CN107115560B - Antibacterial bionic porous titanium implant and preparation method and application thereof - Google Patents
Antibacterial bionic porous titanium implant and preparation method and application thereof Download PDFInfo
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- 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
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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
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- 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
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- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
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- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
- B22F3/222—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by freeze-casting or in a supercritical fluid
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
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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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
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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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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- 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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/24—After-treatment of workpieces or articles
- B22F2003/241—Chemical after-treatment on the surface
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- 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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Abstract
The invention discloses an antibacterial bionic porous titanium implant and a preparation method and application thereof. The antibacterial bionic porous titanium implant is of a cylindrical structure, a radial anisotropic porous structure is formed in the center of a cylinder along the outer circumference of the cylinder, the pore diameter is in gradient distribution from small to large, and the surface of a pore is provided with a needle-shaped micro-nano structure. The preparation method comprises (1) stirring titanium powder and medium solvent under water bath heating condition to prepare slurry; (2) the slurry is subjected to cold solidification and drying to obtain a dry blank sample; (3) drying the blank sample and sintering to obtain a porous titanium implant sample; (4) and sintering the porous titanium implant sample in the mixed atmosphere of inert gas and acetone to obtain the antibacterial bionic porous titanium implant. The antibacterial bionic porous titanium implant has good antibacterial function, excellent osseointegration performance and mechanical performance, and can be widely applied to the medical field.
Description
Technical Field
The invention belongs to the technical field of preparation of orthopedic implants, relates to an antibacterial bionic porous titanium implant and a preparation method and application thereof, and particularly relates to a method for preparing the antibacterial bionic porous titanium implant by using freeze casting and thermal oxidation technologies.
Background
Titanium and titanium alloy have a lot of advantages such as good biocompatibility and mechanical properties as the bone substitute material, but because the elastic modulus of titanium and titanium alloy implant is far higher than the cortex of natural human body, after being implanted into the body as the load-bearing bone substitute material, the titanium and titanium alloy implant is only mechanically integrated with the bone tissue rather than firmly biologically combined, especially when the implant surface is seriously complicated by bacterial growth and reproduction to cause implant loosening and inflammatory reaction of surrounding bone tissue, the risk of failure after the bone implantation operation is increased, thereby limiting the clinical application of the titanium and titanium alloy implant.
The novel bone implant needs to generate special response and interaction with living bone tissue cells, so that osteoblasts can be induced to develop into viable new bone tissues or organs under physiological environment, namely, good osseointegration performance. Therefore, the bionic porous titanium implant which is similar to the human bone tissue pore morphology and pore size and has good mechanical property is one of important research directions of the bone implant. The formation of a good bone implant-bone combination interface is the key point of successful implant implantation, and the regulation of osteoblast behavior on the surface of a material and osteoblast adhesion proliferation capacity, and the inhibition of the growth and reproduction of bacteria on the bone implant-bone combination interface are important for the formation of the good bone combination interface, so that the research on how to simultaneously realize the nano surface modification of an implant and enable the implant to have antibacterial performance also becomes one of the hotspots for the research and development of a new generation of antibacterial bionic porous titanium implants.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an antibacterial bionic porous titanium implant with good antibacterial function, excellent osseointegration performance and mechanical performance, and a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
the utility model provides an antibiotic bionical porous titanium implant, antibiotic bionical porous titanium implant is the cylinder structure, has and is radial anisotropic porous structure along cylinder outer circumference cylinder central authorities, porous structure's aperture is the gradient distribution by little to big along cylinder outer circumference cylinder central authorities, porous structure's hole basement surface has the acicular micro-nano structure.
In the above antibacterial bionic porous titanium implant, preferably, the porosity of the antibacterial bionic porous titanium implant is 40% to 70%, the opening ratio is 90% to 99%, the average pore size is 80 μm to 150 μm, the compressive strength is 30MPa to 165MPa, the elastic modulus is 1GPa to 4GPa, the sterilization rate of the antibacterial bionic porous titanium implant on gram-negative bacteria is greater than 90%, and the sterilization rate on gram-positive bacteria is greater than 85%.
As a general inventive concept, the present invention also provides a method for preparing an antibacterial biomimetic porous titanium implant, comprising the steps of:
(1) preparing slurry: continuously stirring and mixing titanium powder and a medium solvent under the water bath heating condition to obtain slurry, wherein the volume fraction of the titanium powder in the slurry is 10-20%;
(2) and (3) cold solidification: pouring the slurry obtained in the step (1) into a pre-cooled mold for cold solidification at the temperature of 20-25 ℃, wherein a cylindrical cavity is arranged in the mold, the mold keeps sealed and heat-insulated, and after the cold solidification, demolding and drying to obtain a dry blank sample;
(3) and (3) sintering: heating the dried blank sample obtained in the step (2) to 400-600 ℃ at a speed of 1-5 ℃/min under a vacuum condition, then heating to 1200-1300 ℃ at a speed of 5-10 ℃/min under an inert atmosphere for sintering, wherein the sintering duration is 1-4 h, and then cooling to room temperature to obtain a porous titanium implant sample;
(4) surface micro-nano structure treatment: and (3) ultrasonically cleaning and drying the porous titanium implant sample obtained in the step (3), heating the obtained dried blank sample to 850-900 ℃ at a speed of 10-15 ℃/min in an inert atmosphere, continuously adding acetone into airflow of the inert atmosphere, controlling the flow rate of the inert gas to be 50-300 sccm, sintering for 45-60 min, and cooling to room temperature after sintering to obtain the antibacterial bionic porous titanium implant.
In the above preparation method of the antibacterial bionic porous titanium implant, preferably, in the step (1), the medium solvent is camphene, and the water bath heating temperature is 60-65 ℃.
In the above preparation method of the antibacterial bionic porous titanium implant, preferably, in the step (1), the stirring time is 2 to 4 hours, the stirring speed is 800 to 1000r/min, and a covering is placed on the stirring container while stirring to reduce solvent evaporation.
In the preparation method of the antibacterial bionic porous titanium implant, preferably, in the step (2), the pre-cooling temperature of the mold is the same as the condensation solidification temperature, the pre-cooling time of the mold is 30-120 min, and the condensation solidification time is 4-6 h.
In the above preparation method of the antibacterial bionic porous titanium implant, preferably, in the step (2), after condensation curing and before demoulding and drying, the sample is further cured after being stored at a low temperature of-18 ℃ to-20 ℃ for 12h to 24 h; the drying is vacuum freeze drying, and the drying time is 24-48 h.
In the above preparation method of the antibacterial bionic porous titanium implant, preferably, in the step (4), the ultrasonic cleaning sequentially adopts acetone, anhydrous ethanol and double distilled water as cleaning liquids, and each cleaning time is 15min to 20 min; the drying temperature is 60-80 ℃, and the drying time is 4-6 h.
In the above preparation method of the antibacterial bionic porous titanium implant, preferably, in the step (4), the acetone is liquid acetone; and stopping adding the acetone after sintering, and naturally cooling to room temperature under the condition of controlling the flow rate of the inert gas to be 500-600 sccm.
As a general inventive concept, the invention also provides an application of the antibacterial bionic porous titanium implant or the antibacterial bionic porous titanium implant prepared by the preparation method.
Compared with the prior art, the invention has the advantages that:
(1) the invention controls the direction of the medium cold solidification in the mould by a freezing casting method (namely, the step (1) to the step (3)), namely, controls the temperature difference of the medium from the periphery of the mould to the center of the mould (namely, the radial temperature difference of the inner cavity of the cylinder, such as the temperature difference formed from 20 ℃ at the periphery to 60 ℃ at the center) during the cold solidification, realizes that the porous titanium implant is in a pore morphology with radial anisotropy and gradient distribution of pore diameter towards the center of the cylinder, and the porous structure of the porous titanium implant is very similar to the bone tissue of a natural human body.
(2) According to the invention, the prepared antibacterial bionic porous titanium implant has good porosity, pore size and excellent mechanical property by controlling and optimizing the technological parameters including the volume ratio of titanium powder, the sintering temperature, the sintering speed, the sintering time and the like of the mixed slurry in the freeze casting, and the condition that bone cells grow into the porous titanium implant to form biological osseointegration is effectively met.
(2) The invention realizes that the nanometer needle-shaped structures are uniformly grown on the surfaces of all three-dimensional pore substrates in the porous titanium implant body by a thermal oxidation method (namely the step (1)), and the length of the needle-shaped structures is about 100-200 nm. Compared with the traditional porous material, the needle-shaped nano structure uniformly distributed in the pores of the bionic porous titanium implant promotes the proliferation and differentiation performance of in vitro osteoblasts and the bone formation, deposition and calcification in vivo by regulating the adsorption effect, biological response and the like of the osteoblasts on the surface of the material, and the osteoblasts differentiate more mature in the pores along with the extension of the implantation time to form firm biological bone integration, thereby having remarkable progress. Meanwhile, the acicular nanostructure effectively inhibits the growth of bacteria around the implant through physical effect, and is a novel surface modified bionic porous titanium implant with antibacterial function, good osseointegration performance and good biocompatibility.
Drawings
Fig. 1 is an SEM image of a cross section of an antibacterial biomimetic porous titanium implant prepared in example 1 of the present invention.
Fig. 2 is an SEM image of the acicular micro-nano structure on the surface of the porous substrate of the antibacterial biomimetic porous titanium implant prepared in example 1 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples are commercially available.
Example 1:
the invention relates to a preparation method of an antibacterial bionic porous titanium implant, which comprises the following steps:
(1) preparing slurry: continuously magnetically stirring and mixing the titanium powder and a medium solvent camphene in a water bath box at the temperature of 60 ℃ for 2 hours at the stirring speed of 800r/min, and placing a covering material above a stirring container to reduce the evaporation of the solvent camphene. The volume fraction of titanium powder in the obtained slurry mixture was 10%.
(2) And (3) cold solidification: placing the cylindrical mold in a water bath tank for precooling for 30 minutes at the precooling temperature of 20 ℃, slowly pouring the prepared slurry into the precooled mold, wherein the inner cavity of the mold is cylindrical, the upper end and the lower end of the mold are kept sealed and insulated, the temperature of the cold solidification is controlled at 20 ℃, and the time of the cold solidification is 4 hours. After the solidification, the mold is taken out and stored at the low temperature of minus 20 ℃ for 12h, and the sample is further solidified. And taking out the sample, demolding, and drying in a freeze vacuum drying oven for 24h to obtain a dried blank sample.
(3) And (3) sintering: and (3) placing the dried blank sample into a sintering furnace, heating to 400 ℃ at a speed of 1 ℃/min under a vacuum condition, then heating to 1200 ℃ at a speed of 5 ℃/min under an argon atmosphere for sintering, wherein the sintering duration is 1h, and naturally cooling to room temperature to obtain the porous titanium implant sample.
(4) Surface micro-nano structure treatment: and (3) sequentially using acetone, absolute ethyl alcohol and double distilled water as cleaning liquids to respectively clean the porous titanium implant sample obtained after sintering for 15min in an ultrasonic cleaning machine, and then drying the porous titanium implant sample in a high-temperature drying oven for 4 hours at 80 ℃. And (2) placing the dried blank sample in a sintering furnace, heating to 850 ℃ at a speed of 10 ℃/min under the argon atmosphere, continuously adding acetone of 25 ℃ into argon gas flow, controlling the flow rate of argon gas to be 50sccm for sintering, keeping the sintering duration for 45min, stopping introducing the acetone, and naturally cooling to room temperature under the condition of controlling the flow rate of argon gas to be 500sccm to obtain the antibacterial bionic porous titanium implant, wherein the antibacterial bionic porous titanium implant has a surface needle-like micro-nano structure.
As shown in fig. 1 and 2, SEM images of the cross section and the pore surface of the antibacterial bionic porous titanium implant prepared in this embodiment show that the implant has a porous structure, and is radially anisotropic along the center of the cylinder in the outer circumferential direction of the cylinder, and the pore diameters are distributed in a gradient manner from small to large, the porous structure is very similar to the natural human bone tissue, the pore surface of the porous implant has a needle-like micro-nano structure, and the length of the needle-like structure is about 100 to 200nm, which illustrates that the method of the present invention can prepare a nano needle-like surface modified antibacterial bionic porous titanium implant. The porous titanium implant of the present embodiment has a porosity of 58.32 + -1.08%, an open porosity of 97.70%, an average pore size of 126.17 + -18.64 μm, a compressive strength of 58.51 + -20.38 MPa, and an elastic modulus of 1.70 + -0.52 GPa. The implant biocompatibility meets the requirements of clinical application. The acicular nanostructure implanted into the pores of the implant can promote the proliferation and differentiation performance of osteoblasts in vitro and the bone formation, deposition and calcification in vivo, and as the implantation time is prolonged, the osteoblasts are more mature in the pores thereof to form firm biological osseointegration.
The antibacterial bionic porous titanium implant prepared by the embodiment can be applied to the field of orthopedic implants and other related medical fields.
Example 2:
the invention discloses a preparation method of an antibacterial bionic porous titanium implant, which comprises the following steps:
(1) preparing slurry: continuously magnetically stirring and mixing the titanium powder and a medium solvent camphene in a water bath box at 65 ℃ for 4 hours at the stirring speed of 1000r/min, and placing a covering material above a stirring container to reduce the evaporation of the solvent camphene. The volume fraction of titanium powder in the obtained slurry mixture was 20%.
(2) And (3) cold solidification: and placing the cylindrical mold in a water bath box for precooling for 30 minutes, wherein the precooling temperature is 20 ℃. Slowly pouring the prepared mixed slurry into a pre-cooled mold, wherein the inner cavity of the transverse mold is cylindrical, and the upper end and the lower end of the mold are sealed and insulated. The cold setting temperature is controlled at 20 ℃, and the curing time is 4 hours. Taking out the mold, storing at-20 deg.C for 12h, and further solidifying the sample. Taking out the sample, demoulding, and drying in a freeze vacuum drying oven for 24 h.
(3) And (3) sintering: and (3) placing the dried blank sample into a sintering furnace, heating to 400 ℃ at a speed of 5 ℃/min under a vacuum condition, then heating to 1200 ℃ at a speed of 10 ℃/min under an argon atmosphere for sintering for 4h, and naturally cooling to room temperature to obtain the porous titanium implant sample.
(4) Surface micro-nano structure treatment: and (3) sequentially using acetone, absolute ethyl alcohol and double distilled water as cleaning liquids to respectively clean the sintered porous titanium implant sample in an ultrasonic cleaning machine for 15min, and then drying the porous titanium implant sample in a high-temperature drying oven for 4 hours at the temperature of 80 ℃. And (3) placing the dried blank sample in a sintering furnace, heating to 850 ℃ at a speed of 15 ℃/min under the argon atmosphere, continuously adding acetone of 25 ℃ into argon gas flow, controlling the flow rate of argon gas to be 300sccm for sintering, keeping the sintering duration to be 45min, stopping introducing the acetone, and naturally cooling to room temperature under the condition that the flow rate of argon gas is 500sccm to obtain the antibacterial bionic porous titanium implant.
Through testing, the nano needle-shaped surface modified antibacterial bionic porous titanium implant is prepared by the method, the antibacterial bionic porous titanium implant is of a cylindrical structure and has a porous structure which is radially anisotropic along the center of the cylinder in the outer circumferential direction of the cylinder, the pore diameters of the porous structure are distributed in a gradient manner from small to large along the center of the cylinder in the outer circumferential direction of the cylinder, and the pore surfaces of the porous structure are of needle-shaped micro-nano structures. The porosity of the product of this example was 45.99. + -. 2.15%, the open porosity 92.50%, the average pore size 94.35. + -. 2.01. mu.m, the compressive strength 147.12. + -. 15.53MPa, and the modulus of elasticity 2.99. + -. 0.12 GPa. The biocompatibility of the implant meets the requirement of clinical application. The acicular nanostructure implanted into the pores of the implant can promote the proliferation and differentiation performance of osteoblasts in vitro and the bone formation, deposition and calcification in vivo, and as the implantation time is prolonged, the osteoblasts are more mature in the pores thereof to form firm biological osseointegration.
Example 3:
the invention discloses a preparation method of an antibacterial bionic porous titanium implant, which comprises the following steps:
(1) preparing slurry: continuously magnetically stirring and mixing the titanium powder and a medium solvent camphene in a water bath box at 60 ℃ for 4 hours at the stirring speed of 800r/min, and placing a covering material above a stirring container to reduce the evaporation of the solvent camphene. The volume fraction of titanium powder in the obtained slurry mixture was 15%.
(2) And (3) cold solidification: the cylindrical mold is placed in a water bath box for precooling for 30 minutes, and the precooling temperature is 25 ℃. Slowly pouring the prepared mixed slurry into a pre-cooled mold, wherein the inner cavity of the mold is cylindrical, and the upper end and the lower end of the mold are sealed and insulated. The cold setting temperature is controlled at 25 ℃, and the curing time is 4 hours. Taking out the mold, storing at-20 deg.C for 12h, and further solidifying the sample. Taking out the sample, demoulding, and drying in a freeze vacuum drying oven for 24 h.
(3) And (3) sintering: and (3) placing the dried blank sample into a sintering furnace, heating to 400 ℃ at a speed of 1 ℃/min under a vacuum condition, then heating to 1300 ℃ at a speed of 10 ℃/min under an argon atmosphere for sintering, wherein the sintering duration is 1h, and naturally cooling to room temperature to obtain the porous titanium implant sample.
(4) Surface micro-nano structure treatment: and (3) sequentially using acetone, absolute ethyl alcohol and double distilled water as cleaning liquids to respectively clean the sintered porous titanium implant sample in an ultrasonic cleaning machine for 15min, and then drying the porous titanium implant sample in a high-temperature drying oven for 4 hours at the temperature of 80 ℃. And placing the obtained dry blank sample in a sintering furnace, heating to 850 ℃ at a speed of 10 ℃/min under the argon atmosphere, continuously adding acetone of 25 ℃ into argon gas flow, sintering at an argon gas flow rate of 200sccm for 45min, stopping introducing the acetone, and naturally cooling to room temperature under the argon gas flow rate of 500sccm to obtain the antibacterial bionic porous titanium implant.
Through testing, the nano needle-shaped surface modified antibacterial bionic porous titanium implant is prepared by the method, the antibacterial bionic porous titanium implant is of a cylindrical structure and has a porous structure which is radially anisotropic along the center of the cylinder in the outer circumferential direction of the cylinder, the pore diameters of the porous structure are distributed in a gradient manner from small to large along the center of the cylinder in the outer circumferential direction of the cylinder, and the pore surfaces of the porous structure are of needle-shaped micro-nano structures. The porosity of the implant of this example was 54.19 + -2.01%, the opening ratio was 94.49%, the average pore size was 104.16 + -16.05 μm, the compressive strength was 113.37 + -25.18 MPa, and the elastic modulus was 2.85 + -0.25 GPa. The implant biocompatibility meets the requirements of clinical application. The acicular nanostructure implanted into the pores of the implant can promote the proliferation and differentiation performance of osteoblasts in vitro and the bone formation, deposition and calcification in vivo, and as the implantation time is prolonged, the osteoblasts are more mature in the pores thereof to form firm biological osseointegration.
In vitro antibacterial experiments:
in-vitro antibacterial experiments carried out by the invention prove that the three bionic porous titanium implants of the embodiment 1, the embodiment 2 and the embodiment 3 can obviously inhibit staphylococcus aureus and escherichia coli.
An in vitro test is carried out by taking 10g tryptone, 5g yeast extract, 10g sodium chloride and 20g agar by using a balance, fully dissolving the components in 1000mL of distilled water, adjusting the pH of the prepared solution to 7.0 by using 0.1mol/L NaOH solution, subpackaging the solution into a high-pressure steam sterilization pot, sterilizing the solution at 121 ℃ for 20min, and then preparing the Phosphate Buffer (PBS). 2, dissolving 2.84g disodium hydrogen phosphate and 1.36g potassium dihydrogen phosphate into 1000mL of distilled water, adjusting the pH of the prepared solution to 7.2-7.4, sterilizing the solution at 121 ℃ for 30min by using pressure steam, (3), respectively testing the antibacterial performance of the samples aiming at gram-negative bacteria and compact-positive bacteria in the test, dripping the selected gram-negative bacteria to represent escherichia coli, selecting gram-positive bacteria to represent staphylococcus aureus, selecting the selected representative bacteria to represent titanium bacteria, inoculating the test sample and the test sample of the titanium bacteria test sample into a sterile test sample, placing the test sample in a sterile test dish, and culturing the test sample in sterile water, and placing the sterile test dish into a sterile test dish, after the sterile test dish, the test sample is inoculated with 1 × 10 mu. mu.1. after the sterile water, the test sample is inoculated with sterile water, and the test sample is inoculated with the sterile water, the test sample, the test dish, the5The standard bacterial liquid of (4); the pipette sucks 100. mu.L of the bacterial solution to the surface of the sample, spreads the solution evenly, and incubate the solution in a 37 ℃ incubator for 24 hours. The pipette sucks 80 μ L of the bacterial liquid from the surface of the sample, and uniformly drops the bacterial liquid in a culture dish of LB culture mediumThe coating is uniform. The coated culture dish was cultured in a 37 ℃ incubator. After 24 hours of incubation, the dishes were removed and the total number of colonies contained on the surface of each sample was counted. The formula for calculating the antibacterial rate is as follows:
wherein K is the antibacterial rate of the sample, A is the average number of bacteria on a blank sample, namely compact titanium, and B is the average number of bacteria on an antibacterial bionic porous titanium test sample.
The results of the antibacterial test show that: the antibacterial performance of the compact titanium control sample and the antibacterial bionic porous titanium sample is detected by adopting a flat plate method, and the sterilization rate is calculated. Table 1 shows the sterilization rates of the antibacterial biomimetic porous titanium test sample to escherichia coli and staphylococcus aureus, and the results show that the antibacterial biomimetic porous titanium implant of the present invention exhibits good antibacterial effects to both staphylococcus aureus and escherichia coli.
TABLE 1 antibacterial test results of antibacterial biomimetic porous titanium
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.
Claims (8)
1. The antibacterial bionic porous titanium implant is characterized by being of a cylindrical structure and having a porous structure which is radially anisotropic along the center of a cylinder in the outer circumferential direction of the cylinder, wherein the pore diameter of the porous structure is distributed in a gradient manner from small to large along the center of the cylinder in the outer circumferential direction of the cylinder, and the surface of a pore substrate of the porous structure is provided with a needle-shaped micro-nano structure;
the porosity of the antibacterial bionic porous titanium implant is 40-70%, the opening rate is 90-99%, the average pore size is 80-150 μm, the compression strength is 30-165 MPa, the elastic modulus is 1-4 GPa, the sterilization rate of the antibacterial bionic porous titanium implant on gram-negative bacteria is more than 90%, and the sterilization rate on gram-positive bacteria is more than 85%;
the preparation method of the antibacterial bionic porous titanium implant is a freeze casting method, and comprises the following steps:
(1) preparing slurry: continuously stirring and mixing titanium powder and a medium solvent under the water bath heating condition to obtain slurry, wherein the volume fraction of the titanium powder in the slurry is 10-20%; the medium solvent is camphene, and the water bath heating temperature is 60-65 ℃;
(2) and (3) cold solidification: pouring the slurry obtained in the step (1) into a pre-cooled mold for cold solidification at the temperature of 20-25 ℃, wherein a cylindrical cavity is arranged in the mold, the mold keeps sealed and heat-insulated, and after the cold solidification, demolding and drying to obtain a dry blank sample;
(3) and (3) sintering: heating the dried blank sample obtained in the step (2) to 400-600 ℃ at a speed of 1-5 ℃/min under a vacuum condition, then heating to 1200-1300 ℃ at a speed of 5-10 ℃/min under an inert atmosphere for sintering, wherein the sintering duration is 1-4 h, and then cooling to room temperature to obtain a porous titanium implant sample;
(4) surface micro-nano structure treatment: and (3) ultrasonically cleaning and drying the porous titanium implant sample obtained in the step (3), heating the obtained dried blank sample to 850-900 ℃ at a speed of 10-15 ℃/min in an inert atmosphere, continuously adding acetone into airflow of the inert atmosphere, controlling the flow rate of the inert gas to be 50-300 sccm, sintering for 45-60 min, and cooling to room temperature after sintering to obtain the antibacterial bionic porous titanium implant.
2. A preparation method of an antibacterial bionic porous titanium implant is a freeze casting method and comprises the following steps:
(1) preparing slurry: continuously stirring and mixing titanium powder and a medium solvent under the water bath heating condition to obtain slurry, wherein the volume fraction of the titanium powder in the slurry is 10-20%; the medium solvent is camphene, and the water bath heating temperature is 60-65 ℃;
(2) and (3) cold solidification: pouring the slurry obtained in the step (1) into a pre-cooled mold for cold solidification at the temperature of 20-25 ℃, wherein a cylindrical cavity is arranged in the mold, the mold keeps sealed and heat-insulated, and after the cold solidification, demolding and drying to obtain a dry blank sample;
(3) and (3) sintering: heating the dried blank sample obtained in the step (2) to 400-600 ℃ at a speed of 1-5 ℃/min under a vacuum condition, then heating to 1200-1300 ℃ at a speed of 5-10 ℃/min under an inert atmosphere for sintering, wherein the sintering duration is 1-4 h, and then cooling to room temperature to obtain a porous titanium implant sample;
(4) surface micro-nano structure treatment: ultrasonically cleaning and drying the porous titanium implant sample obtained in the step (3), heating the obtained dried blank sample to 850-900 ℃ at a speed of 10-15 ℃/min in an inert atmosphere, continuously adding acetone into airflow of the inert atmosphere, controlling the flow rate of the inert gas to be 50-300 sccm, sintering for 45-60 min, and cooling to room temperature after sintering to obtain the antibacterial bionic porous titanium implant;
the antibacterial bionic porous titanium implant is of a cylindrical structure and has a porous structure which is radial anisotropic along the center of the cylinder in the outer circumferential direction, the pore diameter of the porous structure is in gradient distribution from small to large along the center of the cylinder in the outer circumferential direction, and the surface of a pore substrate of the porous structure is provided with a needle-shaped micro-nano structure.
3. The method for preparing an antibacterial bionic porous titanium implant according to claim 2, wherein in the step (1), the stirring time is 2-4 h, the stirring speed is 800-1000 r/min, and a covering is placed on the stirring container while stirring to reduce solvent evaporation.
4. The method for preparing an antibacterial bionic porous titanium implant according to claim 2, wherein in the step (2), the pre-cooling temperature of the mold is the same as the condensation solidification temperature, the pre-cooling time of the mold is 30-120 min, and the condensation solidification time is 4-6 h.
5. The method for preparing an antibacterial bionic porous titanium implant according to any one of claims 2-4, characterized in that in the step (2), after condensation curing and before demoulding and drying, the sample is further cured after being stored at a low temperature of-18 ℃ to-20 ℃ for 12h to 24 h; the drying is vacuum freeze drying, and the drying time is 24-48 h.
6. The preparation method of the antibacterial bionic porous titanium implant according to any one of claims 2 to 4, wherein in the step (4), acetone, anhydrous ethanol and double distilled water are sequentially adopted for ultrasonic cleaning as cleaning liquids, and the cleaning is carried out for 15-20 min respectively; the drying temperature is 60-80 ℃, and the drying time is 4-6 h.
7. The method for preparing an antibacterial bionic porous titanium implant according to any one of claims 2-4, wherein in the step (4), the acetone is liquid acetone; and stopping adding the acetone after sintering, and naturally cooling to room temperature under the condition of controlling the flow rate of the inert gas to be 500-600 sccm.
8. The use of the antibacterial biomimetic porous titanium implant according to claim 1 or the antibacterial biomimetic porous titanium implant prepared by the preparation method according to any one of claims 2 to 7.
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