PE/PEO blends compatibilized by PE brush immobilized on MWNTs: improved interfacial and structural properties

Polyolefin based blends have tremendous commercial importance in view of their exceptional properties. In this study the interface of a biphasic polymer blend of PE (polyethylene) and PEO (polyethylene oxide) has been tailored to reduce the interfacial tension between the phases and to render finer morphology. This was accomplished by employing various strategies like addition of maleated PE (PE grafted maleic anhydride), immobilizing PE chains, ex situ, onto MWNTs by covalent grafting, and in situ grafting of PE chains onto MWNTs during melt processing. Multiwalled nanotubes (MWNTs) with different surface functional groups have been synthesized either a priori or were facilitated during melt mixing at higher temperature. NH2 terminated MWNTs were synthesized by grafting ethylene diamine (EDA) onto carboxyl functionalized carbon nanotubes (COOH(MWNTs) and further, was used to reactively couple with maleated PE to immobilize PE chains on the surface of MWNTs. The covalent coupling of maleated PE with NH2 terminated MWNTs was also realized in situ in the melt extruder at high temperature. Both NH2 terminated MWNTs and the in situ formed PE brush on MWNTs during melt mixing, revealed a significant improvement in the mechanical properties of the blend besides remarkably improving the dispersion of the minor phase (PEO) in the blends. Structural properties of the composites were evaluated and the tensile fractured morphology was assessed using scanning electron microscopy.

Neoarchean continental growth through arc magmatism in the Nilgiri Block, southern India

The formation and growth of continental crust in the Archean have been evaluated through models of subduction-accretion and mantle plume. The Nilgiri Block in southern India exposes exhumed Neoarchean lower crust, uplifted to heights of 2500 m above sea level along the north western margin of the Peninsula. Major lithologies in this block include charnockite with or without garnet, anorthosite-gabbro suite, pyroxenite, amphibolite and hornblende-biotite gneiss (TTG). All these rock types are closely associated as an arc magmatic suite, with diffuse boundaries and coeval nature. The charnockite and hornblende-biotite gneisses (TTG) show SiO2 content varying from 64 to 73 wt.%. The hornblende-biotite gneisses (TTG) are high-Al type with Al2O3 >15 wt.% whereas the charnockites show Al2O3 <15 wt.%. The composition of charnockite is mainly magnesian and calcic to calc-alkaline. The mafic-ultramafic rocks show composition close to that of tholeiitic series. The low values of K(2)o (<3 wt.%), (K/Rb)/K2O (<500), Zr/Ti, and trace element ratios like (La/Yb)n/(Sr/Y), (Y/Nb), (Y + Nb)/Rb, (Y+Ta)/Rb, Yb/Ta indicate a volcanic arc signature for these rocks. The geochemical signature is consistent with arc magmatic rocks generated through oceanic plate subduction. The primitive mantle normalized trace element patterns of these rocks display enrichment in large ion lithophile elements (LILE) and comparable high field strength elements (HFSE) in charnockite and hornblende-biotite gneisses (TTG) consistent with subduction-related origin. Primitive mantle normalized REE pattern displays an enrichment in LREE in the chamockite and hornblende-biotite gneisses (TTG) as compared to a flat pattern for the mafic rocks. The chondrite normalized REE patterns of zircons of all the rock types reveal cores with high HREE formed at ca. 2700 Ma and rims with low HREE formed at 2500-2450 Ma. Log-transformed La/Th-Nb/Th-Sm/Th-Yb/Th discrimination diagram for the mafic and ultramafic rocks from Nilgiri displays a transition from mid-oceanic ridge basalt (MORB) to island arc basalt (IAB) suggesting a MORB source. The U-Pb zircon data from the charnockites, mafic granulites and hornblende-biotite gneisses (TTG) presented in our study show that the magma generation during subduction and accretion events in this block occurred at 2700-2500 Ma. Together with the recent report on Neoarchean supra-subduction zone ophiolite suite at its southern margin, the Nilgiri Block provides one of the best examples for continental growth through vertical stacking and lateral accretion in a subduction environment during the Neoarchean. (c) 2014 Elsevier B.V. All rights reserved.

Assessing the critical concentration of NH2 terminal groups on the surface of MWNTs towards chain scission of PC in PC/SAN blends: effect on dispersion, electrical conductivity and EMI shielding

The localization and dispersion quality of as received NH2 terminated multiwall carbon nanotubes (MWNT-I) and ethylene diamine (EDA) functionalized MWNTs in melt mixed blends of polycarbonate ( PC) and poly(styrene-co-acrylonitrile) (SAN) were assessed in this study using rheo-electrical and electromagnetic interference (EMI) shielding measurements. In order to improve the dispersion quality and also to selectively localize MWNTs in the PC phase of the blends, EDA was grafted onto MWNTs by two different strategies like diazonium reaction of the para-substituted benzene ring of MWNTs with EDA ( referred to as MWNT-II) and acylation of carboxyl functionalized MWNTs with thionyl chloride ( referred to as MWNT-III). By this approach we could systematically vary the concentration of NH2 functional groups on the surface of MWNTs at a fixed concentration (1 wt%) in PC/SAN blends. XPS was carried to evaluate the % concentration of N in different MWNTs and was observed to be highest for MWNT-III manifesting in a large surface coverage of EDA on the surface of MWNTs. Viscoelastic properties and melt electrical conductivities were measured to assess the dispersion quality of MWNTs using a rheo-electrical set-up both in the quiescent as well as under steady shear conditions. Rheological properties revealed chain scission of PC in the presence of MWNT-III which is due to specific interactions between EDA and PC leading to smaller PC grafts on the surface of MWNTs. The observed viscoelastic properties in the blends were further correlated with the phase morphologies under quiescent and annealed conditions. Electromagnetic interference (EMI) shielding effectiveness in X and K-u-band frequencies were measured to explore these composites for EMI shielding applications. Interestingly, MWNT-II showed the highest electrical conductivity and EMI shielding in the blends.

Non-equilibrium segmental dynamics driven by multiwall carbon nanotubes in PS/PVME blends

The present paper discusses the effect of multiwall carbon nanotubes (MWNTs) on the structural relaxation and the intermolecular cooperativity in dynamically asymmetric blends of PS/PVME (polystyrene/poly(vinyl methyl ether)). The temperature regime where chain connectivity effects dominate the thermodynamic concentration fluctuation (T/T-g > 0.75, T-g is the glass transition temperature of the blends) was studied using dielectric spectroscopy (DS). Interestingly, in the blends with MWNTs a bimodal distribution of relaxation was obtained in the loss modulus spectra. This plausibly is due to different environments experienced by the faster component (PVME) in the presence of MWNTs. The segmental dynamics of PVME was observed to be significantly slowed down in the presence of MWNTs and an Arrhenius-type behavior, weakly dependent on temperature, is observed at higher frequencies. This non-equilibrium dynamics of PVME is presumed to be originating from interphase regions near the surface of MWNTs. The length scale of the cooperative rearranging region (xi CRR) at T-g, assessed by calorimetric measurements, was observed to be higher in the case of blends with MWNTs. An enhanced molecular level miscibility driven by MWNTs in the blends corroborates with the larger xi CRR and comparatively more number of segments in CRR (in contrast to neat blends) around T-g. The configurational entropy and length scale of the cooperative volume was mapped as a function of temperature in the temperature regime, Tg < T < T-g + 60 K. The blends phase separated by spinodal decomposition which further led to an interconnected PVME network in PS. This further led to materials with very high electrical conductivity upon demixing.

The influence of mesoporous silica in low T-g cyclic olefin copolymer nanocomposite films: Mechanical and moisture barrier studies

In this study, mesoporous silica-cyclic olefin copolymer nanocomposite films were fabricated by solution casting. With an increase in silica loading, the stiffness of the matrix increased. The nanocomposite film shows increased strain to failure with moisture after aging by matrix plasticization. The storage modulus and loss factor for samples with silica content show better results compared with pristine polymer, as indicated by dynamic mechanical analysis. The interaction between filler-polymer chain exhibit hydrophobicity compared to the neat polymer. Water absorption studies at room temperature and near the T-g of the polymer (similar to 64 degrees C) were carried out. The nanocomposites up to 4 wt% filler reduces the water diffusion by forming hydrogen and chemical bonding. The result by calcium degradation test method for moisture permeability and Schottky structured organic device encapsulation under weathering condition confirms the effective reinforcement effect of silica particles in the matrix. (C) 2014 Elsevier Ltd. All rights reserved.

Imprints of Archean to Neoproterozoic crustal processes in the Madurai Block, Southern India

Madurai Block, the largest crustal block in the Southern Granulite Terrane (SGT) of Peninsular India, preserves the imprints of multistage tectonic evolution. Here, we present U-Pb and Hf isotope data on zircons from a charnockite-granite suite in the north-western part of this block. The oscillatory zoning, and the LREE to HREE enriched patterns of the zircons with positive Ce and negative Eu anomalies suggest that the zircon cores are of magmatic origin, with ages in the range of 2634-2435 Ma implying Neoarchean-Paleoproterozoic magmatism followed by subsequent metamorphism and protocontinent formation in the north-western part of the Madurai Block. A regional 550-500 Ma metamorphic overprint is also preserved in the zircons coinciding with the final amalgamation of the Gondwana supercontinent. The Hf isotopic data suggest that the granite and charnockite were derived from isotopically heterogeneous juvenile crustal domains and the charnockites show a significant contribution of mantle-derived components. Therefore, the Hf isotopic data reflect mixing of crustal and mantle-derived sources for the generation of Neoarchean crust in the north-western Madurai Block, possibly in a suprasubduction zone setting during continent building processes. (c) 2014 Elsevier Ltd. All rights reserved.

Correlation between Optical Properties and Nanomorphology of Fluoranthene-Based Conjugated Copolymer

Nanoparticles of conjugated polymers are receiving attention due to their interesting optical properties. Here we report nanoparticles of fluoranthene-based conjugated copolymer prepared by the Suzuki coupling reaction. The copolymer forms nanoparticles by the spontaneous self-assembly after evaporation of organic solvent. The mean diameter of the nanoparticles can be manipulated by varying solvent composition. We investigated the parameters that govern the nanostructured morphology of polymer by systematic variation of good and poor solvent. The UV vis and time-resolved fluorescence spectroscopy measurement reveal the use of poor solvent in the organization of nanostructures. Furthermore, transmission electron microscopy highlights the importance of rigidity of the polymer backbone in morphological development.

Electromagnetic Interference Shielding Materials Derived from Gelation of Multiwall Carbon Nanotubes in Polystyrene/Poly(methyl methacrylate) Blends

Blends of polystyrene (PS) and poly(methyl methacrylate) (PMMA) with different surface-functionalized multiwall carbon nanotubes (MWNTs) were prepared by solution blending to design materials with tunable EMI (electromagnetic interference) shielding. Different MWNTs like pristine, amine (similar to NH2), and carboxyl acid (similar to COOH) functionalized were incorporated in the polymer by solution blending. The specific interaction driven localization of MWNTs in the blend during annealing was monitored using contact mode AFM (atomic force microscopy) on thin films. Surface composition of the phase separated blends was further evaluated using X-ray photoelectron spectroscopy (XPS). The localization of MWNTs in a given phase in the bulk was further supported by selective dissolution experiments. Solution-casted PS/PMMA (50/50, wt/wt) blend exhibited a cocontinuous morphology on annealing for 30 min, whereas on longer annealing times it coarsened into matrix-droplet type of morphology. Interestingly, both pristine MWNTs and NH2-MWNTs resulted in interconnected structures of PMMA in PS matrix upon annealing, whereas COOH-MWNTs were localized in the PMMA droplets. Room-temperature electrical conductivity and electromagnetic shielding effectiveness (SE) were measured in a broad range of frequency. It was observed that both electrical conductivity and SE were strongly contingent on the type of surface functional groups on the MWNTs. The thermal conductivity of the blends was measured with laser flash technique at different temperatures. Interestingly, the SE for blends with pristine and NH2-MWNTs was >-24 dB at room temperature, which is commercially important, and with very marginal variation in thermal conductivity in the temperature range of 303-343 K. The gelation of MWNTs in the blends resulted in a higher SE than those obtained using the composites.

Shear induced crystallization in different polymorphic forms of PVDF induced by surface functionalized MWNTs in PVDF/PMMA blends

Shear induced crystallization in PVDF/PMMA blends, especially at higher fractions of PMMA, can be quite interesting in understanding the structure-property correlation and processing of these blends. In a recent submission (Phys. Chem. Chem. Phys., 2014, 16, 2693-2704), we clearly demonstrated, using dielectric spectroscopy, that the origin of segmental relaxations concerning the crystalline segments of PVDF in PVDF/PMMA blends in the presence of MWNTs (multiwalled nanotubes) was strongly contingent on the size of the crystallite. We now understand that the fraction of PMMA in the blends governs the origin of polymorphism in PVDF. This motivated us to systematically study the effect of shear on the crystallization behavior of PVDF especially in blends with different polymorphic forms of PVDF. Two model blends were selected; one with a mixture of alpha and beta crystals and the other predominantly rich in alpha crystals. Initially, physical ageing, at different oscillation frequencies (1 rad s(-1) and 0.1 rad s(-1)), was monitored by melt rheology and subsequently, the effect of steady shear was probed in situ without changing the history of the samples. Intriguingly, the rate of crystallization was observed to be significantly higher for higher oscillation frequencies, which essentially suggest that shear has induced crystallization in the blends. More interestingly, the effect of steady shear was more pronounced in the blends rich in alpha crystals (bigger crystallites as observed from SAXS) and at lower oscillation frequencies.

Polyolefin based antibacterial membranes derived from PE/PEO blends compatibilized with amine terminated graphene oxide and maleated PE

In this study, various strategies like amine terminated GO (GO-NH2), in situ formed polyethylene grafted GO (PE-g-GO) and their combinations with maleated PE (maleic anhydride grafted PE) were adopted to reactively compatibilize blends of low density polyethylene (LDPE) and polyethylene oxide (PEO). These blends were further explored to design porous, antibacterial membranes for separation technology and the flux and the resistance across the membranes were studied systematically. It was observed that GO-NH2 led to uniform dispersion of PEO in a PE matrix and further resulted in a significant improvement in the mechanical properties of the blends when combined with maleated PE. The efficiency of various compatibilizers was further studied by monitoring the evolution of morphology as a function of the annealing time. It was observed that besides rendering uniform dispersion of PEO in PE and improving the mechanical properties, GO-NH2 further suppresses the coalescence in the blends. As the melt viscosities of the phases differ significantly, there is a gradient in the morphology as also manifested from scanning acoustic microscopy. Hence, the membranes were designed by systematically reducing the thickness of the as-pressed samples to expose the core as the active area for flux calculations. Selected membranes were also tested for their antibacterial properties by inoculating E. coli culture with the membranes and imaging at different time scales. This study opens new avenues to develop PE based cost effective anti-microbial membranes for water purification.

An unusual demixing behavior in PS-PVME blends in the presence of nanoparticles

The effect of silver nanoparticles (sNP) on the demixing and the evolution of morphology in off-critical blends of 90/10 and 10/90 (wt/wt) PS/PVME polystyrene/poly(vinyl methyl ether)] was probed here using shear rheology and optical microscopy. The faster component (PVME) has a higher molecular weight (80 kDa) than the slower component (PS, 35 kDa), which makes this system quite interesting to study with respect to the evolving morphology, as the blends transit through the binodal and the spinodal envelopes. An unusual demixing behavior was observed in both PVME rich and PS rich blends. Temperature modulated differential scanning calorimetry measurements showed that the T-g value for the blends with sNP was slightly lower than that of the neat blends. A decreased volume of cooperativity at T-g suggests confined segmental dynamics in the presence of sNP. Although, the addition of sNP had no influence on the thermodynamic demixing temperature, it significantly altered the elasticity of the minor component during the transition of the blend from the homogeneous to the heterogeneous state. This is manifested from energetically driven localization of the sNP in the PVME phase during demixing. As a direct consequence of this, the formation of the microstructures upon demixing was observed to be delayed in the presence of sNP. Interestingly, in the intermediate quench depth, the higher viscoelastic phase evolved as an interconnected network, which subsequently coarsened into discrete droplets in the late stages for the 90/10 PS/PVME blends. Similar observations were made for 10/90 PS/PVME blends where threads of PVME appeared at deeper quench depths in the presence of sNP. The interconnected network formation of the minor phase (here PVME), which is also the faster component in the blend, was different from the usual demixing behavior.

Polyolefin based antibacterial membranes derived from PE/PEO blends compatibilized with amine terminated graphene oxide and maleated PE

In this study, various strategies like amine terminated GO (GO-NH2), in situ formed polyethylene grafted GO (PE-g-GO) and their combinations with maleated PE (maleic anhydride grafted PE) were adopted to reactively compatibilize blends of low density polyethylene (LDPE) and polyethylene oxide (PEO). These blends were further explored to design porous, antibacterial membranes for separation technology and the flux and the resistance across the membranes were studied systematically. It was observed that GO-NH2 led to uniform dispersion of PEO in a PE matrix and further resulted in a significant improvement in the mechanical properties of the blends when combined with maleated PE. The efficiency of various compatibilizers was further studied by monitoring the evolution of morphology as a function of the annealing time. It was observed that besides rendering uniform dispersion of PEO in PE and improving the mechanical properties, GO-NH2 further suppresses the coalescence in the blends. As the melt viscosities of the phases differ significantly, there is a gradient in the morphology as also manifested from scanning acoustic microscopy. Hence, the membranes were designed by systematically reducing the thickness of the as-pressed samples to expose the core as the active area for flux calculations. Selected membranes were also tested for their antibacterial properties by inoculating E. coli culture with the membranes and imaging at different time scales. This study opens new avenues to develop PE based cost effective anti-microbial membranes for water purification.

Anomalous structural relaxations in PVDF rich blends with PMMA in the presence of surface functionalized CNTs

The structural relaxations in PVDF rich blends with PMMA can be quite interesting in understanding the origin of the different molecular relaxations associated with the crystalline and amorphous phases, crystal-amorphous interphase and the segmental motions. In light of our recent findings, we understood that the origin of these molecular relaxations were strongly contingent on the concentration of PMMA in the blend, crystalline morphology and the surface functional moieties on multiwall carbon nanotubes (CNTs). In addition, for the blends with concentration of PMMA >= 25 wt%, the structural relaxations often merge and are dielectrically indistinguishable. In this study, we attempted to determine the critical width in composition where the structural relaxations can be distinctly realized both in the control as well as blends with amine functionalized CNTs (NH2-CNTs). Intriguingly, we observed that in a narrow zone in composition (with PMMA concentration >= 10 wt% and <= 25 wt%), the molecular relaxations can be dielectrically distinguished and they often merge for all other compositions. Furthermore, we attempted to understand how this critical width in composition is related to the crystalline morphology using small angle X-ray scattering and polarizing optical microscopy and the crystal structure using FTIR and Raman spectroscopy. We now understand that although the formation of beta crystals in the blends has no direct correlation with the observed molecular relaxations, the amorphous miscibility and the interphase regions seem to be dictating the origin of different molecular relaxations in the blends. The latter was observed to be strongly contingent on the concentration of PMMA in the blends.

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.

Electromagnetic interference shielding through MWNT grafted Fe3O4 nanoparticles in PC/SAN blends

In this study, multiwall carbon nanotubes (MWNTs) were chemically grafted onto dopamine anchored iron oxide (Fe3O4) nanoparticles via diazotization reaction to design electromagnetic (EM) shielding materials based on PC (polycarbonate)/SAN poly (styrene-co-acrylonitrile)] blends. A two step mixing protocol was adopted to selectively localize the nanoparticles in a given phase of the blends. In the first step, MWNT-g-Fe3O4 nanoparticles were solution blended with PC, followed by dilution with SAN during melt mixing in the subsequent step. This strategy, besides improving the quality of dispersion of MWNTs in the blends, facilitated enhanced EM interference shielding effectiveness (SE). Both, the MWNTs and the modified MWNTs, selectively localized in the PC phase and led to high electrical conductivity, in striking contrast to PC filled MWNT composites. The SE was measured on toroidal samples over a broad range of frequencies; X-band (8.2-12 GHz) and K-u-band (12-18 GHz). It was observed that the shielding mechanism mostly involved reflection in the blends with MWNTs, whereas absorption dominated in the case of blends with MWNT-g-Fe3O4. To realize the efficacy of this strategy, a few compositions were prepared by physical mixing MWNTs with Fe3O4 nanoparticles. Intriguingly, blends with MWNT-g-Fe3O4 nanoparticles manifested enhanced microwave absorption over physically mixed nanoparticles. An SE of -32.5 dB was observed (at 18 GHz) for MWNT (3 wt%)-g-Fe3O4 (3 vol%) in PC/SAN blends.