Kinetics of phase separation in polymer mixtures: A molecular dynamics study

We present detailed results from a molecular dynamics (MD) simulation of phase-separation kinetics in polymer mixtures. Our MD simulations naturally incorporate hydrodynamic effects. We find that polymeric phase separation (with dynamically symmetric components) is in the same universality class as segregation of simple fluids: the degree of polymerization only slows down the segregation kinetics. For d = 2 polymeric fluids, the domain growth law is L(t) similar to t(phi) with phi showing a crossover from 1/3 -> 1/2 -> 2/3. For d = 3 polymeric fluids, we see the crossover phi = 1/3 -> 1. Our MD simulations do not yet access the inertial hydrodynamic regime (with L similar to t(2/3)) of phase separation in 3-d fluids. (C) 2014 AIP Publishing LLC.

Effect of functional groups on separating carbon dioxide from CO2/N-2 gas mixtures using edge functionalized graphene nanoribbons

Development of microporous adsorbents for separation and sequestration of carbon dioxide from flue gas streams is an area of active research. In this study, we assess the influence of specific functional groups on the adsorption selectivity of CO2/N-2 mixtures through Grand Canonical Monte Carlo (GCMC) simulations. Our model system consists of a bilayer graphene nanoribbon that has been edge functionalized with OH, NH2, NO2, CH3 and COOH. Ab initio Moller-Plesset (MP2) calculations with functionalized benzenes are used to obtain binding energies and optimized geometries for CO2 and N-2. This information is used to validate the choice classical forcefields in GCMC simulations. In addition to simulations of adsorption from binary mixtures of CO2 and N-2, the ideal adsorbed solution theory (IAST) is used to predict mixture isotherms. Our study reveals that functionalization always leads to an increase in the adsorption of both CO2 and N-2 with the highest for COOH. However, significant enhancement in the selectivity for CO2 is only seen with COOH functionalized nanoribbons. The COOH functionalization gives a 28% increase in selectivity compared to H terminated nanoribbons, whereas the improvement in the selectivity for other functional groups are much Enure modest. Our study suggests that specific functionalization with COOH groups can provide a material's design strategy to improve CO2 selectivity in microporous adsorbents. Synthesis of graphene nanoplatelets with edge functionalized COOH, which has the potential for large scale production, has recently been reported (Jeon el, al., 2012). (C) 2014 Elsevier Ltd. All rights reserved,

NESTED SPARSE BAYESIAN LEARNING FOR BLOCK-SPARSE SIGNALS WITH INTRA-BLOCK CORRELATION

In this work, we address the recovery of block sparse vectors with intra-block correlation, i.e., the recovery of vectors in which the correlated nonzero entries are constrained to lie in a few clusters, from noisy underdetermined linear measurements. Among Bayesian sparse recovery techniques, the cluster Sparse Bayesian Learning (SBL) is an efficient tool for block-sparse vector recovery, with intra-block correlation. However, this technique uses a heuristic method to estimate the intra-block correlation. In this paper, we propose the Nested SBL (NSBL) algorithm, which we derive using a novel Bayesian formulation that facilitates the use of the monotonically convergent nested Expectation Maximization (EM) and a Kalman filtering based learning framework. Unlike the cluster-SBL algorithm, this formulation leads to closed-form EMupdates for estimating the correlation coefficient. We demonstrate the efficacy of the proposed NSBL algorithm using Monte Carlo simulations.

Tailoring the interface of an immiscible polymer blend by a mutually miscible homopolymer grafted onto graphene oxide: outstanding mechanical properties

A unique strategy was adopted here to improve the compatibility between the components of an immiscible polymer blend and strengthen the interface. PMMA, a mutually miscible polymer to both PVDF and ABS, improved the compatibility between the phases by localizing at the blends interface. This was supported by the core-shell formation with PMMA as the shell and ABS as the core as observed from the SEM micrographs. This phenomenon was strongly contingent on the concentration of PMMA in the blends. This strategy was further extended to localize graphene oxide (GO) sheets at the blends interface by chemically coupling it to PMMA (PMMA-g-GO). A dramatic increment of ca. 84% in the Young's modulus and ca. 124% in the yield strength was observed in the presence of PMMA-g-GO with respect to the neat blends. A simultaneous increment in both the strength and the modulus was observed in the presence of PMMA-g-GO whereas, only addition of GO resulted in a moderate improvement in the yield strength. This study reveals that a mutually miscible polymer can render compatibility between the immiscible pair and can improve the stress transfer at the interface.

Effects of temperature and clay content on water absorption characteristics of modified MMT clay/cyclic olefin copolymer nanocomposite films: Permeability, dynamic mechanical properties and the encapsulated organic device performance

In the present study, amino-silane modified layered organosilicates were used to reinforce cyclic olefin copolymer to enhance the thermal, mechanical and moisture impermeable barrier properties. The optimum clay loading (4%) in the nanocomposite increases the thermal stability of the film while further loading decreases film stability. Water absorption behavior at 62 degrees C was carried out and compared with the behavior at room temperature and 48 degrees C. The stiffness of the matrix increases with clay content and the recorded strain to failure for the composite films was lower than the neat film. Dynamic mechanical analysis show higher storage modulus and low loss modulus for 2.5-4 wt% clay loading. Calcium degradation test and device encapsulation also show the evidence of optimum clay loading of 4 wt% for improved low water vapor transmission rates compared to other nanocomposite films. (C) 2014 Elsevier Ltd. All rights reserved.

Composition dependent non-ideality in aqueous binary mixtures as a signature of avoided spinodal decomposition

We explore the potential energy landscape of structure breaking binary mixtures (SBBM) where two constituents dislike each other, yet remain macroscopically homogeneous at intermediate to high temperatures. Interestingly, we find that the origin of strong composition dependent non-ideal behaviour lies in its phase separated inherent structure. The inherent structure (IS) of SBBM exhibits bi-continuous phase as is usually formed during spinodal decomposition. We draw analogy of this correlation between non-ideality and phase separation in IS to explain observation of non-ideality in real aqueous mixtures of small amphiphilic solutes, containing both hydrophilic and hydrophobic groups. Although we have not been able to obtain IS of these liquids, we find that even at room temperature these liquids sustain formation of fluctuating, transient bi-continuous phase, with limited lifetime (tau less than or similar to 20 ps). While in the model (A, B) binary mixture, the non-ideal composition dependence can be considered as a fluctuation from a phase separated state, a similar scenario is expected to be responsible for the unusually strong non-ideality in these aqueous binary mixtures.

Layered Exact-Repair Regenerating Codes via Embedded Error Correction and Block Designs

A new class of exact-repair regenerating codes is constructed by stitching together shorter erasure correction codes, where the stitching pattern can be viewed as block designs. The proposed codes have the help-by-transfer property where the helper nodes simply transfer part of the stored data directly, without performing any computation. This embedded error correction structure makes the decoding process straightforward, and in some cases the complexity is very low. We show that this construction is able to achieve performance better than space-sharing between the minimum storage regenerating codes and the minimum repair-bandwidth regenerating codes, and it is the first class of codes to achieve this performance. In fact, it is shown that the proposed construction can achieve a nontrivial point on the optimal functional-repair tradeoff, and it is asymptotically optimal at high rate, i.e., it asymptotically approaches the minimum storage and the minimum repair-bandwidth simultaneously.

Modification of crosslinked chitosan membrane using NaY zeolite for pervaporation separation of water-isopropanol mixtures

The blocked diisocyanate crosslinked chitosan membrane was modified by incorporating different mass% of NaY zeolite. The physico-chemical properties of resulting composite membranes were studied using Fourier transform infrared spectroscopy (FTIR), wide-angle X-ray diffraction (WAXD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The mechanical properties of the membranes were studied using universal testing machine (UTM). After measuring the equilibrium swelling, membranes were subjected to pervaporation for separation of water-isopropanol mixtures. Both flux and selectivity were increased with increasing NaY zeolite content in the membranes. The membrane containing 40 mass% of NaY zeolite exhibited the highest separation selectivity of 11,241 with a flux of 11.37 x 10(-2) kg/m(2) h for 10 mass% of water in the feed. The total flux and flux of water are almost overlapping each other, suggesting that these membranes could be effectively used to break the azeotropic point of water-isopropanol mixture. From the temperature dependent diffusion and permeation values, the Arrhenius activation parameters were estimated. All the composite membranes exhibited lower activation energy compared to crosslinked membrane, indicating that the permeants require less energy during the process because of molecular sieving action attributed to the presence of sodalite and super cages in the framework of Nay zeolite. The Henry's mode of sorption dominates the process, giving an endothermic contribution. (C) 2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Enhanced Efficacy of Pluronic Copolymer Micelle Encapsulated SCR7 against Cancer Cell Proliferation(a)

5,6-Bis(benzylideneamino)-2-mercaptopyrimidin-4-ol (SCR7) is a new anti cancer molecule having capability to selectively inhibit non-homologous end joining (NHEJ), one of the DNA double strand break (DSB) repair pathways inside the cells. In spite of the promising potential as an anticancer agent, hydrophobicity of SCR7 decreases its bioavailability. Herein the entrapment of SCR7 in Pluronic copolymer is reported. The size of the aggregates was determined by transmission electron microscopy (TEM) and dynamic light scattering (DLS) which yields an average diameter of 23 nm. SCR7 encapsulated micelles (ES) were also characterized by small-angle neutron scattering (SANS). Evaluation of its biological properties by using a variety of techniques, including Trypan blue, MTT and Live-dead cell assays, reveal that encapsulated SCR7 can induce cytotoxicity in cancer cell lines, being more effective in breast cancer cell line. Encapsulated SCR7 treatment resulted in accumulation of DNA breaks within the cells, resulting in cell cycle arrest at G1 phase and activation of apoptosis. More importantly, we found approximate to 5 fold increase in cell death, when encapsulated SCR7 was used in comparison with SCR7 alone.

Adaptive executions of hyperbolic block-structured AMR applications on GPU systems

A block-structured adaptive mesh refinement (AMR) technique has been used to obtain numerical solutions for many scientific applications. Some block-structured AMR approaches have focused on forming patches of non-uniform sizes where the size of a patch can be tuned to the geometry of a region of interest. In this paper, we develop strategies for adaptive execution of block-structured AMR applications on GPUs, for hyperbolic directionally split solvers. While effective hybrid execution strategies exist for applications with uniform patches, our work considers efficient execution of non-uniform patches with different workloads. Our techniques include bin-packing work units to load balance GPU computations, adaptive asynchronism between CPU and GPU executions using a knapsack formulation, and scheduling communications for multi-GPU executions. Our experiments with synthetic and real data, for single-GPU and multi-GPU executions, on Tesla S1070 and Fermi C2070 clusters, show that our strategies result in up to a 3.23 speedup in performance over existing strategies.

Pluronic copolymer encapsulated SCR7 as a potential anticancer agent

Nonhomologous end joining (NHEJ) of DNA double strand breaks (DSBs) inside cells can be selectively inhibited by 5,6-bis-(benzylideneamino)-2-mercaptopyrimidin-4-ol (SCR7) which possesses anticancer properties. The hydrophobicity of SCR7 decreases its bioavailability which is a major setback in the utilization of this compound as a therapeutic agent. In order to circumvent the drawback of SCR7, we prepared a polymer encapsulated form of SCR7. The physical interaction of SCR7 and Pluronic (R) copolymer is evident from different analytical techniques. The in vitro cytotoxicity of the drug formulations is established using the MTT assay.

Seismic response of reduced-scale modular block and rigid faced reinforced walls through shaking table tests

This paper focuses on understanding the seismic response of geosynthetic reinforced retaining walls through shaking table tests on models of modular block and rigid faced reinforced retaining walls. Reduced-scale models of retaining walls reinforced with geogrid layers were constructed in a laminar box mounted on a uniaxial shaking table and subjected to various levels of sinusoidal base shaking. Models were instrumented with ultrasonic displacement sensors, earth pressure sensors and accelerometers. Effects of backfill density, number of reinforcement layers and reinforcement type on the performance of rigid faced and modular block walls were studied through different series of model tests. Performances of the walls were assessed in terms of face deformations, crest settlement and acceleration amplification at different elevations and compared. Modular block walls performed better than the rigid faced walls for the same level of base shaking because of the additional support derived by stacking the blocks with an offset. Type and quantity of reinforcement has significant effect on the seismic performance of both the types of walls. Displacements are more sensitive to relative density of the backfill and decrease with increasing relative density, the effect being more pronounced in case of unreinforced walls compared to the reinforced ones. Acceleration amplifications are not affected by the wall facing and inclusion of reinforcement. (C) 2015 Elsevier Ltd. All rights reserved.

ELEVATION OF HEAT REJECTION TEMPERATURE IN TRANSCRITICAL CONDENSING CYCLES USING CO2+PROPANE MIXTURES

In this paper, a detailed thermodynamic performance analysis of a transcritical condensing (TC) cycle is performed with pure CO2 and a blend of 48.5 % propane with 51.5 % CO2 as working fluids. A realistic thermodynamic model is used incorporating irreversibilities in turbo-machineries and heat exchangers. The Key finding is that the addition of propane elevates the heat rejection temperature, but does not impair any of the performance indicators. Such a fluid may be useful for power generation in concentrated solar power applications by using which a hike of up to 2 % can be realized in the thermal efficiency of a power plant.

Neoarchean arc magmatism followed by high-temperature, high-pressure metamorphism in the Nilgiri Block, southern India

The Nilgiri Block, southern India is an exhumed lower crust formed through arc magmatic processes in the Neoarchean. The main lithologies in this terrane include charnockites, gneisses, volcanic tuff, metasediments, banded iron formation and mafic-ultramafic bodies. Mafic-ultramafic rocks are present towards the northern and central part of the Nilgiri Block. We examine the evolution of these mafic granulites/metagabbros by phase diagram modeling and U-Pb sensitive high resolution ion microprobe (SHRIMP) dating. They consist of a garnet-clinopyroxene-plagioclase-hornblende-ilmenite +/- orthopyroxene +/- rutile assemblage. Garnet and clinopyroxene form major constituents with labradorite and orthopyroxene as the main mineral inclusions. Labradorite, identified using Raman analysis, shows typical peaks at 508 cm(-1), 479 cm(-1), 287 cm(-1) and 177 cm(-1). It is stable along with orthopyroxene towards the low-pressure high-temperature region of the granulite fades (M1 stage). Subsequently, orthopyroxene reacted with plagioclase to form the peak garnet + clinopyroxene + rutile assemblage (M2 stage). The final stage is represented by amphibolite facies-hornblende and plagioclase-rim around the garnet-clinopyroxene assemblage (M3 stage). Phase diagram modeling shows that these mafic granulites followed an anticlockwise P-T-t path during their evolution. The initial high-temperature metamorphism (M1 stage) was at 850-900 degrees C and similar to 9 kbar followed by high-pressure granulite fades metamorphism (M2 stage) at 850-900 degrees C and 14-15 kbar. U-Pb isotope studies of zircons using SHRIMP revealed late Neoarchean to early paleoproterozoic ages of crystallization and metamorphism respectively. The age data shows that these mafic granulites have undergone arc magmatism at ca. 25392 +/- 3 Ma and high-temperature, high-pressure metamorphism at ca. 2458.9 +/- 8.6 Ma. Thus our results suggests a late Neoarchean arc magmatism followed by early paleoproterozoic high-temperature, high-pressure granulite facies metamorphism due to the crustal thickening and suturing of the Nilgiri Block onto the Dharwar Craton. (C) 2015 Elsevier B.V. All rights reserved.

Archean tectonics and crustal evolution of the Biligiri Rangan Block, southern India

The Southern Granulite Terrain in India is a collage of crustal blocks ranging in age from Archean to Neoproterozoic. This study investigate the tectonic evolution of one of the northernmost block- the Biligiri Block (BRB) through a multidisciplinary approach involving field investigation, petrographic studies, LA-ICPMS zircon U-Pb geochronology, Hf isotopic analyses, metamorphic P-T phase diagram computations, and crustal thickness modeling. The garnet bearing quartzofeldspathic gneiss from the central BRB preserve Mesoarchean magmatic zircons with ages between 3207 and 2806 Ma and positive epsilon Hf value (+2.7) which possibly indicates vestiges of a Mesoarchean primitive continental crust. The occurrence of quartzite-iron formation intercalation as well as ultramafic lenses along the western boundary of the BRB is interpreted to indicate that the Kollegal structural lineament is a possible paleo-suture. Phase diagram computation of a metagabbro from the southwestern periphery of the Kollegal suture zone reveals high-pressure (similar to 18.5 kbar) and medium-temperature (similar to 840 degrees C) metamorphism, likely during eastward subduction of the Western Dharwar oceanic crust beneath the Mesoarchean BRB. In the model presented here, slab subduction, melting and underplating processes generated arc magmatism and subsequent charnockitization within the BRB between ca. 2650 Ma and ca. 2498 Ma. These results thus reveal Meso- to Neoarchean tectonic evolution of the BRB. The spatial variation of crustal thickness, derived from flexure inversion technique, provides additional constraints on the tectonic linkage of the BRB with its surrounding terrains. In conjunction with published data, the Moyar and the Kollegal suture zones are considered to mark the trace of ocean closure along which the Nilgiri and Biligiri Rangan Blocks accreted on to the Western Dharwar Craton. (C) 2016 Elsevier B.V. All rights reserved.