阅读说明：本技术 一种具有超疏水微纳米颗粒表面的材料及其制备方法 (Material with super-hydrophobic micro-nano particle surface and preparation method thereof ) 是由 刘慧� 张莉 罗欢 毛庆辉 于 2021-09-16 设计创作，主要内容包括：本发明属于材料制备技术领域,公开了一种具有超疏水微纳米颗粒表面的材料及其制备方法。制备方法包括：S1.将PDMS加入THF与DMF的混合溶剂中,超声至完全溶解,得到PDMS疏水涂层液；S2.将PMMA和PDMS加入THF与DMF的混合溶剂中,超声至完全溶解,得到PMMA/PDMS超疏水涂层液；S3.将所述PDMS疏水涂层液喷涂在基底上,得到PDMS@疏水表面基底；S4.将所述PMMA/PDMS超疏水涂层液喷涂在PDMS@疏水表面基底上,具有超疏水微纳米颗粒表面的材料。该制备方法简单,制备得到的材料超疏水性能良好。(The invention belongs to the technical field of material preparation, and discloses a material with a super-hydrophobic micro-nano particle surface and a preparation method thereof. The preparation method comprises the following steps: s1, adding PDMS into a mixed solvent of THF and DMF, and performing ultrasonic treatment until the PDMS is completely dissolved to obtain PDMS hydrophobic coating liquid; s2, adding PMMA and PDMS into a mixed solvent of THF and DMF, and performing ultrasonic treatment until the PMMA and PDMS are completely dissolved to obtain PMMA/PDMS super-hydrophobic coating liquid; s3, spraying the PDMS hydrophobic coating liquid on a substrate to obtain a PDMS @ hydrophobic surface substrate; and S4, spraying the PMMA/PDMS super-hydrophobic coating liquid on a PDMS @ hydrophobic surface substrate, wherein the PMMA/PDMS super-hydrophobic coating liquid is provided with a material on the surface of super-hydrophobic micro-nano particles. The preparation method is simple, and the prepared material has good super-hydrophobic property.)

1. A preparation method of a material with a super-hydrophobic micro-nano particle surface is characterized by comprising the following steps:

s1, adding PDMS into a mixed solvent of THF and DMF, and performing ultrasonic treatment until the PDMS is completely dissolved to obtain PDMS hydrophobic coating liquid;

s2, adding PMMA and PDMS into a mixed solvent of THF and DMF, and performing ultrasonic treatment until complete dissolution to obtain a PMMA/PDMS superhydrophobic coating solution, wherein the mass ratio of PMMA to PDMS to the mixed solvent of THF and DMF is (1-3): (1-3): 20;

s3, spraying the PDMS hydrophobic coating liquid on a substrate by adopting an electrostatic spinning device to obtain a PDMS @ hydrophobic surface substrate;

s4, spraying the PMMA/PDMS super-hydrophobic coating liquid on a PDMS @ hydrophobic surface substrate by adopting an electrostatic spinning device, wherein the PMMA/PDMS super-hydrophobic coating liquid is provided with a material on the surface of super-hydrophobic micro-nano particles;

wherein the conditions of the electrospinning device are as follows: the voltage is 15V, the flow rate is 0.05-0.5 mL/h, and the receiving distance is 15 cm.

2. The method according to claim 1, wherein the mass ratio of THF to DMF in the mixed solvent of THF and DMF is 1: 1.

3. The method according to claim 2, wherein in step S1, the mass ratio of the PDMS to the mixed solvent of THF and DMF is (1-4): 20.

4. the production method according to claim 2, wherein in step S2, the mass ratio of the PDMS, the PMMA, and the mixed solvent of THF and DMF is 1: 20.

5. the method of claim 1, wherein in step S3, the substrate is selected from one of fabric, glass, titanium sheet, paper, and wood.

6. The method according to claim 1, wherein in step S4, the flow rate of the electrospinning device is 0.5 mL/h.

7. The material with the super-hydrophobic micro-nano particle surface prepared by the preparation method of any one of claims 1 to 6.

Technical Field

The invention belongs to the technical field of material preparation, and relates to a material with a super-hydrophobic micro-nano particle surface and a preparation method thereof.

Background

The super-hydrophobic surface (the static contact angle is more than 150 degrees and the rolling contact angle is less than 10 degrees) has wide application in the aspects of self-cleaning, corrosion resistance, oil-water separation, pollution resistance, ice resistance, surface patterning, drag reduction and the like. The roughened surface and the low surface energy are two main factors for preparing the super-hydrophobic surface, and stable bubbles exist between rough fine seams with low surface energy, and can form a barrier layer at the interface of a water drop and a solid structure, so that a non-wetting state is ensured. The existing methods for constructing the superhydrophobic surface include sol-gel method, anodic oxidation, chemical vapor deposition, chemical etching, dipping method, etc., which have many problems in practical application, such as limited experimental conditions, complicated operation procedures, time consuming, substrate limitation, etc. Therefore, it is necessary to develop a simple, economical, time-saving and environment-friendly method for preparing a superhydrophobic surface. In addition, fluorocarbon compounds are often used to construct a wettable surface, however, these fluorine-containing compounds are not only expensive but also pose potential threats to human health and the environment, so the development of an economical and environmentally friendly raw material is very necessary.

Disclosure of Invention

The invention aims to provide a material with a super-hydrophobic micro-nano particle surface and a preparation method thereof.

The invention provides the following technical scheme:

a preparation method of a material with a super-hydrophobic micro-nano particle surface comprises the following steps:

s1, adding PDMS into a mixed solvent of THF and DMF, and performing ultrasonic treatment until the PDMS is completely dissolved to obtain PDMS hydrophobic coating liquid;

s2, adding PMMA and PDMS into a mixed solvent of THF and DMF, and performing ultrasonic treatment until complete dissolution to obtain a PMMA/PDMS superhydrophobic coating solution, wherein the mass ratio of PMMA to PDMS to the mixed solvent of THF and DMF is (1-3): (1-3): 20;

s3, spraying the PDMS hydrophobic coating liquid on a substrate by adopting an electrostatic spinning device to obtain a PDMS @ hydrophobic surface substrate;

s4, spraying the PMMA/PDMS super-hydrophobic coating liquid on a PDMS @ hydrophobic surface substrate by adopting an electrostatic spinning device, wherein the PMMA/PDMS super-hydrophobic coating liquid is provided with a material on the surface of super-hydrophobic micro-nano particles;

wherein the conditions of the electrospinning device are as follows: the voltage is 15V, the flow rate is 0.05-0.5 mL/h, and the receiving distance is 15 cm.

Further, in the mixed solvent of THF and DMF, the mass ratio of THF to DMF is 1: 1.

Further, in step S1, the mass ratio of the PDMS to the mixed solvent of THF and DMF is (1-4): 20.

further, in step S2, the mass ratio of the PDMS, the PMMA, and the mixed solvent of THF and DMF is 1: 20.

further, in step S3, the substrate is selected from one of fabric, glass, titanium sheet, paper, and wood.

Further, in step S4, the flow rate of the electrospinning device was 0.5 mL/h.

The invention also provides a material with the super-hydrophobic micro-nano particle surface, which is prepared by the preparation method.

Compared with the prior art, the surface prepared by the invention has the advantage of good super-hydrophobicity, and the preparation process is simple and convenient, has no subsequent treatment, and saves time and energy; the substrate is universal and can be constructed on the surfaces of various substrates; and the raw materials are low in cost, easy to obtain, free of fluorine, economical, environment-friendly and suitable for the requirement of environment-friendly development.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein the content of the first and second substances,

fig. 1 is a surface SEM image of three materials having a superhydrophobic micro-nano particle surface prepared in example 1 of the present invention;

fig. 2 is a surface SEM image of the material having the superhydrophobic micro-nano particle surface prepared in embodiment 2 of the present invention;

FIG. 3 is a surface SEM image of a material having a PDMS/PMMA hybrid coated (fibrous) surface prepared in comparative example 3;

FIG. 4 is an SEM image of the surface coating of the materials obtained in comparative example 1, comparative example 2 and example 1 (electrospinning apparatus flow rate of 0.5 mL/h);

FIG. 5 static contact angles of the surface coatings of the materials obtained in comparative example 1, comparative example 2 and example 1 (electrospinning apparatus flow rate of 0.5 mL/h).

Detailed Description

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the teaching of the present invention, and equivalents also fall within the scope of the claims of the present application.

Example 1

S1, weighing 1g of PDMS, 10g of THF and 10g of DMF (mass ratio of 1: 10), mixing and adding into a beaker, performing ultrasonic treatment at 40 ℃ to completely dissolve the PDMS and the THF to obtain a hydrophobic coating liquid, designing a liquid drop transportation path on the surface of a substrate by using cotton fabric as the substrate, and spraying the hydrophobic coating liquid on the transportation path through an electrostatic spinning device under the conditions that the voltage is 15V, the flow is 0.5mL/h and the receiving distance is 15cm to obtain the substrate with the PDMS hydrophobic coating surface;

s2, weighing 1g of PMMA, 1g of PDMS, 10g of THF and 10g of DMF (mass ratio of 1: 10) and adding into a beaker, and carrying out ultrasonic treatment at 40 ℃ to completely dissolve the PMMA, the PDMS, the THF and the DMF to obtain the super-hydrophobic coating liquid. And (3) spraying the super-hydrophobic coating liquid on the surface of a PDMS hydrophobic coating of a cotton fabric substrate by an electrostatic spinning device, wherein the electrostatic spraying condition is that the voltage is 15V, the flow control is 0.05mL/h, 0.1mL/h and 0.5mL/h, the receiving distance is 15cm, and three different materials with the super-hydrophobic micro-nano particle surface are obtained, and an SEM image is shown in figure 1.

In FIG. 1, (a) is an SEM image of the surface of a PDMS/PMMA superhydrophobic coating obtained by controlling the flow rate to 0.05 mL/h; (b) the figure is an SEM image of the surface of a PDMS/PMMA super-hydrophobic coating obtained by controlling the flow rate to be 0.1 mL/h; (c) the figure is an SEM image of the surface of a PDMS/PMMA superhydrophobic coating obtained by controlling the flow at 0.5 mL/h. According to FIG. 1, in the electrostatic spraying condition, when the flow rate is 0.05mL/h, 0.1mL/h and 0.5mL/h, the diameter of the obtained PDMS/PMMA particles is gradually increased, which means that the increase of the flow rate (spinning speed) of the electrostatic spinning device can improve the super-hydrophobic property of the finally obtained PDMS/PMMA mixed coating. In addition, as can be seen from fig. 1, the surface of the PDMS/PMMA superhydrophobic coating is micro-nano particles.

Example 2

S1, weighing 4g of PDMS, 10g of THF and 10g of DMF (mass ratio of 4: 10), mixing and adding into a beaker, performing ultrasonic treatment at 40 ℃ to completely dissolve the PDMS and the THF to obtain a hydrophobic coating liquid, designing a liquid drop transportation path on the surface of a substrate by using cotton fabric as the substrate, and spraying the hydrophobic coating liquid on the transportation path through an electrostatic spinning device under the conditions that the voltage is 15V, the flow is 0.5mL/h and the receiving distance is 15cm to obtain the substrate with the PDMS hydrophobic coating surface;

s2, weighing 3g of PMMA, 3g of PDMS, 10g of THF and 10g of DMF (mass ratio of 3: 10) and adding into a beaker, and carrying out ultrasonic treatment at 40 ℃ to completely dissolve the PMMA, the PDMS, the THF and the DMF to obtain the super-hydrophobic coating liquid. The super-hydrophobic coating liquid is sprayed on the surface of a PDMS hydrophobic coating of a cotton fabric substrate through an electrostatic spinning device, the electrostatic spraying condition is that the voltage is 15V, the flow rate is controlled to be 0.5mL/h, the receiving distance is 15cm, the surface of the PDMS/PMMA super-hydrophobic coating is formed on the surface of the PDMS hydrophobic coating of the cotton fabric substrate, an SEM image is shown in figure 2, and the obtained coating surface has both fibers and particles from figure 2.

Comparative example 1: obtaining a substrate with a PDMS hydrophobic coating surface

Weighing 1g of PDMS, 10g of THF and 10g of DMF (mass ratio of 1: 10) and mixing and adding into a beaker, carrying out ultrasonic treatment at 40 ℃ to completely dissolve the PDMS, so as to obtain a hydrophobic coating liquid, using a cotton fabric as a substrate, designing a liquid drop transportation path on the surface of the substrate, and spraying the hydrophobic coating liquid on the transportation path through an electrostatic spinning device under the conditions that the voltage is 15V, the flow is 0.5mL/h and the receiving distance is 15cm, so as to obtain the substrate with the PDMS hydrophobic coating surface.

Comparative example 2: substrate with PMMA coated surface

Weighing 1g of PMMA, 10g of THF and 10g of DMF (mass ratio of 1: 10) and mixing and adding into a beaker, carrying out ultrasonic treatment at 40 ℃ to completely dissolve the PMMA to obtain a hydrophobic coating liquid, using cotton fabric as a substrate, designing a liquid drop transportation path on the surface of the substrate, and spraying the hydrophobic coating liquid on the transportation path through an electrostatic spinning device under the conditions that the voltage is 15V, the flow is 0.5mL/h and the receiving distance is 15cm to obtain the substrate with the PMMA coating surface.

Comparative example 3: PDMS/PMMA hybrid coating (fibrous) surface

Weighing 4g of PMMA, 4g of PDMS, 10g of THF and 10g of DMF (mass ratio of 2: 5) into a beaker, and performing ultrasonic treatment at 40 ℃ to completely dissolve the PMMA, the PDMS, the THF and the DMF to obtain the super-hydrophobic coating liquid. Continuously spraying the super-hydrophobic coating liquid on a cotton fabric substrate through an electrostatic spinning device under the electrostatic spraying condition that the voltage is 15V, the flow is 0.5mL/h, the receiving distance is 15cm, and obtaining the surface of the PDMS/PMMA mixed coating, wherein an SEM image is shown in figure 3.

Comparative example 4: PDMS/PMMA micro-nano particle super-hydrophobic surface (no PDMS spraying first)

Weighing 1g of PMMA, 1g of PDMS, 10g of THF and 10g of DMF (mass ratio of 1: 10) into a beaker, and performing ultrasonic treatment at 40 ℃ to completely dissolve the PMMA, the PDMS and the THF to obtain the super-hydrophobic coating liquid. Continuously spraying the super-hydrophobic coating liquid on a cotton fabric substrate through an electrostatic spinning device under the electrostatic spraying condition that the voltage is 15V, the flow is 0.5mL/h, and the receiving distance is 15cm, so as to obtain the surface of the PDMS/PMMA mixed coating.

FIG. 4 is an SEM image of the surface coating of the materials obtained in comparative example 1, comparative example 2 and example 1 (electrospinning apparatus flow rate of 0.5 mL/h). Wherein, the figure (a) is the SEM image of the surface of the PDMS hydrophobic coating in the material obtained in the comparative example 1, the figure (b) is the SEM image of the surface of the PMMA coating in the material obtained in the comparative example 2, and the figure (c) is the SEM image of the surface of the PDMS/PMMA superhydrophobic coating in the material obtained in the example 1 when the flow rate of the electrostatic spinning device is 0.5 mL/h.

FIG. 5 shows the static contact angles of the surface coatings of the materials obtained in comparative example 1, comparative example 2 and example 1 (the flow rate of the electrospinning device is 0.5 mL/h). Wherein (a) is the static contact angle of the surface of the PDMS hydrophobic coating in the material obtained in comparative example 1, (b) is the static contact angle of the surface of the PMMA coating in the material obtained in comparative example 2, and (c) is the static contact angle of the surface of the PDMS/PMMA superhydrophobic coating in the material obtained in example 1 when the flow rate of the electrospinning device is 0.5 mL/h.

As can be seen from fig. 4 and 5, the surface of the PDMS hydrophobic coating layer presents a gel layer without a rough structure, and the static contact angle is 121.7 °; the surface of the PMMA coating is covered by a layer of uniform particles, and the static contact angle is 151.8 degrees, which shows that the PMMA component can realize the construction of a uniform particle structure by an electrostatic spraying technology; the surface of the PDMS/PMMA superhydrophobic coating also presents a layer of uniform particles, and the contact angle is further improved to 164.8 degrees, which shows that compared with the surface of the PMMA coating, the surface energy of the system is further reduced by adding the PDMS component, and the superhydrophobic performance is improved.

Test example

Sample 1: the material with the PDMS/PMMA superhydrophobic coating surface is obtained when the flow rate of the electrostatic spinning device in the embodiment 1 is 0.5 mL/h;

sample 2: and (3) the material with the super-hydrophobic surface of the PDMS/PMMA micro-nano particles obtained in the comparative example 4 (PDMS is not sprayed in advance).

Water washing durability test: the durability test of the sample 1 and the sample 2 was carried out under the condition of 2A by water washing according to AACC61-2006 standard method, and after 5 times of water washing test, the test results are shown in the following table. It can be seen that the static contact angle of the surface of sample 2 is reduced to 123.7 °, and the static contact angle of the surface of sample 1 is reduced only by a small amount, still reaching 153.2 °.

Rubbing fastness test: the results of the rubbing test performed 200 times by rubbing sample 1 and sample 2 in the same direction at a speed of 3cm s-1 using untreated cotton as an abrasive are shown in the following table. It can be seen that the static contact angle of the surface of sample 2 is reduced to 100.6 deg., and the static contact angle of the surface of sample 1 is reduced only to a small extent, still reaching 151.6 deg..

Washing durability test and rubbing fastness test results surface: the PDMS is firstly sprayed on the surface of the substrate, so that the bonding force between the super-hydrophobic surface of the PDMS/PMMA micro-nano particles sprayed again and the substrate can be increased, and the substrate is not easy to damage.

While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.