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This study developed a novel 3D-printable poly(vinylidene fluoride) (PVDF)-based nanocomposite incorporating 6 wt% graphene nanoplatelets (GNPs) with programmable characteristics for resistive heating applications. The results highlighted the significant effect of a controlled printing direction (longitudinal, diagonal, and transverse) on the electrical, thermal, Joule heating, and thermo-resistive properties of the printed structures. The 6 wt% GNP/PVDF nanocomposite exhibited a high electrical conductivity of 112 S·m−1 when printed in a longitudinal direction, which decreased significantly in other directions. The Joule heating tests confirmed the material's efficiency in resistive heating, with the maximum temperature reaching up to 65 °C under an applied low voltage of 2 V at a raster angle of printing of 0°, while the heating Tmax decreased stepwise with 10 °C at the 45° and the 90° printing directions. The repeatability of the Joule heating performance was verified through multiple heating and cooling cycles, demonstrating consistent maximum temperatures across several tests. The effect of sample thickness, controlled by the number of printed layers, was investigated, and the results underscore the advantages of programmable 3D printing orientation in thin layers for enhanced thermal stability, tailored electrical conductivity, and efficient Joule heating capabilities of 6 wt% GNP/PVDF composites, positioning them as promising candidates for next-generation 3D-printed electronic devices and self-heating applications. [ABSTRACT FROM AUTHOR]

The investigation of new composite materials possessing low weight but not at the expense of their mechanical performance is of great interest in terms of reducing energy consumption in many industrial applications. This study is focused on the nanomechanical characterization of high-density polyethylene (HDPE)-based composite specimens modified with equal loadings of graphene nanoplatelets (GNPs) and/or multiwall carbon nanotubes (MWCNTs). Quasi-static nanoindentation analysis revealed the impact of the carbon nanofillers on the receiving of nanocomposites with higher nanohardness and reduced modulus of elasticity, reaching values of 0.146 GPa and 3.57 GPa, respectively. The role of the indentation size effect in elastic polymer matrix was assessed by applying three distinct peak forces. Nanoscratch experiments depicted the tribological behavior of the composite samples and inferred the influence of the carbon nanofillers on the values of the coefficient of friction (COF). It seems that the incorporation of 4 wt% GNPs in the polymer structure improves the scratch resistance of the material, resulting in a higher value of the exerted lateral force and therefore leading to the detection of a higher coefficient of friction at scratch of 0.401. A considerable pile-up response of the scratched polymer specimens was observed by means of in-situ SPM imaging of the tested surface sample area. The sway of the carbon nanoparticles on the composite pile-up behavior and the effect of the pile-up on the measured friction coefficients have been explored. [ABSTRACT FROM AUTHOR]

In recent years, conductive polymer nanocomposites have gained significant attention due to their promising thermoresistive and Joule heating properties across a range of versatile applications, such as heating elements, smart materials, and thermistors. This paper presents an investigation of semi-crystalline polyvinylidene fluoride (PVDF) nanocomposites with 6 wt.% carbon-based nanofillers, namely graphene nanoplatelets (GNPs), multi-walled carbon nanotubes (MWCNTs), and a combination of GNPs and MWCNTs (hybrid). The influence of the mono- and hybrid fillers on the crystalline structure was analyzed by X-ray diffraction (XRD) and differential scanning calorimetry (DSC). It was found that the nanocomposites had increased amorphous fraction compared to the neat PVDF. Furthermore, nanocomposites enhanced the β phase of the PVDF by up to 12% mainly due to the presence of MWCNTs. The resistive properties of the nanocompositions were weakly affected by the temperature in the analyzed temperature range of 25–100 °C; nevertheless, the hybrid filler composites were proven to be more sensitive than the monofiller ones. The Joule heating effect was observed when 8 and 10 V were applied, and the compositions reached a self-regulating effect at around 100–150 s. In general, the inclusion in PVDF of nanofillers such as GNPs and MWCNTs, and especially their hybrid combinations, may be successfully used for tuning the self-regulated Joule heating properties of the nanocomposites. [ABSTRACT FROM AUTHOR]

In the last decades, one of the most critical issues concerning the control on the processing, structure and properties of nanocomposites is related to the dispersion of nanofiller in the polymer matrix and internal interactions resulting in percolation. In this study, we investigate the rheological behavior in oscillatory and steady shear flow of poly(lactic) acid based nanocomposites incorporating 0 – 12 wt% graphene nanoplates (GNP) and multi-walled carbon nanotubes (OH-MWCNT). The effect of the filler contents and aspect ratio on the viscosity and viscoelastic response is evaluated. Three rheological techniques are used for estimation of rheological percolation threshold. Due to different aspect ratio and state of dispersion of GNP and MWCNTs the percolation threshold differs significantly for both compositions ϕp ≤ 1.5 wt% for MWCNT/PLA and ϕp ≤ 5 wt% for GNP/PLA. The larger the aspect ratio of nanofiller, the lower is the rheological percolation threshold. The visualized structure by TEM analysis confirms the rheological predictions for both type composites. The index of flow was estimated by the power law slope of the flow curves and a better dispersion was assumed for MWCNTs in comparison with GNPs due to the surface modification. Based on the rheological percolation threshold and the flow index, nanocomposites were classified in three groups: Newtonian, percolated composites and elastic solids. Both characteristics are used to select the printing parameters for the three groups of nanocomposites, suitable for fused deposition modeling (FDM).

The current state of the art on material science emphasizes recent research efforts aimed at designing novel materials characterized by low-density and advanced properties. The present article reports the experimental, theoretical and simulation results on the thermal behavior of 3D printed discs. Filaments of pure poly (lactic acid) PLA and filled with 6 wt% of graphene nanoplatelets (GNPs) are used as feedstocks. Experiments indicate that the introduction of graphene enhances the thermal properties of the resulting materials since the conductivity passes from the value of 0.167 [W/mK] for unfilled PLA to 0.335 [W/mK] for reinforced PLA, which corresponds to a significantly improvement of 101%. Exploiting the potential of 3D printing, different air cavities have been intentionally designed to develop new lightweight and more cost-effective materials without compromising their thermal performances. Furthermore, some cavities are equal in volume but different in the geometry; it is necessary to investigate how this last characteristic and its possible orientations affect the overall thermal behavior compared to that of an air-free specimen. The influence of air volume is also investigated. Experimental results are supported by theoretical analysis and simulation studies based on the finite element method. The results aim to be a valuable reference resource in the field of design and optimization of lightweight advanced materials. [ABSTRACT FROM AUTHOR]

Nowadays, a strong demand exists for printable materials with multifunctionality and proper rheological properties to overcome the limitations to deposit layer-by-layer in additive extrusion. The present study discusses rheological properties related to the microstructure of hybrid poly (lactic) acid (PLA) nanocomposites filled with graphene nanoplatelets (GNP) and multiwall carbon nanotubes (MWCNT) to produce multifunctional filament for 3D printing. The alignment and slip effects of 2D-nanoplatelets in the shear-thinning flow are compared with the strong reinforcement effects of entangled 1D-nanotubes, which govern the printability of nanocomposites at high filler contents. The mechanism of reinforcement is related to the network connectivity of nanofillers and interfacial interactions. The measured shear stress by a plate–plate rheometer of PLA, 1.5% and 9% GNP/PLA and MWCNT/PLA shows an instability for high shear rates, which is expressed as shear banding. A rheological complex model consisting of the Herschel–Bulkley model and banding stress is proposed for all considered materials. On this basis, the flow in the nozzle tube of a 3D printer is studied by a simple analytical model. The flow region is separated into three different regions in the tube, which match their boundaries. The present model gives an insight into the flow structure and better explains the reasons for printing enhancement. Experimental and modeling parameters are explored in designing printable hybrid polymer nanocomposites with added functionality. [ABSTRACT FROM AUTHOR]

Polylactic acid (PLA) containing 12 wt% of nanofillers, such as multi‐walled carbon nanotubes (MWCNTs), graphene nanoplates (GNPs), is considered to obtain a non‐conventional filament suitable for additive manufacturing (AM) process with enhanced thermal and electrical properties. In details, three‐dimensional (3D) printed specimens obtained by means of fused deposition modeling (FDM) are experimentally characterized in terms of thermal conductivity and relative permittivity. The results are interpreted on the basis of the different features of the fillers and their interaction with the PLA, as evidenced by a morphological analysis. It is found better thermal transport by using two‐dimensional (2D) shape nanoparticles (GNPs) with an improvement of about 260% respect to the unfilled polymer most likely due to its favorable arrangement and the lower thermal boundary resistance between the two phases, matrix, and fillers. Differently, mono‐dimensional filler like MWCNTs is to be preferred in order to obtain higher value for the relative permittivity, due to the enhancement of the interfacial polarization and the presence of functionalized groups. It is found a value of 5.35 × 103 much greater than that of 3.7 measured for pure PLA. Given the good combined thermal and dielectric properties, such materials are promising candidates for packaging applications with electromagnetic (EM) shielding capability. [ABSTRACT FROM AUTHOR]

Polymer composites filled with high thermal and electrical conductivity nanofillers show enhanced thermo‐electric properties which encourage their use in heat transfer applications. In the present study, nanocomposites based on polylactic acid (PLA) containing up to 9 wt% of multi‐walled carbon nanotubes (trade name: N7000) and graphene nanoplates (trade name: TNIGNP) are produced via melt compounding and then morphologically, electrically, and thermally investigated. The results are correlated to the different characteristic of the fillers and their interaction with the PLA. At the highest investigated filler concentration, an electrical conductivity of about 2 S m–1 and a thermal conductivity of 0.725 W m–1 K–1 are measured respectively for nanocomposites based on N7000 and TNIGNP, which are decisively higher than the values measured for unfilled PLA (5.9 ×∙10–2 S m–1 and 0.205 W m–1 K–1). Moreover, multiphysics simulations are performed on the best performing nanocomposites for evaluating their thermo‐electric properties when an electrical heating or a direct heat flux are applied. [ABSTRACT FROM AUTHOR]

Nanomechanical definition of the properties of composite specimens based on polylactic acid (PLA) was made in the present study. Research activities with accent on biodegradable polymer nanocomposites have fundamental significance originated from the worldwide plastic waste pollution. To receive hybrid nanocomposites with high level of homogeneity, the low cost and environmentally friendly melt extrusion method has been applied. The role of graphene nanoplatelets (GNPs) and multiwall carbon nanotubes (MWCNTs) as reinforcing nanoparticles dispersed in the polymer matrix was thoroughly investigated. Quasi-static nanoindentation analysis was enriched by performance of accelerated property mapping and nanodynamic mechanical testing in order to fully describe the nanoscale surface homogeneity and stress relaxation behavior of the nanocomposite specimens. That novelty of the research approach had a well-marked contribution over the detection of the new samples' nanomechanical features as a function of the type of carbon nanofiller. Refined nanoscratch experiments uncovered the resistance of the materials against notches by means of measurement of the coefficient of friction and accurate estimation of the residual penetration depth. [ABSTRACT FROM AUTHOR]

In this work, we designed and studied two synthetic routes, based on modified Hummers method, to obtain graphene oxide (GO), and investigated their influence on the performance of polypropylene (PP)/GO nanocomposites. The two synthetic routes differed in the application condition of the oxidizing agent, potassium permanganate (KMnO4), which was added either as a powder (GO‐P) or as a water solution (GO‐S). This apparently subtle synthetic change yielded GOs with different degrees of oxidation and particle sizes, where GO‐P presented a higher oxidation degree and smaller particles. The different GOs were then melt‐blended with PP and the correlation between their different chemical/morphological structures and the nanocomposites' thermomechanical/rheological properties were evaluated. The milder oxidation process suffered by GO‐S, and consequent less hydrophilic character, yielded a PP/GO‐S nanocomposite with improved performance as the consequence of a better matrix/filler chemical affinity, mainly in compositions with lower GO‐S contents. The thermal stability was increased by more than 10°C when 0.1 wt% GO‐S was inserted into PP. When compared to the composition with 0.1 wt% GO‐P, the increase was 13°C. Reinforcing effects were also observed in that sample (with 0.1 wt% GO‐S), which exhibited the highest storage modulus and complex viscosity. These results suggest that tailoring the GO's oxidation degree and morphology is a key point to obtain an ideal interfacial interaction between phases. [ABSTRACT FROM AUTHOR]

In this study, the structure, electrical and thermal properties of ten polymer compositions based on polylactic acid (PLA), low-cost industrial graphene nanoplates (GNP) and multi-walled carbon nanotubes (MWCNT) in mono-filler PLA/MWCNT and PLA/GNP systems with 0–6 wt.% filler content were investigated. Filler dispersion was further improved by combining these two carbon nanofillers with different geometric shapes and aspect ratios in hybrid bi-filler nanocomposites. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopy exhibited uniform dispersion of nanoparticles in a polymer matrix. The obtained results have shown that for the mono-filler systems with MWCNT or GNP, the electrical conductivity increased with decades. Moreover, a small synergistic effect was observed in the GNP/MWCNT/PLA bi-filler hybrid composites when combining GNP and CNT at a ratio of 3% GNP/3% CNT and 1.5% GNP:4.5% CNT, showing higher electrical conductivity with respect to the systems incorporating individual CNTs and GNPs at the same overall filler concentration. This improvement was attributed to the interaction between CNTs and GNPs limiting GNP aggregation and bridging adjacent graphene platelets thus, forming a more efficient network. Thermal conductivity increases with higher filler content; this effect was more pronounced for the mono-filler composites based on PLA and GNP due to the ability of graphene to better transfer the heat. Morphological analysis carried out by electron microscopy (SEM, TEM) and Raman indicated that the nanocomposites present smaller and more homogeneous filler aggregates. The well-dispersed nanofillers also lead to a microstructure which is able to better enhance the electron and heat transfer and maximize the electrical and thermal properties. The obtained composites are suitable for the production of a multifunctional filament with improved electrical and thermal properties for different fused deposition modelling (FDM) 3D printing applications and also present a low production cost, which could potentially increase the competitiveness of this promising market niche. [ABSTRACT FROM AUTHOR]

Poly(lactic acid)/graphene and poly(lactic acid)/carbon nanotube nanocomposites were prepared by an easy and low-cost method of melt blending of preliminary grinded poly(lactic acid) (PLA) with nanosized carbon fillers used as powder. Morphological, structural and mechanical properties were investigated to reveal the influence of carbon nanofiller on the PLA–based composite. The dependence of tensile strength on nanocomposite loading was defined by a series of experiments over extruded filaments using a universal mechanical testing instrument. The applying the XRD technique disclosed that compounds crystallinity significantly changed upon addition of multi walled carbon nanotubes. We demonstrated that Raman spectroscopy can be used as a quick and unambiguous method to determine the homogeneity of the nanocomposites in terms of carbon filler dispersion in a polymer matrix. [ABSTRACT FROM AUTHOR]

Resistivity and low‐frequency (10 Hz–20 kHz) noise characteristics of composite materials with multi‐walled carbon nanotubes (MWCNTs) of different surface treatment, that is, MWCNTs covered with bisphenol‐A based liquid epoxy resin (epoxy‐grafted) and polyethylene polyamine (amino‐grafted), have been carried out over the temperature range from 73 to 380 K. The resistivity of the investigated materials decreases with temperature increase up to 250 K; at higher temperatures polymer matrix expansion leads to the resistivity increase and above 340 K the conductivity in the matrix becomes significant. Low‐frequency noise spectra of the investigated materials are 1/fα‐type and noise spectral density is proportional to the squared voltage. The observed fluctuations in the investigated materials are resistance fluctuations. The conduction in the investigated composites is caused by tunneling inside and between MWCNTs controlled by charge carrier capture and release processes in localized states. MWCNT's surface treatment by polyethylene polyamine leads to the larger density of surface states what causes lower resistivity and more intensive low‐frequency fluctuations. POLYM. COMPOS., 39:E1224–E1230, 2018. © 2018 Society of Plastics Engineers [ABSTRACT FROM AUTHOR]

ABSTRACT 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. [ABSTRACT FROM AUTHOR]

Poly(lactic) acid (PLA) film with 2 wt% mixed carbon nanofillers of graphene nanoplates (GNPs) and multiwall carbon nanotubes (MWCNTs) in a weight ratio of 1:1 with impurities of fullerene and carbon black (CB) was produced by layer-to-layer deposition and hot pressing. The release of carbon nanoparticles from the film was studied at varying time–temperature conditions and simulants. Migrants in simulant solvents were examined with laser diffraction analysis and transmission electron microscopy (TEM). Film integrity and the presence of migrants on the film surfaces were visualised by scanning electron microscopy (SEM). The partial dissolution of PLA polymer in the solvents was confirmed by swelling tests and differential scanning calorimetry (DSC). Nanoparticle migrants were not detected in the simulants (at the LOD 0.020 μm of the laser diffraction analysis) after migration testing at 40°C for 10 days. However, high-temperature migration testing at 90°C for 4 h provoked a release of GNPs from the film into ethanol, acetic acid and oil-based food simulants. Short carbon nanotubes were observed rarely to release in the most aggressive acetic acid solvent. Obviously, the enhanced molecular mobility at temperatures above the glass transition and partial dissolution of PLA polymer by the food simulant facilitate the diffusion processes. Moreover, shape, size and concentration of nanoparticles play a significant role. Flexible naked GNPs (lateral size 100–1000 nm) easily migrate when the polymer molecules exhibit enhanced mobility, while fibrous MWCNTs (> 1 μm length) formed entangled networks on the film surfaces as the PLA polymer is partly dissolved, preventing their release into food simulants. The impurities of fullerenes and CB (5–30 nm) were of minor concentration in the polymer, therefore their migration is low or undetectable. The total amount of released migrants is below overall migration limits. [ABSTRACT FROM PUBLISHER]

Polymer composites containing nanofillers are among the most promising research fields for advanced materials. Carbon nanotubes (CNTs) are considered an ideal inclusion for polymer nanocomposites due to superior electrical, thermal, and mechanical properties which can be explained with the unique atomic structure of the nanotubes. Multi-walled carbon nanotubes (MWCNTs) are used as extremely strong nano-reinforcements for composites to produce a new generation of fiber-reinforced plastics with better application properties. In this experimental study, PP/MWCNT polymer nanocomposites with nanofiller concentrations in the range of 0.05–1 wt% MWCNT and the maleic anhydride amount from 0 to 7.5 wt% were investigated. An experimental study is conducted to examine the influence of MWCNT and compatibilizer contents on the thermal, mechanical, and viscoelastic properties of polypropylene (PP)/MWCNT nanocomposites. Extruded samples are characterized by differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), and microindentation tests. Standard Berkovich indentation test determined by residual surface impression method based on load–displacement curves was used. DSC results show an increase in the crystallization temperature of maleinated PP with the increase of MWCNT contents proving the nucleation effect of CNTs. DMTA results prove the good modification properties of maleic anhydride in MWCNT/PP nanocomposites at 0.05 wt% nanotubes concentration. Elastic moduli, obtained from both DMTA and microindentation, are compared to investigate the difference between surface and bulk mechanical properties of nanocomposites with increasing nanotubes concentration. Measured values of elastic moduli are within comparable ranges, but the absolute values are different. [ABSTRACT FROM AUTHOR]

The study is focused on joint effects of two nanofillers in polypropylene (PP) reinforced with 3 wt% organo-clay (ОC) and 0.1-5 wt% multi-wall carbon nanotubes (MWCNTs). The composites were produced by extrusion and characterized by rheology, differential scanning calorimeter (DSC), thermally stimulated depolarization currents (TSDC), and dielectric relaxation spectroscopy (DRS). Rheological data indicates а formation of a network structure related to percolation above 1 wt% nanotubes. The flow activation energy ( Ea) decreases above the percolation threshold, thus, the presence of clay improves the debundling of MWCNTs and releases the segmental motion of polymer chains. The clay does not affect the crystallization behavior of PP, but the nucleation is enhanced strongly by the MWCNTs. Dielectric measurements reveal that the presence of clay affects the molecular mobility of PP at the amorphous phase. The DSC results imply that around 80°C a cold crystallization process occur in the PP phase which has a significant impact on the dielectric segmental relaxation process and gives rise to the appearance of an additional process, the so called 'interfacial' relaxation process. This new relaxation process in the three-phase composites was attributed to an interfacial polarization process due to blocking of charge carriers at polymer/clay interfaces. POLYM. COMPOS., 37:2756-2769, 2016. © 2015 Society of Plastics Engineers [ABSTRACT FROM AUTHOR]

ABSTRACT Chitosan coating of polyethylene (PE) was proposed as a new procedure to improve its biocompatibility and surface properties. The functionalization of the PE film surface by covalent bonding of chitosan coating and its effect on the surface mechanical properties, as surface elasticity, stiffness, and adhesion (that are important in different biological processes) were investigated by nano-indentation, scratch, and atomic force microscopy. It has been established that chitosan grafting onto corona functionalized PE surface using various coupling agents significantly improves the surface hardness and elastic modulus although they decrease in depth of the layer. Compared to the neat PE substrate, the chitosan coated samples show significant improved friction properties and tear resistance. The surface roughness features correlate with the micro-mechanical parameters. Therefore, the covalent immobilization of the chitosan onto PE leads to a stable coating with better mechanical performance being recommended as a promising material for medical applications and food packaging. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42344. [ABSTRACT FROM AUTHOR]

Epoxy/alumina nanocomposites of various compositions were prepared by dispersing modified and nonmodified boehmite nanoparticles in diglycidyl ether of bisphenol-A using diethylenetriamine as curing agent. Measurements of the viscosity of the nanodispersions provided information on particle-particle and particle-resin interactions. The structure of the nanocomposites was studied by scanning electron microscopy on fractured samples. Effects of nanoparticles on polymer dynamics was studied in detail by dynamic mechanical thermal analysis and two dielectric techniques, broadband dielectric relaxation spectroscopy and thermally stimulated depolarization currents. Three secondary relaxations, γ, β, and ω, the segmental α relaxation associated with the glass transition, and an interfacial relaxation, in the order of increasing frequency/decreasing temperature, were observed and studied. A correlation between viscosity (of the nanodispersions), storage modulus, glass transition temperature, real part of dielectric permittivity, and ductility of the nanocomposites was observed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011 [ABSTRACT FROM AUTHOR]

Overheating effect is a crucial issue in different fields. Thermally conductive polymer-based heat sinks, with lightweight and moldability features as well as high-performance and reliability, are promising candidates in solving such inconvenience. The present work deals with the experimental evaluation of the temperature effect on the thermophysical properties of nanocomposites made with polylactic acid (PLA) reinforced with two different weight percentages (3 and 6 wt%) of graphene nanoplatelets (GNPs). Thermal conductivity and diffusivity, as well as specific heat capacity, are measured in the temperature range between 298.15 and 373.15 K. At the lowest temperature (298.15 K), an improvement of 171% is observed for the thermal conductivity compared to the unfilled matrix due to the addition of 6 wt% of GNPs, whereas at the highest temperature (372.15 K) such enhancement is about of 155%. Some of the most important mechanical properties, mainly hardness and Young's modulus, maximum flexural stress, and tangent modulus of elasticity, are also evaluated as a function of the GNPs content. Moreover, thermal simulations based on the finite element method (FEM) have been carried out to predict the thermal performance of the investigated nanocomposites in view of their practical use in thermal applications. Results seem quite suitable in this regard. [ABSTRACT FROM AUTHOR]

Many research efforts have been directed towards enhancing the thermal properties of polymers, since they are classically regarded as thermal insulators. To this end, the present study focuses on the thermal investigation of poly(lactic acid) (PLA) filled with two types of carbon nanotubes (trade names: TNIMH4 and N7000), two type of graphene nanoplatelets (trade names: TNIGNP and TNGNP), or their appropriate combination. A significant increase in the thermal conductivity by 254% with respect to that of unfilled polymer was achieved in the best case by using 9 wt% TNIGNP, resulting from its favorable arrangement and the lower thermal boundary resistance between the two phases, matrix and filler. To theoretically assist the design of such advanced nanocomposites, Design of Experiments (DoE) and Response Surface Method (RSM) were employed, respectively, to obtain information on the conditioning effect of each filler loading on the thermal conductivity and to find an analytical relationship between them. The numerical results were compared with the experimental data in order to confirm the reliability of the prediction. Finally, a simulation study was carried out with Comsol Multiphysics® for a comparative study between two heat sinks based on pure PLA, and to determine the best thermally performing nanocomposite with a view towards potential use in heat transfer applications. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

In the present study, polylactic acid (PLA) enriched with carbonaceous particles like multi-walled carbon nanotubes (MWCNTs), graphene nanoplates (GNPs) or a combination of both up 12 wt % of loading are used for producing 3D-printed specimens with fused deposition modeling (FDM) technology which are then experimentally and theoretically investigated. The goal is to propose a non-conventional filaments indicated for additive manufacturing process with improved dielectric and thermal properties, compared to the performances exhibited by the unfilled polymer. In the light of the above, a wide dielectric spectroscopy and a thermal analysis, supported by a morphological investigation, are performed. The results highlight that the introduction of 1-dimensional filler (MWCNTs) are more suitable for improving the dielectric properties of the resulting materials, due to the enhancement of the interfacial polarization and the presence of functionalized groups, whereas 2-dimensional nanoparticles (GNPs) better favor the thermal conduction mechanisms thanks to the lower thermal boundary resistance between the two phases, polymer/filler. In particular, with a loading of 12 wt % of MWCNTs the relative permittivity reaches the value of 5.35 × 103 much greater than that of 3.7 measured for unfilled PLA while for the thermal conductivity the enhancement with 12 wt % of GNPs is about 261% respect the thermal behavior of the neat polymer. The experimental results are correlated to theoretical findings, whereas a design of experiment (DoE) approach is adopted for investigating how the different fillers influence the dielectric and thermal performances of the 3D-printed parts, thus assisting the design of such innovative materials that appear promising for development and applications in the electromagnetic (EM) field and heat transfer. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

In this study, the effects of three processing stages: filament extrusion, 3D printing (FDM), and hot-pressing are investigated on electrical conductivity and tensile mechanical properties of poly(lactic) acid (PLA) composites filled with 6 wt.% of multiwall carbon nanotubes(MWCNTs), graphene nanoplatelets (GNPs), and combined fillers. The filaments show several decades' higher electrical conductivity and 50–150% higher values of tensile characteristics, compared to the 3D printed and the hot-pressed samples due to the preferential orientation of nanoparticles during filament extrusion. Similar tensile properties and slightly higher electrical conductivity are found for the hot-pressed compared to the 3D printed samples, due to the reduction of interparticle distances, and consequently, the reduced tunneling resistances in the percolated network by hot pressing. Three structural types are observed in nanocomposite filaments depending on the distribution and interactions of fillers, such as segregated network, homogeneous network, and aggregated structure. The type of structural organization of MWCNTs, GNPs, and combined fillers in the matrix polymer is found determinant for the electrical and tensile properties. The crystallinity of the 3D printed samples is higher compared to the filament and hot-pressed samples, but this structural feature has a slight effect on the electrical and tensile properties. The results help in understanding the influence of processing on the properties of the final products based on PLA composites. [ABSTRACT FROM AUTHOR]

The dependence of transmission/absorption of terahertz (THz) radiation on strain in graphene is investigated experimentally and with the aid of ab initio calculations. By applying strain to chosen graphene layer(s), the effective sheet conductance can be fine‐tuned to necessary value to design tunable passive THz components (such as shields, filters, polarizers, etc.) utilizing the high absorption ability of graphene. The positive influence of non‐perfectness of chemically vapor deposited (CVD) graphene for strong tunability versus mechanical deformations is also discussed. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

The aging, annealing, and reprocessing of the biodegradable poly (lactic) acid (PLA) based composite films incorporating graphene and carbon nanotubes were investigated in this work. Various monofiller and bifiller nanocomposite films with 6 wt.% filler content were produced by a solution-phase technique followed by extrusion. The freshly produced films were compared with the aged films after 18 months of shelf life in a room environment. The effects of aging, annealing, and melt reprocessing on the crystalline structure, the thermal stability, the hardness, and Young's modulus were analyzed by differential scanning calorimetry (DSC), TGA, and nanoindentation methods. The fresh and the aged samples were found to have semi-crystalline materials with 3%–7% crystallinity, while the crystallinity was significantly enhanced to 34%–38% by annealing at 80 °C and subsequent slow cooling. A good dispersion was observed in the bifiller films with filler ratios of 4.5:1.5 and 1.5:4.5 [graphene nanoplatelets (GNP) to carbon nanotubes (CNT)], which affected the crystallization processes. The reprocessing at 200 °C followed by fast cooling resulted in amorphous films, which significantly reduced the hardness and Young's modulus. The nanoindentation properties were dependent on the dispersion of nanofillers at the surfaces. The efficiency of annealing and reprocessing for the recovery and the reuse of aged nanocomposite films is discussed herein. The paper underlines that properties of the nanocomposites under investigation were influenced not only by the composition, the chemical nature of the added filler, and the processing condition, but also by the aging processes, which in turn depended on the type of nanopartcles added to PLA and the compositions. The paper provides valuable information for selection of material and processing conditions. [ABSTRACT FROM AUTHOR]

Influences of different nanocomposite loadings in poly(lactic acid) (PLA) matrix on resulting hardness and elasticity were examined in nanoindentation experiments. The following study was focused on the nanomechanical properties of PLA reinforced with graphene nanoplatelets (GNPs) and multiwall carbon nanotubes (MWCNTs) by using Berkovich type pyramidal nanoindenter. A masterbatch strategy was developed to disperse GNP and MWCNT into PLA by melt blending. Young's modulus and nanohardness of as‐prepared nanocomposites were characterized as a function of the graphene and carbon nanotubes loading. The nanoindentation analysis reveals that these carbon nanofillers improve the mechanical stability of the nanocomposites GNP/PLA, MWCNT/PLA, and GNP/MWCNT/PLA. That improvement of mechanical properties strongly depends on the fillers content. It was found that the best mechanical performance was achieved for the compound having 6 wt % graphene and 6 wt % MWCNTs in the PLA matrix. The received values for nanohardness and Young's modulus are among the highest reported for PLA‐based nanocomposites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47260. [ABSTRACT FROM AUTHOR]

The limitation of poor mechanical stability and difficulties in printing electrically conductive components can be overcome owing to the recent introduction of nanotechnology into the field of additive manufacturing (AM) and the consequent development of nonconventional polymer nanocomposites suitable for 3D printing. In the present work, different weight percentages (up to 6 wt % in total) of carbon-based nanostructures—multiwalled carbon nanotubes (MWCNTs), graphene nanoplatelets (GNPs), and a combination of both fillers (MWCNTs/GNPs)—were incorporated into poly(lactic) acid (PLA, Ingeo™) in an attempt to overcome several limitations of conventional 3D manufacturing based on insulating materials. Solution blending and melt mixing were the two fabrication methods adopted for preparation of the samples under test. A comparison of the morphological, rheological, and electrical properties of the resulting nanocomposites was carried out. Moreover, for the same weight concentrations, the influence of physical and geometrical features (i.e., functionalization and aspect ratio) of the embedded fillers was also investigated. Rheological methods were applied to control the quality of fillers dispersion in PLA matrix. The rheological percolation threshold was considered as reference in order to evaluate the internal structure of nanodispersions. TEM visualization, combined with rheological characterizations, was used for efficient control of the nanofiller dispersion. DC characterization revealed that lower electrical percolation thresholds and higher values of electrical conductivity were achieved using fillers with a larger aspect ratio and melt mixing, respectively. Moreover, given the possibility of obtaining complex and appropriate shapes for electromagnetic compatibility (EC) applications, electromagnetic (EM) response of the nanocomposites at the highest filler concentration was investigated in GHz and THz regions. It was found that the electromagnetic shielding efficiency (EMI) of nanocomposites strongly depended on the aspect ratio of the nanofillers, whereas the type of processing technique did not have a significant effect. Therefore, a careful choice of methods and materials must be made to address the final application for which these materials and further 3D printed architectures are designed. [ABSTRACT FROM AUTHOR]