 3V-10V voltage, dealloying is carried out on the porous composite material after the stress relief annealing for 1 h-3 h, and the concentration of the NaOH solution is 1 mol/L-3 mol/L. When the titanium alloy powder is TC4ELI titanium alloy powder, because Al element in the TC4ELI titanium alloy can generate irreversible damage to a human nervous system if excessive dissolution is carried out in the process of being implanted into a human body, a dealloying method is adopted to prepare micro-nano holes on the surface of a porous composite material subjected to stress relief annealing, under the condition that a potentiostat applies voltage, alloy element Al in a certain thickness layer on the surface of the porous composite material subjected to stress relief annealing is selectively dissolved to form a three-dimensional grid structure by utilizing different electrode potential differences of Ti and Al in a NaOH solution and the reaction of Al and NaOH to generate selective dissolution so as to reduce the content of the dissolved Al element on the surface in the implantation process, the surface dealloying method solves the toxicity problem caused by excessive release of the Al element in the TC4ELI titanium alloy in the implantation process, and enables the surface of the porous composite material subjected to form a nano-scale porous structure after the stress relief annealing, the bonding force of the graphene oxide composite titanium alloy medical material and a substrate is enhanced, the nano-scale porous structure simulates a bone tissue structure, the biocompatibility of the graphene oxide composite titanium alloy medical material is improved, the selective dissolution of the Al element is accelerated by controlling the voltage and the time, and the thickness of the poor Al layer is controlled.
Compared with the prior art, the invention has the following advantages:
1. the graphene oxide is introduced into the titanium-based material, and the biological corrosion resistance and the comprehensive mechanical property of the titanium-based material are combined with the biological compatibility and the antibacterial property of the graphene oxide, so that the crystal grains are refined, the antibacterial property, the wear resistance and the strength are improved, the graphene oxide composite titanium-based medical material is ensured to have excellent comprehensive mechanical property, biological activity and antibacterial property, the preparation method has the advantages that the micro-nano holes are prepared, the structure of human bone tissues is simulated, the graphene oxide composite titanium-based medical material and surrounding bone tissues can be quickly combined into a good bone, the applicability of the graphene oxide composite titanium-based medical material is improved, the controllable release is realized, a channel is provided for the transmission of nutrient substances, the transportation of the graphene oxide composite titanium-based medical material and nutrient substances in bones and the growth of cells at all levels are facilitated, and the preparation method is applied to the fields of orthopedics and the like.
2. The graphene oxide composite titanium-based medical material has bioactivity and antibacterial property from the inside to the surface, and the problem of falling off of an implant coating caused by long-term corrosion of body fluid exists in the traditional method of only modifying the surface of the material.
3. According to the invention, the porous composite material has a porous structure through 3D printing, the porous structure is designed according to the porosity, the elastic modulus of the graphene oxide composite titanium-based medical material is reduced to match with a bone, the biocompatibility of the graphene oxide composite titanium-based medical material is increased, the graphene oxide composite titanium-based medical material is well combined with the bone, a part of residual stress remained in the metal after the 3D printing process is finished is removed through stress-removing annealing, and the metal chemical activity of the porous composite material is improved.
4. The method has the advantages of short processing period, no restriction by material shapes, good processing effect and good application prospect.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
Fig. 1 is an SEM image of the graphene oxide composite TC4ELI titanium alloy medical material prepared in example 1 of the present invention.
Fig. 2 is an SEM image of the graphene oxide composite TLM titanium alloy medical material prepared in embodiment 2 of the present invention.
Fig. 3 is an SEM image of the graphene oxide composite titanium medical material prepared in example 3 of the present invention.
Detailed Description
Example 1
The embodiment comprises the following steps:
adding graphene oxide into ethanol, performing ultrasonic treatment, dissolving all graphene oxide to obtain a graphene oxide solution, and then putting the graphene oxide solution into a freeze dryer for freeze drying to obtain graphene oxide powder; the conditions of freeze drying are as follows: the vacuum degree is 1Pa, and the temperature is-30 ℃;
step two, putting the graphene oxide powder and TC4ELI titanium alloy powder obtained in the step one into a vacuum ball-milling tank, introducing liquid nitrogen around the vacuum ball-milling tank for cooling, and starting the vacuum ball-milling tank for ball milling to obtain mixed powder; the mass fraction of the graphene oxide powder in the mixed powder is 0.1%, and the particle size of the TC4ELI titanium alloy powder is 15-25 μm;
step three, loading the mixed powder obtained in the step two into a 3D printer for 3D printing to obtain a porous composite material; the porosity of the porous composite material is 30%;
step four, stress relief annealing is carried out on the porous composite material obtained in the step three;
fifthly, preparing micro-nano holes on the surface of the porous composite material subjected to stress relief annealing in the fourth step to obtain the graphene oxide composite TC4ELI titanium alloy medical material; the method for preparing the micro-nano holes is a dealloying method; the dealloying method comprises the following steps: and (3) in NaOH solution, a constant potential rectifier is adopted to apply 10V voltage, dealloying is carried out on the porous composite material after the stress relief annealing for 1h, and the concentration of the NaOH solution is 2 mol/L.
Through detection, the graphene oxide composite TC4ELI titanium alloy medical material prepared by the embodiment has the advantages of 27GPa of elastic modulus, 420MPa of tensile strength and 530MPa of compressive strength, and has strong supporting force when being applied to artificial segmental bones.
Fig. 1 is an SEM image of the graphene oxide composite TC4ELI titanium alloy medical material prepared in this embodiment, and as can be seen from fig. 1, the surface of the graphene oxide composite TC4ELI titanium alloy medical material has a uniform three-dimensional nano-grid structure, which is beneficial to adhesion and growth of cells.
Example 2
The embodiment comprises the following steps:
adding graphene oxide into deionized water, performing ultrasonic treatment, dissolving all the graphene oxide to obtain a graphene oxide solution, and then putting the graphene oxide solution into a freeze dryer for freeze drying to obtain graphene oxide powder; the conditions of freeze drying are as follows: the vacuum degree is 5Pa, and the temperature is-40 ℃;
step two, putting the graphene oxide powder and the TLM titanium alloy powder obtained in the step one into a vacuum ball-milling tank, introducing liquid nitrogen around the vacuum ball-milling tank for cooling, and starting the vacuum ball-milling tank for ball milling to obtain mixed powder; the mass fraction of the graphene oxide powder in the mixed powder is 5%, and the particle size of the TLM titanium alloy powder is 20-30 μm;
step three, loading the mixed powder obtained in the step two into a 3D printer for 3D printing to obtain a porous composite material; the porosity of the porous composite material is 50%;
step four, stress relief annealing is carried out on the porous composite material obtained in the step three;
fifthly, preparing micro-nano holes on the surface of the porous composite material subjected to stress relief annealing in the fourth step to obtain the graphene oxide composite TLM titanium alloy medical material; the method for preparing the micro-nano holes is a dealloying method; the dealloying method comprises the following steps: in a mixed acid solution, a constant potential rectifier is adopted to apply a voltage of 5V, dealloying is carried out on the porous composite material after the stress relief annealing for 60min, and the mixed acid solution contains 1% of NaF and 10% of HNO by mass3。
Through detection, the graphene oxide composite TLM titanium medical material prepared by the embodiment has the elastic modulus of 25GPa, the tensile strength of 310MPa and the compressive strength of 380MPa, is matched with the mechanical property of human bones in the aspects of bone repair and replacement, reduces or eliminates the stress shielding problem, is favorable for bone tissue to grow in due to a porous structure, is favorable for transmission of body fluid and nutrient substances due to a through porous structure, and has the advantage of accelerating the healing process.
Fig. 2 is an SEM image of the graphene oxide composite TLM titanium alloy medical material prepared in this embodiment, and as can be seen from fig. 2, the surface of the graphene oxide composite TLM titanium alloy medical material has a uniform nanoporous structure, and the average pore size is 17.35nm, which is beneficial to differentiation and proliferation of cells.
Example 3
The embodiment comprises the following steps:
adding graphene oxide into ethanol, performing ultrasonic treatment, dissolving all graphene oxide to obtain a graphene oxide solution, and freeze-drying the graphene oxide solution in a freeze dryer to obtain graphene oxide powder; the conditions of freeze drying are as follows: the vacuum degree is 10Pa, and the temperature is-50 ℃;
step two: putting the graphene oxide powder obtained in the step one and titanium powder with the mass purity of 99% into a vacuum ball-milling tank, introducing liquid nitrogen around the vacuum ball-milling tank for cooling, and starting the vacuum ball-milling tank for ball milling to obtain mixed powder; the mass fraction of graphene oxide powder in the mixed powder is 10%, and the particle size of the titanium powder is 25-40 μm;
step three, loading the mixed powder obtained in the step two into a 3D printer for 3D printing to obtain a porous composite material; the porosity of the porous composite material is 80%;
step four, stress relief annealing is carried out on the porous composite material obtained in the step three;
fifthly, preparing micro-nano holes on the surface of the porous composite material subjected to stress relief annealing in the fourth step to obtain the graphene oxide composite titanium medical material; the method for preparing the micro-nano holes is a micro-arc oxidation method; the process of the micro-arc oxidation method comprises the following steps: and in a mixed aqueous solution, controlling the voltage of micro-arc oxidation to be 350V, the duty ratio to be 20 percent and the frequency to be 100Hz, and performing micro-arc oxidation on the porous composite material subjected to stress relief annealing for 3min, wherein the mixed solution contains calcium phosphate with the concentration of 8mol/L and NaOH with the concentration of 4 mol/L.
Through detection, the graphene oxide composite titanium medical material prepared by the embodiment has the advantages of elastic modulus of 15GPa, tensile strength of 95MPa and compressive strength of 130MPa, and has the advantage of low elastic modulus matched with bone tissues when being applied to a titanium implant, and the prepared porous structure not only has a supporting effect, but also is beneficial to increase the area of the implant combined with the bone, and promotes the adhesion and growth of the bone tissues.
Fig. 3 is an SEM image of the graphene oxide composite titanium medical material prepared in embodiment 3 of the present invention, and it can be seen from fig. 3 that the surface of the graphene oxide composite titanium medical material has a volcano-crater-like porous morphology, the pore diameter of the crater is about 48nm, and smaller pores are irregularly distributed on the porous wall, which is beneficial to transport of nutrients and growth of cells.
Example 4
The embodiment comprises the following steps:
adding graphene oxide into ethanol, performing ultrasonic treatment, dissolving all graphene oxide to obtain a graphene oxide solution, and then putting the graphene oxide solution into a freeze dryer for freeze drying to obtain graphene oxide powder; the conditions of freeze drying are as follows: the vacuum degree is 3Pa, and the temperature is-35 ℃;
step two, putting the graphene oxide powder and TC4ELI titanium alloy powder obtained in the step one into a vacuum ball-milling tank, introducing liquid nitrogen around the vacuum ball-milling tank for cooling, and starting the vacuum ball-milling tank for ball milling to obtain mixed powder; the mass fraction of the graphene oxide powder in the mixed powder is 0.5%, and the particle size of the TC4ELI titanium alloy powder is 20-30 μm;
step three, loading the mixed powder obtained in the step two into a 3D printer for 3D printing to obtain a porous composite material; the porosity of the porous composite material is 40%;
step four, stress relief annealing is carried out on the porous composite material obtained in the step three;
fifthly, preparing micro-nano holes on the surface of the porous composite material subjected to stress relief annealing in the fourth step to obtain the graphene oxide composite TC4ELI titanium alloy medical material; the method for preparing the micro-nano holes is a dealloying method; the dealloying method comprises the following steps: and (3) in NaOH solution, a constant potential rectifier is adopted to apply a voltage of 5V, and the porous composite material after stress relief annealing is subjected to dealloying for 2h, wherein the concentration of the NaOH solution is 3 mol/L.
Through detection, the graphene oxide composite TC4ELI titanium alloy medical material prepared by the embodiment has the advantages of elastic modulus of 29GPa, tensile strength of 415MPa and compressive strength of 526MPa, and strong supporting force when being applied to artificial segmental bones.
Example 5
The embodiment comprises the following steps:
adding graphene oxide into ethanol, performing ultrasonic treatment, dissolving all graphene oxide to obtain a graphene oxide solution, and then putting the graphene oxide solution into a freeze dryer for freeze drying to obtain graphene oxide powder; the conditions of freeze drying are as follows: the vacuum degree is 7Pa, and the temperature is-45 ℃;
step two, putting the graphene oxide powder and TC4ELI titanium alloy powder obtained in the step one into a vacuum ball-milling tank, introducing liquid nitrogen around the vacuum ball-milling tank for cooling, and starting the vacuum ball-milling tank for ball milling to obtain mixed powder; the mass fraction of the graphene oxide powder in the mixed powder is 3%, and the particle size of the TC4ELI titanium alloy powder is 25-40 μm;
step three, loading the mixed powder obtained in the step two into a 3D printer for 3D printing to obtain a porous composite material; the porosity of the porous composite material is 60%;
step four, stress relief annealing is carried out on the porous composite material obtained in the step three;
fifthly, preparing micro-nano holes on the surface of the porous composite material subjected to stress relief annealing in the fourth step to obtain the graphene oxide composite TC4ELI titanium alloy medical material; the method for preparing the micro-nano holes is a dealloying method; the dealloying method comprises the following steps: and (3) in NaOH solution, a potentiostat is adopted to apply 3V voltage, and the porous composite material after stress relief annealing is subjected to dealloying for 3h, wherein the concentration of the NaOH solution is 1 mol/L.
Through detection, the graphene oxide composite TC4ELI titanium alloy medical material prepared by the embodiment has the advantages of elastic modulus of 28GPa, tensile strength of 417MPa and compressive strength of 528MPa, and strong supporting force when being applied to artificial segmental bones.
Example 6
The embodiment comprises the following steps:
adding graphene oxide into deionized water, performing ultrasonic treatment, dissolving all the graphene oxide to obtain a graphene oxide solution, and then putting the graphene oxide solution into a freeze dryer for freeze drying to obtain graphene oxide powder; the conditions of freeze drying are as follows: the vacuum degree is 6Pa, and the temperature is-40 ℃;
step two, putting the graphene oxide powder and the TLM titanium alloy powder obtained in the step one into a vacuum ball-milling tank, introducing liquid nitrogen around the vacuum ball-milling tank for cooling, and starting the vacuum ball-milling tank for ball milling to obtain mixed powder; the mass fraction of graphene oxide powder in the mixed powder is 7%, and the particle size of the TLM titanium alloy powder is 15-25 μm;
step three, loading the mixed powder obtained in the step two into a 3D printer for 3D printing to obtain a porous composite material; the porosity of the porous composite material is 60%;
step four, stress relief annealing is carried out on the porous composite material obtained in the step three;
fifthly, preparing micro-nano holes on the surface of the porous composite material subjected to stress relief annealing in the fourth step to obtain the graphene oxide composite TLM titanium alloy medical material; the method for preparing the micro-nano holes is a dealloying method; the dealloying method comprises the following steps: in a mixed acid solution, a constant potential rectifier is adopted to apply a voltage of 20V, and the dealloying annealing is carried out on the porous composite material for 20min, wherein the mixed acid solution contains NaF with the mass fraction of 0.5% and substancesHNO with 12% of quantity fraction3。
Through detection, the graphene oxide composite TLM titanium medical material prepared by the embodiment has the elastic modulus of 28GPa, the tensile strength of 304MPa and the compressive strength of 382MPa, is matched with the mechanical property of human bones in the aspects of bone repair and replacement, reduces or eliminates the stress shielding problem, is favorable for bone tissue to grow in due to a porous structure, is favorable for transmission of body fluid and nutrient substances due to a through porous structure, and has the advantage of accelerating the healing process.
Example 7
The embodiment comprises the following steps:
adding graphene oxide into deionized water, performing ultrasonic treatment, dissolving all the graphene oxide to obtain a graphene oxide solution, and then putting the graphene oxide solution into a freeze dryer for freeze drying to obtain graphene oxide powder; the conditions of freeze drying are as follows: the vacuum degree is 4Pa, and the temperature is-45 ℃;
step two, putting the graphene oxide powder and the TLM titanium alloy powder obtained in the step one into a vacuum ball-milling tank, introducing liquid nitrogen around the vacuum ball-milling tank for cooling, and starting the vacuum ball-milling tank for ball milling to obtain mixed powder; the mass fraction of the graphene oxide powder in the mixed powder is 2%, and the particle size of the TLM titanium alloy powder is 25-40 μm;
step three, loading the mixed powder obtained in the step two into a 3D printer for 3D printing to obtain a porous composite material; the porosity of the porous composite material is 50%;
step four, stress relief annealing is carried out on the porous composite material obtained in the step three;
fifthly, preparing micro-nano holes on the surface of the porous composite material subjected to stress relief annealing in the fourth step to obtain the graphene oxide composite TLM titanium alloy medical material; the method for preparing the micro-nano holes is a dealloying method; the dealloying method comprises the following steps: in a mixed acid solution, a constant potential rectifier is adopted to apply a voltage of 10V, dealloying is carried out on the porous composite material after the stress relief annealing for 40min, and the mixed acidThe solution contains NaF with the mass fraction of 2 percent and HNO with the mass fraction of 8 percent3。
Through detection, the graphene oxide composite TLM titanium medical material prepared by the embodiment has the elastic modulus of 27GPa, the tensile strength of 313MPa and the compressive strength of 378MPa, is matched with the mechanical property of human bones in the aspects of bone repair and replacement, reduces or eliminates the stress shielding problem, is favorable for bone tissue to grow in due to a porous structure, is favorable for transmission of body fluid and nutrient substances due to a through porous structure, and has the advantage of accelerating the healing process.
Example 8
The embodiment comprises the following steps:
adding graphene oxide into ethanol, performing ultrasonic treatment, dissolving all graphene oxide to obtain a graphene oxide solution, and freeze-drying the graphene oxide solution in a freeze dryer to obtain graphene oxide powder; the conditions of freeze drying are as follows: the vacuum degree is 10Pa, and the temperature is-50 ℃;
step two: putting the graphene oxide powder obtained in the step one and titanium powder with the mass purity of 99% into a vacuum ball-milling tank, introducing liquid nitrogen around the vacuum ball-milling tank for cooling, and starting the vacuum ball-milling tank for ball milling to obtain mixed powder; the mass fraction of graphene oxide powder in the mixed powder is 10%, and the particle size of the titanium powder is 25-35 μm;
step three, loading the mixed powder obtained in the step two into a 3D printer for 3D printing to obtain a porous composite material; the porosity of the porous composite material is 60%;
step four, stress relief annealing is carried out on the porous composite material obtained in the step three;
fifthly, preparing micro-nano holes on the surface of the porous composite material subjected to stress relief annealing in the fourth step to obtain the graphene oxide composite titanium medical material; the method for preparing the micro-nano holes is a micro-arc oxidation method; the process of the micro-arc oxidation method comprises the following steps: and in a mixed aqueous solution, controlling the voltage of micro-arc oxidation to be 300V, the duty ratio to be 15 percent and the frequency to be 80Hz, and performing micro-arc oxidation on the porous composite material subjected to stress relief annealing for 8min, wherein the mixed solution contains calcium phosphate with the concentration of 9mol/L and NaOH with the concentration of 5 mol/L.
Through detection, the graphene oxide composite titanium medical material prepared by the embodiment has the advantages of elastic modulus of 17GPa, tensile strength of 105MPa and compressive strength of 127MPa, and has the advantage of low elastic modulus matched with bone tissues when being applied to a titanium implant, and the prepared porous structure not only has a supporting effect, but also is beneficial to increase the area of the implant combined with bone, and promotes the adhesion and growth of the bone tissues.
Example 9
The embodiment comprises the following steps:
adding graphene oxide into ethanol, performing ultrasonic treatment, dissolving all graphene oxide to obtain a graphene oxide solution, and freeze-drying the graphene oxide solution in a freeze dryer to obtain graphene oxide powder; the conditions of freeze drying are as follows: the vacuum degree is 9Pa, and the temperature is-45 ℃;
step two: putting the graphene oxide powder obtained in the step one and titanium powder with the mass purity of 99% into a vacuum ball-milling tank, introducing liquid nitrogen around the vacuum ball-milling tank for cooling, and starting the vacuum ball-milling tank for ball milling to obtain mixed powder; the mass fraction of graphene oxide powder in the mixed powder is 8%, and the particle size of the titanium powder is 15-25 μm;
step three, loading the mixed powder obtained in the step two into a 3D printer for 3D printing to obtain a porous composite material; the porosity of the porous composite material is 40%;
step four, stress relief annealing is carried out on the porous composite material obtained in the step three;
fifthly, preparing micro-nano holes on the surface of the porous composite material subjected to stress relief annealing in the fourth step to obtain the graphene oxide composite titanium medical material; the method for preparing the micro-nano holes is a micro-arc oxidation method; the process of the micro-arc oxidation method comprises the following steps: and in a mixed aqueous solution, controlling the voltage of micro-arc oxidation to be 320V, the duty ratio to be 17 percent and the frequency to be 90Hz, and performing micro-arc oxidation on the porous composite material subjected to stress relief annealing for 6min, wherein the mixed solution contains calcium phosphate with the concentration of 7mol/L and NaOH with the concentration of 3 mol/L.
Through detection, the graphene oxide composite titanium medical material prepared by the embodiment has the advantages of elastic modulus of 16GPa, tensile strength of 94MPa and compressive strength of 135MPa, and has the advantage of low elastic modulus matched with bone tissues when being applied to a titanium implant, and the prepared porous structure not only has a supporting effect, but also is beneficial to increase the area of the implant combined with the bone, and promotes the adhesion and growth of the bone tissues.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.

Claims (8)

1. A preparation method of a graphene oxide composite titanium-based medical material is characterized by comprising the following steps:
step one, placing graphene oxide into deionized water or ethanol, performing ultrasonic treatment to obtain a graphene oxide solution, and then performing freeze drying on the graphene oxide solution to obtain graphene oxide powder;
step two, putting the graphene oxide powder and the titanium-based powder obtained in the step one into a vacuum ball-milling tank for ball-milling to obtain mixed powder; the titanium-based powder is titanium powder or titanium alloy powder;
step three, loading the mixed powder obtained in the step two into a 3D printer for 3D printing to obtain a porous composite material;
step four, stress relief annealing is carried out on the porous composite material obtained in the step three;
step five, preparing micro-nano holes on the surface of the porous composite material subjected to stress relief annealing in the step four to obtain the graphene oxide composite titanium-based medical material; the method for preparing the micro-nano holes is a dealloying method or a micro-arc oxidation method.
2. The method for preparing graphene oxide composite titanium-based medical material according to claim 1, wherein the freeze-drying conditions in the first step are as follows: the vacuum degree is 1 Pa-10 Pa, and the temperature is-30 ℃ to-50 ℃.
3. The method for preparing graphene oxide composite titanium-based medical material according to claim 1, wherein in the second step, the particle size of the titanium-based powder is 15 μm to 40 μm, the titanium alloy powder is TLM titanium alloy powder or TC4ELI titanium alloy powder, and liquid nitrogen is introduced around the vacuum ball-milling tank for cooling.
4. The method for preparing a graphene oxide composite titanium-based medical material according to claim 1, wherein the mass fraction of the graphene oxide powder in the mixed powder in the second step is 0.1-10%.
5. The method for preparing a graphene oxide composite titanium-based medical material according to claim 1, wherein the porosity of the porous composite material in the step three is 30-80%.
6. The method for preparing graphene oxide compounded titanium-based medical material according to claim 3, wherein when the titanium-based powder is titanium powder, the method for preparing the micro-nano holes in the fifth step is a micro-arc oxidation method, and the process of the micro-arc oxidation method is as follows: in a mixed aqueous solution, controlling the voltage of micro-arc oxidation to be 300-350V, the duty ratio to be 15-20% and the frequency to be 80-100 Hz, and carrying out micro-arc oxidation on the porous composite material subjected to stress relief annealing for 3-8 min, wherein the mixed solution contains calcium phosphate with the concentration of 7-9 mol/L and NaOH with the concentration of 3-5 mol/L.
7. The method for preparing graphene oxide composite titanium-based medical material according to claim 3, wherein when the titanium alloy powder is TLM titanium alloy powder, the micro-nano holes are prepared in step fiveThe method is a dealloying method, and the dealloying method comprises the following steps: in a mixed acid solution, a constant potential rectifier is adopted to apply a voltage of 5V-20V, dealloying is carried out on the porous composite material after the stress relief annealing for 20 min-60 min, and the mixed acid solution contains 0.5-2% of NaF and 8-12% of HNO by mass3；
8. The method for preparing graphene oxide compounded titanium-based medical material according to claim 3, wherein when the titanium alloy powder is TC4ELI titanium alloy powder, the method for preparing the micro-nano holes in the fifth step is a dealloying method, and the dealloying method comprises the following steps: in NaOH solution, a constant potential rectifier is adopted to apply 3V-10V voltage, dealloying is carried out on the porous composite material after the stress relief annealing for 1 h-3 h, and the concentration of the NaOH solution is 1 mol/L-3 mol/L.
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Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102586786A (en) * 2012-03-19 2012-07-18 上海交通大学医学院附属第九人民医院 Method for forming graded multi-hole shape on titanium surface
CN103088348A (en) * 2011-11-02 2013-05-08 中国科学院金属研究所 Preparation method of titanium surface porous structure layer bioactive ceramic membrane with low elasticity modulus
CN104805323A (en) * 2015-03-23 2015-07-29 武汉理工大学 Graphene/titanium composite material and preparation method thereof
CN104975335A (en) * 2015-06-04 2015-10-14 西北有色金属研究院 Preparation method of composite coating on surface of titanium alloy dental implant
CN104985183A (en) * 2015-06-12 2015-10-21 华南协同创新研究院 Low-elasticity-modulus titanium-based jawbone implant and preparation method thereof
CN105063400A (en) * 2015-09-16 2015-11-18 哈尔滨工业大学 Preparation method for nanometer porous titanium
US20170088969A1 (en) * 2015-09-25 2017-03-30 Jackson State University Method for obtaining a composite coating on titanium implants for tissue engineering
CN106923936A (en) * 2017-03-31 2017-07-07 中国人民解放军第四军医大学 The design preparation method of the personalized customization 3D printing porous titanium alloy segmental prosthese rebuild for large segmental bone defect
CN107185039A (en) * 2017-07-14 2017-09-22 中国人民解放军第四军医大学 A kind of porous metals bone implant material and its preparation method and application
CN107469142A (en) * 2017-08-23 2017-12-15 杨蕾 A kind of antibacterial modified nano composite material for promoting osteogenic growth and preparation method thereof
CN108014369A (en) * 2018-01-24 2018-05-11 山东建筑大学 A kind of preparation method of the compound bone material of renewable titanium-based
CN108578763A (en) * 2018-04-18 2018-09-28 上海交通大学 The dentistry implant and preparation method thereof that graphene is modified
US20180280143A1 (en) * 2017-03-30 2018-10-04 Devendra Gorhe Methods of modifying the porous surface of implants
CN110152056A (en) * 2019-05-27 2019-08-23 吉林大学 A method of functional ionic is rapidly introduced into titanium alloy surface
CN110528048A (en) * 2019-08-30 2019-12-03 广东省新材料研究所 A kind of titanium alloy implant Bio-surface active coating and preparation method thereof

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103088348A (en) * 2011-11-02 2013-05-08 中国科学院金属研究所 Preparation method of titanium surface porous structure layer bioactive ceramic membrane with low elasticity modulus
CN102586786A (en) * 2012-03-19 2012-07-18 上海交通大学医学院附属第九人民医院 Method for forming graded multi-hole shape on titanium surface
CN104805323A (en) * 2015-03-23 2015-07-29 武汉理工大学 Graphene/titanium composite material and preparation method thereof
CN104975335A (en) * 2015-06-04 2015-10-14 西北有色金属研究院 Preparation method of composite coating on surface of titanium alloy dental implant
CN104985183A (en) * 2015-06-12 2015-10-21 华南协同创新研究院 Low-elasticity-modulus titanium-based jawbone implant and preparation method thereof
CN105063400A (en) * 2015-09-16 2015-11-18 哈尔滨工业大学 Preparation method for nanometer porous titanium
US20170088969A1 (en) * 2015-09-25 2017-03-30 Jackson State University Method for obtaining a composite coating on titanium implants for tissue engineering
US20180280143A1 (en) * 2017-03-30 2018-10-04 Devendra Gorhe Methods of modifying the porous surface of implants
CN106923936A (en) * 2017-03-31 2017-07-07 中国人民解放军第四军医大学 The design preparation method of the personalized customization 3D printing porous titanium alloy segmental prosthese rebuild for large segmental bone defect
CN107185039A (en) * 2017-07-14 2017-09-22 中国人民解放军第四军医大学 A kind of porous metals bone implant material and its preparation method and application
CN107469142A (en) * 2017-08-23 2017-12-15 杨蕾 A kind of antibacterial modified nano composite material for promoting osteogenic growth and preparation method thereof
CN108014369A (en) * 2018-01-24 2018-05-11 山东建筑大学 A kind of preparation method of the compound bone material of renewable titanium-based
CN108578763A (en) * 2018-04-18 2018-09-28 上海交通大学 The dentistry implant and preparation method thereof that graphene is modified
CN110152056A (en) * 2019-05-27 2019-08-23 吉林大学 A method of functional ionic is rapidly introduced into titanium alloy surface
CN110528048A (en) * 2019-08-30 2019-12-03 广东省新材料研究所 A kind of titanium alloy implant Bio-surface active coating and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
余建明等: "《放射医学技术高级教程》", 31 October 2016 *
吴国忠等: "《辐射技术与先进材料》", 31 March 2016 *
胡长伟: "《纳米材料的生态毒性效应与环境释放风险》", 28 February 2015 *
薛云飞等: "《先进金属基复合材料》", 30 April 2019 *

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