阅读说明：本技术 一种防霜透光的静电纺丝薄膜及其制备方法和应用 (Anti-frost light-transmitting electrostatic spinning film and preparation method and application thereof ) 是由 谢柢丰 王国勇 连建设 孙贵训 于 2020-11-26 设计创作，主要内容包括：本发明适用于防霜技术领域,提供了一种防霜透光的静电纺丝薄膜及其制备方法和应用,该制备方法包括以下步骤：将至少一种纺丝液进行静电纺丝,得到半成品薄膜；所述纺丝液包括疏水性聚合物和有机溶剂,其中,疏水性聚合物的质量百分比浓度为4%~25%；将半成品薄膜置于饱和食盐水上,形成所述静电纺丝薄膜。该制备方法制得的静电纺丝薄膜抑制结霜的效果极佳,透光性良好,其纳米纤维尺寸均匀,具有较好的疏水性,具有致密的孔径,并且薄膜下方的饱和食盐水,能够有效吸附周围空气中的水分,从而使得薄膜周围形成干区,抑制结霜,可以使得抑制结霜时间高达30分钟以上,不出现冰晶。(The invention is suitable for the technical field of frost prevention, and provides a frost-prevention light-transmission electrostatic spinning film, a preparation method and application thereof, wherein the preparation method comprises the following steps: carrying out electrostatic spinning on at least one spinning solution to obtain a semi-finished film; the spinning solution comprises a hydrophobic polymer and an organic solvent, wherein the mass percentage concentration of the hydrophobic polymer is 4% -25%; and placing the semi-finished film on saturated salt water to form the electrostatic spinning film. The electrostatic spinning film prepared by the preparation method has the advantages of excellent frosting inhibition effect, good light transmission, uniform nanofiber size, good hydrophobicity and compact pore size, and the saturated salt solution below the film can effectively adsorb moisture in the surrounding air, so that a dry area is formed around the film, frosting is inhibited, the frosting inhibition time can be up to more than 30 minutes, and no ice crystal appears.)

1. The preparation method of the anti-frost light-transmitting electrostatic spinning film is characterized by comprising the following steps of:

carrying out electrostatic spinning on at least one spinning solution to obtain a semi-finished film; the spinning solution comprises a hydrophobic polymer and an organic solvent, wherein the mass percentage concentration of the hydrophobic polymer is 4% -25%;

and placing the semi-finished film on saturated salt water to form the electrostatic spinning film.

2. The method for preparing the anti-frost light-transmitting electrospun film according to claim 1, wherein the step of electrospinning at least one spinning solution to obtain a semi-finished film specifically comprises:

respectively carrying out electrostatic spinning on the spinning solution A and the spinning solution B to form fibers, and spraying out the fibers together to enable the fibers formed by the spinning solution B to wrap the fibers formed by the spinning solution A, so that a coaxial wrapping state is formed, and a semi-finished film is obtained; the spinning solution A and the spinning solution B both comprise hydrophobic polymers and organic solvents, the mass percentage concentration of the hydrophobic polymers in the spinning solution A is 4% -25%, and the mass percentage concentration of the hydrophobic polymers in the spinning solution B is 4% -25%.

3. The method for preparing the electrostatic spinning film with frost prevention and light transmission functions as claimed in claim 1 or 2, wherein the hydrophobic polymer is at least one of polymethyl methacrylate, polystyrene and polyvinylidene fluoride.

4. The method for preparing the anti-frost light-transmitting electrospun film according to claim 1 or 2, wherein the organic solvent is at least one of N, N-dimethylformamide and tetrahydrofuran.

5. The method for preparing the anti-frost light-transmitting electrospun film according to claim 1 or 2, wherein in the step, the voltage of electrospinning is 15-25 kV.

6. An electrospun film prepared by the process of any one of claims 1 to 5.

7. The frostproof and light-transmitting electrospun film according to claim 6, wherein the electrospun film has a water contact angle of not less than 143.563 ° and a light transmittance of not less than 90%.

8. Use of the electrospun film of claim 6 or 7 for the preparation of an anti-frost material.

Technical Field

The invention belongs to the technical field of frost prevention, and particularly relates to a frost-prevention light-transmission electrostatic spinning film, and a preparation method and application thereof.

Background

The accumulation of frost often leads to inconvenience and sometimes serious consequences for the life of people. Even in industrial applications, presents economic and safety problems. The ice and frost layers often present serious problems due to the covering of the surface, such as: (1) poor visibility on the glass of transportation means such as airplanes, cars, trains, etc.; (2) poor visibility of traffic lights and surveillance systems; (3) a decrease in the efficiency of the solar heat exchanger and the power generation efficiency; (4) breakage of transmission lines in winter; (5) aerodynamic performance deteriorates; (6) the air quality decreases and the performance of the aircraft wing decreases. The solution to these problems is usually to heat the cold surface or to spray antifreeze.

However, these methods are not only inefficient, but also cause environmental pollution and make defrosting difficult. Ice and frost formation conditions are nucleation sites and freezing points. Most of the traditional frost-proof and anti-icing materials are super-hydrophobic surfaces, and once the super-hydrophobic surfaces are iced, the deicing becomes extremely difficult. Furthermore, during daily use, dust and impurities are not inhibited from forming, and the ambient humidity and also the air flow are not predictable. Thus the nucleation site cannot prevent production. Therefore, frost prevention can only be achieved by lowering the freezing point. Therefore, how to reduce the freezing point is realized, the cost is low, the preparation process is simple, the frost prevention function can be realized on the basis of light transmission, and the key of the preparation is to reduce the freezing point.

Disclosure of Invention

The embodiment of the invention aims to provide a preparation method of an anti-frost light-transmitting electrostatic spinning film, and aims to solve the problems in the background art.

The embodiment of the invention is realized in such a way that the preparation method of the anti-frost light-transmitting electrostatic spinning film is characterized by comprising the following steps:

carrying out electrostatic spinning on at least one spinning solution to obtain a semi-finished film; the spinning solution comprises a hydrophobic polymer and an organic solvent, wherein the mass percentage concentration of the hydrophobic polymer is 4% -25%;

and placing the semi-finished film on saturated salt water to form the electrostatic spinning film.

As a preferable scheme of the embodiment of the present invention, the step of performing electrostatic spinning on at least one spinning solution to obtain a semi-finished film specifically includes:

respectively carrying out electrostatic spinning on the spinning solution A and the spinning solution B to form fibers, and spraying out the fibers together to enable the fibers formed by the spinning solution B to wrap the fibers formed by the spinning solution A, so that a coaxial wrapping state is formed, and a semi-finished film is obtained; the spinning solution A and the spinning solution B both comprise hydrophobic polymers and organic solvents, the mass percentage concentration of the hydrophobic polymers in the spinning solution A is 4% -25%, and the mass percentage concentration of the hydrophobic polymers in the spinning solution B is 4% -25%.

In another preferred embodiment of the present invention, the hydrophobic polymer is at least one of polymethyl methacrylate, polystyrene, and polyvinylidene fluoride.

In another preferred embodiment of the present invention, the organic solvent is at least one of N, N-dimethylformamide and tetrahydrofuran.

In another preferable embodiment of the invention, in the step, the voltage of electrostatic spinning is 15 to 25 kV.

The embodiment of the invention also aims to provide an electrostatic spinning film prepared by the preparation method.

As another preferable scheme of the embodiment of the invention, the water contact angle of the electrostatic spinning film is not less than 143.563 degrees, and the light transmittance is not less than 90 percent.

The embodiment of the invention also aims to provide an application of the electrostatic spinning film in preparing an anti-frost material.

The preparation method of the anti-frost light-transmitting electrostatic spinning film provided by the embodiment of the invention has the following beneficial effects:

(1) the electrostatic spinning film prepared by the invention has excellent effect of inhibiting frosting, the nano fibers have uniform size, better hydrophobicity and compact pore size, and saturated salt solution below the film can effectively adsorb water in surrounding air, so that a dry area is formed around the film to inhibit frosting, the frosting inhibition time can reach more than 30 minutes, and ice crystals are not generated.

(2) The electrostatic spinning film prepared by the invention has good light transmittance, can reach 90% of light transmittance in a visible light range, and can be used for cleaning objects below the film.

(3) The electrostatic spinning film prepared by the invention has good corrosion resistance, and can increase the corrosion resistance of a metal substrate.

(4) The preparation method provided by the invention has the advantages of simple process, high forming efficiency, repeatability and low cost, and can be used for industrial production.

Drawings

FIG. 1 is a scanning electron micrograph of an electrospun film prepared according to example 1.

Fig. 2 is a contact angle test chart of the electrospun film prepared in example 1.

FIG. 3 is a graph showing the transmittance of the electrospun film prepared in example 1.

FIG. 4 is a graph showing a comparison of the light transmittance of electrospun films prepared in examples 1-4.

FIG. 5 is a Zeiss micrograph of the electrospun film prepared in example 1 on a cold stage.

FIG. 6 is a photomicrograph of the electrospun film prepared in example 1 on a cold stage.

Fig. 7 is a photograph of hydrochloric acid droplets of the electrospun film prepared in example 1.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The embodiment provides a preparation method of a frost-proof light-transmitting electrostatic spinning film, which comprises the following steps:

s1, adding polyvinylidene fluoride into N, N-dimethylformamide, and stirring for 8 hours by using a magnetic stirrer to prepare a spinning solution A with the mass percentage concentration of 15% for later use; adding polymethyl methacrylate into N, N-dimethylformamide, and stirring for 8 hours by using a magnetic stirrer to prepare spinning solution B with the mass percentage concentration of 25% for later use.

S2, placing the prepared spinning solution A and the prepared spinning solution B in a pushing injection A and a pushing injection B of an electrostatic spinning machine respectively, placing a stainless steel net on a receiver, enabling the distance between a spray head and the receiver to be 15cm, enabling the spinning voltage to be 20kV, finally forming a thin nanofiber film layer on the stainless steel net, enabling fibers formed by the spinning solution B to wrap the fibers formed by the spinning solution A, forming a coaxial wrapping state, and obtaining a semi-finished product film.

S3, placing the semi-finished film on saturated salt water to form the anti-frost light-transmitting electrostatic spinning film.

Example 2

The embodiment provides a preparation method of a frost-proof light-transmitting electrostatic spinning film, which comprises the following steps:

s1, adding polyvinylidene fluoride into N, N-dimethylformamide, stirring for 8 hours by using a magnetic stirrer, and preparing a spinning solution with the mass percentage concentration of 15% for later use.

S2, placing the prepared spinning solution in a pushing injection mode of an electrostatic spinning machine, placing a stainless steel net on a receiver, enabling the distance between a spray head and the receiver to be 15cm, enabling the spinning voltage to be 15kV, and finally forming a thin nanofiber membrane on the stainless steel net to obtain a semi-finished product membrane.

S3, placing the semi-finished film on saturated salt water to form the electrostatic spinning film.

Example 3

The embodiment provides a preparation method of a frost-proof light-transmitting electrostatic spinning film, which comprises the following steps:

s1, adding polymethyl methacrylate into N, N-dimethylformamide, stirring for 8 hours by using a magnetic stirrer, and preparing a spinning solution with the mass percentage concentration of 25% for later use.

S2, placing the prepared spinning solution in a pushing injection mode of an electrostatic spinning machine, placing a stainless steel net on a receiver, enabling the distance between a spray head and the receiver to be 15cm, enabling the spinning voltage to be 15kV, and finally forming a thin nanofiber membrane on the stainless steel net to obtain a semi-finished product membrane.

S3, placing the semi-finished film on saturated salt water to form the electrostatic spinning film.

Example 4

The embodiment provides a preparation method of a frost-proof light-transmitting electrostatic spinning film, which comprises the following steps:

s1, adding polymethyl methacrylate into N, N-dimethylformamide, and stirring for 8 hours by using a magnetic stirrer to prepare spinning solution A with the mass percentage concentration of 4% for later use; adding polystyrene into N, N-dimethylformamide to prepare a spinning solution B with the mass percentage concentration of 6%, adding fumed silica with the mass fraction of 0.5% into the spinning solution B, and stirring for 8 hours by using a magnetic stirrer for later use.

S2, placing the prepared spinning solution A and the prepared spinning solution B in a pushing injection A and a pushing injection B of an electrostatic spinning machine respectively, placing a stainless steel net on a receiver, enabling the distance between a spray head and the receiver to be 15cm, enabling the spinning voltage to be 15kV, finally forming a thin nanofiber film layer on the stainless steel net, enabling fibers formed by the spinning solution B to wrap the fibers formed by the spinning solution A, forming a coaxial wrapping state, and obtaining a semi-finished product film.

S3, placing the semi-finished film on saturated salt water to form the anti-frost light-transmitting electrostatic spinning film.

Example 5

The embodiment provides a preparation method of a frost-proof light-transmitting electrostatic spinning film, which comprises the following steps:

s1, adding polyvinylidene fluoride into tetrahydrofuran, stirring for 8 hours by using a magnetic stirrer, and preparing spinning solution A with the mass percentage concentration of 25% for later use; adding polymethyl methacrylate into N, N-dimethylformamide, and stirring for 8 hours by using a magnetic stirrer to prepare spinning solution B with the mass percentage concentration of 4% for later use.

S2, placing the prepared spinning solution A and the prepared spinning solution B in a pushing injection A and a pushing injection B of an electrostatic spinning machine respectively, placing a stainless steel net on a receiver, enabling the distance between a spray head and the receiver to be 30cm, enabling the spinning voltage to be 20kV, finally forming a thin nanofiber film layer on the stainless steel net, enabling fibers formed by the spinning solution B to wrap the fibers formed by the spinning solution A, forming a coaxial wrapping state, and obtaining a semi-finished product film.

S3, placing the semi-finished film on saturated salt water to form the anti-frost light-transmitting electrostatic spinning film.

Example 6

The embodiment provides a preparation method of a frost-proof light-transmitting electrostatic spinning film, which comprises the following steps:

s1, adding polyvinylidene fluoride into a mixed solvent in which N, N-dimethylformamide and tetrahydrofuran are mixed according to the volume ratio of 1:4, stirring for 8 hours by using a magnetic stirrer, and preparing a spinning solution A with the mass percentage concentration of 20% for later use; adding polymethyl methacrylate into a mixed solvent in which N, N-dimethylformamide and tetrahydrofuran are mixed according to the volume ratio of 1:4, stirring for 8 hours by using a magnetic stirrer, and preparing a spinning solution B with the mass percentage concentration of 16% for later use.

S2, placing the prepared spinning solution A and the prepared spinning solution B in a pushing injection A and a pushing injection B of an electrostatic spinning machine respectively, placing a stainless steel net on a receiver, enabling the distance between a spray head and the receiver to be 10cm, enabling the spinning voltage to be 25kV, finally forming a thin nanofiber film layer on the stainless steel net, enabling fibers formed by the spinning solution B to wrap the fibers formed by the spinning solution A, forming a coaxial wrapping state, and obtaining a semi-finished product film.

S3, placing the semi-finished film on saturated salt water to form the anti-frost light-transmitting electrostatic spinning film.

Example 7

The embodiment provides a preparation method of a frost-proof light-transmitting electrostatic spinning film, which comprises the following steps:

s1, adding polyvinylidene fluoride into tetrahydrofuran, stirring for 8 hours by using a magnetic stirrer, and preparing spinning solution A with the mass percentage concentration of 10% for later use; adding polymethyl methacrylate into tetrahydrofuran, stirring for 8 hours by using a magnetic stirrer, and preparing spinning solution B with the mass percentage concentration of 10% for later use.

S2, placing the prepared spinning solution A and the prepared spinning solution B in a pushing injection A and a pushing injection B of an electrostatic spinning machine respectively, placing a stainless steel net on a receiver, enabling the distance between a spray head and the receiver to be 20cm, enabling the spinning voltage to be 20kV, finally forming a thin nanofiber film layer on the stainless steel net, enabling fibers formed by the spinning solution B to wrap the fibers formed by the spinning solution A, forming a coaxial wrapping state, and obtaining a semi-finished product film.

S3, placing the semi-finished film on saturated salt water to form the anti-frost light-transmitting electrostatic spinning film.

Experimental example:

1. the electrospun film prepared in example 1 was observed by a Scanning Electron Microscope (SEM) at a low magnification, and the result is shown in fig. 1. As can be seen from FIG. 1, the electrospun film prepared by the method of the invention has the advantages of interlaced fibers and high strength.

2. The electrospun film prepared in example 1 was subjected to a water contact angle test, and the result thereof is shown in fig. 2. As can be seen from fig. 2, the contact angle of the electrospun film prepared in example 1 is 143.563 °, which proves that the film has strong hydrophobicity, combines with the intricate structure between fibers, can better realize corrosion resistance, prevents surface liquid drops from entering into metal, can not allow water drops to gather on the surface, and can form a dry area on the surface of the film to delay frosting time by matching with the saturated saline solution below.

3. The electrospun film prepared in example 1 was subjected to a light transmittance test, and the result is shown in fig. 3. As can be seen from FIG. 3, the characters below the film and the characters outside the film are basically not different, and the characters below the film can be clearly seen, which proves that the film has better light transmission. In addition, the comparison results of the light transmittance of the electrospun films prepared in examples 1 to 4 are shown in fig. 4, and it can be seen from fig. 4 that the light transmittance of the electrospun film prepared in example 1 reaches 90% in the visible light range, which proves that the electrospun film provided by the example of the invention has good light transmittance.

4. A zeiss microscope photograph of the electrospun film prepared in example 1 on a cold stage is shown in fig. 5, a macroscopic photograph of the electrospun film prepared in example 1 on a cold stage is shown in fig. 6, and a photograph of hydrochloric acid droplets of the electrospun film prepared in example 1 is shown in fig. 7. As can be seen from fig. 5 and 6, in the case that most of the frost is formed on the cooling stage, the electrospun film on the stainless steel mesh in the middle does not change, and thus the good frost resistance is proved. As can be seen from fig. 7, when hydrochloric acid was placed on the electrospun film, it can be seen that the hydrochloric acid formed a spherical shape, so the electrospun film could have better corrosion resistance.

Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.