Molecular junctions for thermal transport between graphene nanoribbons: covalent bonding vs. interdigitated chains

Proper design and manufacturing thermal bridges based on molecular junctions at the contact between graphene platelets or other thermally conductive nanoparticles would provide a fascinating way to produce efficient heat transport networks for the exploitation in heat management applications. In this work, using Non Equilibrium Molecular Dynamics, we calculated thermal conductance of alkyl chains used as molecular junctions between two graphene nanoribbons, both as covalently bound and Van der Waals interdigitated chains. Effect of chain length, grafting density, temperature and chain interdigitation were systematically studied. A clear reduction of conductivity was found with increasing chain length and decreasing grafting density, while lower conductivity was observed for Van der Waals interdigitated chains compared to covalently bound ones. The importance of molecular junctions in enhancing thermal conductance at graphene nanoribbons contacts was further evidenced by calculating the conductance equivalence between a single chain and an overlapping of un-functionalized graphene sheets. As an example, one single pentyl covalently bound chain was found to have a conductance equivalent to the overlapping of an area corresponding to about 152 carbon atoms. These results contribute to the understanding of thermal phenomena occurring within networks of thermally conductive nanoparticles, including graphene nanopapers and graphene-based polymer nanocomposites, which are or high interest for the heat management application in electronics and generally in low-temperature heat exchange and recovery

Three Organic/inorganic Nanolayers on Flexible Foam Allow Retaining Superior Flame Retardancy Performance Upon Mechanical Compression Cycles

The water-based deposition of flame retardant coatings on flexible polyurethane foams has attracted great interest among the scientific community due to the great performances associated with this technology. Unfortunately, this approach results inefficient as it requires a high number of steps in order to achieve the desired properties. In this paper, we report the production of flame-retardant foams by means of the simple deposition of only three nanoparticles containing layers. The composition and order of the deposited layer has been designed in order to provide specific flame retardant actions, targeting the delayed release of polymer decomposition products to the gas phase, the dilution of these flammable products with water, and the intumescent barrier formation. The morphology of the coated foams after the adsorption of each layer has been investigated by scanning electron microscopy, demonstrating the ability of each adsorbed layer to completely wrap the complex 3D structure of the foam. This three layers-based coating produces a protective exoskeleton that is capable of self-extinguishing the flame in standard flammability tests, leaving the foam almost unaffected (final residue 98%). In forced combustion tests by cone calorimetry, treated foams showed considerably reduced combustion rates, with reduced peak of heat release rate (−50%) as well as consistent reduction in the smoke optical density (−51%) and the total smoke release (−34%). In addition, treated foams have been demonstrated to maintain the ability to self-extinguish the flame as well as reduced combustion rates and smoke production even after being subjected to 100 compression cycles

Layer-by-Layer Assembly of Efficient Flame Retardant Coatings Based On High Aspect Ratio Graphene Oxide and Chitosan Capable of Preventing Ignition of PU Foam

The layer-by-layer (LbL) technique is adopted for the construction of multilayers encompassing chitosan and graphene oxide (GO) platelets capable of improving the flame retardant properties open cell PU foams. The LbL assembly follows a linear growth regime as evaluated by infrared spectroscopy and yields a multilayer structure where GO platelets are embedded within a chitosan continuous matrix. 3 and 6 bi-layers (BL) can efficiently coat the complex 3D structure of the foam and substantially improve its flame retardant properties. 3BL only add 10% to the original mass and can suppress the melt dripping during flammability and reduce both the peak of heat release rate by 54% and the total smoke released by 59% in forced combustion tests. Unprecedented among other LbL assemblies employed for FR purposes, the deposition 6BL is capable of slowing down the release of combustible volatile to the limits of non-ignitability thus preventing ignition in half of the specimens during cone calorimetry tests. This has been ascribed to the formation of a protective coating where the thermally stable char produced by chitosan serves as a continuous matrix embedding GO platelets, which control volatile release while mechanically sustaining the PU foam structure

Thermal Evolution of Nanocomposites. When Nanoparticles are Effective in Polymer Fire Retardancy

A decade of research and development concerning polymer nanocomposites has shown the essential features of their combustion process. Nanocomposites actually display a fire retardant behaviour because they avoid fire propagation by dripping of hot and flaming polymer particles and reduce the rate of combustion. The mechanism involved in nanocomposites fire retardance is based on formation on heating of a ceramic protective, insulating layer on the surface of the burning material resulting from coalescence of nanofillers enclosing char from surface polymer charring, catalysed by the nanofiller. The thermal evolution of nanocomposites to the fire protective structure is discussed in relation with dispersion and distribution of the nanofillers in the polymer matrix either as it results from nanocomposite preparation or from its thermal evolution. Evaluation of the fire retardant performance of polymer nanocomposites in fire tests representing different fire scenarios (i.e. ignition, flammability and forced combustion) will be discussed in this talk

Star-shaped furoate-PCL: An effective compound for the development of graphite nanoplatelets-based films

The aim of this study was to improve the dispersibility of graphite nanoplatelets (GNP) in films based on poly(ε-caprolactone) (PCL). To this end, a star-shaped PCL with furoate-like end groups (PCL-Fur), potentially capable of interacting/reacting with the surface of the graphene layers through Diels-Alder reactions, was synthesized by enzymatic catalysis. PCL-Fur was applied for film development by blending it with a commercial high molecular weight PCL (PCL-L) and GNP. The reactivity of GNP with respect to furoate groups was demonstrated by studying the thermal behavior of the GNP/methyl 2-furoate system, while the dispersibility of graphite in the solution containing PCL-Fur was studied by UV–Vis measurements. GNP proved to be well dispersed and adhered to the polymer matrix in the PCL-L/PCL-Fur/GNP composite films prepared by casting, in contrast to the films based on the neat PCL-L. This fine GNP dispersion resulted in films characterized by high electrical conductivity

Effects of Graphite Oxide Nanoparticle Size on the Functional Properties of Layer-by-Layer Coated Flexible Foams

The exploitation of self-assembled coatings comprising graphite oxide (GO) nanoplates has been recently demonstrated as a promising route to improve the fire safety of flexible polyurethane (PU) foams. However, limited knowledge has been gathered on the correlations between the physical and chemical properties of different GO grades and the performance obtained in this application. This work addresses the effects of the nanoparticle dimensions on the layer-by-layer (LbL) assembly and flame-retardant properties of GO-based coatings deposited on PU foams. To this aim, three GO bearing different lateral sizes and thicknesses were selected and LbL-assembled with chitosan (CHIT). Coating growth and morphology were evaluated by FTIR and FESEM, respectively. The resulting CHIT/GO assemblies were demonstrated to be capable of slowing down the combustion of the PU both in flammability and forced combustion tests. In addition, compressive stress/strain tests pointed out that the LbL-coated foams (22–24 kg/m3) could easily replace denser commercial PU foam (40–50 kg/m3) with weight reduction potentials in the transport field. These results are correlated with the properties of the employed GO. The production of assemblies characterized by a high density of CHIT/GO interfaces is identified as the main parameter controlling the FR efficiency and the mechanical properties of the coatings

A Novel Electrostimulated Drug Delivery System Based on PLLA Composites Exploiting the Multiple Functions of Graphite Nanoplatelets

A novel drug delivery system based on poly(l-lactide) (PLLA), graphite, and porphyrin was developed. In particular, 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin (THPP) was chosen because, besides its potential as codispersing agent of graphite, it is a pharmacologically active molecule. Graphite nanoplatelets, homogeneously dispersed in both the neat PLLA and the PLLA/porphyrin films, which were prepared by solution casting, turned out to improve the crystallinity of the polymer. Moreover, IR measurements demonstrated that unlike PLLA/porphyrin film, where the porphyrin was prone to aggregate causing variable concentration throughout the sample, the system containing also GNP was characterized by a homogeneous dispersion of the above molecule. The effect of graphite nanoplatelets on the thermal stabilization, electrical conductivity, and improvement of mechanical properties of the polymer resulted to be increased by the addition of the porphyrin to the system, thus demonstrating the role of the molecule in ameliorating the filler dispersion in PLLA. The porphyrin release from the composite film, occurring both naturally and with the application of an electrical field, was measured using an UV-vis spectrophotometer. Indeed, voltage application turned out to improve significantly the kinetic of drug release. The biocompatibility of the polymer matrix as well as the mechanical and thermal properties of the composite together with its electrical response makes the developed material extremely promising in biological applications, particularly in the drug delivery field

Evaluation of the charge transfer kinetics of spin-coated BiVO4 thin films for sun-driven water photoelectrolysis

tThe present research work focuses on bismuth vanadate (BiVO4) thin films deposited on FTO-coated glasselectrodes through the spin-coating technique, and discusses the influence of different film morphologies(dense and porous) on the physicochemical properties and photoelectrochemical (PEC) performance ofthe as-prepared photoanodes, for the water splitting reaction. The surface recombination phenomenon,which is one of the main issues of BiVO4, has been quantified by means of two distinct approaches: tran-sient photocurrent measurements and electrochemical impedance spectroscopy (EIS). This phenomenonhas resulted to be higher in the porous material, thus a poorer performance has been observed than inthe dense material. In order to increase the BiVO4efficiency, a cobalt phosphate (CoPi) catalyst has beenphoto-electrodeposited onto the best BiVO4electrode, employing an optimized technique and a pho-tocurrent of up to 3 mA/cm2at 1.23 V vs. RHE under neutral pH and 1 sun irradiation (100 mW/cm2)has been achieved. The charge transfer kinetics of the BiVO4photoanodes, with and without CoPi, hasalso been quantified. The beneficial effect of this water oxidation catalyst, as well as the influence of thepreparation method on the uniformity of the film and on its actual performance, is discussed in view ofits prospective application in a real PEC device