CN112226104A - Ultraviolet-proof graphene coating with hierarchical pore structure, ultraviolet-proof material and preparation method of ultraviolet-proof graphene coating - Google Patents
Ultraviolet-proof graphene coating with hierarchical pore structure, ultraviolet-proof material and preparation method of ultraviolet-proof graphene coating Download PDFInfo
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Abstract
The invention provides an ultraviolet-proof graphene coating with a hierarchical pore structure, an ultraviolet-proof material and a preparation method of the ultraviolet-proof graphene coating. The invention assembles the porous graphene nano-sheets with the aperture of 5-20nm and the transverse dimension of 15-80nm into the porous graphene nano-sheets with the aperture of 20-100nm and a thickness of 100-200 nm. The ultraviolet-proof material is prepared by modifying the surface of a base material by using polystyrene or polyaniline, soaking the modified base material in graphene dispersion liquid containing sodium bicarbonate, and then dropwise adding dilute hydrochloric acid; in this process, graphene is adsorbed on the modified substrate surface while CO from sodium bicarbonate metathesis is produced2Promoting the formation of a porous structure between the graphene nano sheets; and finally, taking out the substrate to clean the surface to obtain the graphene ultraviolet-proof material. According to the invention, a hierarchical pore structure is formed by the nanometer pore diameter of the nanometer sheets and the pores among the nanometer sheets, and the hierarchical pore structure has a remarkable shielding effect on ultraviolet rays.
Description
Technical Field
The invention relates to the technical field of ultraviolet-proof functional materials, in particular to an ultraviolet-proof graphene coating with a hierarchical pore structure, an ultraviolet-proof material and a preparation method of the ultraviolet-proof graphene coating.
Background
In recent years, people have come to appreciate that ultraviolet light can cause various injuries to human health. Therefore, various anti-ultraviolet protective products are increasingly popular with consumers, such as anti-ultraviolet cosmetics, skin care products, and products such as textiles, doors, windows, and vehicle glass.
Ultraviolet screening agents can be generally divided into two main classes, one class is organic ultraviolet absorbent, mainly comprises benzophenones, benzotriazoles, salicylates, oxalic anilide and the like, the compounds have the common point that the structures contain hydroxyl, can absorb energy and convert the energy into heat energy to be dissipated in the processes of forming stable hydrogen bonds, hydrogen bond chelate rings and the like, and are mainly used for finishing fabric coatings; the other is an inorganic nano ultraviolet absorbent which mainly comprises titanium dioxide nano particles, cerium dioxide nano particles, zinc oxide nano particles and the like, and ultraviolet shielding is realized mainly through reflection and scattering of ultraviolet rays. Although the inorganic nano ultraviolet absorbent has outstanding light and heat stability, the inorganic nano ultraviolet absorbent is easy to agglomerate; meanwhile, the inorganic nano particles have strong photocatalytic activity, and can accelerate the aging and degradation of the polymer coating under the action of ultraviolet rays, thereby greatly reducing the service life of the coating.
Graphene is a monolayer of carbon atoms closely packed into a two-dimensional hexagonal honeycomb lattice structure, which is currently the thinnest material known. The nano graphene microchip is a novel carbon nano light material, has a unique monoatomic layer two-dimensional crystal structure and a huge specific surface area, is widely researched due to the characteristics of ultrahigh strength, electric conductivity, thermal conductivity, reflectivity and the like, and the thickness (1-3nm) of the nano graphene microchip is far smaller than the wavelength (100 plus 400nm) of ultraviolet rays, so that the scattering of the ultraviolet rays is easily promoted; the absorption peak of the nano graphene in an ultraviolet band is 270nm, an electron-hole pair is easily generated, and the nano graphene has the function of absorbing ultraviolet rays; in addition, the two-dimensional plane structure has high reflection efficiency on various light rays and an ideal shielding effect. Based on the characteristics, the nano graphene nanoplatelets have ideal ultraviolet shielding effect and can be applied to preparation of ultraviolet shielding products.
However, the graphene is in a nanometer level and is easy to agglomerate, so that the ultraviolet resistance of the graphene is seriously affected. In some researches, graphene is directly prepared into a dispersion liquid for storage, but the use range is limited, and the content of the graphene in the dispersion liquid is not suitable to be too high.
In view of the above, there is a need to design an improved graphene dispersion method to prepare an ultraviolet-proof graphene coating with a hierarchical pore structure, so as to solve the above problems.
Disclosure of Invention
The invention aims to provide an ultraviolet-proof graphene coating with a hierarchical pore structure, an ultraviolet-proof material and a preparation method thereof.
In order to achieve the purpose, the invention provides an ultraviolet-proof graphene coating with a hierarchical pore structure, the ultraviolet-proof graphene coating with the hierarchical pore structure comprises porous graphene nano sheets with the pore diameter of 5-20nm and the transverse dimension of 15-80nm, and the porous graphene nano sheets are mutually staggered to form the ultraviolet-proof graphene coating with the hierarchical pore structure with the pore diameter of 20-100nm and the thickness of 100-200 nm.
As a further improvement of the invention, the ultraviolet-proof graphene coating has UPF > 700, T (UVA) less than 1.5 percent and T (UVB) less than 0.1 percent.
As a further improvement of the present invention, the porous graphene nanoplatelets are prepared by:
s1, ultrasonically dispersing graphene oxide sheets with the transverse size of 0.2-1 mu m in a solvent, then adding a metal salt solution, carrying out coordination balance in the solution, and carrying out centrifugal separation to obtain a graphene oxide-metal ion ligand;
s2, dispersing the graphene oxide-metal ion ligand obtained in the step S1 in a quartz beaker filled with water and ethanol in a volume ratio of 1:4-6, and then adding benzene or cyclohexane into the quartz beaker while performing ultrasonic dispersion to enable the volume ratio of the benzene or cyclohexane to the sum of the water and the ethanol to be 5-10:1, so as to obtain a graphene oxide-metal ion ligand reaction solution;
s3, placing the quartz beaker containing the reaction liquid in the step S2 into a microwave liquid phase discharge device, introducing argon gas, removing air, irradiating for 10-60min by using microwave with the emission power of 200-1600W, removing metal salt in the reaction liquid by acid washing, and finally performing centrifugal separation to obtain the porous graphene nanosheet.
The invention also provides a preparation method of the graphene ultraviolet-proof material, which comprises the following steps:
s1, adding the porous graphene nanosheets and sodium bicarbonate into a dispersing solvent according to a mass ratio of 1:2-4, and performing ultrasonic dispersion uniformly to obtain a dispersion liquid with the graphene mass fraction of 30% -40%;
s2, modifying the surface of a base material to be coated by adopting polystyrene or polyaniline, then soaking the modified base material into the dispersion liquid obtained in the step S1, then slowly dropwise adding dilute hydrochloric acid into the dispersion liquid, and taking out the base material after a layer of ultraviolet-proof graphene coating with a hierarchical pore structure, wherein the pore diameter of the ultraviolet-proof graphene coating is 20-100nm, and the thickness of the ultraviolet-proof graphene coating is 100-200nm, is self-assembled on the surface of the base material;
and S3, washing the surface of the base material taken out in the step S2 by using deionized water, and drying to obtain the graphene ultraviolet-proof material.
As a further improvement of the invention, in step S1, the dispersion solvent is a mixed solvent composed of water and an alcohol organic solvent in a volume ratio of 1: 0.5-1.5.
As a further improvement of the present invention, in step S2, the method for modifying the surface of the substrate to be coated with polystyrene or polyaniline is graft modification or coating modification.
As a further improvement of the invention, in step S2, the concentration of the dilute hydrochloric acid is 1-3mol/L, and the dropping rate is 1-3 mL/min; the molar ratio of the dilute hydrochloric acid to the sodium bicarbonate is 1: 1.05-1.2.
As a further improvement of the invention, the graphene ultraviolet-proof material has UPF > 700, T (UVA) less than 1.5 percent and T (UVB) less than 0.1 percent.
As a further improvement of the present invention, in step S2, the substrate includes but is not limited to one of textile, glass, metal or car body paint.
The invention also provides a graphene ultraviolet-proof material which is prepared by the preparation method.
The invention has the beneficial effects that:
1. according to the invention, the porous graphene nanosheets with the aperture of 5-20nm and the transverse dimension of 15-80nm are assembled into the ultraviolet-proof graphene coating with the aperture of 20-100nm and the thickness of 100-200nm, and a hierarchical pore structure is formed through the nanometer apertures of the nanosheets and the pores among the nanosheets, so that the structure, especially the nanometer aperture structure, is favorable for improving the scattering effect on ultraviolet rays, and therefore, the integral shielding effect on the ultraviolet rays can be obviously improved.
2. The method comprises the steps of firstly modifying the surface of a base material by adopting polystyrene or polyaniline, then soaking the base material into graphene dispersion liquid containing sodium bicarbonate, and then dropwise adding dilute hydrochloric acid, wherein in the process, graphene is adsorbed on the surface of the modified base material, and CO generated by double decomposition of sodium bicarbonate is generated2Promoting the formation of a porous structure between the graphene nano sheets; and finally, taking out the substrate to clean the surface to obtain the graphene ultraviolet-proof material. In the process, the surface of the base material is modified by polystyrene or polyaniline, and the polystyrene or polyaniline and the porous graphene have good hydrophobic and pi-electron interaction, so that the adsorption and deposition of the porous graphene on the surface can be promoted; meanwhile, the sodium bicarbonate in the dispersion liquid is decomposed under the action of hydrochloric acid to generate carbon dioxide, and the carbon dioxide forms bubbles in the dispersion liquid to promote the porous structure to be formed among the porous graphene nano sheets. So as to operate. Can not only prevent the excessive stacking and agglomeration of the graphene nano sheets, but also promote the nano sheets to be mutually arrangedA pore structure is formed.
3. According to the self-made porous graphene nanosheet, graphene oxide and magnetic metal particles are coordinated, carboxyl, carbonyl and the like on the surface of the graphene oxide are easy to form coordination bonding with metal ions, and the obtained graphene oxide-metal ion ligand has excellent microwave absorption capacity; and then, etching by utilizing microwave liquid phase discharge, wherein the metal ion coordination sites are preferentially etched and removed from the surface of the graphene oxide together with the coordinated chemical groups, so that nanopores are formed on the surface of the graphene oxide, and meanwhile, partial reduction of the graphene oxide is equivalently realized. In addition, bubbles generated by microwave liquid phase discharge are beneficial to dispersion of graphene and can be prevented from agglomerating, so that the self-made porous graphene nanosheet is uniform in size distribution and good in dispersibility.
4. The ultraviolet-proof graphene coating with the hierarchical pore structure provided by the invention can be suitable for various base materials such as textile fabrics, glass products, metal products, vehicle body paint films and the like, can realize ultraviolet-proof protection on vehicle bodies when being used for coating the surface of the vehicle body paint film, and has the advantages of obvious ultraviolet-proof effect and strong practicability.
Drawings
Fig. 1 is a transmission electron microscope image of a porous graphene nanosheet used in the present invention.
Fig. 2 is a transmission electron microscope image of the ultraviolet-proof graphene coating with the hierarchical pore structure.
Fig. 3 is an atomic force microscope image of the ultraviolet-proof graphene coating with the hierarchical pore structure.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the aspects of the present invention are shown in the drawings, and other details not closely related to the present invention are omitted.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides an ultraviolet-proof graphene coating with a hierarchical pore structure, which comprises porous graphene nanosheets with the pore diameter of 5-20nm and the transverse dimension of 15-80nm, wherein the porous graphene nanosheets are mutually staggered to form the ultraviolet-proof graphene coating with the hierarchical pore structure, the pore diameter of 20-100nm and the thickness of 100-200 nm.
Wherein the UPF of the ultraviolet-proof graphene coating is more than 700, T (UVA) is less than 1.5%, and T (UVB) is less than 0.1%. In addition, the research result of the invention shows that the porous graphene nano sheet with the pore diameter of 5-20nm and the transverse size of 15-80nm also has a good absorption effect on ultraviolet rays.
The porous graphene nanoplatelets are prepared by the following steps:
(1) ultrasonically dispersing graphene oxide sheets with the transverse dimension of 0.2-1 mu m in a solvent, then adding a metal salt solution, carrying out coordination balance in the solution, and carrying out centrifugal separation to obtain a graphene oxide-metal ion ligand; the solvent is one or more of deionized water, absolute ethyl alcohol and N, N-dimethylformamide; the metal salt solution is a metal inorganic salt solution of iron, nickel or cobalt. After the magnetic metal particles are coordinated with the graphene oxide, the wave absorbing capacity of the graphene oxide can be obviously improved, so that the generation of microwave plasma etching is facilitated.
(2) Dispersing the graphene oxide-metal ion ligand obtained in the step (1) in a quartz beaker filled with water and ethanol in a volume ratio of 1:4-6, and then adding benzene or cyclohexane into the quartz beaker while performing ultrasonic dispersion so that the volume ratio of the benzene or cyclohexane to the sum of the water and the ethanol is 5-10:1, thereby obtaining a graphene oxide-metal ion ligand reaction liquid.
In the step, the graphene oxide-metal ion ligand is firstly dispersed in a mixed solvent consisting of water and ethanol, the polar solvent is beneficial to uniform dispersion of the graphene oxide-metal ion ligand, but the content of water is not too high, otherwise, water molecules can absorb microwaves to cause excessive microwave dissipation and influence the etching effect in the subsequent microwave irradiation. However, the presence of water can generate radicals such as hydrogen when microwave liquid-phase plasma is emitted, and contributes to the reduction of graphene oxide. Then adding benzene or cyclohexane and other nonpolar solvents with weak wave absorbing capacity, wherein the solvents hardly absorb microwaves, and the graphene oxide-metal ion ligand is favorable for absorbing microwaves to generate microwave plasma etching.
(3) And (3) placing the quartz beaker containing the reaction liquid in the step (2) into a microwave liquid phase discharge device, introducing argon gas, removing air, irradiating for 10-60min by using 1600W microwave with the emission power of 200-.
In this process, two main reaction processes occur, the first: benzene or cyclohexane in the solution is used as a main solvent, the benzene or cyclohexane has weaker wave-absorbing capacity, and the graphene oxide-metal ion ligand has stronger wave-absorbing capacity, so that the graphene oxide-metal ion ligand absorbs microwaves, particularly the microwave absorbing capacity at the metal ion coordination point is stronger, microwave etching preferentially occurs at the metal ion coordination point, the graphene oxide-metal ion ligand is removed from the surface of graphene oxide, and nanopores are formed on the surface of the graphene oxide-metal ion ligand, so that the high controllability of the porous structure of the graphene nanosheet is realized; meanwhile, functional groups such as carboxyl, carbonyl and the like on the surface of the graphene oxide are removed from the surface of the graphene oxide, so that partial reduction of the graphene oxide is realized. Secondly, a reaction system in the quartz beaker is subjected to microwave liquid phase discharge due to the existence of a small amount of water in the solution to generate hydrogen radicals, and the graphene oxide is further reduced to obtain the cellular porous graphene; meanwhile, bubbles generated by microwave liquid phase discharge contribute to dispersion of graphene, and agglomeration of graphene can be prevented. The porous graphene nanosheet prepared in the way is good in dispersity and is more beneficial to preparation of a coating.
A preparation method of a graphene ultraviolet-proof material comprises the following steps:
s1, adding the porous graphene nanosheets and sodium bicarbonate into a dispersing solvent according to a mass ratio of 1:2-4, and performing ultrasonic dispersion uniformly to obtain a dispersion liquid with the graphene mass fraction of 30% -40%;
s2, modifying the surface of a base material to be coated by adopting polystyrene or polyaniline, then soaking the modified base material into the dispersion liquid obtained in the step S1, then slowly dropwise adding dilute hydrochloric acid into the dispersion liquid, and taking out the base material after a layer of ultraviolet-proof graphene coating with a hierarchical pore structure, wherein the pore diameter of the ultraviolet-proof graphene coating is 20-100nm, and the thickness of the ultraviolet-proof graphene coating is 100-200nm, is self-assembled on the surface of the base material;
and S3, washing the surface of the base material taken out in the step S2 by using deionized water, and drying to obtain the graphene ultraviolet-proof material. In the process, the surface of the base material is modified by polystyrene or polyaniline, and the polystyrene or polyaniline and the porous graphene have good hydrophobic and pi-electron interaction, so that the adsorption and deposition of the porous graphene on the surface can be promoted; meanwhile, the sodium bicarbonate in the dispersion liquid is decomposed under the action of hydrochloric acid to generate carbon dioxide, and the carbon dioxide forms bubbles in the dispersion liquid to promote the porous structure to be formed among the porous graphene nano sheets. So as to operate. The graphene nano-sheets can be prevented from being excessively stacked and agglomerated, and a pore structure can be formed among the sheets.
In step S1, the dispersion solvent is a mixed solvent of water and an alcohol organic solvent at a volume ratio of 1: 0.5-1.5.
In step S2, the method for modifying the surface of the substrate to be coated with the polystyrene or polyaniline is graft modification or coating modification.
In step S2, the concentration of the dilute hydrochloric acid is 1-3mol/L, and the dropping rate is 1-3 mL/min; the molar ratio of the dilute hydrochloric acid to the sodium bicarbonate is 1: 1.05-1.2.
The graphene ultraviolet-proof material has the UPF of more than 700, T (UVA) of less than 1.5 percent and T (UVB) of less than 0.1 percent.
In step S2, the substrate includes, but is not limited to, one of textile, glass, metal, or car body paint. When the substrate is an automotive body paint film, the automotive body paint film needs to have acid resistance.
Example 1
Referring to fig. 2, the ultraviolet-proof graphene coating with the hierarchical pore structure includes porous graphene nanosheets with a pore diameter of 5-20nm and a transverse dimension of 15-80nm, and the porous graphene nanosheets are staggered with each other to form the ultraviolet-proof graphene coating with the hierarchical pore structure, wherein the pore diameter of 40-60nm and the thickness of about 120 nm. Conflict 2 shows that the porous graphene nanoplatelets of the present embodiment are interlaced with each other, so as to form a coating layer with a pore size of about 40-60nm, and the dispersion is relatively uniform.
In the present embodiment, the porous graphene nanoplatelets may be commercially available or may be self-made.
The self-made porous graphene nanosheet can be prepared by the following method:
(1) ultrasonically dispersing graphene oxide sheets (carbon atom mass content is about 80%) with the transverse dimension of 0.2 mu m and the thickness of 3nm in deionized water, and then adding Co (NO)3)2·6H2Performing centrifugal separation on the O solution after the O solution is subjected to coordination balance in the solution to obtain a graphene oxide-metal ion ligand;
(2) dispersing the graphene oxide-metal ion ligand in a quartz beaker filled with a mixed solvent consisting of deionized water and ethanol in a volume ratio of 1:5, and then adding benzene into the quartz beaker while performing ultrasonic dispersion until the volume ratio of the benzene to the sum of the water and the ethanol is 8:1, so as to obtain a graphene oxide-metal ion ligand reaction solution with the concentration of 20 g/L;
(3) and (3) placing the quartz beaker containing the reaction solution in the step (2) into a microwave liquid-phase discharge device, introducing argon into the microwave liquid-phase discharge device, exhausting air, then emitting microwaves with the power of 800W, irradiating the microwaves for 20min, removing the reaction solution, washing the reaction solution with hydrochloric acid to remove metal salts, then washing the reaction solution with ethanol and water, and finally performing centrifugal separation to obtain the cellular porous graphene.
Referring to fig. 1, the part of the ellipse in the figure is the porous structure obtained by etching, which illustrates that the prepared cellular porous graphene has a transverse dimension of 10-40nm and a pore diameter of 5-10 nm. It can be seen that the lateral dimensions of the graphene oxide lamellae are also reduced by etching during microwave irradiation. Through detection, the mass content of carbon atoms in the obtained cellular porous graphene is about 99.3%.
And compounding the ultraviolet-proof graphene coating with a base material to be protected to obtain the ultraviolet-proof material. In this embodiment, the substrate to be protected may be a textile fabric, a glass article, a metal article, or the like. The textile fabric can be cotton fabric, polyester-cotton fabric, nylon fabric and the like; the glass product can be used for ultraviolet protection of doors and windows, vehicle glass and the like.
In this embodiment, the preparation method of the graphene ultraviolet-proof material is as follows:
s1, adding the porous graphene nanosheet and sodium bicarbonate into a mixed solvent composed of water and ethanol in a volume ratio of 1:1 according to a mass ratio of 1:3, and performing ultrasonic dispersion uniformly to obtain a porous graphene dispersion liquid with the mass fraction of graphene being 35%.
S2, coating and modifying the surface of a polyester-cotton fabric to be coated by adopting polystyrene, then soaking the modified polyester-cotton fabric into the porous graphene dispersion liquid obtained in the step S1, slowly dropwise adding dilute hydrochloric acid with the concentration of 2mol/L into the dispersion liquid, keeping the dropwise adding rate at 50 drops/min, and dropwise adding hydrochloric acid according to the molar ratio of 1:1.1 to sodium bicarbonate; and after a layer of ultraviolet-proof graphene coating with the aperture of 40-60nm and the thickness of about 120nm is self-assembled on the surface of the base material, taking out the polyester-cotton fabric. In the process, the surface of the polyester-cotton fabric is modified by polystyrene, and the polystyrene and the porous graphene have good hydrophobic and pi-electron interaction, so that the adsorption and deposition of the porous graphene on the surface can be promoted; meanwhile, the sodium bicarbonate in the dispersion liquid is decomposed under the action of hydrochloric acid to generate carbon dioxide, and the carbon dioxide forms bubbles in the dispersion liquid to promote the porous structure to be formed among the porous graphene nano sheets. So as to operate. The graphene nano-sheets can be prevented from being excessively stacked and agglomerated, and a pore structure can be formed among the sheets.
And S3, cleaning the surface of the base material taken out in the step S2 by using deionized water, removing substances such as sodium bicarbonate, hydrochloric acid and sodium chloride remained on the surface, and drying to obtain the graphene ultraviolet-proof fabric. As shown in fig. 3, it can be seen from the surface depth distribution that the ultraviolet-proof graphene coating layer with the hierarchical pore structure prepared in the embodiment has a depth distribution of-23.5 to 27.1nm on the surface, wherein most of the ultraviolet-proof graphene coating layers are in a depth distribution of-15 to 15nm, which indicates that a pore structure is formed between graphene nanosheets and graphene sheets.
The graphene ultraviolet-proof fabric prepared in the embodiment is subjected to ultraviolet-proof performance test according to the standard GB/T18830-2009, and the test result shows that the average value of ultraviolet protection coefficients (UPF) is 757, the ultraviolet light transmittance T (UVA) is 1.27%, and the ultraviolet light transmittance T (UVB) is 0.05%, which are far better than the ultraviolet-proof standard value.
Example 2
A graphene ultraviolet screening material, which is different from that of example 1 in that, in step S2, the polystyrene is replaced with polyaniline. The rest is substantially the same as that of embodiment 1, and will not be described herein.
The average Ultraviolet Protection Factor (UPF) of this example was 750, the ultraviolet transmittance T (UVA) was 1.24%, and the ultraviolet transmittance T (UVB) was 0.06%.
Examples 3 to 8
Examples 3 to 8 provide graphene ultraviolet screening materials, which are different from example 1 in that, in step S1, the mass ratio m of the porous graphene nanoplatelets to the sodium bicarbonate is1:m2Volume ratio of water to ethanol V1:V2And the graphene mass fraction W is shown in table 1. It is composed of
He is substantially the same as example 1 and will not be described in detail.
TABLE 1 preparation conditions and UV protection test results for examples 3-8
| Examples | m1:m2 | V1:V2 | W(％) | UPF | T(UVA) | T(UVB) |
| 3 | 1:2 | 1:1 | 35 | 741 | 1.29 | 0.06 |
| 4 | 1:4 | 1:1 | 35 | 736 | 1.27 | 0.08 |
| 5 | 1:3 | 1:0.5 | 35 | 735 | 1.29 | 0.07 |
| 6 | 1:3 | 1:1.5 | 35 | 745 | 1.29 | 0.08 |
| 7 | 1:3 | 1:1 | 30 | 737 | 1.27 | 0.07 |
| 8 | 1:3 | 1:1 | 40 | 742 | 1.28 | 0.06 |
As can be seen from table 1, as the mass ratio of the porous graphene nanosheet to the sodium bicarbonate is increased, that is, as the content of the sodium bicarbonate is reduced, the ultraviolet protection coefficient (UPF) is increased and then decreased, the ultraviolet transmittance t (UVA) is gradually increased, and t (UVB) is gradually decreased, which indicates that the ultraviolet protection effect of the UVA band is gradually decreased, and the ultraviolet protection effect of the UVB band is gradually increased. This is probably because when the content of sodium bicarbonate is reduced, the amount of generated bubbles is reduced, so that the pore size between the prepared nanosheets of the ultraviolet-resistant graphene coating is reduced, and the smaller pore size may be more favorable for scattering of the UVB band. With the increase of the ethanol content in the solvent, the ultraviolet protection coefficient (UPF) is increased and then reduced, and the ultraviolet light transmittance T (UVA) and the ultraviolet light transmittance T (UVB) are reduced and then increased, which indicates that the improvement of the ultraviolet protection effect is not facilitated by the excessively low and high ethanol content. This is probably because the alcohol organic solvent is favorable for promoting the adsorption and deposition of graphene on the surface of polystyrene, but when the ethanol content is high, the dissolution and reaction of sodium bicarbonate and hydrochloric acid are not favorable, and thus the ultraviolet protection effect is reduced. When the concentration of the porous graphene nanosheet is increased, the ultraviolet protection coefficient (UPF) is increased and then reduced, T (UVA) is gradually increased, and T (UVB) is gradually reduced, which indicates that the concentration of the porous graphene nanosheet is increased, and the shielding of a UVB wave band is facilitated. This is probably because the higher the content of the porous graphene nanoplatelets, the smaller the pore size between the nanoplatelets, but when the content is too high, the agglomerated stacking may occur, which is not favorable for shielding ultraviolet rays.
Example 9
Compared with the embodiment 1, the difference of the graphene ultraviolet-proof material is that the preparation method of the graphene ultraviolet-proof material is as follows:
s1, adding the porous graphene nanosheet and sodium bicarbonate into a mixed solvent composed of water and ethanol in a volume ratio of 1:1 according to a mass ratio of 1:3, and performing ultrasonic dispersion uniformly to obtain a porous graphene dispersion liquid with the mass fraction of graphene being 35%.
S2, coating and modifying the surface of a vehicle body paint film to be coated by adopting polyaniline, then soaking the modified vehicle body paint film into the porous graphene dispersion liquid obtained in the step S1, slowly dropwise adding dilute hydrochloric acid with the concentration of 2mol/L into the dispersion liquid, keeping the dropwise adding rate at 50 drops/min, and dropwise adding hydrochloric acid according to the molar ratio of 1:1.1 to sodium bicarbonate; and after a layer of ultraviolet-proof graphene coating with the aperture of 40-60nm and the thickness of about 120nm is self-assembled on the surface of the base material, taking out the paint film of the vehicle body. After the polyaniline is adopted to coat and modify the car body paint film, the acid resistance of the surface is improved. In other embodiments, the polyaniline may also be mixed with the vehicle body finish slurry to form the vehicle body finish when the vehicle body finish is prepared.
And S3, cleaning the surface of the base material taken out in the step S2 by using deionized water, removing substances such as sodium bicarbonate, hydrochloric acid and sodium chloride remained on the surface, and drying to obtain the graphene anti-ultraviolet vehicle body paint film.
The rest is substantially the same as that of embodiment 1, and will not be described herein.
The test result shows that the average value of the ultraviolet protection coefficient (UPF) is 789, the ultraviolet transmittance T (UVA) is 1.21%, and the ultraviolet transmittance T (UVB) is 0.05%, which indicates that the graphene ultraviolet-proof coating provided by the invention is also suitable for ultraviolet protection of a vehicle body paint film.
Comparative example 1
Compared with the embodiment 1, the graphene ultraviolet-proof material is different in that the porous graphene nanosheets are replaced by non-porous graphene nanosheets. The rest is substantially the same as that of embodiment 1, and will not be described herein.
Comparative example 2
Compared with example 1, the graphene ultraviolet-proof material is different in that sodium bicarbonate is not added in step S1, and hydrochloric acid is not dropwise added in step S2. The rest is substantially the same as that of embodiment 1, and will not be described herein.
Comparative example 3
Compared with the example 1, the difference of the graphene ultraviolet-proof material is that in the step S2, the surface of the polyester cotton fabric is not coated and modified by polystyrene. The rest is substantially the same as that of embodiment 1, and will not be described herein.
Comparative example 4
A graphene ultraviolet screening material, compared to example 1, is different in that, in step S2, the dropping rate of hydrochloric acid is 3.5mL/min, that is, about 70 drops/min. The rest is substantially the same as that of embodiment 1, and will not be described herein.
TABLE 2 UV protection test results for comparative examples 1-4
| Comparative example | UPF | T(UVA) | T(UVB) |
| 1 | 658 | 1.36 | 0.12 |
| 2 | 632 | 1.37 | 0.11 |
| 3 | 689 | 1.31 | 0.09 |
| 4 | 701 | 1.29 | 0.10 |
As can be seen from table 2, when the nonporous graphene nanoplatelets are used, the Ultraviolet Protection Factor (UPF) is significantly reduced, and t (uva) and t (uvb) are significantly increased, which indicates that the graphene coating prepared from the nonporous graphene nanoplatelets is not good for shielding ultraviolet rays. When sodium bicarbonate is not added, the nano sheets are not beneficial to forming a uniform porous structure, the ultraviolet protection coefficient (UPF) is also remarkably reduced, and T (UVA) and T (UVB) are remarkably increased. When the surface of the base material is not coated and modified by polystyrene, the adsorption and deposition rate of the porous graphene nanosheets is reduced, and the formation of a uniform porous structure is also facilitated, so that the ultraviolet shielding effect is reduced. When the dropping rate of the hydrochloric acid is too fast, the hydrogen carbonate is violently metathesized to generate gas, and the formation of a uniform porous structure is not facilitated, so that the ultraviolet shielding effect is also reduced.
In conclusion, the ultraviolet-proof graphene coating with the pore diameter of 20-100nm and the thickness of 100-200nm is assembled by the porous graphene nanosheets with the pore diameter of 5-20nm and the transverse dimension of 15-80 nm. Firstly, modifying the surface of a base material by adopting polystyrene or polyaniline, then soaking the base material into graphene dispersion liquid containing sodium bicarbonate, and then dropwise adding dilute hydrochloric acid, wherein in the process, graphene is adsorbed on the surface of the modified base material, and CO generated by double decomposition of sodium bicarbonate is used2Promoting the formation of a porous structure between the graphene nano sheets; and finally, taking out the substrate to clean the surface to obtain the graphene ultraviolet-proof material. According to the invention, the hierarchical pore structure is formed by the nanometer pore diameter of the nanometer sheets and the pores among the nanometer sheets, and the structure, especially the nanometer pore diameter structure, is beneficial to improving the scattering effect on ultraviolet rays, so that the integral shielding effect on the ultraviolet rays can be obviously improved.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (10)
1. The ultraviolet-proof graphene coating with the hierarchical pore structure is characterized by comprising porous graphene nanosheets with the pore diameter of 5-20nm and the transverse dimension of 15-80nm, wherein the porous graphene nanosheets are mutually staggered to form the ultraviolet-proof graphene coating with the hierarchical pore structure with the pore diameter of 20-100nm and the thickness of 100-200 nm.
2. The ultraviolet-proof graphene coating with a hierarchical pore structure according to claim 1, wherein the ultraviolet-proof graphene coating has a UPF of more than 700, a T (UVA) of less than 1.5%, and a T (UVB) of less than 0.1%.
3. The ultraviolet-shielding graphene coating with a hierarchical pore structure according to claim 1, wherein the porous graphene nanoplatelets are prepared by the following steps:
s1, ultrasonically dispersing graphene oxide sheets with the transverse size of 0.2-1 mu m in a solvent, then adding a metal salt solution, carrying out coordination balance in the solution, and carrying out centrifugal separation to obtain a graphene oxide-metal ion ligand;
s2, dispersing the graphene oxide-metal ion ligand obtained in the step S1 in a quartz beaker filled with water and ethanol in a volume ratio of 1:4-6, and then adding benzene or cyclohexane into the quartz beaker while performing ultrasonic dispersion to enable the volume ratio of the benzene or cyclohexane to the sum of the water and the ethanol to be 5-10:1, so as to obtain a graphene oxide-metal ion ligand reaction solution;
s3, placing the quartz beaker containing the reaction liquid in the step S2 into a microwave liquid phase discharge device, introducing argon gas, removing air, irradiating for 10-60min by using microwave with the emission power of 200-1600W, removing metal salt in the reaction liquid by acid washing, and finally performing centrifugal separation to obtain the porous graphene nanosheet.
4. A preparation method of a graphene ultraviolet-proof material is characterized by comprising the following steps:
s1, adding the porous graphene nanosheet and sodium bicarbonate of any one of claims 1 to 3 into a dispersion solvent according to a mass ratio of 1:2-4, and performing ultrasonic dispersion uniformly to obtain a dispersion liquid with the graphene mass fraction of 30-40%;
s2, modifying the surface of a base material to be coated by adopting polystyrene or polyaniline, then soaking the modified base material into the dispersion liquid obtained in the step S1, then slowly dropwise adding dilute hydrochloric acid into the dispersion liquid, and taking out the base material after a layer of ultraviolet-proof graphene coating with a hierarchical pore structure, wherein the pore diameter of the ultraviolet-proof graphene coating is 20-100nm, and the thickness of the ultraviolet-proof graphene coating is 100-200nm, is self-assembled on the surface of the base material;
and S3, washing the surface of the base material taken out in the step S2 by using deionized water, and drying to obtain the graphene ultraviolet-proof material.
5. The method for preparing the graphene ultraviolet-proof material according to claim 4, wherein in step S1, the dispersion solvent is a mixed solvent composed of water and an alcohol organic solvent in a volume ratio of 1: 0.5-1.5.
6. The method for preparing the graphene ultraviolet-proof material according to claim 4 or 5, wherein in step S2, the method for modifying the surface of the substrate to be coated by polystyrene or polyaniline is graft modification or coating modification.
7. The method for preparing the graphene ultraviolet-proof material according to claim 4 or 6, wherein in step S2, the concentration of the dilute hydrochloric acid is 1-3mol/L, and the dropping rate is 1-3 mL/min; the molar ratio of the dilute hydrochloric acid to the sodium bicarbonate is 1: 1.05-1.2.
8. The method for preparing the graphene UV-blocking material according to claim 4, wherein the UPF of the graphene UV-blocking material is more than 700, T (UVA) is less than 1.5%, and T (UVB) is less than 0.1%.
9. The method for preparing the graphene ultraviolet-proof material according to claim 4, wherein in step S2, the substrate includes but is not limited to one of textile fabric, glass product, metal product or car body paint film.
10. The graphene ultraviolet-proof material is characterized by being prepared by the preparation method of any one of claims 4 to 9.
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