Synthesis and Electrical Percolation of Highly Amorphous Polyvinyl Alcohol/Reduced Graphene Oxide Nanocomposite.

Polyvinyl alcohol is the most commercially water-soluble biodegradable polymer, and it is in use for a wide range of applications. It shows good compatibility with most inorganic/organic fillers, and enhanced composites may be prepared without the need to introduce coupling agents and interfacial modifiers. The patented high amorphous polyvinyl alcohol (HAVOH), commercialized with the trade name G-Polymer, can be easily dispersed in water and melt processed. HAVOH is particularly suitable for extrusion and can be used as a matrix to disperse nanocomposites with different properties. In this work, the optimization of the synthesis and characterization of HAVOH/reduced graphene oxide (rGO) nanocomposite obtained by the solution blending process of HAVOH and Graphene Oxide (GO) water solutions and 'in situ' reduction of GO is studied. The produced nanocomposite presents a low percolation threshold (~1.7 wt%) and high electrical conductivity (up to 11 S/m) due to the uniform dispersion in the polymer matrix as a result of the solution blending process and the good reduction level of GO. In consideration of HAVOH processability, the conductivity obtained by using rGO as filler, and the low percolation threshold, the nanocomposite presented here is a good candidate for the 3D printing of a conductive structure.

Laser Patterning of Aligned Carbon Nanotubes Arrays: Morphology, Surface Structure, and Interaction with Terahertz Radiation.

The patterning of arrays of aligned multi-walled carbon nanotubes (MWCNTs) allows creating metastructures for terahertz (THz) applications. Here, the strips and columns from MWCNTs vertically grown on silicon substrates are prepared using CO2 laser treatment. The tops of the patterned arrays are flat when the laser power is between 15 and 22 W, and craters appear there with increasing power. Laser treatment does not destroy the alignment of MWCNTs while removing their poorly ordered external layers. The products of oxidative destruction of these layers deposit on the surfaces of newly produced arrays. The oxygen groups resulting from the CO2 laser treatment improve the wettability of nanotube arrays with an epoxy resin. We show that the patterned MWCNT arrays absorb the THz radiation more strongly than the as-synthesized arrays. Moreover, the pattern influences the frequency behavior of the absorbance.

Thermal and Electromagnetic Properties of Polymer Holey Structures Produced by Additive Manufacturing.

Multifunctional 3D-printed holey structures made of composite polymers loaded with nanocarbon were designed to serve simultaneously as GHz-radiation absorbing layers and heat conductors. The geometry of the structures was devised to allow heat to be easily transferred through, with special attention paid to thermal conductivity. Numerical calculations and a simple homogenization theory were conducted in parallel to address this property. Different structures have been considered and compared. The electromagnetic shielding effectiveness of the produced holey structures was measured in the microwave range.

THz Spectroscopy as a Versatile Tool for Filler Distribution Diagnostics in Polymer Nanocomposites.

Polymer composites containing nanocarbon fillers are under intensive investigation worldwide due to their remarkable electromagnetic properties distinguished not only by components as such, but the distribution and interaction of the fillers inside the polymer matrix. The theory herein reveals that a particular effect connected with the homogeneity of a composite manifests itself in the terahertz range. Transmission time-domain terahertz spectroscopy was applied to the investigation of nanocomposites obtained by co-extrusion of PLA polymer with additions of graphene nanoplatelets and multi-walled carbon nanotubes. The THz peak of permittivity's imaginary part predicted by the applied model was experimentally shown for GNP-containing composites both below and above the percolation threshold. The physical nature of the peak was explained by the impact on filler particles excluded from the percolation network due to the peculiarities of filler distribution. Terahertz spectroscopy as a versatile instrument of filler distribution diagnostics is discussed.

Terahertz Optics of Materials with Spatially Harmonically Distributed Refractive Index.

The electromagnetic properties of structures with spatially periodic distributed graded refractive index were investigated in the terahertz frequency range. The band structure and electromagnetic response of material with harmonically distributed refractive index were calculated and analyzed. The analytical expressions for frequencies of the first and second bandgap are derived. 3D printed gyroid based architectures were proven to be harmonically graded refractive index structures with designed bandgaps in THz frequency ranges. The transmission coefficient of thermoplastic polyurethane-based samples were experimentally measured in the frequency range 100-500 GHz and compared with theoretical results. Due to losses in the real world produced samples, the predicted response is significantly dumped in the terahertz range and only traces of band gaps are experimentally observed. This funding paves the way toward a new generation of 3D printed THz components for gradient-index optics applications.

On the Synergistic Effect of Multi-Walled Carbon Nanotubes and Graphene Nanoplatelets to Enhance the Functional Properties of SLS 3D-Printed Elastomeric Structures.

Elastomer-based porous structures realized by selective laser sintering (SLS) are emerging as a new class of attractive multifunctional materials. Herein, a thermoplastic polyurethane (TPU) powder for SLS was modified by 1 wt.% multi-walled carbon nanotube (MWCNTs) or a mixture of MWCNTs and graphene (GE) nanoparticles (70/30 wt/wt) in order to investigate on both the synergistic effect provided by the two conductive nanostructured carbonaceous fillers and the correlation between formulation, morphology, and final properties of SLS printed porous structures. In detail, porous structures with a porosity ranging from 20% to 60% were designed using Diamond (D) and Gyroid (G) unit cells. Results showed that the carbonaceous fillers improve the thermal stability of the elastomeric matrix. Furthermore, the TPU/1 wt.% MWCNTs-GE-based porous structures exhibit excellent electrical conductivity and mechanical strength. In particular, all porous structures exhibit a robust negative piezoresistive behavior, as demonstrated from the gauge factor (GF) values that reach values of about -13 at 8% strain. Furthermore, the G20 porous structures (20% of porosity) exhibit microwave absorption coefficients ranging from 0.70 to 0.91 in the 12-18 GHz region and close to 1 at THz frequencies (300 GHz-1 THz). Results show that the simultaneous presence of MWCNTs and GE brings a significant enhancement of specific functional properties of the porous structures, which are proposed as potential actuators with relevant electro-magnetic interference (EMI) shielding properties.

Essential Nanostructure Parameters to Govern Reinforcement and Functionality of Poly(lactic) Acid Nanocomposites with Graphene and Carbon Nanotubes for 3D Printing Application.

Poly(lactic) acid nanocomposites filled with graphene nanoplatelets (GNPs) and multiwall carbon nanotubes (MWCNTs) are studied, varying the filler size, shape, and content within 1.5-12 wt.%. The effects of the intrinsic characteristics of nanofillers and structural organization of nanocomposites on mechanical, electrical, thermal, and electromagnetic properties enhancement are investigated. Three essential rheological parameters are identified, which determine rheology-structure-property relations in nanocomposites: the degree of dispersion, percolation threshold, and interfacial interactions. Above the percolation threshold, depending on the degree of dispersion, three structural organizations are observed in nanocomposites: homogeneous network (MWCNTs), segregated network (MWCNTs), and aggregated structure (GNPs). The rheological and structural parameters depend strongly on the type, size, shape, specific surface area, and functionalization of the fillers. Consequently, the homogeneous and segregated network structures resulted in a significant enhancement of tensile mechanical properties and a very low electrical percolation threshold, in contrast to the aggregated structure. The high filler density in the polymer and the low number of graphite walls in MWCNTs are found to be determinant for the remarkable shielding efficiency (close to 100%) of nanocomposites. Moreover, the 2D shaped GNPs predominantly enhance the thermal conductivity compared to the 1D shaped MWCNTs. The proposed essential structural parameters may be successfully used for the design of polymer nanocomposites with enhanced multifunctional properties for 3D printing applications.

The Phosphate-Based Composite Materials Filled with Nano-Sized BaTiO3 and Fe3O4: Toward the Unfired Multiferroic Materials.

The composite material filled with nano-sized BaTiO3 and Fe3O4 was designed and studied. The aluminium phosphate ceramics was used as a matrix. The XRD analysis demonstrates only the crystalline structure of the fillers used. The thermogravimetric analysis proves the thermal stability of the composites up to 950 K. The Maxwell-Wagner relaxation was observed in the dielectric spectra of the investigated composites. The dielectric spectroscopy proves the close contact between the nanoparticles with the different ferroic ordering. The phosphate-based composites have been proved to be a prospective candidate for the multiphase multiferroic materials design and development.

Nanocarbon/Poly(Lactic) Acid for 3D Printing: Effect of Fillers Content on Electromagnetic and Thermal Properties.

Electromagnetic and thermal properties of a non-conventional polymer nanocomposite based on thermoplastic Polylactic acid (PLA, Ingeo™) filled, in different weight percentage, with multi-walled carbon nanotubes (MWCNTs), graphene nanoplatelets (GNPs), as well as a mixture of both fillers (MWCNTs/GNPs), are analyzed. The combination of notable electrical, thermal, and electromagnetic (EM) properties of the carbon fillers, in concentrations above the percolation threshold, together with the good processability of the PLA matrix gives rise to innovative filaments for 3D printing. In particular, the shielding efficiency (SE) in the frequency range 26-37 GHz of samples increases from 0.20 dB of unfilled PLA up to 13.4 dB for composites containing MWCNTs and GNPs, corresponding to 4% and 95% of SE, respectively. The thermal conductivity of the PLA loaded with 12 wt % of GNPs is 263% higher than that of the unfilled polymer, whereas an improvement of about 99% and 190% is detected for the PLA matrix loaded with MWCNTs and both fillers, respectively. The EM and thermal characterization is combined with a morphological investigation allowing us to correlate the dispersion states of the fillers within the polymer matrix with the observed EM and thermal properties. The EM and thermal characteristics exhibited by the nanocomposites make them suitable for packaging applications of electronic devices with electromagnetic interference (EMI) shielding and thermal dissipation features.