Influence of dopants on the impermeability of graphene.

Graphene has attracted much attention as an impermeable membrane and a protective coating against oxidation. While many theoretical studies have shown that defect-free graphene is impermeable, in reality graphene inevitably has defects in the form of grain boundaries and vacancies. Here, we study the effects of N-dopants on the impermeability of few-layered graphene (FLG) grown on copper using chemical vapor deposition. The grain boundaries in FLG have minimal impact on their permeability to oxygen as they do not provide a continuous channel for gas transport due to high tortuosity. However, we experimentally show that the N-dopants in FLG display multiple configurations that create structural imperfections to selectively allow gas molecules to permeate. We used a comprehensive array of tools including Raman spectroscopy, X-ray photoelectron spectroscopy, optically stimulated electron emission measurements, and density functional theory of N-doped graphene on copper to elucidate the effects of dopant configuration on the impermeability of graphene. Our results clearly show that oxygen can permeate through graphene with non-graphitic nitrogen dopants that create pores in graphene and oxidize the underlying Cu substrate while graphitic nitrogen dopants do not show any changes compared to the pristine form. Furthermore, we observed that the work function of graphene can be tuned effectively by changing the dopant configuration.

Direct measurement of shear properties of microfibers.

As novel fibers with enhanced mechanical properties continue to be synthesized and developed, the ability to easily and accurately characterize these materials becomes increasingly important. Here we present a design for an inexpensive tabletop instrument to measure shear modulus (G) and other longitudinal shear properties of a micrometer-sized monofilament fiber sample, such as nonlinearities and hysteresis. This automated system applies twist to the sample and measures the resulting torque using a sensitive optical detector that tracks a torsion reference. The accuracy of the instrument was verified by measuring G for high purity copper and tungsten fibers, for which G is well known. Two industrially important fibers, IM7 carbon fiber and Kevlar(®) 119, were also characterized with this system and were found to have G = 16.5 ± 2.1 and 2.42 ± 0.32 GPa, respectively.

Mechanical resonances of helically coiled carbon nanowires.

Despite their wide spread applications, the mechanical behavior of helically coiled structures has evaded an accurate understanding at any length scale (nano to macro) mainly due to their geometrical complexity. The advent of helically coiled micro/nanoscale structures in nano-robotics, nano-inductors, and impact protection coatings has necessitated the development of new methodologies for determining their shear and tensile properties. Accordingly, we developed a synergistic protocol which (i) integrates analytical, numerical (i.e., finite element using COMSOL) and experimental (harmonic detection of resonance; HDR) methods to obtain an empirically validated closed form expression for the shear modulus and resonance frequency of a singly clamped helically coiled carbon nanowire (HCNW), and (ii) circumvents the need for solving 12th order differential equations. From the experimental standpoint, a visual detection of resonances (using in situ scanning electron microscopy) combined with HDR revealed intriguing non-planar resonance modes at much lower driving forces relative to those needed for linear carbon nanotube cantilevers. Interestingly, despite the presence of mechanical and geometrical nonlinearities in the HCNW resonance behavior the ratio of the first two transverse modes f2/f1 was found to be similar to the ratio predicted by the Euler-Bernoulli theorem for linear cantilevers.

Development and testing of a silver chloride-impregnated activated carbon for aqueous removal and sequestration of iodide.

Silver impregnated activated carbon (SIAC) can effectively remove iodide from water and sequester it in the form of AgI(s)). Given the extremely insoluble nature of AgI(s), the spent SIAC can be safely disposed of in land burial facilities. However, when the molar ratio of silver to iodide is greater than one, which is typical for waters contaminated with iodide, unreacted silver on the SIAC leached into solution with decreasing pH. To minimize silver leaching, a silver chloride impregnated activated carbon (SIAC-Cl) was produced from a SIAC. Scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) and X-Ray Diffraction (XRD) analyses confirmed the presence of silver chloride on the SIAC-Cl. Batch isotherm experiments conducted at pH 5, 7 and 8 showed that the iodide uptakes of SIAC-Cl and SIAC were similar and independent of pH. SEM/EDX and XRD analyses after reaction with iodide indicated that chloride was exchanged with iodide to form AgI(s) on the SIAC-Cl. Batch leaching experiments demonstrated that leaching of silver from SIAC-Cl under acidic conditions was significantly lower than from SIAC. The performance of SIAC and SIAC-Cl for practical applications was evaluated by conducting column experiments using a radioactively contaminated groundwater that included 129I. SIAC and SIAC-Cl showed similar degrees of iodide uptake. However, a significant degree of silver leaching, about 50% of the total silver, occurred from the SIAC during the course of the column experiments, whereas silver leaching from SIAC-Cl was remarkably low (only 6% of the total silver). SIAC-Cl appears to be a suitable getter material to remove and sequester iodide from contaminated waste streams.

Evaluation of a conceptual model for the subsurface transport of plutonium involving surface mediated reduction of PuV to PuIV.

A conceptual model is proposed to explain the transport behavior of plutonium in laboratory columns packed with a sandy coastal soil from the U.S. Department of Energy (DOE)'s Savannah River Site. The column transport experiments involved the introduction of a finite step input of plutonium, predominately in the +5 oxidation state, into the columns followed by elution with a low-carbonate solution of 0.02 M NaClO4 at pH 3, 5, and 8. Total plutonium concentrations were measured in the effluent as a function of time. These elution profiles suggest at least two distinct physical/chemical forms of plutonium, each with a different mobility. To explain the observed behavior, the following conceptual model was evaluated: [1] equilibrium partitioning of plutonium (V) and plutonium (IV) between the aqueous and sorbed phases as defined by pH-dependent, oxidation-state specific distribution coefficients and [2] kinetic reduction of plutonium (V) to plutonium (IV) in the sorbed phase. The conceptual model was applied to the column experiments through a one-dimensional advective/dispersive mathematical model, and predictions of the mathematical model were compared with the experimental data. Overall, the model was successful in predicting some of the major features observed in the experiments. It also yielded quantitative estimates of the rate constant for surface mediated reduction of plutonium (V) to plutonium (IV) that were of the same order (10(-4) to 10(-5) s(-1)) as those calculated from batch data both for this soil and for goethite.