While the dispersion of nanomaterials is known to be effective in enhancing the thermal conductivity and specific heat capacity of fluids, the mechanisms behind this enhancement remain to be elucidated. Herein, we report on highly stable, surfactant-free graphene nanofluids, based on N,N-dimethylacetamide (DMAc) and N,N-dimethylformamide (DMF), with enhanced thermal properties. An increase of up to 48% in thermal conductivity and 18% in specific heat capacity was measured. The blue shift of several Raman bands with increasing graphene concentration in DMF indicates that there is a modification in the vibrational energy of the bonds associated with these modes, affecting all the molecules in the liquid. This result indicates that graphene has the ability to affect solvent molecules at long-range, in terms of vibrational energy. Density functional theory and molecular dynamics simulations were used to gather data on the interaction between graphene and solvent, and to investigate a possible order induced by graphene on the solvent. The simulations showed a parallel orientation of DMF towards graphene, favoring π-π stacking. Furthermore, a local order of DMF molecules around graphene was observed suggesting that both this special kind of interaction and the induced local order may contribute to the enhancement of the fluid's thermal properties.
We report on the structural, mechanical and thermal analysis of 40 nm thick polystyrene-blockpoly (ethylene oxide) (PS-b-PEO) block copolymer (BCP) films coated with evaporated chromium layers of different thicknesses (1, 2 and 5 nm). Solvent annealing processes allow the structural control of the BCP films morphology by re-arranging the position of the PEO cylinders parallel to the substrate plane. High-vacuum scanning thermal microscopy and ultrasonic force microscopy measurements performed in ambient pressure revealed that the nanometer thick metal coated layers strongly influence the heat dissipation in the BCP films and the local surface stiffness of the individual BCP domains, respectively. The measured tip-sample effective thermal resistance decreases from 6.1×10 7 to 2.5×10 7 KW -1 with increasing Cr film thickness. In addition, scanning probe microscopy measurements allow the thermal and mechanical mapping of the two segregated polymer domains (PEO-PS) of sub-50 nm characteristic sizes, with sub-15 nm thermal spatial resolution. The results revealed the effect of the surface morphology of the BCP and the incorporation of the metal film on the nanoscale thermal properties and volume self-assembly on the mechanical properties. The findings from this study provide insight in the formation of high aspect ratio BCP-metal structures with the more established applications in lithography. In addition, knowledge on the thermal and mechanical properties at the nanoscale is required in emergent applications, such as thermal management, where the BCP is part of the final structure or device.
Mechanochemistry has attracted a lot of attention over the last few decades with a rapid growth in the number of publications due to its unique features. However, very little is known about how mechanical energy is converted into chemical energy. Most of the published works using mechanochemistry neglect the required attention to the experimental parameters and their effect over the resulting products, what makes extremely difficult to reproduce the results from lab to lab. Moreover, if it is taken into consideration the broad range of experimental conditions used in different studies, it is quite difficult to compare results and set optimum conditions. As a result, mechanochemistry is generally viewed as a "black box". The aim of this work is to provide some insight into mechanochemistry. Thus, a simple kinematic-kinetic approach that allows the full parametrization of mechanically induced reactions is proposed. In an analogous way to thermally activated process, it is shown that kinetic modeling can serve to parametrize and model mechanically induced reactions as a function of the milling parameters with great reliability, thereby gaining prediction capability. As a way of example, this methodology has been applied for the first time to the mechanochemical reaction of Co and Sb to form CoSb3, a skutterudite-type thermoelectric material. Moreover, the universality of this methodology has also been validated with data from the literature. A key feature of the proposed kinematickinetic approach is that it can be extrapolated to other mechanically induced reactions, either inorganic or organic.
Here, we describe selected work on the development and study of nanofluids based on graphene and reduced graphene oxide both in aqueous and organic electrolytes. A thorough study of thermal properties of graphene in amide organic solvents (N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone) showed a substantial increase of thermal conductivity and specific heat upon graphene integration in those solvents. In addition to these thermal studies, our group has also pioneered a distinct line of work on electroactive nanofluids for energy storage. In this case, reduced graphene oxide (rGO) nanofluids in aqueous electrolytes were studied and characterized by cyclic voltammetry and charge-discharge cycles (i.e., in new flow cells). In addition, hybrid configurations (both hybrid nanofluid materials and hybrid cells combining faradaic and capacitive activities) were studied and are summarized here.
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