CN107892784B - Polymer-based nanocomposite and preparation method thereof - Google Patents
Polymer-based nanocomposite and preparation method thereof Download PDFInfo
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Abstract
The invention provides a polymer-based nano composite material and a preparation method thereof, belonging to the technical field of electronic composite materials. The formula volume ratio of the polymer-based nanocomposite material is as follows: 10-20% of carbon material filler coated with silver nanoparticles and 80-90% of polymer. The polymer-based nano composite material prepared by the invention has the remarkable advantages of high thermal conductivity, low dielectric constant, low dielectric loss and the like, and the preparation process is simple and easy to implement, has low cost and is very favorable for being applied to large-scale industrial production of electronic packaging materials.
Description
Technical Field
The invention belongs to the technical field of electronic composite materials, and particularly relates to a preparation method for coating metal nanoparticles on the surfaces of different carbon materials, a polymer-based nano composite material taking the carbon materials as a filler and a preparation method thereof.
Background
At present, heat conducting materials are used in the fields of electronic communication, heat exchange engineering application, heating engineering application, generator application and the like. The heat conducting materials mainly comprise metal materials and heat conducting polymer matrix composite materials. The heat-conducting polymer-based nano composite material is a great concern in the field of heat-conducting materials because of the advantages of corrosion resistance, light weight, low price, simple forming process and the like. However, the thermal conductivity of the polymer is very small, so that the selection and preparation of the filler with high thermal conductivity are the key points for improving the polymer-based nanocomposite material, so that the polymer-based nanocomposite material is comprehensively utilized and is more widely applied to the field of heat conduction materials.
Carbon materials are widely used in the field of functional materials due to their ultrahigh thermal conductivity and electrical conductivity. Materials such as multi-walled carbon nanotubes, single-walled carbon nanotubes, carbon nanofibers, graphite flakes, graphene and the like utilized in the research are also hot spots for the research of current heat conduction materials. At present, engineering application is already realized by using carbon materials as mobile phone heat dissipation materials, and how to improve the performance is also the key point of the next research.
Through the search of the literature, the literature and the patent which are the same as those of the invention are not found, and some patents and literatures similar to the experiment of coating the carbon nano tube by using the silver nano particles are searched, but most of the synthesized silver nano particles are coated on the surface of the carbon nano tube through mixing treatment, and the coated silver nano material has larger size, and the preparation principle of the filler is that the reduction and the coating of the silver nano particles are completed in one step, one material is simultaneously used as a reducing agent and a coupling agent, and the particle size of the silver nano particles is about 10nm, so that the preparation process greatly improves the preparation efficiency and reduces the cost. In previous studies, no similar preparation process was found. The following are patents that the applicant has searched for relating to the present invention:
wangzhecheng, Xuxun, Wuzhengtao, a composite conductive adhesive for electronic packaging and a preparation method thereof, application number: 201410059910.7, application publication number: CN 103805118A.
Disclosure of Invention
The invention aims to provide a polymer-based nano composite material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a polymer-based nano composite material is prepared by mixing a polymer serving as a matrix and a carbon material coated with silver nanoparticles serving as a filler, wherein the silver nanoparticles are obtained by direct reduction in a solution and are uniformly attached to the surface of the carbon material, and a silver nanoparticle coating layer is formed on the surface of the carbon material.
Furthermore, the volume fraction of the carbon material coated by the silver nanoparticles in the polymer-based nano composite material is 10-20%, and the volume fraction of the polymer matrix is 80-90%.
Further, the carbon material is a multi-wall carbon nanotube, a single-wall carbon nanotube, a carbon nanofiber, a graphite sheet, a graphene material and a mixed material of a plurality of carbon materials; the polymer matrix is epoxy resin, polyimide, polyvinyl alcohol, polyethylene, polypropylene, polyvinylidene fluoride or a copolymer thereof.
Further, the diameter of the multi-wall carbon nano tube is 30-50nm, the length of the multi-wall carbon nano tube is 1-2 mu m, the diameter of the single-wall carbon nano tube is 1nm-20nm, the length of the single-wall carbon nano tube is 1-2 mu m, the diameter of the carbon nano tube is 100-150 nm, the length of the carbon nano tube is 3-5 mu m, the thickness of the graphite flake is 200nm, the diameter of the graphite flake is 3-4 mu m, the thickness of the graphene is 2-5nm, the diameter of the graphene is 2-3 mu m, and the particle size of the silver nano particles of the coating layer is 5-10 nm.
Further, the carbon material coated with the silver nanoparticles is prepared by a sol-gel method, benzyl mercaptan is used as a coupling agent and a reducing agent, silver nitrate is used as a precursor of the silver nanoparticles, and the silver nanoparticles are directly reduced on the surface of the carbon material in a solution environment and are uniformly attached to the surface of the carbon material.
Further, the carbon material coated with the silver nanoparticles and the polymer matrix can be compounded by a powder direct blending method and a solution mixing method, and a measurable sample is prepared by a hot press molding process or a tape casting process.
A method for preparing the polymer-based nanocomposite material comprises the following steps:
the method comprises the following steps: respectively carrying out water bath ultrasonic dispersion treatment on the carbon material powder;
step two: preparing a coupling agent solution and a silver nanoparticle precursor solution;
step three: mixing a carbon material and a coupling agent solution, firstly carrying out magnetic stirring for five minutes, and then uniformly coating the coupling agent on the surface of the carbon material by using an ultrasonic dispersion method to form a coupling agent coating layer;
step four: dropwise adding the silver nanoparticle precursor solution into the mixed solution by using a sol-gel method, and uniformly mixing;
step five: magnetically stirring the mixed solution for 48 hours to fully react, after the reaction is finished, centrifuging the obtained mixed solution, washing the mixed solution for 3 to 5 times by using an ethanol solution, and then drying the mixed solution in a drying oven at the temperature of 60 ℃ for 12 hours to obtain a carbon material coated with silver nanoparticles;
step six: mixing the carbon material powder obtained in the fifth step with a polymer matrix, selecting a powder direct blending method to uniformly mix the matrix and the filler, adding the mixed powder into a hot-pressing grinding tool by using a hot-pressing forming process, heating and then carrying out pressure-maintaining forming to obtain a polymer-based composite material;
step seven: after the fifth step, the obtained carbon material powder and the water-soluble polymer matrix can be mixed in a solution environment by adopting a solution mixing method, and then a film sample is prepared by utilizing a casting method.
Further, the sol-gel method is a method for preparing a nano material in a liquid environment, and comprises the steps of adding a reaction precursor and a reducing agent material one by one in an ethanol solution environment at normal temperature or under a heating condition, and fully mixing and reacting reactants by using a magnetic stirring method.
Further, the solvent is a 99.7% absolute ethyl alcohol organic solvent, the silver nanoparticle precursor is a silver nitrate solution, and the coupling agent and the reducing agent are benzyl mercaptan solutions.
Further, the hot-press molding process comprises the following steps: adding the mixed powder into a hot-pressing die, applying 50MPa pressure in an environment with the temperature of 250 ℃, and maintaining the pressure for 25 minutes.
The preparation principle of the filler is that the reduction and coating of the silver nanoparticles are completed in one step, benzyl mercaptan is used as a reducing agent and a coupling agent, and the particle size of the silver nanoparticles is 5-10nm, so that the preparation process greatly improves the preparation efficiency and reduces the cost.
The invention has the beneficial effects that:
according to the invention, the carbon material is coated with the silver nanoparticles on the surface, so that the dispersibility of the carbon material serving as a filler in the polymer-based nano composite material and the compatibility of the carbon material with a polymer matrix are improved, and the thermal conductivity of the polymer-based nano composite material is improved. On the other hand, a method of mixing and adding a one-dimensional two-dimensional carbon material is adopted, and basically internal interaction links of the polymer are formed to form an effective heat conduction path, so that the heat conductivity of the composite material is greatly improved.
The polymer-based nano composite material prepared by the invention has the remarkable advantages of high thermal conductivity, low dielectric constant, low dielectric loss and the like. The preparation process is simple and easy to implement, the chemical synthesis process is basically completed at normal temperature, the cost is low, and the possibility is brought to industrial scale production (such as industrial production of electronic packaging materials) and application.
Drawings
Fig. 1 is a TEM microstructure photograph of multi-walled carbon nanotubes coated with silver nanoparticles prepared in example 1.
Fig. 2 is a TEM microstructure photograph of the graphene sheet coated with silver nanoparticles prepared in example 4.
Detailed Description
The invention is further illustrated below with reference to the examples. It should be noted that the present invention is not limited to the following embodiments according to the technical solution of the present invention, and those skilled in the art can make some insubstantial modifications and adjustments to the present invention based on the following contents to achieve the object of the present invention.
Example 1:
in the embodiment, PVA (polyvinyl alcohol) is used as a polymer matrix, and a multi-walled carbon nanotube coated with silver nanoparticles is used as a filler to prepare a polymer-based nanocomposite material, wherein the composite material is calculated and weighed, wherein the polymer matrix accounts for 90% by volume and the filler accounts for 10% by volume. The preparation method comprises the following steps:
1) weighing 50mg of multi-walled carbon nanotubes, determining that the multi-walled carbon nanotubes contain no impurities through XRD test analysis, determining that the diameter of the carbon nanotubes is 10nm through SEM scanning analysis, dissolving the multi-walled carbon nanotubes in 100mL of absolute ethyl alcohol, and performing ultrasonic dispersion for 1h under 560W power;
2) preparing a silver nitrate solution: weighing 1.336g of silver nitrate solid, and weighing 400mL of absolute ethyl alcohol as a solvent to prepare a silver nitrate ethanol solution with the concentration of 0.02M for later use;
3) preparing a benzyl mercaptan solution: measuring 20 mul (about 1 drop) of benzyl mercaptan liquid, measuring 7mL of absolute ethyl alcohol, dropwise adding the benzyl mercaptan liquid into the absolute ethyl alcohol, and uniformly stirring to obtain a benzyl mercaptan solution for later use;
4) mixing the prepared silver nitrate solution and benzyl mercaptan solution, and magnetically stirring for 48 hours at normal temperature at the rotating speed of 600 rpm;
5) adding the dispersed multi-walled carbon nanotube alcohol solution into the mixed solution prepared in the step (4), magnetically stirring for 15min, and then placing the mixed solution in a water bath ultrasonic environment for treatment for 6h with the ultrasonic power of 200 w;
6) centrifuging the mixed solution obtained in the step (5), and washing for 3 times by using absolute ethyl alcohol;
7) filtering the mixed solution through a PTFE membrane (0.22 mu m) in the step (6), and then performing vacuum drying treatment on the solid obtained through filtering to obtain a multi-wall carbon nanotube powder sample coated with silver nanoparticles (with the diameter of 5 nm);
8) weighing 3g of PVA solid, heating in an oil bath at the temperature of 95 ℃ to dissolve the PVA solid in deionized water to prepare 50mL of PVA solution, and standing until bubbles disappear for later use;
9) adding the filler powder obtained in the step (7) into the PVA solution prepared in the step (8), magnetically stirring for 30min, then carrying out ultrasonic treatment for 1h to uniformly mix the filler in the PVA matrix, and standing until bubbles disappear to carry out molding and sample preparation;
10) and (4) forming the polymer-based mixed solution obtained in the step (9) by a tape casting method, and drying at 50 ℃ to obtain a film sample of the polymer-based nanocomposite.
In the embodiment, benzyl mercaptan is used as a coupling agent and a reducing agent for silver nanoparticles, absolute ethyl alcohol is used as a reaction solvent, a multi-walled carbon nanotube material coated by the silver nanoparticles is prepared through reaction, and the multi-walled carbon nanotube material is used as a filler and PVA is used as a polymer matrix to prepare the multi-walled carbon nanotube-silver nanoparticles/PVA composite material.
A TEM microstructure photograph of the multi-walled carbon nanotube material in which silver nanoparticles are coated is shown in fig. 1.
The dispersibility of the multiwalled carbon nanotube filler coated by the silver nanoparticles in the polymer matrix applied in the polymer-based nanocomposite material with the structure is obviously superior to that of the multiwalled carbon nanotube material which is not coated. And the good dispersion performance of the filler in the polymer matrix also enables the filler to form a connecting and interacting heat conduction path in the matrix well, so that the overall heat conduction performance is improved. Through the test and analysis of the thermal conductivity coefficient of the sample, the thermal conductivity of the polymer-based nano composite material can reach 11.2W/mK.
Example 2:
in the embodiment, the PVA is used as the polymer matrix, the silver nanoparticle-coated single-walled carbon nanotube is used as the filler, the polymer-based nanocomposite material is prepared, the volume fraction of the polymer matrix in the composite material is 80%, the volume fraction of the filler is 20%, and the composite material is weighed in a conversion manner. The preparation method comprises the following steps:
1) weighing 50mg of single-walled carbon nanotubes, determining that the single-walled carbon nanotubes contain no impurities through XRD test analysis, determining that the diameter of the single-walled carbon nanotubes is 10nm through SEM scanning analysis, dissolving the single-walled carbon nanotubes in 100mL of absolute ethyl alcohol, and ultrasonically dispersing for 1h under 560W power;
2) preparing a silver nitrate solution: weighing 1.336g of silver nitrate solid, and weighing 400mL of absolute ethyl alcohol as a solvent to prepare a silver nitrate ethanol solution with the concentration of 0.02M for later use;
3) preparing a benzyl mercaptan solution: measuring 20 mul (about 1 drop) of benzyl mercaptan liquid, measuring 7mL of absolute ethyl alcohol, dropwise adding the benzyl mercaptan liquid into the absolute ethyl alcohol, and uniformly stirring to obtain a benzyl mercaptan solution for later use;
4) mixing the prepared silver nitrate solution and benzyl mercaptan solution, and magnetically stirring for 48 hours at normal temperature at the rotating speed of 600 rpm;
5) adding the dispersed single-walled carbon nanotube alcohol solution into the mixed solution prepared in the step (4), magnetically stirring for 15min, and then placing the mixed solution in a water bath ultrasonic environment for treatment for 6h with the ultrasonic power of 200 w;
6) centrifuging the mixed solution obtained in the step (5), and washing with absolute ethyl alcohol for 4 times;
7) filtering the mixed solution through a PTFE membrane (0.22 mu m) in the step (6), and then carrying out vacuum drying treatment on the solid obtained through filtering to obtain a single-walled carbon nanotube powder sample coated by silver nanoparticles (5 nm);
8) weighing 3g of PVA solid, heating in an oil bath at the temperature of 95 ℃ to dissolve the PVA solid in deionized water to prepare 50mL of PVA solution, and standing until bubbles disappear for later use;
9) adding the filler powder obtained in the step (7) into the PVA solution prepared in the step (8), magnetically stirring for 30min, then carrying out ultrasonic treatment for 1h to uniformly mix the filler in the PVA matrix, and standing until bubbles disappear to carry out molding and sample preparation;
10) and (4) forming the polymer-based mixed solution obtained in the step (9) by a tape casting method, and drying at 50 ℃ to obtain a film sample of the polymer-based nanocomposite.
After the preparation process of example 2, the silver nanoparticle coated single-walled carbon nanotube/PVA composite material was obtained.
Example 3:
in the embodiment, the PVA is used as the polymer matrix, the nano carbon fiber coated with the silver nano particles is used as the filler, the polymer matrix in the composite material accounts for 80% by volume, and the filler accounts for 20% by volume, and the composite material is prepared by conversion and weighing. The preparation method comprises the following steps:
1) weighing 50mg of carbon nanofibers, determining that the carbon nanotubes contain no impurities through XRD test analysis, determining that the diameter of the carbon nanotubes is 10nm through SEM scanning analysis, dissolving the carbon nanofibers in 100mL of absolute ethyl alcohol, and performing ultrasonic dispersion for 1h under 560W of power;
2) preparing a silver nitrate solution: weighing 1.336g of silver nitrate solid, and weighing 400mL of absolute ethyl alcohol as a solvent to prepare a silver nitrate ethanol solution with the concentration of 0.02M for later use;
3) preparing a benzyl mercaptan solution: measuring 20 mul (about 1 drop) of benzyl mercaptan liquid, measuring 7mL of absolute ethyl alcohol, dropwise adding the benzyl mercaptan liquid into the absolute ethyl alcohol, and uniformly stirring to obtain a benzyl mercaptan solution for later use;
4) mixing the prepared silver nitrate solution and benzyl mercaptan solution, and magnetically stirring for 48 hours at normal temperature at the rotating speed of 600 rpm;
5) adding the dispersed carbon nanofiber alcohol solution into the mixed solution prepared in the step (4), magnetically stirring for 15min, and then placing the mixed solution in a water bath ultrasonic environment for treatment for 6h with the ultrasonic power of 200 w;
6) centrifuging the mixed solution obtained in the step (5), and washing the mixed solution for 5 times by using absolute ethyl alcohol;
7) filtering the mixed solution through a PTFE membrane (0.22 mu m) in the step (6), and then performing vacuum drying treatment on the solid obtained through filtering to obtain a nano carbon fiber powder sample coated by silver nano particles (10 nm);
8) weighing 3g of PVA solid, heating in an oil bath at the temperature of 95 ℃ to dissolve the PVA solid in deionized water to prepare 50mL of PVA solution, and standing until bubbles disappear for later use;
9) adding the filler powder obtained in the step (7) into the PVA solution prepared in the step (8), magnetically stirring for 30min, then carrying out ultrasonic treatment for 1h to uniformly mix the filler in the PVA matrix, and standing until bubbles disappear to carry out molding and sample preparation;
10) and (4) forming the polymer-based mixed solution obtained in the step (9) by a tape casting method, and drying at 50 ℃ to obtain a film sample of the polymer-based nanocomposite.
The carbon nanofiber/PVA composite material coated with silver nanoparticles was obtained through the preparation process of example 3.
Example 4:
in this embodiment, a polymer-based nanocomposite is prepared by using PI (polyimide) as a matrix and using a two-dimensional graphene material coated with silver nanoparticles as a filler, where the volume fraction of the polymer matrix in the composite is 80%, and the volume fraction of the filler is 20%, and the polymer-based nanocomposite is calculated and weighed. The preparation method comprises the following steps:
1) weighing 50mg of graphene powder, determining that the graphene powder does not contain impurities through XRD test analysis, determining that the thickness of the graphene material is 9nm through SEM scanning analysis, dissolving the graphene powder in 100mL of absolute ethyl alcohol, and performing ultrasonic dispersion for 1h under 560W power;
2) preparing a silver nitrate solution: weighing 1.336g of silver nitrate solid, and weighing 400mL of absolute ethyl alcohol as a solvent to prepare a silver nitrate ethanol solution with the concentration of 0.02M for later use;
3) preparing a benzyl mercaptan solution: measuring 20 mul (about 1 drop) of benzyl mercaptan liquid, measuring 7mL of absolute ethyl alcohol, dropwise adding the benzyl mercaptan liquid into the absolute ethyl alcohol, and uniformly stirring to obtain a benzyl mercaptan solution for later use;
4) mixing the prepared silver nitrate solution and benzyl mercaptan solution, and magnetically stirring for 48 hours at normal temperature at the rotating speed of 600 rpm;
5) adding the well dispersed graphene powder alcohol solution into the mixed solution prepared in the step (4), magnetically stirring for 15min, and then placing the mixed solution in a water bath ultrasonic environment for treatment for 6h with ultrasonic power of 200 w;
6) centrifuging the mixed solution obtained in the step (5), and washing for 3 times by using absolute ethyl alcohol;
7) filtering the mixed solution through a PTFE membrane (0.22 mu m) in the step (6), and then performing vacuum drying treatment on the solid obtained through filtering to obtain a graphene powder sample coated by silver nanoparticles (10 nm);
8) weighing 3g of PI solid, grinding and mixing the filler powder obtained in the step (7) and PI, placing the mixture in a die, hot-pressing the mixture on a press at the temperature of 250 ℃ and the pressure of 50MPa for 25 minutes, and obtaining the graphene-silver nanoparticle/PI polymer matrix added nano composite material after hot-press molding.
After the preparation process of embodiment 4, the graphene/PI composite material coated with the silver nanoparticles is obtained, wherein a TEM microstructure photograph of the graphene material coated with the silver nanoparticles is shown in fig. 2.
Example 5:
in this embodiment, the polymer-based nanocomposite is prepared by using PI as a matrix and using a graphite sheet coated with silver nanoparticles as a filler, where a volume fraction of the polymer matrix in the composite is 80% and a volume fraction of the filler is 20%, where each station of graphene and multi-walled carbon nanotubes is 10%, and the graphene and the multi-walled carbon nanotubes are converted and weighed. The preparation method comprises the following steps:
1) weighing 25mg of graphite powder, respectively determining that the graphite powder does not contain impurities through XRD test analysis, mixing the graphite powder, dissolving the graphite powder in 100mL of absolute ethyl alcohol, and ultrasonically dispersing for 1h under 560W power;
2) preparing a silver nitrate solution: weighing 1.336g of silver nitrate solid, and weighing 400mL of absolute ethyl alcohol as a solvent to prepare a silver nitrate ethanol solution with the concentration of 0.02M for later use;
3) preparing a benzyl mercaptan solution: measuring 20 mul (about 1 drop) of benzyl mercaptan liquid, measuring 7mL of absolute ethyl alcohol, dropwise adding the benzyl mercaptan liquid into the absolute ethyl alcohol, and uniformly stirring to obtain a benzyl mercaptan solution for later use;
4) mixing the prepared silver nitrate solution and benzyl mercaptan solution, and magnetically stirring for 48 hours at normal temperature at the rotating speed of 600 rpm;
5) adding the alcohol solution of the dispersed graphite flakes into the mixed solution prepared in the step (4), magnetically stirring for 15min, and then placing the mixed solution in a water bath ultrasonic environment for treatment for 6h with ultrasonic power of 200 w;
6) centrifuging the mixed solution obtained in the step (5), and washing with absolute ethyl alcohol for 4 times;
7) after the step (6), filtering the mixed solution through a PTFE membrane (0.22 mu m), and then performing vacuum drying treatment on the solid obtained through filtering to obtain a graphite powder sample subjected to silver nanoparticle coating treatment;
8) weighing 3g of PI solid, grinding and mixing the mixed filler powder obtained in the step (7) with PI, placing the mixture in a die, hot-pressing the mixture on a press at the temperature of 250 ℃ and the pressure of 50MPa for 25 minutes, and obtaining the polymer-based nanocomposite material with the 1-2 composite structure added with the graphite/silver nanoparticles/PI after hot-press molding.
After the preparation process of example 5, the graphite/PI composite material coated with silver nanoparticles was obtained.
Example 6:
in this embodiment, the polymer-based nanocomposite is prepared by using PI as a matrix and using a two-dimensional graphene material coated with silver nanoparticles and a one-dimensional multi-walled carbon nanotube as a filler, where a volume fraction of the polymer matrix in the composite is 80% and a volume fraction of the filler is 20%, and each of the graphene and the multi-walled carbon nanotube is 10% and weighed through conversion. The preparation method comprises the following steps:
1) weighing 25mg of each of graphene and multi-walled carbon nanotube powder, respectively determining that the graphene and multi-walled carbon nanotube powder do not contain impurities through XRD test analysis, mixing the graphene and multi-walled carbon nanotube powder, dissolving the mixture in 100mL of absolute ethyl alcohol, and ultrasonically dispersing the mixture for 1h under 560W power;
2) preparing a silver nitrate solution: weighing 1.336g of silver nitrate solid, and weighing 400mL of absolute ethyl alcohol as a solvent to prepare a silver nitrate ethanol solution with the concentration of 0.02M for later use;
3) preparing a benzyl mercaptan solution: measuring 20 mul (about 1 drop) of benzyl mercaptan liquid, measuring 7mL of absolute ethyl alcohol, dropwise adding the benzyl mercaptan liquid into the absolute ethyl alcohol, and uniformly stirring to obtain a benzyl mercaptan solution for later use;
4) mixing the prepared silver nitrate solution and benzyl mercaptan solution, and magnetically stirring for 48 hours at normal temperature at the rotating speed of 600 rpm;
5) adding an alcohol solution mixed with the dispersed graphene and the multi-walled carbon nanotubes into the mixed solution prepared in the step (4), magnetically stirring for 15min, and then placing the mixed solution in a water bath ultrasonic environment for treatment for 6h with the ultrasonic power of 200 w;
6) centrifuging the mixed solution obtained in the step (5), and washing for 3 times by using absolute ethyl alcohol;
7) after the step (6), filtering the mixed solution through a PTFE membrane (0.22 mu m), and then performing vacuum drying treatment on the solid obtained through filtering to obtain a graphene and multi-wall carbon nanotube powder sample coated by silver nanoparticles;
8) weighing 3g of PI solid, grinding and mixing the mixed filler powder obtained in the step (7) with PI, placing the mixture in a die, hot-pressing the mixture on a press at the temperature of 250 ℃ and the pressure of 50MPa for 25 minutes, and obtaining the polymer-based nanocomposite material with the 1-2 composite structure of the multi-walled carbon nano tube/silver nano particle-graphene/silver nano particle/PI after hot-press molding.
In this embodiment, on one hand, the carbon material coated with the silver nanoparticles described in embodiments 1 and 4 is combined, so that the dispersibility of the carbon material in the polymer matrix can be improved, and on the other hand, the carbon material with one-dimensional and two-dimensional structures is added at the same time, so that the two-dimensional material can form a heat conduction path in the polymer matrix, and the one-dimensional material plays a role in mutual connection between two-dimensional graphenes, so that the filler integrally forms an effective three-dimensional heat conduction path, thereby effectively improving the heat conduction performance of the composite material. Through test and analysis on the thermal conductivity of the sample, the thermal conductivity of the multi-walled carbon nanotube/silver nanoparticle-graphene/silver nanoparticle/PI composite material can reach 6W/mK.
Many examples can be listed in the above embodiments, and details are not repeated here, so long as the carbon material and the carbon material are different, or the inorganic material with different high thermal conductivity is used as the filler, and the organic solvent and the polymer matrix in the preparation process can be prepared into polymer-based nanocomposite materials with different microstructures and different filler materials within the process parameters given by the preparation method.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (7)
1. A method for preparing a polymer-based nanocomposite, comprising the steps of:
the method comprises the following steps: respectively carrying out water bath ultrasonic dispersion treatment on the carbon material powder;
step two: preparing a coupling agent solution and a silver nanoparticle precursor solution, wherein the silver nanoparticle precursor is silver nitrate;
step three: mixing a carbon material and a coupling agent solution, firstly carrying out magnetic stirring for five minutes, and then uniformly coating the coupling agent on the surface of the carbon material by using an ultrasonic dispersion method to form a coupling agent coating layer; the coupling agent is benzyl mercaptan, and the benzyl mercaptan is also used as a reducing agent;
step four: dropwise adding the silver nanoparticle precursor solution into the mixed solution by using a sol-gel method, and uniformly mixing;
step five: magnetically stirring the mixed solution for 48 hours to fully react, after the reaction is finished, centrifuging the obtained mixed solution, washing the mixed solution for 3 to 5 times by using an ethanol solution, and then drying the mixed solution in a drying oven at the temperature of 60 ℃ for 12 hours to obtain a carbon material coated with silver nanoparticles; namely, under the environment of solution, silver nanoparticles are directly reduced on the surface of the carbon material and are uniformly attached to the surface of the carbon material;
step six: mixing the carbon material powder obtained in the fifth step with a polymer matrix, selecting a powder direct blending method to uniformly mix the matrix and the filler, adding the mixed powder into a hot-pressing grinding tool by using a hot-pressing forming process, heating and then carrying out pressure-maintaining forming to obtain a polymer-based composite material;
step seven: after the fifth step, the obtained carbon material powder and the water-soluble polymer matrix can be mixed in a solution environment by adopting a solution mixing method, and then a film sample is prepared by utilizing a tape casting method;
the carbon material is a multi-wall carbon nanotube, a single-wall carbon nanotube, a carbon nanofiber, a graphite flake, a graphene material and a mixed material of a plurality of carbon materials; the polymer matrix is polyimide or polyvinyl alcohol.
2. The method for preparing the polymer-based nanocomposite material according to claim 1, wherein the volume fraction of the carbon material coated with the silver nanoparticles in the polymer-based nanocomposite material is 10 to 20%, and the volume fraction of the polymer matrix is 80 to 90%.
3. The preparation method of the polymer-based nanocomposite material according to claim 2, wherein the diameter of the multi-walled carbon nanotube is 30-50nm, the length of the multi-walled carbon nanotube is 1-2 μm, the diameter of the single-walled carbon nanotube is 1nm-20nm, the length of the single-walled carbon nanotube is 1-2 μm, the diameter of the carbon nanofiber is 100-150 nm, the length of the carbon nanofiber is 3-5 μm, the thickness of the graphite flake is 200nm, the diameter of the graphite flake is 3-4 μm, the thickness of the graphene is 2-5nm, the diameter of the graphene is 2-3 μm, and the particle size of the silver nanoparticle of the coating layer is 5-10 nm.
4. The method for preparing the polymer-based nanocomposite material as claimed in claim 1, wherein the carbon material coated with the silver nanoparticles and the polymer matrix are compounded by a powder direct blending method or a solution mixing method, and a measurable sample is prepared by a hot press molding process or a tape casting process.
5. The method for preparing a polymer-based nanocomposite as claimed in claim 1, wherein the sol-gel method is a method for preparing a nanomaterial in a liquid environment, and comprises the steps of adding a reaction precursor and a reducing agent material one by one in an ethanol solution environment under normal temperature or heating conditions, and sufficiently mixing and reacting reactants by a magnetic stirring method.
6. The method for preparing a polymer-based nanocomposite material according to claim 1, wherein in the second step, a coupling agent solution and a silver nanoparticle precursor solution are prepared by using 99.7% absolute ethyl alcohol as a solvent.
7. The method for preparing polymer-based nanocomposite material according to claim 1, wherein the hot press molding process comprises the steps of: adding the mixed powder into a hot-pressing die, applying 50MPa pressure in an environment with the temperature of 250 ℃, and maintaining the pressure for 25 minutes.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102758264A (en) * | 2011-04-28 | 2012-10-31 | 中国科学院化学研究所 | Polymer nanofiber and preparation method and application of functional/hybrid material thereof |
| WO2016069220A1 (en) * | 2014-10-29 | 2016-05-06 | Arisdyne Systems, Inc. | Process for dispersing particles in filled resin compositions |
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| CN102181168B (en) * | 2011-03-08 | 2014-01-22 | 东莞华科电子有限公司 | Polymer matrix composite material and production method of polymer matrix composite material |
| CN104710733B (en) * | 2015-04-07 | 2016-09-07 | 嘉兴学院 | A kind of heat-resistance antibacterial poly-lactic acid material and preparation method thereof |
| CN104830031B (en) * | 2015-05-15 | 2018-11-02 | 华中科技大学 | A kind of epoxy resin composite material and preparation method thereof having both heat conduction and antistatic property |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102758264A (en) * | 2011-04-28 | 2012-10-31 | 中国科学院化学研究所 | Polymer nanofiber and preparation method and application of functional/hybrid material thereof |
| WO2016069220A1 (en) * | 2014-10-29 | 2016-05-06 | Arisdyne Systems, Inc. | Process for dispersing particles in filled resin compositions |
Non-Patent Citations (1)
| Title |
|---|
| 《石墨烯/无机纳米颗粒复合材料的制备及性能研究》;施闽;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;清华控股有限公司;20130331(第3期);B020-116 * |
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