CN114164563A - Nano piezoelectric fiber film material and preparation method and application thereof - Google Patents

Nano piezoelectric fiber film material and preparation method and application thereof Download PDF

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Publication number
CN114164563A
CN114164563A CN202111333667.XA CN202111333667A CN114164563A CN 114164563 A CN114164563 A CN 114164563A CN 202111333667 A CN202111333667 A CN 202111333667A CN 114164563 A CN114164563 A CN 114164563A
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nano
piezoelectric fiber
fiber film
nano piezoelectric
vinyl acetate
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陈善良
赵志成
李顺
邓伟
刘勇
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Guangdong Yina New Material Technology Co ltd
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Foshan Southern China Institute For New Materials
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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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/23—Solid substances, e.g. granules, powders, blocks, tablets
    • 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
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • 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
    • 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
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
    • D06C3/00—Stretching, tentering or spreading textile fabrics; Producing elasticity in textile fabrics

Abstract

The invention discloses a nano piezoelectric fiber film material and a preparation method and application thereof. In a first aspect of the present application, a nano piezoelectric fiber membrane material is provided, which includes a base material and a reinforcement material, wherein the reinforcement material is dispersed in the base material, the base material includes poly (vinylidene cyanide/vinyl acetate), and the reinforcement material includes a two-dimensional nano piezoelectric material. According to the nano piezoelectric fiber film material, a certain amount of two-dimensional nano piezoelectric material is introduced into P (VDCN/VAC), and the two materials are matched with each other, so that the composite material has higher electric activity content while the flexibility and transparency of the P (VDCN/VAC) material are maintained, and the piezoelectric sterilization performance of the material is effectively improved.

Description

Nano piezoelectric fiber film material and preparation method and application thereof
Technical Field
The application relates to the technical field of sterilization piezoelectric materials, in particular to a nano piezoelectric fiber film material and a preparation method and application thereof.
Background
At present, there are three main sterilization techniques, which are respectively: using a germicide, heat treatment and radiation treatment. The bactericide has short sterilization time, but can not be used repeatedly, most bactericides have volatility and have certain damage to human bodies and environment, and heat treatment and radiation treatment are harmful to the human bodies. Therefore, the methods are not suitable for sterilization in the daily contact fields of the human body such as mobile phone screens, elevator buttons, handrails and the like. Based on the above knowledge, it is important to adopt a novel sterilization technology in the above scenario.
In recent years, nano piezoelectric materials are the focus of research in the field of new materials, and when an external force acts on the nano piezoelectric materials to apply weak pressure (touch, pressing and the like), the nano piezoelectric materials can generate active free radicals to kill bacteria. Piezoelectric materials can be classified into two major types, i.e., inorganic piezoelectric materials and organic piezoelectric materials, according to the difference of the components, among the organic piezoelectric materials, poly (vinylidene cyanide/vinyl acetate) (P (VDCN/VAC)) is an organic piezoelectric material with high transparency, good flexibility and high thermal stability, but the sterilization effect is not ideal through detection, so that it is necessary to provide a P (VDCN/VAC) material with higher sterilization performance.
Disclosure of Invention
The present application is directed to solving at least one of the problems in the prior art. Therefore, the application provides a nano piezoelectric fiber film material with higher sterilization performance. The application also relates to a preparation method of the nano piezoelectric fiber film material and an application of the nano piezoelectric fiber film material.
According to a first aspect of the application, a nano piezoelectric fiber film material is provided, and the nano piezoelectric fiber film material comprises a base material and a reinforcement material, wherein the reinforcement material is dispersed in the base material, the base material comprises 70-100 parts by mass of poly (vinylidene cyanide/vinyl acetate), and the reinforcement material comprises 2-15 parts by mass of a two-dimensional nano piezoelectric material.
The nano piezoelectric fiber film material according to the embodiment of the application has at least the following beneficial effects:
according to the nano piezoelectric fiber film material, a certain amount of two-dimensional nano piezoelectric material is introduced into P (VDCN/VAC), and the two materials are matched with each other, so that the composite material has higher electric activity content while the flexibility and transparency of the P (VDCN/VAC) material are maintained, and the piezoelectric sterilization performance of the material is effectively improved.
In some embodiments of the present application, the two-dimensional nano-piezoelectric material is a two-dimensional transition metal chalcogenide.
In some embodiments of the present application, the two-dimensional transition metal chalcogenide is selected from MoSe2、MoS2、MoTe2、WS2、WSe2、WTe2、SnS、SnSe、In2Se3、In2S3At least one of (1).
In some embodiments of the present application, the two-dimensional transition metal chalcogenide is selected from MoSe2、MoS2、MoTe2、WS2、WSe2、WTe2、SnS、SnSe、In2Se3、In2S3At least two of them.
In a second aspect of the present application, a nano piezoelectric fiber film is provided, which includes the aforementioned nano piezoelectric fiber film material.
In a third aspect of the present application, a method for preparing a nano piezoelectric fiber film is provided, which includes the following steps:
dissolving poly (vinylidene cyanide/vinyl acetate) in an organic solvent, adding a two-dimensional piezoelectric nano material, and uniformly stirring to obtain a spinning solution;
and (3) taking the spinning solution, carrying out electrostatic spinning to obtain a film material, and carrying out electric field polarization to obtain the nano piezoelectric fiber film.
In some embodiments herein, the organic solvent is selected from at least one of dimethyl sulfoxide, dimethylformamide, dimethyl carbonate, diethyl carbonate.
In some embodiments of the present application, the parameters of electrospinning are set as follows: the voltage is 5-20 kV, the liquid outlet speed is 1-5 mL/h, the environment humidity is 20-50%, the environment temperature is 20-30 ℃, the spinning distance is 15-20 cm, and the spinning time is 10-20 h.
In some embodiments of the present application, the thin film material is further subjected to uniaxial stretching treatment before electric field polarization, and the stretching ratio is preferably 2 to 4, and more preferably 3.
In some embodiments of the present application, poly (vinylidene cyanide/vinyl acetate) is prepared as follows: dissolving vinylidene cyanide and vinyl acetate in a reaction solvent to obtain a reaction solution; and adding an initiator into the reaction solution to carry out polymerization reaction to obtain poly (vinylidene cyanide/vinyl acetate).
In some embodiments of the present application, the amount of each of the vinylidene cyanide and the vinyl acetate is 35 to 50 parts by mass.
In some embodiments of the present application, the vinylidene cyanide and vinyl acetate are present in a molecular ratio of 1: 1 is converted to the corresponding mass part ratio.
In some embodiments of the present application, the amounts of the vinylidene cyanide, the vinyl acetate, and the two-dimensional nano-piezoelectric material are 40 to 46 parts by mass, 42 to 48 parts by mass, and 2 to 12 parts by mass, respectively.
In some embodiments of the present application, the amounts of the vinylidene cyanide, the vinyl acetate, the initiator and the two-dimensional nano-piezoelectric material are 40 to 46 parts by mass, 42 to 48 parts by mass, 2 to 4 parts by mass and 2 to 10 parts by mass, respectively.
In some embodiments herein, the initiator is benzoyl peroxide. It is understood that other molecules capable of initiating the polymerization of vinylidene cyanide and vinyl acetate are also within the scope of the present initiator.
In some embodiments of the present application, the two-dimensional nano-piezoelectric material is subjected to ultrasonic exfoliation prior to use.
In some embodiments herein, the reaction solvent is an organic solvent selected from at least one of benzene, toluene, xylene, butylbenzene, biphenyl.
In some embodiments of the present application, the parameters of the electric field polarization are set as: polarizing at 140-180 ℃ and under the electric field intensity of 30-60 MV/m for 1-2 hours. All traces of solvent can be removed simultaneously during the constant temperature polarization process by this condition.
In a fourth aspect of the present application, there is provided a surface sterilization method of an object, the surface sterilization method including the steps of: and contacting the nano piezoelectric fiber film with the surface of an object, and pressing the nano piezoelectric fiber film.
In a fifth aspect of the present application, there is provided an application of the aforementioned nano piezoelectric fiber film material or nano piezoelectric fiber film in the preparation of sterilization products or sterilization of surfaces of objects.
In some embodiments of the present application, the species against which the bactericidal is directed comprises at least one of Staphylococcus aureus (s. aureus), Escherichia coli (e.coli), Candida albicans (C albicans).
The nano piezoelectric fiber film provided by the application is mainly prepared by taking an amorphous copolymer of vinylidene cyanide and vinyl acetate as a matrix and taking a two-dimensional piezoelectric nano material as a reinforcement through electrostatic spinning combined with uniaxial stretching and electric field polarization. This nanometer piezoelectric fiber film has good transparency, high electrical activity, outstanding mechanical properties and dielectric properties, consequently can produce bigger electric field, and bactericidal effect is better, and when the exogenic action exerted weak pressure (like touching, pressing etc.) to this nanometer piezoelectric fiber film, it can produce active free radical, plays the effect of automatic kill superficial bacterium. Moreover, due to the high transparency and flexibility of the nano piezoelectric fiber film, the nano piezoelectric fiber film can be widely applied to sterilization in various fields of daily contact of human bodies such as mobile phone shells, elevator buttons, computer keyboards and other wearable devices, and can prevent bacterial propagation on the premise of ensuring beauty.
Additional aspects and advantages of the present application will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the present application.
Drawings
Fig. 1 is a scanning electron microscope picture of a cross section of a nano piezoelectric fiber thin film prepared in example 1 of the present application.
Fig. 2 is a result of detecting killing rates of different bacteria by the nano piezoelectric fiber films prepared in example 1 and comparative examples 1 and 2 in the application.
Fig. 3 is a detection result of the visible light transmittance of the nano piezoelectric fiber film prepared in example 1 of the present application.
Fig. 4 is a detection result of the visible light transmittance of the nano piezoelectric fiber film prepared in example 2 of the present application.
Fig. 5 is a result of detecting killing rates of different bacteria by the nano piezoelectric fiber film prepared in example 2 of the present application.
Fig. 6 is a result of detecting the killing rate of the nano piezoelectric fiber film on different bacteria, which is prepared in comparative example 3 of the present application.
Detailed Description
The conception and the resulting technical effects of the present application will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, and not all embodiments, and other embodiments obtained by those skilled in the art without inventive efforts based on the embodiments of the present application belong to the protection scope of the present application.
The following detailed description of embodiments of the present application is provided for the purpose of illustration only and is not intended to be construed as a limitation of the application.
In the description of the present application, the meaning of a plurality is one or more, the meaning of a plurality is two or more, and the above, below, exceeding, etc. are understood as excluding the present number, and the above, below, within, etc. are understood as including the present number. If the first and second are described for the purpose of distinguishing technical features, they are not to be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
In the description of the present application, reference to the description of the terms "one embodiment," "some embodiments," "an illustrative embodiment," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Example 1
The embodiment provides a nano piezoelectric fiber film, and the raw materials for preparing the nano piezoelectric fiber film comprise: 43 parts by mass of vinylidene cyanide, 47.5 parts by mass of vinyl acetate, 3.5 parts by mass of benzoyl peroxide, and 6 parts by mass of MoSe2. The preparation method of the nano piezoelectric fiber film comprises the following steps:
(1) vinylidene cyanide, vinyl acetate and MoSe2Drying at 70 deg.C for 24 h.
(2) Dissolving the dried vinylidene cyanide and vinyl acetate in 50mL benzene solution respectively, mixing the solutions, dripping benzoyl peroxide as an initiator, and keeping the temperature in a water bath at 45 ℃ for 2 hours to obtain a precipitate containing poly (vinylidene cyanide/vinyl acetate).
(3) Washing the precipitate with distilled benzene, dissolving the solid in dimethyl formamide solution, and adding benzene solution to separate out the precipitate to obtain white solid.
(4) The obtained white solid was dissolved in 10mL of dimethylformamide solution, and MoSe was added thereto2Ultrasonically dispersing the mixture in a solution to obtain a spinning solution, and preparing a film with the thickness of about 60 mu m under the conditions that the liquid outlet speed is 1.5mL/h, the direct-current voltage is 20kV, the environmental humidity is 30%, the environmental temperature is 26 ℃, the spinning distance is 20cm, and the electrostatic spinning time is 5 h.
(5) The obtained film was uniaxially stretched at a stretching ratio of 3, and then the film was subjected to polarization at a constant temperature of 150 ℃ for 2 hours at an electric field strength of 30MV/m while removing all traces of the solvent to obtain a nano piezoelectric fiber film.
Fig. 1 is a scanning electron microscope picture of a cross section of the nano piezoelectric fiber thin film prepared. As can be seen from the figure, the piezoelectric composite material of nanometer scale is obtained by electrostatic spinning.
Piezoelectric sterilization performance detection experiment:
taking the nano piezoelectric fiber film as a test sample, uniformly dispersing the bacterial colony solution on the test sample, then covering a layer of clean quartz plate, intermittently pressing the quartz plate by fingers, and detecting the bacterial colony number on the test sample after 2 minutes. Taking a clean quartz plate as a reference sample, uniformly dispersing the colony solution with the same volume and concentration on the reference sample, covering a layer of clean quartz plate, intermittently pressing the quartz plate by fingers, and detecting the number of colonies on the reference sample after 2 minutes. The killing rate of the nano piezoelectric fiber film is calculated as follows:
percent killing rate (%) - (number of colonies of control sample-number of colonies of test sample)/number of colonies of control sample × 100%
Referring to fig. 2, it is detected that the nano piezoelectric fiber film prepared in example 1 has a killing rate of 96.53% to bacteria within 2 minutes.
In addition, the visible light head reflectivity tester is used for measuring the transmittance of the nano piezoelectric fiber film to visible light, and the result is shown in fig. 3, and it can be seen from the graph that the transmittance of the nano piezoelectric fiber film to visible light of each wave band is up to 79.1%, and the nano piezoelectric fiber film has high transparency.
Example 2
The embodiment provides a nano piezoelectric fiber film, and the raw materials for preparing the nano piezoelectric fiber film comprise: 44 parts by mass of vinylidene cyanide, 48 parts by mass of vinyl acetate, 2 parts by mass of benzoyl peroxide, and 6 parts by mass of MoS2. The preparation method of the nano piezoelectric fiber film comprises the following steps:
(1) mixing vinylidene cyanide, vinyl acetate and MoS2Drying at 70 deg.C for 24 h.
(2) Dissolving the dried vinylidene cyanide and vinyl acetate in 50mL benzene solution respectively, mixing the solutions, dripping benzoyl peroxide as an initiator, and keeping the temperature in a water bath at 45 ℃ for 2 hours to obtain a precipitate containing poly (vinylidene cyanide/vinyl acetate).
(3) Washing the precipitate with distilled benzene, dissolving the solid in dimethyl sulfoxide solution, and adding benzene solution to separate out the precipitate to obtain white solid.
(4) The obtained white solid was dissolved in 10mL of a dimethylsulfoxide amine solution, and MoS was added2Ultrasonically dispersing the mixture in a solution to obtain a spinning solution, and preparing a film with the thickness of about 60 mu m under the conditions that the liquid outlet speed is 1mL/h, the direct-current voltage is 15kV, the environmental humidity is 30%, the environmental temperature is 26 ℃, the spinning distance is 15cm, and the electrostatic spinning time is 6 h.
(5) The obtained film was uniaxially stretched at a stretching ratio of 3, and then the film was subjected to polarization at a constant temperature of 150 ℃ for 2 hours at an electric field strength of 30MV/m while removing all traces of the solvent to obtain a nano piezoelectric fiber film.
The results of measuring the transmittance and the sterilization rate of the nano piezoelectric fiber film prepared in this example are shown in fig. 4 and 5, wherein the transmittance is 77.8% and the sterilization rate is about 95%, and the results show that the nano piezoelectric fiber film prepared in this example has similar sterilization effect and transparency to those of example 1.
Example 3
The embodiment provides a nano piezoelectric fiber film, and the raw materials for preparing the nano piezoelectric fiber film comprise: 44 parts by mass of vinylidene cyanide, 48 parts by mass of vinyl acetate, 2 parts by mass of benzoyl peroxide, and 6 parts by mass of In2Se3. The preparation method of the nano piezoelectric fiber film comprises the following steps:
(1) vinylidene cyanide, vinyl acetate and In2Se3Drying at 70 deg.C for 24 h.
(2) Dissolving the dried vinylidene cyanide and vinyl acetate in 50mL benzene solution respectively, mixing the solutions, dripping benzoyl peroxide as an initiator, and keeping the temperature in a water bath at 45 ℃ for 2 hours to obtain a precipitate containing poly (vinylidene cyanide/vinyl acetate).
(3) Washing the precipitate with distilled benzene, dissolving the solid in dimethyl formamide solution, and adding benzene solution to separate out the precipitate to obtain white solid.
(4) The obtained white solid was dissolved In 10mL of dimethylformamide solution, and In was added2Se3Ultrasonically dispersing the mixture in a solution to obtain a spinning solution, and preparing a film with the thickness of about 60 mu m under the conditions that the liquid outlet speed is 1.5mL/h, the direct-current voltage is 20kV, the environmental humidity is 30%, the environmental temperature is 26 ℃, the spinning distance is 20cm, and the electrostatic spinning time is 5 h.
(5) The obtained film was uniaxially stretched at a stretching ratio of 3, and then the film was subjected to polarization at a constant temperature of 150 ℃ for 2 hours at an electric field strength of 30MV/m while removing all traces of the solvent to obtain a nano piezoelectric fiber film.
The nano piezoelectric fiber film prepared in the embodiment has similar sterilization effect and transparency as those of the embodiment 1.
Example 4
The embodiment provides a nano piezoelectric fiber film, and the raw materials for preparing the nano piezoelectric fiber film comprise: 44 parts by mass of vinylidene cyanide, 48 parts by mass of vinyl acetate, 2 parts by mass of benzoyl peroxide, and 6 parts by mass of In2S3. The preparation method of the nano piezoelectric fiber film comprises the following steps:
(1) vinylidene cyanide, vinyl acetate and In2S3Drying at 70 deg.C for 24 h.
(2) Dissolving the dried vinylidene cyanide and vinyl acetate in 50mL benzene solution respectively, mixing the solutions, dripping benzoyl peroxide as a catalyst, and keeping the temperature in a water bath at 45 ℃ for 2 hours to obtain a precipitate containing poly (vinylidene cyanide/vinyl acetate).
(3) Washing the precipitate with distilled benzene, dissolving the solid in dimethyl formamide solution, and adding benzene solution to separate out the precipitate to obtain white solid.
(4) The prepared white solid was dissolved In 10mL of dimethylformamide solution, and In was added2S3Ultrasonically dispersing in the solution to obtain spinning solutionThe film is prepared under the conditions of the liquid outlet speed of 1mL/h, the direct current voltage of 20kV, the environmental humidity of 30 percent, the environmental temperature of 26 ℃, the spinning distance of 15cm and the electrostatic spinning time of 6h, and the thickness is about 60 mu m.
(5) The obtained film was uniaxially stretched at a stretching ratio of 3, and then the film was subjected to polarization at a constant temperature of 160 ℃ for 2 hours at an electric field strength of 40MV/m while removing all traces of the solvent to obtain a nano piezoelectric fiber film.
The nano piezoelectric fiber film prepared in the embodiment has similar sterilization effect and transparency as those of the embodiment 1.
Example 5
The embodiment provides a nano piezoelectric fiber film, and the raw materials for preparing the nano piezoelectric fiber film comprise: 44 parts by mass of vinylidene cyanide, 48 parts by mass of vinyl acetate, 2 parts by mass of benzoyl peroxide and 6 parts by mass of SnS. The preparation method of the nano piezoelectric fiber film comprises the following steps:
(1) the vinylidene cyanide, vinyl acetate and SnS were dried at 70 ℃ for 24 h.
(2) Dissolving the dried vinylidene cyanide and vinyl acetate in 50mL benzene solution respectively, mixing the solutions, dripping benzoyl peroxide as a catalyst, and keeping the temperature in a water bath at 45 ℃ for 2 hours to obtain a precipitate containing poly (vinylidene cyanide/vinyl acetate).
(3) Washing the precipitate with distilled benzene, dissolving the solid in dimethyl formamide solution, and adding benzene solution to separate out the precipitate to obtain white solid.
(4) Dissolving the obtained white solid in 12mL of dimethylformamide solution, then dispersing SnS in the solution by ultrasonic to obtain spinning solution, and preparing a film with the thickness of about 60 mu m under the conditions of the liquid outlet speed of 1mL/h, the direct current voltage of 20kV, the environmental humidity of 30%, the environmental temperature of 26 ℃, the spinning distance of 15cm and the electrostatic spinning time of 6 h.
(5) The obtained film was uniaxially stretched at a stretching ratio of 3, and then the film was subjected to polarization at a constant temperature of 150 ℃ for 2 hours at an electric field strength of 40MV/m while removing all traces of the solvent to obtain a nano piezoelectric fiber film.
The nano piezoelectric fiber film prepared in the embodiment has similar sterilization effect and transparency as those of the embodiment 1.
Comparative experiment
Comparative example 1
The comparative example provides a nano piezoelectric fiber film, which is prepared from the following raw materials: 45.5 parts by mass of vinylidene cyanide, 50 parts by mass of vinyl acetate and 4.5 parts by mass of benzoyl peroxide. The preparation method of the nano piezoelectric fiber film comprises the following steps:
(1) the vinylidene cyanide and vinyl acetate were dried at 70 ℃ for 24 h.
(2) Dissolving the dried vinylidene cyanide and vinyl acetate in 50mL benzene solution respectively, mixing the solutions, dripping benzoyl peroxide as an initiator, and keeping the temperature in a water bath at 45 ℃ for 2 hours to obtain a precipitate containing poly (vinylidene cyanide/vinyl acetate).
(3) Washing the precipitate with distilled benzene, dissolving the solid in dimethyl formamide solution, and adding benzene solution to separate out precipitate to obtain white solid.
(4) Dissolving the prepared white solid in 10mL of dimethylformamide solution to obtain spinning solution, and preparing a film with the thickness of about 60 mu m under the conditions of liquid outlet speed of 1.5mL/h, direct current of 20kV, spinning distance of 20cm and electrostatic spinning time of 5 h.
(5) The obtained film was uniaxially stretched at a stretching ratio of 3, and then the film was subjected to polarization at a constant temperature of 150 ℃ for 2 hours at an electric field strength of 30MV/m while removing all traces of the solvent to obtain a nano piezoelectric fiber film.
Comparative example 2
The comparative example is a two-dimensional MoSe2The sheet is used as a nano piezoelectric sterilization membrane layer material for testing, and the specific testing method comprises the following steps:
(1) 6 parts by mass of two-dimensional MoSe2The tablets were dispersed in 200mL of ultrapure water.
(2) After dispersing for 2 hours, adopting a vacuum filtration method to filter the two-dimensional MoSe2The sheets are filtered on a filter membraneThe filter was then inverted on a clean quartz plate.
(3) After the filter membrane is taken down, the bacterial colony is uniformly dispersed in two-dimensional MoSe2And covering a layer of clean quartz plate on the wafer.
(4) The quartz plate is intermittently pressed by fingers, and the number of colonies is detected after 2 minutes.
Referring to fig. 2, it can be seen that the killing rate of the nano piezoelectric fiber film prepared in comparative example 1 to the bacteria in 2 minutes is only 40-50%, while the killing rate of comparative example 2 is 65-75%, and the killing rates of the nano piezoelectric fiber film and the nano piezoelectric fiber film are far lower than that of example 1 by more than 96%. Therefore, after the nano piezoelectric fiber film is prepared by combining the two materials, the killing rate of each strain is remarkably improved.
Comparative example 3
The comparative example provides a nano piezoelectric fiber film, which is prepared from the following raw materials: 44 parts by mass of metacyanoethylene, 48 parts by mass of vinyl acetate, 2 parts by mass of benzoyl peroxide and 6 parts by mass of nano potassium-sodium niobate. The preparation method of the nano piezoelectric fiber film comprises the following steps:
(1) the metacyanoethylene, vinyl acetate and potassium sodium niobate are dried for 24 hours at 70 ℃.
(2) Dissolving the dried vinylidene cyanide and vinyl acetate in 50mL benzene solution respectively, mixing the solutions, dripping benzoyl peroxide as a catalyst, and keeping the temperature in a water bath at 45 ℃ for 2 hours to obtain a precipitate containing poly (vinylidene cyanide/vinyl acetate).
(3) Washing the precipitate with distilled benzene, dissolving the solid in dimethyl formamide solution, and adding benzene solution to separate out the precipitate to obtain white solid.
(4) Dissolving the prepared white solid in 10mL of dimethylformamide solution, ultrasonically dispersing potassium-sodium niobate in the solution to obtain spinning solution, and preparing a film with the thickness of about 60 mu m under the conditions of liquid outlet speed of 1mL/h, direct current voltage of 20kV, spinning distance of 15cm and electrostatic spinning time of 6 h.
(5) The obtained film was uniaxially stretched at a stretching ratio of 3, and then the film was subjected to polarization at a constant temperature of 160 ℃ for 2 hours at an electric field strength of 40MV/m while removing all traces of the solvent to obtain a nano piezoelectric fiber film.
The detection result of the piezoelectric sterilization performance is shown in fig. 6, and it can be seen from the figure that the sterilization efficiency of the comparative example to various bacteria is only maintained at about 70-80%, and the effect difference of more than 90% can be achieved compared with the embodiment is obvious. It can be seen that the nano potassium sodium niobate used in this comparative example is also a nano piezoelectric material, but the nano piezoelectric fiber film material prepared by the same method as the present solution is far inferior to example 1 in piezoelectric sterilization performance.
Example 6
The embodiment provides a nano piezoelectric fiber film, and the raw materials for preparing the nano piezoelectric fiber film comprise: 41 parts by mass of vinylidene cyanide, 45 parts by mass of vinyl acetate, 2 parts by mass of benzoyl peroxide, 3 parts by mass of SnS and 9 parts by mass of WSe2. The preparation method of the nano piezoelectric fiber film comprises the following steps:
(1) vinylidene cyanide, vinyl acetate, SnS and WSe2Drying at 70 deg.C for 24 h.
(2) Dissolving the dried vinylidene cyanide and vinyl acetate in 50mL benzene solution respectively, mixing the solutions, dripping benzoyl peroxide as a catalyst, and keeping the temperature in a water bath at 45 ℃ for 2 hours to obtain a precipitate containing poly (vinylidene cyanide/vinyl acetate).
(3) Washing the precipitate with distilled benzene, dissolving the solid in dimethyl formamide solution, and adding benzene solution to separate out the precipitate to obtain white solid.
(4) The obtained white solid was dissolved in 12mL of dimethylformamide solution, and SnS and WSe were added2Ultrasonically dispersing in the solution to obtain a spinning solution, and preparing a film with the thickness of about 60 mu m under the conditions of the liquid outlet speed of 1mL/h, the direct-current voltage of 20kV, the spinning distance of 15cm and the electrostatic spinning time of 6 h.
(5) The obtained film was uniaxially stretched at a stretching ratio of 3, and then the film was subjected to polarization at a constant temperature of 150 ℃ for 2 hours at an electric field strength of 40MV/m while removing all traces of the solvent to obtain a nano piezoelectric fiber film.
Through detection, the nano piezoelectric fiber film prepared in the embodiment has slightly inferior bactericidal effect and transparency compared with the nano piezoelectric fiber film prepared in the embodiment 1.
The present application has been described in detail with reference to the embodiments, but the present application is not limited to the embodiments described above, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present application. Furthermore, the embodiments and features of the embodiments of the present application may be combined with each other without conflict.

Claims (10)

1. The nano piezoelectric fiber film material is characterized by comprising a base material and a reinforcement material, wherein the reinforcement material is dispersed in the base material, the base material comprises 70-100 parts by mass of poly (vinylidene cyanide/vinyl acetate), and the reinforcement material comprises 2-15 parts by mass of a two-dimensional nano piezoelectric material.
2. The nano-piezoelectric fiber membrane material of claim 1, wherein the two-dimensional nano-piezoelectric material is a two-dimensional transition metal chalcogenide.
3. The nano-piezoelectric fiber film material of claim 2, wherein the two-dimensional transition metal chalcogenide is selected from MoSe2、MoS2、MoTe2、WS2、WSe2、WTe2、SnS、SnSe、In2Se3、In2S3At least one of (1).
4. A nano-piezoelectric fiber membrane comprising the nano-piezoelectric fiber membrane material according to any one of claims 1 to 3.
5. The method for preparing the nano piezoelectric fiber film according to claim 4, comprising the steps of:
dissolving poly (vinylidene cyanide/vinyl acetate) in an organic solvent, adding a two-dimensional piezoelectric nano material, and uniformly stirring to obtain a spinning solution;
and (3) taking the spinning solution, carrying out electrostatic spinning to obtain a film material, and carrying out electric field polarization to obtain the nano piezoelectric fiber film.
6. The method according to claim 5, wherein the thin film material is further subjected to uniaxial stretching treatment before electric field polarization.
7. The method according to claim 5, wherein the electric field polarization is set to have parameters of: polarizing at 140-180 ℃ and under the electric field intensity of 30-60 MV/m for 1-2 hours.
8. A method for sterilizing the surface of an object, comprising bringing the nano piezoelectric fiber film according to claim 4 into contact with the surface of the object and pressing the nano piezoelectric fiber film.
9. Use of the nano-piezoelectric fiber film material of any one of claims 1 to 3 or the nano-piezoelectric fiber film of claim 4 in the preparation of a sterilization product or sterilization of the surface of an object.
10. The use of claim 9, wherein the bactericidal target species comprises at least one of staphylococcus aureus, escherichia coli, candida albicans.
CN202111333667.XA 2021-11-11 2021-11-11 Nano piezoelectric fiber film material and preparation method and application thereof Pending CN114164563A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108121475A (en) * 2016-11-29 2018-06-05 乐金显示有限公司 Touch sensitive elements and the display device including the touch sensitive elements
CN111270414A (en) * 2020-03-23 2020-06-12 清华大学深圳国际研究生院 Flexible piezoelectric fiber membrane and preparation method and application thereof
CN111363277A (en) * 2020-04-27 2020-07-03 南京航空航天大学 Polymer-based piezoelectric film and preparation method and application thereof
CN113101971A (en) * 2021-03-15 2021-07-13 山东师范大学 PVDF/MoS2AuNPS material and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108121475A (en) * 2016-11-29 2018-06-05 乐金显示有限公司 Touch sensitive elements and the display device including the touch sensitive elements
CN111270414A (en) * 2020-03-23 2020-06-12 清华大学深圳国际研究生院 Flexible piezoelectric fiber membrane and preparation method and application thereof
CN111363277A (en) * 2020-04-27 2020-07-03 南京航空航天大学 Polymer-based piezoelectric film and preparation method and application thereof
CN113101971A (en) * 2021-03-15 2021-07-13 山东师范大学 PVDF/MoS2AuNPS material and preparation method and application thereof

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