CN113307992B - Graphene composite antibacterial master batch and preparation method thereof - Google Patents
Graphene composite antibacterial master batch and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of graphene, and particularly relates to a graphene composite antibacterial master batch and a preparation method thereof. Aiming at the problems of serious pollution, poor antibacterial effect and the like of the existing method for preparing graphene antibacterial particles, the invention provides a preparation method of an antibacterial master batch compounded by graphene and resin, which comprises the following steps: a. dissolving copper acetate in propylene glycol solution to prepare nano cuprous oxide powder; b. dissolving stearic acid, adding glucose under stirring, dropwise adding a silver acetate solution to prepare nano silver sol, and preparing to obtain the graphene composite antibacterial agent; c. adding the resin master batch, the graphene composite antibacterial agent and the high-carbon alkane, and mixing to prepare the copper-silver-graphene composite antibacterial master batch. The method reduces the using amount of the reducing agent, avoids the generation of toxic gas NO2, can ensure that the prepared nanoparticles are below 9 nanometers, has better antibacterial effect and wide application field, and has good practical value.
Description
Technical Field
The invention belongs to the technical field of graphene, and particularly relates to an antibacterial master batch compounded by graphene and resin and a preparation method thereof.
Background
The antibacterial effect of the antibacterial agent is to disturb and destroy the physiological, biochemical and metabolic activities related to the microbial cells, thereby killing or inhibiting the growth and reproduction of the microorganisms. The different antibacterial agents may act by different mechanisms, and even the same antibacterial agent may exhibit different antibacterial mechanisms under different environmental conditions.
The antibacterial action of the antibacterial agent for plastics is usually exerted by the contained metal ions, and the contact reaction mechanism of the metal ions and microbial cells is as follows, the metal ions have positive charges, when trace metal ions contact the cell membranes of the microbes, the metal ions and the negatively charged cell membranes are subjected to coulomb attraction to be firmly combined, and the metal ions penetrate the cell membranes to enter the bacterial cells and react with sulfydryl, amino and the like on proteins in the bacterial bodies. The structure of the active center of cellular proteins is destroyed, causing the microorganism to die or lose its ability to divide and proliferate. The activities of the metal ions for killing and inhibiting bacteria are decreased in the following order: ag + > Hg2+ > Cu2+ > Cd2+ > Cr3+ > Ni2+ > Pb2+ > Co4+ > Zn2+ > Fe3 +. Ag + is the first one because it has strong redox activity (. + -. 0.798eV, 25 ℃) in addition to the complexation reaction of other metal ions, and its structure is stable by the redox reaction, so the antibacterial action of Ag + is the strongest, and in addition, the antibacterial action of Cu2+ is also strong.
Silver is generally used as an antibacterial agent in the form of a nano-silver antibacterial agent, but its preparation has many problems, mainly: firstly, it is difficult to ensure that the prepared silver particles are in the nanometer level; secondly, the prepared silver particles are agglomerated due to thermodynamic instability, so that the antibacterial effect of the silver particles is influenced, or the selected dispersing agent has poor effect, so that the subsequent processing and application are influenced; thirdly, silver nitrate is used as a silver source, and toxic gas nitrogen dioxide is generated in the preparation process to pollute air; fourthly, the nano silver is used for playing an antibacterial role, and the cost is higher.
The graphene oxide sheet is a product obtained by chemically oxidizing and stripping graphite powder, and the graphene oxide is a single atomic layer and can be expanded to tens of microns in transverse dimension at any time. Thus, its structure spans the typical dimensions of general chemistry and material science. Graphene oxide can be considered a non-traditional soft material with the properties of polymers, colloids, films, and amphiphilic molecules. Graphene oxide has long been considered as a hydrophilic substance because of its superior dispersibility in water, but related experimental results show that graphene oxide is actually amphiphilic and exhibits a property distribution of hydrophilic to hydrophobic from the edge to the center of a graphene sheet. Therefore, the graphene oxide may exist at an interface as a surfactant and reduce energy between interfaces.
In the existing research, graphene also has certain antibacterial performance. If the silver and the graphene are prepared into the antibacterial material together, the antibacterial effect is better than that of the silver alone.
Patent CN110841890A discloses a preparation method of a silver nanostructure protected by a graphene-PVP hybrid coating. The method takes PVP as a dispersing agent, takes ethylene glycol and AgNO3 as a reducing agent and an oxidizing agent respectively to prepare nano silver particles, and transfers graphene to the surface of a silver nano structure to form a graphene-PVP mixed coating, so that the oxidation of the silver nano material is inhibited, and the application scene of the silver nano material is widened. However, the method has some defects, PVP is used as a dispersing agent, the dispersing effect is poor, and lactam groups contained in PVP have extremely strong affinity to the silver nanoparticles, so that the contact of the silver nanoparticles with the outside is influenced after the PVP is coated on the surface of the silver, and the antibacterial performance of the PVP is influenced. Secondly, the toxic gas NO2 is generated by taking silver nitrate as an oxidant, and the atmosphere is polluted.
Therefore, the existing method for preparing the graphene/silver nanoparticles has various problems of serious pollution, poor antibacterial effect and the like, and needs to be further improved.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the existing method for preparing the graphene antibacterial particles has the problems of serious pollution, poor antibacterial effect and the like.
The technical scheme for solving the technical problems comprises the following steps: a preparation method of graphene and resin compounded antibacterial master batch is provided. The method comprises the following steps:
a. dissolving copper acetate in a propylene glycol solution to obtain a copper acetate propylene glycol solution with the copper acetate concentration of 0.4-0.8 mol/L; cooling, centrifuging, filtering, taking filter residue, cleaning and vacuum drying to obtain nano cuprous oxide powder;
b. b, dissolving stearic acid, adding glucose under the stirring condition, then dropwise adding a silver acetate solution, continuously stirring for 3-5 hours to prepare a deep red nano silver sol, adding the cuprous oxide powder obtained in the step a, continuously stirring for 1-2 hours, carrying out centrifugal separation, cleaning the obtained precipitate, adding graphene and deionized water, mixing uniformly, and carrying out spray drying treatment to obtain a graphene composite antibacterial agent;
c. uniformly stirring resin master batches, a graphene composite antibacterial agent and high-carbon alkane, and then extruding by adopting a double-screw co-extrusion device, wherein the mass ratio of the resin master batches is 92.9-99.0%, the mass ratio of the graphene composite antibacterial agent is 1.0-7.0%, the mass ratio of the high-carbon alkane is 0-0.1%, the temperatures of 12 temperature zones of an extruder are respectively set to be 130 ℃, 140 ℃, 150 ℃, 165 ℃, 180 ℃, 195 ℃, 210 ℃, 230 ℃, 215 ℃, 200 ℃, 190 ℃ and 180 ℃, and the rotating speed of a main machine is set to be 400-900 rpm; and cooling the extruded resin line by pure water at room temperature, cutting the resin line into granules by a granulator, removing irregular granules by a fine vibrating screen, ventilating, and completely cooling and drying to obtain the graphene composite antibacterial master batch.
In the step a, in order to uniformly mix the copper acetate propylene glycol solution, the copper acetate propylene glycol solution is heated in a constant-temperature oil bath for 2-4 hours at the temperature of 120-160 ℃. Preferably a constant temperature oil bath at 130 ℃.
In the step a, the concentration of the copper acetate propylene glycol solution is 0.4-0.8 mol/L.
Wherein, in the step a, the copper acetate propylene glycol solution is sealed in a stainless steel reactor with a tetrafluoroethylene liner.
In the step b, the stearic acid is dissolved at the temperature of 80 ℃ under stirring and is dissolved in the mixed solution of ammonia water and distilled water.
In the step b, the mass ratio of the glucose to the stearic acid to the silver acetate to the cuprous oxide is 7-8: 1-2: 2-3: 2.
Preferably, in the step b, the mass ratio of the glucose to the stearic acid to the silver acetate to the cuprous oxide is 8:1:3: 2.
And in the step b, the precipitate is washed twice by using ethanol and acetone respectively.
Wherein, the spray drying conditions of the step b are as follows: the feeding speed is 300 mL/min < -1 >, the inlet temperature is 160-250 ℃, the outlet temperature is 80-150 ℃, the pressure difference of a cyclone separator is 80mmH2O, and the rotating speed of an atomizing disc is 1500-2500 rpm.
In the step c, the average particle size of the graphene composite antibacterial agent is less than or equal to 8 microns, and preferably less than or equal to 3 microns.
In the step c, the specific operation of uniformly stirring is as follows: stirring at 1500-2500 rpm for 15-20 min.
Wherein, in step c, the number of carbon atoms in the alkane molecule is required to be more than or equal to 20 by the high-carbon alkane.
In step c, the resin masterbatch comprises at least one of polyethylene, polypropylene, polylactic acid, ethylene-vinyl alcohol copolymer, acrylonitrile-butadiene-styrene copolymer, polybutylene terephthalate, polyvinyl chloride, polyethylene terephthalate, polyamide or polycarbonate.
The invention also provides the graphene and resin composite antibacterial master batch prepared by the method.
The invention has the beneficial effects that:
the invention provides a preparation method of graphene composite antibacterial master batch, which adopts glucose and silver acetate for reaction, reduces the using amount of a reducing agent, and avoids the generation of toxic gas NO 2. In addition, stearic acid is used as a dispersing agent, so that the dispersing effect of the nano silver is improved, the nano silver is ensured to be below 9 nanometers, and the nano silver can be more easily washed and removed by an organic solvent. The invention also introduces the nano copper part to replace the nano silver, the prepared composite antibacterial agent has better antibacterial effect, lower cost and good miscibility with PE resin, and the PE antibacterial preservative film prepared from the composite antibacterial agent has good antibacterial property, film-forming tensile strength and breaking strength. The antibacterial rate of the PE antibacterial preservative film prepared by the method on escherichia coli is more than 98%, the elongation at break can reach 170%, and the average tensile strength can reach 15 MPa. The graphene composite antibacterial master batch disclosed by the invention is good in antibacterial effect and wide in application field, can be applied to film products, pipes and injection molding products, or can be used as a processing raw material of other plastic products, and is suitable for popularization and application.
Detailed Description
The invention provides a preparation method of graphene and resin compounded antibacterial master batch, which comprises the following steps:
a. dissolving copper acetate in a propylene glycol solution to obtain a copper acetate propylene glycol solution with the copper acetate concentration of 0.4-0.8 mol/L; cooling, centrifuging, filtering, taking filter residue, cleaning and vacuum drying to obtain nano cuprous oxide powder;
b. b, dissolving stearic acid, adding glucose under the stirring condition, then dropwise adding a silver acetate solution, continuously stirring for 3-5 hours to prepare a deep red nano silver sol, adding the cuprous oxide powder obtained in the step a, continuously stirring for 1-2 hours, carrying out centrifugal separation, cleaning the obtained precipitate, adding graphene and deionized water, mixing uniformly, and carrying out spray drying treatment to obtain a graphene composite antibacterial agent;
c. uniformly stirring resin master batches, a graphene composite antibacterial agent and high-carbon alkane, and then extruding by adopting a double-screw co-extrusion device, wherein the mass ratio of the resin master batches is 92.9-99.0%, the mass ratio of the graphene composite antibacterial agent is 1.0-7.0%, the mass ratio of the high-carbon alkane is 0-0.1%, the temperatures of 12 temperature zones of an extruder are respectively set to be 130 ℃, 140 ℃, 150 ℃, 165 ℃, 180 ℃, 195 ℃, 210 ℃, 230 ℃, 215 ℃, 200 ℃, 190 ℃ and 180 ℃, and the rotating speed of a main machine is set to be 400-900 rpm; and cooling the extruded resin line by pure water at room temperature, cutting the resin line into granules by a granulator, removing irregular granules by a fine vibrating screen, ventilating, and completely cooling and drying to obtain the graphene composite antibacterial master batch. The settings for the 12 temperature zones are constant, if near or at their periphery are acceptable.
The graphene composite antibacterial master batch prepared by the invention contains nano cuprous oxide powder and nano silver sol, wherein the nano cuprous oxide and the nano silver can synergistically play an antibacterial role, and the antibacterial effect is better. On the other hand, when the nano silver is prepared, glucose and silver acetate are adopted for reaction, and compared with the existing method, the raw materials are easy to obtain, safe and nontoxic, and green production can be realized.
The graphene composite antibacterial master batch also comprises resin master batches (polyethylene, polypropylene, ABS or other common resins), eicosane and higher alkanes. Due to the fluidity and the infiltration performance of the high-carbon alkane, the graphene antibacterial agent is uniformly dispersed in the resin master batch, and is decomposed and volatilized in the subsequent high-temperature process, so that the residual quantity is extremely low. Almost can be ignored, and the influence of the additive on the product performance is effectively reduced.
In the step a, in order to uniformly mix the copper acetate propylene glycol solution, the copper acetate propylene glycol solution is heated in a constant-temperature oil bath for 2-4 hours at the temperature of 120-160 ℃. Preferably a constant temperature oil bath at 130 ℃.
Wherein, in the step a, the concentration of the copper acetate propylene glycol solution is 0.7 mol/L.
In step a, in order to prevent the carboxylic acid generated by the reaction from corroding the reaction vessel, the copper acetate propylene glycol solution is hermetically stored in a stainless steel reactor with a tetrafluoroethylene liner.
In the step b, the stearic acid is dissolved at the temperature of 80 ℃ under stirring and is dissolved in the mixed solution of ammonia water and distilled water.
In the step b, glucose is used as a reducing agent, silver acetate and cuprous oxide are used as oxidizing agents, glucose needs to be relatively excessive for complete reaction of the oxidizing agents, and the introduced copper needs to partially replace silver, so that the mass ratio of the glucose to the stearic acid to the silver acetate to the cuprous oxide is 7-8: 1-2: 2-3: 2.
Preferably, in the step b, the mass ratio of the glucose to the stearic acid to the silver acetate to the cuprous oxide is 8:1:3: 2.
And in the step b, the precipitate is washed twice by using ethanol and acetone respectively.
Wherein the spray drying conditions of the step b are as follows: the feeding speed is 300 mL/min < -1 >, the inlet temperature is 160-250 ℃, the outlet temperature is 80-150 ℃, the pressure difference of a cyclone separator is 80mmH2O, and the rotating speed of an atomizing disc is 1500-2500 rpm.
In the step c, the average grain diameter of the graphene composite antibacterial agent is less than or equal to 8 microns, and preferably less than or equal to 3 microns.
In the step c, the specific operation of uniformly stirring is as follows: stirring at the rotating speed of 1500-2500 rpm for 15-20 min.
The resin masterbatch in step c of the present invention may be a commonly used resin material, such as polyethylene, polypropylene, polylactic acid, ethylene-vinyl alcohol copolymer, acrylonitrile-butadiene-styrene copolymer, polybutylene terephthalate, polyvinyl chloride, polyethylene terephthalate, polyamide, or polycarbonate.
The invention also provides the graphene composite polyethylene antibacterial master batch prepared by the method.
The following examples are intended to illustrate specific embodiments of the present invention without limiting the scope of the invention to the examples.
The various starting materials used in the examples are all common commercial products.
Embodiment 1 preparation of graphene composite polyethylene antibacterial preservative film by using the method
The specific operation steps are as follows:
1. adding a proper amount of copper acetate into the propylene glycol solution, fully stirring to completely dissolve the copper acetate, and preparing 0.7mol/L copper acetate propylene glycol solution;
2. adding the prepared solution into a stainless steel reactor with a tetrafluoroethylene lining for sealing treatment, then placing the stainless steel reactor into constant-temperature oil bath heating equipment, and heating at the constant temperature of 130 ℃ to ensure that copper acetate and propylene glycol fully react for 4 hours;
3. after the reaction solution is cooled, carrying out centrifugal filtration, repeatedly washing filter residues with deionized water, and carrying out vacuum drying to obtain nano cuprous oxide powder;
4. adding 1.00g of stearic acid into 1.00g of ammonia water and 100.00mL of distilled water, and stirring in a magnetic stirrer at 80 ℃ for 10 min;
5. continuously stirring at constant temperature, firstly adding 8.00g of glucose, then dropwise adding 80mL0.40mol/L silver acetate solution, and continuously stirring for 4h to prepare the deep red nano silver sol. Adding 2.00g of cuprous oxide powder prepared in the previous step into the sol, and continuously stirring for 2 hours;
6. performing centrifugal separation, cleaning the obtained precipitate with ethanol and acetone twice respectively, adding graphene and deionized water, and stirring with a magnetic stirrer for 30min to fully mix;
7. and (3) treating the mixed solution by using a spray drying method, pumping the mixed solution into a high-speed turntable of spray drying equipment, carrying out centrifugal atomization to obtain micro droplets, carrying out cyclone drying, and collecting by using a cyclone separator to obtain the graphene composite antibacterial agent containing the copper and silver nano particles. The spray drying conditions are that the feeding speed is 300 mL/min < -1 >, the inlet temperature is 170 ℃, the outlet temperature is 120 ℃, the pressure difference of a cyclone separator is 80mmH2O, and the rotating speed of an atomizing disc is 2000 rpm.
8. Grinding the composite antibacterial agent powder to an average particle size of 8 μm or less, more preferably 3 μm or less;
9. and (3) adding 93.0% of polyethylene master batch, 6.9% of graphene composite antibacterial agent and 0.1% of high-carbon alkane in percentage by weight into a mixing hopper, and stirring at 2000rpm for 20 min. The mixture was extruded using a twin-screw co-extrusion apparatus, the temperatures in the 12 zones of the extruder were set at 130 ℃, 140 ℃, 150 ℃, 165 ℃, 180 ℃, 195 ℃, 210 ℃, 230 ℃, 215 ℃, 200 ℃, 190 ℃, 180 ℃ respectively, and the rotational speed of the main frame was set at 800 rpm.
10. And cooling the extruded resin wire by using pure water at room temperature, cutting the resin wire into granules by using a granulator, removing irregular granules by using a fine vibrating screen, ventilating, and completely cooling and drying to obtain the polyethylene composite master batch compounded with the graphene antibacterial agent.
11. The preparation method comprises the steps of stirring and mixing the PE resin with the mass ratio of 10:1 and the polyethylene composite master batch prepared by the invention, uniformly stirring in a stirrer, and then obtaining the antibacterial preservative film product according to the steps of hopper feeding → material plasticizing extrusion → inflation traction → air ring cooling → herringbone clamping plate → traction roller traction → corona treatment → film rolling.
Embodiment 2 preparation of graphene composite polyethylene antibacterial preservative film by using the method
The difference from the example 1 is that the solvent concentration in the copper acetate propylene glycol solution is 0.6mol/L, the oil bath heating temperature is 120 ℃, the glucose mass is 7.00g, the stearic acid mass is 1.00g, the silver acetate is 2.50g, and the cuprous oxide is 2.00 g; grinding the composite antibacterial agent powder to an average particle size of 6 mu m; when the polyethylene composite master batch is prepared, the raw materials comprise 97.0 percent of polyethylene master batch, 2.9 percent of graphene composite antibacterial agent and 0.1 percent of high-carbon alkane in percentage by weight.
Embodiment 3 preparation of graphene composite polyethylene antibacterial preservative film by using the method
The difference from the example 1 is that the solvent concentration in the copper acetate propylene glycol solution is 0.5mol/L, the oil bath heating temperature is 140 ℃, the glucose mass is 8.00g, the stearic acid mass is 1.00g, the silver acetate is 2.50g, and the cuprous oxide is 2.00 g; grinding the composite antibacterial agent powder to an average particle size of 5 mu m; when the polyethylene composite master batch is prepared, the raw materials comprise 95 weight percent of the polyethylene master batch, 4.95 weight percent of the graphene composite antibacterial agent and 0.05 weight percent of high-carbon alkane.
Embodiment 4 preparation of graphene composite polyethylene antibacterial preservative film by using the method
The difference from the example 1 is that the solvent concentration in the copper acetate propylene glycol solution is 0.4mol/L, the oil bath heating temperature is 150 ℃, the glucose mass is 7.00g, the stearic acid mass is 1.00g, the silver acetate is 2.50g, and the cuprous oxide is 2.00 g; grinding the composite antibacterial agent powder to an average particle size of 2 mu m; when the polyethylene composite master batch is prepared, the raw materials comprise 96 percent of polyethylene master batch, 3.95 percent of graphene composite antibacterial agent and 0.05 percent of high-carbon alkane in percentage by weight.
Comparative example 5 preparation of cling film Using pure PE resin
The difference from example 1 is that the raw material used is pure PE resin, and no polyethylene composite masterbatch is used.
The performance of the wrap films prepared in examples 1 to 4 and comparative example 5 was measured, and the results are shown in table 1 below.
TABLE 1 preservative film Performance index test
The experimental results show that after the graphene composite polyethylene antibacterial master batch prepared by the invention is added into the common PE preservative film, the antibacterial property, the film-forming tensile strength and the breaking strength of the common PE preservative film can be effectively enhanced, especially the effects of resisting escherichia coli, staphylococcus aureus and candida albicans are obviously enhanced, and the common PE preservative film has a good antibacterial effect.
Claims (8)
1. The preparation method of the antibacterial master batch compounded by graphene and resin is characterized by comprising the following steps:
a. dissolving copper acetate in a propylene glycol solution to obtain a copper acetate propylene glycol solution with the copper acetate concentration of 0.4-0.8 mol/L; sealing the copper acetate propylene glycol solution in a stainless steel reactor with a tetrafluoroethylene lining, heating for 2-4 h at the constant temperature of 120-160 ℃ in an oil bath, cooling, centrifuging, filtering, taking filter residues, cleaning and drying in vacuum to obtain nano cuprous oxide powder;
b. b, dissolving stearic acid, adding glucose under the stirring condition, then dropwise adding a silver acetate solution, continuously stirring for 3-5 hours to prepare a deep red nano silver sol, adding the cuprous oxide powder obtained in the step a, continuously stirring for 1-2 hours, carrying out centrifugal separation, cleaning the obtained precipitate, adding graphene and deionized water, mixing uniformly, and carrying out spray drying treatment to obtain a graphene composite antibacterial agent; the mass ratio of the glucose to the stearic acid to the silver acetate to the cuprous oxide is 7-8: 1-2: 2-3: 2;
c. uniformly stirring resin master batches, a graphene composite antibacterial agent and high-carbon alkane, and then extruding by adopting a double-screw co-extrusion device, wherein the mass ratio of the resin master batches is 92.9-99.0%, the mass ratio of the graphene composite antibacterial agent is 1.0-7.0%, the mass ratio of the high-carbon alkane is 0-0.1%, the temperatures of 12 temperature zones of an extruder are respectively set to be 130 ℃, 140 ℃, 150 ℃, 165 ℃, 180 ℃, 195 ℃, 210 ℃, 230 ℃, 215 ℃, 200 ℃, 190 ℃ and 180 ℃, and the rotating speed of a main machine is set to be 400-900 rpm; and cooling the extruded resin line by pure water at room temperature, cutting the resin line into granules by a granulator, removing irregular granules by a fine vibrating screen, ventilating, and completely cooling and drying to obtain the graphene composite antibacterial master batch.
2. The preparation method of the graphene composite antibacterial masterbatch according to claim 1, characterized in that: and c, dissolving the stearic acid in the step b at the dissolving temperature of 80 ℃ under stirring, and dissolving the stearic acid in a mixed solution of ammonia water and distilled water.
3. The preparation method of the graphene composite antibacterial masterbatch according to claim 1, characterized in that: and b, cleaning the precipitate twice by using ethanol and acetone respectively.
4. The preparation method of the graphene composite antibacterial masterbatch according to claim 1, characterized in that: the spray drying conditions of the step b are as follows: the feeding speed is 300 mL/min－1The inlet temperature is 160-250 ℃, the outlet temperature is 80-150 ℃, the pressure difference of the cyclone separator is 80mmH2O, and the rotating speed of the atomizing disc is 1500-2500 rpm.
5. The preparation method of the graphene composite antibacterial masterbatch according to claim 1, characterized in that: the average grain diameter of the graphene composite antibacterial agent in the step b is less than or equal to 8 mu m.
6. The preparation method of the graphene composite antibacterial masterbatch according to claim 1, characterized by comprising the following steps: the concrete operation of uniformly stirring in the step c is as follows: stirring at 1500-2500 rpm for 15-20 min.
7. The preparation method of the graphene composite antibacterial masterbatch of claim 1 is characterized by comprising the following steps: the resin master batch in the step c comprises at least one of polyethylene, polypropylene, polylactic acid, ethylene-vinyl alcohol copolymer, acrylonitrile-butadiene-styrene copolymer, polybutylene terephthalate, polyvinyl chloride, polyethylene terephthalate, polyamide or polycarbonate.
8. The graphene composite antibacterial master batch prepared by the preparation method of any one of claims 1 to 7.
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| CN113881100B (en) * | 2021-09-24 | 2023-04-25 | 深圳环能石墨烯科技有限公司 | Ag/Cu 2 O/rGO nano composite antibacterial agent, antibacterial master batch and preparation method thereof |
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| CN103567431A (en) * | 2012-07-24 | 2014-02-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Nanometer silver colloid solution and preparation method thereof |
| CN110128731A (en) * | 2019-05-23 | 2019-08-16 | 福州大学 | Graphene/polyethylene composite antibacterial film |
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| CN103567431A (en) * | 2012-07-24 | 2014-02-12 | 上海纳米技术及应用国家工程研究中心有限公司 | Nanometer silver colloid solution and preparation method thereof |
| CN110128731A (en) * | 2019-05-23 | 2019-08-16 | 福州大学 | Graphene/polyethylene composite antibacterial film |
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