Passivation Dynamics in the Anisotropic Deposition and Stripping of Bulk Magnesium Electrodes During Electrochemical Cycling.

Although rechargeable magnesium (Mg) batteries show promise for use as a next generation technology for high-density energy storage, little is known about the Mg anode solid electrolyte interphase and its implications for the performance and durability of a Mg-based battery. We explore in this report passivation effects engendered during the electrochemical cycling of a bulk Mg anode, characterizing their influences during metal deposition and dissolution in a simple, nonaqueous, Grignard electrolyte solution (ethylmagnesium bromide, EtMgBr, in tetrahydrofuran). Scanning electron microscopy images of Mg foil working electrodes after electrochemical polarization to dissolution potentials show the formation of corrosion pits. The pit densities so evidenced are markedly potential-dependent. When the Mg working electrode is cycled both potentiostatically and galvanostatically in EtMgBr these pits, formed due to passive layer breakdown, act as the foci for subsequent electrochemical activity. Detailed microscopy, diffraction, and spectroscopic data show that further passivation and corrosion results in the anisotropic stripping of the Mg {0001} plane, leaving thin oxide-comprising passivated side wall structures that demark the {0001} fiber texture of the etched Mg grains. Upon long-term cycling, oxide side walls formed due to the pronounced crystallographic anisotropy of the anodic stripping processes, leading to complex overlay anisotropic, columnar structures, exceeding 50 µm in height. The passive responses mediating the growth of these structures appear to be an intrinsic feature of the electrochemical growth and dissolution of Mg using this electrolyte.

Generalizing thermodynamic properties of bulk single-walled carbon nanotubes.

The enthalpy and Gibbs free energy thermodynamical potentials of single walled carbon nanotubes were studied of all types (armchairs, zig-zags, chirals (n>m), and chiral (n

Infrared spectral model for subwavelength particles of mixed composition based on the spectra of individual particles with calibration data for airborne dust.

A Mie-Bruggeman spectral model is presented which predicts the orientationally averaged, infrared spectra of individual mixed-composition particles or the average spectrum of collections of such particles. The model uses parameters extracted from sets of individual particle spectra of pure materials known to be in subject mixtures. The spectra of both calibrants and subject particles were recorded by trapping size-selected particles in the holes of plasmonic metal mesh. Calibrating data is presented for quartz, calcite, dolomite, three clays, gypsum, polyethylene, and living organic material (yeast cells). The individual particle spectra of these calibrants are averaged to account for crystal orientation effects, fit by a Mie theory model, and tabulated herein as dielectric functions of each component. The component dielectric functions are combined in this model with Bruggeman effective medium theory producing a spectral prediction for mixed-composition particles. The Mie-Bruggeman model was used to analyze the composition of dust from our lab air [K. E. Cilwa et al. J. Phys. Chem. C 2011, 115, 16910] based on the average spectrum of the dust particles. The model does a reasonable job of characterizing the dust in our laboratory air exhibiting promise for future applications. This work presents the model and illustrates potential; however, much more work will be required before its accuracy as a quantitative analytical method is established.

Spectral challenges of individual wavelength-scale particles: strong phonons and their distorted lineshapes.

Beyond our own interest in airborne particulate matter, the prediction of extinction and absorption spectra of single particles of mixed composition has wide use in astronomy, geology, atmospheric sciences, and nanotechnology. Single particle spectra present different challenges than traditional spectroscopic approaches. To quantify the amount of a material in a bulk sample (molecules in solution or the gas phase), one might employ the Beer-Lambert law assuming a simple slab-type assay geometry and averaging over orientation, whereas with single particles one might have a specific orientation and require a nonlinear, Mie-like particle theory. The complicating single particle issues include: strong and broad scattering at wavelengths similar to the particle size, phonon lineshape phase shifting, particle shape effects, distortion of transition lineshapes by strong vibrational bands, bi- and trirefringence, crystal orientation effects including dispersion, and composition mixtures. This work uses a combination of three-dimensional finite difference time domain (3D-FDTD) calculations and experimental infrared spectra on single, crystalline quartz particles to illustrate some of the challenges--in particular the distortion of lineshapes by strong phonons that lie within a range of strong scattering. It turns out that many mineral dust components in the inhalable size range have strong phonons. A Mie-Bruggeman model for single particle spectra is presented to isolate the effects of strong phonons on lineshapes which has utility for analysing the spectra of single, mixed-composition particles. This model will ultimately enable the determination of volume fractions of components in single particles that are mixtures of many materials with strong phonons, as are the dust particles breathed into people's lungs.

Single Airborne Dust Particles using Plasmonic Metal Films with Hole Arrays.

An airborne dust particle is trapped in the hole of a plasmonic metal film with a patterned array of holes (mesh) by pumping air through the mesh. Both scatter-free infrared spectra and scanning electron images are obtained on the same individual airborne dust particle, showing the feasibility of multiple, nondestructive experiments on a single, subwavelength particle. Ultimately, this may help to elucidate the effect of shape, orientation, and crystallinity on IR dust particle spectra.

Developing Plasmonics Under the Infrared Microscope: From Ni Nanoparticle Arrays to Infrared Micromesh.

Microscopes typically collect light over large ranges of angles dispersing plasmonic resonances. While this is an advantage for recording spectra of microscopic particles, it is a disadvantage for sensing by resonance shifts. Adaptations are described herein which enable one to identify, manipulate, and examine narrow plasmonic resonances under a microscope. Noting more general familiarity with metal nanoparticle arrays, a useful perspective is offered by relating the optical transmission of small Ni nanoparticle arrays to that of Ni metal films with microhole arrays, i.e., infrared-active mesh. This perspective also includes the connection to traditional dispersion studies, a new microscope method to measure the propagation length of surface-plasmon-polariton-mediated resonances, and the shifting of resonance positions by latex microspheres in the holes of mesh. A useful perspective is offered by relating the optical transmission of small Ni nanoparticle arrays to that of Ni metal films with microhole arrays, i.e., infrared-active mesh.

Modifying infrared scattering effects of single yeast cells with plasmonic metal mesh.

The scattering effects in the infrared (IR) spectra of single, isolated bread yeast cells (Saccharomyces cerevisiae) on a ZnSe substrate and in metal microchannels have been probed by Fourier transform infrared imaging microspectroscopy. Absolute extinction [(3.4±0.6)×10(-7) cm(2) at 3178 cm(-1)], scattering, and absorption cross sections for a single yeast cell and a vibrational absorption spectrum have been determined by comparing it to the scattering properties of single, isolated, latex microspheres (polystyrene, 5.0 µm in diameter) on ZnSe, which are well modeled by the Mie scattering theory. Single yeast cells were then placed into the holes of the IR plasmonic mesh, i.e., metal films with arrays of subwavelength holes, yielding "scatter-free" IR absorption spectra, which have undistorted vibrational lineshapes and a rising generic IR absorption baseline. Absolute extinction, scattering, and absorption spectral profiles were determined for a single, ellipsoidal yeast cell to characterize the interplay of these effects.

Propagation lengths of surface plasmon polaritons on metal films with arrays of subwavelength holes by infrared imaging spectroscopy.

Metal films with arrays of subwavelength holes (mesh) exhibit extraordinary transmission resonances to which many attribute a role for surface plasmon polaritons (SPPs); others debated this point. Experimental measurements of propagation lengths are presented under conditions that pertain to the use of SPPs for surface spectroscopy. The lateral extent of electromagnetic propagation along the mesh surface is measured by recording absorption spectra of a line of latex microspheres as a function of distance away from the line along the mesh. Measurements reveal an exponential functional form for decay of absorption signal laterally from the absorption source. Results at 697 cm(-1), which are closest to the strongest transmission resonance of the mesh, reveal a 1/e propagation distance along the surface of 17.8+/-2.9 microm. This is 40% larger than the lattice spacing implicating the holes as the SPP damping mechanism, however, this is significantly shorter than smooth metal expectations.