Understanding solvent spreading for Langmuir deposition of nanomaterial films: a Hansen solubility parameter approach

In order to prepare high-quality Langmuir films of two-dimensional materials it is important to select a solvent optimized for both exfoliation and spreading at the air-water interface. Whilst it is generally accepted that exfoliation and stabilisation of two-dimensional materials is well-described using the Hansen solubility parameter theory, a complementary description of solvent spreading behaviour is lacking. To this end we develop an understanding of solvent spreading using a Hansen solubility parameter framework. Our model accurately predicts the behaviour of both water-immiscible and water-miscible solvents in Langmuir film formation experiments. We demonstrate that spreading behaviour can be modified by controlling the surface pressure of the subphase using an amphiphilic species and accordingly utilise this approach to determine the maximum spreading pressure for a selection of solvents. Ultimately, by building on this understanding we open up additional routes to optimize the preparation of Langmuir films of two-dimensional materials and other nanoparticles

Functional liquid structures by emulsification of graphene and other two-dimensional nanomaterials

Pickering emulsions stabilised with nanomaterials provide routes to a range of functional macroscopic assemblies. We demonstrate the formation and properties of water-in-oil emulsions prepared through liquid-phase exfoliation of graphene. Due to the functional nature of the stabiliser, the emulsions exhibit conductivity due to inter-particle tunnelling. We demonstrate a strain sensing application with a large gauge factor of ~40; the highest reported in a liquid. Our methodology can be applied to other two-dimensional layered materials opening up applications such as energy storage materials, and flexible and printable electronics

The impact of oceanic near-inertial waves on climate

Author Posting. © American Meteorological Society, 2013. This article is posted here by permission of American Meteorological Society for personal use, not for redistribution. The definitive version was published in Journal of Climate 26 (2013): 2833–2844, doi:10.1175/JCLI-D-12-00181.1.The Community Climate System Model, version 4 (CCSM4) is used to assess the climate impact of wind-generated near-inertial waves (NIWs). Even with high-frequency coupling, CCSM4 underestimates the strength of NIWs, so that a parameterization for NIWs is developed and included into CCSM4. Numerous assumptions enter this parameterization, the core of which is that the NIW velocity signal is detected during the model integration, and amplified in the shear computation of the ocean surface boundary layer module. It is found that NIWs deepen the ocean mixed layer by up to 30%, but they contribute little to the ventilation and mixing of the ocean below the thermocline. However, the deepening of the tropical mixed layer by NIWs leads to a change in tropical sea surface temperature and precipitation. Atmospheric teleconnections then change the global sea level pressure fields so that the midlatitude westerlies become weaker. Unfortunately, the magnitude of the real air-sea flux of NIW energy is poorly constrained by observations; this makes the quantitative assessment of their climate impact rather uncertain. Thus, a major result of the present study is that because of its importance for global climate the uncertainty in the observed tropical NIW energy has to be reduced.This research was funded as part of the Climate Process Team on internal wave-driven mixing with NSF Grant Nr E0968771 at NCAR.2013-11-0

Finite-size scaling in silver nanowire films: design considerations for practical devices

We report the first application of finite-size scaling theory to nanostructured percolating networks, using silver nanowire (AgNW) films as a model system for experiment and simulation. AgNWs have been shown to be a prime candidate for replacing Indium Tin Oxide (ITO) in applications such as capacitive touch sensing. While their performance as large area films is well-studied, the production of working devices involves patterning of the films to produce isolated electrode structures, which exhibit finite-size scaling when these features are sufficiently small. We demonstrate a generalised method for understanding this behaviour in practical rod percolation systems, such as AgNW films, and study the effect of systematic variation of the length distribution of the percolating material. We derive a design rule for the minimum viable feature size in a device pattern, relating it to parameters which can be derived from a transmittance-sheet resistance data series for the material in question. This understanding has direct implications for the industrial adoption of silver nanowire electrodes in applications where small features are required including single-layer capacitive touch sensors, LCD and OLED display panels

Carbon nanofoam supercapacitor electrodes with enhanced performance using a water-transfer process

Carbon nanofoam (CNF) is a highly porous,amorphous carbon nanomaterial that can be produced through the interaction of a high-fluence laser and a carbon-based target material. The morphology and electrical properties of CNF make it an ideal candidate for super-capacitor applications. In this paper, we prepare and characterize CNF supercapacitor electrodes through two different processes, namely, a direct process and a water-transfer process. We elucidate the influence of the production process on the microstructural properties of the CNF, as well as the final electrochemical performance. We show that a change in morphology due to capillary forces doubles the specific capacitance of the wet-transferred CNF electrodes

Surfactant-free liquid-exfoliated copper hydroxide nanocuboids for non-enzymatic electrochemical glucose detection

To facilitate printable sensing solutions particles need to be suspended and stabilised in a liquid medium. Hansen parameters were used to identify that alcohol–water blends are ideal for stabilising colloidal copper hydroxide in dispersion. The suspended material can be further separated in various size fractions with a distinct cuboid geometry which was verified using atomic force microscopy. This facilitates the development of Raman spectroscopic metrics for determining particle sizes. This aspect ratio is related to the anisotropic crystal structure of the bulk crystallites. As the size of the nanocuboids decreases electrochemical sensitivity of the material increases due to an increase in specific surface area. Electrochemical glucose sensitivity was investigated using both cyclic voltammetry and chronoamperometry. The sensitivity is noted to saturate with film thickness. The electrochemical response of 253 mA M−1 cm−2 up to 0.1 mM and 120 mA cm−2 up to 0.6 mM allow for calibration of potential devices. These results indicate suitability for use as a glucose sensor and, due to the surfactant-free, low boiling point solvent approach used to exfoliate the nanocuboids, it is an ideal candidate for printable solutions. The ease of processing will also allow this material to be integrated in composite films for improved functionality in future devices

Ultrasensitive strain gauges enabled by graphene-stabilized silicone emulsions

Here, an approach is presented to incorporate graphene nanosheets into a silicone rubber matrix via solid stabilization of oil‐in‐water emulsions. These emulsions can be cured into discrete, graphene‐coated silicone balls or continuous, elastomeric films by controlling the degree of coalescence. The electromechanical properties of the resulting composites as a function of interdiffusion time and graphene loading level are characterized. With conductivities approaching 1 S m−1, elongation to break up to 160%, and a gauge factor of ≈20 in the low‐strain linear regime, small strains such as pulse can be accurately measured. At higher strains, the electromechanical response exhibits a robust exponential dependence, allowing accurate readout for higher strain movements such as chest motion and joint bending. The exponential gauge factor is found to be ≈20, independent of loading level and valid up to 80% strain; this consistent performance is due to the emulsion‐templated microstructure of the composites. The robust behavior may facilitate high‐strain sensing in the nonlinear regime using nanocomposites, where relative resistance change values in excess of 107 enable highly accurate bodily motion monitoring

Mid-infrared electrochromics enabled by intraband modulation in carbon nanotube networks

Tuneable infrared properties, such as transparency and emissivity, are highly desirable for a range of applications, including thermal windows and emissive cooling. Here, we demonstrate the use of carbon nanotube networks spray-deposited onto an ionic liquid-infused membrane to fabricate devices with electrochromic modulation in the mid-infrared spectrum, facilitating control of emissivity and apparent temperature. Such modulation is enabled by intraband transitions in unsorted single-walled carbon nanotube networks, allowing the use of scalable nanotube inks for printed devices. These devices are optimized by varying film thickness and sheet resistance, demonstrating the emissivity modulation (from ∼0.5 to ∼0.2). These devices and the understanding thereof open the door to selection criteria for infrared electrochromic materials based on the relationship between band structure, electrochemistry, and optothermal properties to enable the development of solution-processable large-area coatings for widespread thermal management applications

Raman metrics for molybdenum disulfide and graphene enable statistical mapping of nanosheet populations

The growing research interest and uptake of layered nanomaterials for real-world applications require efficient, reliable, high-quality characterisation methods. Liquid-exfoliated graphene has well-established Raman spectroscopic metrics for mean size and thickness. In association with the high-resolution mapping process described here, distributions of nanosheet properties can be reconstructed. Here, we develop new, robust metrics for length and layer number of MoS₂ nanosheets, developed using resonant Raman spectroscopy, applicable to both liquid- and mechanically-exfoliated MoS₂. The use of metricised Raman mapping analysis, here demonstrated for graphene and MoS₂, facilitates the standardisation of characterisation, allowing the correlation of size- and thickness-sensitive applications’ performance with materials properties