CN114045611A - Preparation method of zinc oxide nanofiber membrane - Google Patents
Preparation method of zinc oxide nanofiber membrane Download PDFInfo
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- CN114045611A CN114045611A CN202111361825.2A CN202111361825A CN114045611A CN 114045611 A CN114045611 A CN 114045611A CN 202111361825 A CN202111361825 A CN 202111361825A CN 114045611 A CN114045611 A CN 114045611A
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 363
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 181
- 239000002121 nanofiber Substances 0.000 title claims abstract description 59
- 239000012528 membrane Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 105
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 105
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000007385 chemical modification Methods 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims description 35
- 238000000498 ball milling Methods 0.000 claims description 32
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 20
- 239000011324 bead Substances 0.000 claims description 11
- 150000003384 small molecules Chemical class 0.000 claims description 9
- 229920001661 Chitosan Polymers 0.000 claims description 6
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 claims description 3
- 229920001046 Nanocellulose Polymers 0.000 claims description 3
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 241001673966 Magnolia officinalis Species 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 29
- 241000588724 Escherichia coli Species 0.000 abstract description 9
- 241000191967 Staphylococcus aureus Species 0.000 abstract description 9
- 238000012360 testing method Methods 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 3
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- 239000000243 solution Substances 0.000 description 71
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- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 230000008569 process Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 6
- 235000018417 cysteine Nutrition 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
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- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 125000000415 L-cysteinyl group Chemical group O=C([*])[C@@](N([H])[H])([H])C([H])([H])S[H] 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
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Images
Classifications
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/4309—Polyvinyl alcohol
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/13—Physical properties anti-allergenic or anti-bacterial
Abstract
The invention provides a preparation method of a zinc oxide nanofiber membrane, which comprises the following steps: carrying out mechanical-chemical modification on nano zinc oxide, a small molecular reagent and water to obtain a nano zinc oxide colloidal solution; mixing polyvinyl alcohol with the nano zinc oxide colloidal solution to obtain a polyvinyl alcohol/zinc oxide solution; and (3) carrying out electrostatic spinning on the polyvinyl alcohol/zinc oxide solution to obtain the zinc oxide nanofiber membrane. The PVA is used as a base material and is compounded with the modified nano zinc oxide dispersion liquid to prepare a uniform PVA/nano ZnO solution, and the nano fiber film is prepared by adopting an electrostatic spinning method; and (3) testing the antibacterial performance of the obtained film, wherein when the concentration of the added nano ZnO is 10000ppm, the antibacterial rate of the nanofiber film on escherichia coli reaches 99.98%, and the antibacterial rate on staphylococcus aureus reaches 99.99%.
Description
Technical Field
The invention relates to the technical field of fiber membranes, in particular to a preparation method of a zinc oxide nanofiber membrane.
Background
In recent years, nanofibers have been extensively studied due to unique properties and applications, their high surface area to volume ratio, large length to diameter ratio, and light weight make them suitable for many applications such as filtration, drug delivery, tissue engineering, sensors, protective clothing, food processing, and microelectronics, among others. Currently, there are many methods for producing nanofibers, such as self-assembly, phase separation, and electrospinning, among which electrospinning is a common method for producing nanofibers with diameters ranging from a few nanometers to several micrometers, which is simpler and less costly.
Nano zinc oxide (nano zno) has good biocompatibility, and thus has wide applications in the fields of industry, medicine and the like, such as biosensors, bio-imaging devices, ultraviolet protective materials and the like. The nano zinc oxide has good biocompatibility and broad-spectrum antibacterial performance, but the commercially available nano zinc oxide is easy to agglomerate, so that the antibacterial effect of the nano zinc oxide is influenced. PVA is a non-toxic, biodegradable and biocompatible semi-crystalline polymer, which has received extensive attention in the synthesis of novel functionalized nanomaterials and is low in cost and high in yield.
Heretofore, researchers have blended PVA with ZnO for electrostatic spinning for novel adsorbents for nanostructure binding; or by utilizing the excellent photocatalytic efficiency and nontoxicity of zinc oxide, a nanofiber-based photocatalytic self-cleaning surface nanocomposite is developed and applied to removing environmental pollutants, but the antibacterial effect of ZnO is not exerted.
Disclosure of Invention
The invention aims to provide a preparation method of a zinc oxide nanofiber membrane, and the zinc oxide nanofiber membrane provided by the invention has smooth fibers, uniform dispersion of nano zinc oxide in the fibers, and good antibacterial effect and biodegradability.
In view of the above, the present application provides a method for preparing a zinc oxide nanofiber membrane, comprising the following steps:
carrying out mechanical-chemical modification on nano zinc oxide, a small molecular reagent and water to obtain a nano zinc oxide colloidal solution;
mixing polyvinyl alcohol with the nano zinc oxide colloidal solution to obtain a polyvinyl alcohol/zinc oxide solution;
and (3) carrying out electrostatic spinning on the polyvinyl alcohol/zinc oxide solution to obtain the zinc oxide nanofiber membrane.
Preferably, the particle size of the nano zinc oxide is 60-100 nm.
Preferably, the small molecule reagent is selected from one or more of L-cysteine, chitosan, mangnolia officinalis, polyvinylpyrrolidone and carboxymethyl chitosan, and the mass ratio of the nano zinc oxide to the small molecule reagent is (1-10): 1.
preferably, the mass ratio of the nano zinc oxide to the water is 1: (100 to 10000).
Preferably, the mechanical-chemical modification is ball milling.
Preferably, the ball milling time is 1-8 h, the rotating speed is 200-800 r/min, and the temperature is 20-40 ℃.
Preferably, the ball-milled medium is zirconia beads with the particle size of 0.1-0.5 mm, and the mass ratio of the nano zinc oxide to the ball-milled medium is 1: (100 to 20000).
Preferably, the concentration of the polyvinyl alcohol in the polyvinyl alcohol/zinc oxide solution is 10-20 wt%.
Preferably, the advancing speed of the electrostatic spinning is 0.3-0.9 mL/min, and the voltage is 10-25 KV.
Preferably, the average diameter of the zinc oxide nanocellulose in the zinc oxide nanofiber membrane is 600-700 nm.
The application provides a preparation method of a zinc oxide nanofiber membrane, which comprises the steps of firstly carrying out mechanical-chemical modification on nano zinc oxide, a small molecular reagent and water to obtain a nano zinc oxide colloidal solution, then mixing polyvinyl alcohol and the nano zinc oxide colloidal solution to obtain a polyvinyl alcohol/zinc oxide solution, and finally carrying out electrostatic spinning on the polyvinyl alcohol/zinc oxide colloidal solution to obtain the zinc oxide nanofiber membrane. In the process of preparing the zinc oxide nanofiber membrane, the modified nano zinc oxide has excellent antibacterial performance and good dispersibility by grafting the nano zinc oxide with a small molecular reagent; experimental results show that the Minimum Inhibitory Concentration (MIC) of the zinc oxide nanofiber membrane prepared by the method is 4-8 ppm for staphylococcus aureus and 8-16 ppm for escherichia coli, and is about 200 times lower than that of commercially available nano zinc oxide, namely the antibacterial performance of the zinc oxide nanofiber membrane is about 200 times higher than that of the commercially available nano zinc oxide.
Drawings
FIG. 1 is a macroscopic photograph of PVA/nano ZnO nanofiber membrane prepared in example 1 of the present invention;
FIG. 2 is an SEM picture and an EDS energy spectrum analysis picture of the PVA/nano ZnO nanofiber membrane prepared in example 1 of the present invention;
FIG. 3 is a diameter distribution statistical chart of PVA/nano ZnO nanofiber membranes prepared in example 1 of the present invention;
FIG. 4 is a microscope photograph of PVA/nano ZnO nanofiber films prepared in examples of the present invention and comparative examples;
FIG. 5 is a photomicrograph of the zinc oxide of the present invention with an excess amount added.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In view of the antibacterial requirement of the zinc oxide nanofiber membrane in the prior art, the preparation method of the biodegradable nanofiber membrane with the antibacterial effect comprises the steps of dissolving polyvinyl alcohol (PVA) in a chemically modified nano zinc oxide colloidal solution to obtain a monodisperse and uniform mixed solution, and finally preparing the nano fiber membrane by using an electrostatic spinning method. Specifically, the embodiment of the invention discloses a preparation method of a zinc oxide nanofiber membrane, which comprises the following steps:
carrying out mechanical-chemical modification on nano zinc oxide, a small molecular reagent and water to obtain a nano zinc oxide colloidal solution;
mixing polyvinyl alcohol with the nano zinc oxide colloidal solution to obtain a polyvinyl alcohol/zinc oxide solution;
and (3) carrying out electrostatic spinning on the polyvinyl alcohol/zinc oxide solution to obtain the zinc oxide nanofiber membrane.
According to the invention, in the process of preparing the nano zinc oxide colloidal solution, firstly, the nano zinc oxide, the small molecular reagent and the water are subjected to mechanical-chemical modification; in the process, the mechanical-chemical modification is a ball milling mode, namely mixing nano zinc oxide, a small molecular reagent, water and a ball milling medium, carrying out ball milling, and removing the ball milling medium to obtain a monodisperse and uniform nano zinc oxide aqueous antibacterial colloidal solution grafted by the small molecular reagent; more specifically, the ball milling may be performed in a planetary ball mill. After the ball milling is finished, standing still for 10-30 min, then taking out the ball milling tank, and removing the ball milling medium.
In the ball milling process, the ball milling time is 1-8 h; more preferably, the ball milling time is 2h to 8 h. Experimental research shows that the dispersion state of the nano zinc oxide in water can be influenced by the ball milling time, and more uniform and transparent colloid can be obtained by controlling the ball milling time, so that a better antibacterial effect is obtained. The medium for ball milling is zirconia beads with the particle size of 0.1 mm-0.5 mm; preferably, the medium for ball milling is zirconia beads, and the particle size is 0.1 mm-0.2 mm. The mass ratio of the nano zinc oxide to the ball-milling medium is (1:100) - (1: 20000). The temperature of the ball milling is 20-40 ℃. The ball milling is carried out under normal pressure, the pH value of the liquid is kept between 6.5 and 6.8 during ball milling, and the experiment is not seriously affected basically due to the change of external conditions. Preferably, the rotation speed of the ball mill is 200 r/min-800 r/min. More preferably, the rotation speed of the ball mill is 700 r/min. Compared with the method of mixing the nano zinc oxide, the small molecular reagent and the water and then stirring or ultrasonically stirring, the method adds a ball milling process to mix the nano zinc oxide, the small molecular reagent and the water, effectively grafts the small molecular reagent on the nano zinc oxide, obviously improves the dispersibility of the nano zinc oxide, and prepares a colloid which is more uniform and transparent and has more excellent antibacterial performance.
In the application, the mass ratio of the nano zinc oxide to the small molecule reagent is (10:1) - (1: 1); more specifically, the mass ratio of the nano zinc oxide to the small molecule reagent includes, but is not limited to, 1:1, 2:1, 3:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10: 1; more preferably, the mass ratio of the nano zinc oxide to the small molecule reagent is (1:1) - (4: 1); if the content of the nano zinc oxide is too low, no antibacterial effect is achieved, and if the content of the nano zinc oxide is too high, no film is formed, as shown in fig. 5, if the nano zinc oxide is excessively added, a large number of beads are formed, and a smooth fiber film cannot be formed. The small molecule agent may be selected from one or more of L-cysteine, chitosan, Magnolia officinalis, polyvinylpyrrolidone and carboxymethyl chitosan, and in a specific embodiment, the small molecule agent is selected from L-cysteine. The mass ratio of the nano zinc oxide to the water is (1:100) - (1: 10000); more specifically, the mass ratio of the nano zinc oxide to the water is (1: 200) - (1: 10000); it is understood that the mass ratio of the nano zinc oxide to the water includes, but is not limited to: 1:200, 1:500, 1:1000, 1:1500, 1:2000, 1:2500, 1:3000, 1:3500, 1:4000, 1:4500, 1:5000, 1:6000, 1:7000, 1:8000, 1:9000 or 1: 10000.
Preferably, the water is deionized water, can be prepared by a laboratory, and has a pH of 6.5-6.8. Preferably, the particle size of the nano zinc oxide is 60 nm-100 nm. The nano zinc oxide can be common nano zinc oxide sold in the market, the purity of the nano zinc oxide is 99.99%, and the nano zinc oxide is in an aggregate.
In the optimization process, the antibacterial performance of the micromolecule L-cysteine coated nano zinc oxide solution with different purities is found to be different. Preferably, the purity of the L-cysteine is BR grade.
And removing the ball milling medium after ball milling to obtain the micromolecule reagent grafted nano zinc oxide waterborne antibacterial colloid.
According to the application, polyvinyl alcohol (PVA) and nano zinc oxide colloidal solution are mixed to obtain polyvinyl alcohol/zinc oxide solution; the PVA is commercially available PVA particles, is dissolved in the nano zinc oxide colloidal solution, is heated in a water bath at 50-100 ℃ for 3-5 hours at the rotating speed of 700-1000 rpm to prepare a uniform PVA/nano zinc oxide solution with the PVA concentration of 10-20 wt%, and is kept stand for 24 hours to remove bubbles for later use.
Carrying out electrostatic spinning on the polyvinyl alcohol/zinc oxide solution to obtain a zinc oxide nano cellulose membrane; in the process, the electrostatic spinning machine is preheated for 1 hour at the set temperature of 30-40 ℃ and the humidity of 30-40 degrees. Then filling the PVA/nano zinc oxide solution into a 10mL injector, placing the injector on a propeller for fixing, selecting a 20mm needle head to be connected with a high-voltage power supply, setting the left and right amplitude of the propeller to be 5cm, setting the propelling speed to be 0.3-0.9 mL/min, setting the voltage to be 10-25 KV, setting the receiving distance to be 15cm, and selecting a roller as a receiving device.
In a preferred embodiment, it was found during the optimization that the fiber diameter of the spun film is related to the concentration of PVA added, the speed of advancement, the voltage, and the like. Adjusting the PVA concentration to be 10-20 wt%, keeping other conditions unchanged, and gradually thickening the spinning fiber; adjusting the advancing speed to be 0.3-0.9 mL/min, keeping other conditions unchanged, and gradually thickening the spinning fibers; and (3) adjusting the spinning voltage to be 10-25 KV, keeping other conditions unchanged, and gradually thinning the spinning fibers.
PVA is selected as a base material and is compounded with the modified nano zinc oxide dispersion liquid to prepare a uniform PVA/nano ZnO solution, and a nano fiber film is prepared by adopting an electrostatic spinning method; and (3) testing the antibacterial performance of the obtained film, wherein when the concentration of the added nano ZnO is 10000ppm, the antibacterial rate of the nanofiber film on escherichia coli reaches 99.98%, and the antibacterial rate on staphylococcus aureus reaches 99.99%.
The preparation method provided by the invention is simple, the reagent is cheap and environment-friendly, and the obtained PVA/nano zinc oxide nano fiber membrane is dissolved in water and is easy to treat; the PVA/nano zinc oxide nano fiber membrane has smooth fiber, nano zinc oxide particles are uniformly dispersed in the fiber, the PVA/nano zinc oxide nano fiber membrane has good antibacterial effect and is biodegradable, and the diameter of the fiber of the spinning membrane is adjustable. The nano zinc oxide film prepared by the method has application potential in the fields of masks, protective clothing, masks, dressings, tissue engineering scaffolds, drug carriers and the like.
For further understanding of the present invention, the following examples are provided to illustrate the preparation method of the nano zinc oxide cellulose thin film provided by the present invention in detail, and the scope of the present invention is not limited by the following examples.
Example 1
a. Weighing 0.5g of commercially available zinc oxide particles and 0.1g of cysteine in 50mL of deionized water, adding 100g of zirconia beads, placing in a ball mill at 400rpm, and ball-milling at 37 ℃ for 3 hours to obtain a nano zinc oxide colloidal solution with the zinc oxide concentration of 10000 ppm;
b. weighing 1.5g of PVA particles, dissolving the PVA particles in 10g of nano zinc oxide colloidal solution, placing the solution on a magnetic stirrer, heating the solution in a water bath at the temperature of 80 ℃ until the PVA particles are completely dissolved, preparing a PVA/nano ZnO solution with the concentration of 15 wt%, and standing for 24 hours to remove bubbles;
c. the prepared PVA/nano ZnO solution is filled into a 10mL injector and fixed on a propeller of an electrostatic spinning machine, a needle head with the diameter of 20mm is selected to be connected with a high-voltage power supply, the left and right amplitudes of the propeller are set to be 5cm, the propelling speed is set to be 0.5mL/min, the voltage is 15KV, the receiving distance is 15cm, and a roller is selected as a receiving device; the PVA/nano ZnO nanofiber membrane is obtained, the physical photograph is shown in figure 1, and as can be seen from figure 1, the PVA/nano ZnO nanofiber membrane obtained through electrostatic spinning is light and thin in texture, easy to process and cut and uniform in color, which indicates that nano zinc oxide is uniformly dispersed in fibers;
d. the obtained PVA/nano ZnO nanofiber membrane is characterized by a scanning electron microscope, as shown in figure 2, as can be seen from figure 2, the PVA/nano ZnO nanofiber is flat and smooth, the fibers are uniformly distributed, and no bulge, no node and the like are seen; in addition, the uniform distribution of Zn element in the fiber can be seen through EDS energy spectrum analysis pictures, and the agglomeration phenomenon does not occur, which shows that the nano zinc oxide can be well dispersed in a water phase system and form stable colloidal solution and can be successfully loaded into the PVA fiber through an electrostatic spinning method; fig. 3 is a diameter distribution statistical chart of the PVA/nano zno nanofiber membrane prepared in this example, and as can be seen from fig. 3, the average diameter of the nanofibers in the PVA/nano zno nanofiber membrane of the present application is about 630 nm.
e. The obtained PVA/nano zno nanofiber membrane was subjected to an antibacterial test as in the second row of table 1.
Example 2
a. Weighing 0.5g of commercially available zinc oxide particles and 0.1g of cysteine in 50mL of deionized water, adding 100g of zirconia beads, placing the mixture in a ball mill at 400rpm for ball milling at 37 ℃ for 3 hours to obtain a nano zinc oxide colloidal solution with the zinc oxide concentration of 10000ppm, and uniformly mixing 7.5mL of 10000ppm of nano zinc oxide colloidal solution with 2.5mL of deionized water to obtain a nano zinc oxide colloidal solution with the zinc oxide concentration of 7500 ppm;
b. weighing 1.5g of PVA particles, dissolving the PVA particles in 10g of 7500ppm nano zinc oxide colloidal solution, placing the solution on a magnetic stirrer, heating the solution in a water bath at 80 ℃ until the PVA particles are completely dissolved, preparing a PVA/nano ZnO solution with the concentration of 15 wt%, and standing for 24h to remove bubbles;
c. the prepared PVA/nano ZnO solution is filled into a 10mL injector and fixed on a propeller of an electrostatic spinning machine, a needle head with the diameter of 20mm is selected to be connected with a high-voltage power supply, the left and right amplitudes of the propeller are set to be 5cm, the propelling speed is set to be 0.5mL/min, the voltage is 15KV, the receiving distance is 15cm, and a roller is selected as a receiving device; obtaining a PVA/nano ZnO nanofiber membrane;
d. the obtained PVA/nano zno nanofiber membrane was subjected to an antibacterial test as in the third row of table 1.
Example 3
a. Weighing 0.5g of commercially available zinc oxide particles and 0.1g of cysteine in 50mL of deionized water, adding 100g of zirconia beads, placing the mixture in a ball mill at 400rpm for ball milling at 37 ℃ for 3 hours to obtain a nano zinc oxide colloidal solution with the zinc oxide concentration of 10000ppm, and uniformly mixing 5mL of 10000ppm of nano zinc oxide colloidal solution with 5mL of deionized water to obtain a nano zinc oxide colloidal solution with the zinc oxide colloidal solution concentration of 5000 ppm;
b. weighing 1.5g of PVA particles, dissolving the PVA particles in 10g of 5000ppm nano zinc oxide colloidal solution, placing the solution on a magnetic stirrer, heating the solution in a water bath at 80 ℃ until the PVA particles are completely dissolved, preparing a PVA/nano ZnO solution with the concentration of 15 wt%, and standing for 24 hours to remove bubbles;
c. the prepared PVA/nano ZnO solution is filled into a 10mL injector and fixed on a propeller of an electrostatic spinning machine, a needle head with the diameter of 20mm is selected to be connected with a high-voltage power supply, the left and right amplitudes of the propeller are set to be 5cm, the propelling speed is set to be 0.5mL/min, the voltage is 15KV, the receiving distance is 15cm, and a roller is selected as a receiving device; obtaining a PVA/nano ZnO nanofiber membrane;
d. the obtained PVA/nano zno nanofiber membrane was subjected to an antibacterial test as in the fourth row of table 1.
Example 4
a. Weighing 0.5g of commercially available zinc oxide particles and 0.1g of cysteine, adding 100g of zirconia beads into 50mL of deionized water, placing the mixture in a ball mill at 400rpm, and carrying out ball milling at 37 ℃ for 3 hours to obtain a nano zinc oxide colloidal solution with the zinc oxide concentration of 10000ppm, and uniformly mixing 2.5mL of the nano zinc oxide colloidal solution with the zinc oxide colloidal concentration of 2500ppm with 7.5mL of deionized water;
b. weighing 1.5g of PVA particles, dissolving the PVA particles in 10g of 2500ppm nano zinc oxide colloidal solution, placing the solution on a magnetic stirrer, heating the solution in a water bath at 80 ℃ until the PVA particles are completely dissolved, preparing a PVA/nano ZnO solution with the concentration of 15 wt%, and standing for 24 hours to remove bubbles;
c. the prepared PVA/nano ZnO solution is filled into a 10mL injector and fixed on a propeller of an electrostatic spinning machine, a needle head with the diameter of 20mm is selected to be connected with a high-voltage power supply, the left and right amplitudes of the propeller are set to be 5cm, the propelling speed is set to be 0.5mL/min, the voltage is 15KV, the receiving distance is 15cm, and a roller is selected as a receiving device; obtaining a PVA/nano ZnO nanofiber membrane;
d. the obtained PVA/nano zno nanofiber membrane was subjected to an antibacterial test as in the fifth row of table 1.
Example 5
a. Weighing 0.5g of commercially available zinc oxide particles and 0.1g of cysteine in 50mL of deionized water, adding 100g of zirconia beads, placing in a ball mill at 400rpm, and ball-milling at 37 ℃ for 3 hours to obtain a nano zinc oxide colloidal solution with the zinc oxide concentration of 10000 ppm;
b. weighing 2.0g of PVA particles, dissolving the PVA particles in 10g of nano zinc oxide colloidal solution, placing the solution on a magnetic stirrer, heating the solution in a water bath at the temperature of 80 ℃ until the PVA particles are completely dissolved, preparing a PVA/nano ZnO solution with the concentration of 20 wt%, and standing for 24 hours to remove bubbles;
c. the prepared PVA/nano ZnO solution is filled into a 10mL injector and fixed on a propeller of an electrostatic spinning machine, a needle head with the diameter of 20mm is selected to be connected with a high-voltage power supply, the left and right amplitudes of the propeller are set to be 5cm, the propelling speed is set to be 0.9mL/min, the voltage is 10KV, the receiving distance is 15cm, and a roller is selected as a receiving device;
d. the obtained PVA/nano zno nanofiber film was characterized by optical microscopy as in fig. 4 a.
Example 6
a. Weighing 0.5g of commercially available zinc oxide particles and 0.1g of cysteine in 50mL of deionized water, adding 100g of zirconia beads, placing in a ball mill at 400rpm, and ball-milling at 37 ℃ for 3 hours to obtain a nano zinc oxide colloidal solution with the zinc oxide concentration of 10000 ppm;
b. weighing 1.0g of PVA particles, dissolving the PVA particles in 10mL of nano zinc oxide colloidal solution, placing the solution on a magnetic stirrer, heating the solution in a water bath at 80 ℃ until the PVA particles are completely dissolved, preparing 10 wt% PVA/nano ZnO solution, and standing the solution for 24 hours to remove bubbles;
c. the prepared PVA/nano ZnO solution is filled into a 10mL injector and fixed on a propeller of an electrostatic spinning machine, a needle head with the diameter of 20mm is selected to be connected with a high-voltage power supply, the left and right amplitudes of the propeller are set to be 5cm, the propelling speed is set to be 0.9mL/min, the voltage is 25KV, the receiving distance is 15cm, and a roller is selected as a receiving device;
d. the obtained PVA/nano zno nanofiber film was characterized by optical microscopy as shown in fig. 4 b.
Comparative example 1
a. Weighing 1.5g of PVA particles, dissolving in 10mL of deionized water, placing on a magnetic stirrer, heating in a water bath at 80 ℃ until the PVA particles are completely dissolved to prepare a 15 wt% PVA solution, and standing for 24h to remove bubbles.
b. The prepared PVA solution is filled into a 10mL injector and fixed on a propeller of an electrostatic spinning machine, a 20mm needle head is selected to be connected with a high-voltage power supply, the left and right amplitude of the propeller is set to be 5cm, the propelling speed is set to be 0.3mL/min, the voltage is set to be 15KV, the receiving distance is 15cm, and a roller is selected as a receiving device.
c. The PVA nanofiber membrane obtained was subjected to line light microscopy characterization as shown in fig. 4 c.
d. The obtained PVA nanofiber membranes were subjected to an antibacterial test as shown in table 1.
TABLE 1 data table of antibacterial properties of nanofiber membranes prepared in examples and comparative examples
| Sample name | Test items | Staphylococcus aureus | Escherichia coli |
| PVA | Rate of inhibition of bacteria | 0 | 0 |
| PVA/nanoZnO-10000ppm | Rate of inhibition of bacteria | 99.99％ | 99.98％ |
| PVA/nanoZnO-7500ppm | Rate of inhibition of bacteria | 99.99％ | 99.96％ |
| PVA/nanoZnO-5000ppm | Rate of inhibition of bacteria | 99.99％ | 99.95％ |
| PVA/nanoZnO-2500ppm | Rate of inhibition of bacteria | 99.99％ | 99.86％ |
And (3) carrying out antibacterial performance detection on the PVA/nano ZnO nanofiber membrane prepared after adding different ppm of nano ZnO. As can be seen from the table, the pure PVA fiber membrane has no bacteriostatic property on Escherichia coli, and the bacteriostatic rate is 0; when the added nano ZnO is 10000ppm, the inhibition rate to escherichia coli is 99.98%, and the inhibition rate to staphylococcus aureus is 99.99%; when 7500ppm of nano ZnO is added, the inhibition rate to colon bacillus is 99.96 percent, and the inhibition rate to staphylococcus aureus is 99.99 percent; when the amount of added nano ZnO is 5000ppm, the inhibition rate of the nano ZnO on escherichia coli is 99.95 percent, and the inhibition rate on staphylococcus aureus is 99.99 percent; when the amount of the added nano ZnO is 2500ppm, the inhibition rate of the nano ZnO on escherichia coli is 99.86%, and the inhibition rate on staphylococcus aureus is 99.99%. The result shows that the nano zinc oxide colloidal solution developed in a laboratory and PVA are prepared into a film through an electrostatic spinning method, and then the film has an inhibition effect on escherichia coli and staphylococcus aureus, so that the nano fiber film with an antibacterial effect is successfully prepared.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of a zinc oxide nanofiber membrane comprises the following steps:
carrying out mechanical-chemical modification on nano zinc oxide, a small molecular reagent and water to obtain a nano zinc oxide colloidal solution;
mixing polyvinyl alcohol with the nano zinc oxide colloidal solution to obtain a polyvinyl alcohol/zinc oxide solution;
and (3) carrying out electrostatic spinning on the polyvinyl alcohol/zinc oxide solution to obtain the zinc oxide nanofiber membrane.
2. The preparation method according to claim 1, wherein the nano zinc oxide has a particle size of 60 to 100 nm.
3. The preparation method according to claim 1 or 2, wherein the small molecule reagent is selected from one or more of L-cysteine, chitosan, magnolia officinalis, polyvinylpyrrolidone and carboxymethyl chitosan, and the mass ratio of the nano zinc oxide to the small molecule reagent is (1-10): 1.
4. the preparation method according to claim 1 or 2, wherein the mass ratio of the nano zinc oxide to the water is 1: (100 to 10000).
5. The method of claim 1, wherein the mechanical-chemical modification is by ball milling.
6. The preparation method of claim 5, wherein the ball milling time is 1-8 h, the rotation speed is 200-800 r/min, and the temperature is 20-40 ℃.
7. The preparation method of claim 5, wherein the ball-milled medium is zirconia beads with the particle size of 0.1-0.5 mm, and the mass ratio of the nano-zinc oxide to the ball-milled medium is 1: (100 to 20000).
8. The method according to claim 1, wherein the concentration of the polyvinyl alcohol in the polyvinyl alcohol/zinc oxide solution is 10 to 20 wt%.
9. The method according to claim 1, wherein the electrostatic spinning is carried out at a forwarding speed of 0.3 to 0.9mL/min and a voltage of 10 to 25 KV.
10. The preparation method of claim 1, wherein the average diameter of the zinc oxide nanocellulose in the zinc oxide nanofiber membrane is 600-700 nm.
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