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CN112647287A - Super-hydrophobic material with hierarchical coarse structure and preparation method and application thereof - Google Patents

Super-hydrophobic material with hierarchical coarse structure and preparation method and application thereof Download PDF

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CN112647287A
CN112647287A CN202011496963.7A CN202011496963A CN112647287A CN 112647287 A CN112647287 A CN 112647287A CN 202011496963 A CN202011496963 A CN 202011496963A CN 112647287 A CN112647287 A CN 112647287A
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metal oxide
super
superhydrophobic
microspheres
titanium
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CN112647287B (en
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李望良
李艳香
杨玉洁
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Institute of Process Engineering of CAS
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Abstract

本发明涉及一种具有阶层粗糙结构的超疏水材料，其特征在于：基底材料表面具有二次粗糙结构的金属氧化物微球，其外表面再修饰有低表面能物质层。本发明进一步涉及所述材料的制备方法和用途。本发明具有阶层粗糙结构的超疏水材料制备工艺简单、材料稳定性好，在自清洁、防水防污、减阻降噪、油水分离等领域具有优异效果。

Figure 202011496963

The invention relates to a super-hydrophobic material with a hierarchical rough structure, which is characterized in that: the surface of the base material has a metal oxide microsphere with a secondary rough structure, and the outer surface is further modified with a low surface energy substance layer. The present invention further relates to the preparation method and use of said material. The superhydrophobic material with hierarchical rough structure has simple preparation process and good material stability, and has excellent effects in the fields of self-cleaning, waterproof and antifouling, drag reduction and noise reduction, oil-water separation and the like.

Figure 202011496963

Description

Super-hydrophobic material with hierarchical coarse structure and preparation method and application thereof
Technical Field
The invention belongs to the field of nano composite material preparation, and particularly relates to a super-hydrophobic material with a hierarchical coarse structure, and a preparation method and application thereof.
Background
The super-hydrophobic material has wide application prospect in the fields of self-cleaning, water resistance, pollution prevention, noise reduction, water treatment and the like due to excellent water repellency. However, the simple coating of the surface of the solid material with the conventional fluorine and silicon materials has difficulty in achieving the superhydrophobic property of the material.
Studies have shown that the hydrophobicity of a material surface is determined by the surface energy and the surface roughness. Therefore, increasing the hydrophobicity of the film surface increases the roughness and decreases the surface energy.
Most coating materials are low surface energy materials containing fluorine, and the materials are toxic and expensive. The surface grafting modification can cause certain damage to the membrane body, so that the strength of the membrane is reduced. At present, a coating material with lower surface energy is generally adopted for constructing a super-hydrophobic surface, and a micro-scale or even nano-scale rough structure is manufactured by a physical and chemical method, or a micro-nano-scale rough structure of the surface is constructed firstly and then the surface energy is reduced. Based on the principle, various methods for constructing the super-hydrophobic surface, such as a vapor deposition method, a chemical etching method, a sol-gel method, an electrostatic spinning method, a layer-by-layer self-assembly method, a spraying method and the like, are available.
CN106811957A discloses a preparation method of an emulsion-separated super-hydrophobic surface, which comprises the steps of firstly preparing silicon dioxide particles, then adding a silane coupling agent to obtain super-hydrophobic coating liquid, finally soaking a fabric in the super-hydrophobic coating liquid, and drying to construct the fabric surface with super-hydrophobicity.
CN201710904266.2 discloses a method for preparing a super-hydrophobic material, which comprises soaking a substrate material in a precursor solution of titanium dioxide (TiO2), silicon dioxide (SiO2), cerium oxide (CeO2) nanoparticles, a solution containing nanoparticles, or a hydrosol containing nanoparticles, treating, drying to obtain a substrate material with a micron-nanometer composite coarse structure, and then soaking and drying in a silane coupling agent solution or a fluorosilane solution.
CN104802488A discloses a preparation method of a super-hydrophobic coating with a hierarchical coarse structure for oil-water separation, wherein spherical SiO with two particle sizes of 10-50nm and 70-500nm is assembled on the surface of a stainless steel screen mesh by a layer-by-layer electrostatic self-assembly method2Nano particles and then a layer of low surface energy substance is modified to obtain the super-hydrophobic coating.
Most of the methods firstly prepare the nano particles, and then construct roughness through mixing and coating, in the process, the nano particles are easy to aggregate, so that poor repeatability and material waste are caused, and although the electrostatic self-assembly method can avoid agglomeration and aggregation of the nano particles to a certain extent, electrostatic interaction is caused, and the bonding degree and stability of the nano particles and a substrate are poor.
Aiming at the problems, the invention provides a super-hydrophobic material with a special rough structure, wherein nano particles grow in situ on the surface of a base material and are connected with a substrate through chemical bonds, the nano particles are not easy to fall off, and in-situ nucleation and crystallization avoid particle agglomeration.
Disclosure of Invention
The invention aims to provide a super-hydrophobic material with a hierarchical rough structure, which comprises a base material and metal oxide microspheres grown in situ on the surface of the base material, wherein the outer surfaces of the microspheres are further modified with a low-surface-energy material layer.
Wherein the metal oxide microspheres are composed of metal oxide nanoparticles with the particle size of 3-10nm, and the diameter of the microspheres is within the range of 30-500 nm. The metal oxide microspheres make the surface of the super-hydrophobic material show a rough structure, and the metal oxide nanoparticles make the surface of the microsphere also show a rough structure similar to a strawberry structure, so that the double roughness constructed by the metal oxide microspheres and the metal oxide nanoparticles composing the microspheres makes the surface of the super-hydrophobic material have a hierarchical rough structure (also called a secondary rough structure).
The metal oxides include titanium dioxide (TiO2), silicon dioxide (SiO2), cerium oxide (CeO2) and ferroferric oxide (Fe3O 4).
The low surface energy material may be selected from any one or more of trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltriethoxysilane, hexadecyltrimethylsiloxane, Octadecyltrichlorosilane (OTS), hexafluorobutylpropyltrimethoxysilane, trimethoxysilane, octadecylmethacrylate, stearic acid.
The substrate material may be in the form of a sheet, fibre, fabric or filter membrane, and the material may be selected from cellulose, cellulose derivatives, nylon, polyethersulfone, polyether sulfone, polypropylene, polyvinylidene fluoride, polyacrylonitrile and the like.
Accordingly, the superhydrophobic material can be used as a sheet, fiber, fabric, or filter membrane.
The superhydrophobic material having a rough structure according to the present invention may have a water contact angle of more than 150 °.
The invention further relates to a preparation method of the super-hydrophobic material with the hierarchical coarse structure, which comprises the following steps:
(1) performing alkali liquor treatment or dopamine coating on the substrate material, and modifying functional groups such as hydroxyl, amino and the like on the surface;
(2) immersing the fiber or the filter membrane with the surface provided with the hydroxyl or amino functional group obtained in the step (1) into a mixture containing a metal oxide precursor and a solvent;
(3) adjusting the pH value of the solution;
(4) carrying out microwave irradiation reaction for a period of time at a certain temperature and normal pressure;
(5) then taking out, cooling, washing and drying;
(6) modifying the surface of the material with the metal oxide.
The lye treatment or dopamine coating described in step (1) can be applied using methods known to those skilled in the art.
The metal oxide precursor in the step (2) may be any one or more of n-butyl titanate, titanium isopropoxide, titanium sulfate, titanyl sulfate, titanium tetrachloride, ethyl orthosilicate, cerium nitrate, cerium carbonate or ferric chloride. The volume ratio of the titanium dioxide precursor to the solvent is 1 (5-200), preferably 1 (8-150), and more preferably 1 (10-100). The solvent is a mixture of water and/or small molecule alcohol. The mixture of the small molecular alcohols is any one or a mixture of at least two of methanol, ethanol or propanol.
In step (3), the pH value is 1-6, preferably 2-5. The adjustment of the pH may be performed by adding any one of hydrochloric acid, sulfuric acid, acetic acid, or citric acid, or a mixture of at least two thereof, in order to suppress hydrolysis of the metal oxide precursor.
In the step (4), the temperature of the microwave irradiation reaction is 50 to 120 ℃, and more preferably 70 to 100 ℃.
The normal pressure refers to a condition of 0.5 to 2 normal atmospheres, preferably 1 normal atmosphere.
The output power of the microwave irradiation reaction is 5-500W, preferably 20-460W, and further preferably 50-420W.
The irradiation time of the microwave irradiation reaction is 5-120min, preferably 10-60 min.
In the step (5), cooling the product obtained in the step (4) to room temperature; the washing solvent is water and/or ethanol. The drying mode is vacuum drying, the temperature of the vacuum drying is 30-70 ℃, and the time of the vacuum drying is 1-15h, preferably 1-12 h.
The modification method of the low surface energy substance comprises a chemical vapor deposition method (CVD), a dip coating method, a grafting method and an electrostatic spraying method.
The invention also relates to application of the super-hydrophobic material with the hierarchical coarse structure in the fields of self-cleaning, water resistance, pollution prevention, resistance reduction, noise reduction, oil-water separation and the like.
For example, the superhydrophobic material of the present invention can be used to treat oil and water mixtures including, but not limited to, oily wastewater generated during production in, for example, oil refineries, metallurgy, steel works, cold rolling mills, paint mills, petrochemical plants. The material has high affinity with oil, so that oil drops are easy to aggregate and coarsen. When the superhydrophobic material of the present invention is used in the form of a porous membrane, the oil phase after aggregation and coarsening passes through the pores of the membrane, and the water phase is blocked at one side of the membrane due to the hydrophobicity of the material, thereby achieving oil-water separation.
According to the invention, the metal oxide microspheres with secondary coarse structures are grown in situ on the surface of the substrate material by microwave-assisted heating in-situ hydrolysis, and then the low-surface-energy substance layer is modified, so that the obtained super-hydrophobic coating material has good stability. The method is green and simple, the nano particles grow in situ on the surface of the base material and are connected with the substrate through chemical bonds, the nano particles are not easy to fall off, and the agglomeration of the particles can be avoided through in-situ nucleation and crystallization. In addition, microwave-assisted heating has the advantages of high reaction rate, uniform heating and reaction time saving.
When the mixture is placed into a microwave reactor for irradiation, polar molecules (such as deionized water) can strongly absorb microwave radiation, the temperature of the reaction system is rapidly increased within minutes, a large number of metal oxide crystal nuclei are formed instantaneously, the small crystal nuclei have high surface free energy, and in order to reduce the free energy of the system, a more stable system is formed, the small crystals are gathered together to form particle aggregates, and the particle aggregates are further spontaneously assembled into larger particles with an inner pore structure through curing (Ostwald), and finally, the surface morphology with a secondary coarse structure is formed.
Drawings
FIG. 1 is a photograph of the contact angle of water in air of the superhydrophobic material of example 1 of the invention.
Fig. 2 is a scanning electron micrograph of the superhydrophobic material of example 4 of the present invention, wherein it can be seen that the surface of the material has a rough structure formed by metal oxide microspheres, and the surface of each metal oxide microsphere also has a rough structure.
Fig. 3 is an atomic force microscope image of the superhydrophobic material of example 4 of the invention, in which it can be seen that the surface roughness of the material is rough and uneven, and is calculated to be about 6-10nm, which is mainly due to the multilevel structure formed by stacking metal oxide nanoparticles of different particle sizes.
FIG. 4 is a photograph showing the effect of separating emulsified oil and water using the superhydrophobic material prepared in example 1 according to the present invention in example 5, wherein the left bottle is an unseparated oil-water mixture solution and the right bottle is water after separation.
Detailed Description
The following examples are intended to illustrate the present invention more specifically, but the present invention is not limited to these examples at all, and those skilled in the art can make various modifications within the technical idea of the present invention.
Unless otherwise specified, materials and reagents used in the examples of the present invention are commercially available; the experimental methods used are all conventional methods.
Example 1
(1) Dropwise adding 1.0mL of titanyl sulfate into 150mL of deionized water which is continuously stirred for dispersion, and slowly dropwise adding sulfuric acid to adjust the pH value to 3;
(2) adding cotton fabric (2cm x 2cm) into the mixture, placing the mixture in a microwave reactor under normal pressure for microwave irradiation, wherein the reaction temperature is 70 ℃, the reaction power is 150W, the reaction time is 45min, after the reaction is finished, cooling to room temperature, taking out, washing with deionized water (100ml x 3), and performing vacuum drying at 30 ℃ for 48 hours to obtain TiO2-cotton fabric.
(3) Mixing mercaptosiloxane, deionized water and ethanol according to the proportion of 4:6:9, and stirring for 1h at normal temperature to obtain a mercaptosiloxane solution. Followed by subjecting the above TiO to2-immersing the cotton fabric in a mercaptosiloxane solution for 2h to obtain mercapto-TiO 2-cotton fabric.
(4) Preparing a 5 wt% octadecyl methacrylate solution, adding 2 wt% benzoin ether (compared with the mass of alkyl ester), stirring at normal temperature until the solution is dissolved, then dipping the mercapto-TiO 2-cotton fabric into the solution, and illuminating for 30min under ultraviolet illumination. After the reaction, the mixture was washed 3 times with a solvent and cured and dried at 50 ℃ for 12 hours. The alkyl chain with hydrophobicity is grafted to the surface of the material through the generation of C-S, so that the hydrophobic material with stable performance is obtained. The contact angle of water in the air of the obtained modified cotton fabric is tested to reach 151 degrees (figure 1).
Example 2
(1) Commercially available 2g of acrylonitrile fiber was treated with 5 wt% potassium persulfate solution;
(2) dropwise adding 1.0mL of titanyl sulfate into 100mL of deionized water which is continuously stirred for dispersion, and slowly dropwise adding sulfuric acid to adjust the pH value to 4;
(3) and (2) immersing the treated acrylonitrile fiber into the mixture, placing the mixture in a microwave reactor under normal pressure for microwave irradiation, wherein the reaction temperature is 80 ℃, the reaction power is 80W, the reaction time is 10min, after the reaction is finished, cooling to room temperature, washing with deionized water (100ml x 3), and vacuum-drying at 50 ℃ for 24 hours.
(4) Putting the polyacrylonitrile fiber with the rough structure grown with TiO2 into a sealed container, adding hexafluorobutyl propyl trimethoxy silane, and evaporating and depositing low surface energy substances onto the surface of the polyacrylonitrile fiber with the rough structure at 200 ℃ to obtain the super-hydrophobic polyacrylonitrile fiber. The contact angle of water in air reaches 156 deg..
Example 3:
(1) a commercially available nylon microporous membrane was immersed in a dopamine solution (0.2g of dopamine, 0.24g of Tris-HCl and 200mL of water) to modify the surface of the porous filter with a polydopamine layer.
(2) 10mL of titanium tetrachloride is dropwise added into 100mL of ethanol and deionized water which are continuously stirred and dispersed, wherein the volume ratio of the ethanol to the deionized water is 1:5, and meanwhile, citric acid is slowly dropwise added to adjust the pH value to 4.
(3) And (2) immersing the nylon membrane treated in the step (1) into the mixture, placing the nylon membrane in a microwave reactor under normal pressure for microwave irradiation, wherein the reaction temperature is 50 ℃, the reaction power is 240W, the reaction time is 30min, after the reaction is finished, cooling to room temperature, washing with deionized water (100ml x 3), and vacuum-drying at 80 ℃ for 24 hours.
(4) And (3) putting the rough-structure nylon membrane with the grown TiO2 into a sealed container, adding tridecafluorooctyltriethoxysilane, and evaporating and depositing low-surface-energy substances onto the surface of the rough-structure nylon membrane at 180 ℃ to obtain the super-hydrophobic filter membrane. The contact angle of water in air reaches 152 deg..
Example 4:
(1) dropwise adding 1.0mL of titanyl sulfate into 100mL of deionized water which is continuously stirred for dispersion, and slowly dropwise adding sulfuric acid to adjust the pH value to 2;
(2) adding commercially available 1g cellulose fiber into the mixture, placing the mixture in a microwave reactor under normal pressure for microwave irradiation, wherein the reaction temperature is 90 ℃, the reaction power is 100W, the reaction time is 20min, after the reaction is finished, cooling the mixture to room temperature, washing the mixture with deionized water (100ml x 3), and performing vacuum drying at 30 ℃ for 48 hours.
The cellulose fiber with the coarse structure, on which the TiO2 grows, is immersed in a solution of octadecyl trichlorosilane for 1 hour, taken out and dried at 80 ℃ to obtain the super-hydrophobic cellulose fiber. The contact angle of water in air was measured to be 151 °.
Example 5:
1000ppm of the hexadecane-water emulsion was filtered through the superhydrophobic cotton fabric obtained in example 1 to separate the oil-water mixture. As can be clearly seen from fig. 4, the turbid oil-water mixture before separation is a clear and transparent liquid (water) after separation, and the oil-water separation efficiency is as high as 99.5%, indicating that the oil-water separation effect is excellent.

Claims (10)

1.一种具有阶层粗糙结构的超疏水材料，包括基底材料和在基底材料表面原位生长的金属氧化物微球，且所述微球外表面进一步修饰有低表面能物质层。1. A superhydrophobic material with a hierarchical rough structure, comprising a base material and metal oxide microspheres grown in situ on the surface of the base material, and the outer surface of the microspheres is further modified with a low surface energy substance layer. 2.根据权利要求1所述的超疏水材料，其中所述基底材料选自纤维素、纤维素衍生物、尼龙、聚醚砜、聚醚醚砜、聚丙烯、聚偏氟乙烯和聚丙烯腈；所述金属氧化物包括二氧化钛、二氧化硅、氧化铈和四氧化三铁。2. The superhydrophobic material of claim 1, wherein the base material is selected from the group consisting of cellulose, cellulose derivatives, nylon, polyethersulfone, polyetherethersulfone, polypropylene, polyvinylidene fluoride and polyacrylonitrile ; The metal oxides include titanium dioxide, silicon dioxide, cerium oxide and ferric oxide. 3.根据权利要求1所述的超疏水材料，其中所述金属氧化物微球由粒径为3-10nm的金属氧化物纳米粒子构成，微球的直径在30-500nm范围。3. The superhydrophobic material according to claim 1, wherein the metal oxide microspheres are composed of metal oxide nanoparticles with a particle size of 3-10 nm, and the diameter of the microspheres is in the range of 30-500 nm. 4.根据权利要求1所述的超疏水材料，其中所述低表面能物质材料选自三氟丙基三甲氧基硅烷、三氟丙基三乙氧基硅烷、十三氟辛基三乙氧基硅烷、十六烷基三甲基硅氧烷、十八烷基三氯硅烷、六氟丁基丙基三甲氧基硅烷、三甲氧基硅烷、甲基丙烯酸十八烷基酯、硬酯酸中的任一种或多种。4. The superhydrophobic material according to claim 1, wherein the low surface energy material is selected from the group consisting of trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltriethoxysilane Silane, Cetyltrimethylsiloxane, Octadecyltrichlorosilane, Hexafluorobutylpropyltrimethoxysilane, Trimethoxysilane, Octadecyl Methacrylate, Stearic Acid any one or more of. 5.根据权利要求1-4任一项所述的超疏水材料的制备方法，包括如下步骤：5. according to the preparation method of the superhydrophobic material described in any one of claim 1-4, comprise the steps: (1)将基底材料进行碱液处理或者多巴胺涂层，在表面修饰羟基、氨基等官能团；(2)将步骤(1)所得表面带有羟基或氨基官能团的纤维或滤膜浸入包含有金属氧化物前驱体和溶剂的混合物中；(3)调节溶液pH；(4)在一定温度和常压下进行微波辐照反应一段时间；(5)之后，取出，冷却、洗涤、干燥；和(6)在生长有金属氧化物的材料表面修饰低表面能物质。(1) Alkaline treatment or dopamine coating is performed on the base material, and functional groups such as hydroxyl and amino groups are modified on the surface; (2) The fibers or filter membranes with hydroxyl or amino functional groups on the surface obtained in step (1) are immersed in a fiber containing metal oxide (3) adjust the pH of the solution; (4) carry out microwave irradiation reaction at a certain temperature and normal pressure for a period of time; (5) after that, take out, cool, wash, and dry; and (6) ) to modify low surface energy species on the surface of the grown metal oxide material. 6.根据权利要求书5所述的方法，其中在步骤(2)中，所述二氧化钛前驱体选自钛酸正丁酯、异丙醇钛、硫酸钛、硫酸氧钛、四氯化钛中、正硅酸乙酯、硝酸铈盐、碳酸铈盐和氯化铁中的任意一种或多种；所述二氧化钛前驱体和溶剂的体积比为1:5-200，优选为1:8-150，进一步优选1:10-100。6. The method according to claim 5, wherein in step (2), the titanium dioxide precursor is selected from n-butyl titanate, titanium isopropoxide, titanium sulfate, titanium oxysulfate, and titanium tetrachloride , any one or more of ethyl orthosilicate, cerium nitrate, cerium carbonate and ferric chloride; the volume ratio of the titanium dioxide precursor and the solvent is 1:5-200, preferably 1:8- 150, more preferably 1:10-100. 7.根据权利要求书5所述的方法，其中在步骤(4)中，所述微波辐照反应的温度为50-120℃，进一步优选为70-100℃；所述微波辐照反应的输出功率为5-500W，优选为20-460W，进一步优选为50-420W；所述微波辐照反应的辐照时间为5-120min，优选为10-60min。7. The method according to claim 5, wherein in step (4), the temperature of the microwave irradiation reaction is 50-120°C, more preferably 70-100°C; the output of the microwave irradiation reaction is The power is 5-500W, preferably 20-460W, more preferably 50-420W; the irradiation time of the microwave irradiation reaction is 5-120min, preferably 10-60min. 8.根据权利要求书5所述的方法，其中低表面能物质的修饰方法包括化学气相沉积法、浸渍涂层、接枝、静电喷雾方法。8. The method according to claim 5, wherein the modification method of the low surface energy substance comprises chemical vapor deposition, dip coating, grafting, and electrostatic spraying. 9.根据权利要求1-4任一项所述的超疏水材料在自清洁、防水防污、减阻降噪、油水分离领域的用途。9. Use of the superhydrophobic material according to any one of claims 1-4 in the fields of self-cleaning, waterproofing and antifouling, drag reduction and noise reduction, and oil-water separation. 10.根据权利要求9所述的用途，其中所述油水分离为用于分离炼油厂、冶金、钢铁厂、冷轧厂、油漆厂、石化厂在生产过程中产生的含油废水。10. The use according to claim 9, wherein the oil-water separation is used to separate oily wastewater produced in the production process of oil refineries, metallurgy, iron and steel plants, cold rolling plants, paint plants, and petrochemical plants.
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