Positive temperature coefficient and structural relaxations in selectively localized MWNTs in PE/PEO blends

The dispersion state of multiwall carbon nanotubes (MWNTs) in melt mixed polyethylene/polyethylene oxide (PE/PEO) blends has been assessed by both surface and volume electrical conductivity measurements and the structural relaxations have been assessed by broadband dielectric spectroscopy. The selective localization of MWNTs in the blends was controlled by the flow characteristics of the components, which led to their localization in the energetically less favored phase (PE). The electrical conductivity and positive temperature co-efficient (PTC) measurements were carried out on hot pressed samples. The neat blends exhibited only a negative temperature coefficient (NTC) effect while the blends with MWNTs exhibited both a PTC and a NTC at the melting temperatures of PE and PEO respectively. These phenomenal changes were corroborated with the different crystalline morphology in the blends. It was deduced that during compression molding, the more viscous PEO phase spreads less in contrast to the less viscous PE phase. This has further resulted in a gradient in morphology as well as the distribution state of the MWNTs in the samples and was supported by scanning electron and scanning acoustic microscopy (SAM) studies and contact angle measurements. SAM from different depths of the samples revealed a gradient in the microstructure in the PE/PEO blends which is contingent upon the flow characteristics of the components. Interestingly, the surface and volume electrical conductivity was different due to the different dispersion state of the MWNTs at the surface and bulk. The observed surface and volume electrical conductivity measurements were corroborated with the evolved morphology during processing. The structural relaxations in both PE and PEO were discerned from broadband dielectric spectroscopy. The segmental dynamics below and above the melting temperature of PEO were significantly different in the presence of MWNTs.

Role of pH controlled DNA secondary structures in the reversible dispersion/precipitation and separation of metallic and semiconducting single-walled carbon nanotubes

Single-stranded DNA (ss-DNA) oligomers (dA(20), d(C(3)TA(2))(3)C-3] or dT(20)) are able to disperse single-walled carbon nanotubes (SWNTs) in water at pH 7 through non-covalent wrapping on the nanotube surface. At lower pH, an alteration of the DNA secondary structure leads to precipitation of the SWNTs from the dispersion. The structural change of dA(20) takes place from the single-stranded to the A-motif form at pH 3.5 while in case of d(C(3)TA(2))(3)C-3] the change occurs from the single-stranded to the i-motif form at pH 5. Due to this structural change, the DNA is no longer able to bind the nanotube and hence the SWNT precipitates from its well-dispersed state. However, this could be reversed on restoring the pH to 7, where the DNA again relaxes in the single-stranded form. In this way the dispersion and precipitation process could be repeated over and over again. Variable temperature UV-Vis-NIR and CD spectroscopy studies showed that the DNA-SWNT complexes were thermally stable even at similar to 90 degrees C at pH 7. Broadband NIR laser (1064 nm) irradiation also demonstrated the stability of the DNA-SWNT complex against local heating introduced through excitation of the carbon nanotubes. Electrophoretic mobility shift assay confirmed the formation of a stable DNA-SWNT complex at pH 7 and also the generation of DNA secondary structures (A/i-motif) upon acidification. The interactions of ss-DNA with SWNTs cause debundling of the nanotubes from its assembly. Selective affinity of the semiconducting SWNTs towards DNA than the metallic ones enables separation of the two as evident from spectroscopic as well as electrical conductivity studies.

Local stability of a gravitating filament: a dispersion relation

Filamentary structures are ubiquitous in astrophysics and are observed at various scales. On a cosmological scale, matter is usually distributed along filaments, and filaments are also typical features of the interstellar medium. Within a cosmic filament, matter can contract and form galaxies, whereas an interstellar gas filament can clump into a series of bead-like structures that can then turn into stars. To investigate the growth of such instabilities, we derive a local dispersion relation for an idealized self-gravitating filament and study some of its properties. Our idealized picture consists of an infinite self-gravitating and rotating cylinder with pressure and density related by a polytropic equation of state. We assume no specific density distribution, treat matter as a fluid, and use hydrodynamics to derive the linearized equations that govern the local perturbations. We obtain a dispersion relation for axisymmetric perturbations and study its properties in the (kR, kz) phase space, where kR and kz are the radial and longitudinal wavenumbers, respectively. While the boundary between the stable and unstable regimes is symmetrical in kR and kz and analogous to the Jeans criterion, the most unstable mode displays an asymmetry that could constrain the shape of the structures that form within the filament. Here the results are applied to a fiducial interstellar filament, but could be extended for other astrophysical systems, such as cosmological filaments and tidal tails.

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.

Confinement enhances dispersion in nanoparticle-polymer blend films

Polymer nanocomposites constitute an important class of materials whose properties depend on the state of dispersion of the nanoparticles in the polymer matrix. Here we report the first observations of confinement-induced enhancement of dispersion in nanoparticle-polymer blend films. Systematic variation in the dispersion of nanoparticles with confinement for various compositions and matrix polymer chain dimensions has been observed. For fixed composition, strong reduction in glass transition temperature, T-g, is observed with decreasing blend-film thickness. The enhanced dispersion occurs without altering the polymer-particle interactions and seems to be driven by enhanced matrix-chain orientation propensity and a tendency to minimize the density gradients within the matrix. This implies the existence of two different mechanisms in polymer nanocomposites, which determines their state of dispersion and glass transition.

Size Modulation of Colloidal Au Nanoparticles via Digestive Ripening in Conjunction with a Solvated Metal Atom Dispersion Method: An Insight Into Mechanism

Digestive ripening, a postsynthetic treatment of colloidal nanoparticles, is a versatile method to produce monodisperse nanoparticles and to prepare various bimetallic nanostructures. The mechanism of this process is largely unknown. Herein, we present a systematic study conducted using Au nanoparticles prepared by a solvated metal atom dispersion method to probe the mechanistic aspects of digestive ripening. In our study, experimental conditions such as concentration of capping agent, reaction time, and temperature, were found to influence the course of the digestive ripening process. Here it is shown that, during digestive ripening under reflux, nanoparticles within an optimum size window are conserved, and surface etching facilitated mass transfer resulted in monodisperse nanoparticles. Overall, digestive ripening can be considered as a kinetically controlled thermodynamic process.

Dispersion of polymer grafted nanoparticles in polymer nanocomposite films: Insights from surface x-ray scattering and microscopy

Dispersion of nanoparticles in polymer nanocomposite films determines the application potential of these systems as novel materials with unique physical properties. Grafting polymers to, mostly inorganic, nanoparticles has been suggested as an effective strategy to enhance dispersion and hence the efficacy of materials. In this review, we discuss the various parameters which control dispersion of polymer grafted nanoparticles in polymer nanocomposite films. We discuss how surface x-ray scattering and microscopy can provide complementary and unique information in thin polymer nanocomposite films to unravel the subtle interplay of entropic and surface interactions, mediated by confinement, that leads to enhanced dispersion of the nanoparticles in these films. (C) 2014 AIP Publishing LLC.

Metal-organic chemical vapor-deposited cobalt oxide films as negative electrodes for thin film Li-ion battery

In this study, thin films of cobalt oxide (Co3O4) have been grown by the metal-organic chemical vapor deposition (MOCVD) technique on stainless steel substrate at two preferred temperatures (450 degrees C and 500 degrees C), using cobalt acetylacetonate dihydrate as precursor. Spherical as well as columnar microstructures of Co3O4 have been observed under controlled growth conditions. Further investigations reveal these films are phase-pure, well crystallized and carbon-free. High-resolution TEM analysis confirms that each columnar structure is a continuous stack of minute crystals. Comparative study between these Co3O4 films grown at 450 degrees C and 500 degrees C has been carried out for their application as negative electrodes in Li-ion batteries. Our method of electrode fabrication leads to a coating of active material directly on current collector without any use of external additives. A high specific capacity of 1168 micro Ah cm(-2) mu m(-1) has been measured reproducibly for the film deposited at 500 degrees C with columnar morphology. Further, high rate capability is observed when cycled at different current densities. The Co3O4 electrode with columnar structure has a specific capacity 38% higher than the electrode with spherical microstructure (grown at 450 degrees C). Impedance measurements on the Co3O4 electrode grown at 500 degrees C also carried out to study the kinetics of the electrode process. (C) 2014 Published by Elsevier B.V.

Kinetics of dispersion of nanoparticles in thin polymer films at high temperature

We report the first detailed study of the kinetics of dispersion of nanoparticles in thin polymer films using temperature dependent in situ X-ray scattering measurements. We show a comparably enhanced dispersion at higher temperatures for systems which are otherwise phase segregated at room temperature. Detailed analysis of the time dependent X-ray reflectivity and diffuse scattering data allows us to explore the out-of-plane and in-plane mobility of the nanoparticles in the polymer films. While the out-of-plane motion is diffusive with a diffusion coefficient almost two orders of magnitude lower than that expected in bulk polymer, the in-plane one is found to be super-diffusive resulting in significantly larger in-plane displacement at similar time scales. We discuss the origin of the observed highly anisotropic motion of nanoparticles due to their slaved motion with respect to the anisotropic chain orientation and consequent diffusivity anisotropy of matrix chains. We also suggest strategies to utilize these observations to kinetically improve dispersion in otherwise thermodynamically segregated polymer nanocomposite films.

Pair dispersion of turbulent premixed flame elements

Flame particles are mathematical points comoving with a reacting isoscalar surface in a premixed flame. In this Rapid Communication, we investigate mean square pair separation of flame particles as a function of time from their positions tracked in two sets of direct numerical simulation solutions of H-2-air turbulent premixed flames with detailed chemistry. We find that, despite flame particles and fluid particles being very different concepts, a modified Batchelor's scaling of the form = C-F ( (F)(0) Delta(F)(0))(2/3)t(2) holds for flame particle pair dispersion. The proportionality constant, however, is not universal and depends on the isosurface temperature value on which the flame particles reside. Following this, we attempt to analytically investigate the rationale behind such an observation.

Water Dispersible, Positively and Negatively Charged MoS2 Nanosheets: Surface Chemistry and the Role of Surfactant Binding

Stable aqueous dispersions of atomically thin layered MoS2 nanosheets have been obtained by sonication in the presence of ionic surfactants. The dispersions are stabilized by electrostatic repulsion between the sheets, and we show that the sign of the charge on the MoS2 nanosheets, either positive or negative, can be can be controlled by the choice of the surfactant. Using techniques from solution NMR, we show that the surfactant chains are weakly bound to the MoS2 sheets and undergo rapid exchange with free surfactant chains present in the dispersion. In situ nuclear Overhauser effect spectroscopic measurements provide direct evidence that the surfactant chains lie flat, arranged randomly on the basal plane of the MoS2 nanosheets with their charged headgroup exposed. These results provide a chemical perspective for understanding the stability of these inorganic nanosheets in aqueous dispersions and the origin of the charge on the sheets.

Demonstration of helicase activity in the nonstructural protein, NSs, of the negative-sense RNA virus, Groundnut bud necrosis virus

The nonstructural protein NSs, encoded by the S RNA of groundnut bud necrosis virus (GBNV) (genus Tospovirus, family Bunyaviridae) has earlier been shown to possess nucleic-acid-stimulated NTPase and 50 a phosphatase activity. ATP hydrolysis is an essential function of a true helicase. Therefore, NSs was tested for DNA helicase activity. The results demonstrated that GBNV NSs possesses bidirectional DNA helicase activity. An alanine mutation in the Walker A motif (K189A rNSs) decreased DNA helicase activity substantially, whereas a mutation in the Walker B motif resulted in a marginal decrease in this activity. The parallel loss of the helicase and ATPase activity in the K189A mutant confirms that NSs acts as a non-canonical DNA helicase. Furthermore, both the wild-type and K189A NSs could function as RNA silencing suppressors, demonstrating that the suppressor activity of NSs is independent of its helicase or ATPase activity. This is the first report of a true helicase from a negative-sense RNA virus.

Tailoring the dispersion of multiwall carbon nanotubes in co-continuous PVDF/ABS blends to design materials with enhanced electromagnetic interference shielding

Highly conducting composites were derived by selectively localizing multiwall carbon nanotubes (MWNTs) in co-continuous PVDF/ABS (50/50, wt/wt) blends. The electrical percolation threshold was obtained between 0.5 and 1 wt% MWNTs as manifested by a dramatic increase in the electrical conductivity by about six orders of magnitude with respect to the neat blends. In order to further enhance the electrical conductivity of the blends, the MWNTs were modified with amine terminated ionic liquid (IL), which, besides enhancing the interfacial interaction with PVDF, facilitated the formation of a network like structure of MWNTs. This high electrical conductivity of the blends, at a relatively low fraction (1 wt%), was further explored to design materials that can attenuate electromagnetic (EM) radiation. More specifically, to attenuate the EM radiation by absorption, a ferroelectric phase was introduced. To accomplish this, barium titanate (BT) nanoparticles chemically stitched onto graphene oxide (GO) sheets were synthesized and mixed along with MWNTs in the blends. Intriguingly, the total EM shielding effectiveness (SE) was enhanced by ca. 10 dB with respect to the blends with only MWNTs. In addition, the effect of introducing a ferromagnetic phase (Fe3O4) along with IL modified MWNTs was also investigated. This study opens new avenues in designing materials that can attenuate EM radiation by selecting either a ferroelectric (BT-GO) or a ferromagnetic phase (Fe3O4) along with intrinsically conducting nanoparticles (MWNTs).

Negative hyperconjugation and red-, blue- or zero-shift in X-Z center dot center dot center dot Y complexes

A generalized explanation is provided for the existence of the red-and blue-shifting nature of X-Z bonds (Z = H, halogens, chalcogens, pnicogens, etc.) in X-Z center dot center dot center dot Y complexes based on computational studies on a selected set of weakly bonded complexes and analysis of existing literature data. The additional electrons and orbitals available on Z in comparison to H make for dramatic differences between the H-bond and the rest of the Z-bonds. The nature of the X-group and its influence on the X-Z bond length in the parent X-Z molecule largely controls the change in the X-Z bond length on X-Z center dot center dot center dot Y bond formation; the Y-group usually influences only the magnitude of the effects controlled by X. The major factors which control the X-Z bond length change are: (a) negative hyperconjugative donation of electron density from X-group to X-Z sigma* antibonding molecular orbital (ABMO) in the parent X-Z, (b) induced negative hyperconjugation from the lone pair of electrons on Z to the antibonding orbitals of the X-group, and (c) charge transfer (CT) from the Y-group to the X-Z sigma* orbital. The exchange repulsion from the Y-group that shifts partial electron density at the X-Z sigma* ABMO back to X leads to blue-shifting and the CT from the Y-group to the sigma* ABMO of X-Z leads to red-shifting. The balance between these two opposing forces decides red-, zero- or blue-shifting. A continuum of behaviour of X-Z bond length variation is inevitable in X-Z center dot center dot center dot Y complexes.