CN108728042B - Application of azobenzene-graphene composite material in preparation of anti-icing material - Google Patents
Application of azobenzene-graphene composite material in preparation of anti-icing material Download PDFInfo
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Abstract
The invention discloses an application of an azobenzene-graphene composite material in preparation of an anti-icing material. And DSC detection shows that the energy density of the prepared dispersed orange/graphene composite material is 150-250 Wh/kg. And detecting the contact angle to measure that the contact angle between the surface of the topological structure and the liquid drop is 140-160 degrees. The prepared anti-icing material has good anti-icing effect by detecting the surface shearing force, and the surface shearing force is measured to be 3-5 kPa.
Description
Technical Field
The invention belongs to the field of composite functional materials, and particularly relates to an application of an azobenzene-graphene composite material in preparation of an anti-icing material, which has an important application prospect in the aspects of future solar energy application and airplane anti-icing.
Background
Icing is a normal phenomenon in nature, and liquid-phase water naturally releases heat to ice at subzero. At present, except for a few cases, people suffer from various hazards. The icing of car windows, generator blades, wires and cables can cause inconvenience and even life danger to people's life. For the airplane with higher safety factor requirement, the airplane often flies or passes through the cloud layer, so the airplane can often encounter a low-temperature and high-humidity supercooled environment in the air even if the airplane does not run in winter, and the damage of the icing phenomenon to the airplane is most direct and obvious. Therefore, the research on the anti-icing material is always the most important research in China. Owing to the popularity of bionics, researchers find a new and considerable breakthrough in bionic anti-icing by discovering and analyzing peculiar super-hydrophobic or anti-freezing phenomena and mechanisms of some organisms in the nature at the present stage.
The disperse orange is a widely researched photoresponsive material, and has cis-isomer and trans-isomer. The trans-cis isomerization can occur under the action of ultraviolet-visible light, mechanical pressure and electrostatic excitation. Under the irradiation of ultraviolet light with specific wavelength, the trans-configuration dispersed orange can be converted into cis-configuration; under visible light and heat, the cis configuration can revert to the trans configuration. Meanwhile, the two have stereoisomerism, and physical and chemical properties such as dipole moment and the like have obvious difference. The method is used as a hard template method, and the alumina template method has the advantages of simple process, cheap and easily-obtained materials, convenient post-treatment and the like, and has great advantages in the application of nano topological structures.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides the application of the azobenzene-graphene composite material in preparing the anti-icing material, and prepares the heat-storable disperse orange/graphene hybrid material into a corresponding topological structure by using an alumina template method, and coats the topological structure on the surface of an airplane to achieve the effect of assisting the airplane anti-icing.
The technical purpose of the invention is realized by the following technical scheme:
the heat storage anti-icing material based on the alumina template and the preparation method thereof are carried out according to the following steps:
step 1, uniformly dispersing graphene oxide in water, adjusting the pH value to 8-10 by using sodium carbonate, simultaneously adding sodium borohydride, and standing at 80-90 ℃ for 2-5 hours to enable an oxidation group on the graphene oxide to perform a reduction reaction.
In step 1, 10 to 30 parts by mass of graphene oxide is used; 3-5 parts of sodium borohydride.
In step 1, the mixture is left at 85 to 90 ℃ for 2 to 4 hours.
In the step 1, after reaction, carrying out centrifugation, filtration and distilled water washing to obtain the redox graphene; RGO was then redispersed in water by ultrasound; after reduction, part of the oxidized groups on the graphene oxide are subjected to reduction reaction, so that the content of the oxidized groups is reduced, the steric hindrance of the oxidized groups such as carboxyl is reduced, and the graphene is changed from yellow in an oxidized state to black in a partially reduced state.
Step 2, azobenzene and NaNO are mixed2Dissolving in deionized water at room temperature, and dropping the solution into hydrochloric acid to form diazonium salt; adding diazonium salt into the redox graphene obtained in the step 1) for reaction to obtain azobenzene/stoneAn graphene composite.
In step 2, 2-3 parts by mass of azobenzene and NaNO22-3 parts by mass of deionized water, 30-50 parts by mass of deionized water, and 10-20 parts by mass of hydrochloric acid which is an aqueous solution of hydrogen chloride and has a concentration of 1-2 mol/L.
In step 2, the mass ratio of the diazonium salt to the redox graphene is (30-60): (80-100), preferably (40-55): (85-90).
In step 2, azobenzene is disperse orange 3, purchased from Acros, a technique of santitaceae.
In step 2, the product is washed alternately with water, ethanol and DMF and dried in an oven at 70-80 ℃.
And 3, uniformly dispersing the azobenzene/graphene composite material prepared in the step 2 in ethanol to form an ethanol solution of the azobenzene/graphene composite material, impregnating the ethanol solution of the azobenzene/graphene composite material with a porous alumina template to enable the azobenzene/graphene composite material to enter a porous structure of the alumina template, drying to enable a solvent ethanol to volatilize, curing and molding the azobenzene/graphene composite material in the porous structure of the alumina template, and removing the alumina template with alkali liquor to obtain the heat storage and anti-icing material based on the alumina template.
In the step 3, the azobenzene/graphene composite material is uniformly dispersed in ethanol, wherein the mass fraction of the azobenzene/graphene composite material is 10-15%.
In the step 3, the alkali liquor is sodium hydroxide aqueous solution or potassium hydroxide aqueous solution, and the concentration is 3-5 mol/L.
In step 3, specifically, the azobenzene/graphene composite material prepared in step 2 is uniformly dispersed in ethanol, and is dropped on the surface of the processed silicon wafer to spread the silicon wafer, then a porous alumina template is gently placed above the composite material solution to enable the azobenzene/graphene composite material to enter the porous structure of the alumina template, the solvent is volatilized in a drying oven, after the sample is taken out, the sample is placed in a sodium hydroxide solution, the alumina template is removed by using an alkali liquor, the sample is gently washed by using deionized water, and the sample is placed in a culture dish to be dried in the air to obtain the azobenzene/graphene composite material with a topological structure (namely, the heat storage anti-icing material depending on the porous structure of the alumina template).
The azobenzene-graphene composite material is prepared according to the step 1 and the step 2 of the preparation method, and when the azobenzene-graphene composite material is used, the composite material with the porous structure based on the alumina template is obtained according to the step 3.
The characterization was performed by UV spectroscopy and IR spectroscopy, as shown in FIGS. 1 and 2. The polymer has absorption peaks of corresponding azo and benzene rings, wherein an n-pi absorption peak of the dispersed orange/graphene composite material is at 400nm, and a pi-pi absorption peak of the dispersed orange/graphene composite material is at 250 nm. As shown in FIG. 2, a characteristic absorption peak corresponding to the polymer can be seen. Wherein 1400cm-1At 1720cm, where N is equal to N peak-1Is a C ═ O peak at 1228cm-1Is C-0 peak, 3400cm-1And 3600cm-1Is NH2Peak of (2). From the SEM photograph, the composite material with obvious group peak structure on the surface, namely the composite material with porous structure based on the alumina template, can be seen.
The technical scheme of the invention adopts a diazonium salt method. Firstly, azobenzene (such as disperse orange) is compounded with pretreated redox graphene, and the obtained disperse orange/graphene composite material has greatly improved energy value and half-life compared with disperse orange small molecules, and is beneficial to solar heat storage. The surface of the composite material is prepared by an alumina template method to obtain a surface topological structure, so that the material has good hydrophobic property. The two phases are combined, so that a good anti-icing effect can be achieved. And DSC detection shows that the energy density of the prepared dispersed orange/graphene composite material is 150-250 Wh/kg. And detecting the contact angle to measure that the contact angle between the surface of the topological structure and the liquid drop is 140-160 degrees. The prepared anti-icing material has good anti-icing effect by detecting the surface shearing force, and the surface shearing force is measured to be 3-5 kPa.
Drawings
Fig. 1 is a uv absorption spectrum of the dispersed orange/graphene composite material of the present invention.
Fig. 2 is an infrared absorption spectrum of the dispersed orange/graphene composite material of the present invention.
Fig. 3 is a scanning electron micrograph (1) of the dispersed orange/graphene composite material of the present invention.
Fig. 4 is a scanning electron micrograph (2) of the dispersed orange/graphene composite material of the present invention.
Detailed Description
The following examples are provided to further illustrate the technical solutions of the present invention, but not to limit the scope of the present invention. Here, one part is one part by mass, g. The ultraviolet spectrum instrument is a general type of Beijing Pujingyu, and the type is as follows: TU-1901; the infrared spectrometer is BRUKER, TENSOR 27; the scanning electron microscope is Hitachi, Japan, model: s-4800; the contact angle measuring instrument is manufactured by Shanghai Zhongchen company, and has the following model: JC 2000D; the shearing force is measured on the surface of the material by using an overlapping method, and the operation method is shown in the following steps of (Hujian forest, ice-coated insulator (long) string flashover characteristic under low pressure and direct current discharge model research [ D ] Chongqing: university of Chongqing ]. Azobenzene is commercially available disperse orange 3, CAS:730-40-5, manufacturer: acros shanghai taitan science and technology; DCS was obtained using a model Q20 instrument from TA, USA, and the energy density was measured directly by differential scanning calorimetry, the whole procedure followed the following procedure: (1) the temperature is balanced at 25 ℃; (2) heating at 5 deg.C/min, 20 deg.C/min and 40 deg.C/min respectively, and (3) heating to 180 deg.C and holding for 1 min; (4) cooling to 25 deg.C at 5 deg.C/min, 20 deg.C/min, and 40 deg.C/min; (5) and then heating is carried out for the second time at 5 ℃/min, 20 ℃/min and 40 ℃/min, and the actual heat release energy sum of different samples at different heating rates can be calculated through the integral area of heat flow to time.
Example 1
1) Pre-treating redox graphene: adjusting the pH value of 10 parts of the aqueous solution of graphene oxide to 8 by using sodium carbonate, dissolving the aqueous solution of graphene oxide in a sodium borohydride solution, and standing the solution at 85 ℃ for 2 hours; carrying out centrifugation, filtration and washing with distilled water to obtain the redox graphene; RGO was then redispersed in water by ultrasound;
2) preparing a dispersed orange/graphene composite material: 1 part of azobenzene and 1 part of NaNO2Dissolving in deionized water at room temperature, and dropping the solution into hydrochloric acid to form diazonium salt; adding a diazonium salt toAdding the graphene oxide into 2 parts of the redox graphene obtained in the step 1) for reaction; and (3) alternately cleaning the obtained product with water, ethanol and DMF, and drying in an oven at 70 ℃ to obtain the azobenzene/graphene composite material.
3) Formation of nanotopography: dripping ethanol solution of a dispersed orange/graphene composite material with the mass fraction of 10% on the surface of a treated silicon wafer to spread the silicon wafer, then placing a porous alumina template above the composite material solution gently, volatilizing the solvent in a drying oven, taking out the porous alumina template, placing a sample in 3mol/L sodium hydroxide solution, dissolving the alumina template, washing the alumina template with deionized water gently, placing the alumina template in a culture dish, and airing the alumina template to obtain the dispersed orange/graphene composite material with a topological structure.
The energy density of the prepared dispersed orange/graphene composite material was determined to be 150Wh/kg by DSC detection. The contact angle of the topological structure surface and the liquid drop is 140 degrees through contact angle detection. The material has good anti-icing effect through surface shearing force detection, and the surface shearing force is 3 kPa.
Example 2
1) Pre-treating redox graphene: adjusting the pH value of 20 parts of the aqueous solution of graphene oxide to 9 by using sodium carbonate, dissolving the aqueous solution of graphene oxide in a sodium borohydride solution, and standing the solution at 85 ℃ for 2 hours; carrying out centrifugation, filtration and washing with distilled water to obtain the redox graphene; RGO was then redispersed in water by ultrasound;
4) preparing a dispersed orange/graphene composite material: 2 parts of azobenzene and 2 parts of NaNO2Dissolving in deionized water at room temperature, and dropping the solution into hydrochloric acid to form diazonium salt; adding diazonium salt into 5 parts of redox graphene obtained in the step 1) to react; and (3) alternately cleaning the obtained product with water, ethanol and DMF, and drying in an oven at 70 ℃ to obtain the azobenzene/graphene composite material.
5) Formation of nanotopography: dropping an ethanol solution of a dispersed orange/graphene composite material with the mass fraction of 13% on the surface of a treated silicon wafer to spread the silicon wafer, then gently placing a porous alumina template above the composite material solution, volatilizing the solvent in a drying box, taking out the porous alumina template, placing a sample in a 4mol/L sodium hydroxide solution, dissolving the alumina template, gently cleaning the alumina template with deionized water, placing the alumina template in a culture dish, and airing the alumina template to obtain the dispersed orange/graphene composite material with a topological structure.
The energy density of the prepared dispersed orange/graphene composite material was determined to be 200Wh/kg by DSC detection. The contact angle of the topological structure surface and the liquid drop is measured to be 150 degrees through contact angle detection. Through surface shearing force detection, the prepared composite material has a good anti-icing effect, and the surface shearing force is measured to be 4 kPa.
Example 3
1) Pre-treating redox graphene: adjusting the pH value of 30 parts of the aqueous solution of graphene oxide to 10 by using sodium carbonate, dissolving the aqueous solution of graphene oxide in a sodium borohydride solution, and standing the solution at 85 ℃ for 2 hours; carrying out centrifugation, filtration and washing with distilled water to obtain the redox graphene; RGO was then redispersed in water by ultrasound;
6) preparing a dispersed orange/graphene composite material: 3 parts of azobenzene and 3 parts of NaNO2Dissolving in deionized water at room temperature, and dropping the solution into hydrochloric acid to form diazonium salt; adding diazonium salt into 9 parts of redox graphene obtained in the step 1) to react; and (3) alternately cleaning the obtained product with water, ethanol and DMF, and drying in an oven at 70 ℃ to obtain the azobenzene/graphene composite material.
7) Formation of nanotopography: dropping 15% of ethanol solution of the dispersed orange/graphene composite material on the surface of the treated silicon wafer to spread the silicon wafer, then placing a porous alumina template above the composite material solution gently, volatilizing the solvent in a drying box, taking out the porous alumina template, placing the sample in 5mol/L sodium hydroxide solution, dissolving the alumina template, washing the alumina template with deionized water gently, placing the alumina template in a culture dish, and airing the alumina template to obtain the dispersed orange/graphene composite material with a topological structure.
The energy density of the prepared dispersed orange/graphene composite material was determined to be 250Wh/kg by DSC detection. The contact angle of the topological structure surface and the liquid drop is measured to be 160 degrees through contact angle detection. Through surface shearing force detection, the prepared material has a good anti-icing effect, and the surface shearing force is measured to be 5 kPa.
The preparation of the material of the present invention was achieved by adjusting the process parameters in accordance with the present disclosure, and exhibited substantially the same properties as the examples described above. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (4)
1. The application of the azobenzene-graphene composite material in preparing the anti-icing material is characterized in that when the azobenzene-graphene composite material is used, the azobenzene/graphene composite material is uniformly dispersed in ethanol to form an ethanol solution of the azobenzene/graphene composite material, and the mass fraction of the azobenzene/graphene composite material is 10% -15%; soaking an ethanol solution of an azobenzene/graphene composite material in a porous alumina template to enable the azobenzene/graphene composite material to enter a porous structure of the alumina template, drying to enable a solvent ethanol to volatilize, curing and molding the azobenzene/graphene composite material in the porous structure of the alumina template, and removing the alumina template by using an alkali liquor, wherein the azobenzene-graphene composite material is prepared according to the following steps:
step 1, uniformly dispersing graphene oxide in water, adjusting the pH value to 8-10 by using sodium carbonate, simultaneously adding sodium borohydride, and standing at 80-90 ℃ for 2-5 hours to enable an oxidation group on the graphene oxide to perform a reduction reaction;
step 2, azobenzene and NaNO are mixed2Dissolving in deionized water at room temperature, and dropping the solution into hydrochloric acid to form diazonium salt; weighing; adding nitrogen salt into the redox graphene obtained in the step 1) for reaction to obtain an azobenzene/graphene composite material; 2-3 parts of azobenzene and NaNO22-3 parts by mass of deionized water, 30-50 parts by mass of deionized water, and 10-20 parts by mass of hydrochloric acid which is an aqueous solution of hydrogen chloride and has a concentration of 1-2 mol/L; the mass ratio of the diazonium salt to the redox graphene is (30-60): (80-100).
2. The use of the azobenzene-graphene composite material according to claim 1 in the preparation of an anti-icing material, wherein in step 1, 10 to 30 parts by mass of graphene oxide; 3-5 parts by mass of sodium borohydride; standing at 85-90 deg.C for 2-4 hr.
3. The use of the azobenzene-graphene composite material according to claim 1 in the preparation of an anti-icing material, wherein in step 2, the mass ratio of the diazonium salt to the redox graphene is (40-55): (85-90).
4. The use of the azobenzene-graphene composite material according to claim 1 in the preparation of an anti-icing material, wherein in step 2, azobenzene is dispersed orange.
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| CN103641106A (en) * | 2013-11-29 | 2014-03-19 | 中山大学附属第一医院 | Preparation method of nano sulfonated graphene and application of nano sulfonated graphene as gene transfer material |
| CN105969321A (en) * | 2016-05-30 | 2016-09-28 | 天津大学 | Double-branch azobenzene/graphene energy storage material and preparing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103641106A (en) * | 2013-11-29 | 2014-03-19 | 中山大学附属第一医院 | Preparation method of nano sulfonated graphene and application of nano sulfonated graphene as gene transfer material |
| CN105969321A (en) * | 2016-05-30 | 2016-09-28 | 天津大学 | Double-branch azobenzene/graphene energy storage material and preparing method |
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| 石墨烯/偶氮杂化材料研究进展;王东瑞等;《中国科学：化学》;20120930;第42卷(第5期);636-643 * |
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