CN113289059A - Copper-containing mesoporous bioglass-magnesium metal composite antibacterial material and preparation method and application thereof - Google Patents
Copper-containing mesoporous bioglass-magnesium metal composite antibacterial material and preparation method and application thereof Download PDFInfo
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- 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 copper-containing mesoporous bioglass-magnesium metal composite antibacterial material as well as a preparation method and application thereof. The preparation method comprises the steps of firstly forming an oil-in-water phase by adopting an improved one-pot method to obtain mixed gel, and then removing the organic template agent by high-temperature calcination to finally obtain the copper-containing mesoporous bioglass nanospheres; after copper-containing mesoporous bioglass nano particles are mixed with magnesium metal powder, a laser powder bed melting technology is utilized to prepare the multifunctional copper-containing mesoporous bioglass-magnesium metal composite antibacterial material. The multifunctional composite material prepared by the invention has good antibacterial performance and bone-promoting function, and the copper-containing mesoporous bioglass is nano-particles with uniform shapes, and can release copper ions to realize excellent antibacterial performance. Meanwhile, the excellent mesoporous structure can release copper ions in a sustained and controlled manner, so that the long-term antibacterial effect is realized.
Description
Technical Field
The invention belongs to the field of multifunctional biomedical materials, and particularly relates to a copper-containing mesoporous bioglass-magnesium metal composite antibacterial material as well as a preparation method and application thereof.
Background
The magnesium alloy has natural degradability, good biocompatibility and mechanical properties matched with human bones, so that the magnesium alloy has great potential in clinical application of bone implants. After being implanted into a human body, the magnesium alloy not only plays a good supporting role, but also can be gradually degraded to promote bone healing and bone repair, can be used for temporarily replacing bones and meet the clinical requirements of bone implants. And magnesium is an essential trace element of human body, participates in metabolism of human body, and can promote proliferation and differentiation of osteoblast and inhibit formation of osteoclast. Therefore, the magnesium alloy has great potential in the medical field of bone repair. However, during the surgical procedures of bone filling and bone repair, the bone implantation site is easily infected with bacteria, causing serious problems such as local infection and osteomyelitis.
The metal with antibacterial property is introduced into the bone implant material to prepare the multifunctional antibacterial bone implant material, which is a very effective bacteriostasis means. However, if the metal is directly introduced into the magnesium alloy, a second phase is easily formed, especially because the standard potential of Mg is low, the formed second phase is easy to form a galvanic cell with the magnesium matrix, and the magnesium is degraded too fast, so that the integrity of the mechanical structure is damaged earlier, and the application of bone repair is not facilitated.
The mesoporous bioglass has been widely studied in the treatment of bone diseases due to the excellent characteristics of ordered arrangement of mesopores, large specific surface area, good biocompatibility and the like. The mesoporous bioglass has the advantages of large specific surface area and high pore volume, endows the mesoporous bioglass with excellent drug or therapeutic ion loading and slow release capacity, can carry antibiotics, antibacterial agents or growth factors as a local drug delivery system, and can be used for developing multifunctional biomaterials. In addition, ions of the mesoporous bioglass can exchange with protons in a reaction medium to finally form a silicon-rich gel layer, so that an amorphous calcium phosphate layer is easily formed on the surface of the magnesium substrate, a good protection effect on the magnesium substrate is achieved, and the degradation of magnesium is further delayed.
However, the prior art has no report that mesoporous bioglass is adopted to load metal with antibacterial property to be introduced into bone implant materials.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a copper-containing mesoporous bioglass-magnesium metal composite antibacterial material with excellent antibacterial effect and optimal degradation speed, and a preparation method and application thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention relates to a copper-containing mesoporous bioglass-magnesium composite antibacterial material, which consists of a magnesium metal matrix and copper-containing mesoporous bioglass dispersed in the magnesium metal matrix, wherein the mass fraction of the copper-containing mesoporous bioglass in the copper-containing mesoporous bioglass-magnesium composite antibacterial material is 4-10 wt%.
The inventor finds that the ordered mesoporous structure of the mesoporous bioglass provides a good carrier for loading copper, can release copper ions in a sustained and controlled manner, and realizes a long-term antibacterial effect. Meanwhile, along with the slow degradation of magnesium, copper ions are slowly released, so that the infection of bacteria to the bone implant is inhibited. And the mesoporous bioglass is contacted with body fluid, and by utilizing the advantages of unique mesoporous structure, large specific surface area, pore volume and the like of the mesoporous bioglass, a good mineralization effect can be generated on a magnesium matrix, a compact calcium-phosphorus protective layer is formed on the surface, the magnesium metal degradation is further delayed, the corrosion rate of magnesium is reduced, and meanwhile, the better connectivity between bones and bone implants can be realized.
In the process of experimental exploration, the inventor tries a large amount of antibacterial metals, and finally finds that the antibacterial effect can be greatly improved and the magnesium degradation can be slowed down only by loading copper in the mesoporous bioglass, and the mesoporous bioglass has good biocompatibility. Even silver with stronger antibacterial performance is loaded on the mesoporous bioglass, the antibacterial performance of the mesoporous bioglass is weaker than that of copper. Copper is a trace element necessary for human body, the biochemical function in human body is mainly catalysis, the normal hematopoietic function of human body is maintained, the copper participates in iron metabolism and erythropoiesis, the angiogenesis promoting capability can be realized, and silver has certain harm to human body.
Through further detection, the inventor finds that excellent antibacterial effect can be obtained by loading copper on mesoporous bioglass, and on one hand, a large amount of SiO exists on mesoporous channels, walls and surfaces of the mesoporous bioglass-And PO-Electronegative groups capable of reacting with Cu2+The positive ions have good electrostatic adsorption effect. Moreover, since the mesoporous bioglass has a large specific surface area, the exposed electronegative groups are increased, and thus a higher loading amount can be realized. On the other hand, Cu can act as a donor and acceptor of electrons, when Cu + and Cu2+In between, a redox reaction occurs. The redox potential of copper can vary in the range of 200-800 mv, and the redox properties of copper can cause significant damage to bacteria. In addition, the redox property can generate a large amount of hydroxyl radicals, and the extremely active hydroxyl radicals can participate in some harmful reactions to molecules, such as the generation of oxidized proteins and lipids, thereby further generating good antibacterial effect.
Preferably, in the copper-containing mesoporous bioglass, the mass fraction of copper is 2-5 wt%, the shape of the copper-containing mesoporous bioglass is spherical, the particle size is 100-300nm, and the diameter of the mesoporous is 2-10 nm.
More preferably, in the copper-containing mesoporous bioglass, the mass fraction of copper is 5 wt%; the copper-containing mesoporous bioglass is spherical, the particle size is 100-150nm, and the mesoporous aperture is 2-4 nm.
Preferably, in the copper-containing mesoporous bioglass-magnesium composite bacteriostatic material, the extraction solution is used for culturing escherichia coli, and the number of escherichia coli colonies cultured for 7 days is counted to be 100-500.
Preferably, the degradation rate of the copper-containing mesoporous bioglass-magnesium composite material is 0.2-0.35 mm/year.
The invention relates to a preparation method of a copper-containing mesoporous bioglass-magnesium composite antibacterial material, which comprises the following steps:
step one
Dissolving an organic template agent, triethanolamine, a phosphorus source and a calcium source in water to obtain an aqueous phase solution; mixing a silicon source and cyclohexane to obtain an oil phase solution; slowly adding the oil phase solution into the water phase solution to form an oil-in-water phase; adding a copper source, stirring for reaction to obtain mixed sol-gel, then centrifugally cleaning to obtain blue precipitate, drying and calcining to obtain the copper-containing mesoporous bioglass;
step two
And (2) mixing the copper-containing mesoporous bioglass prepared in the step one with magnesium powder, performing ball milling to obtain copper-containing mesoporous bioglass-magnesium mixed powder, and performing melting forming by using a laser powder bed to obtain the copper-containing mesoporous bioglass-magnesium alloy composite antibacterial material.
According to the invention, an improved one-pot method is adopted to load copper into mesoporous bioglass, and then a laser powder bed melting technology is used to prepare the copper-containing mesoporous bioglass-magnesium metal composite antibacterial material. The copper-containing mesoporous bioglass prepared by the preparation method can maintain high specific surface area and pore volume and can maintain Cu2+The sustained release of the active ingredients can obviously inhibit the viability of bacteria and achieve good antibacterial effect.
Preferably, in the first step, the organic template is cetyltrimethylammonium bromide (CTAB), and the solid-liquid mass volume ratio of CTAB to water is 2-6g:100ml, preferably 3-5g:100 ml.
In the invention, the organic template CTAB mainly serves as a mesoporous pore-forming agent to guide the generation of mesopores. The addition amount needs to be effectively controlled, and if the CTAB content is too small, the aperture of the synthesized mesoporous bioglass is too small, the exposed pore canal and pore wall area are too small, and Cu cannot be effectively loaded. Too much CTAB content can cause the pore diameter to be too large, and the pore wall of the mesoporous bioglass is too thin, so that the collapse of the gap is caused, and the Cu loading is reduced.
In addition, in the improved one-pot method, the triethanolamine organic solvent used is weakly alkaline in hydrolysis, and is used for regulating and controlling the pH value of the hydrolysis. When ph is controlled to be 7-10, the interaction between the organic amine molecules and silicate is stronger than 1, so that stable chelation can be formed, and the Cu-loaded dendritic mesoporous glass can be effectively prepared.
In actual operation, the water used is deionized water.
Preferably, in the first step, the volume ratio of the aqueous phase solution to the oil phase solution is 3-5: 1. the inventors have found that a stable mesoporous structure can be obtained by controlling the volume ratio of the aqueous phase solution to the oil phase solution within the above range. If the aqueous phase is too much, it is difficult to form a stable mesoporous structure.
Preferably, in step one, the calcium source is calcium nitrate tetrahydrate or calcium chloride.
Preferably, in the first step, the phosphorus source is triethyl phosphate.
Preferably, in the step one, the silicon source is tetraethoxysilane.
Preferably, in the first step, the copper source is copper chloride or copper nitrate.
Preferably, in the first step, the temperature of the stirring reaction is 30-60 ℃, and the time of the stirring reaction is 5-11 h.
In the practical operation process, preferably, magnetic stirring is adopted, and the inventor finds that the reaction temperature needs to be effectively controlled, and only the temperature is controlled within the scope of the invention, the copper-containing mesoporous bioglass with the required morphology can be obtained.
Preferably, in the first step, in the mixed sol-gel, the molar ratio of copper element: calcium element: phosphorus element: the silicon element is 2-5:5-20:5-15: 60-80.
Preferably, in the step one, deionized water and alcohol are adopted for centrifugal cleaning, the rotation speed of the centrifugal cleaning is 2000-.
Preferably, in the first step, the calcination environment is a vacuum environment, and the calcination temperature is 600-700 ℃; the calcining time is 5-8 h.
Preferably, in the second step, in the copper-containing mesoporous bioglass-magnesium mixed powder, the mass fraction of the copper-containing mesoporous bioglass is 4 to 10 wt%, and preferably 5 to 8 wt%.
Preferably, in the second step, the rotation speed of the ball mill is 100-500rad/min, and the ball milling time is 1-5 h.
Further preferably, in the second step, the rotation speed of the ball milling is 200-.
Preferably, in the second step, when the laser powder bed is melted and formed, the laser power is 70-120W, and the scanning speed is 80-140 mm/s.
Further preferably, in the second step, when the laser powder bed is melted and formed, the laser power is 80-100W, and the scanning speed is 100-120 mm/s.
The invention relates to an application of a copper-containing mesoporous bioglass-magnesium alloy composite antibacterial material, which is applied as a bone implant material.
Compared with the prior art, the invention has the following beneficial effects:
(1) by using the mesoporous bioglass as a carrier, copper with an antibacterial effect can be loaded more easily. If copper is directly added to the magnesium matrix, MgCu is easily formed2And (4) phase(s). The standard potential of the second phase is higher than that of magnesium, so that the second phase and a magnesium matrix are easy to form a microscopic primary battery, and the degradation rate of the magnesium matrix is accelerated. Because the grain size of Cu is smaller than that of Ca, Cu can partially replace the lattice position of Ca in the mesoporous bioglass through chemical reaction in the synthesis process, and the loading capacity of copper can be improved. Thus, the use of mesoporous bioglass as a carrier to introduce copper into a magnesium bone implant can avoid the formation of MgCu2And more importantly, copper ions can be released in the degradation process, so that a better antibacterial effect is realized.
(2) The copper-containing mesoporous bioglass particles are nano-scale microspheres, are regular and uniform in shape, and have an average particle size of 150 nm. The small-size nano particles can be more dispersedly distributed in the magnesium powder, so that the fluidity of the composite powder is increased, and 3D printing is more facilitated. In addition, when the magnesium metal composite material is prepared by adopting a laser powder bed melting technology, the uniformly dispersed nano particles can obviously improve the molding quality of the magnesium composite material. In the process of magnesium metal degradation, the uniform dispersion state can realize the uniform release of copper ions, and compared with common copper-carrying particles, the copper-carrying particle has more advantages on the antibacterial effect. In addition, when the nano particles uniformly dispersed in the magnesium matrix contact with body fluid, the surface can be uniformly mineralized, so that a more compact and uniform calcium-phosphorus layer is formed, and the corrosion of the magnesium matrix is obviously delayed.
(3) The mesoporous bioglass can perform ion exchange with solute in the dissolving process, and further can form a silicon-rich gel layer in a matrix, and can attract Ca in a medium2+And PO4 3-And forming an amorphous calcium phosphate layer, thereby realizing the purpose of inducing the deposition of calcium phosphate and forming a 'protective layer'. Meanwhile, the mesoporous bioglass has a huge specific surface area and can provide more calcium-phosphorus nucleation sites, so that the surface of the substrate is promoted to be mineralized to form a compact calcium-phosphorus layer. The structure not only can play a role in protecting the magnesium matrix so as to delay degradation, but also can promote the growth of new bones at the interface.
In conclusion, the copper-containing mesoporous bioglass synthesized, the used laser selective melting technology and the content of the mesoporous bioglass in the composite material are crystals which are subjected to numerous experiments and creative work by the inventor, and the copper-containing mesoporous bioglass prepared by controlling the content of the copper-containing mesoporous bioglass and adjusting the process parameters of the laser powder bed melting technology improves the antibacterial effect and the corrosion resistance of the magnesium implant, and is expected to be applied to the field of biomedicine.
Drawings
Fig. 1 microscopic morphology of the copper-containing mesoporous bioglass microsphere powder of example 1.
FIG. 2 adsorption and desorption curves and pore size analysis of mesoporous bioglass microsphere powder in example 1.
Fig. 3 shows the antibacterial effect of the copper-containing mesoporous bioglass-magnesium composite antibacterial material in example 1.
Detailed Description
The invention will be further illustrated by the following specific examples.
Example 1
The method comprises the following steps: preparing copper-containing mesoporous bioglass nano-particles,
(1) 3.6g of cetyltrimethylammonium bromide (CTAB) and 0.12mL of Triethanolamine (TEA) were dissolved in 100mL of deionized water and magnetically stirred for 1h at 50 ℃.
(2) 1.22ml of triethyl phosphate (TEP) and 2.88g of Calcium Nitrate (CN) were added to the system of step (1) in sequence, each step being stirred for 30min at intervals of magnetic stirring.
(3) 16ml of tetraethyl orthosilicate (TEOS) and 20ml of cyclohexane were added to the system of the previous step (2) by forming a mixed oil phase, sonicating for 15 minutes,
(4) 0.8g of copper (Cu) chloride was added to the system of step (3) and magnetically stirred at 50 ℃ for 12h until a white precipitate was formed.
(5) And (4) centrifuging the solution obtained in the step (4), and washing the solution for 3 times by using deionized water to obtain a white precipitate.
(6) And (5) placing the white precipitate obtained in the step (5) in a vacuum drying oven, setting the temperature to be 80 ℃, and drying for 24 hours to obtain white powder.
(7) And (4) placing the white powder obtained in the step (6) in a tubular heating furnace, heating to 600 ℃, heating for 5 hours, cooling to room temperature, and taking out to obtain the copper-containing mesoporous bioglass nano microspheres.
The microstructure characterization of the obtained copper-containing mesoporous bioglass nano-scale shows that: the copper-containing mesoporous bioglass has small particle size, uniform shape, high copper-carrying content and average particle diameter of about 100nm, as shown in figure 1. The obtained nitrogen adsorption-desorption curve of the mesoporous bioglass is shown in figure 2, wherein the interpolation graph is a mesoporous aperture distribution graph. The nitrogen adsorption-desorption isotherm has an obvious H3 type hysteresis loop, the average pore diameter is 2.3nm, and the specific surface area is 480.7m2g-1。
Step two: preparing a copper-containing mesoporous bioglass microsphere-magnesium metal composite antibacterial material.
(1) The mesoporous bioglass is designed to contain 5% of Cu by mass, and 0.5g of copper-containing mesoporous bioglass powder and 9.5g of magnesium alloy powder (with the average particle size of 60 mu m) are weighed. And performing ball milling in the protective gas atmosphere of argon to obtain mixed powder, wherein the rotating speed of the ball milling is 200rad/min, and the ball milling time is 3 h.
(2) Under the protection of high-purity argon atmosphere, the laser power is 80W, the scanning speed is 100mm/s, and the laser spot is 70 μm. And melting the mixture by a laser powder bed to obtain the copper-containing mesoporous bioglass-magnesium metal composite material.
Tests show that compared with the mesoporous bioglass without Cu, the copper-containing mesoporous bioglass magnesium composite material has higher Cu and Si release solubility, and the number of cultured escherichia coli colonies is less and the bacteriostatic effect is better through in vitro bacterial tests.
Ion solubility was measured after 7 days by immersion in simulated body fluid: cu2+＝152.9ppm，Si4+74.2 ppm; meanwhile, the number of the bacterial colonies of the escherichia coli is counted, and the result shows that the number of the bacterial colonies of the copper-containing mesoporous bioglass magnesium composite material is 120, and the number of the bacterial colonies is obviously reduced. Moreover, SEM observation shows that the surface is covered with a large amount of calcium-phosphorus layers, and the surface has good biocompatibility. The calculated degradation rate was 0.30 mm/year.
Example 2
The other conditions were the same as in example 1 except that the mesoporous bioglass was designed to contain 2.0% by mass of Cu and 0.5g of copper-containing mesoporous bioglass powder and 9.5g of magnesium-zinc alloy powder (average particle size 50 μm) were weighed out according to the design group distribution. And performing ball milling in the protective gas atmosphere of argon to obtain mixed powder, wherein the rotating speed of the ball milling is 300rad/min, and the ball milling time is 3 h. The mixed powder is used as a raw material, magnesium metal of the strontium-containing mesoporous bioglass is prepared by a laser powder bed melting process, and in the preparation process, the laser power is 80W, the scanning speed is 100mm/s, and the laser spot is 80 mu m
Tests show that compared with the mesoporous bioglass containing 5 percent of Cu,the mesoporous bioglass containing 2.0 percent of Cu releases lower ion solubility, and the Cu content is lower2+＝94.6ppm，Si4+66.5 ppm; through in vitro bacteria test, the number of cultured escherichia coli colonies is about 800, and the bacteriostatic effect is obviously lower. The degradation rate of the alloy is 0.33 mm/year.
Example 3
The other conditions were the same as in example 1 except that the mesoporous bioglass was designed to contain 3.0% by mass of Cu and 0.4g of copper-containing mesoporous bioglass powder and 9.6g of magnesium-zinc alloy powder (average particle size 50 μm) were weighed out according to the design group distribution. And performing ball milling in the protective gas atmosphere of argon to obtain mixed powder, wherein the rotating speed of the ball milling is 300rad/min, and the ball milling time is 2 h. The mixed powder is used as a raw material, magnesium metal of the strontium-containing mesoporous bioglass is prepared by a selective laser melting process, and in the preparation process, the laser power is 80W, the scanning speed is 100mm/s, and the laser spot is 80 microns.
According to the formula, in the example 3, the mesoporous bioglass containing 3.0% of Cu releases ion solubility: cu2+＝108.6ppm，Si4+87.5 ppm; through in vitro bacteria test, the number of the cultured escherichia coli colonies is about 500, and the bacteriostatic effect is improved. The degradation rate of the obtained copper-containing mesoporous bioglass-magnesium composite material is 0.35 mm/year.
Example 4
The other conditions were the same as in example 1 except that the mesoporous bioglass was designed to contain 4.0% by mass of Cu and 0.4g of copper-containing mesoporous bioglass powder and 9.6g of magnesium alloy powder (average particle size 50 μm) were weighed out according to the design group distribution. And performing ball milling in the protective gas atmosphere of argon to obtain mixed powder, wherein the rotating speed of the ball milling is 300rad/min, and the ball milling time is 2 h. The mixed powder is used as a raw material, magnesium metal of the copper-containing mesoporous bioglass is prepared by a selective laser melting process, and in the preparation process, the laser power is 90W, the scanning speed is 120mm/s, and the laser spot is 100 mu m
In example 4, the mesoporous bioglass containing 4.0% Cu was tested to release ion solubility: cu2+＝180.9ppm，Si4+110.8 ppm; by in vitroAnd in bacterial tests, the number of cultured escherichia coli colonies is about 300, and the bacteriostatic effect is obviously improved. The degradation rate of the obtained copper-containing mesoporous bioglass-magnesium composite material is 0.42 mm/year.
During the course of the present study, many other solutions were tried, but the performance of the obtained product was far inferior to the examples.
Comparative example 1
The other conditions were the same as in example 1 except that: the mass fraction of Cu contained in the designed mesoporous bioglass is 1.0%, and the component ratio of the synthesized mesoporous bioglass is 1:14:5: 80. Tests show that compared with mesoporous bioglass containing magnesium metal with the mass fraction of Cu being 5%, the prepared alloy has weak ion release capacity, the number of cultured escherichia coli colonies is about 2000, the antibacterial effect is obviously not improved, and the degradation rate is 0.45 mm/year.
Comparative example 2
The other conditions were the same as in example 1 except that: the mass fraction of Cu contained in the designed mesoporous bioglass is 8%, and the component ratio of the synthesized mesoporous bioglass is Cu: Ca: P: Si: 8:12:5: 80. Tests show that compared with the mesoporous bioglass containing 5 mass percent of magnesium metal of Cu, the release capacity of the prepared alloy ions is basically unchanged, the number of cultured escherichia coli colonies is about 200, the antibacterial effect is obviously not improved much, and the degradation speed is 0.45 mm/year.
Comparative example 3
The other conditions were the same as in example 1 except that: the mass ratio of bioglass/magnesium powder is 1%, 0.1g of copper-containing mesoporous bioglass powder and 9.9g of magnesium alloy powder (average particle size 50 μm) are weighed. Tests show that compared with magnesium metal with the mass of 5% of bioglass/magnesium powder, the prepared alloy has weak ion release capacity, the number of cultured escherichia coli colonies is about 2000, the antibacterial effect is not improved, and the degradation rate is 1.0 mm/year.
Comparative example 4
The other conditions were the same as in example 1 except that: 1.1g of copper-containing mesoporous bioglass powder and 8.9g of magnesium alloy powder (average particle size of 50 μm) were weighed so that the mass ratio of bioglass to magnesium powder was 11%. Tests show that compared with magnesium metal with the mass of 5% of bioglass/magnesium powder, the prepared alloy has weak ion release capacity, the number of cultured escherichia coli colonies is about 1500, the antibacterial effect is not greatly improved, and the degradation rate is 0.44 mm/year.
Comparative example 5
The other conditions were the same as those in example 1, except that the metal Ag was added to the mesoporous glass instead of the metal Cu. Tests show that compared with the mesoporous bioglass containing Cu, the mesoporous bioglass containing Ag has higher synthesis cost, the antibacterial effect is not as good as that of Cu, the antibacterial effect is not greatly improved compared with that of copper, and the degradation rate is 0.44 mm/year.
Comparative example 6
The other conditions were the same as in example 1 except that the mesoporous bioglass was changed to a common bioglass. Tests show that compared with mesoporous bioglass, the content of Cu which can be loaded by common bioglass is lower, and basically no antibacterial effect exists.
Comparative example 7
The other conditions were the same as those in example 1, except that the content of CTAB, an organic template, was added in an amount of 10g when synthesizing the Cu-containing mesoporous bioglass. Tests show that compared with the mesoporous bioglass added with 5g CTAB, the synthesized mesoporous bioglass has irregular shape and poor dispersibility and is gathered together. When the magnesium-based composite material is added into a magnesium matrix, the formed part is low in density, a second phase is easy to agglomerate together, a formed calcium-phosphorus layer is few, and the degradation rate is increased to 0.78 mm/year.
Comparative example 8
The other conditions were the same as in example 1, except that: when the copper-containing mesoporous bioglass is synthesized, the stirring temperature is 20 ℃. Tests show that the synthesized bioglass particles are large, the nucleation rate is low, and the bioglass particles are irregular in shape and different in size. When the mineral is added into a magnesium matrix, the dispersibility is poor, the quality of the aggregate is poor, the mineralization effect is poor, and the degradation rate is increased to 0.78 mm/year.
Claims (10)
1. A copper-containing mesoporous bioglass-magnesium metal composite antibacterial material is characterized in that: the copper-containing mesoporous bioglass-magnesium composite antibacterial material is characterized by comprising a magnesium metal matrix and copper-containing mesoporous bioglass dispersed in the magnesium metal matrix, wherein the mass fraction of the copper-containing mesoporous bioglass in the copper-containing mesoporous bioglass-magnesium composite antibacterial material is 4-10 wt%.
2. The multifunctional copper-containing mesoporous bioglass-magnesium metal composite antibacterial material as claimed in claim 1, characterized in that: in the copper-containing mesoporous bioglass, the mass fraction of copper is 2-5 wt%, the shape of the copper-containing mesoporous bioglass is spherical, the particle size is 100-300nm, and the diameter of a mesoporous is 2-10 nm.
3. The preparation method of the multifunctional copper-containing mesoporous bioglass-magnesium metal composite antibacterial material according to claim 1 or 2, which is characterized by comprising the following steps:
step one
Dissolving an organic template agent, triethanolamine, a phosphorus source and a calcium source in water to obtain an aqueous phase solution; mixing a silicon source and cyclohexane to obtain an oil phase solution; slowly adding the oil phase solution into the water phase solution to form an oil-in-water phase; adding a copper source, stirring for reaction to obtain mixed sol-gel, then centrifugally cleaning to obtain blue precipitate, drying and calcining to obtain the copper-containing mesoporous bioglass;
step two
And (2) mixing the copper-containing mesoporous bioglass prepared in the step one with magnesium powder, performing ball milling to obtain copper-containing mesoporous bioglass-magnesium mixed powder, and performing melting forming by using a laser powder bed to obtain the copper-containing mesoporous bioglass-magnesium alloy composite antibacterial material.
4. The preparation method of the copper-containing mesoporous bioglass-magnesium alloy composite antibacterial material according to claim 3, which is characterized by comprising the following steps:
in the first step, the organic template is CTAB, and the solid-liquid mass-volume ratio of CTAB to water is as follows: 2-6g, 100 ml.
5. The multifunctional copper-containing mesoporous bioglass-magnesium metal composite antibacterial material and the preparation method thereof according to claim 3, characterized in that,
in the first step, the volume ratio of the water phase solution to the oil phase solution is 3-5: 1,
in the first step, the calcium source is calcium nitrate tetrahydrate or calcium chloride,
in the first step, the phosphorus source is triethyl phosphate,
in the first step, the silicon source is tetraethoxysilane,
in the first step, the copper source is copper chloride or copper nitrate.
6. The multifunctional copper-containing mesoporous bioglass-magnesium metal composite antibacterial material and the preparation method thereof according to claim 3, wherein the preparation method comprises the following steps:
in the first step, the temperature of the stirring reaction is 30-60 ℃, the time of the stirring reaction is 5-11h,
in the first step, in the mixed sol-gel, in terms of molar ratio, the ratio of copper element: calcium element: phosphorus element: the silicon element is 2-5:5-20:5-15: 60-80.
7. The multifunctional copper-containing mesoporous bioglass-magnesium metal composite antibacterial material and the preparation method thereof according to claim 3, wherein the preparation method comprises the following steps:
in the first step, deionized water and alcohol are adopted for centrifugal cleaning, the rotating speed of the centrifugal cleaning is 2000-,
in the first step, the calcination environment is a vacuum environment, and the calcination temperature is 600-700 ℃; the calcining time is 5-8 h.
8. The multifunctional copper-containing mesoporous bioglass-magnesium metal composite antibacterial material and the preparation method thereof according to claim 3, wherein the preparation method comprises the following steps:
in the second step, in the copper-containing mesoporous bioglass-magnesium mixed powder, the mass fraction of the copper-containing mesoporous bioglass is 5-8 wt%,
in the second step, the rotation speed of the ball milling is 200-.
9. The multifunctional copper-containing mesoporous bioglass-magnesium metal composite antibacterial material and the preparation method thereof according to claim 3, wherein the preparation method comprises the following steps:
in the second step, when the laser powder bed is melted and formed, the laser power is 70-120W, and the scanning speed is 80-140 mm/s.
10. The copper-containing mesoporous bioglass-magnesium metal composite as claimed in claim 1 or 2, wherein: the copper-containing mesoporous bioglass-magnesium composite antibacterial material is applied as a bone implant material.
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