CN114059233A - Transparent nanofiber membrane, preparation method thereof and application of transparent nanofiber membrane to transparent mask - Google Patents
Transparent nanofiber membrane, preparation method thereof and application of transparent nanofiber membrane to transparent mask Download PDFInfo
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- CN114059233A CN114059233A CN202111360739.XA CN202111360739A CN114059233A CN 114059233 A CN114059233 A CN 114059233A CN 202111360739 A CN202111360739 A CN 202111360739A CN 114059233 A CN114059233 A CN 114059233A
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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
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
- A41D13/05—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches protecting only a particular body part
- A41D13/11—Protective face masks, e.g. for surgical use, or for use in foul atmospheres
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
- A41D31/14—Air permeable, i.e. capable of being penetrated by gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/54—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
- B01D46/543—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms using membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
- D01D5/0084—Coating by electro-spinning, i.e. the electro-spun fibres are not removed from the collecting device but remain integral with it, e.g. coating of prostheses
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Abstract
The invention relates to a transparent nanofiber membrane, a preparation method thereof and application thereof on a transparent mask, wherein the preparation method comprises the following steps: preparing a high molecular polymer into a transparent nanofiber membrane by adopting an electrostatic spinning process and a special receiving base material; the special receiving substrate is an insulating substrate which is of a plane net structure as a whole, the basic unit I forming the plane net structure is of a plane structure formed by connecting a regular hexagonal support and three linear supports, one ends of the three linear supports are converged at the center of the regular hexagonal support, and the other ends of the three linear supports are respectively connected with three nonadjacent vertexes of the regular hexagonal support; the special receiving substrate is coated on the peripheral surface of the grounded roller; the average thickness of the finally prepared transparent nanofiber membrane is 1-20 mu m, and the average thickness of the main body part is 0.2-4 mu m; the fibers of the main body part are arranged in a certain orientation, and the orientation degree is more than 80%; the application is as follows: is used for manufacturing the transparent mask. The method is simple, and the prepared fiber membrane has high transparency and high porosity.
Description
Technical Field
The invention belongs to the technical field of masks, and relates to a transparent nanofiber membrane, a preparation method thereof and application thereof to a transparent mask.
Background
Flexible, transparent films or fibrous films or substrates have attracted considerable attention in the fields of smart wear, electronic skin, air filtration, biomedical and personal protection. Conventional transparent films or substrates, such as glass and Polyester (PET), Polyethylene (PE) plastic, etc., do not fully meet the needs of emerging application areas that require transparent materials with excellent absorption, breathability (large specific surface area, high porosity) and flexibility. For example, smart wearable or electronic skins are becoming more popular, and existing transparent film materials cannot simultaneously exhibit high light transmittance and good air permeability; air pollution causes serious harm to human health, and the existing filter material has high filtering performance but poor light transmittance; particularly in the field of personal protection, in recent years, due to the outbreak and spread of the new coronary pneumonia epidemic situation, people all over the world suffer from the suffering caused by the epidemic situation, the mask made of the fiber membrane material is used as the simplest, effective and commonly used personal protection tool and plays an irreplaceable role in resisting the epidemic situation, because many infectious diseases are transmitted by taking pollution particles in the air as carriers, and the mask can effectively intercept the particles in the air. However, the existing fiber membrane material mask is not transparent, which brings inconvenience to daily life of people (affects mobile phone face brushing and station face recognition systems), and also affects communication between doctors and patients. The existing transparent mask is prepared from solid transparent plastic plates (PE, PP, PC and the like), and has poor air permeability and poor protection effect.
In recent years, new transparent materials have attracted attention, and transparent flexible nano paper made of cellulose or chitin nano fibers has been developed. The obtained nano paper has higher light transmittance and good mechanical property, and is expected to replace the traditional plastic film. However, the preparation process of the nanopaper involves complicated chemical treatment, and the material has low porosity or no pores and poor air permeability. Wood has been widely used for many years due to its excellent properties, and transparent wood materials have also been reported. After chemical treatment, the transparent film prepared by mechanical pressure or resin filling has higher transparency and other excellent properties, which are superior to those of the traditional glass. However, the transparent wood film material is solid, loses the structural advantages of the wood, lacks interconnected pores, and requires a complicated chemical process, and consumes energy and time in the preparation process. Therefore, it is a great challenge and urgent need to prepare a transparent film material having excellent adsorptivity, gas permeability (large specific surface area, high porosity) and flexibility by a low-cost, simple process.
Electrospinning technology allows easy production of continuous micro-or nanofibers from different materials (polymers, carbon, ceramics, etc.), which has proven to be an efficient method for manufacturing micro-or nanofibers. The electrostatic spinning fiber membrane prepared by the method has small holes, high porosity, large specific surface area, excellent flexibility and strong mechanical properties. However, the transparency of electrospun fiber membranes is extremely difficult due to the severe light reflection and scattering of micro-and nanofibers. Many reports have been made on the preparation of electrospun transparent fiber membranes, which can be divided into two categories: one is to pack a polymer into a fiber membrane, which can produce a transparent nanocomposite; for example, a two-part novolac epoxy resin is added to an electrospun nylon-4, 6 film; the nylon-6 nano-fiber film is filled with cellulose acetate; polyacrylonitrile (PAN)/Polyurethane (PU) composite nanofiber membrane is heated to melt PU to obtain transparency; this method of achieving transparent fiber membranes loses the fiber structure and porosity, while micro-or nanofibers only play a reinforcing role; another is to reduce the thickness of the electrostatically spun fibrous membrane; the thinner the fiber film, the higher the light transmittance; for example, ultra-thin nanofiber or nano-arachnoid air filters with high performance are manufactured in conjunction with electrospinning/reticulation techniques; however, the disadvantages are poor mechanical properties and harsh process conditions, which means that the nano-spider web is too thin at a thickness of around 30nm, cannot be used independently, and is time-consuming to prepare. In a word, the existing method for preparing the transparent electrostatic spinning fiber membrane is complex, and the advantages of the fiber membrane are lost.
Therefore, the development of transparent electrostatically spun fibrous membranes with high light transmittance, high porosity and self-support remains a great challenge.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a transparent nanofiber membrane, a preparation method thereof and application thereof to a transparent mask. The transparent nanofiber membrane material with the high-luminous-flux structure is designed and prepared for the first time, the transparent fiber membrane mask is prepared on the basis, the prepared series of transparent fiber membranes have excellent light transmittance (up to 96%), high porosity (greater than or equal to 80%), and the prepared transparent mask has excellent light transmittance (greater than or equal to 80%) and PM0.3Filtering performance (filtering efficiency is more than 90% and pressure resistance is less than 100 Pa).
In order to achieve the purpose, the invention adopts the following scheme:
a preparation method of transparent nanofiber membrane adopts electrostatic spinning process and special receiving base material to prepare high molecular polymer into transparent nanofiber membrane;
the special receiving substrate is an insulating substrate (generally made of polyamide and polyester materials) which is of a plane net structure as a whole, a basic unit I forming the plane net structure is of a plane structure formed by connecting a regular hexagonal support and three linear supports, one ends of the three linear supports are converged at the center of the regular hexagonal support, the other ends of the three linear supports are respectively connected with three vertexes of the regular hexagonal support, and the three vertexes are not adjacent to each other on the regular hexagonal support;
the special receiving substrate is coated on the circumferential surface of the roller (can be completely coated or only partially coated, and the special receiving substrate can be fixedly connected with the roller through gluing or other modes), the roller is grounded, so that an electric field can be formed between the needle point and the roller, and the roller can drive the special receiving substrate to rotate to uniformly deposit fibers on the substrate.
As a preferred technical scheme:
in the preparation method of the transparent nanofiber membrane, the side length of the regular hexagon is 1.0-2.5 mm (preferably 1.50 mm); the thickness of the regular hexagon stent and the straight stent is 100-200 μm (preferably 150 μm, if the cross section of the stent is circular, the thickness is the diameter of the circle, and if the cross section of the stent is square, the thickness is the side length of the square).
In the above method for preparing the transparent nanofiber membrane, the high molecular polymer is one or more of Polyurethane (PU), Polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), Cellulose Acetate (CA), polymethyl methacrylate (PMMA), Polyamide (PA), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyethylene oxide (PEO), chitosan, and chitin.
According to the preparation method of the transparent nanofiber membrane, the electrostatic spinning parameters are as follows: the concentration of the spinning solution is 8-11 wt%, the filling speed is 0.3-1.0 ml/h, the spinning voltage is 10-25 kV, the rotating speed of a roller is 40-60 rpm, the receiving distance is 10-20 cm, the temperature is 25 +/-2 ℃, and the relative humidity is 35-45%.
The invention also provides a transparent nanofiber membrane prepared by the preparation method of the transparent nanofiber membrane, the transparent nanofiber membrane is integrally in a plane structure, and the basic unit II forming the plane structure is a regular hexagon structure formed by nanofibers in a special arrangement mode, wherein the special arrangement mode is as follows: the fibers in the basic unit II are divided into three parts, the fibers at the edge of the regular hexagon structure are marked as a first part, the fibers on three connecting lines between the center of the regular hexagon and three non-adjacent vertexes of the regular hexagon are marked as a second part, and the fibers at the rest positions are marked as a third part;
the average thickness of the transparent nanofiber membrane is 1-20 mu m, and the average thickness of the third part of the fiber membrane is 0.2-4 mu m; the fibers of the third part are arranged in a certain orientation, and the orientation degree is more than 80 percent;
the average thickness was measured as follows: utilizing a CHY-C2 thickness gauge to perform thickness test on the fiber membrane, cutting a sample to 10 multiplied by 10cm, and uniformly selecting 10 points on the surface of the sample to perform thickness test, and finally obtaining the average thickness;
the orientation degree test method comprises the following steps: calculated by measuring birefringence with an optical microscope;
the projected area of the fibers of the third portion is 60% or more of the projected area of the basic unit II.
As a preferred technical scheme:
in the transparent nanofiber membrane as described above, the fibers of the first part are aligned in an orientation direction a, where a is a direction parallel to each side of a regular hexagon in the regular hexagon structure (i.e., the fibers at the edge of the regular hexagon structure are parallel to which side at the edge of a certain side), the fibers of the second part are aligned in an orientation direction B, and B is a direction parallel to each connection line (i.e., the fibers at three connection lines between the center of the regular hexagon and three non-adjacent vertexes of the regular hexagon are parallel to which connection line at which connection line).
In the transparent nanofiber membrane as described above, the average diameter of the nanofibers was 200 nm.
According to the transparent nanofiber membrane, the light transmittance of the transparent nanofiber membrane is 50-96%, the porosity is 80-92%, and the tensile strength is 25-30 MPa;
the method for testing the light transmittance comprises the following steps: and testing the whole film by using an ultraviolet-visible spectrophotometer.
The porosity test method comprises the following steps: p ═ V ═0-V)/V0]×100％＝[1-V/V0]X is 100%; wherein, P is porosity,%; v0Is the volume of the material in the natural state, or apparent volume, cm3Or m3(ii) a V is the absolute dense volume of the material, cm3Or m3；
The tensile strength test method comprises the following steps: and testing by using a universal strength tester.
The invention also provides the application of the transparent nanofiber membrane to the transparent mask, the transparent mask is of a three-layer structure, the middle layer is composed of the transparent nanofiber membrane, the upper layer and the lower layer are both composed of transparent gauze screens with the light transmittance (the same as the test method) of more than 96%, and the thickness of each transparent gauze screen is 50-200 mu m.
As a preferred technical scheme:
in the application, the light transmittance of the transparent mask (the test method is the same as the above) is more than 45 percent, and the PM is0.3When the filtering performance is tested, the filtering efficiency is more than 90 percent, and the pressure resistance is less than 100 Pa; the test method of the filtration efficiency and the piezoresistance refers to GB 2626-2006.
The principle of the invention is as follows:
the invention provides a transparent nanofiber membrane mask and a preparation method thereof, which utilize an electrostatic spinning technology and an autonomously designed receiving base material to prepare a high-transparency nanofiber membrane (as shown in figure 1) in one step, and on the basis, the transparent nanofiber membrane is used for preparing a mask with excellent PM0.3A transparent fiber membrane mask with filtering performance.
The autonomously designed receiving substrate in this process has special structural features (as shown in fig. 2 and 3) and is composed of two parts: the first part is a regular hexagonal frame and the second part is a herringbone frame. The special structural characteristics determine that the prepared fiber membrane has a special high-luminous-flux structure, so that high light transmittance is realized. The material of the receiving substrate was a polyamide 6 or polyester material with a thickness of 150 μm and a side length of 1.50 mm.
The transparent fiber membrane prepared by the method has a high luminous flux structure (as shown in figure 4), and the structure consists of three parts: the first part is a regular hexagon with fibers collectively stacked, the second part is a herringbone with fibers collectively stacked, and the third part is a region where fibers are stacked between the regular hexagon and the herringbone. The thick representative fibers had a large amount of accumulated, and the thin representative fibers had a small amount of accumulated. At the same time, the fibers are highly oriented in all three sections.
The forming process of the fiber membrane is closely related to the distribution of the electric field, and the base materials with different structures have different influences on the electric field. As shown in fig. 5, which is a simulation diagram of electric field distribution of the rectangular frame, the regular hexagonal frame and the base material in the method in the electric field, it can be seen that the electric field is mainly concentrated and distributed in the middle area of the rectangular frame and the regular hexagonal frame, which causes concentrated accumulation of fibers in the middle area and poor light transmittance; in contrast, in the receiving substrate designed according to the present invention, the electric field is more distributed over nine frames and less distributed between frames, which results in concentrated accumulation of fibers on the frames and less accumulation of fibers in the areas between frames, so that light is mainly transmitted through this area, thereby achieving high transparency. The electron micrographs in fig. 5 are respectively the fibrous films obtained from the three substrates of different structures described above.
The fibers are highly aligned in the third section, probably due to the special electric field created in the region between the frames (as shown in fig. 6). When the positively charged jet approaches the receiving substrate, electrostatic forces, i.e., coulomb forces, are generated between the oppositely charged fiber jet and the grounded receiving substrate surface, and electrostatic tensile forces in opposite directions are formed under the interaction of the electric field lines and coulomb forces and are distributed in parallel between the two electrodes. This causes the fibers to be drawn between the two electrodes and aligned parallel at an angle between the two electrodes, thereby forming an oriented fiber structure.
The principle of the fiber membrane structure for realizing high transparency is as follows: firstly, the fibers are mainly distributed on the regular hexagons and the herringbone, the area between the regular hexagons and the herringbone is distributed in a small amount, and according to the Fermat's theorem, the light is transmitted along the shortest distance, when the light irradiates the surface of the fiber film, the light can preferentially pass through the third part with less fiber content and thin thickness, so that the transmission loss of the light is greatly reduced; secondly, the fibers are oriented in each part, and the oriented structure can reduce the multi-stage reflection of light, shorten the effective propagation path of the light and be beneficial to the maintenance of light intensity.
Compared with the fiber membrane in the prior art, the fiber membrane is more transparent under the premise of the same thickness, because:
the prior art fiber films have a high surface roughness and a strong reflection of light, which makes most of the fibers appear white. In addition, the fiber film is a mixture composed of polymer fibers and a large amount of air, and interface reflection occurs at the interface between the fibers and the air due to the difference between the refractive index of the fibers and the refractive index of the air, which is expressed as light scattering inside the fiber film, wherein the larger the difference between the refractive indexes is, the more the air content is, and the more serious the scattering inside the fiber film is. Light reflection and light scattering cause the fiber membrane material to have low transmittance and difficult transparency.
The fiber membrane in the prior art is a disordered fiber membrane with randomly distributed fibers, the optical path is very complex and tortuous, the surface reflection and the internal scattering are very serious, the optical loss is huge, and the light transmission is poor.
The invention is designed in such a way that light can pass through the intermediate orientation structure region as far as possible, the fiber content of the intermediate orientation structure region is low, the intermediate orientation structure region is thin, and the orientation structure reduces interface reflection, so that the light loss is low. In the structure designed by the invention, the thickness of the fiber film is mainly embodied by fibers stacked on the frame, the fiber content on the frame is high, the thickness is large, but the area occupation ratio of the frame part is small relative to the fiber film, and the optical loss is further controlled. Thus, the fiber film of the present invention is more transparent.
Advantageous effects
Compared with the solid traditional transparent membrane materials (glass, PET plates and the like) and the fiber-reinforced transparent composite materials, the finally prepared transparent fiber membrane has an adjustable pore structure and porosity, can maintain the shape and structure of the fiber, and has excellent air permeability and filtering performance.
Drawings
FIG. 1 is a flow chart of the preparation of a transparent fibrous membrane of the present invention;
FIG. 2 is a schematic structural diagram of a basic unit I constituting a planar network structure according to the present invention;
FIG. 3 is a schematic view of the overall structure of a special receiving substrate according to the present invention;
FIG. 4 is a schematic structural view of a basic unit II constituting a planar structure according to the present invention;
FIG. 5 is an electron microscope image of electric field simulation of base materials with different structures and fiber films correspondingly formed, wherein the left image of the upper row is the electric field simulation of a rectangular base material, the middle image is the electric field simulation of a regular hexagonal base material, the right image is the electric field simulation of the base material of the invention, the left image of the lower row is the electron microscope image of the fiber films formed by the rectangular base material, the middle image is the electron microscope image of the fiber films formed by the regular hexagonal base material, and the right image is the electron microscope image of the fiber films formed by the base material of the invention;
FIG. 6 is a schematic diagram showing a mechanism of forming an alignment structure in the present invention;
fig. 7 is an optical photograph of five different light transmittance fiber films of the present invention, wherein T represents light transmittance.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The specific sources or structural parameters of the high molecular polymer adopted in the invention are as follows:
example 1
A preparation method of transparent nanofiber membrane adopts electrostatic spinning process and special receiving base material to prepare high molecular polymer (polyurethane) into transparent nanofiber membrane;
the special receiving substrate is an insulating substrate which is of a plane net structure as a whole, the basic unit I forming the plane net structure is a plane structure formed by connecting a regular hexagonal support and three linear supports, one ends of the three linear supports are converged at the center of the regular hexagonal support, the other ends of the three linear supports are respectively connected with three vertexes of the regular hexagonal support, and the three vertexes are not adjacent to each other on the regular hexagonal support; the side length of the regular hexagon is 1 mm; the thicknesses of the regular hexagon support and the linear support are both 100 micrometers;
the special receiving base material is coated on the circumferential surface of the roller, and the roller is grounded;
the parameters of electrostatic spinning are as follows: the concentration of the spinning solution was 8 wt%, the infusion speed was 0.3ml/h, the spinning voltage was 25kV, the drum speed was 40rpm, the take-up distance was 10cm, the temperature was 25. + -. 2 ℃ and the relative humidity was 35%.
The finally prepared transparent nanofiber membrane is integrally in a planar structure, and a basic unit II forming the planar structure is a regular hexagon structure formed by nanofibers in a special arrangement mode, wherein the special arrangement mode is as follows: the fibers in the basic unit II are divided into three parts, the fibers at the edge of the regular hexagon structure are marked as a first part, the fibers on three connecting lines between the center of the regular hexagon and three non-adjacent vertexes of the regular hexagon are marked as a second part, and the fibers at the rest positions are marked as a third part;
the fibers of the first part are arranged in an orientation with an orientation direction A, wherein A is a direction parallel to each side of a regular hexagon in a regular hexagon structure, the fibers of the second part are arranged in an orientation with an orientation direction B, and B is a direction parallel to each connecting line;
the average thickness of the transparent nanofiber membrane was 1 μm, and the average thickness of the fiber membrane of the third portion was 0.2 μm; the fibers of the third part are arranged in a certain orientation, and the orientation degree is 85 percent; the projected area of the fibers of the third part is 60% of the projected area of the basic unit II; the average diameter of the nanofibers was 200 nm; the transparent nanofiber membrane had a light transmittance of 84% (photo shown in the left two panels of fig. 7), a porosity of 80%, and a tensile strength of 30 MPa.
The finally prepared transparent nanofiber membrane is used in the middle layer of the transparent mask, the transparent mask is of a three-layer structure, the upper layer and the lower layer are both formed by transparent gauze gauzes with the light transmittance of 96%, and the thickness of each transparent gauze is 50 micrometers;
the light transmittance of the transparent mask is 75%, and PM is0.3When the filtering performance is tested, the filtering efficiency is 91 percent, and the pressure resistance is 50 Pa.
Comparative example 1
A method for preparing a fibrous membrane, which is substantially the same as that of example 1, except that the special receiving substrate is used, the basic unit I constituting the planar network structure in the special receiving substrate of comparative example 1 is composed of only a regular hexagonal scaffold (as shown in the middle of the upper row of fig. 5), and the size of the regular hexagonal scaffold is the same as that of example 1.
The average thickness of the finally prepared nanofiber membrane is 1 mu m; the average diameter of the nanofibers was 200 nm; the nanofiber membrane had a light transmittance of 50%, a porosity of 70%, and a tensile strength of 20 MPa.
Comparing example 1 with comparative example 1, it can be seen that the nanofiber film of example 1 has higher light transmittance, higher porosity and higher tensile strength, because example 1 is designed to have a structure in which light mainly passes through the middle orientation structure region, the fiber content of the middle orientation structure region is low, the fiber content is thin, and the orientation structure reduces interface reflection, so that the light loss is low; the fiber film prepared in the comparative example 1 is a disordered fiber film with randomly distributed fibers, the optical path is very complicated and tortuous, the surface reflection and the internal scattering are very serious, the optical loss is huge, and the light transmittance is poor.
Example 2
A method for preparing transparent nanofiber membrane, adopt the electrostatic spinning process and special receiving substrate to make the high molecular polymer (polyacrylonitrile) into the transparent nanofiber membrane;
the special receiving substrate is an insulating substrate which is of a plane net structure as a whole, the basic unit I forming the plane net structure is a plane structure formed by connecting a regular hexagonal support and three linear supports, one ends of the three linear supports are converged at the center of the regular hexagonal support, the other ends of the three linear supports are respectively connected with three vertexes of the regular hexagonal support, and the three vertexes are not adjacent to each other on the regular hexagonal support; the side length of the regular hexagon is 1.5 mm; the thicknesses of the regular hexagon support and the linear support are both 150 micrometers;
the special receiving base material is coated on the circumferential surface of the roller, and the roller is grounded;
the parameters of electrostatic spinning are as follows: the concentration of the spinning solution was 9 wt%, the infusion speed was 0.5ml/h, the spinning voltage was 15kV, the drum speed was 50rpm, the take-up distance was 15cm, the temperature was 25. + -. 2 ℃ and the relative humidity was 40%.
The finally prepared transparent nanofiber membrane is integrally in a planar structure, and a basic unit II forming the planar structure is a regular hexagon structure formed by nanofibers in a special arrangement mode, wherein the special arrangement mode is as follows: the fibers in the basic unit II are divided into three parts, the fibers at the edge of the regular hexagon structure are marked as a first part, the fibers on three connecting lines between the center of the regular hexagon and three non-adjacent vertexes of the regular hexagon are marked as a second part, and the fibers at the rest positions are marked as a third part;
the fibers of the first part are arranged in an orientation with an orientation direction A, wherein A is a direction parallel to each side of a regular hexagon in a regular hexagon structure, the fibers of the second part are arranged in an orientation with an orientation direction B, and B is a direction parallel to each connecting line;
the average thickness of the transparent nanofiber membrane was 5 μm, and the average thickness of the fiber membrane of the third portion was 1 μm; the fibers of the third part are arranged in a certain orientation, and the orientation degree is 90 percent; the projected area of the fibers of the third portion is 62% of the projected area of the basic unit II; the average diameter of the nanofibers was 200 nm; the transparent nanofiber membrane had a light transmittance of 90% (photograph shown in the left panel of fig. 7), a porosity of 85%, and a tensile strength of 25 MPa.
The finally prepared transparent nanofiber membrane is used in the middle layer of the transparent mask, the transparent mask is of a three-layer structure, the upper layer and the lower layer are both formed by transparent gauze gauzes with the light transmittance of 97%, and the thickness of each transparent gauze is 150 micrometers;
the light transmittance of the see-through mask was 82%, PM0.3When the filtering performance is tested, the filtering efficiency is 92 percent, and the pressure resistance is 30 Pa.
Example 3
A preparation method of a transparent nanofiber membrane comprises the steps of preparing a high-molecular polymer (polyvinylidene fluoride) into the transparent nanofiber membrane by adopting an electrostatic spinning process and a special receiving base material;
the special receiving substrate is an insulating substrate which is of a plane net structure as a whole, the basic unit I forming the plane net structure is a plane structure formed by connecting a regular hexagonal support and three linear supports, one ends of the three linear supports are converged at the center of the regular hexagonal support, the other ends of the three linear supports are respectively connected with three vertexes of the regular hexagonal support, and the three vertexes are not adjacent to each other on the regular hexagonal support; the side length of the regular hexagon is 2 mm; the thicknesses of the regular hexagon support and the linear support are both 150 micrometers;
the special receiving base material is coated on the circumferential surface of the roller, and the roller is grounded;
the parameters of electrostatic spinning are as follows: the concentration of the spinning solution was 10 wt%, the infusion speed was 1ml/h, the spinning voltage was 15kV, the drum speed was 60rpm, the take-up distance was 15cm, the temperature was 25. + -. 2 ℃ and the relative humidity was 45%.
The finally prepared transparent nanofiber membrane is integrally in a planar structure, and a basic unit II forming the planar structure is a regular hexagon structure formed by nanofibers in a special arrangement mode, wherein the special arrangement mode is as follows: the fibers in the basic unit II are divided into three parts, the fibers at the edge of the regular hexagon structure are marked as a first part, the fibers on three connecting lines between the center of the regular hexagon and three non-adjacent vertexes of the regular hexagon are marked as a second part, and the fibers at the rest positions are marked as a third part;
the fibers of the first part are arranged in an orientation with an orientation direction A, wherein A is a direction parallel to each side of a regular hexagon in a regular hexagon structure, the fibers of the second part are arranged in an orientation with an orientation direction B, and B is a direction parallel to each connecting line;
the average thickness of the transparent nanofiber membrane was 10 μm, and the average thickness of the fiber membrane of the third portion was 2 μm; the fibers of the third part are arranged in a certain orientation, and the orientation degree is 88%; the projected area of the fibers of the third portion is 64% of the projected area of the basic unit II; the average diameter of the nanofibers was 200 nm; the transparent nanofiber membrane had a light transmittance of 80% (photograph shown in the left three panels of fig. 7), a porosity of 88%, and a tensile strength of 26 MPa.
The finally prepared transparent nanofiber membrane is used in the middle layer of the transparent mask, the transparent mask is of a three-layer structure, the upper layer and the lower layer are both formed by transparent gauze gauzes with the light transmittance of 96%, and the thickness of each transparent gauze is 100 micrometers;
the light transmittance of the transparent mask is 65%, and PM is0.3When the filtering performance is tested, the filtering efficiency is 95 percent, and the pressure resistance is 40 Pa.
Example 4
A preparation method of transparent nanofiber membrane, adopt the static spinning process and special receiving substrate to make the high molecular polymer (cellulose acetate) into the transparent nanofiber membrane;
the special receiving substrate is an insulating substrate which is of a plane net structure as a whole, the basic unit I forming the plane net structure is a plane structure formed by connecting a regular hexagonal support and three linear supports, one ends of the three linear supports are converged at the center of the regular hexagonal support, the other ends of the three linear supports are respectively connected with three vertexes of the regular hexagonal support, and the three vertexes are not adjacent to each other on the regular hexagonal support; the side length of the regular hexagon is 2.5 mm; the thicknesses of the regular hexagon support and the linear support are both 200 mu m;
the special receiving base material is coated on the circumferential surface of the roller, and the roller is grounded;
the parameters of electrostatic spinning are as follows: the concentration of the spinning solution was 11 wt%, the infusion speed was 1ml/h, the spinning voltage was 20kV, the drum speed was 50rpm, the take-up distance was 20cm, the temperature was 25. + -. 2 ℃ and the relative humidity was 40%.
The finally prepared transparent nanofiber membrane is integrally in a planar structure, and a basic unit II forming the planar structure is a regular hexagon structure formed by nanofibers in a special arrangement mode, wherein the special arrangement mode is as follows: the fibers in the basic unit II are divided into three parts, the fibers at the edge of the regular hexagon structure are marked as a first part, the fibers on three connecting lines between the center of the regular hexagon and three non-adjacent vertexes of the regular hexagon are marked as a second part, and the fibers at the rest positions are marked as a third part;
the fibers of the first part are arranged in an orientation with an orientation direction A, wherein A is a direction parallel to each side of a regular hexagon in a regular hexagon structure, the fibers of the second part are arranged in an orientation with an orientation direction B, and B is a direction parallel to each connecting line;
the average thickness of the transparent nanofiber membrane was 15 μm, and the average thickness of the fiber membrane of the third portion was 3 μm; the fibers of the third part are arranged in a certain orientation, and the orientation degree is 85 percent; the projected area of the fibers of the third part is 63% of the projected area of the basic unit II; the average diameter of the nanofibers was 200 nm; the transparent nanofiber membrane had a light transmittance of 78% (shown in the left four panels of fig. 7), a porosity of 90%, and a tensile strength of 27 MPa.
The finally prepared transparent nanofiber membrane is used in the middle layer of the transparent mask, the transparent mask is of a three-layer structure, the upper layer and the lower layer are both formed by transparent gauze gauzes with the light transmittance of 97%, and the thickness of each transparent gauze is 150 micrometers;
the light transmittance of the transparent mask is 55%, and PM is0.3When the filtering performance is tested, the filtering efficiency is 98 percent, and the pressure resistance is 60 Pa.
Example 5
A preparation method of transparent nanofiber membrane adopts electrostatic spinning process and special receiving base material to prepare high molecular polymer (polymethyl methacrylate) into transparent nanofiber membrane;
the special receiving substrate is an insulating substrate which is of a plane net structure as a whole, the basic unit I forming the plane net structure is a plane structure formed by connecting a regular hexagonal support and three linear supports, one ends of the three linear supports are converged at the center of the regular hexagonal support, the other ends of the three linear supports are respectively connected with three vertexes of the regular hexagonal support, and the three vertexes are not adjacent to each other on the regular hexagonal support; the side length of the regular hexagon is 1.5 mm; the thicknesses of the regular hexagon support and the linear support are both 150 micrometers;
the special receiving base material is coated on the circumferential surface of the roller, and the roller is grounded;
the parameters of electrostatic spinning are as follows: the concentration of the spinning solution was 9 wt%, the infusion speed was 1ml/h, the spinning voltage was 10kV, the drum speed was 50rpm, the take-up distance was 15cm, the temperature was 25. + -. 2 ℃ and the relative humidity was 40%.
The finally prepared transparent nanofiber membrane is integrally in a planar structure, and a basic unit II forming the planar structure is a regular hexagon structure formed by nanofibers in a special arrangement mode, wherein the special arrangement mode is as follows: the fibers in the basic unit II are divided into three parts, the fibers at the edge of the regular hexagon structure are marked as a first part, the fibers on three connecting lines between the center of the regular hexagon and three non-adjacent vertexes of the regular hexagon are marked as a second part, and the fibers at the rest positions are marked as a third part;
the fibers of the first part are arranged in an orientation with an orientation direction A, wherein A is a direction parallel to each side of a regular hexagon in a regular hexagon structure, the fibers of the second part are arranged in an orientation with an orientation direction B, and B is a direction parallel to each connecting line;
the average thickness of the transparent nanofiber membrane was 20 μm, and the average thickness of the fiber membrane of the third portion was 4 μm; the fibers of the third part are arranged in a certain orientation, and the orientation degree is 82 percent; the projected area of the fibers of the third portion is 65% of the projected area of the basic unit II; the average diameter of the nanofibers was 200 nm; the transparent nanofiber membrane had a light transmittance of 50%, a porosity of 91%, and a tensile strength of 28 MPa.
The finally prepared transparent nanofiber membrane is used in the middle layer of the transparent mask, the transparent mask is of a three-layer structure, the upper layer and the lower layer are both formed by transparent gauze gauzes with the light transmittance of 96%, and the thickness of each transparent gauze is 200 mu m;
the light transmittance of the transparent mask was 45%, PM0.3When the filtering performance is tested, the filtering efficiency is 99 percent, and the pressure resistance is 70 Pa.
Example 6
A preparation method of transparent nanofiber membrane adopts electrostatic spinning process and special receiving base material to prepare high molecular polymer (polyamide) into transparent nanofiber membrane;
the special receiving substrate is an insulating substrate which is of a plane net structure as a whole, the basic unit I forming the plane net structure is a plane structure formed by connecting a regular hexagonal support and three linear supports, one ends of the three linear supports are converged at the center of the regular hexagonal support, the other ends of the three linear supports are respectively connected with three vertexes of the regular hexagonal support, and the three vertexes are not adjacent to each other on the regular hexagonal support; the side length of the regular hexagon is 1.5 mm; the thicknesses of the regular hexagon support and the linear support are both 200 mu m;
the special receiving base material is coated on the circumferential surface of the roller, and the roller is grounded;
the parameters of electrostatic spinning are as follows: the concentration of the spinning solution was 9 wt%, the infusion speed was 0.5ml/h, the spinning voltage was 20kV, the drum speed was 60rpm, the take-up distance was 15cm, the temperature was 25. + -. 2 ℃ and the relative humidity was 45%.
The finally prepared transparent nanofiber membrane is integrally in a planar structure, and a basic unit II forming the planar structure is a regular hexagon structure formed by nanofibers in a special arrangement mode, wherein the special arrangement mode is as follows: the fibers in the basic unit II are divided into three parts, the fibers at the edge of the regular hexagon structure are marked as a first part, the fibers on three connecting lines between the center of the regular hexagon and three non-adjacent vertexes of the regular hexagon are marked as a second part, and the fibers at the rest positions are marked as a third part;
the fibers of the first part are arranged in an orientation with an orientation direction A, wherein A is a direction parallel to each side of a regular hexagon in a regular hexagon structure, the fibers of the second part are arranged in an orientation with an orientation direction B, and B is a direction parallel to each connecting line;
the average thickness of the transparent nanofiber membrane was 5 μm, and the average thickness of the fiber membrane of the third portion was 1 μm; the fibers of the third part are arranged in a certain orientation, and the orientation degree is 95 percent; the projected area of the fibers of the third part is 70% of the projected area of the basic unit II; the average diameter of the nanofibers was 200 nm; the transparent nanofiber membrane had a light transmittance of 96%, a porosity of 92%, and a tensile strength of 29 MPa.
The finally prepared transparent nanofiber membrane is used in the middle layer of the transparent mask, the transparent mask is of a three-layer structure, the upper layer and the lower layer are both formed by transparent gauze gauzes with the light transmittance of 96%, and the thickness of each transparent gauze is 100 micrometers;
the light transmittance of the transparent mask is 90%, and PM is0.3When the filtering performance is tested, the filtering efficiency is 98 percent, and the pressure resistance is 10 Pa.
Claims (10)
1. A preparation method of a transparent nanofiber membrane is characterized by comprising the following steps: preparing a high molecular polymer into a transparent nanofiber membrane by adopting an electrostatic spinning process and a special receiving base material;
the special receiving substrate is an insulating substrate which is of a plane net structure as a whole, the basic unit I forming the plane net structure is a plane structure formed by connecting a regular hexagonal support and three linear supports, one ends of the three linear supports are converged at the center of the regular hexagonal support, the other ends of the three linear supports are respectively connected with three vertexes of the regular hexagonal support, and the three vertexes are not adjacent to each other on the regular hexagonal support;
the special receiving substrate is coated on the circumferential surface of the roller, and the roller is grounded.
2. The method of claim 1, wherein the side length of the regular hexagon is 1.0-2.5 mm; the thicknesses of the regular hexagon support and the linear support are both 100-200 mu m.
3. The method of claim 1, wherein the polymer is at least one of polyurethane, polyacrylonitrile, polyvinylidene fluoride, cellulose acetate, polymethyl methacrylate, polyamide, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl butyral, polyethylene oxide, chitosan, and chitin.
4. The method for preparing a transparent nanofiber membrane as claimed in claim 1, wherein the parameters of electrospinning are as follows: the concentration of the spinning solution is 8-11 wt%, the filling speed is 0.3-1.0 ml/h, the spinning voltage is 10-25 kV, the rotating speed of a roller is 40-60 rpm, the receiving distance is 10-20 cm, the temperature is 25 +/-2 ℃, and the relative humidity is 35-45%.
5. The transparent nanofiber membrane prepared by the method for preparing a transparent nanofiber membrane as claimed in any one of claims 1 to 4, wherein: the transparent nanofiber membrane is of a plane structure as a whole, and a basic unit II forming the plane structure is a regular hexagon structure formed by nanofibers in a special arrangement mode, wherein the special arrangement mode is as follows: the fibers in the basic unit II are divided into three parts, the fibers at the edge of the regular hexagon structure are marked as a first part, the fibers on three connecting lines between the center of the regular hexagon and three non-adjacent vertexes of the regular hexagon are marked as a second part, and the fibers at the rest positions are marked as a third part;
the average thickness of the transparent nanofiber membrane is 1-20 mu m, and the average thickness of the third part of the fiber membrane is 0.2-4 mu m; the fibers of the third part are arranged in a certain orientation, and the orientation degree is more than 80 percent;
the projected area of the fibers of the third portion is 60% or more of the projected area of the basic unit II.
6. The transparent nanofiber membrane as claimed in claim 5, wherein the fibers of the first portion are aligned in an orientation direction A, A being a direction parallel to each side of a regular hexagon in a regular hexagonal structure, respectively, and the fibers of the second portion are aligned in an orientation direction B, B being a direction parallel to each connecting line, respectively.
7. The transparent nanofiber membrane of claim 5, wherein the nanofibers have an average diameter of 200 nm.
8. The transparent nanofiber membrane as claimed in claim 5, wherein the transparent nanofiber membrane has a light transmittance of 50 to 96%, a porosity of 80 to 92%, and a tensile strength of 25 to 30 MPa.
9. The use of the transparent nanofiber membrane as claimed in any one of claims 5 to 8 in a transparent mask, wherein: the transparent mask is of a three-layer structure, the middle layer is composed of a transparent nanofiber membrane, the upper layer and the lower layer are composed of transparent gauze meshes with light transmittance of more than 96%, and the thickness of each transparent gauze mesh is 50-200 microns.
10. Use according to claim 9, wherein the transparency mask has a light transmission of more than 45% and PM0.3When the filtering performance is tested, the filtering efficiency is more than 90 percent, and the pressure resistance is less than 100 Pa.
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