CN112969356A - Preparation method of polyurethane/graphene nanosheet/sponge composite material - Google Patents
Preparation method of polyurethane/graphene nanosheet/sponge composite material Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 118
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000002135 nanosheet Substances 0.000 title claims abstract description 99
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 33
- 239000004814 polyurethane Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 45
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims abstract description 38
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 230000006835 compression Effects 0.000 abstract description 11
- 238000007906 compression Methods 0.000 abstract description 11
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- 230000002238 attenuated effect Effects 0.000 abstract description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 20
- 239000002064 nanoplatelet Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 11
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- 239000006260 foam Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
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- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- CRBHXDCYXIISFC-UHFFFAOYSA-N 2-(Trimethylammonio)ethanolate Chemical compound C[N+](C)(C)CC[O-] CRBHXDCYXIISFC-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0088—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a plurality of shielding layers; combining different shielding material structure
Abstract
The invention discloses a preparation method of a polyurethane/graphene nanosheet/sponge composite material, which comprises the following steps: dispersing graphene nanosheets serving as solutes into deionized water, and stirring and ultrasonically treating to obtain a graphene nanosheet water dispersion solution; then soaking the cuboid nano sponge into the graphene nanosheet solution, ultrasonically dispersing for several times, and drying to obtain a nano sponge material wrapped by the graphene nanosheets; and finally, wrapping the nano sponge material wrapped by the graphene nanosheets with thermoplastic polyurethane to obtain the polyurethane/graphene nanosheet/sponge composite material. The graphene nanosheets wrap the nano sponge to form a conductive network porous structure, so that electromagnetic waves can be attenuated through electrical loss. Due to the protection of the thermoplastic polyurethane layer and the inherent elasticity of the nano-sponge, the prepared composite material has excellent electromagnetic shielding performance even if subjected to severe physical and chemical damages and long-term compression cycles.
Description
Technical Field
The invention belongs to the technical field of composite material preparation, and particularly relates to a preparation method of a polyurethane/graphene nanosheet/sponge composite material.
Background
Is urgently neededHigh-performance electromagnetic shielding interference materials are needed to eliminate increasingly serious electromagnetic radiation caused by the explosive development of electronic equipment, and the electromagnetic radiation can cause adverse effects on human health and the electronic equipment. Although metals are considered to be the best electromagnetic shielding materials due to excellent conductivity, their application is severely restricted by the disadvantages of easy oxidation, easy corrosion, high density, high processing cost, environmental pollution, and the like. In recent years, the conductive polymer composite material is considered as the most promising electromagnetic shielding material due to the advantages of corrosion resistance, design flexibility, easy processing, low density and the like, particularly high wave-absorbing performance. Generally, conductive polymer composites require large amounts of fillers to achieve satisfactory electromagnetic shielding performance, which greatly sacrifices their mechanical and processing properties. Therefore, it is important to obtain an efficient EMI shielding material at a low loading. One strategy to address this problem is to build a three-dimensional conductive network in a conductive polymer composite. Graphene is an ideal filler for building such a conductive network due to its high conductivity and large aspect ratio. However, the preparation methods commonly used at present, such as electrodeposition, chemical vapor deposition, supercritical CO2Foaming and the like, the process is complex and time-consuming, and the requirement of large-scale production is difficult to meet. Meanwhile, since the carbon material has poor compressibility and elasticity, it is difficult to synthesize a stable 3D structure, which is easily collapsed and deformed when compressed, which severely limits further practical applications. Therefore, the development of a simple and economical three-dimensional electromagnetic shielding material with high electromagnetic shielding performance and deformation resistance is still a long-standing task.
In recent years, commercially available cellular materials, such as nanosponges, polyurethane foams and melamine foams, have received great attention from the scientific and industrial community because of their interconnected three-dimensional framework and open pore structure. Due to the porous structure of the foam, the low-cost foam can be used as a template, and a 3D conductive network with better performance is prepared by a simpler method. The electromagnetic shielding material not only needs to seek excellent electromagnetic shielding performance, but also needs to consider various complex environments. Therefore, it is a current goal to uniformly distribute the filler at a thin thickness to form a robust conductive network to achieve excellent electromagnetic shielding performance.
Disclosure of Invention
The invention aims to provide a preparation method of a polyurethane/graphene nanosheet/sponge composite material, and solves the problem of poor electromagnetic shielding property of the existing porous material.
The technical scheme adopted by the invention is that the preparation method of the polyurethane/graphene nanosheet/sponge composite material is implemented according to the following steps:
and 3, wrapping the nano sponge material wrapped by the graphene nanosheets with thermoplastic polyurethane to obtain the polyurethane/graphene nanosheet/sponge composite material.
The present invention is also characterized in that,
in the step 1, the mass ratio of the graphene nanosheets to the deionized water is 1: 100, respectively; the ultrasonic treatment time is 30min-1 h.
In the step 2, the drying temperature is 60-70 ℃, and the drying time is 10-30 min; the size of the cuboid nanosponges was 22.58mm 10.14mm 2 mm.
In the step 2, the ultrasonic dispersion times are 1-3; the time of ultrasonic dispersion is 30min-1h each time.
In step 3, the method specifically comprises the following steps: and (3) dripping a thermoplastic polyurethane solution on the upper surface of the nano sponge material wrapped by the graphene nanosheets, and allowing the thermoplastic polyurethane solution to enter the nano sponge material through natural permeation to obtain the polyurethane/graphene nanosheets/sponge composite material.
The thermoplastic polyurethane solution is prepared from the following components in percentage by mass of 1: 9, mixing the thermoplastic polyurethane particles with water; the mass ratio of the thermoplastic polyurethane solution to the nano sponge material wrapped by the graphene nanosheets is 250: 1.
the invention has the beneficial effects that:
in the method, the conductivity of the graphene nanosheet is utilized to perform an electrical loss on the electromagnetic wave, so that the electromagnetic shielding performance of the electromagnetic wave is improved. Meanwhile, the impedance matching of the interface is reduced by utilizing the porous structure of the nano sponge, so that the electromagnetic waves can better enter the composite material; the electromagnetic wave is reflected and scattered for many times by utilizing the internal porous structure, so that the electromagnetic shielding performance of the composite material is improved; the graphene nanosheets wrap the nano sponge to form a conductive network porous structure, so that electromagnetic waves can be attenuated through electrical loss. Finally, due to the protection of the thermoplastic polyurethane layer and the inherent elasticity of the nanosponges, the prepared composite material has excellent electromagnetic shielding properties even after being subjected to severe physical and chemical damage and long-term compression cycles. In addition, the method has the advantages of simple preparation process, quick operation and low production cost.
Drawings
FIG. 1 is an SEM image of a nanosponge of the present invention;
fig. 2 is a low-magnification SEM image of the graphene nanoplatelet-coated nanosponent prepared in example 1;
fig. 3 is a high-magnification SEM image of the graphene nanoplatelet-coated nanosponent prepared in example 1;
fig. 4 is a low-magnification SEM image of the graphene nanoplatelet-coated nanosponsive material prepared in example 2;
fig. 5 is a high-magnification SEM image of the graphene nanoplatelet-coated nanosponsive material prepared in example 2;
fig. 6 is a low-magnification SEM image of the graphene nanoplatelet-coated nanosponsive material prepared in example 3;
fig. 7 is a high-magnification SEM image of the graphene nanoplatelet-coated nanosponsive material prepared in example 3;
fig. 8 is an SEM image of the polyurethane/graphene nanoplatelet/sponge composite prepared in example 1;
fig. 9 is an SEM image of the polyurethane/graphene nanosheet/sponge composite prepared in example 2;
fig. 10 is an SEM image of the polyurethane/graphene nanoplatelet/sponge composite prepared in example 3;
FIG. 11 is a graph of the conductivity and resistance of the composites prepared in examples 1-3 as a function of ultrasonic cycling;
FIG. 12 is a bar graph of absorption efficiency as a function of ultrasonic cycle number for composites prepared in examples 1-3;
FIG. 13 is a graph of the EMI SE of the composite prepared in example 3 before and after 100 compression-release cycles.
Detailed Description
The present invention will be described in detail with reference to the following detailed description and accompanying drawings.
The invention relates to a preparation method of a polyurethane/graphene nanosheet/sponge composite material, which is implemented according to the following steps:
the average thickness of the graphene nano-sheet is less than 30nm, and the specific surface area is 60m2(ii)/g, provided by Xiamen Konna graphene Co., Ltd.;
the mass ratio of the graphene nanosheets to the deionized water is 1: 100, respectively; the ultrasonic treatment time is 30min-1 h;
the nanometer sponge is provided by Beijing Kolin American high-tech materials Co;
the drying temperature is 60-70 ℃, and the drying time is 10-30 min;
the number of ultrasonic dispersion is 1-3; the time of ultrasonic dispersion is 30min-1h each time;
the size of the cuboid nano sponge is 22.58mm x 10.14mm x 2 mm;
the method specifically comprises the following steps: the thermoplastic polyurethane solution is dripped on the upper surface of the nano sponge material wrapped by the graphene nanosheets and enters the nano sponge material through natural permeation, so that the thermoplastic polyurethane wraps the nano sponge material loaded with the graphene nanosheets to prevent the graphene nanosheets from falling off, and the polyurethane/graphene nanosheets/sponge composite material can be obtained;
the thermoplastic polyurethane solution is prepared from the following components in percentage by mass of 1: 9, mixing the thermoplastic polyurethane particles with water;
the mass ratio of the thermoplastic polyurethane solution to the nano sponge material wrapped by the graphene nanosheets is 250: 1;
the thermoplastic polyurethane particles had a hardness of S58A and a density of 1.21g/cm3Supplied by the Lodvishhong Basff group, Germany.
Example 1
The invention relates to a preparation method of a polyurethane/graphene nanosheet/sponge composite material, which is implemented according to the following steps:
the mass ratio of the graphene nanosheets to the deionized water is 1: 100, respectively; the ultrasonic treatment time is 30 min;
the drying temperature is 60 ℃, and the drying time is 10 min; the number of ultrasonic dispersion was 1; the time of ultrasonic dispersion is 30min each time; the size of the cuboid nano sponge is 22.58mm x 10.14mm x 2 mm;
and 3, dripping a thermoplastic polyurethane solution on the upper surface of the nano sponge material wrapped by the graphene nanosheets, and allowing the thermoplastic polyurethane solution to enter the nano sponge material through natural permeation to obtain the polyurethane/graphene nanosheets/sponge composite material.
Example 2
The invention relates to a preparation method of a polyurethane/graphene nanosheet/sponge composite material, which is implemented according to the following steps:
the mass ratio of the graphene nanosheets to the deionized water is 1: 100, respectively; the ultrasonic treatment time is 40 min;
the drying temperature is 65 ℃, and the drying time is 15 min;
the number of ultrasonic dispersion was 2; the time of ultrasonic dispersion is 40min each time;
the size of the cuboid nano sponge is 22.58mm x 10.14mm x 2 mm;
and 3, dripping a thermoplastic polyurethane solution on the upper surface of the nano sponge material wrapped by the graphene nanosheets, and allowing the thermoplastic polyurethane solution to enter the nano sponge material through natural permeation, so that the thermoplastic polyurethane wraps the nano sponge material loaded with the graphene nanosheets, the graphene nanosheets are prevented from falling off, and the polyurethane/graphene nanosheet/sponge composite material is obtained.
Example 3
The invention relates to a preparation method of a polyurethane/graphene nanosheet/sponge composite material, which is implemented according to the following steps:
the mass ratio of the graphene nanosheets to the deionized water is 1: 100, respectively; the ultrasonic time is 1 h;
the drying temperature is 70 ℃, and the drying time is 30 min;
the number of ultrasonic dispersion was 3; the time of ultrasonic dispersion is 1h each time;
the size of the cuboid nano sponge is 22.58mm x 10.14mm x 2 mm;
and 3, dripping a thermoplastic polyurethane solution on the upper surface of the nano sponge material wrapped by the graphene nanosheets, and allowing the thermoplastic polyurethane solution to enter the nano sponge material through natural permeation, so that the thermoplastic polyurethane wraps the nano sponge material loaded with the graphene nanosheets, the graphene nanosheets are prevented from falling off, and the polyurethane/graphene nanosheet/sponge composite material is obtained.
Fig. 1 is an SEM image of a nanosponge, and it can be seen that the nanosponge exhibits a typical three-dimensional porous microstructure, which provides a basis for N-x to construct a rich conductive path.
Fig. 2 and 3 are a low-magnification SEM image and a high-magnification SEM image of the graphene nanoplatelet-coated nanosponent prepared in example 1, respectively; fig. 4 and 5 are a low-magnification SEM image and a high-magnification SEM image of the graphene nanoplatelet-coated nanosponent prepared in example 2, respectively; fig. 6 and 7 are a low-magnification SEM image and a high-magnification SEM image of the graphene nanoplatelet-coated nanosponent prepared in example 3, respectively; as can be seen from the SEM images of the samples at low magnification, the conductive network becomes more complete as the ultrasound period increases. A small amount of graphene nanosheets are distributed on the surface of the sample prepared in example 1, and a sponge has more holes and defects. From the SEM image of the sample with high magnification, it can be seen that, with the increase of the period of the ultrasonic wave, a more compact and perfect graphene nanosheet network can be formed. The interconnected graphene nano sheets are not only a coating on the surface of the sponge, but also filled in pores of the nano sponge. This phenomenon can be explained as: under the strong action of high-energy shock waves and micro-jet caused by collapse of cavitation bubbles in the ultrasonic crushing process, the nano sponge expands in deionized water and is immersed in the graphene nanosheet suspension, and the graphene nanosheets are adsorbed to the surface and holes of the sponge. Thus, the conductive path is successfully constructed after the solvent is removed.
Fig. 8, 9 and 10 are SEM images of the polyurethane/graphene nanoplatelet/sponge composite prepared in example 1, example 2 and example 3, respectively, and it can be seen that the surface of the nano-sponge material wrapped by the graphene nanoplatelets is covered by a thin thermoplastic polyurethane layer, and the network structure is hardly changed during the permeation process. Meanwhile, the thermoplastic polyurethane layer can enable the graphene nanosheets to tightly cover the nano sponges, and meanwhile, the integrity of the conductive network can be protected in the mechanical compression/release process.
Fig. 11 is the change of the conductivity and the resistance of the polyurethane/graphene nano-sheet/sponge composite material prepared in example 1, example 2 and example 3 with the ultrasonic cycle. As the ultrasound period increases, the conductivity of the material increases significantly. The composite material prepared in example 1 showed a high conductivity of 4.1S/m, far exceeding the target value (1S/m) for commercial applications. And the composite material prepared in the example 3 shows excellent conductivity of 45.2S/m, which is higher by one order of magnitude than that of the composite material prepared in the example 1. The significant improvement of the conductivity is mainly attributed to the increase of the ultrasonic cycle times and the increase of the graphene loading capacity, so that a more complete graphene nanosheet network is formed.
Fig. 12 is a histogram of absorption efficiency as a function of the number of ultrasonic cycles of the polyurethane/graphene nanoplatelet/sponge composite prepared in example 1, example 2 and example 3. The results show that the shielding efficiency of the composite is mainly determined by absorption rather than reflection. This shows that the prepared material has strong electromagnetic wave absorption capacity, mainly because the porous structure increases the electromagnetic wave conduction path and reduces reflection, the electromagnetic wave is reflected continuously on the porous wall and finally converted into heat energy to be dissipated.
Fig. 13 is an EMISE of the polyurethane/graphene nanoplatelet/sponge composite prepared in example 3 before and after 100 compression-release cycles. The composite material exhibits reversible compression over a large strain range and can recover almost to the initial point after stress relief. To further evaluate the cyclic compression performance of the composite, 100 cyclic compression-release tests were performed at 60% strain with no residual strain and good recovery performance. Accordingly, the EMI shielding durability after compression release deformation of the composite material was evaluated. Notably, the composite maintained a superior EMI SE of 34.3dB even after 100 compression-release cycles.
The shielding mechanism of the thermoplastic polyurethane/graphene nanosheet/nano sponge composite material for incident electromagnetic waves is that when the electromagnetic waves impact the surface of a sample, impedance mismatch is caused by free electrons on the surface of the highly-conductive graphene nanosheet, and only a small part of the electromagnetic waves are reflected. The residual electromagnetic waves penetrate through the surface and interact with high-density electrons of the graphene nanosheets, and the charge carriers generate micro-current, so that ohmic loss is caused, and the energy of the electromagnetic waves is consumed. The electromagnetic waves entering the material are then reflected and scattered multiple times in the interconnecting porous conductive network until they are completely absorbed and dissipated as thermal energy. The interconnected porous structure enables the prepared foam to have more active sites and interfaces, can perform multiple internal reflection and scattering, can greatly prolong the transmission path of incident electromagnetic waves, and obviously improves the electromagnetic interference shielding performance. This mechanism gives a reasonable explanation for the efficient emi shielding effectiveness of the fabricated material dominated by the absorption mode.
The method of the invention prepares the composite material with rich conductive network porous structure by a simple method, and simultaneously improves the impedance matching. The unique porous structure design enables electromagnetic waves to enter the composite material more easily, and increases the propagation path of the electromagnetic waves, thereby improving the wave absorbing performance of the composite material.
The invention relates to a preparation method of a thermoplastic polyurethane/graphene nanosheet/nano sponge composite material, which takes a nano sponge framework as a matrix and successfully prepares nano sponge wrapped by graphene nanosheets through repeated layer-by-layer self-assembly. The porous nanoskeleton with interconnected graphene nanosheets is encapsulated with a thermoplastic polyurethane. Thanks to this unique three-dimensional conductive network, the thermoplastic polyurethane/graphene nanoplatelets/nanosponges composite material has high conductivity and excellent electromagnetic interference shielding effectiveness. Importantly, due to the protection of the thermoplastic polyurethane layer and the inherent elasticity of the nanosponges, the emi shielding performance is reliable even after the composite material prepared has undergone severe physical and chemical damage and long compression cycles. In view of the outstanding comprehensive performance of the thermoplastic polyurethane/graphene nanosheet/nano sponge composite material, the work provides a simple and extensible preparation method of the efficient electromagnetic interference shielding composite material for the next generation of portable and wearable electronic equipment.
Claims (6)
1. A preparation method of a polyurethane/graphene nanosheet/sponge composite material is characterized by comprising the following steps:
step 1, dispersing graphene nanosheets serving as solutes into deionized water, and stirring and ultrasonically treating at normal temperature to obtain a graphene nanosheet water dispersion solution;
step 2, soaking the cuboid-shaped nano sponge into the graphene nanosheet solution, ultrasonically dispersing for a plurality of times, and drying to completely evaporate the solvent to obtain a nano sponge material wrapped by the graphene nanosheets;
and 3, wrapping the nano sponge material wrapped by the graphene nanosheets with thermoplastic polyurethane to obtain the polyurethane/graphene nanosheet/sponge composite material.
2. The preparation method of the polyurethane/graphene nano sheet/sponge composite material according to claim 1, wherein in the step 1, the mass ratio of the graphene nano sheet to the deionized water is 1: 100, respectively; the ultrasonic treatment time is 30min-1 h.
3. The preparation method of the polyurethane/graphene nanosheet/sponge composite material according to claim 1, wherein in the step 2, the drying temperature is 60-70 ℃ and the drying time is 10-30 min; the size of the cuboid nanosponges was 22.58mm 10.14mm 2 mm.
4. The preparation method of the polyurethane/graphene nano sheet/sponge composite material according to claim 1, wherein in the step 2, the number of ultrasonic dispersion is 1-3; the time of ultrasonic dispersion is 30min-1h each time.
5. The preparation method of the polyurethane/graphene nanosheet/sponge composite material according to claim 1, wherein in the step 3, specifically: and (3) dripping a thermoplastic polyurethane solution on the upper surface of the nano sponge material wrapped by the graphene nanosheets, and allowing the thermoplastic polyurethane solution to enter the nano sponge material through natural permeation to obtain the polyurethane/graphene nanosheets/sponge composite material.
6. The preparation method of the polyurethane/graphene nanosheet/sponge composite material as claimed in claim 5, wherein the thermoplastic polyurethane solution is prepared from the following components in a mass ratio of 1: 9, mixing the thermoplastic polyurethane particles with water; the mass ratio of the thermoplastic polyurethane solution to the nano sponge material wrapped by the graphene nanosheets is 250: 1.
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