CN109574507B - Nano-scale spherical bioactive glass and preparation method thereof - Google Patents
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Abstract
The invention provides nano-scale spherical bioactive glass and a preparation method thereof, wherein the preparation method comprises the following steps: (1) dissolving a surfactant in a mixed solvent to obtain a mixed solution, and adding an alkaline catalyst to adjust the pH value of the mixed solution to obtain an alkaline mixed solution; (2) sequentially adding a silicon source, a calcium source and a phosphorus source into the alkaline mixed liquid obtained in the step (1), and continuously stirring at a high speed after each addition to obtain a bioactive glass sol liquid; (3) washing the bioactive glass sol liquid obtained in the step (2) to obtain wet gel precipitate, and then putting the wet gel precipitate into an oven for drying to obtain bioactive glass powder; (4) after washing and drying, the obtained bioactive glass powder is placed in a high-temperature furnace for heat treatment to obtain the nano-scale spherical bioactive glass. The nano-scale spherical bioactive glass prepared by the invention has smaller particle size and complete spherical shape, and can be used for drug loading and bone repair materials.
Description
Technical Field
The invention belongs to the technical field of bioactive glass, and particularly relates to nanoscale spherical bioactive glass and a preparation method thereof.
Background
The fusion method is utilized by Hench and the like in 1971 to prepare the bioactive glass with good biocompatibility, and through more than forty years of development, the preparation of the bioactive glass mainly comprises the fusion method, the sol-gel method and the improvement
Method, sol-gel method and improved
The method can prepare the spherical bioactive glass; improved
The method belongs to one of soft template methods, and the prepared spherical bioactive glass is mainly used for bone repair and drug loading and slow release.
The nano-scale particles can enter and stay in cell lysosomes and can be used as carriers needing sustained release of drugs, the bioactive glass has good bioactivity, decomposition products are all components needed by cells, the damage to the cells is small, the degradation rate is moderate, and the bioactive glass has the potential of being used as carriers of sustained release of drugs.
In the prior art, surfactants such as Cetyl Trimethyl Ammonium Bromide (CTAB) and the like are mainly used for synthesizing the nano-scale spherical bioactive glass as a template, the particle size of the prepared bioactive glass is generally larger than 100nm, particles with the particle size of about 20nm can be prepared by utilizing 3-aminopropyltrimethoxysilane, and the particles are incomplete in spherical shape and obvious in agglomeration. The surface energy of the nano-scale spherical bioactive glass is larger, the nano-scale spherical bioactive glass is extremely easy to agglomerate in the preparation process to form larger bioactive glass groups, and meanwhile, when the particle size is smaller, the spherical shape of the synthesized bioactive glass is often incomplete, so that no process capable of preparing spherical bioactive glass with the particle size of dozens of nanometers, good dispersibility and complete spherical particle shape exists in the prior art.
Therefore, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide nanoscale spherical bioactive glass and a preparation method thereof, so that the nanoscale spherical bioactive glass with smaller particle size is prepared, the spherical bioactive glass with a mesoporous structure is obtained by a simple process technology, the dispersibility is good, the spherical particles are complete in shape, and the nanoscale spherical bioactive glass has a wide application prospect when being applied to loading and slow release of medicines.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of nano-scale spherical bioactive glass comprises the following steps:
(1) dissolving a surfactant in a mixed solvent to obtain a mixed solution, and then adding an alkaline catalyst to adjust the pH value of the mixed solution to 9-10 to obtain an alkaline mixed solution;
(2) sequentially adding a silicon source, a calcium source and a phosphorus source into the alkaline mixed liquid obtained in the step (1), and continuously stirring at a high speed after each addition to obtain a bioactive glass sol liquid;
(3) washing the bioactive glass sol liquid obtained in the step (2) to obtain wet gel precipitate, and then putting the wet gel precipitate into an oven for drying to obtain white bioactive glass powder;
(4) after washing and drying, the obtained white bioactive glass powder is placed in a high-temperature furnace for heat treatment, and the surfactant and the impurity organic components are removed, so that the nano-scale spherical bioactive glass is obtained.
In the preparation method of the nano-scale spherical bioactive glass, preferably, the surfactant in the step (1) is a compound system of a triblock polymer of a nonionic surfactant and a cationic surfactant.
The preparation method of the nano-scale spherical bioactive glass is excellentOptionally, the triblock polymer of the nonionic surfactant is P123 and the molecular formula is PEO20PPO70PEO20PEO is a polyethylene oxide unit, PPO is a polypropylene oxide unit;
the cationic surfactant is cetyl trimethyl ammonium bromide.
In the preparation method of the nano spherical bioactive glass, the mass ratio of P123 to cetyl trimethyl ammonium bromide is preferably (25-150): 1.
In the preparation method of the nano spherical bioactive glass, preferably, the silicon source in the step (2) is tetraethoxysilane;
the calcium source in the step (2) is calcium nitrate tetrahydrate;
the phosphorus source in the step (2) is orthophosphoric acid.
In the preparation method of the nano-scale spherical bioactive glass, preferably, the molar ratio of the silicon source, the calcium source and the phosphorus source is (65-80): (20-30): (2-7);
the mass ratio of the surfactant to the silicon source is (0.755-0.78): 2.
In the preparation method of the nano spherical bioactive glass, preferably, the silicon source is added in the step (2), and then the high-speed stirring is carried out at the rotating speed of 700-1000 rpm for 0.5-2 h.
In the preparation method of the nano-scale spherical bioactive glass, preferably, the alkaline catalyst in the step (1) is ammonia water;
preferably, the adding proportion of the ammonia water is that the volume ratio of the silicon source to the ammonia water is (2-9): 1.
Preferably, the concentration of ammonia is 28%.
In the preparation method of the nano-scale spherical bioactive glass, preferably, the temperature of heat treatment in the high-temperature furnace in the step (4) is 500-600 ℃, and the heat preservation time is 2-5 h.
A nano-scale spherical bioactive glass prepared by a preparation method of the nano-scale spherical bioactive glass.
Compared with the closest prior art, the technical scheme provided by the invention has the following excellent effects:
the preparation method of the nano spherical bioactive glass has the advantages of simple operation, mild reaction conditions and cheap and easily-obtained raw materials; the nano-scale spherical bioactive glass with the mesoporous structure and the particle size of 30-90 nm is obtained through a compounding system of the nonionic surfactant and the cationic surfactant, the particle size is reduced, the complete morphology of spherical particles is maintained, and the nano-scale spherical bioactive glass can be widely applied to loading and controlled release of medicines.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. Wherein:
FIG. 1 is a scanning electron microscope image of a nano-sized spherical bioactive glass of example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the nano-sized spherical bioactive glass of example 2 in the invention;
FIG. 3 is a scanning electron microscope image of the nano-sized spherical bioactive glass of example 3 in the invention;
FIG. 4 is a scanning electron microscope image of the nano-sized spherical bioactive glass of example 4 in the invention;
FIG. 5 is a scanning electron microscope image of the nano-sized spherical bioactive glass of example 5 in the invention;
FIG. 6 is a scanning electron microscope image of the nano-sized spherical bioactive glass of example 6 in the invention;
FIG. 7 is a scanning electron micrograph of a spherical bioactive glass having a size of nanometer in accordance with comparative example 1 of the present invention;
FIG. 8 is a scanning electron micrograph of a spherical bioactive glass having a nano-scale structure according to comparative example 2 of the present invention;
FIG. 9 is a scanning electron micrograph of the spherical bioactive glass having a size of nanometers of comparative example 4 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The invention provides a nano-scale spherical bioactive glass and a preparation method thereof, the prepared nano-scale spherical bioactive glass has small particle size, complete spherical particle shape and good bioactivity, and is mainly synthesized by using a complex system of a triblock polymer of a nonionic surfactant and a Cetyl Trimethyl Ammonium Bromide (CTAB) of a cationic surfactant as a template and adopting a soft template method.
The preparation method mainly comprises two steps: firstly, dissolving triblock polymer P123 and CTAB in a mixed solvent of water and ethanol, uniformly stirring, adding 28% ammonia water to adjust the pH value of the mixed solution, then respectively adding a silicon source, a calcium source and a phosphorus source, and stirring to obtain a sol liquid; and finally, washing and drying the sol liquid, and performing high-temperature treatment in a high-temperature furnace for a period of time to obtain the nano spherical bioactive glass with small particle size, high specific surface area and porosity.
The principle of preparing the spherical bioglass mainly comprises the following steps: a silicon source is hydrolyzed under an alkaline condition to form a spherical silica network, and calcium and phosphorus are combined with a large amount of Si-OH on the silica network to realize the doping of the calcium and the phosphorus; removing organic matters in the glass by high-temperature treatment to obtain the nano-scale spherical bioactive glass. The spherulites prepared by the preparation method have smaller particle size, higher specific surface area and porosity, simultaneously have good bioactivity, and have great application prospect in the aspect of drug loading.
The invention provides a preparation method of nano-scale spherical bioactive glass, which comprises the following steps:
(1) dissolving a surfactant in a mixed solvent to obtain a mixed solution, adding an alkaline catalyst to adjust the pH value of the mixed solution to 9-10 to obtain an alkaline mixed solution, and preparing spherical bioactive glass by using a soft template method;
in a specific embodiment of the present invention, the surfactant in step (1) is a combination system of a triblock polymer of a nonionic surfactant and a cationic surfactant.
In a specific embodiment of the invention, the nonionic surfactant is P123 and the molecular formula is PEO20PPO70PEO20PEO is a polyethylene oxide unit, PPO is a polypropylene oxide unit; the cationic surfactant is cetyltrimethylammonium bromide (CTAB).
In a specific embodiment of the invention, the mass ratio of P123 to CTAB is (25-150): 1 (e.g., 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, 55:1, 60:1, 65:1, 70:1, 75:1, 80:1, 85:1, 90:1, 95:1, 100:1, 105:1, 110:1, 115:1, 120:1, 125:1, 130:1, 135:1, 140:1, 145: 1).
In the specific embodiment of the invention, the mixed solvent is a mixture of water and absolute ethyl alcohol;
in a specific embodiment of the invention, the basic catalyst is ammonia; preferably, the ammonia water is added in a volume ratio of the silicon source to the ammonia water of (2-9: 1) (e.g., 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 4:1, 4.2:1, 4.4:1, 4.6:1, 4.8:1, 5:1, 5.2:1, 5.4:1, 5.6:1, 5.8:1, 6:1, 6.2:1, 6.4:1, 6.6:1, 6.8:1, 7:1, 7.2:1, 7.4:1, 7.6:1, 7.8:1, 8:1, 8.2:1, 8.4:1, 8.6:1, 8.8:1, 9: 1); preferably, the concentration of ammonia is 28%.
(2) Sequentially adding a silicon source, a calcium source and a phosphorus source into the alkaline mixed liquid obtained in the step (1), and continuously stirring at a high speed after each addition to obtain a bioactive glass sol liquid;
in a specific embodiment of the present invention, the silicon source in step (2) is tetraethoxysilane;
the calcium source in the step (2) is calcium nitrate tetrahydrate;
the phosphorus source in the step (2) is orthophosphoric acid.
In a specific embodiment of the invention, the molar ratio of the silicon source, the calcium source and the phosphorus source is (65-80): (20-30): (2-7) (e.g., 65:20:2, 65:20:3, 65:20:4, 65:20:5, 65:20:6, 65:20:7, 65:25:2, 65:25:3, 65:25:4, 65:25:5, 65:25:6, 65:25:7, 65:30:2, 65:30:3, 65:30:4, 65:30:5, 65:30:6, 65:30:7, 70:20:2, 70:20:3, 70:20:4, 70:20:5, 70:20:6, 70:20:7, 70:25:2, 70:25:3, 70:25:4, 70:25:5, 70:25:6, 70:25:7, 70:30:2, 70:30:3, 70:30:4, 70:30:5, 70:30:6, 70:30:7, 75:20:7, 75:20:5, 75:20:5, 70:20:7, 5, 70: 5, and a, 75:25:2, 75:25:3, 75:25:4, 75:25:5, 75:25:6, 75:25:7, 75:30:2, 75:30:3, 75:30:4, 75:30:5, 75:30:6, 75:30:7, 80:20:2, 80:20:3, 80:20:4, 80:20:5, 80:20:6, 80:20:7, 80:25:2, 80:25:3, 80:25:4, 80:25:5, 80:25:6, 80:25:7, 80:30:2, 80:30:3, 80:30:4, 80:30:5, 80:30:6, 80:30: 7). Preferably, the molar ratio of the silicon source, the calcium source and the phosphorus source is 70:25: 5.
In a specific embodiment of the present invention, the mass ratio of the surfactant to the silicon source is (0.755-0.78): 2 (e.g., 0.756:2, 0.757:2, 0.758:2, 0.759:2, 0.76:2, 0.761:2, 0.762:2, 0.763:2, 0.764:2, 0.765:2, 0.766:2, 0.767:2, 0.768:2, 0.769:2, 0.77:2, 0.771:2, 0.772:2, 0.773:2, 0.774:2, 0.775:2, 0.776:2, 0.777:2, 0.778:2, 0.779: 2).
In an embodiment of the present invention, the high speed stirring speed after the silicon source is added in step (2) is 700-1000 rpm (e.g. 720rpm, 740rpm, 760rpm, 780rpm, 800rpm, 820rpm, 840rpm, 860rpm, 880rpm, 900rpm, 920rpm, 940rpm, 960rpm, 980rpm), and the time is 0.5-2 h (e.g. 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9 h).
(3) And (3) washing the bioactive glass sol liquid obtained in the step (2) to obtain wet gel precipitate, and then putting the wet gel precipitate into an oven for drying to obtain white bioactive glass powder.
(4) And (3) after washing and drying, placing the white bioactive glass powder obtained in the step (3) in a high-temperature furnace for heat treatment, and removing the surfactant and the impurity organic components to obtain the nano-scale spherical bioactive glass.
In an embodiment of the invention, the temperature of the heat treatment in the high temperature furnace is 500-600 ℃ (such as 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃), and the heat preservation time is 2-5 h (such as 3h, 4h, 5 h). Preferably, the temperature of the heat treatment in the high-temperature furnace is 550 ℃, and the holding time is 4 h.
Example 1
The preparation method of the nano-scale spherical bioactive glass provided by the embodiment comprises the following steps:
(1) firstly, 0.75g P123 and 0.02g CTAB are added into a solvent of 40ml of absolute ethyl alcohol and 10ml of distilled water, and stirred for 12 hours at 40 ℃ to be completely dissolved, so as to obtain a mixed solution;
to the mixed solution was added 0.33ml of 28% aqueous ammonia solution at a pH of about 9 to obtain a basic mixture.
(2) Adding 2.2ml of tetraethoxysilane into the alkaline mixed solution obtained in the step 1), stirring for 1h at 40 ℃, wherein the stirring speed is 1000rpm, and obtaining a solution I after the stirring is finished;
adding 1.41g of calcium nitrate tetrahydrate into the solution I, stirring for 30min at 40 ℃, wherein the stirring speed is 500rpm, and obtaining a solution II after the stirring is finished;
and adding 0.1ml of orthophosphoric acid into the second solution, stirring at the temperature of 40 ℃ for 12 hours at the stirring speed of 500rpm to obtain the bioactive glass sol liquid after the stirring is finished.
(3) Washing the bioactive glass sol liquid obtained in the step 2) with distilled water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃ for 24 hours to obtain white bioactive glass powder.
(4) Washing and drying, and then carrying out high-temperature treatment on the white bioactive glass powder obtained in the step 3) for 4 hours at 550 ℃ in a high-temperature furnace to remove a surfactant and other impurity organic components, so as to obtain the nano-scale spherical bioactive glass.
As shown in fig. 1, the nano-scale spherical bioactive glass obtained in this example is tested to obtain a scanning electron microscope image, and it can be known from the image that the nano-scale spherical bioactive glass prepared in this example has an average particle size of 37.78nm and a spherical morphology.
Example 2
The preparation method of the nano-scale spherical bioactive glass provided by the embodiment comprises the following steps:
(1) firstly, 0.75g P123 and 0.005g CTAB are added into a solvent of 40ml of absolute ethyl alcohol and 10ml of distilled water, and stirred for 12 hours at 40 ℃ to be completely dissolved, so as to obtain a mixed solution;
to the mixed solution was added 0.33ml of 28% aqueous ammonia solution at a pH of about 9 to obtain a basic mixture.
(2) Adding 2.2ml of tetraethoxysilane into the alkaline mixed solution obtained in the step 1), stirring for 1h at 40 ℃, wherein the stirring speed is 1000rpm, and obtaining a solution I after the stirring is finished;
adding 1.41g of calcium nitrate tetrahydrate into the solution I, stirring for 30min at 40 ℃, wherein the stirring speed is 500rpm, and obtaining a solution II after the stirring is finished;
and adding 0.1ml of orthophosphoric acid into the second solution, stirring at the temperature of 40 ℃ for 12 hours at the stirring speed of 500rpm to obtain the bioactive glass sol liquid after the stirring is finished.
(3) Washing the bioactive glass sol liquid obtained in the step 2) with distilled water and absolute ethyl alcohol for 3 times respectively, and drying at 60 ℃ for 24 hours to obtain white bioactive glass powder.
(4) Washing and drying, and then carrying out high-temperature treatment on the white bioactive glass powder obtained in the step 3) for 4 hours at 550 ℃ in a high-temperature furnace to remove a surfactant and other impurity organic components, so as to obtain the nano-scale spherical bioactive glass.
As shown in fig. 2, the nano-scale spherical bioactive glass obtained in this example is tested to obtain a scanning electron micrograph, and after analyzing the spectrogram, it is known that the nano-scale spherical bioactive glass prepared in this example has a particle size of 47.21nm and a spherical morphology.
Example 3
In this example, the amount of tetraethoxysilane added in step (2) was changed to 2.57ml, the amount of calcium nitrate tetrahydrate was changed to 0.927g, and the amount of orthophosphoric acid added was changed to 124. mu.l, and the other method steps were the same as in example 1 and will not be described again.
As shown in fig. 3, the nano-scale spherical bioactive glass obtained in this example is tested to obtain a scanning electron microscope image, and after analyzing the image, it is known that the nano-scale spherical bioactive glass prepared in this example has a particle size of about 77.65nm and a spherical morphology.
Example 4
In this example, the amount of ethyl orthosilicate added in step (2) was changed to 2.86ml, the amount of calcium nitrate tetrahydrate was changed to 0.73g, and the amount of orthophosphoric acid was changed to 71. mu.1. Other method steps are the same as embodiment 1 and are not described herein again.
As shown in fig. 4, the nano-scale spherical bioactive glass obtained in this example is tested to obtain a scanning electron microscope image, and after analyzing the image, the nano-scale spherical bioactive glass prepared in this example is found to have a particle size of 86.37nm and a spherical morphology.
Example 5
In this example, the temperature of the heat treatment in the high temperature furnace in step (1) was changed to 600 ℃, and the other method steps are the same as those in example 1 and will not be described again.
As shown in fig. 5, the nano-scale spherical bioactive glass obtained in this embodiment is tested to obtain a scanning electron micrograph, and after analyzing the micrograph, it is known that the nano-scale spherical bioactive glass prepared in this embodiment has a particle size of 35.56nm and a spherical morphology.
Example 6
In this embodiment, the high temperature treatment time in the high temperature furnace in step (1) is changed to 2h, and the other method steps are the same as those in embodiment 1 and will not be described again.
As shown in fig. 6, the nano-scale spherical bioactive glass obtained in this example is tested to obtain a scanning electron microscope image, and after analyzing the image, it is known that the nano-scale spherical bioactive glass prepared in this example has a particle size of 41.35 and a spherical morphology.
Comparative example 1
In the comparison, the adding amount of CTAB in the step (1) is changed to 0.1g, and other methods and steps are the same as those in example 1 and are not repeated herein.
As shown in fig. 7, the nano-scale spherical bioactive glass obtained in the comparative example is tested to obtain a scanning electron microscope image, and after analyzing the image, the spherical bioactive glass prepared in the comparative example has a particle size of more than 600nm, a spherical shape and serious agglomeration phenomenon.
Comparative example 2
In the comparison, the amount of ammonia added in step (1) was changed to 2ml, and the other methods and steps were the same as in example 1 and will not be described herein again.
As shown in fig. 8, the nano-scale spherical bioactive glass obtained in the comparative example is tested to obtain a scanning electron microscope image, and after analyzing the image, the bioactive glass prepared in the comparative example is seriously agglomerated, is not spherical basically, and is a particle agglomerate.
Comparative example 3
In the comparison, in the step (2), tetraethoxysilane is added into the alkaline mixed solution obtained in the step 1), stirring is carried out for 1 hour at the stirring speed of 200rpm, and gel is obtained after the stirring is finished, and other methods and steps are the same as those in the example 1 and are not repeated.
In this comparative example, the addition of ethyl orthosilicate resulted in a gel-like material, and nanoscale spherical bioactive glass could not be obtained.
Comparative example 4
In this comparison, the phosphorus source in step (2) of example 1 was changed to triethyl phosphate, and the other methods and steps were the same as in example 1 and will not be described again.
The nano-scale spherical bioactive glass obtained in the comparative example is tested to obtain a scanning electron microscope image 9, and after the image is analyzed, the particle size of the spherical bioactive glass prepared in the comparative example is about 42.52nm, the appearance is spherical, but the agglomeration phenomenon is serious.
The preparation process adopts a soft template method, no phase separation exists in a liquid phase, the micelle size is small, and compared with a micro-emulsion method, the size of the obtained spherical bioactive glass is smaller. The phosphorus source raw material adopts orthophosphoric acid, so that the particle size of the particles can be effectively reduced. After adding tetraethoxysilane, continuously stirring for a period of time at a higher rotating speed, and then adding a calcium source and a phosphorus source to ensure that the bioactive glass sol liquid particles are fine, so that the nano-scale spherical bioactive glass with the particle size of 30-90 nm and the mesoporous structure is finally obtained, and the nano-scale spherical bioactive glass is uniformly dispersed and spherical.
Because tetraethoxysilane has a large number of silicon hydroxyl groups after hydrolysis, is easy to combine with calcium ions to form gel, and cannot generate spherical bioactive glass, the invention needs higher stirring speed to prevent the gel from forming, and simultaneously, larger shearing force is helpful for reducing the particle size.
In summary, the following steps: the nanometer spherical bioactive glass provided by the invention uses a compound system of a nonionic surfactant and a cationic surfactant as a template agent, and is prepared by a soft template method, wherein the specific preparation method mainly comprises two steps, namely, firstly, triblock polymer P123 and CTAB are dissolved in a mixed solvent of water and ethanol and are uniformly stirred, then, alkaline catalyst ammonia water is added to adjust the pH value of the mixed solution, then, a silicon source, a calcium source and a phosphorus source are respectively added, and a sol liquid is obtained by stirring; and finally, washing and drying the sol liquid, and performing high-temperature treatment in a high-temperature furnace for a period of time to obtain the nano spherical bioactive glass with small particle size, high specific surface area and porosity.
The nano-scale spherical bioactive glass prepared by the invention has rich pore structures, and the nano-scale spherical bioactive glass with the mesoporous structure and the particle size of 30-90 nm is obtained through a compound system of a nonionic surfactant and a cationic surfactant in a proper proportion, so that the particle size is reduced, the spherical morphology is maintained, and the nano-scale spherical bioactive glass can be used for loading and controlled release of medicines.
The preparation method adopts a soft template method, the liquid phase does not have split phase, the size of the prepared micelle can be very small, and the size of the microemulsion drop formed by water and an organic solvent in the preparation method in the prior art, such as the microemulsion method, is larger. In the preparation method, orthophosphoric acid is used as a phosphorus source, and the phosphorus source can obviously reduce the particle size. According to the invention, the silicon source, the calcium source and the phosphorus source are sequentially added into the alkaline mixed liquid obtained in the step (1), and as gel is easily formed at low rotating speed and nano-scale spherical bioactive glass cannot be obtained, continuous high-speed stirring is carried out after each addition, and the particle size can be effectively reduced by adopting faster stirring rotating speed.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. A preparation method of nano-scale spherical bioactive glass is characterized by comprising the following steps:
(1) dissolving a surfactant in a mixed solvent to obtain a mixed solution, and then adding an alkaline catalyst to adjust the pH value of the mixed solution to 9-10 to obtain an alkaline mixed solution; the alkaline catalyst is ammonia water;
(2) sequentially adding a silicon source, a calcium source and a phosphorus source into the alkaline mixed liquid obtained in the step (1), and continuously stirring at a high speed after each addition to obtain a bioactive glass sol liquid; after the silicon source is added, the high-speed stirring is carried out at the rotating speed of 700-1000 rpm for 0.5-2 h; the silicon source is tetraethoxysilane; the calcium source is calcium nitrate tetrahydrate; the phosphorus source is orthophosphoric acid; the mass ratio of the surfactant to the silicon source is (0.755-0.78): 2; the adding proportion of the ammonia water is that the volume ratio of the silicon source to the ammonia water is (2-9): 1; the mass concentration of the ammonia water is 28%;
(3) washing the bioactive glass sol liquid obtained in the step (2) to obtain wet gel precipitate, and then putting the wet gel precipitate into an oven for drying to obtain white bioactive glass powder;
(4) after washing and drying, placing the obtained white bioactive glass powder in a high-temperature furnace for heat treatment, and removing a surfactant and impurity organic components to obtain nano-scale spherical bioactive glass;
the surfactant is a compound system of a triblock polymer of a nonionic surfactant and a cationic surfactant;
the triblock polymer of the nonionic surfactant is P123, and the molecular formula is PEO20PPO70PEO20PEO is a polyethylene oxide unit, PPO is a polypropylene oxide unit;
the cationic surfactant is cetyl trimethyl ammonium bromide;
the mass ratio of the P123 to the hexadecyl trimethyl ammonium bromide is (25-150) to 1;
the molar ratio of the silicon source to the calcium source to the phosphorus source is (65-80): (20-30): (2-7).
2. The method for preparing nano spherical bioactive glass according to claim 1, wherein the temperature of the heat treatment in the high temperature furnace in the step (4) is 500-600 ℃, and the holding time is 2-5 h.
3. A nanoscale spherical bioactive glass prepared by the method for preparing nanoscale spherical bioactive glass as claimed in claim 1 or 2.
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