A new type of lightweight material produced by 3D printing consisting of nano-carbon doped polymer layer followed by a dielectric polymer layer is proposed. We performed temperature dependent characterization and measured the electromagnetic (EM) response of the samples in the GHz and THz range. The temperature dependent structural characteristics, crystallization, and melting were observed to be strongly affected by the presence and the number of nano-carbon doped layers in the sandwich structure. The electromagnetic measurements show a great potential of such a type of periodic material for electromagnetic compatibility applications in microwave frequency range. Sandwich structures containing only two nano-carbon layers already become not transparent to the microwaves, giving an electromagnetic interference shielding efficiency at the level of 8-15 dB. A sandwich consisting of one nano-carbon doped and one polymer layer is opaque for THz radiation, because of 80% of absorption. These studies serve as a basis for design and realization of specific optimal geometries of meta-surface type with the 3D printing technique, in order to reach a high level of electromagnetic interference shielding performance for real world EM cloaking and EM ecology applications. V
The study compared the effects of swelling and dissolution of a matrix polymer by food simulants on the release of graphene nanoplates (GNPs) and multiwall carbon nanotubes (MWCNTs) from poly(lactic) acid (PLA) and polypropylene (PP) composite films. The total migration was determined gravimetrically in the ethanol and acetic acid food simulants at different time and temperature conditions, while migrants were detected by laser diffraction analysis and transmission electron microscopy. Swelling, thermal analysis, and scanning electron microscopy were applied to characterize the degradation of polymer films at the migration conditions. The release of nanoparticles was found in a high‐temperature migration test of 4 h at 90 °C. The hydrolytic dissolution of the PLA polymer in the food simulants caused a migration of GNPs (>100 nm) from the PLA/GNP/MWCNT films into the simulant solvents, while the entangled MWCNTs formed a network on the film surface, preventing their migration from the PLA composite films. In contrast, the PP polymer slightly swells in ethanol solvents, allowing some short carbon nanotubes to be released from the surface and cut edges of the PP/MWCNT film into food simulants. Mathematical modeling of diffusion was applied that accounts for type of polymer, time–temperature conditions, and solvent concentration; model parameters were validated with experimental results. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45469.
We constructed a new type of light-weight, nanocarbon based thin film material having good mechanical properties, thermal stability, and electromagnetic shielding efficiency. Our method, 3D printing combined with hot pressing, is a cheap and industrially upscalable process. First a sandwich structure was created by layer-tolayer deposition of alternating 100 μm thick nanocarbon containing plastic layers and 100 μm thick pristine plastic layers, repeated as building blocks. The 3D printed samples were hot pressed to obtain thin films of 10-30 μm thickness. We used a commercial nanocarbon 3D printing filament (Black Magic). TEM investigations revealed the nanocarbon filler to be a mixture of graphene sheets, short carbon nanotubes, fishbone nanotubes, graphitic nanoparticles, and carbon black. Small-angle X-ray scattering and X-ray diffraction studies showed some amorphization of the nanocarbon filler as a consequence of the hot pressing. The nanoindentation hardness, nanoscratch hardness, and Young's modulus increase gradually by increasing the number of layers in the films, due to an increase of the amount of nanocarbon filler. Microwave absorption also increases continuously with the number of nanocarbon layers, reaching 40% for 3 nanocarbon layers. We demonstrate that unlike most conventional composites loaded with nanocarbons having pronounced dielectric properties, when the real part of permittivity Re(ε) is much higher than its imaginary part Im(ε) at high frequencies, a combination of 3D printing and hot pressing allows the fabrication of composites with Re ε ≈ Im ε in a very broad frequency range (0.2-0.6 THz). Our new 3D printed-hot pressed thin films may compete with the CVD graphene sandwiches in electromagnetic shielding applications because of their easier processability and low cost.
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