Dispersing Carbon Nanotubes with Ionic Surfactants under Controlled Conditions: Comparisons and Insight.

A fundamental understanding of the mechanisms involved in the surfactant-assisted exfoliation and dispersion of carbon nanotubes (CNTs) in water calls for well-controlled experimental methodologies and reliable comparative metrics. We have assessed the ability of several ionic surfactants to disperse single and multiwalled carbon nanotubes, resorting to a stringently controlled sonication-centrifugation method for the preparation of the dispersions. The CNT concentration was accurately measured for a wide range of surfactant concentration, using combined thermogravimetric analysis and UV-vis spectroscopy. The obtained dispersibility curves yield several quantitative parameters, which in turn allow for the effects of nanotube morphology and surfactant properties (aromatic rings, chain length, headgroup charge, and cmc) to be assessed and rationalized, both in terms of dispersed nanotube mass and surface area. The data also indicate that the CNT-surfactant association follows patterns that are markedly different from other equilibrium processes governed by hydrophobicity (such as micellization); in particular, the surfactant concentration needed for maximum dispersibility, c(s,max), and the number of surfactant molecules per unit CNT area at c(s,max) are shown to depend linearly on chain length. The results further suggest that the presence of micelles in the exfoliation process is not a key factor either for starting CNT dispersibility or attaining its saturation value.

Critical parameters in exfoliating graphite into graphene.

Dispersing graphite into few-layers graphene sheets (GS) in water is very appealing as an environmental-friendly, low-cost, low-energy method of obtaining graphene. Very high GS concentrations in water (0.7 mg mL(-1)) were obtained by optimizing the nature of dispersant and the type of ultra-sonic generator. We find that a multi-step sonication procedure involving both tip and bath sources considerably enhances the yield of exfoliated GS. Raman and transmission electron microscopy indicate few-layers graphene patches with typical size of ∼0.65 µm in one dimension and ∼0.35 µm in the other. These were further employed in combination with water-dispersed CNTs to fabricate conductive transparent electrodes for a molecularly-controlled solar-cell with an open-circuit voltage of 0.53 V.

Disperse-and-Mix: Oil as an 'Entrance Door' of Carbon-Based Fillers to Rubber Composites.

Oil was employed as an 'entrance door' for loading rubber with carbon-based fillers of different size and dimensionalities: 1D carbon nanotubes (CNTs), 2D graphene nanoplatelets (GNPs), and 3D graphite. This approach was explored, as a proof of concept, in the preparation of tire tread, where oil is commonly used to reduce the viscosity of the composite mixture. Rubber was loaded with carbon black (CB, always used) and one or more of the above fillers to enhance the thermal and mechanical properties of the composite. The CNT-loaded system showed the best enhancement in mechanical properties, followed by the CNT-GNP one. Rubber loaded with both graphite and GNP showed the best enhancement in thermal conductivity (58%). The overall enhancements in both mechanical and thermal properties of the various systems were analyzed through an overall relative efficiency index in which the total filler concentration in the system is also included. According to this index, the CNT-loaded system is the most efficient one. The oil as an 'entrance door' is an easy and effective novel approach for loading fillers that are in the nanoscale and provide high enhancement of properties at low filler concentrations.

Graphene-graphite hybrid epoxy composites with controllable workability for thermal management.

The substantial heat generation in highly dense electronic devices requires the use of materials tailored to facilitate efficient thermal management. The design of such materials may be based on the loading of thermally conductive fillers into the polymer matrix applied - as a thermal interface material - on the interface between two surfaces to reduce contact resistance. On the one hand, these additives enhance the thermal conductivity of the composite, but on the other hand, they increase the viscosity of the composite and hence impair its workability. This in turn could negatively affect the device-matrix interface. To address this problem, we suggest a tunable composite material comprising a combination of two different carbon-based fillers, graphene nanoplatelets (GNPs) and graphite. By adjusting the GNP:graphite concentration ratio and the total concentration of the fillers, we were able to fine tune the thermal conductivity and the workability of the hybrid polymer composite. To facilitate the optimal design of materials for thermal management, we constructed a 'concentration-thermal conductivity-viscosity phase diagram'. This hybrid approach thus offers solutions for thermal management applications, providing both finely tuned composite thermal properties and workability. We demonstrate the utility of this approach by fabricating a thermal interface material with tunable workability and testing it in a model electronic device.

Graphite-to-Graphene: Total Conversion.

The rush to develop graphene applications mandates mass production of graphene sheets. However, the currently available complex and expensive production technologies are limiting the graphene commercialization. The addition of a protective diluent to graphite during ball-milling is demonstrated to result in a game-changer yield (>90%) of defect-free graphene, whose size is controlled by the milling energy and the diluent type.

Mechanical agitation induces counterintuitive aggregation of pre-dispersed carbon nanotubes.

Mechanical agitation is commonly used to fragment and disperse insoluble materials in liquids. However, here we show that when pristine single-walled carbon nanotubes pre-dispersed in water are subject to vortex-shaking for very short periods (typically 10-60s, power density ∼0.002WmL-1), re-aggregation counterintuitively occurs. The initial dispersions are produced using surfactants as dispersants and powerful tip sonication (∼1WmL-1) followed by centrifugation. Detailed imaging by light and electron microscopies shows that the vortex-induced aggregates consist of loose networks (1-102µm in size) of intertwined tubes and thin bundles. The average aggregate size increases with vortexing time in an apparently logarithmic manner and depends on the dispersant used, initial concentration of nanotubes and size distribution of bundles. The aggregation is, nonetheless, reversible: if the vortex-shaken dispersions are mildly bath-sonicated (∼0.03WmL-1), the flocs break down and re-dispersal occurs. Molecular insight for the mechanism behind this surprising phenomenon is put forth.

Graphene-Based Hybrid Composites for Efficient Thermal Management of Electronic Devices.

Thermal management has become a critical aspect in next-generation miniaturized electronic devices. Efficient heat dissipation reduces their operating temperatures and insures optimal performance, service life, and efficacy. Shielding against shocks, vibrations, and moisture is also imperative when the electronic circuits are located outdoors. Potting (or encapsulating) them in polymer-based composites with enhanced thermal conductivity (TC) may provide a solution for both thermal management and shielding challenges. In the current study, graphene is employed as a filler to fabricate composites with isotropic ultrahigh TC (>12 W m(-1) K(-1)) and good mechanical properties (>30 MPa flexural and compressive strength). To avoid short-circuiting the electronic assemblies, a dispersion of secondary ceramic-based filler reduces the electrical conductivity and synergistically enhances the TC of composites. When utilized as potting materials, these novel hybrid composites effectively dissipate the heat from electronic devices; their operating temperatures decrease from 110 to 37 °C, and their effective thermal resistances are drastically reduced, by up to 90%. The simple filler dispersion method and the precise manipulation of the composite transport properties via hybrid filling offer a universal approach to the large-scale production of novel materials for thermal management and other applications.