Electrolyte stability determines scaling limits for solid-state 3D Li ion batteries

Rechargeable, all-solid-state Li ion batteries (LIBs) with high specific capacity and small footprint are highly desirable to power an emerging class of miniature, autonomous microsystems that operate without a hardwire for power or communications. A variety of three-dimensional (3D) LIB architectures that maximize areal energy density has been proposed to address this need. The success of all of these designs depends on an ultrathin, conformal electrolyte layer to electrically isolate the anode and cathode while allowing Li ions to pass through. However, we find that a substantial reduction in the electrolyte thickness, into the nanometer regime, can lead to rapid self-discharge of the battery even when the electrolyte layer is conformal and pinhole free. We demonstrate this by fabricating individual, solid-state nanowire core-multishell LIBs (NWLIBs) and cycling these inside a transmission electron microscope. For nanobatteries with the thinnest electrolyte, ≈110 nm, we observe rapid self-discharge, along with void formation at the electrode/electrolyte interface, indicating electrical and chemical breakdown. With electrolyte thickness increased to 180 nm, the self-discharge rate is reduced substantially, and the NWLIBs maintain a potential above 2 V for over 2 h. Analysis of the nanobatteries' electrical characteristics reveals space-charge limited electronic conduction, which effectively shorts the anode and cathode electrodes directly through the electrolyte. Our study illustrates that, at these nanoscale dimensions, the increased electric field can lead to large electronic current in the electrolyte, effectively shorting the battery. The scaling of this phenomenon provides useful guidelines for the future design of 3D LIBs.     

Antimicrobial properties and thermal stability of polycarbonate modified with 1‐alkyl‐3‐methylimidazolium tetrafluoroborate ionic liquids

Four water immiscible ionic liquids (ILs): 1‐hexyl‐3‐methylimidazolium tetrafluoroborate, 1‐heptyl‐3‐methylimidazolium tetrafluoroborate, 1‐octyl‐3‐methylimidazolium tetrafluoroborate and 1‐dodecyl‐3‐methylimidazolium tetrafluoroborate have been synthesized. Polycarbonate (PC) films containing ILs were prepared by solvent casting from methylene chloride solutions. Scanning electron microscopy measurements showed the high homogeneity of PC/IL films with the IL content up to 4 wt %. The tendency to IL aggregation was observed for polymeric films with higher IL content (5%). PC/IL composites were found to have the reduced thermal decomposition temperature under both an air and a nitrogen atmosphere in comparison with the neat PC. The effect of IL content on the antimicrobial activity of PC films against Escherichia coli bacteria was studied. Pronounced antimicrobial efficacy was revealed for PC/IL films for all studied ILs starting from 3 wt % of IL. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40050.     

A novel approach to determine wet restitution coefficients through a unified correlation and energy analysis

Wet particle interactions are observed in many applications, for example, pharmaceutical, food, agricultural, polymerization, agglomeration, and coating, in which an accurate evaluation of the wet restitution coefficient (e_wet) is crucial to understand the particle flowability, operating conditions and product size distribution. Experiments were performed to measure the wet restitution coefficient by impacting a spherical particle on a stationary plate covered with a thin liquid layer of water or glycerol solution in this work. Furthermore, novel approaches for estimation of e_wet were developed using dimensional analysis (using the Buckingham π theorem and regression analysis) in combination with energy budget analysis. In the correlation development, the dominant physical properties of solid and liquid, particle impact velocity and liquid layer thickness are grouped into well‐known dimensionless numbers viz. Reynolds, Weber and Stokes. Whereas in the energy analysis, the energy dissipation rates were determined for five distinct collision phases, that is, dipping, dry collision, undipping, formation and breakage of the liquid bridge, and added mass. The efficacy of the developed approaches was analyzed by comparing obtained results with experiments and an elastohydrodynamic model, and a modified elastohydrodynamic model. © 2014 American Institute of Chemical Engineers AIChE J, 61: 769–779, 2015     

Bulk and interface boundary diffusion in group IV hexagonal close-packed metals and alloys

Bulk and grain boundary (GB) self-diffusion and substitutional solute diffusion in group IV hexagonal close-packed (hcp) metals (α-Ti, α-Zr, and α-Hf) are reviewed. The recent results obtained on high-purity materials are shown to approach closely the “intrinsic” diffusion characteristics. The enhancement effect of fast-diffusing impurities (such as Fe, Ni, or Co) is discussed for both self-and substitutional bulk solute diffusion in terms of the interstitial solubility of the impurity atoms. In GB self-diffusion, the impurity effect is found to be less dramatic. The results obtained on high-purity hop materials can be interpreted in terms of intrinsically ‘normal’ vacancy-mediated GB diffusion, with the ratio of GB to volume diffusion activation enthalpies of Q _gb /Q ≈ 0.6. The GB self-diffusion in group IV hcp metals reveals distinct systematics. Bulk self-diffusion and fast interstitial solute diffusion (Fe and Ni) in the hcp phase α ₂-Ti₃Al are reviewed. Interphase boundary diffusion of Ti in the unidirectional lamellar α ₂/γ structure of the two-phase Ti₄₈Al₅₂ alloy is analyzed with respect to the phase boundary structure and GB self-diffusion in α ₂-Ti₃Al. This article is based on a presentation made in the symposium entitled “Defect Properties and Mechanical Behavior of HCP Metals and Alloys” at the TMS Annual Meeting, February 11–15, 2001, in New Orleans, Louisiana, under the auspices of the following ASM committees: Materials Science Critical Technology Sector, Structural Materials Division, Electronic, Magnetic & Photonic Materials Division, Chemistry & Physics of Materials Committee, Joint Nuclear Materials Committee, and Titanium Committee.     

Optical nanosensor platform operating in near-physiological pH range via polymer-brush-mediated plasmon coupling

The nanosensors' platform made of a stimuli-responsive polymer/noble metal nanoparticle composite thin film exploits the combination of the swelling-shrinking transition in a poly(N,N'-dimethylaminoethyl methacrylate) brush and the localized surface plasmon resonance in metal nanoparticles to enable the transduction of changes in the solution pH in the near-physiological range into a pronounced optical signal.     

Principles of minimum variance robust adaptive beamforming design

Robustness is typically understood as an ability of adaptive beamforming algorithm to achieve high performance in the situations with imperfect, incomplete, or erroneous knowledge about the source, propagation media, and antenna array. It is also desired to achieve high performance with as little as possible prior information. In the last decade, several fruitful principles to minimum variance distortionless response (MVDR) robust adaptive beamforming (RAB) design have been developed and successfully applied to solve a number of problems in a wide range of applications. Such principles of MVDR RAB design are summarized here in a single paper. Prof. Gershman has actively participated in the development and applications of a number of such MVDR RAB design principles.     

Structure-Activity Relationship Modeling and Experimental Validation of the Imidazolium and Pyridinium Based Ionic Liquids as Potential Antibacterials of MDR Acinetobacter baumannii and Staphylococcus aureus

Online Chemical Modeling Environment (OCHEM) was used for QSAR analysis of a set of ionic liquids (ILs) tested against multi-drug resistant (MDR) clinical isolate Acinetobacter baumannii and Staphylococcus aureus strains. The predictive accuracy of regression models has coefficient of determination q² = 0.66 − 0.79 with cross-validation and independent test sets. The models were used to screen a virtual chemical library of ILs, which was designed with targeted activity against MDR Acinetobacter baumannii and Staphylococcus aureus strains. Seven most promising ILs were selected, synthesized, and tested. Three ILs showed high activity against both these MDR clinical isolates.     

Preprogrammed Dynamic Microstructured Polymer Interfaces

The advancement of new‐generation complex integrated responsive systems depends on the progress in the development of functional stimuli‐responsive polymer components that could be put together and engineered to perform in concert as an ensemble. This progress report highlights recent substantial progress in the development of such soft‐matter components capable of changes according to preprogrammed scenarios. The components interact via interfaces that play a key role in the performance of the microstructured materials. The list of the most important properties that can be changed by altering the interfaces upon external stimuli includes gating, transport, release, wetting, adhesion, and self‐regeneration (healing) realized in different architectures of soft stimuli‐responsive materials.     

Kollektorbeschichtungen für die EUV‐Lithografie

Collector Coatings for EUV Lithography Extreme ultraviolet lithography (EUVL) is the next generation lithogra phy method operating at the wavelength of 13.5 nm (14 times shorter than current lithography systems), enabling semiconductor scaling to resolutions of 22 nm and below [1]. This paper presents the successful coating of the world's largest ellipsoidal collector mirror for EUV radiation with a diameter of 660 mm ( Fig. 1 ). In order to achieve the required peak reflectivity of more than 65 %, the ellipsoidal collector was coated with a highly reflective, laterally graded multilayer using the dc magnetron sputtering system “NESSY”. A maximum reflectivity of the laterally graded multilayer of more than 65 % was achieved for radii smaller than 220 mm. For radii between 230 mm and 320 mm the reflectivity decreases to a minimum of 58 %. The targeted wavelength remains constant at (13.50 ± 0.05) nm over the entire collector surface which is well within the tight specifications for high volume manufacturing.