Cream for beauty apparatus and preparation method thereof
By using a composite system of aluminum nitride-covered chitosan composite nano-microspheres and Ag nanowires/hydroxyapatite microspheres in cosmetic instrument frost, the problem of insufficient thermal conductivity and antibacterial performance of the frost is solved, and a significant performance improvement is achieved, suitable for high-end beauty applications.
Patent Information
- Application Number
- CN202510678364.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-26
- Publication Date
- 2025-06-24
- Estimated Expiration
- 2045-05-26
AI Technical Summary
The creams in existing beauty instruments are insufficient in terms of thermal conductivity and antibacterial properties, and it is difficult to meet the needs of high-frequency thermal energy conduction and long-term safe use.
The composite system of aluminum nitride-coated chitosan composite nanometer microspheres and Ag nanowires/hydroxyapatite microspheres is adopted to improve the thermal conductivity and antibacterial properties of the frost through the composite structure of porous aluminum nitride hollow microspheres and chitosan and the directional growth of silver nanowires.
It significantly improves the thermal conductivity and antibacterial properties of the cream, solves the problems of poor thermal conductivity and weak antibacteriality, and is suitable for high-end beauty introduction fields.
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Figure CN120189356A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the field of frost creams, and particularly to a frost cream for beauty instruments and a preparation method thereof. Background Art
[0002] With the wide application of scientific and technological beauty devices in the fields of skin care, facial firming, anti-aging, etc., the introduction medium in beauty instruments has gradually developed from traditional creams or gels to functional frost creams. During the use of beauty instruments, as an intermediate material between the skin and the device, the frost cream not only needs to have a good skin touch and lubricity, but also must meet the dual functional requirements of efficient heat conduction and antibacterial and bacteriostatic properties. On the one hand, beauty instruments such as radio frequency, microcurrent, and thermal conductivity instruments generate heat during operation, and the frost cream needs to have good heat conduction ability to achieve efficient energy transfer and ensure uniform distribution of heat on the skin surface, thereby improving the efficiency of the instrument and the user experience; on the other hand, since the frost cream directly acts on the facial skin, it is prone to bacterial growth or contamination during use, so the antibacterial property of the material is crucial for ensuring product safety and extending the service life. In this context, developing a special frost cream for beauty instruments that simultaneously has excellent heat conduction performance and good antibacterial performance can not only significantly improve the overall efficacy of the instrument, but also expand its application scope in high-standard application scenarios such as medical beauty and home care, which is of great significance for promoting the development and upgrading of functional skin care materials.
[0003] Although the application of functional gels in beauty instruments has gradually expanded in recent years, most current frost cream products still face the problems of insufficient heat conduction performance and antibacterial performance, and it is difficult to meet the dual requirements of high-frequency heat conduction and long-term safe use. On the one hand, conventional frost cream formulations mostly use hydrogel matrices and oil-in-water emulsification systems, which have good touch and fluidity, but are limited in heat conduction efficiency and difficult to achieve rapid heat conduction required for efficient energy output of beauty instruments; on the other hand, preservatives or low-efficiency antibacterial components introduced to improve product stability often cannot provide continuous and mild antibacterial effects in the actual use environment, especially prone to microbial growth risks after multiple contacts with the skin or exposure to air. At present, some studies have tried to introduce functional particles into the frost cream to improve the performance. For example, Chinese Patent No. CN101002725A discloses a beauty gel intended to enhance skin nutrition and reduce water loss on the skin surface, but there are still problems of insufficiently ideal heat conduction performance and limited antibacterial effect maintenance time. The fundamental reason is that the functional components are unevenly dispersed in the system, the release is uncontrollable, or the lack of synergistic structure design. Therefore, there is an urgent need to develop a new type of frost cream material with a reasonable structure, synergistic composite functions, and significant performance improvement in heat conduction and antibacterial aspects to meet the higher requirements of high-end beauty instruments for functional introduction media. Summary of the Invention
[0004] (1) Technical problems to be solved The objective of the present invention is to provide a cream for beauty instruments and a preparation method thereof, so as to solve the problems of insufficient thermal conductivity and antibacterial performance of the current cream.
[0005] (2) Technical solutions In order to achieve the above objective, the present invention provides the following technical solutions: A cream for beauty instruments, comprising the following raw materials in parts by weight: 4.0 - 8.0 parts of aluminum nitride-coated chitosan composite nanospheres, 3.5 - 8.0 parts of Ag nanowire / hydroxyapatite microspheres, 40.0 - 60.0 parts of sodium hyaluronate hydrogel, 4.0 - 8.0 parts of cetyl palmitate, 2.0 - 5.0 parts of polyglyceryl-10 stearate, 20.0 - 40.0 parts of a mixed solvent of glycerol and deionized water, 0.5 - 2.0 parts of carbomer 940, and 0.2 - 0.5 parts of triethanolamine; The aluminum nitride-coated chitosan composite nanospheres are composed of porous aluminum nitride hollow microspheres and chitosan coated in its inner cavity; wherein, through-hole structures are evenly distributed on the outer surface of the porous aluminum nitride hollow microspheres, and the hole structures are used to realize the slow release of chitosan; In the mixed solvent of glycerol and deionized water, the volume ratio of glycerol to water is 1:1 - 3:1; The Ag nanowire / hydroxyapatite microspheres are composed of hydroxyapatite microspheres and Ag nanowires loaded on their surfaces; wherein, the Ag nanowires are evenly distributed and stably loaded on the surfaces of the hydroxyapatite microspheres.
[0006] Furthermore, the preparation method of the aluminum nitride-coated chitosan composite nanospheres is as follows: by weight, 0.5 - 0.6 parts of chitosan with a deacetylation degree ≥ 85% and a molecular weight of 50 - 100 kDa, 11.5 - 12.5 parts of glacial acetic acid, and 87.0 - 89.0 parts of deionized water are mixed and stirred at a magnetic stirring rate of 500 - 700 rpm for 4.0 - 6.0 h at 25 - 30 °C, and then filtered through a 0.45 μm filter membrane to obtain a chitosan solution; 95 - 105 parts of pre-dried porous aluminum nitride hollow microspheres are mixed with 48 - 52 parts of the chitosan solution, and ultrasonic treatment is carried out at 40 - 45 °C, with an ultrasonic frequency of 38 - 42 kHz, a power of 190 - 210 W, and a time of 10 - 20 min. Subsequently, filtration is carried out under a vacuum of 0.04 - 0.06 MPa for 18 - 22 min, and stirring is continued at 20 - 25 °C for 1.5 - 2.5 h to form a composite microsphere suspension; 0.48 - 0.52 parts of a 25 wt% aqueous glutaraldehyde solution is added dropwise to the suspension, the pH is adjusted to 5.5 - 6.0 with a 0.01 - 0.03 wt.% hydrochloric acid aqueous solution and stirred at 200 - 300 rpm for 14 - 16 min, washed with deionized water and then centrifuged, with a centrifugation rate of 4800 - 5200 rpm and a time of 4.5 - 5.5 min. The precipitate is collected and pre-frozen at -80 - 70 °C for 11 - 13 h, and then transferred to a vacuum freeze dryer and dried at a pressure ≤ 10 Pa for 24 - 50 h to obtain white to light yellow powdery aluminum nitride-coated chitosan composite nanospheres.
[0007] Furthermore, the method for preparing the porous aluminum nitride hollow microspheres is as follows: by weight, 0.9 - 1.1 parts of polystyrene template microspheres with a particle size of 300 - 500 nm are dispersed in 48 - 52 parts of a mixed solvent with a volume ratio of ethanol to deionized water of 6.5:3.5 - 7.5:2.5. After adding 0.09 - 0.11 parts of polyvinylpyrrolidone, it is dispersed and treated for 8 - 12 min under the conditions of an ultrasonic frequency of 40 - 45 kHz and a power of 80 - 100 W to form a stable suspension; 2.8 - 3.2 parts of aluminum isopropoxide are dissolved in 18 - 22 parts of absolute ethanol, and controlled hydrolysis is carried out by dropping 1.8 - 2.2 parts of deionized water. At the same time, a 0.01 - 0.03 wt.% nitric acid solution is added to adjust the pH to 4.3 - 5.7 to form an aluminum sol precursor; the aluminum sol is added dropwise to the template dispersion system at a rate of 0.5 - 1.5 mL / min, and the stirring speed is maintained at 400 - 600 rpm for a sol-gel coating reaction for 110 - 130 min, and then left to stand and age for 11 - 13 h; the supernatant is removed by centrifugation at a speed of 3500 - 4500 rpm, and the precipitate is collected. It is dried for 11 - 13 h under the conditions of a vacuum degree of -0.08 - 0.10 MPa and a temperature of 58 - 62 °C to obtain porous aluminum nitride hollow precursor microspheres; the precursor is placed in a tube furnace, heated to 900 - 1100 °C at a heating rate of 4 - 6 °C / min, and then ammonia gas with a flow rate of 280 - 320 mL / min is introduced for nitridation treatment. The holding time is 115 - 125 min to completely convert alumina into an aluminum nitride shell layer, and at the same time, the polystyrene template pyrolyzes at 420 - 480 °C to form a hollow structure; the obtained hollow microspheres are dispersed in a 28 - 32% by mass hydrogen peroxide solution, oxidized and etched at a temperature of 40 - 50 °C for 40 - 50 min, and then washed with deionized water until neutral to finally obtain porous aluminum nitride hollow microspheres.
[0008] Furthermore, the average diameter of the aluminum nitride-coated chitosan composite nanospheres is 350 - 550 nm; the average pore diameter of the porous aluminum nitride hollow microspheres is 18 - 30 nm; Furthermore, the mass ratio of the porous aluminum nitride hollow microspheres to chitosan in the aluminum nitride-coated chitosan composite nanospheres is 8:1 - 12:1.
[0009] The preparation of aluminum nitride-coated chitosan composite nanospheres in the present invention is mainly used to enhance the performance of the cream system with heat conduction and antibacterial properties. The core of its design lies in the synergistic improvement of material functions through the composite structure of porous aluminum nitride hollow microspheres and chitosan. In this technical solution, first, porous aluminum nitride microspheres with a hollow structure and through channels are constructed by the polystyrene template method, providing a high specific surface area and a good interfacial carrier for the subsequent coating of functional components; then, chitosan with a relatively high degree of deacetylation and appropriate molecular weight forms a uniform solution in glacial acetic acid solution, and after ultrasonic treatment, suction filtration dispersion and glutaraldehyde cross-linking, effective coating and structure fixation in the inner cavity of porous aluminum nitride are realized. Aluminum nitride, as an inorganic material with good heat conduction characteristics, its hollow porous structure not only provides a channel for heat transfer but also increases the specific surface area of the overall material, contributing to the uniform distribution with other components; while chitosan, with its biocompatibility and antibacterial ability as a natural polymer, introduces a mild and effective antibacterial function into the cream system, and at the same time improves the stability and release behavior of the system by controlling its coating and cross-linking degree. By optimizing the control of the ratio of the two materials, stable composite microspheres are formed in the microstructure, not only improving the basic properties of heat conduction and antibacterial properties, but also achieving comprehensive performance superior to that of single materials through structural complementarity and interfacial action, thus providing reliable support for the high-standard requirements of functional introduction media in beauty instruments.
[0010] Further, the preparation method of the Ag nanowire / hydroxyapatite microspheres is as follows: by weight, 0.9 - 1.1 parts of hydroxyapatite microspheres are dispersed in 18 - 22 parts of anhydrous ethylene glycol. After adding 0.045 - 0.055 parts of polyvinylpyrrolidone, it is treated for 8 - 12 min under the conditions of an ultrasonic frequency of 38 - 42 kHz and a power of 180 - 220 W to form a surface-activated dispersion system. The stirring speed is maintained at 300 - 400 rpm and the temperature is 25 - 30 °C for 25 - 35 min to complete surface modification. 0.16 - 0.18 parts of silver nitrate, 0.28 - 0.32 parts of polyvinylpyrrolidone and 0.09 - 0.11 parts of a ferric chloride solution with a concentration of 0.095 - 0.105 mol / L are successively added to the dispersion system, and then it is transferred to a three-necked flask and heated to a reaction temperature of 120 - 140 °C at a heating rate of 4 - 6 °C / min and an in-situ reduction reaction is carried out for 60 - 90 min under the condition of a stirring rate of 500 - 700 rpm to promote the directional growth of silver ions on the surface of hydroxyapatite to form nanowires. After the reaction, it is naturally cooled to 20 - 25 °C, and the supernatant containing unreacted silver nitrate, free polyvinylpyrrolidone and by-products is removed by centrifugation at a speed of 5800 - 6200 rpm. After collecting the precipitate, it is repeatedly washed 2 - 4 times with an ethanol / water mixed solution with a volume ratio of 0.95:1.05 - 1.05:0.95, and finally dehydrated at a freeze-drying temperature of -50 - -45 °C and a vacuum degree of ≤10 Pa for 10 - 14 h to obtain the Ag nanowire / hydroxyapatite microspheres.
[0011] Furthermore, the preparation method of the hydroxyapatite microspheres is as follows: by weight, 0.8 - 1.2 parts of calcium nitrate tetrahydrate are dissolved in 45 - 55 parts of deionized water to form a calcium source solution, and 0.4 - 0.6 parts of diammonium hydrogen phosphate are dissolved in 45 - 55 parts of deionized water to form a phosphorus source solution. Under the condition that the stirring rate is 400 - 600 rpm, the phosphorus source solution is added dropwise into the calcium source solution at a dropping rate of 1 - 2 mL / min. Meanwhile, ammonia water is added to adjust the pH to 9.5 - 10.5 and the temperature is maintained at 25 - 30 °C to carry out the co-precipitation reaction. After the dropping is completed, stirring is continued for 120 - 180 min to form a hydroxyapatite precursor suspension, which is then transferred to a high-pressure reaction kettle for hydrothermal treatment. The heating rate is 3 - 5 °C / min to the reaction temperature of 120 - 130 °C. During the hydrothermal treatment stage, the pressure in the kettle is maintained at 0.15 - 0.25 MPa, and the holding time is 3.5 - 4.5 h to crystallize the precursor into hydroxyapatite microspheres. After the reaction is completed, the supernatant is separated and removed by centrifugation at a rotational speed of 3000 - 4000 rpm, and the precipitate is collected. It is washed alternately with deionized water and absolute ethanol for 3 - 5 times and then placed in a vacuum drying oven. It is treated for 6 - 8 h under the conditions of a drying temperature of 50 - 70 °C and a vacuum degree of -0.08 - 0.10 MPa to obtain the hydroxyapatite microspheres.
[0012] Furthermore, the mass ratio of Ag nanowires to hydroxyapatite microspheres in the Ag nanowire / hydroxyapatite microspheres is 1:10 - 1:5; Furthermore, the average diameter of the Ag nanowire / hydroxyapatite microspheres is 350 - 600 nm.
[0013] The preparation of Ag nanowire / hydroxyapatite microspheres in the present invention is mainly used to enhance the performance of the cream system for heat conduction and antibacterial properties. Its design is based on the antibacterial activity of noble metal nanostructures and the structural stability of inorganic bioceramic materials, and realizes the synergistic enhancement of multiple functions by constructing a composite microsphere. In this scheme, first, calcium nitrate tetrahydrate and diammonium hydrogen phosphate undergo a coprecipitation reaction under alkaline conditions to form a hydroxyapatite precursor, and hydrothermally treated under controlled temperature and pressure conditions to obtain hydroxyapatite microspheres with stable crystal form and uniform particle size. Such microspheres not only have good biocompatibility and dispersibility, but also provide a high specific surface area for the subsequent directional growth of silver nanowires; subsequently, they are dispersed in anhydrous ethylene glycol and modified and activated by polyvinylpyrrolidone to form a reaction environment on its surface that is conducive to the adsorption and reduction of silver ions. By gradually introducing silver nitrate and ferric chloride solutions into the system, silver ions are promoted to in-situ reduce and self-assemble on the surface of hydroxyapatite to form a silver nanowire structure with a high specific surface area under heating conditions. The formation of silver nanowires not only significantly improves the antibacterial properties of the material, but also helps to improve the heat conduction performance of the cream medium through its excellent electronic and heat conduction characteristics; hydroxyapatite microspheres, while providing a stable carrier, ensure the uniform distribution and structural stability of silver nanowires, reducing the risk of aggregation and migration. The close combination of the two components in structure and the complementary effect in performance enable the composite microsphere to exhibit a better performance integration effect than single materials in terms of heat conduction and antibacterial functions, providing new ideas and technical support for the development of high-performance introduction media for beauty instruments.
[0014] The present invention also discloses a preparation method for a cream used in a beauty instrument, comprising the following steps: S1. Place the sodium hyaluronate hydrogel in a clean container, and under the condition that the stirring rate is 300 - 500 rpm, maintain the temperature at 20 - 30 °C for pre-dispersion treatment, and the stirring time is 10 - 20 min to obtain a sodium hyaluronate hydrogel base system with good uniform fluidity; S2. Add a mixed solvent of glycerol and deionized water to the base system described in S1, and at the same time add carbomer 940. Continuously stir for 20 - 30 min under the condition that the stirring rate is 400 - 600 rpm to fully disperse and pre-swell carbomer, and then let it stand for 5 - 10 min to remove bubbles and stabilize the system structure; S3. Mix cetyl palmitate and polyglyceryl-10 stearate, heat and melt for 10 - 15 min at a magnetic stirring rate of 200 - 400 rpm and a temperature of 65 - 75 °C to form a uniform emulsion phase. Subsequently, add this emulsion phase to the system obtained in S2 at a dropping rate of 1 - 2 mL / min, and maintain the stirring rate at 600 - 800 rpm for emulsification treatment for 15 - 25 min to form a primary emulsion system; S4. Add the aluminum nitride-coated chitosan composite nanospheres to the primary emulsion system described in S3, and disperse them at a temperature of 30-40 °C and a stirring rate of 500-700 rpm for 15-25 min; S5. Add the Ag nanowire / hydroxyapatite microspheres to the dispersion system obtained in S4, maintain the stirring rate at 400-600 rpm and the temperature at 25-35 °C, and continuously stir for 20-30 min.
[0015] S6. Dropwise add triethanolamine to the system obtained in S5, stir at a stirring rate of 300-500 rpm for 10-15 min, then perform degassing treatment at a vacuum degree of 0.05-0.08 MPa for 10-20 min, and finally cool to 20-25 °C to form a homogeneous and stable frost finished product.
[0016] By constructing a composite system of Ag nanowire / hydroxyapatite microspheres and aluminum nitride-coated chitosan composite nanospheres, the present invention effectively improves the thermal conductivity and antibacterial properties of the frost material. The Ag nanowires grow directionally on the surface of the hydroxyapatite microspheres, not only providing high antibacterial activity, but also forming a local heat conduction path at the microscale through their linear conductive structure. The hydroxyapatite serves as a stable carrier, enhancing its dispersibility and biocompatibility. The aluminum nitride hollow microspheres have excellent thermal conductivity and porous structure, and can construct continuous heat flow channels, significantly improving the heat conduction efficiency in the frost. The coating of chitosan not only improves the dispersion stability of the composite microspheres in the aqueous system, but also realizes mild antibacterial by forming a charge interaction with the bacterial cell membrane through its cationic properties. The two types of functional components form a synergistic mechanism in terms of structural configuration, interfacial interaction and functional properties. The strong bactericidal effect of Ag nanowires and the slow-release antibacterial effect of chitosan complement each other, and the rapid heat conduction of aluminum nitride and the microscale heat flow regulation of the silver structure promote each other, achieving double optimization of thermal conductivity and antibacterial properties on the basis of ensuring material stability and biological safety.
[0017] (3) Beneficial technical effects 1. The present invention significantly improves the thermal conductivity and antibacterial properties of the frost through the structural synergy of aluminum nitride and chitosan, overcomes the problems of poor heat conduction and weak antibacterial ability of existing materials, and has good application prospects.
[0018] 2. The present invention significantly improves the thermal conductivity and antibacterial properties of the frost through the structural complementarity of silver nanowires and hydroxyapatite microspheres, solves the problems of poor antibacterial persistence and low heat conduction efficiency of existing materials, is applicable to the high-end beauty introduction field, and shows excellent synergistic advantages and application prospects. Description of the drawings
[0019] Figure 1 It is a morphology diagram of the porous aluminum nitride hollow microspheres prepared in Example 1 of the present invention.
[0020] Figure 2 This is the morphology diagram of the aluminum nitride-coated chitosan composite nanospheres prepared in Example 1 of the present invention.
[0021] Figure 3 This is the XRD phase analysis diagram of the aluminum nitride-coated chitosan composite nanospheres prepared in Example 1 of the present invention.
[0022] Figure 4 This is the morphology diagram of the hydroxyapatite microspheres prepared in Example 1 of the present invention.
[0023] Figure 5 This is the XRD phase analysis diagram of the hydroxyapatite microspheres prepared in Example 1 of the present invention.
[0024] Figure 6 This is the morphology diagram of the Ag nanowire / hydroxyapatite microspheres prepared in Example 1 of the present invention.
[0025] Figure 7 This is the XRD phase analysis diagram of the Ag nanowire / hydroxyapatite microspheres prepared in Example 1 of the present invention. Detailed implementation manners
[0026] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
[0027] Example 1
[0028] A cream for beauty instruments comprises the following raw materials in parts by weight: 4.0 parts of aluminum nitride-coated chitosan composite nanospheres, 3.5 parts of Ag nanowire / hydroxyapatite microspheres, 40.0 parts of sodium hyaluronate hydrogel, 4.0 parts of cetyl palmitate, 2.0 parts of polyglyceryl-10 stearate, 20.0 parts of a mixed solvent of glycerol and deionized water, 0.5 part of carbomer 940, and 0.2 part of triethanolamine; The aluminum nitride-coated chitosan composite nanospheres are composed of porous aluminum nitride hollow microspheres and chitosan coated in their inner cavities; wherein, through-hole structures are uniformly distributed on the outer surface of the porous aluminum nitride hollow microspheres, and the hole structures are used to realize the slow release of chitosan; In the mixed solvent of glycerol and deionized water, the volume ratio of glycerol to water is 1:1; The Ag nanowire / hydroxyapatite microspheres are composed of hydroxyapatite microspheres and Ag nanowires loaded on their surfaces; wherein, the Ag nanowires are uniformly distributed and stably loaded on the surfaces of the hydroxyapatite microspheres.
[0029] The preparation method of the aluminum nitride-coated chitosan composite nanospheres in this example is as follows: by weight, 0.5 part of chitosan with a deacetylation degree ≥85% and a molecular weight of 50 kDa, 11.5 parts of glacial acetic acid and 87.0 parts of deionized water are mixed, and stirred at a magnetic stirring rate of 500 rpm at 25 °C for 4.0 h, and then filtered through a 0.45 μm filter membrane to obtain a chitosan solution; 95 parts of pre-dried porous aluminum nitride hollow microspheres are mixed with 48 parts of the chitosan solution, and ultrasonic treatment is carried out at 40 °C, with an ultrasonic frequency of 38 kHz, a power of 190 W, and a time of 10 min. Subsequently, filtration is carried out under a vacuum of 0.04 MPa for 18 min, and then stirring is continued at 20 °C for 1.5 h to form a composite microsphere suspension; 0.48 part of 25 wt% glutaraldehyde aqueous solution is added dropwise to the suspension, the pH is adjusted to 5.5 with 0.01 wt.% hydrochloric acid aqueous solution and stirred at 200 rpm for 14 min, washed with deionized water and then centrifuged, with a centrifugation rate of 4800 rpm and a time of 4.5 min. The precipitate is collected and pre-frozen at -80 °C for 11 h, and then transferred to a vacuum freeze dryer and dried at a pressure ≤10 Pa for 24 h to obtain white to light yellow powdery aluminum nitride-coated chitosan composite nanospheres.
[0030] The preparation method of the porous aluminum nitride hollow microspheres in this example is as follows: by weight, 0.9 part of polystyrene template microspheres with a particle size of 300 nm are dispersed in 48 parts of a mixed solvent of ethanol and deionized water with a volume ratio of 6.5:3.5. After adding 0.09 part of polyvinylpyrrolidone, dispersion treatment is carried out at an ultrasonic frequency of 40 kHz and a power of 80 W for 8 min to form a stable suspension; 2.8 parts of aluminum isopropoxide is dissolved in 18 parts of absolute ethanol and controlled hydrolysis is carried out by dropping 1.8 parts of deionized water. At the same time, 0.01 wt.% nitric acid solution is added to adjust the pH to 4.3 to form an aluminum sol precursor; the aluminum sol is added dropwise to the template dispersion system at a rate of 0.5 mL / min, and the stirring speed is maintained at 400 rpm for a sol-gel coating reaction for 110 min, and then left to age for 11 h; the supernatant is removed by centrifugation at a speed of 3500 rpm and the precipitate is collected, and dried at a vacuum of -0.08 MPa and a temperature of 58 °C for 11 h to obtain porous aluminum nitride hollow precursor microspheres; the precursor is placed in a tubular furnace, heated to 900 °C at a heating rate of 4 °C / min, and then ammonia gas with a flow rate of 280 mL / min is introduced for nitridation treatment. The holding time is 115 min to completely convert alumina into an aluminum nitride shell layer, and at the same time, the polystyrene template pyrolyzes at 420 °C to form a hollow structure; the obtained hollow microspheres are dispersed in a 28% mass fraction hydrogen peroxide aqueous solution, and after oxidation etching treatment at 40 °C for 40 min, they are washed with deionized water until neutral, and finally porous aluminum nitride hollow microspheres are obtained.
[0031] The average diameter of the aluminum nitride-coated chitosan composite nanospheres in this embodiment is 350 nm; The average pore diameter of the porous aluminum nitride hollow microspheres is 18 nm; In the aluminum nitride-coated chitosan composite nanospheres of this embodiment, the mass ratio of the porous aluminum nitride hollow microspheres to chitosan is 8:1.
[0032] The preparation method of the Ag nanowire / hydroxyapatite microspheres in this embodiment is as follows: By weight, 1.0 part of hydroxyapatite microspheres is dispersed in 19 parts of anhydrous ethylene glycol. After adding 0.048 part of polyvinylpyrrolidone, it is treated for 9 min under the conditions of an ultrasonic frequency of 39 kHz and a power of 192 W to form a surface-activated dispersion system. The stirring speed is maintained at 330 rpm and the temperature is 27°C for 28 min to complete surface modification; 0.17 part of silver nitrate, 0.29 part of polyvinylpyrrolidone, and 0.10 part of a ferric chloride solution with a concentration of 0.098 mol / L are successively added to the dispersion system. It is transferred to a three-necked flask and heated to the reaction temperature of 126°C at a heating rate of 5°C / min and an in-situ reduction reaction is carried out for 69 min under the stirring rate of 560 rpm to promote the directional growth of silver ions on the surface of hydroxyapatite to form nanowires; after the reaction is completed, it is naturally cooled to 21°C, and the supernatant containing unreacted silver nitrate, free polyvinylpyrrolidone, and by-products is separated and removed by centrifugation at a speed of 5920 rpm. After collecting the precipitate, it is repeatedly washed 3 times with an ethanol / water mixed solution with a volume ratio of 0.98:1.02, and finally dehydrated at a freeze-drying temperature of -49°C and a vacuum degree of ≤10 Pa for 11 h to obtain Ag nanowire / hydroxyapatite microspheres.
[0033] The preparation method of the hydroxyapatite microspheres in this example is as follows: by weight, 0.9 parts of calcium nitrate tetrahydrate are dissolved in 48 parts of deionized water to form a calcium source solution, and another 0.5 parts of diammonium hydrogen phosphate are dissolved in 48 parts of deionized water to form a phosphorus source solution. Under the condition that the stirring rate is 460 rpm, the phosphorus source solution is added dropwise into the calcium source solution at a dropping rate of 1.3 mL / min. At the same time, ammonia water is added to adjust the pH to 9.8 and the temperature is maintained at 27°C to carry out a coprecipitation reaction. After the dropping is completed, stirring is continued for 138 min to form a hydroxyapatite precursor suspension. Subsequently, it is transferred to a high-pressure reactor for hydrothermal treatment. The heating rate is 3.6°C / min to the reaction temperature of 123°C. During the hydrothermal treatment stage, the pressure in the reactor is maintained at 0.18 MPa, and the holding time is 3.8 h to crystallize the precursor into hydroxyapatite microspheres. After the reaction is completed, the supernatant is separated and removed by centrifugation at a rotational speed of 3300 rpm, and the precipitate is collected. It is washed 4 times alternately with deionized water and absolute ethanol and then placed in a vacuum drying oven. It is treated for 7 h under the conditions of a drying temperature of 56°C and a vacuum degree of -0.086 MPa to obtain hydroxyapatite microspheres.
[0034] In the Ag nanowire / hydroxyapatite microspheres of this example, the mass ratio of Ag nanowires to hydroxyapatite microspheres is 1:8.5; The average diameter of the Ag nanowire / hydroxyapatite microspheres of this example is 425 nm; The preparation method of a cream for a beauty instrument in this example includes the following steps: S1. Place the sodium hyaluronate hydrogel in a clean container, and under the condition that the stirring rate is 360 rpm, maintain the temperature at 23°C for pre-dispersion treatment. The stirring time is 13 min to obtain a sodium hyaluronate hydrogel base system with good uniform fluidity; S2. Add a mixed solvent of glycerol and deionized water to the base system in S1, and at the same time add carbomer 940. Under the condition that the stirring rate is 460 rpm, continue stirring for 23 min to fully disperse and pre-swell carbomer. Then let it stand for 7 min to remove bubbles and stabilize the system structure; S3. Mix cetyl palmitate and polyglyceryl-10 stearate, and heat and melt them at a magnetic stirring rate of 260 rpm and a temperature of 68°C for 12 min to form a uniform emulsion phase. Subsequently, add this emulsion phase to the system obtained in S2 at a dropping rate of 1.3 mL / min, and maintain the stirring rate at 660 rpm for emulsification treatment for 18 min to form a primary emulsion system; S4. Add the aluminum nitride-coated chitosan composite nanospheres to the primary emulsion system in S3, and disperse them at a temperature of 33°C and a stirring rate of 560 rpm for 18 min; S5. Add the Ag nanowire / hydroxyapatite microspheres into the dispersion system obtained in S4, maintain the stirring rate at 460 rpm and the temperature at 28 °C, and continuously stir for 23 min.
[0035] S6. Dropwise add triethanolamine into the system obtained in S5, stir for 12 min under the condition of a stirring rate of 360 rpm, then perform degassing treatment for 13 min under the condition of a vacuum degree of 0.059 MPa, and finally cool to 21 °C to form a homogeneous and stable frost finished product.
[0036] As can be seen from Figure 1 and Figure 2 the porous aluminum nitride hollow microspheres prepared in Example 1 are in a regular spherical structure as a whole, with through pores uniformly distributed on the surface. After being coated with chitosan, the formed composite nanospheres maintain a good spherical morphology, and the surface structure is denser, indicating that chitosan has achieved effective loading and structural stability in the inner cavity of the aluminum nitride hollow microspheres; Figure 3 The XRD pattern of Figure 4 further verifies the existence of the aluminum nitride crystal structure in the composite microspheres, and no impurity peaks appear, indicating that the chitosan coating process has not changed the crystal phase composition of aluminum nitride; Figure 6 and Figure 5 respectively show the composite morphology of the hydroxyapatite microspheres and the Ag nanowires loaded on them. The former has uniform particle size and a smooth surface, and a uniformly distributed silver nanowire structure can be observed on the surface of the latter, indicating that silver has achieved directional growth on the surface of hydroxyapatite; combined with Figure 7 the XRD analysis of
[0037] Example 2 A frost for beauty instruments, comprising the following raw materials in parts by weight: 5.0 parts of aluminum nitride-coated chitosan composite nanospheres, 4.9 parts of Ag nanowire / hydroxyapatite microspheres, 46.0 parts of sodium hyaluronate hydrogel, 5.0 parts of cetyl palmitate, 3.0 parts of polyglyceryl-10 stearate, 26.0 parts of a mixed solvent of glycerol and deionized water, 1.0 part of carbomer 940, and 0.3 part of triethanolamine; The aluminum nitride-coated chitosan composite nanospheres are composed of porous aluminum nitride hollow microspheres and chitosan coated in its inner cavity; among them, through hole structures are uniformly distributed on the outer surface of the porous aluminum nitride hollow microspheres, and these hole structures are used to achieve the slow release of chitosan; In a mixed solvent of glycerol and deionized water, the volume ratio of glycerol to water is 1.6:1; The Ag nanowire / hydroxyapatite microspheres are composed of hydroxyapatite microspheres and Ag nanowires loaded on their surfaces; among them, the Ag nanowires are uniformly distributed and stably loaded on the surfaces of the hydroxyapatite microspheres.
[0038] The preparation method of the aluminum nitride-coated chitosan composite nanospheres in this example is as follows: by weight, 0.5 part of chitosan with a deacetylation degree ≥85% and a molecular weight of 65 kDa, 11.8 parts of glacial acetic acid and 87.7 parts of deionized water are mixed, and stirred at a magnetic stirring rate of 560 rpm at 26 °C for 4.6 h, and then filtered through a 0.45 μm filter membrane to obtain a chitosan solution; 98 parts of pre-dried porous aluminum nitride hollow microspheres are mixed with 49 parts of the chitosan solution, and ultrasonic treatment is carried out at 41 °C, the ultrasonic frequency is 39 kHz, the power is 196 W, and the time is 13 min, and then suction filtration is carried out for 19 min under a vacuum degree of 0.046 MPa, and then static stirring is carried out at 21 °C for 1.8 h to form a composite microsphere suspension; 0.49 part of 25 wt% glutaraldehyde aqueous solution is added dropwise to the suspension, the pH is adjusted to 5.7 with 0.016 wt.% hydrochloric acid aqueous solution and stirred at 230 rpm for 15 min, washed with deionized water and then centrifuged, the centrifugation rate is 4920 rpm and the time is 4.8 min, the precipitate is collected and pre-frozen at -77 °C for 12 h, and then transferred to a vacuum freeze dryer and dried at a pressure ≤10 Pa for 32 h to obtain white to light yellow powdery aluminum nitride-coated chitosan composite nanospheres.
[0039] The preparation method of the porous aluminum nitride hollow microspheres in this embodiment is as follows: by weight, 1.0 part of polystyrene template microspheres with a particle size of 360 nm is dispersed in 49 parts of a mixed solvent with a volume ratio of ethanol to deionized water of 6.8:3.2. After adding 0.10 part of polyvinylpyrrolidone, it is dispersed and treated for 9 min under the conditions of an ultrasonic frequency of 42 kHz and a power of 86 W to form a stable suspension; 2.9 parts of aluminum isopropoxide is dissolved in 19 parts of absolute ethanol and undergoes controllable hydrolysis by dropping 1.9 parts of deionized water. At the same time, a 0.016 wt.% nitric acid solution is added to adjust the pH to 4.7 to form an aluminum sol precursor; the aluminum sol is added dropwise to the template dispersion system at a rate of 0.8 mL / min, and the stirring speed is maintained at 460 rpm for a sol-gel coating reaction for 116 min, and then left to stand and age for 12 h; the supernatant is discarded by centrifugation at a speed of 3800 rpm, and the precipitate is collected. It is dried for 12 h under the conditions of a vacuum degree of -0.086 MPa and a temperature of 60°C to obtain porous aluminum nitride hollow precursor microspheres; the precursor is placed in a tube furnace, heated to 960°C at a heating rate of 5°C / min, and then ammonia gas with a flow rate of 292 mL / min is introduced for nitridation treatment. The holding time is 118 min to completely convert alumina into an aluminum nitride shell layer. At the same time, the polystyrene template pyrolyzes at 438°C to form a hollow structure; the obtained hollow microspheres are dispersed in a 29% hydrogen peroxide aqueous solution by mass, and after oxidation etching treatment at a temperature of 43°C for 43 min, they are washed with deionized water until neutral, and finally porous aluminum nitride hollow microspheres are obtained.
[0040] The average diameter of the aluminum nitride-coated chitosan composite nanospheres in this embodiment is 410 nm; The average pore diameter of the porous aluminum nitride hollow microspheres is 22 nm; In the aluminum nitride-coated chitosan composite nanospheres of this embodiment, the mass ratio of the porous aluminum nitride hollow microspheres to chitosan is 9:1.
[0041] The preparation method of the Ag nanowire / hydroxyapatite microspheres in this embodiment is as follows: by weight, disperse 0.9 parts of hydroxyapatite microspheres in 18 parts of anhydrous ethylene glycol, add 0.045 parts of polyvinylpyrrolidone, and then treat it for 8 min under the conditions of an ultrasonic frequency of 38 kHz and a power of 180 W to form a surface-activated dispersion system. Maintain the stirring speed at 300 rpm and continue for 25 min at a temperature of 25°C to complete surface modification; successively add 0.16 parts of silver nitrate, 0.28 parts of polyvinylpyrrolidone, and 0.09 parts of a ferric chloride solution with a concentration of 0.095 mol / L to the dispersion system, transfer it to a three-necked flask, heat it to a reaction temperature of 120°C at a heating rate of 4°C / min, and carry out an in-situ reduction reaction for 60 min under a stirring rate of 500 rpm to promote the directional growth of silver ions on the surface of hydroxyapatite to form nanowires; after the reaction is completed, naturally cool it to 20°C, separate and remove the upper clear liquid containing unreacted silver nitrate, free polyvinylpyrrolidone, and by-products at a centrifugal speed of 5800 rpm. After collecting the precipitate, wash it twice repeatedly with an ethanol / water mixed solution with a volume ratio of 0.95:1.05, and finally carry out dehydration treatment for 10 h at a freeze-drying temperature of -50°C and a vacuum degree of ≤10 Pa to obtain Ag nanowire / hydroxyapatite microspheres.
[0042] The preparation method of the hydroxyapatite microspheres in this embodiment is as follows: by weight, dissolve 0.8 parts of calcium nitrate tetrahydrate in 45 parts of deionized water to form a calcium source solution, and dissolve 0.4 parts of diammonium hydrogen phosphate in 45 parts of deionized water to form a phosphorus source solution. Under the condition of a stirring rate of 400 rpm, add the phosphorus source solution dropwise to the calcium source solution at a dropping rate of 1 mL / min, synchronously add ammonia water to adjust the pH to 9.5, and maintain the temperature at 25°C to carry out a coprecipitation reaction. After the dropping is completed, continue to stir for 120 min to form a hydroxyapatite precursor suspension, and then transfer it to a high-pressure reaction kettle for hydrothermal treatment. The heating rate is 3°C / min to a reaction temperature of 120°C. During the hydrothermal treatment stage, keep the pressure in the kettle at 0.15 MPa, and the heat preservation time is 3.5 h to crystallize the precursor into hydroxyapatite microspheres. After the reaction is completed, separate and remove the upper clear liquid at a centrifugal speed of 3000 rpm and collect the precipitate. Wash it 3 times alternately with deionized water and anhydrous ethanol, and then place it in a vacuum drying oven. Treat it for 6 h at a drying temperature of 50°C and a vacuum degree of -0.08 MPa to obtain hydroxyapatite microspheres.
[0043] In the Ag nanowire / hydroxyapatite microspheres of this embodiment, the mass ratio of Ag nanowires to hydroxyapatite microspheres is 1:10; The average diameter of the Ag nanowire / hydroxyapatite microspheres of this embodiment is 350 nm; The preparation method of a cream for a beauty instrument in this embodiment includes the following steps: S1. Place the sodium hyaluronate hydrogel in a clean container, and under the condition of a stirring rate of 300 rpm, maintain the temperature at 20 °C for pre-dispersion treatment for 10 min to obtain a sodium hyaluronate hydrogel base system with good uniform fluidity; S2. Add a mixed solvent of glycerol and deionized water to the base system described in S1, and at the same time add Carbopol 940. Continuously stir at a stirring rate of 400 rpm for 20 min to fully disperse and pre-swell Carbopol 940, and then let it stand for 5 min to remove bubbles and stabilize the system structure; S3. Mix cetyl palmitate and polyglyceryl-10 stearate, and heat and melt at a magnetic stirring rate of 200 rpm and a temperature of 65 °C for 10 min to form a uniform emulsion phase. Then add this emulsion phase to the system obtained in S2 at a dropping rate of 1 mL / min, and maintain the stirring rate at 600 rpm for emulsification treatment for 15 min to form a primary emulsion system; S4. Add the aluminum nitride-coated chitosan composite nanospheres to the primary emulsion system described in S3, and disperse at a temperature of 30 °C and a stirring rate of 500 rpm for 15 min; S5. Add the Ag nanowire / hydroxyapatite microspheres to the dispersion system obtained in S4, maintain the stirring rate at 400 rpm and the temperature at 25 °C, and continuously stir for 20 min.
[0044] S6. Dropwise add triethanolamine to the system obtained in S5, stir at a stirring rate of 300 rpm for 10 min, and then perform degassing treatment at a vacuum degree of 0.05 MPa for 10 min, and finally cool to 20 °C to form a homogeneous and stable cream finished product.
[0045] Example 3 A cream for beauty instruments, comprising the following raw materials in parts by weight: 8.0 parts of aluminum nitride-coated chitosan composite nanospheres, 8.0 parts of Ag nanowire / hydroxyapatite microspheres, 60.0 parts of sodium hyaluronate hydrogel, 8.0 parts of cetyl palmitate, 5.0 parts of polyglyceryl-10 stearate, 40.0 parts of a mixed solvent of glycerol and deionized water, 2.0 parts of Carbopol 940, and 0.5 part of triethanolamine; The aluminum nitride-coated chitosan composite nanospheres are composed of porous aluminum nitride hollow microspheres and chitosan coated in its inner cavity; among them, through-hole structures are uniformly distributed on the outer surface of the shell of the porous aluminum nitride hollow microspheres, and this pore structure is used to realize the slow release of chitosan; In the mixed solvent of glycerol and deionized water, the volume ratio of glycerol to water is 3:1; The Ag nanowire / hydroxyapatite microspheres are composed of hydroxyapatite microspheres and Ag nanowires loaded on their surfaces; among them, the Ag nanowires are uniformly distributed and stably loaded on the surfaces of the hydroxyapatite microspheres.
[0046] The preparation method of the aluminum nitride-coated chitosan composite nanospheres in this example is as follows: by weight, 0.6 parts of chitosan with a deacetylation degree ≥85% and a molecular weight of 100 kDa, 12.5 parts of glacial acetic acid, and 89.0 parts of deionized water are mixed, and stirred at a magnetic stirring rate of 700 rpm for 6.0 h at 30 °C, and filtered through a 0.45 μm filter membrane to obtain a chitosan solution; 105 parts of pre-dried porous aluminum nitride hollow microspheres are mixed with 52 parts of the chitosan solution, and ultrasonic treatment is carried out at 45 °C, the ultrasonic frequency is 42 kHz, the power is 210 W, and the time is 20 min, and then filtered under a vacuum of 0.06 MPa for 22 min, and then stirred at 25 °C for 2.5 h to form a composite microsphere suspension; 0.52 parts of 25 wt% glutaraldehyde aqueous solution is added dropwise to the suspension, the pH is adjusted to 6.0 with 0.03 wt.% hydrochloric acid aqueous solution and stirred at 300 rpm for 16 min, washed with deionized water and then centrifuged, the centrifugation rate is 5200 rpm and the time is 5.5 min, the precipitate is collected and pre-frozen at -70 °C for 13 h, and transferred to a vacuum freeze dryer to dry under a pressure ≤10 Pa for 50 h to obtain white to light yellow powdery aluminum nitride-coated chitosan composite nanospheres.
[0047] The preparation method of the porous aluminum nitride hollow microspheres in this embodiment is as follows: by weight, 1.1 parts of polystyrene template microspheres with a particle size of 500 nm are dispersed in 52 parts of a mixed solvent with a volume ratio of ethanol to deionized water of 7.5:2.5. After adding 0.11 part of polyvinylpyrrolidone, it is dispersed and treated for 12 min under the conditions of an ultrasonic frequency of 45 kHz and a power of 100 W to form a stable suspension; 3.2 parts of aluminum isopropoxide are dissolved in 22 parts of absolute ethanol and controllable hydrolysis is carried out by dropping 2.2 parts of deionized water. At the same time, a 0.03 wt.% nitric acid solution is added to adjust the pH to 5.7 to form an aluminum sol precursor; the aluminum sol is added dropwise to the template dispersion system at a rate of 1.5 mL / min, and the stirring speed is maintained at 600 rpm for a sol-gel coating reaction for 130 min, and then left to stand and age for 13 h; the supernatant is discarded by centrifugation at a speed of 4500 rpm and the precipitate is collected, and dried for 13 h under the conditions of a vacuum of -0.10 MPa and a temperature of 62°C to obtain porous aluminum nitride hollow precursor microspheres; the precursor is placed in a tube furnace, heated to 1100°C at a heating rate of 6°C / min, and then ammonia gas with a flow rate of 320 mL / min is introduced for nitridation treatment. The holding time is 125 min to completely convert alumina into an aluminum nitride shell layer. At the same time, the polystyrene template pyrolyzes at 480°C to form a hollow structure; the obtained hollow microspheres are dispersed in a 32% hydrogen peroxide aqueous solution by mass, and after oxidation etching treatment at a temperature of 50°C for 50 min, they are washed with deionized water until neutral, and finally porous aluminum nitride hollow microspheres are obtained.
[0048] The average diameter of the aluminum nitride-coated chitosan composite nanospheres in this embodiment is 550 nm; The average pore diameter of the porous aluminum nitride hollow microspheres is 30 nm; In the aluminum nitride-coated chitosan composite nanospheres of this embodiment, the mass ratio of the porous aluminum nitride hollow microspheres to chitosan is 12:1.
[0049] The preparation method of the Ag nanowire / hydroxyapatite microspheres in this example is as follows: By weight, 1.0 part of hydroxyapatite microspheres is dispersed in 20 parts of anhydrous ethylene glycol. After adding 0.051 part of polyvinylpyrrolidone, it is treated for 10 min under the conditions of an ultrasonic frequency of 40 kHz and a power of 204 W to form a surface-activated dispersion system. The stirring speed is maintained at 360 rpm and the temperature is 28°C for 31 min to complete surface modification. Then, 0.17 part of silver nitrate, 0.30 part of polyvinylpyrrolidone, and 0.10 part of a ferric chloride solution with a concentration of 0.101 mol / L are successively added to the dispersion system. It is transferred to a three-necked flask and heated to a reaction temperature of 132°C at a heating rate of 5°C / min, and an in-situ reduction reaction is carried out for 78 min under a stirring rate of 620 rpm to promote the directional growth of silver nanowires on the surface of hydroxyapatite. After the reaction ends, it is naturally cooled to 23°C. The upper clear liquid containing unreacted silver nitrate, free polyvinylpyrrolidone, and by-products is removed by centrifugation at a speed of 6040 rpm. After collecting the precipitate, it is repeatedly washed 3 times with an ethanol / water mixed solution with a volume ratio of 1.01:0.99. Finally, dehydration treatment is carried out at a freeze-drying temperature of -48°C and a vacuum degree of ≤10 Pa for 12 h to obtain Ag nanowire / hydroxyapatite microspheres.
[0050] The preparation method of the hydroxyapatite microspheres in this example is as follows: By weight, 1.0 part of calcium nitrate tetrahydrate is dissolved in 50 parts of deionized water to form a calcium source solution, and 0.5 part of diammonium hydrogen phosphate is dissolved in 50 parts of deionized water to form a phosphorus source solution. Under the condition of a stirring rate of 520 rpm, the phosphorus source solution is added dropwise to the calcium source solution at a dropping rate of 1.6 mL / min. At the same time, ammonia water is added to adjust the pH to 10.1 and the temperature is maintained at 28°C to carry out a coprecipitation reaction. After the dropping is completed, stirring is continued for 156 min to form a hydroxyapatite precursor suspension. Subsequently, it is transferred to an autoclave for hydrothermal treatment. The heating rate is 4.2°C / min to a reaction temperature of 126°C. During the hydrothermal treatment stage, the pressure in the autoclave is maintained at 0.21 MPa, and the holding time is 4.1 h to crystallize the precursor into hydroxyapatite microspheres. After the reaction ends, the upper clear liquid is removed by centrifugation at a speed of 3600 rpm and the precipitate is collected. It is alternately washed 4 times with deionized water and anhydrous ethanol and then placed in a vacuum drying oven. It is treated at a drying temperature of 62°C and a vacuum degree of -0.092 MPa for 7 h to obtain hydroxyapatite microspheres.
[0051] In the Ag nanowire / hydroxyapatite microspheres of this example, the mass ratio of Ag nanowires to hydroxyapatite microspheres is 1:7; The average diameter of the Ag nanowire / hydroxyapatite microspheres of this example is 500 nm; A preparation method of a cream for beauty instruments in this embodiment includes the following steps: S1. Place the sodium hyaluronate hydrogel in a clean container, and under the condition of a stirring rate of 420 rpm, maintain the temperature at 26°C for pre-dispersion treatment. The stirring time is 16 min to obtain a sodium hyaluronate hydrogel basic system with good uniform fluidity. S2. Add a mixed solvent of glycerol and deionized water to the basic system described in S1, and at the same time add Carbomer 940. Continuously stir at a stirring rate of 520 rpm for 26 min to fully disperse and pre-swell Carbomer. Then let it stand for 8 min to remove bubbles and stabilize the system structure. S3. Mix cetyl palmitate and polyglyceryl-10 stearate, and heat and melt them at a magnetic stirring rate of 320 rpm and a temperature of 71°C for 13 min to form a uniform emulsion phase. Then add this emulsion phase to the system obtained in S2 at a dropping rate of 1.6 mL / min, and maintain the stirring rate at 720 rpm for emulsification treatment for 21 min to form a primary emulsion system. S4. Add the aluminum nitride-coated chitosan composite nanospheres to the primary emulsion system described in S3, and disperse them at a temperature of 36°C and a stirring rate of 620 rpm for 21 min. S5. Add the Ag nanowire / hydroxyapatite microspheres to the dispersion system obtained in S4, maintain the stirring rate at 520 rpm and the temperature at 31°C, and continuously stir for 26 min.
[0052] S6. Dropwise add triethanolamine to the system obtained in S5, stir at a stirring rate of 420 rpm for 13 min, and then perform degassing treatment at a vacuum degree of 0.068 MPa for 16 min. Finally, cool it to 23°C to form a homogeneous and stable cream product.
[0053] Example 4 A cream for beauty instruments includes the following raw materials in parts by weight: 6.0 parts of aluminum nitride-coated chitosan composite nanospheres, 6.2 parts of Ag nanowire / hydroxyapatite microspheres, 52.0 parts of sodium hyaluronate hydrogel, 6.0 parts of cetyl palmitate, 4.0 parts of polyglyceryl-10 stearate, 32.0 parts of a mixed solvent of glycerol and deionized water, 1.0 part of Carbomer 940, and 0.4 part of triethanolamine; The aluminum nitride-coated chitosan composite nanospheres are composed of porous aluminum nitride hollow microspheres and chitosan coated in its inner cavity; among them, through-hole structures are uniformly distributed on the outer surface of the shell of the porous aluminum nitride hollow microspheres, and this pore structure is used to achieve the slow release of chitosan; In the mixed solvent of glycerol and deionized water, the volume ratio of glycerol to water is 2.2:1; The Ag nanowire / hydroxyapatite microspheres are composed of hydroxyapatite microspheres and Ag nanowires loaded on the surface thereof; wherein, the Ag nanowires are uniformly distributed and stably loaded on the surface of the hydroxyapatite microspheres.
[0054] The preparation method of the aluminum nitride-coated chitosan composite nanospheres in this embodiment is as follows: by weight, 0.6 part of chitosan with a deacetylation degree of ≥85% and a molecular weight of 80 kDa, 12.1 parts of glacial acetic acid and 88.3 parts of deionized water are mixed, and stirred at a magnetic stirring rate of 620 rpm at 28 °C for 5.2 h, and filtered through a 0.45 μm filter membrane to obtain a chitosan solution; 101 parts of pre-dried porous aluminum nitride hollow microspheres are mixed with 50 parts of the chitosan solution, and ultrasonic treatment is carried out at 43 °C, the ultrasonic frequency is 41 kHz, the power is 202 W, and the time is 16 min. Subsequently, filtration is carried out under a vacuum of 0.052 MPa for 20 min, and stirring is continued at 23 °C for 2.1 h to form a composite microsphere suspension; 0.50 part of 25 wt% glutaraldehyde aqueous solution is added dropwise to the suspension, the pH is adjusted to 5.8 with 0.022 wt.% hydrochloric acid aqueous solution and stirred at 260 rpm for 15 min, washed with deionized water and then centrifuged, the centrifugation rate is 5040 rpm and the time is 5.1 min, the precipitate is collected and pre-frozen at -74 °C for 12 h, and transferred to a vacuum freeze dryer to be dried at a pressure of ≤10 Pa for 40 h to obtain white to light yellow powdery aluminum nitride-coated chitosan composite nanospheres.
[0055] The preparation method of the porous aluminum nitride hollow microspheres in this embodiment is as follows: by weight, 1.0 part of polystyrene template microspheres with a particle size of 420 nm is dispersed in 50 parts of a mixed solvent with a volume ratio of ethanol to deionized water of 7.1:2.9. After adding 0.10 part of polyvinylpyrrolidone, it is dispersed and treated for 10 min under the conditions of an ultrasonic frequency of 43 kHz and a power of 92 W to form a stable suspension; 3.0 parts of aluminum isopropoxide is dissolved in 20 parts of absolute ethanol and undergoes controlled hydrolysis by dropping 2.0 parts of deionized water. At the same time, a 0.022 wt.% nitric acid solution is added to adjust the pH to 5.1 to form an aluminum sol precursor; the aluminum sol is added dropwise to the template dispersion system at a rate of 1.1 mL / min, and the stirring speed is maintained at 520 rpm for a sol-gel coating reaction for 122 min, and then left to stand and age for 12 h; the supernatant is removed by centrifugation at a speed of 4100 rpm, and the precipitate is collected. It is dried for 12 h under a vacuum of -0.092 MPa and a temperature of 60°C to obtain porous aluminum nitride hollow precursor microspheres; the precursor is placed in a tubular furnace, heated to 1020°C at a heating rate of 5°C / min, and then ammonia gas with a flow rate of 304 mL / min is introduced for nitridation treatment. The holding time is 121 min to completely convert the aluminum oxide into an aluminum nitride shell layer. At the same time, the polystyrene template pyrolyzes at 456°C to form a hollow structure; the obtained hollow microspheres are dispersed in a 30% by mass hydrogen peroxide solution, oxidized and etched at a temperature of 46°C for 46 min, and then washed with deionized water until neutral to finally obtain porous aluminum nitride hollow microspheres.
[0056] The average diameter of the aluminum nitride-coated chitosan composite nanospheres in this embodiment is 470 nm; The average pore diameter of the porous aluminum nitride hollow microspheres is 25 nm; In the aluminum nitride-coated chitosan composite nanospheres of this embodiment, the mass ratio of the porous aluminum nitride hollow microspheres to chitosan is 10:1.
[0057] The preparation method of the Ag nanowire / hydroxyapatite microspheres in this example is as follows: By weight, 1.1 parts of hydroxyapatite microspheres are dispersed in 22 parts of anhydrous ethylene glycol. After adding 0.055 parts of polyvinylpyrrolidone, it is treated for 12 min under the conditions of an ultrasonic frequency of 42 kHz and a power of 220 W to form a surface-activated dispersion system. The stirring speed is maintained at 400 rpm and the temperature is 30 °C for 35 min to complete surface modification. Then, 0.18 parts of silver nitrate, 0.32 parts of polyvinylpyrrolidone, and 0.11 parts of a ferric chloride solution with a concentration of 0.105 mol / L are successively added to the dispersion system. It is transferred to a three-necked flask and heated to a reaction temperature of 140 °C at a heating rate of 6 °C / min and an in-situ reduction reaction is carried out for 90 min under the condition of a stirring rate of 700 rpm to promote the directional growth of silver nanowires on the surface of hydroxyapatite. After the reaction, it is naturally cooled to 25 °C, and the supernatant containing unreacted silver nitrate, free polyvinylpyrrolidone, and by-products is separated and removed by centrifugation at a speed of 6200 rpm. After collecting the precipitate, it is repeatedly washed 4 times with an ethanol / water mixture with a volume ratio of 1.05:0.95. Finally, dehydration treatment is carried out at a freeze-drying temperature of -45 °C and a vacuum degree of ≤10 Pa for 14 h to obtain Ag nanowire / hydroxyapatite microspheres.
[0058] The preparation method of the hydroxyapatite microspheres in this example is as follows: By weight, 1.2 parts of calcium nitrate tetrahydrate are dissolved in 55 parts of deionized water to form a calcium source solution, and 0.6 parts of diammonium hydrogen phosphate are dissolved in 55 parts of deionized water to form a phosphorus source solution. Under the condition of a stirring rate of 600 rpm, the phosphorus source solution is added dropwise to the calcium source solution at a dropping rate of 2 mL / min. At the same time, ammonia water is added to adjust the pH to 10.5 and the temperature is maintained at 30 °C to carry out a coprecipitation reaction. After the dropping is completed, stirring is continued for 180 min to form a hydroxyapatite precursor suspension. Subsequently, it is transferred to a high-pressure reaction kettle for hydrothermal treatment. The heating rate is 5 °C / min to a reaction temperature of 130 °C. During the hydrothermal treatment stage, the pressure in the kettle is maintained at 0.25 MPa, and the holding time is 4.5 h to crystallize the precursor into hydroxyapatite microspheres. After the reaction, the supernatant is separated and removed by centrifugation at a speed of 4000 rpm and the precipitate is collected. It is alternately washed 5 times with deionized water and anhydrous ethanol and then placed in a vacuum drying oven. It is treated at a drying temperature of 70 °C and a vacuum degree of -0.10 MPa for 8 h to obtain hydroxyapatite microspheres.
[0059] In the Ag nanowire / hydroxyapatite microspheres of this example, the mass ratio of Ag nanowires to hydroxyapatite microspheres is 1:5; The average diameter of the Ag nanowire / hydroxyapatite microspheres of this example is 600 nm; The preparation method of a cream for a beauty instrument in this example includes the following steps: S1. Place the sodium hyaluronate hydrogel in a clean container. Under the condition of a stirring rate of 500 rpm, maintain the temperature at 30 °C for pre-dispersion treatment for 20 min to obtain a sodium hyaluronate hydrogel base system with good uniform fluidity. S2. Add a mixed solvent of glycerol and deionized water to the base system described in S1, and at the same time add Carbomer 940. Continuously stir at a stirring rate of 600 rpm for 30 min to fully disperse and pre-swell Carbomer. Then let it stand for 10 min to remove bubbles and stabilize the system structure. S3. Mix cetyl palmitate and polyglyceryl-10 stearate, and heat and melt it at a magnetic stirring rate of 400 rpm and a temperature of 75 °C for 15 min to form a uniform emulsion phase. Then add this emulsion phase to the system obtained in S2 at a dropping rate of 2 mL / min, and maintain the stirring rate at 800 rpm for emulsification treatment for 25 min to form a primary emulsion system. S4. Add the aluminum nitride-coated chitosan composite nanospheres to the primary emulsion system described in S3, and disperse them at a temperature of 40 °C and a stirring rate of 700 rpm for 25 min. S5. Add the Ag nanowire / hydroxyapatite microspheres to the dispersion system obtained in S4, maintain the stirring rate at 600 rpm and the temperature at 35 °C, and continuously stir for 30 min.
[0060] S6. Dropwise add triethanolamine to the system obtained in S5, stir at a stirring rate of 500 rpm for 15 min, and then perform degassing treatment at a vacuum degree of 0.08 MPa for 20 min, and finally cool to 25 °C to form a homogeneous and stable cream finished product.
[0061] Comparative Example 1 It is basically the same as Example 1, except that in the preparation process of the aluminum nitride-coated chitosan composite nanospheres, an aqueous glutaraldehyde solution was not used for cross-linking. Instead, the porous aluminum nitride hollow microspheres were directly mixed with the chitosan solution and then dried, resulting in the chitosan not being firmly coated in the inner cavity of the aluminum nitride hollow microspheres.
[0062] Comparative Example 2 It is basically the same as Example 1, except that in the preparation method of the porous aluminum nitride hollow microspheres, polyvinylpyrrolidone was not used as a dispersant. Instead, the polystyrene template microspheres were directly dispersed in the mixed solvent.
[0063] Comparative Example 3 It is basically the same as Example 1, except that in the preparation process of the porous aluminum nitride hollow microspheres, the nitriding treatment temperature was 800 °C, resulting in the incomplete conversion of alumina into the aluminum nitride shell layer.
[0064] Comparative Example 4 It is basically the same as Example 1, except that in the preparation process of Ag nanowire / hydroxyapatite microspheres, ferric chloride solution was not added as an auxiliary reducing agent, and only silver nitrate and polyvinylpyrrolidone were used for the reaction, resulting in the inability of silver ions to effectively grow into nanowire structures on the surface of hydroxyapatite.
[0065] Comparative Example 5 It is basically the same as Example 1, except that the porous aluminum nitride hollow microspheres were not coated with chitosan.
[0066] Comparative Example 6 It is basically the same as Example 1, except that silver nanowires were not prepared on the surface of hydroxyapatite microspheres.
[0067] Comparative Example 7 It is basically the same as Example 1, except that the porous aluminum nitride hollow microspheres were not coated with chitosan, and the two were added separately.
[0068] Performance Test: Determination of the thermal conductivity of the frost: The thermal conductivity of the frost was measured by the heat flow method (ASTM D5470 standard). The frost was evenly coated between two parallel copper plates. By heating the upper plate and maintaining the lower plate at a constant temperature, the steady-state heat flux density and temperature gradient were measured, and the thermal conductivity was calculated (λ = Q×d / (A×ΔT)).
[0069] Antibacterial performance: Staphylococcus aureus (ATCC 6538) and Escherichia coli (ATCC 25922) were selected. A bacterial suspension (10^6 CFU / mL) was prepared and evenly coated on a Mueller-Hinton agar plate. The frost sample (50 mg) was filled into an Oxford cup, and the diameter of the inhibition zone was measured after culturing at 37°C for 24 hours.
[0070] Silver ion release kinetics: The frost sample (1 g) was immersed in deionized water (10 mL) and shaken in the dark at 37°C. Samples were taken at 0, 6, 24, and 48 h. After filtering through a 0.22 μm filter membrane, the Ag+ release amount was quantified by inductively coupled plasma mass spectrometry (ICP-MS).
[0071] Rheological properties: The viscosity-shear rate curve (0.1 - 100 s^-1) and the storage modulus (G') - loss modulus (G'') of the frost were tested with a rotational rheometer at 25°C as a function of frequency.
[0072] The performances of the frost in Examples 1 - 4 and Comparative Examples 1 - 7 were summarized in Table 1.
[0073] Table 1 Summary of the performances of the frost in Examples 1 - 4 and Comparative Examples 1 - 7
[0074] As can be seen from Table 1, the degree of nitridation of aluminum nitride directly determines the integrity of the construction of its heat conduction path. Incomplete nitridation will lead to a decrease in the thermal conductivity of the ceramic shell. Whether chitosan is crosslinked and coated affects its fixation and sustained-release characteristics in the microsphere structure, and thus affects the stability and release efficiency of the antibacterial component. The formation of silver nanowires depends on the presence of an auxiliary reducing agent. The absence thereof will cause silver ions to be unable to be directionally reduced to a linear structure, affecting the formation of an efficient heat conduction and antibacterial pathway. The structural uniformity and surface activation degree of hydroxyapatite determine the loading density and distribution uniformity of silver nanowires, and thus affect the silver release behavior and the synergistic heat conduction effect. Whether a dispersant such as polyvinylpyrrolidone is used directly affects the nucleation and dispersion stability of the nanostructure, and affects the integrity of the microsphere structure and the interfacial bonding. Whether an effective composite structure is formed between aluminum nitride and chitosan is related to the synergistic realization of the heat conduction and antibacterial functions of the material. Structural separation will lead to a weakening of the synergistic effect. The simultaneous presence of silver nanowires and chitosan enables the antibacterial mechanism to have dual paths of rapid effect and sustained release. The absence of any component will make the antibacterial effect show periodicity or instability. The integrity of the porous structure determines the specific surface area and component distribution uniformity of the microsphere, thereby affecting the heat-mass synergistic transport ability and mechanical stability of the overall system. The uniformity of the spatial distribution of the components and the interfacial compatibility in the system determine the network structure and rheological behavior of the frost, and thus affect its film-forming property and stability during use.
[0075] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that all equivalent structural transformations made under the concept of the present invention by using the content of the specification and drawings of the present invention should be covered by the protection scope of the claims of the present invention.
Claims
1. A cream for beauty instruments, characterized in that, It comprises the following raw materials in parts by weight: 4.0 - 8.0 parts of aluminum nitride-coated chitosan composite nanospheres, 3.5 - 8.0 parts of Ag nanowire / hydroxyapatite microspheres, 40.0 - 60.0 parts of sodium hyaluronate hydrogel, 4.0 - 8.0 parts of cetyl palmitate, 2.0 - 5.0 parts of polyglyceryl-10 stearate, 20.0 - 40.0 parts of a mixed solvent of glycerol and deionized water, 0.5 - 2.0 parts of carbomer 940, and 0.2 - 0.5 parts of triethanolamine; The aluminum nitride-coated chitosan composite nanospheres are composed of porous aluminum nitride hollow microspheres and chitosan coated in their inner cavities; among them, through-hole structures are uniformly distributed on the outer surface of the porous aluminum nitride hollow microspheres, and this pore structure is used to achieve the slow release of chitosan; In the mixed solvent of glycerol and deionized water, the volume ratio of glycerol to water is 1:1 - 3:1; The Ag nanowire / hydroxyapatite microspheres are composed of hydroxyapatite microspheres and Ag nanowires loaded on their surfaces; among them, the Ag nanowires are uniformly distributed and stably loaded on the surface of the hydroxyapatite microspheres.
2. The cream for beauty instrument according to claim 1, characterized in that, The preparation method of the aluminum nitride-coated chitosan composite nanospheres is as follows: in parts by weight, 0.5 - 0.6 parts of chitosan with a deacetylation degree ≥85% and a molecular weight of 50 - 100 kDa, 11.5 - 12.5 parts of glacial acetic acid, and 87.0 - 89.0 parts of deionized water are mixed, and stirred at a magnetic stirring rate of 500 - 700 rpm at 25 - 30 °C for 4.0 - 6.0 h, and a chitosan solution is obtained by filtering through a 0.45 μm filter membrane; 95 - 105 parts of pre-dried porous aluminum nitride hollow microspheres are mixed with 48 - 52 parts of the chitosan solution, and ultrasonic treatment is carried out at 40 - 45 °C, the ultrasonic frequency is 38 - 42 kHz, the power is 190 - 210 W, and the time is 10 - 20 min. Subsequently, suction filtration is carried out for 18 - 22 min under a vacuum degree of 0.04 - 0.06 MPa, and stirring is continued at 20 - 25 °C for 1.5 - 2.5 h to form a composite microsphere suspension; 0.48 - 0.52 parts of 25 wt% glutaraldehyde aqueous solution is added dropwise to the suspension, the pH is adjusted to 5.5 - 6.0 with 0.01 - 0.03 wt.% hydrochloric acid aqueous solution and stirred at 200 - 300 rpm for 14 - 16 min, washed with deionized water and then centrifuged, the centrifugation rate is 4800 - 5200 rpm and the time is 4.5 - 5.5 min, the precipitate is collected and pre-frozen at -80 - 70 °C for 11 - 13 h, and then transferred to a vacuum freeze dryer and dried under a pressure ≤10 Pa for 24 - 50 h to obtain white to light yellow powdery aluminum nitride-coated chitosan composite nanospheres.
3. The cream for beauty instrument according to claim 2, characterized in that, The preparation method of the porous aluminum nitride hollow microspheres is as follows: by weight, 0.9 - 1.1 parts of polystyrene template microspheres with a particle size of 300 - 500 nm are dispersed in 48 - 52 parts of a mixed solvent with a volume ratio of ethanol to deionized water of 6.5:3.5 - 7.5:2.
5. After adding 0.09 - 0.11 parts of polyvinylpyrrolidone, the mixture is dispersed and treated for 8 - 12 min under the conditions of an ultrasonic frequency of 40 - 45 kHz and a power of 80 - 100 W to form a stable suspension. 2.8 - 3.2 parts of aluminum isopropoxide are dissolved in 18 - 22 parts of absolute ethanol, and controlled hydrolysis is carried out by dropping 1.8 - 2.2 parts of deionized water. At the same time, a 0.01 - 0.03 wt.% nitric acid solution is added to adjust the pH to 4.3 - 5.7 to form an aluminum sol precursor. The aluminum sol is added dropwise to the template dispersion system at a rate of 0.5 - 1.5 mL / min, and the stirring speed is maintained at 400 - 600 rpm for a sol - gel coating reaction for 110 - 130 min, and then left to stand and age for 11 - 13 h. The supernatant is removed by centrifugation at a speed of 3500 - 4500 rpm, and the precipitate is collected. It is dried for 11 - 13 h under a vacuum of -0.08 - -0.10 MPa and a temperature of 58 - 62 °C to obtain porous aluminum nitride hollow precursor microspheres. The precursor is placed in a tube furnace and heated to 900 - 1100 °C at a heating rate of 4 - 6 °C / min, and then ammonia gas with a flow rate of 280 - 320 mL / min is introduced for nitridation treatment. The holding time is 115 - 125 min to completely convert the alumina into an aluminum nitride shell layer. At the same time, the polystyrene template pyrolyzes at 420 - 480 °C to form a hollow structure. The obtained hollow microspheres are dispersed in a 28 - 32% hydrogen peroxide solution by mass fraction, and after oxidation etching treatment at a temperature of 40 - 50 °C for 40 - 50 min, they are washed with deionized water until neutral, and finally porous aluminum nitride hollow microspheres are obtained.
4. The cream for beauty instrument according to claim 1, characterized in that, The average diameter of the aluminum nitride coated chitosan composite nanospheres is 350 - 550 nm; the average pore diameter of the porous aluminum nitride hollow microspheres is 18 - 30 nm.
5. The cream for beauty instrument according to claim 1, characterized in that In the aluminum nitride coated chitosan composite nanospheres, the mass ratio of the porous aluminum nitride hollow microspheres to chitosan is 8:1 - 12:
1.
6. A cream for beauty instrument according to claim 1, characterized in that The preparation method of the described Ag nanowire / hydroxyapatite microspheres is as follows: by weight, disperse 0.9 - 1.1 parts of hydroxyapatite microspheres in 18 - 22 parts of anhydrous ethylene glycol. After adding 0.045 - 0.055 parts of polyvinylpyrrolidone, treat it under the conditions of ultrasonic frequency of 38 - 42 kHz and power of 180 - 220 W for 8 - 12 min to form a surface-activated dispersion system. Maintain the stirring speed at 300 - 400 rpm and continue for 25 - 35 min at a temperature of 25 - 30 °C to complete surface modification. Sequentially add 0.16 - 0.18 parts of silver nitrate, 0.28 - 0.32 parts of polyvinylpyrrolidone, and 0.09 - 0.11 parts of ferric chloride solution with a concentration of 0.095 - 0.105 mol / L to the dispersion system. Transfer it to a three-necked flask and heat it to the reaction temperature of 120 - 140 °C at a heating rate of 4 - 6 °C / min, and carry out an in-situ reduction reaction for 60 - 90 min under the condition of a stirring rate of 500 - 700 rpm to promote the directional growth of silver ions into nanowires on the surface of hydroxyapatite. After the reaction, naturally cool it to 20 - 25 °C, separate and remove the upper clear liquid containing unreacted silver nitrate, free polyvinylpyrrolidone, and by-products at a centrifugal speed of 5800 - 6200 rpm. After collecting the precipitate, wash it repeatedly 2 - 4 times with an ethanol / water mixture with a volume ratio of 0.95:1.05 - 1.05:0.
95. Finally, carry out dehydration treatment for 10 - 14 h at a freeze-drying temperature of -50 - -45 °C and a vacuum degree of ≤10 Pa to obtain Ag nanowire / hydroxyapatite microspheres.
7. A cream for beauty instrument according to claim 6, characterized in that, The preparation method of the described hydroxyapatite microspheres is as follows: by weight, dissolve 0.8 - 1.2 parts of calcium nitrate tetrahydrate in 45 - 55 parts of deionized water to form a calcium source solution. Separately, dissolve 0.4 - 0.6 parts of diammonium hydrogen phosphate in 45 - 55 parts of deionized water to form a phosphorus source solution. Under the condition of a stirring rate of 400 - 600 rpm, add the phosphorus source solution dropwise to the calcium source solution at a dropping rate of 1 - 2 mL / min. Synchronously add ammonia water to adjust the pH to 9.5 - 10.5 and maintain the temperature at 25 - 30 °C to carry out a co-precipitation reaction. After the dropping is completed, continue stirring for 120 - 180 min to form a hydroxyapatite precursor suspension. Subsequently, transfer it to a high-pressure reaction kettle for hydrothermal treatment. The heating rate is 3 - 5 °C / min to the reaction temperature of 120 - 130 °C. During the hydrothermal treatment stage, keep the pressure in the kettle at 0.15 - 0.25 MPa, and the heat preservation time is 3.5 - 4.5 h to crystallize the precursor into hydroxyapatite microspheres. After the reaction, separate and remove the upper clear liquid at a centrifugal speed of 3000 - 4000 rpm and collect the precipitate. Wash it alternately 3 - 5 times with deionized water and anhydrous ethanol, and then place it in a vacuum drying oven. Treat it at a drying temperature of 50 - 70 °C and a vacuum degree of -0.08 - -0.10 MPa for 6 - 8 h to obtain hydroxyapatite microspheres.
8. The cream for beauty instrument according to claim 1, characterized in that, In the described Ag nanowire / hydroxyapatite microspheres, the mass ratio of Ag nanowires to hydroxyapatite microspheres is 1:10 to 1:
5.
9. The cream for beauty instrument according to claim 1, characterized in that, The average diameter of the described Ag nanowire / hydroxyapatite microspheres is 350 - 600 nm.
10. The preparation method of a cream for a beauty instrument according to claim 1, characterized in that, It includes the following steps: S1. Place the sodium hyaluronate hydrogel in a clean container. Under the condition that the stirring rate is 300 - 500 rpm, maintain the temperature at 20 - 30 °C for pre-dispersion treatment, and the stirring time is 10 - 20 min to obtain a sodium hyaluronate hydrogel base system with good uniform fluidity. S2. Add a mixed solvent of glycerol and deionized water to the base system described in S1, and at the same time add Carbopol 940. Continuously stir at a stirring rate of 400 - 600 rpm for 20 - 30 min to fully disperse and pre-swell Carbopol. Then let it stand for 5 - 10 min to remove bubbles and stabilize the system structure. S3. Mix cetyl palmitate and polyglyceryl-10 stearate, heat and melt it at a magnetic stirring rate of 200 - 400 rpm and a temperature of 65 - 75 °C for 10 - 15 min to form a uniform emulsion phase. Then add this emulsion phase to the system obtained in S2 at a dropping rate of 1 - 2 mL / min, and maintain the stirring rate at 600 - 800 rpm for emulsification treatment for 15 - 25 min to form a primary emulsion system. S4. Add the aluminum nitride-coated chitosan composite nanospheres to the primary emulsion system described in S3, and disperse them at a temperature of 30 - 40 °C and a stirring rate of 500 - 700 rpm for 15 - 25 min. S5. Add the Ag nanowire / hydroxyapatite microspheres to the dispersion system obtained in S4, maintain the stirring rate at 400 - 600 rpm and the temperature at 25 - 35 °C, and continuously stir for 20 - 30 min. S6. Dropwise add triethanolamine to the system obtained in S5, stir at a stirring rate of 300 - 500 rpm for 10 - 15 min, and then perform degassing treatment at a vacuum degree of 0.05 - 0.08 MPa for 10 - 20 min, and finally cool to 20 - 25 °C to form a homogeneous and stable cream finished product.
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