Stimuli-responsive weak polyelectrolyte multilayer films: A thin film platform for self triggered multi-drug delivery

Polyelectrolyte multilayer (PEM) thin film composed of weak polyelectrolytes was designed by layer-by-layer (LbL) assembly of poly(allylamine hydrochloride) (PAH) and poly(methacrylic acid) (PMA) for multi-drug delivery applications. Environmental stimuli such as pH and ionic strength showed significant influence in changing the film morphology from pore-free smooth structure to porous structure and favored triggered release of loaded molecules. The film was successfully loaded with bovine serum albumin (BSA) and ciprofloxacin hydrochloride (CH) by modulating the porous polymeric network of the film. Release studies showed that the amount of release could be easily controlled by changing the environmental conditions such as pH and ionic strength. Sustained release of loaded molecules was observed up to 8 h. The fabricated films were found to be biocompatible with epithelial cells during in-vitro cell culture studies. PEM film reported here not only has the potential to be used as self-responding thin film platform for transdermal drug delivery, but also has the potential for further development in antimicrobial or anti-inflammatory coatings on implants and drug-releasing coatings for stents. (C) 2015 Elsevier B.V. All rights reserved.

A Study of Pressure-Dependent Squeeze Film Stiffness as a Resonance Modulator Using Static and Dynamic Measurements

We report on the resonant frequency modulation of inertial microelectromechanical systems (MEMS) structures due to squeeze film stiffness over a range of working pressures. Squeeze film effects have been studied extensively, but mostly in the context of damping and Q-factor determination of dynamic MEMS structures, typically suspended over a fixed substrate with a very thin air gap. Here, we show with experimental measurements and analytical calculations how the pressure-dependent air springs (squeeze film stiffness) change the resonant frequency of an inertial MEMS structure by as much as five times. For capturing the isolated effect of the squeeze film stiffness, we first determine the static stiffness of our structure with atomic force microscope probing and then study the effect of the air spring by measuring the dynamic response of the structure, thus finding the resonant frequencies while varying the air pressure from 1 to 905 mbar. We also verify our results by analytical and Finite Element Method calculations. Our findings show that the pressure-dependent squeeze film stiffness can affect a rather huge range of frequency modulation (>400%) and, therefore, can be used as a design parameter for exploiting this effect in MEMS devices. 2014-0310]

Real-Time Stress Measurements in Germanium Thin Film Electrodes during Electrochemical Lithiation/Delithiation Cycling

An in situ study of stress evolution and mechanical behavior of germanium as a lithium-ion battery electrode material is presented. Thin films of germanium are cycled in a half-cell configuration with lithium metal foil as counter/reference electrode, with 1M LiPF6 in ethylene carbonate, diethyl carbonate, dimethyl carbonate solution (1:1:1, wt%) as electrolyte. Real-time stress evolution in the germanium thin-film electrodes during electrochemical lithiation/delithiation is measured by monitoring the substrate curvature using the multi-beam optical sensing method. Upon lithiation a-Ge undergoes extensive plastic deformation, with a peak compressive stress reaching as high as -0.76 +/- 0.05 GPa (mean +/- standard deviation). The compressive stress decreases with lithium concentration reaching a value of approximately -0.3 GPa at the end of lithiation. Upon delithiation the stress quickly became tensile and follows a trend that mirrors the behavior on compressive side; the average peak tensile stress of the lithiated Ge samples was approximately 0.83 GPa. The peak tensile stress data along with the SEM analysis was used to estimate a lower bound fracture resistance of lithiated Ge, which is approximately 5.3 J/m(2). It was also observed that the lithiated Ge is rate sensitive, i.e., stress depends on how fast or slow the charging is carried out. (C) The Author(s) 2015. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. All rights reserved.

High-kappa TiO2 Thin Film Prepared by Sol-Gel Spin-Coating Method

High-k TiO2 thin film on p-type silicon substrate was fabricated by a combined sol-gel and spin coating method. Thus deposited titania film had anatase phase with a small grain size of 16 nm and surface roughness of congruent to 0.6 nm. The oxide capacitance (C-ox), flat band capacitance (C-FB), flat band voltage (V-FB), oxide trapped charge (Q(ot)), calculated from the high frequency (1 MHz) C-V curve were 0.47 nF, 0.16 nF, -0.91 V, 4.7x10(-12) C, respectively. As compared to the previous reports, a high dielectric constant of 94 at 1 MHz frequency was observed in the devices investigated here and an equivalent oxide thickness (EOT) was 4.1 nm. Dispersion in accumulation capacitance shows a linear relationship with AC frequencies. Leakage current density was found in acceptable limits (2.1e-5 A/cm(2) for -1 V and 5.7e-7 A/cm(2) for +1 V) for CMOS applications.

Effect of Te Addition into As2Se3 Thin Film: Optical Property Study by FTIR and XPS.

In the present work, we report the effect of Te deposition onto As2Se3 film which affects the optical properties. The Te/As2Se3 film was illuminated with 532 nm laser to study the photo induced diffusion. The prepared As2Se3, Te/As2Se3 films were characterized by X-ray diffraction which show a completely amorphous nature. On the basis of optical transmission data carried out by Fourier Transform infrared Spectroscopy, a non direct transition was found for these films. The optical bandgap is found to be decreased with Te deposition and photo darkening phenomena is observed for the diffused film. The change in the optical constants are also supported by the corresponding change in different types of bonds which are being analyzed by X-ray photoelectron spectroscopy.

On the Equivalence of Acoustic Impedance and Squeeze Film Impedance in Micromechanical Resonators

In this work, we address the issue of modeling squeeze film damping in nontrivial geometries that are not amenable to analytical solutions. The design and analysis of microelectromechanical systems (MEMS) resonators, especially those that use platelike two-dimensional structures, require structural dynamic response over the entire range of frequencies of interest. This response calculation typically involves the analysis of squeeze film effects and acoustic radiation losses. The acoustic analysis of vibrating plates is a very well understood problem that is routinely carried out using the equivalent electrical circuits that employ lumped parameters (LP) for acoustic impedance. Here, we present a method to use the same circuit with the same elements to account for the squeeze film effects as well by establishing an equivalence between the parameters of the two domains through a rescaled equivalent relationship between the acoustic impedance and the squeeze film impedance. Our analysis is based on a simple observation that the squeeze film impedance rescaled by a factor of jx, where x is the frequency of oscillation, qualitatively mimics the acoustic impedance over a large frequency range. We present a method to curvefit the numerically simulated stiffness and damping coefficients which are obtained using finite element analysis (FEA) analysis. A significant advantage of the proposed method is that it is applicable to any trivial/nontrivial geometry. It requires very limited finite element method (FEM) runs within the frequency range of interest, hence reducing the computational cost, yet modeling the behavior in the entire range accurately. We demonstrate the method using one trivial and one nontrivial geometry.

High-kappa TiO2 Thin Film Prepared by Sol-Gel Spin-Coating Method

High-k TiO2 thin film on p-type silicon substrate was fabricated by a combined sol-gel and spin coating method. Thus deposited titania film had anatase phase with a small grain size of 16 nm and surface roughness of congruent to 0.6 nm. The oxide capacitance (C-ox), flat band capacitance (C-FB), flat band voltage (V-FB), oxide trapped charge (Q(ot)), calculated from the high frequency (1 MHz) C-V curve were 0.47 nF, 0.16 nF, -0.91 V, 4.7x10(-12) C, respectively. As compared to the previous reports, a high dielectric constant of 94 at 1 MHz frequency was observed in the devices investigated here and an equivalent oxide thickness (EOT) was 4.1 nm. Dispersion in accumulation capacitance shows a linear relationship with AC frequencies. Leakage current density was found in acceptable limits (2.1e-5 A/cm(2) for -1 V and 5.7e-7 A/cm(2) for +1 V) for CMOS applications.

Pattern formation in thin films of polymer solutions: Theory and simulations

Self-assembly has been recognized as an efficient tool for generating a wide range of functional, chemically, or physically textured surfaces for applications in small scale devices. In this work, we investigate the stability of thin films of polymer solutions. For low concentrations of polymer in the solution, long length scale dewetting patterns are obtained with wavelength approximately few microns. Whereas, for concentrations above a critical value, bimodal dispersion curves are obtained with the dominant wavelength being up to two orders smaller than the usual dewetting length scale. We further show that the short wavelength corresponds to the phase separation in the film resulting in uniformly distributed high and low concentration regions. Interestingly, due to the solvent entropy, at very high concentration values of polymer, a re-entrant behaviour is observed with the dominant length scale now again corresponding to the dewetting wavelength. Thus, we show that the binary films of polymer solutions provide additional control parameters that can be utilized for generating functional textured surfaces for various applications. (C) 2016 AIP Publishing LLC.

Optimizing Photovoltaic Response by Tuning Light-Harvesting Nanocrystal Shape Synthesized Using a Quick Liquid-Gas Phase Reaction

The electron recombination lifetime in a sensitized semiconductor assembly is greatly influenced by the crystal structure and geometric form of the light-harvesting semiconductor nanocrystal. When such light harvesters with varying structural characteristics are configured in a photoanode, its interface with the electrolyte becomes equally important and directly influences the photovoltaic efficiency. We have systematically probed here the influence of nanocrystal crystallographic structure and shape on the electron recombination lifetime and its eventual influence on the light to electricity conversion efficiency of a liquid junction semiconductor sensitized solar cell. The light-harvesting cadmium sulfide (CdS) nanocrystals of distinctly different and controlled shapes are obtained using a novel and simple liquid gas phase synthesis method performed at different temperatures involving very short reaction times. High resolution synchrotron X-ray diffraction and spectroscopic studies respectively exhibit different crystallographic phase content and optical properties. When assembled on a mesoscopic TiO2 film by a linker molecule, they exhibit remarkable variation in electron recombination lifetime by 1 order of magnitude, as determined by ac-impedance spectroscopy. This also drastically affects the photovoltaic efficiency of the differently shaped nanocrystal sensitized solar cells.

Evidence for 3D isotropic long range spin-spin interaction near the ferromagnetic transition in bulk and thin film SrRuO3

In the case of metallic ferromagnets there has always been a controversy, i.e. whether the magnetic interaction is itinerant or localized. For example SrRuO3 is known to be an itinerant ferromagnet where the spin-spin interaction is expected to be mean field in nature. However, it is reported to behave like Ising, Heisenberg or mean field by different groups. Despite several theoretical and experimental studies and the importance of strongly correlated systems, the experimental conclusion regarding the type of spin-spin interaction in SrRuO3 is lacking. To resolve this issue, we have investigated the critical behaviour in the vicinity of the paramagnetic-ferromagnetic phase transition using various techniques on polycrystalline as well as (001) oriented SrRuO3 films. Our analysis reveals that the application of a scaling law in the field-cooled magnetization data extracts the value of the critical exponent only when it is measured at H -> 0. To substantiate the actual nature without any ambiguity, the critical behavior is studied across the phase transition using the modified Arrott plot, Kouvel-Fisher plot and M-H isotherms. The critical analysis yields self-consistent beta, gamma and delta values and the spin interaction follows the long-range mean field model. Further the directional dependence of the critical exponent is studied in thin films and it reveals the isotropic nature. It is elucidated that the different experimental protocols followed by different groups are the reason for the ambiguity in determining the critical exponents in SrRuO3.

Optimizing Photovoltaic Response by Tuning Light-Harvesting Nanocrystal Shape Synthesized Using a Quick Liquid-Gas Phase Reaction

The electron recombination lifetime in a sensitized semiconductor assembly is greatly influenced by the crystal structure and geometric form of the light-harvesting semiconductor nanocrystal. When such light harvesters with varying structural characteristics are configured in a photoanode, its interface with the electrolyte becomes equally important and directly influences the photovoltaic efficiency. We have systematically probed here the influence of nanocrystal crystallographic structure and shape on the electron recombination lifetime and its eventual influence on the light to electricity conversion efficiency of a liquid junction semiconductor sensitized solar cell. The light-harvesting cadmium sulfide (CdS) nanocrystals of distinctly different and controlled shapes are obtained using a novel and simple liquid gas phase synthesis method performed at different temperatures involving very short reaction times. High resolution synchrotron X-ray diffraction and spectroscopic studies respectively exhibit different crystallographic phase content and optical properties. When assembled on a mesoscopic TiO2 film by a linker molecule, they exhibit remarkable variation in electron recombination lifetime by 1 order of magnitude, as determined by ac-impedance spectroscopy. This also drastically affects the photovoltaic efficiency of the differently shaped nanocrystal sensitized solar cells.

Evidence for 3D isotropic long range spin-spin interaction near the ferromagnetic transition in bulk and thin film SrRuO3

In the case of metallic ferromagnets there has always been a controversy, i.e. whether the magnetic interaction is itinerant or localized. For example SrRuO3 is known to be an itinerant ferromagnet where the spin-spin interaction is expected to be mean field in nature. However, it is reported to behave like Ising, Heisenberg or mean field by different groups. Despite several theoretical and experimental studies and the importance of strongly correlated systems, the experimental conclusion regarding the type of spin-spin interaction in SrRuO3 is lacking. To resolve this issue, we have investigated the critical behaviour in the vicinity of the paramagnetic-ferromagnetic phase transition using various techniques on polycrystalline as well as (001) oriented SrRuO3 films. Our analysis reveals that the application of a scaling law in the field-cooled magnetization data extracts the value of the critical exponent only when it is measured at H -> 0. To substantiate the actual nature without any ambiguity, the critical behavior is studied across the phase transition using the modified Arrott plot, Kouvel-Fisher plot and M-H isotherms. The critical analysis yields self-consistent beta, gamma and delta values and the spin interaction follows the long-range mean field model. Further the directional dependence of the critical exponent is studied in thin films and it reveals the isotropic nature. It is elucidated that the different experimental protocols followed by different groups are the reason for the ambiguity in determining the critical exponents in SrRuO3.

A Perspective on Computer Assisted Assessment Techniques for Short Free-Text Answers

Computer Assisted Assessment (CAA) has been existing for several years now. While some forms of CAA do not require sophisticated text understanding (e.g., multiple choice questions), there are also student answers that consist of free text and require analysis of text in the answer. Research towards the latter till date has concentrated on two main sub-tasks: (i) grading of essays, which is done mainly by checking the style, correctness of grammar, and coherence of the essay and (ii) assessment of short free-text answers. In this paper, we present a structured view of relevant research in automated assessment techniques for short free-text answers. We review papers spanning the last 15 years of research with emphasis on recent papers. Our main objectives are two folds. First we present the survey in a structured way by segregating information on dataset, problem formulation, techniques, and evaluation measures. Second we present a discussion on some of the potential future directions in this domain which we hope would be helpful for researchers.

Short-Time Beta Relaxation in Glass-Forming Liquids Is Cooperative in Nature

Temporal relaxation of density fluctuations in supercooled liquids near the glass transition occurs in multiple steps. Using molecular dynamics simulations for three model glass-forming liquids, we show that the short-time beta relaxation is cooperative in nature. Using finite-size scaling analysis, we extract a growing length scale associated with beta relaxation from the observed dependence of the beta relaxation time on the system size. We find, in qualitative agreement with the prediction of the inhomogeneous mode coupling theory, that the temperature dependence of this length scale is the same as that of the length scale that describes the spatial heterogeneity of local dynamics in the long-time alpha-relaxation regime.

Combustion and heat transfer characteristics of nanofluid fuel droplets: A short review

With the pressing need to meet an ever-increasing energy demand, the combustion systems utilizing fossil fuels have been the major contributors to carbon footprint. As the combustion of conventional energy resources continue to produce significant Green House gas (GHG) emissions, there is a strong emphasis to either upgrade or find an energy-efficient eco-friendly alternative to the traditional hydrocarbon fuels. With recent developments in nanotechnology, the ability to manufacture materials with custom tailored properties at nanoscale has led to the discovery of a new class of high energy density fuels containing reactive metallic nanoparticles (NPs). Due to the high reactive interfacial area and enhanced thermal and mass transport properties of nanomaterials, the high heat of formation of these metallic fuels can now be released rapidly, thereby saving on specific fuel consumption and hence reducing GHG emissions. In order to examine the efficacy of nanofuels in energetic formulations, it is imperative to first study their combustion characteristics at the droplet scale that form the fundamental building block for any combustion system utilizing liquid fuel spray. During combustion of such multiphase, multicomponent droplets, the phenomenon of diffusional entrapment of high volatility species leads to its explosive boiling (at the superheat limit) thereby leading to an intense internal pressure build-up. This pressure upsurge causes droplet fragmentation either in form of a microexplosion or droplet puffing followed by atomization (with formation of daughter droplets) featuring disruptive burning. Both these atomization modes represent primary mechanisms for extracting the high oxidation energies of metal NP additives by exposing them to the droplet flame (with daughter droplets acting as carriers of NPs). Atomization also serves as a natural mechanism for uniform distribution and mixing of the base fuel and enhancing burning rates (due to increase in specific surface area through formation of smaller daughter droplets). However, the efficiency of atomization depends on the thermo-physical properties of the base fuel, NP concentration and type. For instance, at dense loading NP agglomeration may lead to shell formation which would sustain the pressure upsurge and hence suppress atomization thereby reducing droplet gasification rate. Contrarily, the NPs may act as nucleation sites and aid boiling and the radiation absorption by NPs (from the flame) may lead to enhanced burning rates. Thus, nanoadditives may have opposing effects on the burning rate depending on the relative dominance of processes occurring at the droplet scale. The fundamental idea in this study is to: First, review different thermo-physical processes that occur globally at the droplet and sub-droplet scale such as surface regression, shell formation due to NP agglomeration, internal boiling, atomization/NP transport to flame zone and flame acoustic interaction that occur at the droplet scale and second, understand how their interaction changes as a function of droplet size, NP type, NP concentration and the type of base fuel. This understanding is crucial for obtaining phenomenological insights on the combustion behavior of novel nanofluid fuels that show great promise for becoming the next-generation fuels. (C) 2016 Elsevier Ltd. All rights reserved.