Polyisoprene Captured Sulfur Nanocomposite Materials for High-Areal-Capacity Lithium Sulfur Battery

A polyisoprene-sulfur (PIPS) copolymer and nano sulfur composite material (90 wt % sulfur) is synthesized through inverse vulcanization of PIP polymer with micrometer-sized sulfur particles for high-areal-capacity lithium sulfur batteries. The polycrystalline structure and nanodomain nature of the copolymer are revealed through high-resolution transmission electron microscopy (HRTEM). PIP polymer is also used as binders for the electrode to further capture the dissovlved polysulfides. A high areal capacity of ca. 7.0 mAh/cm2 and stable cycling are achieved based on the PIPS nanosulfur composite with a PIP binder, crucial to commercialization of lithium sulfur batteries. The chemical confinement both at material and electrode level alleviates the diffusion of polysulfides and the shuttle effect. The sulfur electrodes, both fresh and cycled, are analyzed through scanning electron microscopy (SEM). This approach enables scalable material production and high sulfur utilization at the cell level

Accuracy of MAP segmentation with hidden Potts and Markov mesh prior models via Path Constrained Viterbi Training, Iterated Conditional Modes and Graph Cut based algorithms

In this paper, we study statistical classification accuracy of two different Markov field environments for pixelwise image segmentation, considering the labels of the image as hidden states and solving the estimation of such labels as a solution of the MAP equation. The emission distribution is assumed the same in all models, and the difference lays in the Markovian prior hypothesis made over the labeling random field. The a priori labeling knowledge will be modeled with a) a second order anisotropic Markov Mesh and b) a classical isotropic Potts model. Under such models, we will consider three different segmentation procedures, 2D Path Constrained Viterbi training for the Hidden Markov Mesh, a Graph Cut based segmentation for the first order isotropic Potts model, and ICM (Iterated Conditional Modes) for the second order isotropic Potts model. We provide a unified view of all three methods, and investigate goodness of fit for classification, studying the influence of parameter estimation, computational gain, and extent of automation in the statistical measures Overall Accuracy, Relative Improvement and Kappa coefficient, allowing robust and accurate statistical analysis on synthetic and real-life experimental data coming from the field of Dental Diagnostic Radiography. All algorithms, using the learned parameters, generate good segmentations with little interaction when the images have a clear multimodal histogram. Suboptimal learning proves to be frail in the case of non-distinctive modes, which limits the complexity of usable models, and hence the achievable error rate as well. All Matlab code written is provided in a toolbox available for download from our website, following the Reproducible Research Paradigm

Stress corrosion cracking in Al-Zn-Mg-Cu aluminum alloys in saline environments

Copyright 2013 ASM International. This paper was published in Metallurgical and Materials Transactions A, 44A(3), 1230 - 1253, and is made available as an electronic reprint with the permission of ASM International. One print or electronic copy may be made for personal use only. Systematic or multiple reproduction, distribution to multiple locations via electronic or other means, duplications of any material in this paper for a fee or for commercial purposes, or modification of the content of this paper are prohibited.Stress corrosion cracking of Al-Zn-Mg-Cu (AA7xxx) aluminum alloys exposed to saline environments at temperatures ranging from 293 K to 353 K (20 °C to 80 °C) has been reviewed with particular attention to the influences of alloy composition and temper, and bulk and local environmental conditions. Stress corrosion crack (SCC) growth rates at room temperature for peak- and over-aged tempers in saline environments are minimized for Al-Zn-Mg-Cu alloys containing less than ~8 wt pct Zn when Zn/Mg ratios are ranging from 2 to 3, excess magnesium levels are less than 1 wt pct, and copper content is either less than ~0.2 wt pct or ranging from 1.3 to 2 wt pct. A minimum chloride ion concentration of ~0.01 M is required for crack growth rates to exceed those in distilled water, which insures that the local solution pH in crack-tip regions can be maintained at less than 4. Crack growth rates in saline solution without other additions gradually increase with bulk chloride ion concentrations up to around 0.6 M NaCl, whereas in solutions with sufficiently low dichromate (or chromate), inhibitor additions are insensitive to the bulk chloride concentration and are typically at least double those observed without the additions. DCB specimens, fatigue pre-cracked in air before immersion in a saline environment, show an initial period with no detectible crack growth, followed by crack growth at the distilled water rate, and then transition to a higher crack growth rate typical of region 2 crack growth in the saline environment. Time spent in each stage depends on the type of pre-crack (“pop-in” vs fatigue), applied stress intensity factor, alloy chemistry, bulk environment, and, if applied, the external polarization. Apparent activation energies (E a) for SCC growth in Al-Zn-Mg-Cu alloys exposed to 0.6 M NaCl over the temperatures ranging from 293 K to 353 K (20 °C to 80 °C) for under-, peak-, and over-aged low-copper-containing alloys (~0.8 wt pct), they are typically ranging from 20 to 40 kJ/mol for under- and peak-aged alloys, and based on limited data, around 85 kJ/mol for over-aged tempers. This means that crack propagation in saline environments is most likely to occur by a hydrogen-related process for low-copper-containing Al-Zn-Mg-Cu alloys in under-, peak- and over-aged tempers, and for high-copper alloys in under- and peak-aged tempers. For over-aged high-copper-containing alloys, cracking is most probably under anodic dissolution control. Future stress corrosion studies should focus on understanding the factors that control crack initiation, and insuring that the next generation of higher performance Al-Zn-Mg-Cu alloys has similar longer crack initiation times and crack propagation rates to those of the incumbent alloys in an over-aged condition where crack rates are less than 1 mm/month at a high stress intensity factor

Graphene-Based Nanocomposites for Energy Storage

Since the first report of using micromechanical cleavage method to produce graphene sheets in 2004, graphene/graphene-based nanocomposites have attracted wide attention both for fundamental aspects as well as applications in advanced energy storage and conversion systems. In comparison to other materials, graphene-based nanostructured materials have unique 2D structure, high electronic mobility, exceptional electronic and thermal conductivities, excellent optical transmittance, good mechanical strength, and ultrahigh surface area. Therefore, they are considered as attractive materials for hydrogen (H2) storage and high-performance electrochemical energy storage devices, such as supercapacitors, rechargeable lithium (Li)-ion batteries, Li–sulfur batteries, Li–air batteries, sodium (Na)-ion batteries, Na–air batteries, zinc (Zn)–air batteries, and vanadium redox flow batteries (VRFB), etc., as they can improve the efficiency, capacity, gravimetric energy/power densities, and cycle life of these energy storage devices. In this article, recent progress reported on the synthesis and fabrication of graphene nanocomposite materials for applications in these aforementioned various energy storage systems is reviewed. Importantly, the prospects and future challenges in both scalable manufacturing and more energy storage-related applications are discussed

Magnetic pair breaking in disordered superconducting films

A theory for the effects of nonmagnetic disorder on the magnetic pair breaking rate $\alpha$ induced by paramagnetic impurities in quasi two-dimensional superconductors is presented. Within the framework of a strong-coupling theory for disordered superconductors, we find that the disorder dependence of $\alpha$ is determined by the disorder enhancements of both the electron-phonon coupling and the spin-flip scattering rate. These two effects have a tendency to cancel each other. With parameter values appropriate for Pb_{0.9} Bi_{0.1}, we find a pair breaking rate that is very weakly dependent on disorder for sheet resistances 0 < R < 2.5 kOhm, in agreement with a recent experiment by Chervenak and Valles.Comment: 6 pp., REVTeX, epsf, 2 eps figs, final version as publishe

Quasiparticle scattering time in superconducting films: from dirty to clean limit

We study the quasiparticle energy relaxation processes in superconducting Nb films of different thicknesses corresponding to different electron mean free paths in a state far from equilibrium, that is the highly dissipative flux-flow state driven up to the instability point. From the measured current-voltage curves we derive the vortex critical velocity $v^{*}$ for several temperatures. From the $v^{*}(T)$ values, the quasiparticle energy relaxation time $\tau_{\epsilon}$ is evaluated within the Larkin-Ovchinnikov model and numerical calculations of the quasiparticle energy relaxation rates are carried out to support the experimental findings. Besides the expected constant behavior of $\tau_{\epsilon}(T)$ for the dirty samples, we observe a strong temperature dependence of the quasiparticle energy relaxation time in the clean samples. This feature is associated with the increasing contribution from the electron-phonon scattering process as the dirty limit is approached from the clean regime

Simulation of the Relaxation Potential Profile of an ac-dc-ac Test

The relaxation period of the accelerated ac-dc-ac test for coatings is associated with the transient electrochemistry that occurs when the immersed coated system is allowed to return to a stable open-circuit condition after being subjected to a cathodic potential. A mathematical model of the transient electrochemistry that occurs during this relaxation period is presented for coated aluminum. Expressions for the corrosion potential and corrosion current as functions of the local pH at the metal-coating interface were developed using reported experimental results. These expressions enabled the simulation of the transient electrochemistry under the constraint of balanced anodic and cathodic current densities. Regression of the transient relaxation potential profiles to exponential decay functions provided time-constant characterization of the profiles. Simulated results are presented that demonstrate the influences of the coating\u27s porosity and thickness, the applied dc potential and the metal-coating interface condition on the time-constants associated with the relaxation profile. Interpretation of experimentally reported relaxation potential profiles supported the analysis of the simulated results

Correlation between Grafting Density and Confined Crystallization Behavior of Poly(ethylene glycol) Grafted to Silica

The interfacial interactions of polymer-nanoparticles have dramatical effects on the crystallization behavior of grafted polymers. In this study, methoxy polyethylene glycol (MPEG) (molecular weights 750, 2000 and 4000 g mol−1) was grafted onto amino-modified nanosized silica (SiO2-NH2) by the “grafting to” method. The effects of the grafting density and molecular weight on the confined crystallization of grafted MPEG (MPEG-g-SiO2) were systematically investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and wide-angle X-ray scattering (WAXS). It was found that confinement effects are stronger when lower molecular weights of grafted MPEG are employed. These grafted MPEG chains are more difficult to stretch out on SiO2-NH2 surfaces than when they are free in the bulk polymer. Both crystallization temperature (Tc) and crystallinity of grafted MPEG chains decrease with reductions of grafting density. Additionally, covalent bonding effects and interfacial interaction confinement effects are strengthened by the decrease in grafting density, leading to an increase in decomposition temperature and to the disappearance of the self-nucleation Domain (i.e., Domain II), when self-nucleation experiments are performed by DSC. Overall isothermal crystallization kinetics was studied by DSC and the results were analyzed with the Avrami equation. An Avrami index of n≈3 was obtained for neat MPEG (indicating that instantaneous spherulites are formed). However, in the case of MPEG-g-SiO2 with the lowest grafting density, the Avrami index of (n) was less than 1 (first order kinetics or lower), indicating that nucleation is the determining factor of the overall crystallization kinetics, a signature for confined crystallization. At the same time, the crystallization from the melt for this MPEG-g-SiO2 with the lowest grafting density occurs at Tc ≈-30 ºC, a temperature close to the glass transition temperature (Tg) of MPEG, indicating that this confined MPEG crystallizes from homogeneous nuclei.This project was supported by the National Natural Science Foundation of China (21574141) and the Ministry of Science and Technology of China (2017YFE0117800). The authors gratefully acknowledge the funding of project BIODEST, Research and Innovation Staff Exchange (RISE) H2020-MSCA-RISE-2017-778092. The authors thank beamline BL16B1 (Shanghai Synchrotron Radiation Facility) for providing the beam time and helps during experiments

The converb -las in Old Tibetan

In contrast to its description in available grammars and manuals, the converb -las in Old Tibetan is used primarily to mark off the following clause as surprising given the background of the preceding clause. The converb -las enters into two distinct syntactic constructions: after a reduplicated verb it indicates the interruption of a continuous event; and in a three-clause pattern with the converb -kyis, -las introduces a surprise or contrast in the second clause, but -kyis in the third clause returns the sentiment to that of the first clause. Although the examples which demonstrate the use of -las are drawn from Old Tibetan texts, this use continues in later texts