CN111925776B - Preparation method of polypyrrole nanowire interface modified three-dimensional graphene/PDMS composite photo-thermal material - Google Patents
Preparation method of polypyrrole nanowire interface modified three-dimensional graphene/PDMS composite photo-thermal material Download PDFInfo
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Abstract
The invention relates to the technical field of chemical engineering chemistry, and particularly relates to a preparation method of a polypyrrole nanowire interface modified three-dimensional graphene/PDMS composite photo-thermal material. Growing polypyrrole nanowires on the surface of the three-dimensional graphene by adopting an electrochemical pyrrole oxide polymerization method, mixing the polypyrrole nanowires with PDMS, removing bubbles in vacuum, and curing to obtain the polypyrrole nanowire interface modified three-dimensional graphene/PDMS composite material. The polypyrrole nanowire modified three-dimensional graphene/PDMS composite material has a continuous interface phase, the problem of poor compatibility of graphene and PDMS is effectively solved due to the existence of the polypyrrole nanowire, the binding force between the graphene and the PDMS is remarkably improved, various characterization data of the material show that the Young modulus, the electric conductivity, the thermal conductivity, the photo-thermal conversion performance and the like of the modified composite material are remarkably improved, and the composite material obtained by the interface modification technology can be widely applied to the technical fields of high-performance electronic devices and high-tech industries.
Description
Technical Field
The invention relates to the technical field of chemistry and chemical engineering, in particular to a method for interface modification of a three-dimensional graphene/PDMS composite material by polypyrrole nanowires
Background
The three-dimensional graphene/PDMS composite material is a material compounded by three-dimensional graphene and PDMS, and has good flexibility and tensile property; meanwhile, the composite material also has excellent electrical properties, heat-conducting properties, electromagnetic shielding properties and the like. Therefore, the three-dimensional graphene/PDMS composite material has a wide application prospect in the fields of sensors, thermal interface materials, high-performance electronic devices and the like.
The interface phase is a connecting bridge between the composite material filling body and the polymer matrix material, the mechanical property, the electrical property, the heat conducting property and the like of the composite material are obviously influenced by the microscopic nano structure of the interface phase, and the optimization of the microscopic structure of the interface phase is one of the main means for improving the performance of the composite material. Graphene is a single-layer two-dimensional atomic structure crystal and has excellent electron mobility (20000 cm)2V-1S-1) Specific surface area (2630 m)2The heat conductivity is 5000W/m.K, the light transmittance is 97 percent, and the mechanical property is the like. The graphene can be used as a two-dimensional assembly unit to form a macroscopic structure such as a fiber, a film, a foam and the like, and the bulk phase materials can be used as a filler to form a functional composite material with a polymer. The three-dimensional graphene is prepared by using foamed nickel as a template, can form a composite film with PDMS, epoxy resin, polyurethane and the like, and embodies excellent performances such as electrical conductivity, thermal conductivity, electromagnetic shielding and the like. The graphene oxide prepared by the Hummer method can be used as a building unit to prepare a three-dimensional foam structure, common methods comprise a hydrothermal method, an ice template assembly method, a hard template method and the like, but the intrinsic performance of the graphene oxide is severely limited by reducing oxygen-containing functional groups remained on the surface of the graphene oxide, and the performance of the prepared polymer composite material cannot meet the requirement of practical application. The three-dimensional graphene prepared by the chemical vapor deposition method has good crystallinity, graphene sheets grow continuously, and the conductivity is close to that of intrinsic graphene. Therefore, the three-dimensional graphene prepared by the chemical vapor deposition method is an ideal filling body, and various properties of the prepared composite material are expected to meet the harsh requirements of practical application. Research work and patent (CN201210574175.4) of an eminent subject group disclose a light flexible graphene/polymer foam electromagnetic shielding material, preparation and application thereof, and show that three-dimensional graphene prepared by a chemical vapor deposition method is a potential functional filler. However, the three-dimensional graphene prepared by the chemical vapor deposition method has few surface defect structures, low content of oxygen-containing functional groups, and poor interface compatibility and bonding force compared with PDMS. The microstructure of the interface phase between the filler and the polymer matrix presents a plurality of structuresThe defects of poor stress transfer effect, serious interface phonon scattering and high thermal resistance seriously limit the mechanical property, the electric conduction property and the heat conduction property of the composite material. Therefore, the surface nano structure and chemical composition of the three-dimensional graphene prepared by the chemical vapor deposition method are improved, the microscopic nano structure of the interface phase is improved, the compatibility and bonding force between the graphene and the polymer can be increased, phonon scattering is reduced, and the tensile Young modulus, the electric conductivity, the thermal conductivity and other properties of the composite material are improved, so that the interface modification of the graphene/PDMS is a key scientific problem for promoting the practical application of the graphene/PDMS.
The patent (application number CN201811032839.8) discloses a preparation method of graphene-three-dimensional polypyrrole framework composite sponge, but the patent content does not refer to graphene, and the preparation route can only use foamed nickel as a template to obtain a polypyrrole film, but not a foam structure composed of polypyrrole nanowires. The patent (application number CN201610671458.9) discloses a preparation method of a polypyrrole composite graphene foam electrode plate, wherein graphite oxide is used as a raw material, a pyrrole solution is subjected to liquid phase polymerization, and a graphene/polypyrrole electrode plate is obtained after roll pressing, and the performance of a composite material is limited by the restriction of the graphite oxide raw material. The patent (application No. CN201810042999.4) discloses a method for preparing polypyrrole-modified SiC nanowire/graphene foam electromagnetic wave absorbing material, and the patent also uses graphene oxide as raw material and FeCl3The pyrrole polymerization modification route is initiated, and the electromagnetic shielding performance of the material is limited by the influence of the graphene oxide raw material. The patent (application No. 201910816268.5) discloses a method for modifying a carbon fiber/epoxy resin composite material by a graphene interface, which utilizes physical coating of graphene slurry, and cannot ensure uniformity and strong interface bonding force. Patent application No. 201610043545.X discloses a preparation method of a vertically-oriented graphene sheet/high polymer thermal interface material, which also adopts graphene oxide as a raw material, and oxygen-containing functional groups cannot be completely removed, so that the interface quality of the composite material is reduced. The doctor paper of the cross-scale design of the composite material reinforcement and the research of the interface reinforcement mechanism thereof discloses a method for modifying an interface, the material still selects graphene oxide and relates to complex two-step acylAnd (4) carrying out amination grafting reaction. Patent (cn201911257312.x) discloses a method for interface modification of graphene by hyperbranched polyethylene copolymer of terminal branched grafted polysilsesquioxane, but the process relies on ultrasonic dispersion and is not suitable for modifying three-dimensional graphene. Although there are some graphene/polymer interface modification processes in the literature and patents, the methods are only applicable to graphene oxide raw materials, and related reports and patent technologies of polypyrrole nanowire modified chemical vapor deposition graphene processes are not found.
Disclosure of Invention
The technical problem solved by the invention is as follows: the invention overcomes the defects in the prior art, and provides an interface modification method of a three-dimensional graphene and PDMS composite material, which utilizes polypyrrole nanowires directly grown on the surface of the three-dimensional graphene to improve the microscopic nanostructure of an interface phase, improve the compatibility and the bonding force of the three-dimensional graphene and a PDMS matrix phase, and effectively improve the Young modulus, the electric conductivity, the thermal conductivity and other properties of the composite material.
The technical scheme of the invention is as follows: 1. a preparation method of a polypyrrole nanowire interface modified three-dimensional graphene/PDMS composite photo-thermal material comprises the following steps:
step 1: preparing foamed nickel loaded three-dimensional graphene, comprising the following substeps:
step 1.1: cleaning foamed nickel, ultrasonically removing surface organic matters by adopting absolute ethyl alcohol, ultrasonically cleaning by using deionized water, and blow-drying by using nitrogen, argon or air for later use;
step 1.2: using Ar/H2Reducing and removing the metal oxide on the surface of the foamed nickel in the step 1.1 at 900-1000 ℃ by taking the carrier gas as a carrier gas, wherein the carrier gas flow rate is 100/100 sccm;
step 1.3: reducing the carrier gas flow rate and temperature, Ar/H, in step 1.22The carrier gas flow rate is 190-180/10-20 sccm, the growth temperature is 850-900 ℃, and Ar/H is introduced through a valve2Introducing carrier gas into the container filled with anhydrous ethanolAnd (3) introducing ethanol gas into a tubular furnace for graphene growth above the closed container, wherein the graphene growth time is 20-40 min.
Step 1.4: cooling the tube furnace to room temperature, and keeping Ar/H in the cooling process2The flow rate of the carrier gas is 190-180/10-20 sccm, and the foamed nickel loaded three-dimensional graphene is obtained;
step 2: preparing polypyrrole nano wires: immersing the foamed nickel-loaded three-dimensional graphene in the step 1.4 serving as a substrate into electrolyte, and depositing pyrrole nanowires by using a potentiostatic method;
and step 3: preparing a self-supporting polypyrrole nanowire modified three-dimensional graphene material: soaking the graphene and pyrrole materials loaded by the foamed nickel in the step 2 as a substrate into a hydrochloric acid solution of 2-5mol/L, and adding 10-40mg/mL ferric trichloride; soaking for 24 hours, after the nickel is completely etched, taking out the material, washing the material with deionized water until the pH value is neutral, obtaining the self-supporting polypyrrole nanowire modified three-dimensional graphene material, and drying at 40-100 ℃ for later use;
and 4, step 4: placing the self-supporting polypyrrole nanowire modified three-dimensional graphene material obtained in the step 3 into a mold, and mixing PDMS (polydimethylsiloxane) and a curing agent according to the weight ratio of 10: 1, carrying out vacuum filtration and defoaming, and curing at 50-80 ℃ for 12-24 hours to obtain the polypyrrole nanowire interface modified three-dimensional graphene/PDMS composite material.
The further technical scheme of the invention is as follows: the electrolyte in the step 2 contains 20-40mg/mL of sodium perchlorate, 20-40mg/mL of sodium carbonate and 10-40mg/mL of pyrrole monomer.
The further technical scheme of the invention is as follows: the electrolyte adopts a three-electrode system, silver/silver chloride is used as a reference electrode, a platinum sheet is used as a counter electrode, the pyrrole nanowires are deposited by a potentiostatic method of 1-1.5V, and after the preparation is finished, deionized water is used for washing for later use.
Effects of the invention
The invention has the technical effects that: the invention overcomes the defects in the prior art, and provides an interface modification method of a three-dimensional graphene and PDMS composite material, which utilizes polypyrrole nanowires directly grown on the surface of the three-dimensional graphene to improve the microscopic nanostructure of an interface phase, improve the compatibility and the bonding force of the three-dimensional graphene and a PDMS matrix phase, and effectively improve the Young modulus, the electric conductivity, the thermal conductivity and the infrared heat absorption performance of the composite material. Compared with an unmodified three-dimensional graphene/PDMS composite material, the Young modulus of the polypyrrole nanowire modified three-dimensional graphene/PDMS composite material is improved to 9.22mPa from 5.31mPa, the electric conductivity of the composite material is improved to 238 s/m from 142s/m after repeated bending, the thermal conductivity is improved to 0.49W/m.K from 0.36W/m.K, and the infrared heat absorption value at the wavelength of 800 nm is improved by 1.56 times. The polypyrrole nanowire modification method is suitable for interface modification of graphite films, graphene fibers, carbon fiber cloth, carbon paper and the like, and is simple to operate, easy to amplify and uniform in quality.
Drawings
FIG. 1 is a schematic diagram of a three-dimensional graphene growth process
FIG. 2 is a scanning electron microscope image of three-dimensional graphene, wherein (a) is a low magnification and (b) is a high magnification
FIG. 3 is a Raman spectrum of three-dimensional graphene
Fig. 4 is a real object diagram of polypyrrole nanowire modified three-dimensional graphene.
Fig. 5 is a scanning electron microscope picture of self-supporting polypyrrole nanowire modified three-dimensional graphene at different magnifications.
FIG. 6 is a scanning electron microscope picture of a section of an unmodified three-dimensional graphene/PDMS composite material
FIG. 7 is a scanning electron microscope image of a cross section of polypyrrole nano-fiber modified three-dimensional graphene/PDMS composite material
Fig. 8(a) is an unmodified three-dimensional graphene/PDMS composite material, and (b) is a schematic diagram of an interface structure of a polypyrrole nanofiber modified three-dimensional graphene/PDMS composite material.
FIG. 9 is a graph comparing the tensile Young's modulus of PDMS, three-dimensional graphene/PDMS composite (before modification), and polypyrrole nanofiber modified three-dimensional graphene/PDMS composite (after modification)
Fig. 10 is a graph comparing the electrical conductivities of the three-dimensional graphene/PDMS composite (before modification) and the polypyrrole nanofiber modified three-dimensional graphene/PDMS composite (after modification) after 1000 repeated bendings.
Fig. 11(a) is a solid ultraviolet visible-near infrared absorption spectrum diagram of the three-dimensional graphene/PDMS composite material (before modification) and the polypyrrole nanofiber modified three-dimensional graphene/PDMS composite material (after modification), and (b) is a thermal imaging diagram of the modified composite material after infrared light irradiation.
Fig. 12 is a graph comparing thermal conductivities of PDMS, three-dimensional graphene/PDMS composite (before modification), and polypyrrole nanofiber modified three-dimensional graphene/PDMS composite (after modification).
Detailed Description
Referring to fig. 1 to 12, a preparation method of a polypyrrole nanowire interface modified three-dimensional graphene/PDMS composite photo-thermal material includes the following steps:
1. preparing foamed nickel loaded three-dimensional graphene: growing graphene by adopting a chemical vapor deposition method, using a nickel foam carrier and absolute ethyl alcohol as a carbon source, wherein the growth temperature is 850-900 ℃, and Ar/H2The carrier gas flow rate is 190-180/10-20 sccm, and the growth time is 20-40 min. The method specifically comprises the following steps: and preparing the three-dimensional graphene by adopting a chemical vapor deposition method. Firstly, cleaning foamed nickel, ultrasonically washing by adopting absolute ethyl alcohol, ultrasonically washing by adopting deionized water, and blow-drying by using nitrogen, air and argon for later use; removing metal oxide on the surface of the foamed nickel by high-temperature reduction, and using Ar/H2(100/100sccm) as carrier gas, and reducing at 1000 deg.C for 20 min; reducing the temperature of the tube furnace to 880 ℃, and adjusting Ar/H2With a flow rate of 190/10sccm, as shown in FIG. 1, valve 1 was closed, valves 2 and 3 were opened, and Ar/H was added2And introducing carrier gas above a closed container filled with absolute ethyl alcohol, and introducing the ethyl alcohol gas into a tubular furnace for graphene growth for 30 min. Naturally cooling to room temperature, and taking out the three-dimensional graphene loaded by the foamed nickel for later use.
2. Electrochemical oxidative polymerization of polypyrrole nanowires: taking the foamed nickel loaded three-dimensional graphene in the step 1 as a substrate, wherein the size of the foamed nickel loaded three-dimensional graphene is 1cm multiplied by 3cm, the thickness of the foamed nickel loaded three-dimensional graphene is 1.6mm, 50mL of electrolyte contains 20-40mg/mL of sodium perchlorate, 20-40mg/mL of sodium carbonate and 10-40mg/mL of pyrrole monomer, the electrolyte adopts a three-electrode system, and silver/silver chloride is used as a reference electrodeAnd the platinum sheet is a counter electrode, and the pyrrole nanowires are deposited by using a constant potential method of 1-1.5V. If the size of the foamed nickel-loaded three-dimensional graphene substrate is increased, the volume of the electrolyte in the electrolytic cell needs to ensure that the substrate can be completely soaked. The method specifically comprises the following steps: and preparing the polypyrrole nano-wire by electrochemical oxidative polymerization. The foamed nickel loaded three-dimensional graphene is used as a substrate, the size is 1cm multiplied by 3cm, and the thickness is 1.6 mm; 1mL of pyrrole monomer solution is added into 50mL of water containing 1g of sodium perchlorate and 0.5g of sodium carbonate solvent, and ultrasonic treatment is carried out for 30 min; adopts a three-electrode system, silver/silver chloride is used as a reference electrode, and the thickness of the silver/silver chloride is 1cm2The platinum sheet is used as a counter electrode, the pyrrole nanowires are accumulated at 1.2V by a potentiostatic method, the experiment is stopped after 15 minutes, and the solution is washed by deionized water for standby.
3. Preparing a self-supporting polypyrrole nanowire modified three-dimensional graphene material: soaking the foamed nickel-loaded three-dimensional graphene deposited with polypyrrole, obtained in the step 2, into a 2-5mol/L hydrochloric acid solution, and adding 10-40mg/mL ferric trichloride; soaking for 24 hours, after the nickel is completely etched, taking out the material, washing the material with deionized water until the pH value is neutral, obtaining the self-supporting polypyrrole nanowire modified three-dimensional graphene material, and drying at 40-100 ℃ for later use. If the size of the foamed nickel-loaded three-dimensional graphene substrate is increased, the volume of the electrolyte in the electrolytic cell needs to ensure that the material in the step 2 can be completely soaked in the solution. The method specifically comprises the following steps: and removing the foam nickel template, and preparing the self-supporting polypyrrole nanowire modified three-dimensional graphene material. And (3) soaking the polypyrrole-deposited foamed nickel-loaded three-dimensional graphene obtained in the step (2) into 50mL of a mixed solution of ferric trichloride and hydrochloric acid, wherein the concentration of the hydrochloric acid aqueous solution is 3mol/L, the concentration of the ferric trichloride is 20mg/mL, the soaking time is 24 hours, after the nickel is completely etched, taking out the material, washing the material with deionized water until the pH value is neutral, and drying the material at 50 ℃ for later use.
4. Preparing a polypyrrole nanowire interface modified three-dimensional graphene/PDMS composite material: placing a self-supporting polypyrrole nanowire modified three-dimensional graphene material in a mold, and mixing PDMS and a curing agent according to the proportion of 10: 1, vacuum filtering, defoaming, and curing at 50-80 ℃ for 12-24 hours to obtain the composite material. The method specifically comprises the following steps: weighing 5g of PDMS and 0.5g of curing agent, and mechanically stirring for 5min to obtain a mixture; placing the self-supporting polypyrrole nanowire modified three-dimensional graphene material in a 1.6mm deep mold, adding the PDMS mixture into the mold, performing vacuum treatment for defoaming, and curing at 60 ℃ for 24 hours to obtain the polypyrrole nanowire interface modified three-dimensional graphene/PDMS composite material.
The present embodiment is further explained below with reference to the drawings:
the absolute ethyl alcohol in fig. 1 is used as a carbon source for growth of the three-dimensional graphene, and a high-power scanning electron microscope picture in a b picture in fig. 2 shows that the three-dimensional graphene has a smooth surface, poor compatibility with a PDMS interface and weak binding force, so that in the stretching process, due to the crossed binding force between the three-dimensional graphene filler and the PDMS matrix, stress cannot be effectively transferred and dispersed, and the mechanical property of the composite material is limited. The raman spectrum in fig. 3 shows that the defect D band peak on the surface of the three-dimensional graphene is very weak, which indicates that the three-dimensional graphene is high-quality graphene, and the surface has no obvious structural defect, so that the interface compatibility with PDMS is poor. As shown in fig. 2, the surface of the three-dimensional graphene is smooth, but after a telephone deposition experiment, the scanning electron microscope picture of fig. 5 shows that the polypyrrole nanowires are uniformly grown on the surface of the three-dimensional graphene, such a winding structure of the wire stack is beneficial to the immersion of PDMS, and the polypyrrole nanowires are inserted into the matrix of the PDMS, and a mechanical interlocking structure is additionally provided, so that the bonding force of the interface is improved. Fig. 6 clearly shows that there is a cavity defect structure between the three-dimensional graphene and PDMS interface. Fig. 7 shows that the structure between the polypyrrole nanowire-modified three-dimensional graphene and PDMS interface is continuous, the cavity defect disappears, and a continuous interface phase is formed. The high-quality interface phase is beneficial to improving the mechanical, electrical and heat-conducting properties of the composite material. Fig. 8 is a schematic diagram of a discontinuous interface phase of an unmodified three-dimensional graphene and PDMS composite material, and a schematic diagram of a continuous interface phase of a polypyrrole nanowire-modified three-dimensional graphene and PDMS composite material. Fig. 9 shows that the tensile young's modulus of the polypyrrole nanowire modified three-dimensional graphene and PDMS composite material is significantly improved. Fig. 10 shows that the electrical conductivity of the modified composite after repeated bending was 238 s/m, which is significantly higher than the electrical conductivity of the unmodified composite. Fig. 11 shows that the absorption in the infrared region of the modified composite material is obviously enhanced, and infrared light can be effectively converted into heat energy. FIG. 12 shows that after the polypyrrole nanowires are modified, the thermal conductivity of the composite material is 0.49W/m.k, which is significantly higher than that of PDMS and an unmodified control group.
Claims (1)
1. A preparation method of a polypyrrole nanowire interface modified three-dimensional graphene/PDMS composite photo-thermal material is characterized by comprising the following steps:
step 1: the preparation method of the foamed nickel-loaded three-dimensional graphene comprises the following substeps:
step 1.1: cleaning foamed nickel, ultrasonically removing surface organic matters by adopting absolute ethyl alcohol, ultrasonically cleaning by using deionized water, and blow-drying by using nitrogen, argon or air for later use;
step 1.2: using Ar/H2The carrier gas has a carrier gas flow rate of 100/100sccm at 900-1000 sccmoReducing and removing the metal oxide on the surface of the foam nickel in the step 1.1 at the temperature of C;
step 1.3: adjusting the carrier gas flow rate and temperature, Ar/H, in step 1.22The carrier gas flow rate is 190-180/10-20 sccm, the growth temperature is 850-900 ℃, and Ar/H is introduced through a valve2Introducing carrier gas above a closed container filled with absolute ethyl alcohol, and bringing the ethyl alcohol gas into a tubular furnace for graphene growth, wherein the graphene growth time is 20-40 min;
step 1.4: cooling the tube furnace to room temperature, and keeping Ar/H in the cooling process2The flow rate of the carrier gas is 190-180/10-20 sccm, and the foamed nickel loaded three-dimensional graphene is obtained;
step 2: preparing polypyrrole nano wires: immersing the foamed nickel-loaded three-dimensional graphene in the step 1.4 serving as a substrate into electrolyte, and depositing pyrrole nanowires by using a potentiostatic method; the electrolyte in the step 2 comprises 20-40mg/mL of sodium perchlorate, 20-40mg/mL of sodium carbonate and 10-40mg/mL of pyrrole monomer; the electrolyte adopts a three-electrode system, silver/silver chloride is used as a reference electrode, a platinum sheet is used as a counter electrode, the pyrrole nanowires are deposited by using a potentiostatic method of 1-1.5V, and after the preparation is finished, deionized water is used for washing for later use;
and step 3: preparing a self-supporting polypyrrole nanowire modified three-dimensional graphene material: soaking the foamed nickel-loaded graphene and polypyrrole nanowire material in the step 2 serving as a substrate into a 2-5mol/L hydrochloric acid solution, and adding 10-40mg/mL ferric trichloride; soaking for 24 hours, after the nickel is completely etched, taking out the material, washing the material with deionized water until the pH value is neutral, obtaining the self-supporting polypyrrole nanowire modified three-dimensional graphene material, and drying at 40-100 ℃ for later use;
and 4, step 4: placing the self-supporting polypyrrole nanowire modified three-dimensional graphene material in the step 3 into a mold, and mixing PDMS (polydimethylsiloxane) and a curing agent according to the weight ratio of 10: 1, carrying out vacuum filtration and defoaming, and curing at 50-80 ℃ for 12-24 hours to obtain the polypyrrole nanowire interface modified three-dimensional graphene/PDMS composite material.
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