Continuous laser-excited photothermal spectrometry of CdSxSe1-x doped glasses

Photothermal lens measurements and finite element modeling are used to examine the physical changes taking place in optical filter glasses. Colored glass and neutral density filters are found to have a strong positive temperature-dependent refractive index change. The overall positive refractive index change is thought to be a consequence of complex counteracting factors: stress-induced birefringence, polarizability, structural network, and temperature-dependent carrier density changes in the CdSxSe1-x microcrystals that produce optical properties of these glasses. Finite element analysis (FEA) modeling is used to examine the temperature profiles and the goodness of the semi-infinite thermal diffusion solution normally used for thermal lens experiments. The results of FEA were used to optimize experimental parameters and calculate values of dn/dT for the glass by comparison with standard liquid samples.     

Three-dimensional direct-write lithography into photopolymer

We demonstrate a three-dimensional direct-write lithography system capable of writing deeply buried, localized index structures into diffusion-mediated photopolymer. The system is similar to that used for femtosecond writing in glass, but has a number of advantages including greater flexibility in the writing media and the ability to use low power, inexpensive, continuous-wave lasers. This system writes index structures both parallel and perpendicular to the writing beam in different types of photopolymers, providing control over the feature size and shape. We demonstrate that this system can be used to create single-mode waveguides that are deeply embedded in the photopolymer medium.     

Stable cycling of double-walled silicon nanotube battery anodes through solid-electrolyte interphase control

Although the performance of lithium ion-batteries continues to improve, their energy density and cycle life remain insufficient for applications in consumer electronics, transport and large-scale renewable energy storage. Silicon has a large charge storage capacity and this makes it an attractive anode material, but pulverization during cycling and an unstable solid-electrolyte interphase has limited the cycle life of silicon anodes to hundreds of cycles. Here, we show that anodes consisting of an active silicon nanotube surrounded by an ion-permeable silicon oxide shell can cycle over 6,000 times in half cells while retaining more than 85% of their initial capacity. The outer surface of the silicon nanotube is prevented from expansion by the oxide shell, and the expanding inner surface is not exposed to the electrolyte, resulting in a stable solid-electrolyte interphase. Batteries containing these double-walled silicon nanotube anodes exhibit charge capacities approximately eight times larger than conventional carbon anodes and charging rates of up to 20C (a rate of 1C corresponds to complete charge or discharge in one hour).     

Multiscale modeling reveals poisoning mechanisms of MgO-supported Au clusters in CO oxidation

Catalyst deactivation mechanisms on MgO-supported Au(6) clusters are studied for the CO oxidation reaction via first-principle kinetic Monte Carlo simulations and shown to depend on support vacancies. In defect-poor MgO or in the presence of a Mg vacancy, O(2) does not bind to the clusters and the catalyst is poisoned by CO. On Au clusters interacting with O vacancies of the support, O(2) can be chemisorbed and transient activity is observed. In this case, an unexpected catalyst "breathing" mechanism (restructuring) leads to carbonate formation and catalyst deactivation, rationalizing several experimental observations. Our study underscores the importance of the cluster's charge state and dynamics on catalytic activity.     

A decision model for the analysis of ergonomic investments

Costs associated with worker injuries can be high and some suggest investments in ergonomic solutions can lower those costs. However, many employers are still unsure if investing in various ergonomic solutions will generate benefits such as increased production and/or reduce workmen's compensation expenses. Estimating current losses and predicting possible gains provide most of the information needed to decide upon ergonomic investment. This paper presents a model employers can use to predict cost savings from ergonomic investments given certain input factors, including current losses, cost of implementation, and success of implementation.     

Discrete element method investigation on thermally-induced shakedown of granular materials

Temperature change, as a common kind of internal perturbation performed on granular materials, has a significant effect on the bulk properties of granular materials. However, few studies on thermally-induced shakedown under a long-term thermal cycling were reported. In this work, the discrete element method was used to give insight into the thermally-induced shakedown on the fabric and stress states within non-cohesive, frictional granular assemblies. Assemblies were submitted to thermal cycling at a stationary boundary condition after experiencing a one-dimensional compression. Evolution of coordination number, entropy and anisotropy was investigated as well as boundary forces and contact forces. At the same time, effects of the heating rate, the initial vertical load and the magnitude of temperature change were examined. It demonstrates that thermal cycling induces a significant force relaxation within granular materials, while the corresponding granular fabric has a small change. In addition, the entropy and anisotropy decreases with thermal cycling. Moreover, the initial vertical load can constrain the development of thermally-induced fabric change, thereby limiting force relaxation to some degree. Both high heating rate and larger magnitudes of temperature change contribute to more significant force relaxation. However, they cause smaller fabric changes even though they provide larger perturbations.     

Probing the local coordination environment for transition metal dopants in zinc oxide nanowires

It is hypothesized that a highly ordered, relatively defect-free dilute magnetic semiconductor system should act as a weak ferromagnet. Transition-metal-doped ZnO nanowires, being single crystalline, single domain, and single phase, are used here as a model system for probing the local dopant coordination environments using X-ray absorption spectroscopy and diffraction. Our X-ray spectroscopic data clearly show that the dopant resides in a uniform environment, and that the doping does not induce a large degree of disorder in the nanowires. This homogeneous nature of the doping inside the oxide matrix correlates well with observed weakly ferromagnetic behavior of the nanowires.     

Automated liquid-liquid extraction by pneumatic recirculation on a centrifugal microfluidic platform

In this technical note, a liquid-liquid extraction technique was performed using pneumatic liquid recirculation on a centrifugal microfluidic device. Non-contact pneumatic pumping enabled a multi-cycle liquid-liquid extraction process using aqueous iodine in a potassium iodide solution and hexadecane while requiring a minimal amount of space on the device. The extraction process was completely automated on the device following sample introduction and required only 50 s for each extraction cycle. The pumping rate achieved during liquid recirculation was 120 ± 10 μL/min. A recycling process such as the one demonstrated would be difficult to implement in a conventional centrifugal microfluidic system.     

Differential mass spectrometry: a label-free LC-MS method for finding significant differences in complex peptide and protein mixtures

Efficiently identifying and quantifying disease- or treatment-related changes in the abundance of proteins is an important area of research for the pharmaceutical industry. Here we describe an automated, label-free method for finding differences in complex mixtures using complete LC-MS data sets, rather than subsets of extracted peaks or features. The method selectively finds statistically significant differences in the intensity of both high-abundance and low-abundance ions, accounting for the variability of measured intensities and the fact that true differences will persist in time. The method was used to compare two complex peptide mixtures with known peptide differences. This controlled experiment allowed us to assess the validity of each difference found and so to analyze the method's sensitivity and specificity. The method detects both presence versus absence and a 2-fold change in peptide concentration near the limit of detection of the instrument used, where chromatographic peaks may not be sufficiently well defined to be detected in individual samples. The method is more sensitive and gives fewer false positives than subtractive methods that ignore signal variability. Differential mass spectrometry combined with targeted MS/MS analysis of only identified differences may save both computation time and human effort compared to shotgun proteomics approaches.     

Nanostructure fabrication by ultra-high-resolution environmental scanning electron microscopy

Electron beam induced deposition (EBID) is a maskless nanofabrication technique capable of surpassing the resolution limits of resist-based lithography. However, EBID fabrication of functional nanostructures is limited by beam spread in bulk substrates, substrate charging, and delocalized film growth around deposits. Here, we overcome these problems by using environmental scanning electron microscopy (ESEM) to perform EBID and etching while eliminating charging artifacts at the nanoscale. Nanostructure morphology is tailored by slimming of deposits by ESEM imaging in the presence of a gaseous etch precursor and by pre-etching small features into a deposit (using a stationary or a scanned electron beam) prior to a final imaging process. The utility of this process is demonstrated by slimming of nanowires deposited by EBID, by the fabrication of gaps (between 4 and 7 nm wide) in the wires, and by the removal of thin films surrounding such nanowires. ESEM imaging provides a direct view of the slimming process, yielding process resolution that is limited by ESEM image resolution ( approximately 1 nm) and surface roughening occurring during etching.