CN113698661A - Preparation method and self-repairing method of all-weather thermal response quick self-repairing super-hydrophobic sponge - Google Patents
Preparation method and self-repairing method of all-weather thermal response quick self-repairing super-hydrophobic sponge Download PDFInfo
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Abstract
The invention discloses a preparation method and a self-repairing method of an all-weather thermal response quick self-repairing super-hydrophobic sponge, and relates to a preparation method and a self-repairing method of a self-repairing super-hydrophobic sponge. The invention uses benzeneAmine is taken as a monomer, ammonium persulfate is taken as an oxidant, hydrochloric acid is taken as a doping agent, and a low surface energy modifier PDMS is taken as an adhesive to bond MWCNTs and PDA @ WO3Nanoparticles. The self-repairing super-hydrophobic polyurethane sponge with photo-thermal/joule-thermal performance is synthesized by taking polyurethane sponge as a base material and adopting an in-situ chemical oxidative polymerization and simple coating method. At 1.0kW/m2The super-hydrophobicity can be recovered by irradiating for 2min under simulated illumination, when the illumination intensity is insufficient and even the illumination condition is not available, voltage can be applied to realize all-weather thermal response by utilizing the Joule thermal property of the sponge, and the invention is applied to the field of self-repairing super-hydrophobic materials.
Description
Technical Field
The invention belongs to the field of preparation of self-repairing super-hydrophobic materials, and particularly relates to a quick self-repairing super-hydrophobic material with all-weather thermal response and a preparation method thereof.
Background
Superhydrophobic surfaces are a class of surfaces that are extremely repellent to high surface tension liquids, such as water, and are typically constructed by combining appropriate micro-nano roughness structures with low surface energy materials. The super-hydrophobic surface has the characteristics of water resistance, low fluid viscosity and the like, and is widely applied to the fields of self-cleaning, oil-water separation, corrosion prevention, anti-icing, anti-fogging and the like. However, the super-hydrophobic surface is often subjected to corrosive environments such as strong acid, strong alkali and strong oxidizing solution in the using process, and is also damaged and loses super-hydrophobicity due to mechanical abrasion such as friction, water flow scouring and even sand impact. Therefore, there is an urgent need to develop a method for improving the service life of the superhydrophobic surface.
Imparting self-healing properties to superhydrophobic surfaces is a preferred option for extending the lifetime of the surface. At present, a method of storing low surface energy components in a micro-nano rough structure of a super-hydrophobic surface is widely used, and when the super-hydrophobic surface is damaged, the hydrophobic components can be released to finish self-repairing. The self-repairing time is usually long and varies from hours to days. The thermal response can regulate the migration rate of the molecular chain on the microscale through the temperature, and the higher the temperature is, the faster the migration rate of the molecular chain is, so that the thermal response has the advantages of quick effect, easy realization and the like and is widely adopted. However, the existing thermal response repairing method has the problems of single repairing method, long repairing time and poor durability, and the application of the self-repairing super-hydrophobic material is restricted.
Disclosure of Invention
The invention aims to solve the problems of poor durability, single self-repairing method and long repairing time of the existing self-repairing super-hydrophobic material, and provides a preparation method and a self-repairing method of an all-weather thermal response quick self-repairing super-hydrophobic sponge.
The invention relates to a preparation method of an all-weather thermal response quick self-repairing super-hydrophobic sponge, which comprises the following steps of:
dissolving trihydroxymethyl aminomethane hydrochloride in distilled water to prepare trihydroxymethyl aminomethane hydrochloride solution with the concentration of 7.5-8.0g/L, and sequentially adding dopamine and CuSO into the trihydroxymethyl aminomethane hydrochloride solution4·5H2O and H2O2Adding tungsten oxide nano particles, stirring, washing with deionized water and centrifuging after the reaction is finished, and then drying in vacuum to obtain the modified photocatalytic nano particles PDA @ WO3(ii) a Dopamine, CuSO4·5H2The mass-volume ratio of the O, the tungsten oxide nano-particles and the tris hydrochloride solution is (3.8-4.1) g: (2.5-2.8) g: 2 g: 2L; tris-hydroxymethyl aminomethane hydrochloride solution and H2O2The volume ratio of (A) is 1: 0.00258-0.00275;
secondly, preparing an ammonium persulfate solution with the mass concentration of 182.4-182.6 g/L;
mixing the HCl solution and aniline monomer at room temperature, adding the mixture into a substrate polyurethane sponge, adding an ammonium persulfate solution under continuous stirring, stirring until the mixture is fully mixed, then polymerizing for 20-28h in a water bath at 20-25 ℃ under the condition of shading, and reacting to obtain PANI modified sponge; then washing the PANI modified sponge by distilled water and ethanol in sequence, and then drying in vacuum to obtain the dried modified sponge; the mass volume of the aniline monomer and HCl solution is (17.5-20.0) g: 1L, wherein the volume ratio of the ammonium persulfate solution to the HCl solution is 1: 2.9-3.1;
fourthly, taking polydimethylsiloxane, multi-wall carbon nano tube and modified photocatalytic nano particle PDA @ WO3Ultrasonically mixing the modified sponge with ethyl acetate to prepare a suspension, immersing the dried modified sponge in the suspension for ultrasonic treatment, and curing at the temperature of 100-120 ℃ for 1-3h to obtain the quick self-repairing super-hydrophobic sponge with all-weather thermal response; polydimethylsiloxane, multi-walled carbon nanotube and modified photocatalytic nanoparticle PDA @ WO3The mass-to-volume ratio of the ethyl acetate is (7.0-8.5) g: (9.8-11.0) g: (10.0-11.5) g: 1L of the compound.
The invention uses aniline as monomer, ammonium persulfate as oxidant, hydrochloric acid as dopant, and uses low surface energy modifier PDMS as adhesive to bond MWCNTs and PDA @ WO3Nanoparticles. The self-repairing super-hydrophobic polyurethane sponge with photo-thermal/joule-thermal performance is synthesized by taking polyurethane sponge as a base material and adopting an in-situ chemical oxidative polymerization and simple coating method. At 1.0kW/m2The super-hydrophobicity can be recovered by irradiating for 2min under simulated illumination, when the illumination intensity is insufficient and even the illumination condition is not available, voltage can be applied to realize all-weather thermal response by utilizing the joule heat performance of the sponge,
the invention has the following advantages:
(1) the sponge has excellent photo-thermal/joule heat conversion performance at 1.0kW/m2The surface equilibrium temperature of the sponge rapidly reaches 105 ℃ under the illumination of the lamp, and the surface temperature of the sponge can be supplemented by applying extra voltage when the illumination is insufficient.
(2) After the sponge is seriously damaged by mechanochemistry or loses the super-hydrophobic property by oxygen plasma etching, the super-hydrophobicity of the sponge can be 1.0kW/m2Can be recovered after 2min of irradiation under the illumination, and can also be 0.5kW/m2At a light intensity of 20V and at 0.8kW/m2The 16V voltage is applied for recovery under the illumination intensity, the recovery method is diversified, the recovery time is short, and the super-hydrophobicity can be still recovered after 10 times of plasma etching.
(3) The sponge self-repairing super-hydrophobic sponge shows excellent anti-pollution capacity, has good capacity of resisting organic pollutants, and can further prolong the service life of the sponge.
Drawings
FIG. 1 is an SEM image of a self-healing superhydrophobic sponge at low magnification;
FIG. 2 is an SEM image of a self-repairing superhydrophobic sponge under high magnification;
FIG. 3 is a water contact angle of a self-repairing superhydrophobic sponge;
FIG. 4 is a graph showing that electric energy assists solar heating to maintain the surface temperature of the self-repairing superhydrophobic sponge;
FIG. 5 shows WCA changes of a self-repairing superhydrophobic sponge after a sand paper abrasion-self-repairing cycle;
FIG. 6 is a WCA change of a self-repairing superhydrophobic sponge through NaOH corrosion-self-repairing cycle;
FIG. 7 is a self-repairing superhydrophobic sponge pass through O2WCA variation of plasma etch/self-repair cycle;
FIG. 8 shows the WCA change of the sponge after being etched by oxygen plasma for 1min after being irradiated for 10min under different illumination intensities and the time change of the sponge after being restored to a super-hydrophobic state under different illumination intensities;
FIG. 9 is a graph of the UV-VIS absorption curve of Methylene Blue (MB) solution before and after photocatalytic degradation; wherein a is an absorption curve of 30mmp MB, and b is an absorption curve after photocatalytic degradation;
FIG. 10 is a color change before and after photocatalytic degradation in a filter flask containing Methylene Blue (MB) solution.
Detailed Description
The first embodiment is as follows: the embodiment provides a preparation method of an all-weather thermal response quick self-repairing super-hydrophobic sponge, which comprises the following steps:
dissolving trihydroxymethyl aminomethane hydrochloride in distilled water to prepare trihydroxymethyl aminomethane hydrochloride solution with the concentration of 7.5-8.0g/L, and sequentially adding dopamine and CuSO into the trihydroxymethyl aminomethane hydrochloride solution4·5H2O and H2O2Adding tungsten oxide nano particles, stirring, washing with deionized water and centrifuging after the reaction is finished, and then drying in vacuum to obtain the modified photocatalytic nano particles PDA @ WO3(ii) a Dopamine, CuSO4·5H2The mass-volume ratio of the O, the tungsten oxide nano-particles and the tris hydrochloride solution is (3.8-4.1) g: (2.5-2.8) g: 2 g: 2L; tris-hydroxymethyl aminomethane hydrochloride solution and H2O2The volume ratio of (A) is 1: 0.00258-0.00275;
secondly, preparing an ammonium persulfate solution with the mass concentration of 182.4-182.6 g/L;
mixing the HCl solution and aniline monomer at room temperature, adding the mixture into a substrate polyurethane sponge, adding an ammonium persulfate solution under continuous stirring, stirring until the mixture is fully mixed, then polymerizing for 20-28h in a water bath at 20-25 ℃ under the condition of shading, and reacting to obtain PANI modified sponge; then washing the PANI modified sponge by distilled water and ethanol in sequence, and then drying in vacuum to obtain the dried modified sponge; the mass volume of the aniline monomer and HCl solution is (17.5-20.0) g: 1L;
fourthly, taking polydimethylsiloxane, multi-wall carbon nano tube and modified photocatalytic nano particle PDA @ WO3Ultrasonically mixing the modified sponge with ethyl acetate to prepare a suspension, immersing the dried modified sponge in the suspension for ultrasonic treatment, and curing at the temperature of 100-120 ℃ for 1-3h to obtain the quick self-repairing super-hydrophobic sponge with all-weather thermal response; polydimethylsiloxane, multi-walled carbon nanotube and modified photocatalytic nanoparticle PDA @ WO3The mass-to-volume ratio of the ethyl acetate is (7.0-8.5) g: (9.8-11.0) g: (10.0-11.5) g: 1L of the compound.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the concentration of the tris hydrochloride solution in step one was 7.88g/L, and the pH was adjusted to 8.5 using NaOH solution. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: in the step one, dopamine and CuSO4·5H2The mass-volume ratio of the O, the tungsten oxide nanoparticles and the tris hydrochloride solution is 4 g: 2.65 g: 2 g: 2L. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: step by stepIn step one, tris hydrochloride solution and H2O2Is 1: 0.00266. The others are the same as in one of the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: and step two, preparing an ammonium persulfate solution with the mass concentration of 182.56 g/L. The other is the same as one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: the mass volume of the aniline monomer and the HCl solution in the step III is 18.615 g: 1L, and the concentration of the HCl solution is 1 mol/L. The other is the same as one of the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: polydimethylsiloxane, multi-walled carbon nanotube and modified photocatalytic nanoparticle PDA @ WO in the fourth step3The mass-to-volume ratio of ethyl acetate was 7 g: 10 g: 10 g: 1L of the compound. The other is the same as one of the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: the vacuum drying refers to vacuum drying at 60 ℃ for 24 hours. The other is the same as one of the first to seventh embodiments.
The specific implementation method nine: the self-repairing method of the all-weather thermal response quick self-repairing super-hydrophobic sponge comprises the following steps: at 1.0kW/m2Irradiating for 2min under the illumination.
The detailed implementation mode is ten: the self-repairing method of the all-weather thermal response quick self-repairing super-hydrophobic sponge comprises the following steps: at 0.5kW/m2Under the illumination intensity, 20V voltage is applied, and the sponge surface is repaired for 2min after the equilibrium temperature reaches 100-110 ℃.
The concrete implementation mode eleven: the self-repairing method of the all-weather thermal response quick self-repairing super-hydrophobic sponge comprises the following steps: at 0.8kW/m2Under the illumination intensity, 16V voltage is applied, and the sponge surface is repaired for 2min after the equilibrium temperature reaches 100-110 ℃.
Example 1 all weatherPreparation of a quick self-repairing super-hydrophobic sponge with thermal response: 0.1576g of Tris hydrochloride (Tris-HCl) were dissolved in 20mL of distilled water to prepare a solution (pH 8.5 adjusted with NaOH), followed by the sequential addition of 0.04g of Dopamine (DA), CuSO4·5H2O(0.0265g)，H2O2(53.2. mu.L), 2g of tungsten oxide (WO) was rapidly added3) Nanoparticles, stirring was continued for 1 hour. After the reaction was completed, it was washed with deionized water and centrifuged. Placing the mixture at 60 ℃ for vacuum drying for 24h to obtain the modified photocatalytic nano particle PDA @ WO3. 1.8256g of Ammonium Persulfate (APS) was dissolved in 10mL of distilled water to obtain an ammonium persulfate solution. 30mL of HCl (1mol/L) solution and 0.7446g of aniline monomer are mixed for 10min at room temperature, a substrate polyurethane sponge is added, an ammonium persulfate solution is added dropwise with continuous stirring, and the mixture is stirred for 5min to fully mix the oxidant APS and the aniline monomer. Stirring was stopped, and the solution was subjected to shading treatment with tinfoil and polymerized in a water bath at 25 ℃ for 24 hours. After the reaction, the PANI-modified sponge was washed with distilled water and ethanol, and then the sponge was vacuum-dried at 60 ℃ for 24 hours. Taking PDMS (0.07g), MWCNTs (0.10g) and modified photocatalytic nano-particle PDA @ WO3(0.10g) and 10mL ethyl acetate are subjected to ultrasonic treatment for 30min to prepare a suspension, the dried sponge is immersed in the suspension, ultrasonic treatment is carried out for 5min under the power of 360W, and curing is carried out for 2h at the temperature of 120 ℃ to obtain the quick self-repairing super-hydrophobic sponge with all-weather thermal response.
The micro-morphology characterization and wettability of the all-weather thermal response quick self-repairing super-hydrophobic sponge are as follows: as shown in FIG. 1, MWCNTs and PDA @ WO can be observed on the surface of the self-repairing super-hydrophobic sponge3Uniformly distributed, and MWCNTs linked to PANI through the PDMS layer (fig. 2), exhibiting superhydrophobicity (WCA 155 °) (fig. 3).
The photothermal/joule heating performance of the all-weather thermal response quick self-repairing super-hydrophobic sponge is as follows: the self-repairing super-hydrophobic sponge has excellent photo-thermal conversion performance/joule heat conversion performance, and the temperature of the top surface of the sponge rises along with the increase of the sunlight intensity/voltage. When the self-repairing super-hydrophobic sponge is used at night or in rainy days, the light and heat effect of the self-repairing super-hydrophobic sponge can not be influenced due to the fact that the illumination intensity is not guaranteed. At this time, joule heating can be performed on both sides of the sponge by applying an appropriate voltage. As shown in fig. 4Wherein 1 is the illumination intensity of 1.0kW/m2And 2 is the illumination intensity of 0.8kW/m2And 3 is the illumination intensity of 0.5kW/m2X is the illumination start, y is the starting voltage, and z is the closing illumination and voltage; when the concentration is 0.5kW/m2At a light intensity of 20V and at 0.8kW/m2When 16V voltage is applied under the illumination intensity of the sponge, the surface temperature of the sponge can reach the temperature generated under sunlight.
Self-repairability of the all-weather thermal response quick self-repairing super-hydrophobic sponge: as shown in fig. 5, after 100 sandpaper abrasion cycles, the WCA of the superhydrophobic sponge dropped to 145 °, but it recovered to about 152 ° in 2 minutes under simulated sunlight due to the migration of low surface energy species. The self-healing performance of the superhydrophobic sponge on chemical corrosion damage was also studied, as shown in fig. 6, after the sponge was soaked in a strong alkaline solution for 24 hours, the WCA dropped to 145 °, and by exposure to simulated sunlight for 2 minutes, the WCA could be restored to 154 °. These repair results indicate that the loss of superhydrophobicity due to extreme chemical corrosion and physical abrasion can be quickly recovered. The angle of the physical abrasion-self-repairing cycle recovery is gradually reduced, and the repairing time is prolonged to about 10 minutes from the initial 2 min. The recovery angle in the chemical corrosion-self-repair cycle has no downward trend, and the repair time is prolonged from 2min to 15 min. After 10 times of circulation, the super-hydrophobic performance can still be achieved, which indicates that the service life of the material is prolonged and the durability is good.
As shown in FIG. 7, after etching with oxygen plasma for 1min, the sponge surface rapidly changed from superhydrophobicity to superhydrophilicity (WCA ═ 0 deg.), at 1.0kW/m2The WCA of the sponge can be restored to 155 degrees after being placed in the simulated sunlight for 2 min. And passed through for 10 times O2After the plasma etching/self-repairing cycle, the sponge can still recover the super-hydrophobicity, but the repairing time is gradually prolonged.
FIG. 8 shows the change in WCA and the change in time to return to a superhydrophobic state after exposure to different illumination intensities for 10min for a sponge etched with oxygen plasma for 1 min; wherein c is WCA change of the sponge etched by the oxygen plasma for 1min after being irradiated for 10min under different illumination intensities, d is the change of the sponge etched by the oxygen plasma for 1min under different illumination intensitiesThe irradiation time required to restore superhydrophobic performance at intensity. Along with the increase of the illumination intensity, the temperature of the surface of the sponge rises, the water contact angle of the surface of the sponge to be repaired is gradually increased, the repairing time required for recovering to the super-hydrophobic state is gradually shortened, and the repairing time is 1.0kW/m2The super-hydrophobic state can be recovered after 2min of illumination.
The anti-fouling performance of the all-weather thermal response quick self-repairing super-hydrophobic sponge is as follows: the disappearance of the characteristic absorption peak at 664nm of the ultraviolet-visible absorption curve (figure 9) and the colorless filtrate (figure 10) mutually confirm that the self-repairing superhydrophobic sponge shows excellent visible light catalytic degradation capability on organic dye Methylene Blue (MB), and the self-repairing superhydrophobic sponge has good capability of resisting organic pollutants. In addition, due to the excellent super-hydrophobic property (WCA: 155 °, SA: 5 °) of the sponge, water droplets can easily carry away particle contaminants such as dust on the surface of the sponge.
Claims (10)
1. A preparation method of an all-weather thermal response quick self-repairing super-hydrophobic sponge is characterized by comprising the following steps:
dissolving trihydroxymethyl aminomethane hydrochloride in distilled water to prepare trihydroxymethyl aminomethane hydrochloride solution with the concentration of 7.5-8.0g/L, and sequentially adding dopamine and CuSO into the trihydroxymethyl aminomethane hydrochloride solution4·5H2O and H2O2Adding tungsten oxide nano particles, stirring, washing with deionized water and centrifuging after the reaction is finished, and then drying in vacuum to obtain the modified photocatalytic nano particles PDA @ WO3(ii) a Dopamine, CuSO4·5H2The mass-volume ratio of the O, the tungsten oxide nano-particles and the tris hydrochloride solution is (3.8-4.1) g: (2.5-2.8) g: 2 g: 2L; tris-hydroxymethyl aminomethane hydrochloride solution and H2O2The volume ratio of (A) is 1: 0.00258-0.00275;
secondly, preparing an ammonium persulfate solution with the mass concentration of 182.4-182.6 g/L;
mixing the HCl solution and aniline monomer at room temperature, adding the mixture into a substrate polyurethane sponge, adding an ammonium persulfate solution under continuous stirring, stirring until the mixture is fully mixed, then polymerizing for 20-28h in a water bath at 20-25 ℃ under the condition of shading, and reacting to obtain PANI modified sponge; then washing the PANI modified sponge by distilled water and ethanol in sequence, and then drying in vacuum to obtain the dried modified sponge; the mass volume of the aniline monomer and HCl solution is (17.5-20.0) g: 1L, wherein the volume ratio of the ammonium persulfate solution to the HCl solution is 1: 2.9-3.1;
fourthly, taking polydimethylsiloxane, multi-wall carbon nano tube and modified photocatalytic nano particle PDA @ WO3Ultrasonically mixing the modified sponge with ethyl acetate to prepare a suspension, immersing the dried modified sponge in the suspension for ultrasonic treatment, and curing at the temperature of 100-120 ℃ for 1-3h to obtain the quick self-repairing super-hydrophobic sponge with all-weather thermal response; polydimethylsiloxane, multi-walled carbon nanotube and modified photocatalytic nanoparticle PDA @ WO3The mass-to-volume ratio of the ethyl acetate is (7.0-8.5) g: (9.8-11.0) g: (10.0-11.5) g: 1L of the compound.
2. The method for preparing the all-weather thermal response quick self-repairing super-hydrophobic sponge as claimed in claim 1, wherein the concentration of the tris hydrochloride solution in the first step is 7.88g/L, and the pH is adjusted to 8.5 by using NaOH solution.
3. The method for preparing the all-weather thermal response quick self-repairing super-hydrophobic sponge as claimed in claim 1, wherein the dopamine and CuSO are added in the step one4·5H2The mass-volume ratio of the O, the tungsten oxide nanoparticles and the tris hydrochloride solution is 4 g: 2.65 g: 2 g: 2L.
4. The method for preparing the all-weather thermal response quick self-repairing super-hydrophobic sponge as claimed in claim 1, wherein the tris hydrochloride solution and H in the step one2O2Is 1: 0.00266.
5. The method for preparing the all-weather thermal response quick self-repairing super-hydrophobic sponge as claimed in claim 1, wherein in the second step, a solution of ammonium persulfate with a mass concentration of 182.56g/L is prepared.
6. The preparation method of the all-weather thermal response quick self-repairing super-hydrophobic sponge as claimed in claim 1, wherein the mass volume of the aniline monomer and the HCl solution in the step three is 18.615 g: 1L, and the concentration of the HCl solution is 1 mol/L.
7. The preparation method of the all-weather thermal response quick self-repairing super-hydrophobic sponge as claimed in claim 1, wherein the preparation method comprises the following steps of polydimethylsiloxane, multi-walled carbon nanotube and modified photocatalytic nanoparticle PDA @ WO3The mass-to-volume ratio of ethyl acetate was 7 g: 10 g: 10 g: 1L of the compound.
8. The self-repairing method of the all-weather thermal response quick self-repairing super-hydrophobic sponge as claimed in claim 1, characterized in that the self-repairing method comprises: at 1.0kW/m2Irradiating for 2min under the illumination.
9. The self-repairing method of the all-weather thermal response quick self-repairing super-hydrophobic sponge as claimed in claim 1, characterized in that the self-repairing method comprises: at 0.5kW/m2Under the illumination intensity, 20V voltage is applied, and the sponge surface is repaired for 2min after the equilibrium temperature reaches 100-110 ℃.
10. The self-repairing method of the all-weather thermal response quick self-repairing super-hydrophobic sponge as claimed in claim 1, characterized in that the self-repairing method comprises: at 0.8kW/m2Under the illumination intensity, 16V voltage is applied, and the sponge surface is repaired for 2min after the equilibrium temperature reaches 100-110 ℃.
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