CN115595032A - Preparation and application of transparent stretchable super-hydrophobic coating - Google Patents
Preparation and application of transparent stretchable super-hydrophobic coating Download PDFInfo
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- CN115595032A CN115595032A CN202211327419.9A CN202211327419A CN115595032A CN 115595032 A CN115595032 A CN 115595032A CN 202211327419 A CN202211327419 A CN 202211327419A CN 115595032 A CN115595032 A CN 115595032A
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Abstract
The invention belongs to the field of new materials, relates to the research of surface functional materials, and particularly relates to preparation and application of a transparent stretchable super-hydrophobic coating. The preparation method of the flexible transparent super-hydrophobic material comprises the following steps: (1) Preparing a flexible transparent super-hydrophobic Polymer (PMKA) into a dilute solution, and uniformly dispersing by ultrasonic; (2) Soaking various matrixes in the dilute solution for a certain time; (3) And (3) taking out the matrix in the step (2), and drying the matrix in an air-blast drying oven to obtain the super-hydrophobic material. The coating has good mechanical change resistance, can still keep super-hydrophobic after being soaked in various organic solvents and HCl (PH = 1) solution for 196h, and has good chemical corrosion resistance, good adhesion and excellent transparency.
Description
Technical Field
The invention belongs to the field of new materials, relates to the research of surface functional materials, and particularly relates to preparation and application of a transparent stretchable super-hydrophobic coating.
Background
The super-hydrophobic coating is developed rapidly, is applied to various fields such as marine antifouling, ship drag reduction, biological antibiosis, liquid drop control and the like, and along with the expansion of super-hydrophobic application, people have higher and higher requirements on the super-hydrophobic surface. The wear resistance of the super-hydrophobic material is related to the durability of the material, and is an important standard for measuring the super-hydrophobic material. For example: wang et al utilize a reasonable micron-scale armor structure in combination with nanoscale inorganic nanostructures to provide abrasion resistance and water repellency, respectively. The method is successfully applied to the surface of a rigid base material, and can maintain the super-hydrophobicity while greatly improving the wear resistance. In addition, in order to fix the surface micro-nano structure and the substrate and enhance the stability of super-hydrophobicity, a large amount of commercial adhesives, coupling agents and the like are often added, and meanwhile, the characteristics also determine that the strategy is not suitable for flexible surfaces. Recently, superhydrophobic surfaces with anti-deformation properties have become more and more important in various applications, such as flexible electronics, artificial skin, various biomimetic sensors, fabric dressings, and the like. Therefore, the stable and flexible superhydrophobic performance is realized under various operations such as stretching and bending, and the method has important value.
Currently, some progress has been made in flexible, superhydrophobic materials. Li et al utilize Polydimethylsiloxane (PDMS) and Polymercaptopropylmethylsiloxane (PMMS), as well as hydrophobic SiO 2 And (3) crosslinking the nano particles under UV irradiation to obtain the super-hydrophobic bulk material. The material has the tensile strain capacity of 68% and can keep super-hydrophobic under the deformation operations of stretching 50%, bending, twisting and the like. Cho et al coated polyaniline-wool nanostructures onto polytetrafluoroethylene elastic polyurethane fiber matrices to obtain a flexible, breathable superhydrophobic film that still exhibits excellent superhydrophobic performance at 300% strain. Huang et al prepared a polyurethane film by an electrospinning method, soaked in an ethanol solution of nano Carbon Nanotubes (CNTs), and then hydrophobically modified with trichloromethylsilane (MTS). The final superhydrophobic film can be superhydrophobic under conditions of tensile strain of 300%. Gao et al similarly utilize SiO 2 The nanoparticles and graphene build a superhydrophobic stretchable film on an elastic base polyurethane fiber. However, the flexible materials need to be prepared in multiple steps, the operation is complex, and in order to achieve super hydrophobicity, the roughness is constructed by using a large amount of external fillers, and the transparency of the materials is correspondingly sacrificed.
In addition to superhydrophobicity and flexibility, optical transparency of the coating is also a concern because most superhydrophobic coatings are textured at the expense of transparency. Therefore, it is a challenge to develop a coating that is both superhydrophobic, flexible and transparent.
CN202111140204.1 discloses a self-repairing transparent super-hydrophobic polyamide-imide composite film and a preparation method thereof. PAI resin is dissolved in high boiling point solvent, coated on glass substrate and dried, and modified silicon dioxide (SiO) 2 ) Spraying on the surface of PAI wet film, drying to obtain self-repairing transparent super-hydrophobic PAI film. The composite film provided by the invention has the characteristics of good flexibility, optical permeability, hot water impact resistance, self-repairing property and the like, and can be used in the fields of optical devices, solar panels, automobile windshields and the like.
CN202110251044.1 discloses a simple preparation method of a transparent flexible super-hydrophobic film. The method comprises the following steps: (a) Spin coating polydimethylsiloxane on a glass substrate to form a base film and curing; (b) Uniformly mixing carbonyl iron particles and polydimethylsiloxane to form a composite material, and coating the composite material on a base film in a spinning mode to form a composite film; (c) Then moving the glass substrate to the surface of the permanent magnet, and under the action of a magnetic field, the composite material in the step (b) can automatically form a micro-cilium structure; (d) then sending the glass substrate into an oven for curing; (e) Meanwhile, polydimethylsiloxane in the composite film expands to form a final super-hydrophobic film, and finally the super-hydrophobic film automatically falls off from the glass substrate. However, the preparation process of the film is complex, the large-scale production is not easy, and the color of the final film is black and transparent, which influences the use of the film to a certain extent.
Disclosure of Invention
The invention aims to provide a preparation method and application of a flexible transparent stretchable super-hydrophobic coating aiming at the defects of the prior art, wherein the flexible transparent super-hydrophobic coating has high super-hydrophobic stability, wear resistance and transparent appearance.
The invention is realized by the following technical scheme:
a preparation method of a flexible transparent super-hydrophobic material comprises the following steps:
(1) Preparing a flexible transparent super-hydrophobic Polymer (PMKA) into a dilute solution, and uniformly dispersing by ultrasonic;
(2) Soaking various matrixes in the dilute solution for a certain time;
(3) And (3) taking out the matrix in the step (2), and drying the matrix in an air-blast drying oven to obtain the super-hydrophobic material.
Preferably, when the substrate is a glass sheet, the diluted PKMA solution is sprayed on the surface at a position of 10cm-15cm vertical to the surface by using a spray gun (ET 4000, STAT, germany), and the surface is cured for 12 hours at normal temperature.
Preferably, in the step (1), the mass percentage concentration of the dilute solution is 1.5-2.5 wt%; the ultrasonic dispersion time is 15-30 min.
Preferably, in the step (2), the substrate is cotton cloth, wood or glass, and the soaking time is 0.5 to 2 hours, preferably 1 hour.
Preferably, in the step (3), the drying temperature is 70-90 ℃; the drying time is 0.5 to 2 hours. More preferably, drying is carried out in a forced air drying oven at 80 ℃ for 1h.
The invention also provides the flexible transparent super-hydrophobic material prepared by the method, and the flexible transparent super-hydrophobic material is formed by coating a flexible transparent super-hydrophobic Polymer (PMKA) on a substrate; the substrate is cotton cloth, wood or glass.
Preferably, the flexible transparent super-hydrophobic material has the following XPS test data: there are five characteristic peaks in the C1s spectrum: -CF 3 (294.22eV)、-CF 2 (291.92 eV), -C = O (288.86 eV), -C-O (286.41 eV), -C/-C-H (284.77 eV); in the F1s spectrum, -CF appears at 686.70eV 3 Xiaojianfeng, main peak-CF 2 At 689.0 eV. In the Si2p spectrum, characteristic peaks of-Si-O (102.92 eV) and-Si-C (101.92 eV) exist. In the spectrum of O1s, there are characteristic peaks at 534.02eV (-C-O) and 532.57eV (-Si-O). As shown in fig. 6. As shown in fig. 7 (high-fraction spectrum of cotton surface).
The WCA is more than 155 degrees when the epsilon =0% to the epsilon =300% of the modified cotton cloth. The super-hydrophobicity can be kept after 2000 stretching-releasing cycles under six stretching strains of epsilon =50%, epsilon =100%, epsilon =150%, epsilon =200%, epsilon =250% and epsilon =300%, and the WCA can be kept above 154 ℃. The WCA for the same stretch-release cycle number is also greater than 150 ° for different tensile strains.
The coated cotton was subjected to the martindale abrasion test, as shown in figure 13a, and after 1000 cycles of abrasion the WCA of the coated cotton still remained superhydrophobic (WCA =150 °). And testing the super-hydrophobic washing cycle. The coated cotton was washed in 150mL of water at 45 ℃ with 0.15wt% detergent at 50 r/min. After drying, WCA measurements were taken with one wash cycle in 45 min. After 20 washes, the WCA of the coated cotton was still greater than 150 ° as shown in figure 13 b.
After 600 cycles of 500g loaded tape peel, the WCA was still above 150 °. The contact angle of the cotton cloth after 750g of the supporting tape was peeled off was small. However, after 500 peel cycles, the WCA can reach 151 °.
The modified cotton cloth is soaked in organic solution and HCl for 196h and still is super-hydrophobic, and WCA is above 150 ℃. The organic solvent is selected from DMF (N, N-dimethylformamide), THF (tetrahydrofuran), phMe (toluene), EAC (ethyl acetate), HCl, PA (acetone), EA (ethanol). DMF (N, N-dimethylformamide), THF (tetrahydrofuran), phMe (toluene), EAC (ethyl acetate), HCl, PA (acetone) and EA (ethanol) are respectively selected as model pollutants, the coated cotton cloth is soaked, and the static contact angle of the soaked cotton cloth is measured every 24 hours. With increasing soaking time of the various agents, the WCA coated cotton showed a decreasing trend overall, but was still in a superhydrophobic state. And DMF, PA and EA have small influence on the surface of the coated cotton cloth, and WCA is 153.12 degrees, 152.83 degrees and 153.14 degrees respectively after 196 hours of soaking.
Preferably, the flexible transparent super-hydrophobic Polymer (PMKA) is a random copolymer formed by polymerization of three acrylate monomers, namely MMA, PFOA and KH-570.
Preferably, the preparation method of the flexible transparent super-hydrophobic Polymer (PMKA) comprises the following steps:
s1: adding PFOA (perfluorooctyl methyl acrylate), MMA (methyl methacrylate) and KH-570 (3- (trimethoxysilyl) propyl methacrylate) into a container, and uniformly mixing; the mol ratio of PFOA, MMA and KH-570 is (3-5): (3-5): 1, the preferred molar ratio of PFOA, MMA and KH-570 is 4;
s2: AIBN (azobisisobutyronitrile) and ethyl acetate were added. The addition amount of AIBN is 0.5-1.5 wt% of the total weight of the monomers. Preferably, AIBN is added in an amount of 1% by weight based on the total weight of the monomers. The monomers are the general names of PFOA (perfluorooctyl methyl acrylate), MMA (methyl methacrylate) and KH-570 (3- (trimethoxysilyl) propyl methacrylate); the total weight of the monomers is the total weight of PFOA, MMA and KH-570.
The amount of ethyl acetate added is 400-600mL per mole of monomer. Preferably, ethyl acetate is added in an amount of 550 to 600mL per mole of monomer.
S3: in an inert atmosphere, polymerizingA flexible transparent superhydrophobic Polymer (PMKA) should be obtained. Preferably, the inert atmosphere is N 2 Atmosphere or Ar atmosphere. The polymerization reaction is carried out for 2-4h at the temperature of 60-80 ℃.
More preferably, in N 2 Reacting for 3 hours at 70 ℃ in the atmosphere to obtain the flexible transparent super-hydrophobic Polymer (PMKA).
We prepared a very low surface energy, flexible, transparent coating. Three acrylate monomers (MMA, PFOA, KH-570) were polymerized to form a random copolymer. When the flexible transparent super-hydrophobic polymer is prepared into a solution with the concentration of 2wt%, the flexible transparent super-hydrophobic polymer is simply dipped or sprayed on an elastic cotton cloth, wood and other non-planar substrates to obtain the super-hydrophobic material.
The flexible transparent super-hydrophobic polymer has certain flexibility, and can still keep super-hydrophobicity along with the increase of the tensile strain of cotton cloth when being grafted to elastic cotton cloth. Five different tensile strains (e =0% to e = 300%) were selected and the cotton was subjected to a stretch-release cycle test. The superhydrophobicity can be maintained even at a tensile strain of 300%. The modified cotton cloth wettability has excellent mechanical stability and chemical stability, and the coated cotton cloth can still be in a super-hydrophobic state after 2000 stretching (strain is 300%) -releasing cycles. The superhydrophobicity was maintained after 20 wash experiments. And the bouncing behavior of the water drop on the surface of the cotton cloth under different tensile strains is studied, and the water drop can still bounce on the surface of the coated cotton cloth when the tensile strain is 200%.
The coating not only has good mechanical change resistance, but also can keep super-hydrophobic after being soaked in various organic solvents and HCl (PH = 1) solution for 196h, and has good chemical corrosion resistance. In addition, the coating has good adhesion and the coated cotton cloth can be subjected to 20 wash cycles and 1000 martindale abrasion tests and remain superhydrophobic.
The coating has excellent transparency, and the color of the cotton cloth is not affected when the colored cotton cloth is coated. When the transparent glass is coated, the transmittance of the glass is not influenced, and the transparent glass has high transmittance.
Drawings
FIG. 1 preparation of coated cotton;
FIG. 2 shows the color and lyophobicity contrast of cotton cloth with different colors and textures and wood before and after modification;
FIG. 3 shows the process of the water drop sliding down the coated glass surface;
FIG. 4 SEM comparison of cotton cloth: (a-b) before coating, (c-d) after coating;
FIG. 5 element map image of a coated cotton surface;
FIG. 6 XPS spectra of cotton before and after modification;
FIG. 7 high fraction spectrum of cotton surface: (a) C1s, (b) F1s, (C) Si2p, (d) O1s;
FIG. 8 is a stress-strain curve of a polymer film;
fig. 9 optical photographs of the moisture resistance of coated cotton cloth at different tensile strains (from e =0% to e = 300%) on the surface of a water droplet.
FIG. 10 optical photographs of the variation curve of the WCA of the coated cotton cloth and the WCA of the water droplets at different tensile strengths;
figure 11 picture of drop bounce process on coated cotton where epsilon =50% (a), epsilon =100% (b), epsilon =200% (c);
FIG. 12 effect of the number of repeated stretch-release cycles at different stretch strains on the WCA of the wrapped cotton;
FIG. 13 (a) the effect of Martindale abrasion number on WCA for coated cotton at 9KPa pressure, (b) the effect of wash cycle number on WCA for cotton.
FIG. 14 is a schematic illustration of a tape peel test procedure;
FIG. 15 effect of tape peel cycle test on coated cotton WCA;
FIG. 16 variation of WCA of coated cotton cloth in various reagents;
FIG. 17 is a photograph showing a transmittance curve of a modified glass, wherein the inset is a real image of the modified glass.
FIG. 18 is a graph of the results of a nanoindentation test conducted on a polymer film.
Detailed Description
The following examples are further illustrative of the present invention, but the present invention is not limited thereto.
Experimental materials
Main raw materials and reagents: 3- (trimethoxysilyl) propyl methacrylate (KH-570), analytically pure, allantin. Methyl Methacrylate (MMA), analytically pure, aladdin. Perfluorooctyl methyl acrylate (PFOA), analytically pure, wuhanxin Wei Ye chemical Co., ltd. Azobisisobutyronitrile (AIBN), analytically pure, from Aladdin. Ethyl acetate, toluene, tetrahydrofuran, N-dimethylformamide, absolute ethanol, acetone and hydrochloric acid, all of which are analytically pure, national reagent limited. Cotton cloth, purchased in local stores. Tape, 3M company. Wood, purchased in local stores.
Experimental instrument equipment
Main experimental apparatus equipment: optical static contact angle measuring instrument, model SL250, KINO corporation, usa. Spectrophotometer, UV-2600, shimadzu corporation, japan. Martindale abrasion resistant Instrument, GT-7012-M, high-speed rail detection Instrument (Dongguan), inc. High speed camera, V710L, amertek, usa. Microcomputer controlled electronic universal tester, model WDW-02, jennson & ltd & gt instruments & ltd & gt.
Testing and characterization
Mechanical stability test
The coated cotton cloth was cut into discs with a diameter of 4cm and placed in a Martindale abrasion resistant apparatus with an applied pressure of 9 KPa. The instrument was started and contact angles were measured every 100 cycles until 1000 cycles had ceased.
After one wash cycle, a 60mm x 80mm size coated fabric was dipped into 150mL of deionized water containing 0.15wt% soap powder, stirred at a stirring speed of 500rpm/min and a temperature of 45 ℃ for 45min, the washed coated cotton was rinsed clean with deionized water, dried in an oven at 80 ℃ for 45min, and subsequent WCAs measurements were taken. And, the above process was a washing cycle, and the number of washing times of the coated cotton cloth was studied.
Strong tape peeling test: the strong adhesive tape was adhered to the coated cotton surface, the fingers were smoothed, and a 500g/750g weight was rolled across the surface to ensure firm adhesion of the tape, and then one end of the tape was grasped and the tape was pulled off as quickly as possible. This process is a cycle and a new tape is changed every 10 times. The coated cotton was tested for water contact angle every 50 tape peels.
For the elastic modified cotton cloth, the stretching cycle test is carried out under different elongation rates (epsilon =50% -epsilon = 300%). The Water Contact Angles (WCAs) of the coated cotton were measured after 100, 500, 1000, 1500, 2000 stretches at each elongation, respectively.
Chemical stability test
The coated cotton cloth was soaked in a solution of toluene (PhMe), tetrahydrofuran (THF), absolute Ethanol (EA), N-Dimethylformamide (DMF), acetone (PA), ethyl Acetate (EAC), hydrochloric acid (PH = 1), respectively, and every 24 hours, the cotton cloth was taken out, placed in an oven to dry, and the contact angle thereof was measured.
Flexibility test
1mL of the polymer was poured into a circular silica gel mold with a diameter of 6cm, dried at room temperature for 48h, and then placed in an oven at 40 ℃ for 12h. The polymer film was taken out of the mold, stretched using a microcomputer-controlled electronic universal tester, and the stress-strain curve was measured.
Example 1
Preparation of flexible transparent super-hydrophobic polymer
0.02mol of PFOA (perfluorooctylmethyl acrylate), 0.02mol of MMA (methyl methacrylate) and 0.005mol of KH-570 (3- (trimethoxysilyl) propyl methacrylate) were charged into a 100mL single-necked flask, and 1wt% of AIBN (azobisisobutyronitrile) and 25mL of ethyl acetate were added. In N 2 Reacting for 3h at 70 ℃ in an atmosphere to obtain a transparent Polymer (PMKA).
Preparation of flexible transparent super-hydrophobic material
The flexible transparent super-hydrophobic polymer PMKA obtained in the example 1 is prepared into a dilute solution with the concentration of 2wt%, and the solution is uniformly dispersed by ultrasonic treatment for 20 min. Soaking various cotton cloth and wood in the diluted solution for 1h, taking out, placing in a blast drying oven at 80 deg.C for 1h, and drying to obtain super-hydrophobic surface. For the glass sheets, a dilute solution of PMKA was sprayed onto the surface using a spray gun (ET 4000, STAT, germany) at a position of 10cm to 15cm perpendicular to the surface and allowed to cure for 12h at ambient temperature.
Example 2
Preparation of flexible transparent super-hydrophobic polymer
Adding 0.015mol of PFOA (perfluorooctyl methyl acrylate), 0.015mol of MMA (methyl methacrylate) and 0.005mol of KH-570 (3- (trimethoxysilyl) propyl methacrylate) into a container, and uniformly mixing;
0.5% by weight of AIBN (azobisisobutyronitrile) and 19.5ml of ethyl acetate were added;
at N 2 And carrying out polymerization reaction at 60 ℃ for 4h in the atmosphere to obtain a transparent Polymer (PMKA).
Preparation of flexible transparent super-hydrophobic material
Transparent Polymer (PMKA) is prepared into 1.5wt% dilute solution, and is dispersed uniformly by ultrasonic for 15 min.
Various substrates were soaked in the above dilute solution for 2 hours. The substrate is cotton cloth, wood or glass.
Taking out the matrix, and drying the matrix in an air-blast drying oven for 0.5 hour at the drying temperature of 90 ℃; and obtaining the super-hydrophobic material.
Preferably, when the substrate is a glass sheet, the diluted PKMA solution is sprayed on the surface at a position of 10cm-15cm vertical to the surface by using a spray gun (ET 4000, STAT, germany), and the surface is cured for 12 hours at normal temperature.
Example 3
Preparation of flexible transparent super-hydrophobic polymer
Adding 0.025mol of PFOA (perfluorooctylacrylate methyl ester), 0.025mol of MMA (methyl methacrylate) and 0.005mol of KH-570 (3- (trimethoxysilyl) propyl methacrylate) into a container, and uniformly mixing;
1.5wt% of AIBN (azobisisobutyronitrile) and 30.5ml of ethyl acetate were added;
in N 2 And carrying out polymerization reaction for 2h at 80 ℃ in the atmosphere to obtain a transparent Polymer (PMKA).
Preparation of flexible transparent super-hydrophobic material
Transparent Polymer (PMKA) is prepared into 2.5wt% dilute solution, and is dispersed uniformly by ultrasonic for 30min.
Each substrate was immersed in the above dilute solution for 0.5 hour. The substrate is cotton cloth, wood or glass.
Taking out the matrix, and drying the matrix in an air-blast drying oven for 2 hours at the drying temperature of 70 ℃; and obtaining the super-hydrophobic material.
Preferably, when the substrate is a glass sheet, the PKMA diluted solution is sprayed on the surface by using a spray gun (ET 4000, STAT, germany) at a position of 10cm-15cm vertical to the surface, and the mixture is solidified for 12 hours at normal temperature.
Example 4 Performance Studies of transparent Superhydrophobic materials
Preparation and wettability study of transparent super-hydrophobic cotton cloth
Different non-planar substrates (cotton cloth, wood with different colors and different textures) are grafted with the flexible transparent super-hydrophobic polymer synthesized in the example 1 by a simple soaking method, and the preparation process is shown in the figure 1. It can be seen that KH-570-Si- (O-CH) 3 ) 3 Hydrolyzed to-Si- (OH) during the reaction process 3 Can be used as an adhesion layer to be connected with a substrate, and provides a basis for the wear resistance of the coating. And a low surface energy layer can be formed on the surface by connecting PFOA with KH-570 through polymerization reaction, thereby obtaining the super-hydrophobic surface. The polymer has excellent transparency, so that the modified cotton cloth and wood keep the original color, as shown in figure 2. Milk and water droplets remained spherical (WCA =160 ° ± 2 °) on both coated cotton and wood surfaces, which also directly proved successful in modifying cotton and wood. And the modified cotton cloth and wood have excellent water repellency.
For a flat substrate (glass), without a cotton surface roughness structure, the WCA of the coated glass was 120 °. But the water drops can slide down on the glass surface very quickly, and the process only needs 0.3s, as shown in fig. 3.
Surface morphology and surface chemical composition of transparent super-hydrophobic cotton cloth
As shown in fig. 4, SEM tests of the surface of the cotton cloth before and after coating revealed that the surface of the coated cotton cloth was uniformly coated with a substance and also formed some wave structures, which helped to construct the cotton cloth to achieve a roughness condition of superhydrophobic property, compared to the cotton cloth before modification.
In addition, EDS test is carried out on the modified cotton cloth to observe the distribution condition of the elements on the surface of the coated cotton cloth. As shown in fig. 5, four elements of C, O, si, and F are clearly distributed on the surface of the cotton cloth, and the elements are uniformly distributed on the surface of the cotton cloth. This result can prove that the polymer is uniformly coated on the surface of the cotton cloth, i.e. the cotton cloth is successfully modified.
The composite film on the surface of the modified cotton cloth was further analyzed by XPS test. As shown in fig. 6, the cotton before modification has only two characteristic peaks of C and O, while the cotton after modification clearly shows four characteristic peaks of C, O, F and Si, which further proves that the surface of the cotton is modified.
As shown in fig. 7a, there are five characteristic peaks in the C1s spectrum: -CF 3 (294.22eV)、-CF 2 (291.92 eV), -C = O (288.86 eV) -C-O (286.41 eV), -C-C/-C-H (284.77 eV). In the F1s spectrum (FIG. 7 b), it can be seen that a small shoulder peak appears at 686.70eV, which is-CF 3 The other main peak is-CF at 689.0eV 2 . XPS results show, -CF 2 、-CF 3 Appear on the surface of the cotton cloth and play a key role in the super-hydrophobicity of the cotton cloth. In addition, in the Si2p spectrum in FIG. 7C, there are two characteristic peaks-Si-O (102.92 eV) and-Si-C (101.92 eV), respectively. In the spectrum of O1s (FIG. 7 d), the two characteristic peaks at 534.02eV and 532.57eV are-C-O and-Si-O, respectively. This demonstrates the presence of KH-570 on the cotton surface, which aids in grafting the polymer to the cotton surface.
Example 5 investigation of flexibility of Polymer films
To demonstrate that the polymer film has a certain flexibility, we measured and evaluated the elasticity of the polymer film by a stress-strain curve. The preparation method of the polymer film comprises the following steps: 2mL (undiluted) of the PKMA synthesized in example 1 was poured into a circular silica gel mold with a diameter of 6cm, dried at room temperature for 48 hours, placed in an oven at 40 ℃ for 12 hours, and then taken out of the mold to obtain a polymer film.
As shown in FIG. 8, the film had a maximum tensile strength of 1.11MPa and an elongation at break of 345.6%. The samples also exhibited typical elastic behavior, maintaining low stress at low and medium strains and higher stress at high strains.
The polymer film was subjected to nanoindentation experiments, and the test results showed that the hardness of the polymer was 0.23MPa, see FIG. 18. The test adopts an NMT nano-indenter, the nano-indentation is that a rigid pressure head (standard is a berkvoic pressure head) with a regular shape is pressed into the surface of a sample to be tested under the action of gradually increasing external force, and the external force is gradually removed after the external force (or displacement) reaches a preset peak value; in the loading-unloading process, the displacement h of the pressure head and the load P born by the pressure head are recorded by means of a high-precision load-displacement testing technology; and analyzing the obtained P-h curve to obtain the elastic modulus, the hardness and the like of the sample to be tested.
Example 6 stretchability study of transparent superhydrophobic materials
Transparent, mechanically stretch resistant superhydrophobic cotton cloth was prepared using elastic cotton cloth as the substrate. We applied the coated cotton cloth at different tensile strains epsilon (∈ = (L-L) 0 )/L 0 Wherein L is 0 And L is the original length before stretching and the length after stretching, respectively) were investigated. As can be seen in fig. 9, the cotton was gradually stretched and increased from e =0% to e =300% during the cotton change, but the water drop (dyed with methyl blue) could be spherical on the coated cotton surface at different strains, indicating that the superhydrophobicity of the coated cotton has excellent stretch resistance. And to show the wettability of the modified cotton cloth at different strains more accurately, we also measured the WCA of the modified cotton cloth (e =0% to e = 300%). As shown in fig. 10, WCA has better stability with increasing strain of the modified cotton cloth. The WCA of the modified cotton was 160.5 ° at ∈ = 300%. The WCA was greater than 155 ° for modified cotton (e =0% to e = 300%).
In addition, a high-speed camera is used for observing the collision process of the liquid drops and the surface of the modified cotton cloth. The water drop (50 μ L) fell vertically at a distance of approximately 2cm above the modified cotton cloth (under different stresses). This process further demonstrates that the cotton cloth still has excellent superhydrophobicity in the stretched state. As can be seen in fig. 11, the water droplets on the coated cotton cloth with tensile strain of ∈ =50%, ∈ =100%, ∈ =200% all bounce. Wherein the water drop bounces twice on e =50%, e =100% coated cotton and a complete bounce occurs once on e =200% cotton. This indicates that the coated cotton in the stretched state still has very low drop adhesion. The reason why the water drops coated on the cotton cloth with epsilon =200% can only bounce once is that the bounce of the water drops is influenced because the surface roughness of the cotton cloth is greatly changed in the process of large-amplitude tensile strain.
Example 7 mechanical and chemical stability of wettability of coated Cotton cloth
To understand the durability of the superhydrophobicity of the modified cotton, we tested the mechanical, physical and chemical stability of the coated cotton. First we performed the effect of cyclic stretching and release on the wettability of coated cotton at different tensile strains (figure 12). First, at six tensile strains of ∈ =50%, ∈ =100%, ∈ =150%, ∈ =200%, ∈ =250%, ∈ =300%, the superhydrophobicity was maintained after 2000 stretch-release cycles, and the WCA was maintained at 154 ° or higher. Under a fixed tensile strain, the WCA slightly decreases with the increase of the number of stretch-release cycles, but water drops still can keep a super-hydrophobic state on the stretched cotton cloth. Similarly, the WCA for the same stretch-release cycle number is greater than 150 ° for different tensile strains.
In addition, the coated cotton cloth was subjected to a martindale abrasion test to study the abrasion resistance of the cotton cloth wetting property. In fig. 13a, it can be seen that the WCA gradually decreased as the number of wear cycles increased, but even after 1000 cycles of wear the cotton coated WCA remained superhydrophobic (WCA =150 °). This indicates that the coated cotton cloth has excellent abrasion resistance and also has excellent superhydrophobic stability. Also, the coated cotton was subjected to a superhydrophobic wash cycle test. The coated cotton was washed in 150mL of water at 45 ℃ with 0.15wt% detergent at 50 r/min. After drying, WCA measurements were taken with one wash cycle in 45 min. After 20 washes, the WCA of the coated cotton was still greater than 150 ° as shown in figure 13 b. This demonstrates that the coating has good adhesion to cotton cloth and remains on the surface of the cotton cloth even after washing with water containing a detergent.
To further demonstrate the good adhesion of the coating to the cotton substrate, we performed a tape peel test on the cotton. The peeling process is shown in fig. 14. We chose two loads (500 g/750 g) to compact the tape and compare the changes in WCA on the cotton surface after the two loads are handled.
In fig. 15, it can be seen that the WCA remained above 150 ° after 600 cycles for 500g loaded tape peel. This demonstrates that the coating adheres well to the cotton and that the tape stripping process has little effect on the structure of the cotton surface, leaving the coated cotton after stripping still good water repellency. The contact angle of the cotton cloth after peeling of 750g of the supporting tape was small compared to the tape peeling cycle of 500 g. But after 500 peeling cycles, the water repellency is still good, and the WCA can reach 151 degrees.
The super-hydrophobic property of the coated cotton cloth surface is easily influenced by organic solvent [121] . Therefore, we performed organic solvent soaking of the coated cotton cloth to explore the effect of organic solvent soaking on wettability. In fig. 16, DMF (N, N-dimethylformamide), THF (tetrahydrofuran), phMe (toluene), EAC (ethyl acetate), HCl, PA (acetone), EA (ethanol) were selected as model contaminants, respectively, and the coated cotton cloth was soaked, and the static contact angle of the soaked cotton cloth was measured every 24 hours. With increasing soaking time of the various agents, the WCA coated cotton showed a decreasing trend overall, but was still in a superhydrophobic state. And DMF, PA and EA have little influence on the surface of the coated cotton cloth, and WCA is 153.12 degrees, 152.83 degrees and 153.14 degrees respectively after 196 hours of soaking. This demonstrates that the coating has excellent resistance to organic solvents and can remain superhydrophobic even in harsh chemical environments.
Example 8 transparency test
People have higher and higher requirements on the coating, the coating has good performance and visual function, the coating does not influence the beauty of the substrate, and the original appearance becomes one of the basic pursuits of people [56] . Spraying the coating on a glass sheet by a spraying method, and inspectingThe transmittance of the coated glass was measured. As shown in fig. 17, the transmittance of the glass after modification was not much different from that of the glass without modification. Because the nano particles are not in the coating to increase the surface roughness, the coating on the glass surface is smooth, namely the reflectivity of light on the surface is low, so that the transmittance is higher. It is noted that the inset photograph in fig. 17 is taken with the coated glass at a vertical distance from the picture. It can be seen that the glass after modification did not affect the visibility of the glass and had excellent transparency.
By blending the three monomers (MMA, KH-570, PFOA), a random copolymer PKMA was synthesized. When the polymer is prepared into 2wt% solution, non-planar substrates such as cotton cloth and wood are soaked in the solution to obtain the super-hydrophobic material. When the polymer is grafted on elastic cotton cloth, the super-hydrophobicity is still kept along with the increase of the tensile strain of the cotton cloth. The modified cotton cloth has excellent mechanical stability and chemical stability, and can still keep super-hydrophobicity after 1000 cycles of Martindale abrasion resistance test and 20 washing experiments. And the modified cotton cloth is still super-hydrophobic after being soaked in organic solution and HCl for 196 h.
The cotton cloths were subjected to a stretch-release cycle test at different tensile strains (e =0% to e = 300%). At a maximum tensile strain e =300%, the coated cotton cloth remained superhydrophobic after 2000 stretches-releases. At a tensile strain of 200%, the water droplets may still bounce on the coated cotton surface.
The coating has excellent transparency, and the color of the cotton cloth is not affected when the colored cotton cloth is coated. When the transparent glass is coated, the transmittance of the glass is not influenced, and the transparent glass has high transmittance.
Claims (10)
1. A preparation method of a flexible transparent super-hydrophobic material comprises the following steps:
(1) Preparing a flexible transparent super-hydrophobic Polymer (PMKA) into a dilute solution, and uniformly dispersing by ultrasonic;
(2) Soaking various matrixes in the dilute solution for a certain time;
(3) And (3) taking out the matrix in the step (2), and drying the matrix in an air-blast drying oven to obtain the super-hydrophobic material.
2. The method for preparing the flexible transparent superhydrophobic material of claim 1, wherein when the substrate is a glass sheet, the thin solution of PKMA is sprayed on the surface at a position 10cm-15cm perpendicular to the surface using a spray gun (ET 4000, STAT, germany), and cured for 12 hours at normal temperature.
3. The method for preparing the flexible transparent super-hydrophobic material as claimed in claim 1, wherein in the step (1), the diluted solution has a mass percent concentration of 1.5-2.5 wt%; the ultrasonic dispersion time is 15-30 min.
4. The method for preparing the flexible transparent superhydrophobic material of claim 1, wherein in the step (2), the substrate is cotton cloth, wood or glass, and the soaking time is 0.5-2 hours, preferably 1 hour.
5. The method for preparing the flexible transparent superhydrophobic material of claim 1, wherein in the step (3), the drying temperature is 70-90 ℃; the drying time is 0.5 to 2 hours. More preferably, drying is carried out in a forced air drying oven at 80 ℃ for 1h.
6. A flexible transparent superhydrophobic material prepared by the method of any one of claims 1-5.
7. A flexible transparent superhydrophobic material, wherein a flexible transparent superhydrophobic Polymer (PMKA) is coated on a substrate to form the flexible transparent superhydrophobic material; the substrate is cotton cloth, wood or glass.
8. The flexible transparent superhydrophobic material of claim 6 or 7, wherein XPS test data is as follows: there are five characteristic peaks in the C1s spectrum: -CF 3 (294.22eV)、-CF 2 (291.92eV)、-C＝O(288.86eV)、-C-O(286.41eV)、-C-C/-C-H (284.77 eV); in the F1s spectrum, -CF appears at 686.70eV 3 Xiaojianfeng, main peak-CF 2 At 689.0 eV. In the Si2p spectrum, characteristic peaks of-Si-O (102.92 eV) and-Si-C (101.92 eV) exist. In the spectrum of O1s, there are characteristic peaks at 534.02eV (-C-O) and 532.57eV (-Si-O).
9. The flexible transparent superhydrophobic material of claim 6 or 7, wherein the flexible transparent superhydrophobic material has at least one of the following properties:
the WCA is larger than 155 degrees when the epsilon =0% to the epsilon =300% of the modified cotton cloth. The superhydrophobicity can be maintained after 2000 stretch-release cycles under six tensile strains of epsilon =50%, epsilon =100%, epsilon =150%, epsilon =200%, epsilon =250% and epsilon =300%, and the WCA can be maintained above 154 degrees. The WCA is greater than 150 ° at different tensile strains.
After 1000 cycles of abrasion, the WCA coated cotton still remained superhydrophobic (WCA =150 °).
The coated cotton was washed in 150mL of water at 45 ℃ with 0.15wt% detergent at 50 r/min. Taking a washing cycle for 45min, drying, and then carrying out WCA measurement; after 20 washes, the WCA of the coated cotton was still greater than 150 °.
After 600 cycles of 500g loaded tape release, the WCA was still above 150.
The WCA of 750g load tape after 500 peel cycles can reach 151 °.
The modified cotton cloth is soaked in organic solution and HCl for 196h and still is super-hydrophobic, and the WCA is above 150 ℃. The organic solvent is selected from DMF (N, N-dimethylformamide), THF (tetrahydrofuran), phMe (toluene), EAC (ethyl acetate), HCl, PA (acetone), EA (ethanol).
10. The method for preparing a flexible transparent superhydrophobic material of any one of claims 1-5,
the preparation method of the flexible transparent super-hydrophobic Polymer (PMKA) comprises the following steps:
s1: adding PFOA (perfluorooctyl methyl acrylate), MMA (methyl methacrylate) and KH-570 (3- (trimethoxysilyl) propyl methacrylate) into a container, and uniformly mixing; the mol ratio of PFOA, MMA and KH-570 is (3-5): (3-5): 1,
s2: adding AIBN (azobisisobutyronitrile) and ethyl acetate; the addition amount of AIBN is 0.5-1.5 wt% of the total weight of the monomers; the adding amount of the ethyl acetate is 400-600mL per mole of the monomer;
s3: and (3) in an inert atmosphere, carrying out polymerization reaction to obtain the flexible transparent super-hydrophobic Polymer (PMKA). Preferably, the inert atmosphere is N 2 Atmosphere or Ar atmosphere, wherein the polymerization reaction is carried out for 2-4h at the temperature of 60-80 ℃.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102209735A (en) * | 2008-11-11 | 2011-10-05 | 大金工业株式会社 | Method of preparing water- and oil-repellent soil-resistant composition |
| CN109972393A (en) * | 2019-03-12 | 2019-07-05 | 浙江纺织服装职业技术学院 | A kind of super-hydrophobic textile and preparation method thereof |
| CN110590987A (en) * | 2019-09-25 | 2019-12-20 | 华南理工大学 | Fluorine-silicon copolymerized acrylic resin and preparation method and application thereof |
| CN112029032A (en) * | 2020-08-26 | 2020-12-04 | 盐城工学院 | Preparation method of durable fabric waterproof finishing agent and product thereof |
-
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- 2022-10-27 CN CN202211327419.9A patent/CN115595032A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102209735A (en) * | 2008-11-11 | 2011-10-05 | 大金工业株式会社 | Method of preparing water- and oil-repellent soil-resistant composition |
| CN109972393A (en) * | 2019-03-12 | 2019-07-05 | 浙江纺织服装职业技术学院 | A kind of super-hydrophobic textile and preparation method thereof |
| CN110590987A (en) * | 2019-09-25 | 2019-12-20 | 华南理工大学 | Fluorine-silicon copolymerized acrylic resin and preparation method and application thereof |
| CN112029032A (en) * | 2020-08-26 | 2020-12-04 | 盐城工学院 | Preparation method of durable fabric waterproof finishing agent and product thereof |
Non-Patent Citations (1)
| Title |
|---|
| 邢亚男,刘利彬,朱国富: "超疏水超疏油涂层的制备及其性质" * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116285554A (en) * | 2023-03-13 | 2023-06-23 | 华南农业大学 | Preparation method of impact-resistant transparent super-hydrophobic coating |
| CN116285554B (en) * | 2023-03-13 | 2023-09-29 | 华南农业大学 | Preparation method of impact-resistant transparent super-hydrophobic coating |
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