CN112094589B - Preparation and application of environment-friendly low-cost super-hydrophobic powder material - Google Patents
Preparation and application of environment-friendly low-cost super-hydrophobic powder material Download PDFInfo
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- CN112094589B CN112094589B CN202011004944.8A CN202011004944A CN112094589B CN 112094589 B CN112094589 B CN 112094589B CN 202011004944 A CN202011004944 A CN 202011004944A CN 112094589 B CN112094589 B CN 112094589B
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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Abstract
The invention discloses a preparation method and application of an environment-friendly low-cost super-hydrophobic powder material, which comprises the steps of adding 50-90% of absolute ethyl alcohol into a micro-nano material KL, stirring for 1-5min, and performing ultrasonic dispersion for 5-15min to obtain a micro-nano material KL dispersion liquid; sequentially adding the materials in a volume ratio of 1: (1-1.25) a long-chain silane and ethyl orthosilicate; adding sodium nitrate aqueous solution with the molar mass of 1.9-2.1 into the micro-nano material KL mixed solution, and continuously stirring for 10-30 min; carrying out double-electrode electrolytic reaction on the KL mixed solution of the micro-nano material; and (3) after the reaction is finished, carrying out ultrasonic treatment, washing and centrifuging on the solution, and drying to obtain the super-hydrophobic powder. The invention increases the utilization rate of low surface energy substances, improves the yield of the super-hydrophobic material, reduces the preparation cost of the super-hydrophobic material, and shortens the reaction time by adopting a two-electrode system for reaction.
Description
Technical Field
The invention relates to the field of super-hydrophobic materials, in particular to preparation and application of an environment-friendly low-cost super-hydrophobic powder material.
Background
Materials can be classified into super-hydrophobic materials, hydrophilic materials, super-hydrophilic materials and amphoteric materials according to wettability. Generally, the super-hydrophobic surface refers to a material surface with a water contact angle of a certain size of water drop on the material surface larger than 150 degrees and a rolling angle smaller than 10 degrees, and for example, the surfaces of lotus leaves and butterfly wings are typical super-hydrophobic surfaces in nature. The surface of the super-hydrophobic material has excellent functions such as self-cleaning, anti-icing, anti-corrosion, waterproof, anti-fog and the like, so that the super-hydrophobic material has wide application prospects in the fields of aviation, automobiles, corrosion prevention, buildings, drag reduction and the like.
Two aspects of work are generally required to be completed for constructing the super-hydrophobic surface, namely, preparing a rough surface with a micro-nano structure on one hand, and reducing the surface energy of the surface of a material by using a low-surface-energy substance on the other hand. The preparation methods of the commonly used superhydrophobic surface at the present stage include an electrodeposition method, a hydrothermal method, a chemical etching method, a vapor deposition method, a sol-gel method, an electrostatic spinning method, a plasma treatment method, a laser engraving method and the like, and although the methods can effectively prepare the superhydrophobic surface, the methods often need higher required experimental conditions or are only suitable for a specific material substrate, and the problems of not firm combination of a micro-nano structure and the substrate, long preparation time, complex process and the like exist, so that the methods are not convenient for popularization and large-scale practical application on other substrates. In addition, in the process of reducing the surface energy, a fluorine-containing polymer/compound is generally used as a low-surface-energy substance, and a large amount of toxic organic solvents such as acetone, toluene, dichloromethane and the like are used, so that the preparation cost of the super-hydrophobic surface is high, and the problems of environmental pollution, harm to human health and the like can be caused, so that the preparation and application of an environment-friendly low-cost super-hydrophobic powder material capable of effectively solving the problems are needed.
Disclosure of Invention
The invention aims to provide a preparation method and application of an environment-friendly low-cost super-hydrophobic powder material,
in order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention comprises the following steps:
adding 50-90% of absolute ethyl alcohol into the micro-nano material KL, stirring for 1-5min, and performing ultrasonic dispersion for 5-15min to obtain a micro-nano material KL dispersion liquid;
b, sequentially adding 1: (1-1.25) further fully stirring the long-chain silane and the tetraethoxysilane to obtain a KL mixed solution of the micro-nano material;
c, adding a sodium nitrate aqueous solution with the mass of 1.9-2.1 moles into the micro-nano material KL mixed solution, wherein the aqueous solution accounts for 10-100 parts of the total weight of the absolute ethyl alcohol, adjusting the pH to 4.5, and continuously stirring for 10-30 min;
d, carrying out double-electrode electrolytic reaction on the KL mixed solution of the micro-nano material;
and E, after the reaction is finished, carrying out ultrasonic treatment, washing and centrifuging on the solution, and drying to obtain the super-hydrophobic powder.
Further, the micro-nano material KL accounts for 10% -60% of the total reactant mass.
Further, the long-chain silane can be one or more of dodecyl trimethoxy silane, hexadecyl trimethoxy silane and octadecyl triethoxy silane.
Further, the long-chain silane and the tetraethoxysilane account for 4-6% of the total volume of the ethanol water solution.
Further, the electrolyte accounts for 10% -50% of the total volume of the ethanol water solution.
Further, the distance between the electrodes may be 2-4.5cm, and the applied voltage may be 10-45V.
Further, the time of the constant pressure reaction may be 30 to 150 min.
Further, the drying temperature may be 25 to 120 ℃.
Further, the electrolyte is a sodium nitrate aqueous solution.
A super-hydrophobic transparent coating formed by the super-hydrophobic powder material.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, kaolin is introduced as a modified object, the utilization rate of low-surface-energy substances is increased, the yield of the super-hydrophobic material is improved, and the preparation cost of the super-hydrophobic material is reduced.
2. The invention selects all materials such as micro-nano material KL, long-chain silane, ethyl orthosilicate, ethanol solvent and the like, has wide sources, is green and environment-friendly, and is beneficial to sustainable development. The invention is used by combining with various commercial adhesives, is beneficial to increasing the bonding force between the super-hydrophobic surface and the substrate, and has wide application prospect.
Drawings
FIG. 1 is a flow chart of a process;
FIG. 2 is a KL schematic diagram of the original micro-nano material used in the method of example 1
FIG. 3 is a schematic view showing a water contact angle of the prepared superhydrophobic powder;
FIG. 4 is a schematic water contact angle of the super hydrophobic coating prepared in the method of example 1 applied on each substrate;
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be in a manner including, but not limited to, the following examples.
Referring to fig. 1, the present invention comprises the steps of:
adding 50-90% of absolute ethyl alcohol into the micro-nano material KL, stirring for 1-5min, and performing ultrasonic dispersion for 5-15min to obtain a micro-nano material KL dispersion liquid;
b, sequentially adding 1: (1-1.25) further fully stirring the long-chain silane and the long-chain silane of the ethyl orthosilicate and the ethyl orthosilicate to obtain a KL mixed solution of the micro-nano material;
c, adding a sodium nitrate aqueous solution with the mass of 1.9-2.1 moles into the micro-nano material KL mixed solution, wherein the aqueous solution accounts for 10-100 parts of the total weight of the absolute ethyl alcohol, adjusting the pH to 4.5, and continuously stirring for 10-30 min;
d, carrying out double-electrode electrolytic reaction on the KL mixed solution of the micro-nano material;
and E, after the reaction is finished, carrying out ultrasonic treatment, washing and centrifuging on the solution, and drying to obtain the super-hydrophobic powder.
The electrode is selected according to the stability and the conductivity of the electrode in the solution, and the micro-nano material KL can be a series of cheap and environment-friendly materials rich in hydroxyl.
Example 1
Weighing 70ml of absolute ethyl alcohol into a 150ml electrolytic tank, adding 2.25g of micro-nano material KL, magnetically stirring for 1min, and then performing ultrasonic treatment for 10 min; the stirring time is to fully mix the micro-nano material KL with absolute ethyl alcohol, and the ultrasonic treatment is to fully disperse the micro-nano material KL.
Sequentially adding 2.5ml of ethyl orthosilicate and 2.0ml of long-chain silane 1, and stirring for 5 min;
then adding 30ml NaNO3(0.67M) water solution, adjusting pH with glacial acetic acid, and continuing stirring for 30 min; the aqueous sodium nitrate solution mainly functions as an electrolyte, and thus potassium nitrate, potassium chloride, or the like may be used instead.
Taking an electrode 1(1.5cm multiplied by 1.5cm) as an anode and an electrode 2(4.5cm multiplied by 2.25cm) as a cathode, wherein the distance between the electrodes is 4.5cm, performing constant-pressure 30.0V reaction for 90min by using a direct current power supply (a Huatai power supply HAP03-100) under the assistance of stirring, and performing ultrasonic treatment for 5min after the reaction is finished;
separating at 8000rpm for 5min with centrifuge, and washing with anhydrous ethanol for three times;
the white material was collected and dried at 60 ℃ for 6 h.
According to the experimental steps, the preparation method of the super-hydrophobic powder provided by the invention is simple and rapid, the process is environment-friendly, and the raw materials are low in price. As shown in figure 2, the super-hydrophobic powder prepared by the invention has fine particles and no agglomeration phenomenon, as shown in figure 3, the water contact angle of the super-hydrophobic powder prepared by the invention reaches 158 degrees, the rolling angle is less than 5 degrees, and the excellent super-hydrophobicity of the product and the yield of the product provide good conditions for the application of the super-hydrophobic powder.
Example 2
Weighing 80ml of absolute ethyl alcohol into a 150ml electrolytic bath, adding 2.25g of micro-nano material KL, firstly magnetically stirring for 1min, and then carrying out ultrasonic treatment for 10 min;
sequentially adding 2.5ml of ethyl orthosilicate and 2.0ml of long-chain silane 1, and stirring for 5 min;
then adding 30ml NaNO3(0.67M) water solution, adjusting pH with glacial acetic acid, and continuing stirring for 30 min;
taking an electrode 1(1.5cm multiplied by 1.5cm) as an anode and an electrode 2(4.5cm multiplied by 2.25cm) as a cathode, wherein the distance between the electrodes is 4.5cm, performing constant-voltage 40.0V reaction for 90min by using a direct-current power supply (a Huatai power supply HAP03-100) under the assistance of stirring, and performing ultrasonic treatment for 5min after the reaction is finished;
separating at 8000rpm for 5min with centrifuge, and washing with anhydrous ethanol for three times;
the white material was collected and dried at 60 ℃ for 6 h.
From the above experimental procedure, example 2 is different from example 1 in that the volume ratio of ethanol/water used in example 2 is 8/2, but the prepared powder still exhibits super-hydrophobicity, and the contact angle of water reaches 156 °.
A method of preparing superhydrophobic surfaces on various substrates using the superhydrophobic powder of example 1.
Utilizing commercial epoxy resin (E51), and mixing the epoxy resin with the curing agent according to the mass fraction ratio of 10: 3, uniformly mixing;
the super-hydrophobic powder is uniformly coated on the surfaces of glass, magnesium alloy sheets, copper nets and A4 printing paper by a brush coating method, and is solidified for 30min at 60 ℃, the super-hydrophobic powder can be firstly dispersed in absolute ethyl alcohol to prepare a mixed solution with the solid content of 20-100%, and the mixed solution can also be directly used according to actual conditions.
The superhydrophobic powder of example 1 was uniformly dispersed on the surface of each substrate using a 200 mesh screen and cured at room temperature for 6-12 hours.
In the invention, besides adopting the direct current power supply constant voltage reaction, the constant current method can be used for replacing the constant voltage method to carry out the reaction. In the present invention, electrodes 1 and 2 are selected on the premise that they are not reactive with the solution due to their good conductivity, and may be replaced with other electrodes, and other acids such as hydrochloric acid may be used in addition to adjusting the pH with acetic acid.
The superhydrophobic powder prepared in example 1, the method successfully achieved the superhydrophobic state on the surfaces of glass, magnesium alloy sheet, copper mesh, and a4 printing paper. The method combines different adhesives and can be applied to various substrates. The method of using the superhydrophobic powder is not limited to the method shown here, and may be applied by a spray coating method, a brush coating method, a dipping method, or the like, as needed.
The above-mentioned embodiment is only one of the preferred embodiments of the present invention, and should not be used to limit the scope of the present invention, but all the insubstantial modifications or changes made within the spirit and scope of the main design of the present invention, which still solve the technical problems consistent with the present invention, should be included in the scope of the present invention.
Claims (6)
1. The preparation method of the environment-friendly low-cost super-hydrophobic powder material is characterized by comprising the following steps of:
adding 50-90% of absolute ethyl alcohol into a kaolin material, stirring for 1-5min, and performing ultrasonic dispersion for 5-15min to obtain a kaolin material dispersion liquid;
b, sequentially adding 1: (1-1.25) further fully stirring the long-chain silane and the ethyl orthosilicate to obtain a kaolin material mixed solution;
c, adding a sodium nitrate aqueous solution with the mass of 1.9-2.1 mol into the kaolin material mixed solution, wherein the aqueous solution accounts for 10-100 of the total parts of the absolute ethyl alcohol, adjusting the pH to 4.5, and continuously stirring for 10-30 min;
d, carrying out electrolytic reaction on the kaolin material mixed solution under the action of direct current by adopting a double-electrode constant voltage method, wherein the cathode of the electrolytic reaction is a high-hardness graphite cathode or a heat-resistant glass cloth-epoxy resin copper-clad plate cathode, the distance between electrodes of the electrolytic reaction can be 2-4.5cm, and the applied voltage of the electrolytic reaction is 10-45V;
and E, after the reaction is finished, carrying out ultrasonic treatment, washing and centrifuging on the solution, and drying to obtain the super-hydrophobic powder.
2. The method for preparing the environmentally friendly low-cost superhydrophobic powder material according to claim 1, wherein the kaolin material may be 10-60% by mass of the total reactants.
3. The method for preparing the environmentally friendly and low-cost superhydrophobic powder material according to claim 1, wherein the long-chain silane can be one or more of dodecyl trimethoxy silane, hexadecyl trimethoxy silane and octadecyl triethoxy silane.
4. The method for preparing the environmentally friendly low-cost superhydrophobic powder material according to claim 1, wherein the drying temperature can be 25-120 ℃.
5. The method for preparing the environmentally friendly and low-cost superhydrophobic powder material according to claim 1, wherein the time of the constant pressure reaction can be 30-150 min.
6. A superhydrophobic transparent coating formed using the superhydrophobic powder material of any one of claims 1-5.
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| CN106182725A (en) * | 2016-07-07 | 2016-12-07 | 广东工业大学 | A kind of method of molding prepares the method for polymer super-hydrophobic surface micro-nano structure |
| CN106283151A (en) * | 2016-08-30 | 2017-01-04 | 浙江大学 | A kind of preparation method of wear-resisting based superhydrophobic thin films |
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| CN106182725A (en) * | 2016-07-07 | 2016-12-07 | 广东工业大学 | A kind of method of molding prepares the method for polymer super-hydrophobic surface micro-nano structure |
| CN106283151A (en) * | 2016-08-30 | 2017-01-04 | 浙江大学 | A kind of preparation method of wear-resisting based superhydrophobic thin films |
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