CN112900183A - Graphene-based self-snow-melting pavement structure with shape memory function - Google Patents
Graphene-based self-snow-melting pavement structure with shape memory function Download PDFInfo
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- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
- E01C7/00—Coherent pavings made in situ
- E01C7/08—Coherent pavings made in situ made of road-metal and binders
- E01C7/32—Coherent pavings made in situ made of road-metal and binders of courses of different kind made in situ
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
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- E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
- E01C11/00—Details of pavings
- E01C11/24—Methods or arrangements for preventing slipperiness or protecting against influences of the weather
- E01C11/26—Permanently installed heating or blowing devices ; Mounting thereof
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- E—FIXED CONSTRUCTIONS
- E01—CONSTRUCTION OF ROADS, RAILWAYS, OR BRIDGES
- E01C—CONSTRUCTION OF, OR SURFACES FOR, ROADS, SPORTS GROUNDS, OR THE LIKE; MACHINES OR AUXILIARY TOOLS FOR CONSTRUCTION OR REPAIR
- E01C11/00—Details of pavings
- E01C11/24—Methods or arrangements for preventing slipperiness or protecting against influences of the weather
- E01C11/26—Permanently installed heating or blowing devices ; Mounting thereof
- E01C11/265—Embedded electrical heating elements ; Mounting thereof
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Abstract
The utility model provides a graphite alkene base is from melting snow road surface pavement structure with shape memory function, it belongs to the technical field that the road surface melted snow and iced, concretely relates to from melting snow road surface's pavement structure. One purpose of the invention is to solve the problems of poor conductivity, crack resistance and durability of the existing conductive asphalt; the invention aims to solve the problems that the existing graphene heating film is harsh in application environment, short in service life, incapable of improving the existing pavement or high in service life and cost even if the existing pavement is improved. The pavement paving structure comprises a heat insulation layer, a graphene-based conductive asphalt layer, a shape memory polymer layer, an insulating asphalt layer and a surface layer which are sequentially paved on a pavement from bottom to top. The graphene-based self-snow-melting pavement paving structure with the shape memory function can improve the existing pavement. The invention can obtain the graphene-based self-snow-melting pavement paving structure with the shape memory function.
Description
Technical Field
The invention belongs to the technical field of road surface snow melting and deicing, and particularly relates to a pavement structure of a self-snow-melting road surface.
Background
In winter, snow on the road surface and the bridge floor is frozen, frost and the like can lead the anti-skid capability of the road surface to be seriously reduced, and the traffic safety of the road is seriously influenced, so that how to timely and efficiently remove the snow and the ice on the road surface has important significance for guaranteeing the traffic safety and the traffic capacity of the road in winter. The existing snow removing methods mainly comprise manual snow removing, mechanical snow removing and snow melting agent snow removing, but the snow removing methods have aftermath and cannot ensure the timely removal of the accumulated snow. Mechanical snow removal and manual snow removal have with high costs, the shortcoming such as inefficiency and seal that the traffic time is long, and sprinkle the snow salt and can also cause long-term infringement and pollution to afforestation vegetation, soil and water on the one hand, therefore, the electric heat snow removal mode is known as the good initiative snow removal mode of comprehensive performance among numerous road snow removal technologies, consequently, adopts the electrically conductive asphalt pavement or adopts graphite alkene heating film pavement at present gradually.
The conductive asphalt is an intelligent road building material, self-heating is realized by utilizing the electric heating effect of the conductive asphalt, and the conductive asphalt can be widely applied to methods for emergency deicing of asphalt roads, ensuring traffic in winter and the like. After the conductive asphalt is powered on, the temperature of the asphalt pavement covering the accumulated snow can be raised through the heating effect, the ice and the snow can be melted in time, and the harm of the ice and the snow can be effectively eliminated. However, asphalt is an insulator, so that conductive phase materials are added into the prepared conductive asphalt, and the asphalt can conduct electricity through the conductive phase, but the conductivity of the existing conductive asphalt is not ideal, and the existing conductive asphalt is easy to crack and seep water after expansion with heat and contraction with cold, so that the crack resistance and the durability are poor.
Chinese patent CN107100054A discloses a T-shaped beam bridge deck pavement construction method using graphene heating film, which specifically discloses that 5mm graphene heating film is used for heating to shorten the ice-forming period of the bridge deck in winter and accelerate the melting of ice and snow, but the environment adapted to the graphene heating film can only be a plane, and this patent also describes that when laying 5mm graphene heating film, the sundries on the bridge deck base layer need to be removed, so that the diameter of dust, particles or protrusions does not exceed 0.5mm, thereby ensuring the drying and cleanness of the bridge deck base layer and avoiding affecting the heating efficiency of the graphene heating film. The application of the graphene heating film is limited by the harsh planar environment, the graphene heating film is afraid of being broken in 200 times, the service life of the graphene heating film cannot exceed 3 years, the service life of the graphene heating film is short, and the service life of the graphene heating film can be shortened when the graphene heating film is changed by the road surface environment.
Therefore, for newly-built asphalt pavements, old asphalt pavements and old cement concrete pavements, the existing conductive asphalt or graphene heating films cannot be used for paving, and the purposes of snow melting and ice melting are achieved.
Disclosure of Invention
One of the purposes of the invention is to solve the problems of poor conductivity, crack resistance and durability of the existing conductive asphalt;
the invention aims to solve the problems that the existing graphene heating film is harsh in application environment, short in service life, incapable of improving the existing pavement or high in service life and cost even if the existing pavement is improved.
In view of the above technical problems, the present invention provides a graphene-based self-snow-melting pavement structure with shape memory function.
A graphene-based self-snow-melting pavement paving structure with a shape memory function comprises a heat insulation layer, a graphene-based conductive asphalt layer, a shape memory polymer layer, an insulating asphalt layer and a surface layer which are sequentially paved on a pavement from bottom to top; a plurality of electrodes are arranged in the graphene-based conductive asphalt layer at intervals; the interfaces of two adjacent layers of the heat insulation layer, the graphene-based conductive asphalt layer, the shape memory polymer layer and the insulating asphalt layer are respectively bonded through emulsified asphalt adhesives, and the surface layer is laid on the insulating asphalt layer;
the graphene-based conductive asphalt layer consists of 5-10 parts by weight of modified asphalt, 70-120 parts by weight of aggregate, 15-20 parts by weight of mineral powder, a conductive shape memory composite material, modified graphene oxide and carbon fibers; wherein, the conductive shape memory composite material accounts for 5-15% of the weight of the asphalt, the modified graphene oxide accounts for 0.8-3% of the weight of the asphalt, and the carbon fiber accounts for 10-20% of the weight of the asphalt;
the preparation method of the modified asphalt comprises the following steps:
adding TiC and a silane coupling agent into an ethanol solution with the mass fraction of 20-40%, stirring for reaction for 30-60 min, and drying to remove the dissolution to obtain modified TiC;
secondly, firstly heating and melting asphalt at the temperature of 140-160 ℃, then adding the modified TiC and the dispersing agent obtained in the first step, then putting the mixture into a high-speed shearing machine, and carrying out forward rotation shearing for 20-30 min under the condition that the shearing rate is 1000-2000 r/min, and carrying out reverse rotation shearing for 20-30 min under the condition that the shearing rate is 1000-2000 r/min to obtain modified asphalt;
the dispersant in the first step is di (octyl phenol polyoxyethylene ether) phosphate;
the mass ratio of TiC in the first step to asphalt in the second step is (3-8): 100;
the mass ratio of the silane coupling agent in the first step to the asphalt in the second step is (0.5-1): 100;
the mass ratio of the dispersing agent to the asphalt in the second step is (0.2-0.5): 100;
the mass ratio of the volume of the ethanol solution in the first step to the asphalt in the second step is (5 mL-10 mL) 100 g;
the silane coupling agent in the first step is KH-550 or KH-560;
the modified graphene oxide is prepared by the following steps:
firstly, adding graphene oxide and tannic acid into deionized water, and performing ultrasonic dispersion to obtain a graphene oxide/tannic acid solution;
the concentration of the graphene oxide in the graphene oxide/tannic acid solution in the first step is 3-5 mg/L, and the concentration of the tannic acid is 6-10 mg/L;
the power of ultrasonic dispersion in the step one is 200W-400W, and the time of ultrasonic dispersion is 0.5 h-1 h;
secondly, reacting the graphene oxide/tannic acid solution for 8-12 h under the conditions that the reaction temperature is 90-95 ℃ and the stirring speed is 500-1000 r/min to obtain the modified graphene oxide.
The invention has the advantages that:
the graphene-based self-snow-melting pavement paving structure with the shape memory function comprises a heat insulation layer, a graphene-based conductive asphalt layer, a shape memory polymer layer, an insulating asphalt layer and a surface layer which are sequentially paved on a pavement from bottom to top, wherein the surface layer can prolong the service life of the pavement structure, the insulating asphalt layer prevents water from permeating and electric leakage, the heat insulation layer can effectively reduce downward heat transfer and heat loss, so that the heat is transferred to the surface layer upwards, and the heat can melt ice and snow; when an automobile is pressed, the shape memory polymer layer can play a role in buffering and can be reset, so that the pavement structure is prevented from cracking and being damaged when being subjected to gravity, and the graphene-based conductive asphalt layer is protected;
the method uses the tannic acid to modify the graphene oxide, the tannic acid contains a benzene ring, the benzene ring has certain rigidity, the hyperbranched molecules are harder, and the tannic acid has a large number of terminal hydroxyl groups, so that the tannic acid has good compatibility with a polymer matrix and forms a mechanical meshing effect with the resin matrix; meanwhile, the modified graphite oxide can form a conductive network structure with the conductive shape memory composite material and the carbon fiber in the graphene-based conductive asphalt layer, so that the conductivity is increased;
the TiC is used for modifying the asphalt, has good heat conduction, electric conduction and wear resistance, and can improve the heat conduction, electric conduction and wear resistance of the asphalt by modifying the asphalt with the TiC and the silane coupling agent;
fourthly, the modified polyaniline prepared by the invention contains perfluorooctanoic acid which has-CF2-hydrophobic structure, whereby the modified polyaniline has hydrophobicity; the modified polyaniline can be crosslinked with the modified graphene oxide to form a network structure, so that the mechanical property and the conductivity of the conductive shape memory composite material are improved;
the invention provides a graphene-based self-snow-melting pavement paving structure with a shape memory function, which can improve the existing pavement, so that the existing pavement has high cost for melting snow and ice, solves the problems of high cost, low efficiency and long traffic sealing time of environmental pollution caused by chemical snow melting agents and mechanical snow removal and manual snow removal, and also solves the problems of poor conductivity and mechanical strength, easy caulking cracking and water seepage caused by thermal expansion and cold contraction of the existing conductive asphalt, and avoids the use of a graphene heating film; the graphene-based self-snow-melting pavement paving structure with the shape memory function is suitable for the reconstruction of newly-built asphalt pavements, old asphalt pavements and old cement concrete pavements.
The invention can obtain the graphene-based self-snow-melting pavement paving structure with the shape memory function.
Drawings
Fig. 1 is a schematic structural view of a graphene-based self-snow-melting pavement structure with a shape memory function according to the present invention.
Detailed Description
To make the objects, aspects and advantages of the embodiments of the present invention more apparent, the following detailed description clearly illustrates the spirit of the disclosure, and any person skilled in the art, after understanding the embodiments of the disclosure, may make changes and modifications to the technology taught by the disclosure without departing from the spirit and scope of the disclosure.
The first embodiment is as follows: the graphene-based self-snow-melting pavement paving structure with the shape memory function comprises a heat insulation layer 1, a graphene-based conductive asphalt layer 2, a shape memory polymer layer 3, an insulating asphalt layer 4 and a surface layer 5 which are sequentially paved on a pavement from bottom to top; a plurality of electrodes 6 are arranged in the graphene-based conductive asphalt layer 2 at intervals; the adjacent two interfaces of the heat insulation layer 1, the graphene-based conductive asphalt layer 2, the shape memory polymer layer 3 and the insulating asphalt layer 4 are respectively bonded through emulsified asphalt adhesives, and the surface layer 5 is laid on the insulating asphalt layer 4;
the graphene-based conductive asphalt layer 2 consists of 5 to 10 parts by weight of modified asphalt, 70 to 120 parts by weight of aggregate, 15 to 20 parts by weight of mineral powder, a conductive shape memory composite material, modified graphene oxide and carbon fibers; wherein, the conductive shape memory composite material accounts for 5-15% of the weight of the asphalt, the modified graphene oxide accounts for 0.8-3% of the weight of the asphalt, and the carbon fiber accounts for 10-20% of the weight of the asphalt;
the preparation method of the modified asphalt comprises the following steps:
adding TiC and a silane coupling agent into an ethanol solution with the mass fraction of 20-40%, stirring for reaction for 30-60 min, and drying to remove the dissolution to obtain modified TiC;
secondly, firstly heating and melting asphalt at the temperature of 140-160 ℃, then adding the modified TiC and the dispersing agent obtained in the first step, then putting the mixture into a high-speed shearing machine, and carrying out forward rotation shearing for 20-30 min under the condition that the shearing rate is 1000-2000 r/min, and carrying out reverse rotation shearing for 20-30 min under the condition that the shearing rate is 1000-2000 r/min to obtain modified asphalt;
the dispersant in the first step is di (octyl phenol polyoxyethylene ether) phosphate;
the mass ratio of TiC in the first step to asphalt in the second step is (3-8): 100;
the mass ratio of the silane coupling agent in the first step to the asphalt in the second step is (0.5-1): 100;
the mass ratio of the dispersing agent to the asphalt in the second step is (0.2-0.5): 100;
the mass ratio of the volume of the ethanol solution in the first step to the asphalt in the second step is (5 mL-10 mL) 100 g;
the silane coupling agent in the first step is KH-550 or KH-560;
the modified graphene oxide is prepared by the following steps:
adding graphene oxide and tannic acid into deionized water, and performing ultrasonic dispersion to obtain a graphene oxide/tannic acid solution;
the concentration of the graphene oxide in the graphene oxide/tannic acid solution is 3-5 mg/L, and the concentration of the tannic acid is 6-10 mg/L;
the power of ultrasonic dispersion in the step I is 200W-400W, and the time of ultrasonic dispersion is 0.5 h-1 h;
secondly, reacting the graphene oxide/tannic acid solution for 8 to 12 hours at the reaction temperature of between 90 and 95 ℃ and at the stirring speed of between 500 and 1000r/min to obtain the modified graphene oxide.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the shape memory polymer layer 3 is thermotropic shape memory polymer, electric induced shape memory polymer, thermosetting shape memory polymer or thermoplastic shape memory polymer, and the thickness is 0.3 cm-0.5 cm. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the preparation method of the graphene-based conductive asphalt layer 2 comprises the following steps:
firstly, 5 to 10 parts of modified asphalt, 70 to 120 parts of aggregate and 15 to 20 parts of mineral powder in parts by weight; stirring the modified asphalt, the aggregate and the carbon fiber at 170-175 ℃ for 3-5 min, adding the mineral powder, and stirring for 2-3 min to obtain a primary mixed material;
and secondly, adding the conductive shape memory composite material and the modified graphene oxide into the primary mixed material, stirring for 2-3 min at 155-165 ℃, and obtaining the graphene-based conductive asphalt layer 2 by adopting a Marshall compaction method. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: the graphene-based conductive asphalt layer 2 consists of 8 to 10 parts by weight of modified asphalt, 80 to 100 parts by weight of aggregate, 16 to 18 parts by weight of mineral powder, a conductive shape memory composite material, modified graphene oxide and carbon fibers; wherein the conductive shape memory composite material accounts for 8-12% of the weight of the asphalt, the modified graphene oxide accounts for 1-2% of the weight of the asphalt, and the carbon fiber accounts for 12-16% of the weight of the asphalt. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the thickness of the graphene-based conductive asphalt layer 2 is 3 cm-5 cm, and the thickness of the insulating asphalt layer 4 is 0.3 cm-0.6 cm. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: the heat insulation layer 1 is prepared by mixing 75 parts of SBS modified emulsified asphalt and 25 parts of hollow microspheres, and the thickness is 0.3 cm-0.5 cm. The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the surface layer 5 is a preventive maintenance seal or asphalt concrete and has the thickness of 1.5 cm-2.5 cm. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the conductive shape memory composite material is prepared according to the following steps:
firstly, preparing an epoxy resin/modified polyaniline mixture;
firstly, dissolving chitosan into an acetic acid solution, then adding perfluorooctanoic acid, aniline and deionized water, stirring for 20-40 min, then adding an ammonium persulfate aqueous solution, and continuously stirring for 1-2 h to obtain a reaction solution; adjusting the pH value of the reaction solution to be neutral, and then adding absolute ethyl alcohol to obtain a reaction product;
secondly, firstly, cleaning the reaction product by using acetone, then cleaning by using absolute ethyl alcohol, and finally drying to obtain modified polyaniline;
thirdly, adding the modified polyaniline and the epoxy resin into acetone to obtain a suspension, performing ultrasonic treatment on the suspension, and volatilizing the acetone at the temperature of 60-65 ℃ to obtain an epoxy resin/modified polyaniline mixture;
the epoxy resin in the step one is one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin or alicyclic epoxy resin;
the mass ratio of the modified polyaniline to the epoxy resin in the step one is (0.1-0.3): 1;
secondly, adding a curing agent, a CMP-410 epoxy resin active toughening agent and modified graphene oxide into the epoxy resin/modified polyaniline mixture, performing ultrasonic treatment, pouring the mixture into a mold for curing and molding, and demolding to obtain the conductive shape memory composite material;
the curing agent in the second step is phthalic anhydride or diethylenetriamine, and the mass ratio of the curing agent to the epoxy resin in the epoxy resin/modified polyaniline mixture is (20-40): 100;
the mass ratio of the CMP-410 epoxy resin active toughening agent to the epoxy resin in the epoxy resin/modified polyaniline mixture in the step two is (20-30): 100;
the mass ratio of the modified graphene oxide to the epoxy resin in the epoxy resin/modified polyaniline mixture in the step two is (5-10): 100. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: the modified graphene oxide is prepared by the following steps:
firstly, adding graphene oxide and tannic acid into deionized water, and performing ultrasonic dispersion to obtain a graphene oxide/tannic acid solution;
the concentration of the graphene oxide in the graphene oxide/tannic acid solution in the first step is 3-5 mg/L, and the concentration of the tannic acid is 6-10 mg/L;
the power of ultrasonic dispersion in the step one is 200W-400W, and the time of ultrasonic dispersion is 0.5 h-1 h;
secondly, reacting the graphene oxide/tannic acid solution for 8-12 h under the conditions that the reaction temperature is 90-95 ℃ and the stirring speed is 500-1000 r/min to obtain the modified graphene oxide. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is as follows: the mass fraction of the acetic acid solution in the first step is 15-25%; the mol ratio of the perfluorooctanoic acid to the aniline in the first step is 1 (4-7); the ratio of the mass of the chitosan to the volume of the aniline in the first step is (2 g-3 g) to (30 mL-40 mL); the ratio of the mass of the chitosan to the volume of the acetic acid solution in the first step is (2 g-3 g): 200 mL-300 mL; the concentration of the ammonium persulfate aqueous solution in the first step is 0.6-0.7 mol/L; the volume ratio of the acetic acid solution to the deionized water in the first step is 1: 1; the volume ratio of the acetic acid solution to the absolute ethyl alcohol in the first step is 1 (2-3); the volume ratio of the acetic acid solution to the ammonium persulfate aqueous solution in the first step is 1 (0.5-0.8); firstly, cleaning a reaction product for 3-5 times by using acetone, cleaning the reaction product for 3-5 times by using absolute ethyl alcohol, and finally, drying the reaction product in vacuum at the temperature of 60-65 ℃ to obtain modified polyaniline; the curing and forming process in the step two comprises the following steps: firstly, curing for 2 to 4 hours at 60 to 70 ℃, then curing for 2 to 3 hours at 100 to 120 ℃, and finally curing for 2 to 2.5 hours at 130 ℃; the ultrasonic time in the step two is 10 min-15 min. The other steps are the same as those in the first to ninth embodiments.
The present invention will be described in detail below with reference to the accompanying drawings and examples.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1: a graphene-based self-snow-melting pavement paving structure with a shape memory function comprises a heat insulation layer 1, a graphene-based conductive asphalt layer 2, a shape memory polymer layer 3, an insulating asphalt layer 4 and a surface layer 5 which are sequentially paved on a pavement from bottom to top; a plurality of electrodes 6 are arranged in the graphene-based conductive asphalt layer 2 at intervals; the adjacent two interfaces of the heat insulation layer 1, the graphene-based conductive asphalt layer 2, the shape memory polymer layer 3 and the insulating asphalt layer 4 are respectively bonded through emulsified asphalt adhesives, and the surface layer 5 is laid on the insulating asphalt layer 4;
the electrode 6 is a copper mesh electrode;
the graphene-based conductive asphalt layer 2 consists of 10 parts of modified asphalt, 100 parts of aggregate, 16 parts of mineral powder, a conductive shape memory composite material, modified graphene oxide and carbon fiber in parts by weight; the conductive shape memory composite material accounts for 12% of the weight of the asphalt, the modified graphene oxide accounts for 2% of the weight of the asphalt, the carbon fiber accounts for 18% of the weight of the asphalt, and the aggregate is graded by AC-20;
the preparation method of the modified asphalt comprises the following steps:
adding TiC and a silane coupling agent into an ethanol solution with the mass fraction of 30%, stirring for reacting for 60min, and drying to remove the solution to obtain modified TiC;
secondly, firstly heating and melting asphalt at the temperature of 150 ℃, then adding the modified TiC and the dispersing agent obtained in the first step, then putting the mixture into a high-speed shearing machine, and carrying out forward rotation shearing for 25min under the condition that the shearing rate is 2000r/min, and then carrying out reverse rotation shearing for 25min under the condition that the shearing rate is 2000r/min to obtain modified asphalt;
the dispersant in the first step is di (octyl phenol polyoxyethylene ether) phosphate;
the mass ratio of TiC in the step one to asphalt in the step two is 5: 100;
the mass ratio of the silane coupling agent in the step one to the asphalt in the step two is 0.8: 100;
the mass ratio of the dispersing agent to the asphalt in the step two is 0.3: 100;
the mass ratio of the volume of the ethanol solution in the step one to the asphalt in the step two is 10mL to 100 g;
the silane coupling agent in the first step is KH-550;
the modified graphene oxide is prepared by the following steps:
adding graphene oxide and tannic acid into deionized water, and performing ultrasonic dispersion to obtain a graphene oxide/tannic acid solution;
the concentration of the graphene oxide in the graphene oxide/tannic acid solution in the step I is 5mg/L, and the concentration of the tannic acid is 8 mg/L;
the power of ultrasonic dispersion in the step I is 400W, and the time of ultrasonic dispersion is 40 min;
and secondly, reacting the graphene oxide/tannic acid solution for 10 hours at the reaction temperature of 90 ℃ and the stirring speed of 1000r/min to obtain the modified graphene oxide.
The shape memory polymer layer 3 described in example 1 was a polyimide layer prepared from 1, 3-bis (3-aminophenoxy) benzene, bisphenol a type diether dianhydride and 4, 4-oxydiphthalic anhydride, the molar ratio of the mixture of bisphenol a type diether dianhydride and 4, 4-oxydiphthalic anhydride to 1, 3-bis (3-aminophenoxy) benzene was 1:1, and the molar ratio of bisphenol a type diether dianhydride to 4, 4-oxydiphthalic anhydride was 4: 1; the thickness of the polyimide layer was 0.3cm, the shape fixation rate was 99%, and the shape recovery rate was 99%.
The preparation method of the graphene-based conductive asphalt layer 2 described in example 1 is as follows:
firstly, 10 parts of modified asphalt, 100 parts of aggregate and 16 parts of mineral powder in parts by weight; stirring the modified asphalt, the aggregate and the carbon fiber at 170 ℃ for 5min, adding the mineral powder, and stirring for 3min to obtain a primary mixed material;
and secondly, adding the conductive shape memory composite material and the modified graphene oxide into the primary mixed material, stirring for 2min at 160 ℃, and obtaining the graphene-based conductive asphalt layer 2 by adopting a Marshall compaction method.
The thickness of the graphene-based conductive asphalt layer 2 described in example 1 was 4cm, and the thickness of the insulating asphalt layer 4 was 0.3 cm.
The heat insulation layer 1 described in example 1 was prepared by mixing 75 parts of SBS-modified emulsified asphalt and 25 parts of hollow beads, and had a thickness of 0.4 cm.
The facing 5 described in example 1 was asphalt concrete with a thickness of 2 cm.
The conductive shape memory composite of example 1 was prepared according to the following procedure:
firstly, preparing an epoxy resin/modified polyaniline mixture;
dissolving chitosan into an acetic acid solution with the mass fraction of 20%, then adding perfluorooctanoic acid, aniline and deionized water, stirring for 30min, then adding 0.6mol/L ammonium persulfate aqueous solution, and continuing stirring for 1h to obtain a reaction solution; adjusting the pH value of the reaction solution to be neutral, and then adding absolute ethyl alcohol to obtain a reaction product;
the mol ratio of the perfluorooctanoic acid to the aniline in the first step is 1: 5; the volume ratio of the mass of the chitosan to the volume of the aniline is 2g:30 mL; the volume ratio of the mass of the chitosan to the volume of the acetic acid solution is 2g:200 mL; the volume ratio of the acetic acid solution to the deionized water is 1: 1; the volume ratio of the acetic acid solution to the absolute ethyl alcohol is 1: 2; the volume ratio of the acetic acid solution to the ammonium persulfate aqueous solution is 1: 0.6;
secondly, firstly, cleaning the reaction product by using acetone, then cleaning by using absolute ethyl alcohol, and finally drying to obtain modified polyaniline;
firstly, washing a reaction product for 5 times by using acetone, then washing the reaction product for 5 times by using absolute ethyl alcohol, and finally, drying in vacuum at 60 ℃ to obtain modified polyaniline;
thirdly, adding the modified polyaniline and the epoxy resin into acetone to obtain a suspension, performing ultrasonic treatment on the suspension, and volatilizing the acetone at the temperature of 60 ℃ to obtain an epoxy resin/modified polyaniline mixture;
the epoxy resin in the step one is bisphenol A type epoxy resin;
the mass ratio of the modified polyaniline to the epoxy resin in the step one is 0.2: 1;
secondly, adding a curing agent, a CMP-410 epoxy resin active toughening agent and modified graphene oxide into the epoxy resin/modified polyaniline mixture, performing ultrasonic treatment, pouring the mixture into a mold for curing and molding, and demolding to obtain the conductive shape memory composite material;
the curing agent in the second step is diethylenetriamine, and the mass ratio of the curing agent to the epoxy resin in the epoxy resin/modified polyaniline mixture is 35: 100;
the mass ratio of the CMP-410 epoxy resin active toughening agent to the epoxy resin in the epoxy resin/modified polyaniline mixture in the step two is 20: 100;
the mass ratio of the modified graphene oxide to the epoxy resin in the epoxy resin/modified polyaniline mixture in the step two is 8: 100;
the curing and forming process in the step two comprises the following steps: firstly curing for 3h at 65 ℃, then curing for 2h at 110 ℃, and finally curing for 2h at 130 ℃; the ultrasonic time in the step two is 15 min;
the modified graphene oxide in the second step is prepared according to the following steps:
adding graphene oxide and tannic acid into deionized water, and performing ultrasonic dispersion to obtain a graphene oxide/tannic acid solution;
the concentration of the graphene oxide in the graphene oxide/tannic acid solution in the step I is 4mg/L, and the concentration of the tannic acid is 7 mg/L;
the power of ultrasonic dispersion in the step I is 300W, and the time of ultrasonic dispersion is 1 h;
and secondly, reacting the graphene oxide/tannic acid solution for 10 hours at the reaction temperature of 90 ℃ and the stirring speed of 1000r/min to obtain the modified graphene oxide.
The conductive shape memory composite material prepared in example 1 had a resistivity of 0.09 Ω · m and a glass transition temperature of 72 ℃, and could be electrically-thermally driven with a maximum recovery strain of 99.5%.
Example 2: the present embodiment is different from embodiment 1 in that: the graphene-based conductive asphalt layer 2 consists of 8 parts of modified asphalt, 90 parts of aggregate, 15 parts of mineral powder, a conductive shape memory composite material, modified graphene oxide and carbon fiber in parts by weight; the conductive shape memory composite material accounts for 10% of the weight of the asphalt, the modified graphene oxide accounts for 2.5% of the weight of the asphalt, and the carbon fiber accounts for 14% of the weight of the asphalt. The other steps and parameters were the same as in example 1.
Example 3: the present embodiment is different from embodiment 1 in that: the graphene-based conductive asphalt layer 2 consists of 10 parts of modified asphalt, 70 parts of aggregate, 18 parts of mineral powder, a conductive shape memory composite material, modified graphene oxide and carbon fiber in parts by weight; the conductive shape memory composite material accounts for 8% of the weight of the asphalt, the modified graphene oxide accounts for 3% of the weight of the asphalt, and the carbon fiber accounts for 10% of the weight of the asphalt. The other steps and parameters were the same as in example 1.
The graphene-based conductive asphalt layers prepared in examples 1 to 3 were tested for resistivity, high-temperature stability, low-temperature crack resistance, pavement heating effect, water stability and aging properties.
1. And (3) measuring the resistivity:
in the measurement of the resistivity of the graphene-based conductive asphalt layer in the example, the resistivity is measured according to a solid insulating material volume resistivity and surface resistivity test method BT 1410-:
TABLE 1
| Specimen type | Resistivity (omega. m) |
| Example 1 | 1.09 |
| Example 2 | 1.32 |
| Example 3 | 1.17 |
As can be seen from table 1, in the embodiment, the addition of the conductive shape memory composite material, the modified graphene oxide and the carbon fiber can significantly reduce the resistivity of the graphene-based conductive asphalt layer, wherein the resistivity of the conductive shape memory composite material is only 0.09 Ω · m, and the conductive shape memory composite material is modified by polyaniline using chitosan and graphene oxide using tannic acid, so that the tannic acid and the graphene oxide can form a network structure, thereby providing a sufficient electrochemical reaction active region and significantly improving the conductivity of the graphene-based conductive asphalt layer; in addition, the TiC and the silane coupling agent are used for modifying the asphalt, the resistivity of the TiC is about 61 mu omega-m, the TiC is close to metal, and the asphalt has good conductivity, so that the TiC and the coupling agent are used for modifying the asphalt, the conductivity of the asphalt is obviously improved, and the conductivity of the graphene-based conductive asphalt layer is further improved.
2. High temperature stability detection
And (3) according to road engineering asphalt and asphalt mixture test specification JTG E20-2011), evaluating the high-temperature stability of the graphene-based conductive asphalt layer by adopting the dynamic stability of a 60-degree rut test. The high temperature rutting test was carried out on standard formed rutting plate test pieces with test piece dimensions of 300mm x 50mm, the results are shown in table 2 below:
TABLE 2
| Specimen type | Example 1 | Example 2 | Example 3 |
| Dynamic stability times/minutes) | 6087 | 5894 | 5976 |
It can be known from table 2 that, the addition of carbon fiber can form three-dimensional space network structure, play the effect of transmission and muscle, overlap and supply each other with the cohesion of pitch, prevent the slip of aggregate, improved anti deformability, simultaneously because use tannic acid to modify graphite oxide alkene, contain the benzene ring in the tannic acid, the benzene ring has certain rigidity, hyperbranched molecule is harder some, can make carbon fiber carry out resistance to deformation ability through its grid structure and strengthen, simultaneously can interact with electrically conductive shape memory combined material, the stability has been increased, in addition because use TiC to modify pitch, can improve the mechanical properties of pitch.
3. Measurement of Low temperature crack resistance
The graphene-based conductive asphalt layers prepared in examples 1 to 3 were allowed to stand at-10 ℃ for 4 hours, and at room temperature for 4 hours, which was one cycle, and after three consecutive cycles, no crack was found on the surface of the graphene-based conductive asphalt layers prepared in examples 1 to 3.
4. Pavement heating effect test
Sequentially paving the heat insulation layer (1), the graphene-based conductive asphalt layer (2), the shape memory polymer layer (3), the insulating asphalt layer (4) and the surface layer (5) in the embodiments 1-3 on an old asphalt concrete simulated pavement to obtain a test piece with the size of 300mm multiplied by 300 mm; the test piece is placed at-10 ℃, the electrode is connected with a 40V external power supply, and the temperature rise effect of the pavement is shown in table 3;
TABLE 3
As the surface temperature reaches above 0 ℃, ice and snow melting can be realized, and as can be seen from table 3, the graphene-based self-snow-melting pavement structure prepared in examples 1 to 3 has a good heating effect, and can reach above 6 ℃ 120min after the electrodes are connected with a 36V external power supply at-10 ℃, because TiC has good heat conductivity, the asphalt is modified by TiC, and the heat conductivity of the asphalt is improved. Therefore, the graphene self-snow-melting pavement can be used in northern cold areas, and meanwhile, the graphene self-snow-melting pavement prepared by the method is suitable for the reconstruction of newly-built asphalt pavements, old asphalt pavements and old cement concrete pavements.
5. Immersion marshall test and analysis of test results
The water stability of the graphene-based conductive asphalt layer is evaluated according to the test specification JTG E20-2011 of highway engineering asphalt and asphalt mixture in China; soaking in 60 deg.C water for 30min and 48h, respectively, taking out, and comparing stability, the results are shown in Table 4;
TABLE 4
As can be seen from Table 4, the addition of the conductive shape memory composite material containing perfluorooctanoic acid having-CF-and the carbon fibers has an effect of improving the water stability of the graphene-based conductive asphalt layer2The hydrophobic structure increases the difficulty of water entering, so that the water stability of the graphene-based conductive asphalt layer can be increased, and the carbon fibers enhance the crack resistance of the graphene-based conductive asphalt layer, so that the water stability of the graphene-based conductive asphalt layer prepared by the embodiment is better.
6. Aging Properties of asphalt
The aging phenomenon of the asphalt pavement can occur in the using process, and the aging can affect the performance of the asphalt pavement, so the research on the aging performance of the asphalt is very important. In the experiment, the temperature for researching the aging performance of the graphene-based conductive asphalt layer is set to be 170 ℃, the aging time is set to be 80min, and the experimental indexes are the low-temperature residual ductility and the residual penetration ratio after aging, which are shown in table 5;
TABLE 5
As can be seen from table 5, the graphene-based conductive asphalt layers prepared in examples 1 to 3 all have excellent aging properties, because the conductive shape memory composite material, the carbon fiber and the TiC are added in examples 1 to 3, the temperature rise rate of the asphalt is retarded, and the aging resistance of the asphalt is improved.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples for carrying out the invention, and that various changes in form and details may be made therein without departing from the spirit and scope of the invention in practice.
Claims (10)
1. A graphene-based self-snow-melting pavement structure with a shape memory function is characterized by comprising a heat insulation layer (1), a graphene-based conductive asphalt layer (2), a shape memory polymer layer (3), an insulating asphalt layer (4) and a surface layer (5) which are sequentially paved on a pavement from bottom to top; a plurality of electrodes (6) are arranged in the graphene-based conductive asphalt layer (2) at intervals; the heat insulation layer (1), the graphene-based conductive asphalt layer (2), the shape memory polymer layer (3) and the adjacent two interfaces of the insulating asphalt layer (4) are respectively bonded through emulsified asphalt adhesives, and the surface layer (5) is laid on the insulating asphalt layer (4);
the graphene-based conductive asphalt layer (2) is composed of 5-10 parts by weight of modified asphalt, 70-120 parts by weight of aggregate, 15-20 parts by weight of mineral powder, a conductive shape memory composite material, modified graphene oxide and carbon fibers; wherein, the conductive shape memory composite material accounts for 5-15% of the weight of the asphalt, the modified graphene oxide accounts for 0.8-3% of the weight of the asphalt, and the carbon fiber accounts for 10-20% of the weight of the asphalt;
the preparation method of the modified asphalt comprises the following steps:
adding TiC and a silane coupling agent into an ethanol solution with the mass fraction of 20-40%, stirring for reaction for 30-60 min, and drying to remove the dissolution to obtain modified TiC;
secondly, firstly heating and melting asphalt at the temperature of 140-160 ℃, then adding the modified TiC and the dispersing agent obtained in the first step, then putting the mixture into a high-speed shearing machine, and carrying out forward rotation shearing for 20-30 min under the condition that the shearing rate is 1000-2000 r/min, and carrying out reverse rotation shearing for 20-30 min under the condition that the shearing rate is 1000-2000 r/min to obtain modified asphalt;
the dispersant in the first step is di (octyl phenol polyoxyethylene ether) phosphate;
the mass ratio of TiC in the first step to asphalt in the second step is (3-8): 100;
the mass ratio of the silane coupling agent in the first step to the asphalt in the second step is (0.5-1): 100;
the mass ratio of the dispersing agent to the asphalt in the second step is (0.2-0.5): 100;
the mass ratio of the volume of the ethanol solution in the first step to the asphalt in the second step is (5 mL-10 mL) 100 g;
the silane coupling agent in the first step is KH-550 or KH-560;
the modified graphene oxide is prepared by the following steps:
adding graphene oxide and tannic acid into deionized water, and performing ultrasonic dispersion to obtain a graphene oxide/tannic acid solution;
the concentration of the graphene oxide in the graphene oxide/tannic acid solution is 3-5 mg/L, and the concentration of the tannic acid is 6-10 mg/L;
the power of ultrasonic dispersion in the step I is 200W-400W, and the time of ultrasonic dispersion is 0.5 h-1 h;
secondly, reacting the graphene oxide/tannic acid solution for 8 to 12 hours at the reaction temperature of between 90 and 95 ℃ and at the stirring speed of between 500 and 1000r/min to obtain the modified graphene oxide.
2. The graphene-based self-snow-melting pavement structure with the shape memory function according to claim 1, wherein the shape memory polymer layer (3) is a thermotropic shape memory polymer, an electric-induced shape memory polymer, a thermosetting shape memory polymer or a thermoplastic shape memory polymer, and has a thickness of 0.3cm to 0.5 cm.
3. The graphene-based self-snow-melting pavement structure with the shape memory function as claimed in claim 1, wherein the graphene-based conductive asphalt layer (2) is prepared by the following steps:
firstly, 5 to 10 parts of modified asphalt, 70 to 120 parts of aggregate and 15 to 20 parts of mineral powder in parts by weight; stirring the modified asphalt, the aggregate and the carbon fiber at 170-175 ℃ for 3-5 min, adding the mineral powder, and stirring for 2-3 min to obtain a primary mixed material;
and secondly, adding the conductive shape memory composite material and the modified graphene oxide into the primary mixed material, stirring for 2-3 min at 155-165 ℃, and obtaining the graphene-based conductive asphalt layer (2) by adopting a Marshall compaction method.
4. The graphene-based self-snow-melting pavement structure with the shape memory function according to claim 1, wherein the graphene-based conductive asphalt layer (2) is composed of 8-10 parts by weight of modified asphalt, 80-100 parts by weight of aggregate, 16-18 parts by weight of mineral powder, a conductive shape memory composite material, modified graphene oxide and carbon fibers; wherein the conductive shape memory composite material accounts for 8-12% of the weight of the asphalt, the modified graphene oxide accounts for 1-2% of the weight of the asphalt, and the carbon fiber accounts for 12-16% of the weight of the asphalt.
5. The graphene-based self-snow-melting pavement structure with the shape memory function as claimed in claim 1, wherein the thickness of the graphene-based conductive asphalt layer (2) is 3 cm-5 cm, and the thickness of the insulating asphalt layer (4) is 0.3 cm-0.6 cm.
6. The graphene-based self-snow-melting pavement structure with the shape memory function as claimed in claim 1, wherein the thermal insulation layer (1) is prepared by mixing 75 parts of SBS modified emulsified asphalt and 25 parts of cenospheres, and the thickness is 0.3 cm-0.5 cm.
7. The graphene-based self-snow-melting pavement structure with the shape memory function as claimed in claim 1, wherein the surface layer (5) is a preventive curing seal or asphalt concrete and has a thickness of 1.5 cm-2.5 cm.
8. The graphene-based self-snow-melting pavement structure with the shape memory function as claimed in claim 1, wherein the conductive shape memory composite material is prepared by the following steps:
firstly, preparing an epoxy resin/modified polyaniline mixture;
firstly, dissolving chitosan into an acetic acid solution, then adding perfluorooctanoic acid, aniline and deionized water, stirring for 20-40 min, then adding an ammonium persulfate aqueous solution, and continuously stirring for 1-2 h to obtain a reaction solution; adjusting the pH value of the reaction solution to be neutral, and then adding absolute ethyl alcohol to obtain a reaction product;
secondly, firstly, cleaning the reaction product by using acetone, then cleaning by using absolute ethyl alcohol, and finally drying to obtain modified polyaniline;
thirdly, adding the modified polyaniline and the epoxy resin into acetone to obtain a suspension, performing ultrasonic treatment on the suspension, and volatilizing the acetone at the temperature of 60-65 ℃ to obtain an epoxy resin/modified polyaniline mixture;
the epoxy resin in the step one is one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin or alicyclic epoxy resin;
the mass ratio of the modified polyaniline to the epoxy resin in the step one is (0.1-0.3): 1;
secondly, adding a curing agent, a CMP-410 epoxy resin active toughening agent and modified graphene oxide into the epoxy resin/modified polyaniline mixture, performing ultrasonic treatment, pouring the mixture into a mold for curing and molding, and demolding to obtain the conductive shape memory composite material;
the curing agent in the second step is phthalic anhydride or diethylenetriamine, and the mass ratio of the curing agent to the epoxy resin in the epoxy resin/modified polyaniline mixture is (20-40): 100;
the mass ratio of the CMP-410 epoxy resin active toughening agent to the epoxy resin in the epoxy resin/modified polyaniline mixture in the step two is (20-30): 100;
the mass ratio of the modified graphene oxide to the epoxy resin in the epoxy resin/modified polyaniline mixture in the step two is (5-10): 100.
9. The graphene-based self-snow-melting pavement structure with the shape memory function as claimed in claim 8, wherein the modified graphene oxide is prepared by the following steps:
firstly, adding graphene oxide and tannic acid into deionized water, and performing ultrasonic dispersion to obtain a graphene oxide/tannic acid solution;
the concentration of the graphene oxide in the graphene oxide/tannic acid solution in the first step is 3-5 mg/L, and the concentration of the tannic acid is 6-10 mg/L;
the power of ultrasonic dispersion in the step one is 200W-400W, and the time of ultrasonic dispersion is 0.5 h-1 h;
secondly, reacting the graphene oxide/tannic acid solution for 8-12 h under the conditions that the reaction temperature is 90-95 ℃ and the stirring speed is 500-1000 r/min to obtain the modified graphene oxide.
10. The graphene-based self-snow-melting pavement structure with the shape memory function as claimed in claim 8, wherein the mass fraction of the acetic acid solution in the first step is 15% -25%; the mol ratio of the perfluorooctanoic acid to the aniline in the first step is 1 (4-7); the ratio of the mass of the chitosan to the volume of the aniline in the first step is (2 g-3 g) to (30 mL-40 mL); the ratio of the mass of the chitosan to the volume of the acetic acid solution in the first step is (2 g-3 g): 200 mL-300 mL; the concentration of the ammonium persulfate aqueous solution in the first step is 0.6-0.7 mol/L; the volume ratio of the acetic acid solution to the deionized water in the first step is 1: 1; the volume ratio of the acetic acid solution to the absolute ethyl alcohol in the first step is 1 (2-3); the volume ratio of the acetic acid solution to the ammonium persulfate aqueous solution in the first step is 1 (0.5-0.8); firstly, cleaning a reaction product for 3-5 times by using acetone, cleaning the reaction product for 3-5 times by using absolute ethyl alcohol, and finally, drying the reaction product in vacuum at the temperature of 60-65 ℃ to obtain modified polyaniline; the curing and forming process in the step two comprises the following steps: firstly, curing for 2 to 4 hours at 60 to 70 ℃, then curing for 2 to 3 hours at 100 to 120 ℃, and finally curing for 2 to 2.5 hours at 130 ℃; the ultrasonic time in the step two is 10 min-15 min.
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