Evaporative Moisture Loss from Heterogeneous Stone: Material- Environment Interactions During Drying

The complexities of evaporation from structurally and mineralogically heterogeneous sandstone (Locharbriggs Sandstone) are investigated through a laboratory-based experiment in which a variety of environmental conditions are simulated. Data reported demonstrate the significance of material-environment interactions on the spatial and temporal variability of evaporative dynamics. Evaporation from porous stone is determined by the interplay between environmental, material and solution properties, which govern the rate and mode by which water is transmitted to, and subsequently removed from, an evaporating surface. Initially evaporation is marked by high rates of moisture loss controlled by external atmospheric conditions; then, when a critical level of surface moisture content is reached, hydraulic continuity between the stone surface and subsurface is disrupted and the drying front recedes
beneath the surface, evaporation rates decrease and are controlled by the ability of the material to transport water vapour to the surface. Pore size distribution and connectivity, as well as other material properties, control the timing of each stage of evaporation and the nature of the transition.

These experimental data highlight the complexity of evaporation, demonstrating that different regions of the same stone can exhibit varying moisture dynamics during drying and that the rate and nature of evaporative loss differs under different environmental conditions. The results identify the importance of material-environment interactions during drying and that stone micro-environmental conditions cannot be inferred from ambient data alone.
These data have significance for understanding the spatial distribution of stone surface weathering-related morphologies in both the natural and built environments where mineralogical and/or structural heterogeneity creates differences in moisture flux and hence variable drying rates. Such differences may provide a clearer explanation for the initiation and subsequent development of complex weathering responses where areas of significant deterioration can be found alongside areas that exhibit little or no evidence surface breakdown.

Alternative drying techniques for the manufacturing of hydrogel-forming and dissolving microneedle arrays.

Dissolving polymeric microneedle arrays and hydrogel-forming microneedle arrays have attracted much attention during recent years due mainly to their biocompatibility and capacity for enhanced drug delivery. Nevertheless, for the production of this type of devices, typically, a drying step is required. Microneedles are prepared following a micromoulding technique using aqueous blends of Gantrez® S-97. Currently, production of microneedles arrays involves a long drying process of 48 hours. Therefore alternative drying methods were investigated including microwave radiation and hot air convection.

First-Principles Study of the Electronic and Magnetic Properties of Defects in Carbon Nanostructures

Understanding the magnetic properties of graphenic nanostructures is instrumental in future spintronics applications. These magnetic properties are known to depend crucially on the presence of defects. Here we review our recent theoretical studies using density functional calculations on two types of defects in carbon nanostructures: Substitutional doping with transition metals, and sp$^3$-type defects created by covalent functionalization with organic and inorganic molecules. We focus on such defects because they can be used to create and control magnetism in graphene-based materials. Our main results are summarized as follows: i)Substitutional metal impurities are fully understood using a model based on the hybridization between the $d$ states of the metal atom and the defect levels associated with an unreconstructed D$_{3h}$ carbon vacancy. We identify three different regimes, associated with the occupation of distinct hybridization levels, which determine the magnetic properties obtained with this type of doping; ii) A spin moment of 1.0 $\mu_B$ is always induced by chemical functionalization when a molecule chemisorbs on a graphene layer via a single C-C (or other weakly polar) covalent bond. The magnetic coupling between adsorbates shows a key dependence on the sublattice adsorption site. This effect is similar to that of H adsorption, however, with universal character; iii) The spin moment of substitutional metal impurities can be controlled using strain. In particular, we show that although Ni substitutionals are non-magnetic in flat and unstrained graphene, the magnetism of these defects can be activated by applying either uniaxial strain or curvature to the graphene layer. All these results provide key information about formation and control of defect-induced magnetism in graphene and related materials.

Interplay of Defects, Magnetism, Ripples and Strain in Graphene

We present a comprehensive study based on first-principles calculations about the interplay of four important ingredients on the electronic structure of graphene: defects + magnetism + ripples + strain. So far they have not been taken into account simultaneously in a set of ab initio calculations. Furthermore, we focus on the strain dependence of the properties of carbon monovacancies, with special attention to magnetic spin moments. We demonstrated that such defects show a very rich structural and spin phase-diagram with many spin solutions as function of strain. At zero strain the vacancy shows a spin moment of 1.5 Bohrs that increases up to 2 Bohrs with stretching. Changes are more dramatic under compression: the vacancy becomes non-magnetic under a compression larger than 2%. This transition is linked to the structural modifications associated with the formation of ripples in the graphene layer. Our results suggest that such interplay could have important implications for the design of future spintronics devices based on graphene derivatives, as for example a spin-strain switch based on vacancies.