CN114232344B - PM2.5 filtering SPAP film with antibacterial and antifouling functions and preparation method thereof - Google Patents
PM2.5 filtering SPAP film with antibacterial and antifouling functions and preparation method thereof Download PDFInfo
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Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/10—Animal fibres
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/01—Stain or soil resistance
Abstract
The invention discloses a preparation method of a PM2.5 filtering SPAP film with an antibacterial and antifouling function, which comprises the following steps: degumming and cleaning silkworm cocoons, drying to obtain silk fibroin, and dissolving the silk fibroin in a lithium bromide solution; dialyzing the silk fibroin solution after complete dissolution, and freezing after suction filtration to obtain freeze-dried silk fibroin; adding silver nitrate solution into polyurethane solution, and changing the mixed PU-AgNPs solution from transparent to brown yellow; preparing an SFNFs film from the SF solution obtained after dissolving the freeze-dried silk fibroin through electrostatic spinning; carrying out electrostatic spinning deposition on the PU-AgNPs solution on the surface of the SFNFs film to obtain PUNF-AgNPs; the PU solution is electrostatically sprayed on the PUNF-AgNPs layer, so that a three-layer composite SPAP film is obtained, the invention adopts an alternate electrospinning-electrospraying technology, the hydrophilic SFNFs layer has good air permeability and skin affinity, can be used as a friendly biological interface, the PUNSs layer has inherent waterproofness and high surface roughness, is used as a super-hydrophobic antifouling physical barrier, shields invasive PM2.5 threat, and is inserted with an antibacterial filter PUNF-AgNPs in the middle, thus being applicable to secondary filtration and antibacterial.
Description
Technical Field
The invention relates to the field of antibacterial protection or air filtration, in particular to a preparation method of a PM2.5 filtration SPAP membrane with antibacterial and antifouling functions.
Background
With the accelerated development of industrialization, air pollution is increasingly serious, PM2.5 (particles with the diameter less than or equal to 2.5 μm) in the air can enter bronchi to alveoli, and can be deposited in alveoli or absorbed into blood and lymph fluid, and the concentration of the PM2.5 is increased to cause great damage to respiratory system, cardiovascular system, nervous system and the like of human beings. Meanwhile, microorganisms, bacteria and infectious viruses are often attached to air particulate matters, and one of the modes for effectively blocking the transmission of the microorganisms, the bacteria and the infectious viruses is to filter and remove the air particulate matters. Air filtration materials have therefore become a popular focus of attention to protect humans from air pollution.
The traditional air filter material has the defects of weak anti-fouling capability, very small filtering effect on tiny particles, poor protection on viruses and bacteria and the like, and is imperative to develop the filter material with high added value such as antibacterial function and the like in order to make up the defects of the traditional filter material.
Disclosure of Invention
The invention overcomes the defects of the prior art, utilizes alternate electrostatic spinning-electrostatic spraying, takes a Silk Fibroin Nanofiber Substrate (SFNFs) and a polyurethane microsphere layer (PUNSs) as base double-layer films, and deposits a layer of PU nanofiber layer (PUNF-AgNPs) decorated with silver nano particles between the two layers to prepare the SFNFs/PUNF-AgNPs/PUNSs (SPAP) multi-layer composite films, thereby obtaining an air filter material with excellent PM2.5 filtering and antibacterial properties. And provides a PM2.5 filtering SPAP film with antibacterial and antifouling functions and a preparation method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme: the preparation method of the PM2.5 filtering SPAP film with the antibacterial and antifouling functions comprises the following steps: s1: degumming and cleaning silkworm cocoons, drying to obtain silk fibroin, and dissolving the silk fibroin in a lithium bromide solution; dialyzing the silk fibroin solution after complete dissolution, and freezing after suction filtration to obtain freeze-dried silk fibroin; s2: adding silver nitrate solution into polyurethane solution, stirring until the mixed PU-AgNPs solution turns into brown from transparent; s3: preparing an SFNFs film from the SF solution obtained after dissolving the freeze-dried silk fibroin through electrostatic spinning; s4: carrying out electrostatic spinning deposition on the PU-AgNPs solution on the surface of the SFNFs film to obtain PUNF-AgNPs; s5: and (3) carrying out electrostatic spraying on the PU solution on the PUNF-AgNPs layer, thereby obtaining the three-layer composite SPAP film.
In a preferred embodiment of the invention, the SPAP film is treated with ethanol/water vapor to improve the water solubility of SFNFs.
In a preferred embodiment of the invention, in step S1, the molar mass of the lithium bromide solution is 9.3mol/L.
In a preferred embodiment of the present invention, in step S1, the silk fibroin is dissolved in a lithium bromide solution at 60 ℃.
In a preferred embodiment of the present invention, in step S1, the regenerated silk fibroin solution after suction filtration is placed into a refrigerator at-20 ℃ for pre-freezing for at least 12 hours, and then freeze-dried for at least 48 hours to obtain freeze-dried silk fibroin.
In a preferred embodiment of the present invention, in step S3, the lyophilized silk fibroin is dissolved in formic acid solution, and 12wt% SF solution is prepared by magnetic stirring at room temperature.
In a preferred embodiment of the present invention, in step S2, silver nitrate is dissolved in DMF solution, and the solution is stirred to prepare a silver nitrate solution with a mass fraction of 1%.
In a preferred embodiment of the present invention, in step S2, polyurethane particles are stirred at 80 ℃ to prepare a polyurethane solution with a mass fraction of 20%.
In a preferred embodiment of the present invention, in step S2, the silver nitrate solution is added dropwise into the polyurethane solution, stirred at room temperature, heated to 80 ℃ and stirred, so as to reduce nano silver.
In a preferred embodiment of the present invention, in step S5, polyurethane particles are dissolved in DMF solution to prepare a PU solution with a mass fraction of 5%.
The invention also provides a PM2.5 filtering SPAP film with an antibacterial and antifouling function, which is a three-layer composite film, and comprises a Silk Fibroin Nanofiber Substrate (SFNFs) and a polyurethane micro-nanosphere layer (PUNSs), wherein a PU nanofiber layer (PUNF-AgNPs) decorated with silver nano particles is deposited between the Silk Fibroin Nanofiber Substrate (SFNFs) and the polyurethane micro-nanosphere layer (PUNSs).
The invention solves the defects existing in the background technology, and has the following beneficial effects:
according to the invention, SF, PU, agNPs is taken as a material, an alternate electrospinning-electrospraying technology is adopted, and the nanofiber material prepared by the electrospinning technology has small fiber diameter, large specific surface area and high porosity, and is assembled into a sandwich structure, namely an SFNFs/PUNF-AgNPs/PUNSs (SPAP) film, and the sandwich structure is specifically:
firstly, preparing an SF nanofiber (SFNFs) bottom layer by electrospinning, wherein the hydrophilic SFNFs bottom layer has good air permeability and skin affinity, and can be used as a friendly biological interface.
Then, a layer of polyurethane nanofibers (PUNFs) modified by AgNPs is electrodeposited on the bottom layer as a middle layer, wherein the AgNPs are generated by in-situ reduction, and an antibacterial filter PUNF-AgNPs is inserted in the middle layer, so that the polyurethane nanofibers can be used for secondary filtration and antibacterial effect.
Finally, a layer of polyurethane micro-nanospheres (PUNSs) is sprayed electrostatically to assemble a clamp SFNFs/PUNF-AgNPs/PUNSs (SPAP) film, and the PUNSs layer has inherent waterproofness and high surface roughness, is used as a super-hydrophobic antifouling physical barrier, and shields invasive PM2.5 threat.
Therefore, the PM2.5 filter material with the antibacterial and antifouling functions is formed, and can be applied to the aspect of wearable protection.
The invention adopts an electrostatic spinning method to continuously prepare the nanofiber, so that the nanofiber has the advantages of smaller fiber diameter, excellent surface performance, adjustable network geometry and the like. These excellent properties ensure excellent filtration properties of electrospun nanofibers.
Furthermore, the invention utilizes the advantage of better viscosity of the structural layer obtained by electrostatic spinning, the nanofiber can be firmly combined with the base layer, and the limit uniformity of the electrostatic spinning output is better, so that the uniform antibacterial and PM2.5 filtering performances can be provided in a breadth range, and on the other hand, the electrostatic spinning nanofiber can provide higher efficiency volatility, so that a film can not be formed on the surface of a substrate corresponding to the electrostatic spinning, and the mesh-shaped fiber structure capable of realizing the filtering function is ensured to be provided.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art;
FIG. 1 is a TEM image of a nano-Ag particle according to a preferred embodiment of the present invention;
FIG. 2 is a profile of the topography and diameter of various layers of a SPAP film of a preferred embodiment of the present invention;
FIG. 3 is an infrared spectrum of the various layers of the SPAP film of the preferred embodiment of the present invention;
FIG. 4 is a graph of the water vapor transmission rate of a SPAP film of a preferred embodiment of the present invention;
fig. 5 is a graph of PM2.5 filtration performance of a SPAP membrane of a preferred embodiment of the invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
The electrostatic spinning mainly uses the repulsive force of electric charges on the surface of liquid drops to stretch spinning solution into nano fibers, and an electrostatic spinning device mainly comprises a high-voltage power supply, an injection device and a receiving device. The principle of electrostatic spinning is as follows: high pressure is applied to the droplets at the extrusion port of the injection device, creating a jet of charged polymer solution. When the electric field reaches a threshold, a repulsive force of sufficient charge is generated to overcome the surface tension of the droplet, thereby forming a jet. The jet is stretched and the solvent volatilized, and is solidified to form nano fiber which is deposited on the receiving device.
In the electrostatic spinning process, the spinning solution is solidified layer by layer to form fibers which are deposited on the receiving plate, so that a fiber film with a net-shaped structure is formed. The fiber membrane of the structure has small fiber diameter, good continuity and high porosity. However, in the actual operation process of electrostatic spinning, the structure and morphology of the fiber are affected by the changes of spinning parameters and conditions, mainly including solution concentration, surface tension, applied voltage, injection rate, receiving distance, temperature, humidity and the like. These factors together affect the structure of the fiber and the final deposition morphology.
The preparation method of the PM2.5 filtering SPAP film with the antibacterial and antifouling functions comprises the following steps of: silkworm cocoons; anhydrous sodium carbonate (Na 2CO 3), lithium bromide (LiBr, 99%); dialysis tubing (mw=8000-14000); formic acid (98%); n, N-dimethylformamide (DMF, 99.9%); thermoplastic polyurethane (PU, mw=70000); silver nitrate (AgNO 3). All reagents were analytical grade.
The method specifically comprises the following steps:
degumming and dissolving: cutting cocoon into small pieces, adding carbonic acidBoiling in sodium solution, and washing with deionized water after 30 min. Repeating the steps for 3 times, washing the degummed cocoons for 3 times with deionized water, putting into a 40 ℃ oven, and drying to obtain the silk fibroin. Preparing lithium bromide solution, preheatingFor a certain timeAfter that, the silk fibroin was put into a certain amount of lithium bromide solution and dissolved in an oven at 60 ℃.
Dialysis and freeze drying: after complete dissolution, cooling, transferring the silk fibroin solution into a dialysis bag (8 k-14k Da), penetrating for 3d by deionized water, replacing the deionized water every 4h, and after dialysis, carrying out suction filtration. And (3) pre-freezing the regenerated silk fibroin solution subjected to suction filtration in a refrigerator at the temperature of minus 20 ℃ for 12 hours, and then freeze-drying for 48 hours to obtain freeze-dried silk fibroin, and storing the freeze-dried silk fibroin in the refrigerator at the temperature of 4 ℃ for use.
Preparation of spinning solution:
first, a certain amount of lyophilized SF was dissolved in a formic acid solution, and magnetically stirred at room temperature for 12 hours to prepare SF solution for preparing SF nanofiber membranes (SFNFs) (SPAP underlayer).
Dissolving 0.1g of silver nitrate in DMF (dimethyl formamide) solution, stirring and dissolving, and performing ultrasonic treatment for 30min to prepare a silver nitrate solution with the mass fraction of 1%; dissolving polyurethane particles with certain mass in DMF solution, and stirring for 4 hours to prepare polyurethane solution with mass fraction of 20%; and then dropwise adding the silver nitrate solution into the polyurethane solution, stirring at normal temperature for 30min, heating at 80 ℃ and stirring for 10min to reduce nano silver, observing that the nano silver content in the mixed solution is 0.1wt% and the solution turns into brown yellow from transparent, and mixing the PU-AgNPs solution to prepare the interlayer PUNF-AgNPs film of the SPAP film.
And finally, dissolving polyurethane particles with certain mass into DMF solution, and preparing PU solution with mass fraction of 5% for preparing upper polyurethane micro-nano (PUNSs) of the SPAP film by electrostatic spraying.
Preparation of SPAP film:
the SPAP film is prepared by adopting an alternating electrostatic spinning-electrostatic spraying process. Firstly, preparing SFNFs by adopting SF solution to carry out electrostatic spinning at a feed rate of 0.4 ml/h; under the same working parameters, carrying out electrostatic spinning deposition on a PU-AgNPs polymer solution with the flow rate of 1ml/h on the surface of an SFNFs film to obtain the PUNF-AgNPs; finally, a 5wt% PU solution was electrostatically sprayed onto the PUNF-AgNPs layer at a feed rate of 0.8ml/h, thereby obtaining a three-layer composite SPAP film.
Finally, the prepared SPAP film was treated with 75% (v/v) ethanol/water vapor to improve the water solubility of SFNFs, and then dried under vacuum at 50℃for 24 hours to remove the residual solvent.
SPAP films were tested: the experimental instrument is adopted: XS105 electronic balance; DF500 heat collection type constant temperature heating magnetic stirrer; DHG-9070A type electrothermal constant temperature blast drying oven; neofuge 15R type high-speed refrigerated centrifuge; JDF05 type electrospinning machine. The method comprises the following specific steps: scanning electron microscopy (SEM, hitachi S4800, japan) analyzes the morphology of the SPAP film, TEM observes the morphology of the nano Ag, and measures the diameter of the nanofibers or nanoparticles using Image J software; the chemical structure of SPAP films was tested using Fourier infrared spectroscopy (Nicolet iS5 ATR, U.S.; the wettability of each layer of the SPAP film is detected by adopting an automatic video contact angle tester; the air permeability of the SPAP film was studied using the Water Vapor Transmission Rate (WVTR), the samples were covered in air permeable cups containing water at different temperatures, the weight change of the device was monitored, normalized to WVTR, and all tests were repeated three times; evaluation of antimicrobial Properties of textiles according to GB/T20944.3-2008 part 3: the oscillation method is used for testing the bacteriostasis rate of the SPAP film on escherichia coli and staphylococcus aureus; the PM2.5 generator was simulated with burning sandalwood to evaluate the filtration performance of SPAP membranes.
Test results:
fig. 1 is a TEM image of a mixed PU-AgNPs solution, and it can be seen that silver nitrate is heated and reduced by DMF to generate nano Ag, and the micro morphology of the nano Ag is in a more regular sphere shape, and the nano Ag is uniformly dispersed without agglomeration. In fig. 2, a is listed as a macroscopic image; b is SEM image showing the microscopic morphology; the c column is diameter distribution, three layers are opaque in appearance and uniform in structure, and in addition, the SFNFs layer appears white and the PUNF-AgNPs layer appears light brown due to high scattering of the nanofibers, indicating that the silver nanoparticles are generated in situ. Furthermore, the overall SPAP film exhibited a light brown color, indicating that a very thin layer of PUNSs was sufficient to meet the roughness and superhydrophobicity requirements; SFNFs and PUNF-AgNPs layers exhibit porous three-dimensional nanofiber networks consisting of randomly oriented fibers of diameters 275+ -175 nm and 375+ -175 nm; the PUNSs exhibit a uniform nanosphere morphology (about 700nm in diameter) and adhere tightly to the fibers of the PUNFs-AgNPs layer because the initial PUNSs on the surface of the PUNFs-AgNPs are partially cured during electrospraying due to the high boiling point of DMF solvent, resulting in good adhesion between the two layers and improved mechanical stability. More importantly, the PUNSS layer can greatly improve surface roughness, providing higher hydrophobicity.
Chemical structure gap: FIG. 3 is a FTIR spectrum of SFNFs, PUNF-AgNPs, and PUNSs layers. SFNFs layer spectrum at 1625cm -1 、1514cm -1 、1232cm -1 Characteristic peaks appear at the sites, indicating that the SFNFs layer has stronger beta-sheet structure conformation [7 ]]. PUNSs layer at 3330cm -1 The absorption peak at the position belongs to N-H stretching vibration, and the peak value is 2957cm -1 Elastic vibration of C-H corresponding to 1727cm -1 The peak at this point represents the stretching vibration of c=o in PU, while the peak is at 1528cm -1 And 1079cm -1 The characteristic peaks of (a) respectively belong to N-H bending vibration and C-O-C stretching vibration, and the PUNF-AgNPs layer shows similar spectrum, which shows that the AgNPs are physically covered on the PU nanofiber network.
Wettability test: in general, micro-nano level surfaces can achieve higher surface roughness and contact angles. Materials with contact angles between 150 and 180 ° are considered superhydrophobic surfaces, generally having hydrophobic, anti-fog, and anti-fouling properties. The bottom SFNFs are insoluble materials, the contact angle is 47.9+/-2.1 degrees, which indicates that the SFNFs are hydrophilic interfaces, have good skin affinity and biological characteristics and are beneficial to skin contact; the water contact angle of the intermediate layer PUNF-AgNPs was 136.7 ±1.1°, and its hydrophobicity was attributed to the water-repellent property of PU itself and the rough surface of the nanofiber structure, but this hydrophobicity did not ensure good antifouling property. In order to improve the protection capability, a layer of PU nanospheres (PUNSs) is deposited on the PUNF-AgNPs nanofiber, a hierarchical structure with higher surface roughness is created, the contact angle is improved to 152.9 +/-1.3 degrees, the super-hydrophobicity is shown, and external threats such as dust can be resisted. The carbon powder is used as a simulated pollutant to evaluate the antifouling performance of the SPAP film, and the surface of the SPAP film covered by the carbon powder can be easily cleaned by water drops, so that the particle pollutant cannot stay on the surface for a long time, and the protection is promoted.
Water vapor transmission rate: the Water Vapor Transmission Rate (WVTR) is particularly important for wearable filter materials because low WVTR can induce bacterial growth leading to discomfort in wear, while high WVTR can lead to dry skin and reduced protective effects. As can be seen from fig. 4, the WVTR of the SPAP film gradually increases with increasing temperature. The WVTR is generally from about 1.0 to about 40.0mg/cm 2 Between/h, it is recommended that the WVTR of the skin contact be between 8.3 and 10.4mg/cm 2 Between/h [9 ]]. SPAP film has a WVTR of 13.3.+ -. 0.06mg/cm at 37 ℃ 2 And/h, the application requirements of the wearable filter material can be met.
Antibacterial properties: since PM2.5 may carry a large amount of bacteria, which poses a serious threat to human health, the bacteriostatic properties of the filter material are also quite important. Here, the antibacterial property of the SPAP film was evaluated by testing the antibacterial property using an oscillation method. As shown in the first table, the antibacterial rate of the SPAP film on escherichia coli is more than 99%, the antibacterial rate of the SPAP film on staphylococcus aureus is 98.5%, and according to GB/T20944.3-2008 standard, the antibacterial rate of a sample on staphylococcus aureus and escherichia coli is more than or equal to 70.00%, so that the SPAP film has an antibacterial effect. Through tests, the SPAP antibacterial rate meets the standard requirement, has excellent antibacterial effect, and enhances the bacterial filtering capability of the SPAP film on PM 2.5.
TABLE 1 antibacterial Performance test results of SPAP films
PM2.5 filtration performance: PM2.5 is one of the greatest threats facing humans, and achieving PM2.5 filtration is of great importance to protecting human health. The pollutant particles produced by burning sandalwood are generally used as model Particle (PM) pollutants, wherein the burning sandalwood can produce PM particles with different particle sizes and CO and NO similar to tail gas 2 、SO 2 And the like, as well as Volatile Organic Compounds (VOCs), such as benzene, aldehydes, polycyclic aromatic hydrocarbons, and the like. Model PMThe contaminants were placed on the inlet side of the PM counter sensor, connected to a computer, and the PM2.5 concentration at the outlet was recorded in real time. The inlet is blocked by a SPAP film and a medical mask, the filtering efficiency is calculated by the detected PM2.5 density before and after the SPAP film and the medical mask are blocked, the filtering efficiency is continuously tested for 20min, and the filtering efficiency is calculated every 2 min. As can be seen from fig. 5, the SPAP membrane has a filtration efficiency (96.5%) superior to that of the conventional medical mask (66.7%) and a good PM2.5 filtration capacity, which was confirmed by SEM, and a large number of contaminant particles have been absorbed and blocked by the outer layer of the SPAP membrane (puns, PUNF-AgNPs).
In conclusion, the PM2.5 filtering SPAP film with the antibacterial and antifouling functions is prepared by the alternating electrostatic spinning and electrostatic spraying technology. When the SF concentration of the SFNFs layer is 12wt%, the PU concentration of the PUNF-AgNPs layer is 20wt%, the nano silver content is 0.1wt%, and the PU concentration of the PUNSs layer is 5%, the fiber morphology of each layer of the obtained SPAP film is good. A series of performance tests are carried out on the filtering membrane, and the result shows that the contact angle of the outer layer of the filtering membrane is 152.9 +/-1.3 degrees, the filtering membrane has good hydrophobic and antifouling effects, and can be used as a physical barrier for blocking external dust while filtering PM 2.5; the water vapor transmission rate at 37 ℃ is 13.3+/-0.06 mg/cm 2 And/h, the requirements of the wearable filter material can be met; antibacterial tests show that the SPAP film has good antibacterial effect on escherichia coli and staphylococcus aureus with the rate of more than 98.00%; PM2.5 test results show that the filtering efficiency of the SPAP film is 96.5 percent, which is superior to that of the common medical mask. Comprehensively known, the multi-layer composite PM2.5 filter membrane prepared by the invention has better performance and antibacterial and antifouling functions,
the above-described preferred embodiments according to the present invention are intended to suggest that, from the above description, various changes and modifications can be made by the person skilled in the art without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (9)
1. The preparation method of the PM2.5 filtering SPAP film with the antibacterial and antifouling functions is characterized by comprising the following steps of: the method comprises the following steps:
s1: degumming and cleaning cocoons, drying to obtain silk fibroin, dissolving the silk fibroin in a lithium bromide solution to obtain a silk fibroin solution, dialyzing the silk fibroin solution, and freezing the silk fibroin solution after suction filtration to obtain freeze-dried silk fibroin;
s2: adding silver nitrate solution into polyurethane solution, stirring until the mixed PU-AgNPs solution turns into brown from transparent;
s3: preparing an SFNFs film from the SF solution obtained after dissolving the freeze-dried silk fibroin through electrostatic spinning;
s4: carrying out electrostatic spinning deposition on the PU-AgNPs solution on the surface of the SFNFs film to obtain PUNF-AgNPs;
s5: electrostatic spraying of the PU solution on the PUNF-AgNPs layer, so that a three-layer composite SPAP film is obtained;
the SPAP film comprises:
the three-layer composite film comprises a Silk Fibroin Nanofiber Substrate (SFNFs) and a polyurethane micro-nanosphere layer (PUNSs), and a PU nanofiber layer (PUNF-AgNPs) decorated with silver nano particles is deposited between the Silk Fibroin Nanofiber Substrate (SFNFs) and the polyurethane micro-nanosphere layer (PUNSs).
2. The method for preparing the PM2.5 filtration SPAP membrane with the antibacterial and antifouling functions according to claim 1, wherein the method comprises the following steps of: the SPAP film is treated with ethanol/water vapor to improve the water solubility of SFNFs.
3. The method for preparing the PM2.5 filtration SPAP membrane with the antibacterial and antifouling functions according to claim 1, wherein the method comprises the following steps of: in the step S1, the molar mass of the lithium bromide solution is 9-10 mol/L.
4. The method for preparing the PM2.5 filtration SPAP membrane with the antibacterial and antifouling functions according to claim 1, wherein the method comprises the following steps of: in step S1, the silk fibroin is dissolved in a lithium bromide solution at 50 ℃ or higher.
5. The method for preparing the PM2.5 filtration SPAP membrane with the antibacterial and antifouling functions according to claim 1, wherein the method comprises the following steps of: in the step S1, the regenerated silk fibroin solution after suction filtration is placed into a refrigerator with the temperature of minus 10 ℃ to minus 20 ℃ to be pre-frozen for at least 12h, and then is frozen and dried for at least 48h to obtain the freeze-dried silk fibroin.
6. The method for preparing the PM2.5 filtration SPAP membrane with the antibacterial and antifouling functions according to claim 1, wherein the method comprises the following steps of: in the step S3, the freeze-dried silk fibroin is dissolved in a formic acid solution, and an SF solution with the weight percent of 11-13% is prepared by magnetic stirring at room temperature.
7. The method for preparing the PM2.5 filtration SPAP membrane with the antibacterial and antifouling functions according to claim 1, wherein the method comprises the following steps of: in the step S2, silver nitrate is dissolved in DMF solution, and is stirred and dissolved to prepare silver nitrate solution with the mass fraction range of 0.5-1%; the polyurethane particles are stirred at 70-90 ℃ to prepare polyurethane solution with the mass fraction range of 20-25%.
8. The method for preparing the PM2.5 filtration SPAP membrane with the antibacterial and antifouling functions according to claim 1, wherein the method comprises the following steps of: in the step S2, the silver nitrate solution is dripped into the polyurethane solution, stirred at normal temperature, heated to more than 70 ℃ and stirred, so as to reduce nano silver.
9. The method for preparing the PM2.5 filtration SPAP membrane with the antibacterial and antifouling functions according to claim 1, wherein the method comprises the following steps of: in the step S5, polyurethane particles are dissolved in DMF solution, and PU solution with mass fraction ranging from 3% to 6% is prepared.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103361885A (en) * | 2013-06-28 | 2013-10-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of antibacterial silk fibroin fibrous membrane |
| CN106282153A (en) * | 2016-08-31 | 2017-01-04 | 武汉大学 | Sandwich micro nanometer fiber composite membrane of loading microorganisms and its preparation method and application |
| CN106422522A (en) * | 2015-08-11 | 2017-02-22 | 清华大学 | Silk nano-fiber-based air filtering device |
| CN107441848A (en) * | 2017-08-08 | 2017-12-08 | 华东理工大学 | A kind of surface has fibroin albumen nano-filtration membrane, the preparation method and applications of micro nano structure |
| CN107469631A (en) * | 2017-08-01 | 2017-12-15 | 东华大学 | A kind of two-dimension netted superfine nanofiber composite fluid filtering material and preparation method thereof |
| CN107557893A (en) * | 2017-08-01 | 2018-01-09 | 东华大学 | A kind of two-dimension netted superfine nano-fiber material of electrostatic direct-injection and preparation method thereof |
| CN111514659A (en) * | 2020-05-04 | 2020-08-11 | 南通大学 | Nano cobweb antibacterial composite air filtering material and preparation method thereof |
-
2022
- 2022-01-24 CN CN202210078986.9A patent/CN114232344B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103361885A (en) * | 2013-06-28 | 2013-10-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of antibacterial silk fibroin fibrous membrane |
| CN106422522A (en) * | 2015-08-11 | 2017-02-22 | 清华大学 | Silk nano-fiber-based air filtering device |
| CN106282153A (en) * | 2016-08-31 | 2017-01-04 | 武汉大学 | Sandwich micro nanometer fiber composite membrane of loading microorganisms and its preparation method and application |
| CN107469631A (en) * | 2017-08-01 | 2017-12-15 | 东华大学 | A kind of two-dimension netted superfine nanofiber composite fluid filtering material and preparation method thereof |
| CN107557893A (en) * | 2017-08-01 | 2018-01-09 | 东华大学 | A kind of two-dimension netted superfine nano-fiber material of electrostatic direct-injection and preparation method thereof |
| CN107441848A (en) * | 2017-08-08 | 2017-12-08 | 华东理工大学 | A kind of surface has fibroin albumen nano-filtration membrane, the preparation method and applications of micro nano structure |
| CN111514659A (en) * | 2020-05-04 | 2020-08-11 | 南通大学 | Nano cobweb antibacterial composite air filtering material and preparation method thereof |
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