Down the Dimensionality Lane: Thermal Conductivity Enhancement in Carbon-Based Liquid Dispersions.

Carbon allotropes of different dimensionality, i.e., 1D-carbon nanotubes, 2D-graphene nanoplatelets, and 3D-graphite, possess high thermal conductivity (TC > 2000 W/m K). They are, therefore, excellent candidates for filler material aiming at increasing the TC of composites used for thermal management. However, preparing aqueous dispersions of these materials is challenging due to their strong van der Waals attraction, leading to aggregation and subsequent precipitation. Reported dispersion methodologies have failed to disperse large microscale fillers, which are essential for efficient thermal management. In this work, we suggest to "kinetically arrest" the dispersion by using sepiolite, a fiberlike clay, that effectively disperses all three carbon dimensionalities. We explore the effect of filler dimensionality and properties (lateral size, thickness, defect density) on the dispersion TC enhancement. Modeling the TC by the effective medium approach allows lumping all the intrinsic properties of the filler into a single parameter termed "effective TC", providing an accurate prediction of the experimentally measured TC. We show that, by judicious choice of filler, the TC of both water and a water-ethylene glycol mixture can be enhanced by 31% using graphene nanoplatelets of 15 µm in lateral size. We believe that the guidelines obtained in this work provide a useful tool for designing future liquid composites with enhanced thermal properties.

Trapped and Alone: Clay-Assisted Aqueous Graphene Dispersions.

Dispersing graphene sheets in liquids, in particular water, could enhance the transport properties (like thermal conductivity) of the dispersion. Yet, such dispersions are difficult to achieve since graphene sheets are prone to aggregate and subsequently precipitate due to their strong van der Waals interactions. Conventional dispersion approaches, such as surface treatment of the sheets either by surfactant adsorption or by chemical modification, may prevent aggregation. Unfortunately, surfactant-assisted graphene dispersions are typically of low concentration (<0.2 wt %) with relatively small sheets (<1 µm lateral size) while chemical modification is punished by increased defect density within the sheets. We investigate here a new approach in which the concentration of dispersed graphene in water is enhanced by the addition of a fibrous clay mineral, sepiolite. As we demonstrate, the clay particles in water form a kinetically arrested particle network within which the graphene sheets are effectively trapped. This mechanism keeps graphene sheets of high lateral size (∼4 µm) dispersed at high concentrations (∼1 wt %). We demonstrate the application of such dispersions as cooling liquids for thermal management solutions, where a 26% enhancement in the thermal conductivity is achieved as compared to that in a filler-free fluid.

Vegetable-Oil-Based Intelligent Ink for Oxygen Sensing.

An oil-based composite is employed to monitor the exposure to oxygen inside food packaging, aiming at evaluating the package integrity and the freshness of food. The composite is an oxygen-sensitive printable ink consisting of electrically conductive silver microflakes, embedded in a vegetable oil matrix. The sensitivity of the oil to oxygen is driven by its high content of unsaturated fatty acids that polymerize and shrink upon exposure to atmospheric oxygen. Shrinkage increases the silver concentration and induces percolation, manifested by a steep increase in the electrical conductivity of the composite. We found that the electrical conductivity of the composite is related to its exposure time to air. Employing linseed oil as a matrix demonstrates an increase in electrical conductivity from 10-11 to 10-3 S/cm after only 6 days of exposure to air. We also show that this time span could be modified by changing the oil type to fit various expiration periods of food products.

Short and Soft: Multidomain Organization, Tunable Dynamics, and Jamming in Suspensions of Grafted Colloidal Cylinders with a Small Aspect Ratio.

The yet virtually unexplored class of soft colloidal rods with a small aspect ratio is investigated and shown to exhibit a very rich phase and dynamic behavior, spanning from liquid to nearly melt state. Instead of the nematic order, these short and soft nanocylinders alter their organization with increasing concentration from isotropic liquid with random orientation to small domains with preferred local orientation and eventually a multidomain arrangement with a local orientational order. The latter gives rise to a kinetically suppressed state akin to structural glass with detectable terminal relaxation, which, on further increasing concentration, reveals features of hexagonally packed order as in ordered block copolymers. The respective dynamic response comprises four regimes, all above the overlapping concentration of 0.02 g/mL:(I) from 0.03 to 0.1 g/mol, the system undergoes a liquid-to-solidlike transition with a structural relaxation time that grows by 4 orders of magnitude. (II) From 0.1 to 0.2 g/mL, a dramatic slowing-down is observed and is accompanied by an evolution from isotropic to a multidomain structure. (III) Between 0.2 and 0.6 g/mol, the suspensions exhibit signatures of shell interpenetration and jamming, with the colloidal plateau modulus depending linearly on concentration. (IV) At 0.74 g/mL, in the densely jammed state, the viscoelastic signature of hexagonally packed cylinders from microphase-separated block copolymers is detected. These properties set short and soft nanocylinders apart from long colloidal rods (with a large aspect ratio) and provide insights for fundamentally understanding the physics in this intermediate soft colloidal regime and for tailoring the flow properties of nonspherical soft colloids.