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Porous carbon nanospheres have received enormous attention due to their various applications. Although several elegant strategies exist for the synthesis of relatively large carbon nanospheres (>ca. 100 nm), the synthesis of carbon nanospheres with well-defined, tunable ultra-small sizes (

We report an efficient route for ferroelectric polar β phase generation in poly(vinylidene fluoride) (PVDF) through incorporation of amine functionalized, porous silica (MCM-41 and fumed silica) based nanofillers. These porous highly functionalized surfaces exhibit the efficient secondary interaction with polymer chain via hydrogen bonding. Structural analysis through FTIR, XRD, and TEM confirm high degree of ferroelectric polar β phase generation of PVDF through incorporation of amino modified porous silica nanofillers. Optimized loading (5 wt %) of amine functionalized, porous silica in PVDF matrix enhances relative intensity of β phase up to 75%. Disappearance of spherulite structure of PVDF with amino modified porous silica nanofillers, as confirmed through POM, TEM, SEM and AFM studies also supports the above conclusion. The P-E hysteresis loop at sweep voltage of ±50 V of a thin PVDF-amino modified porous nanofiller film shows excellent ferroelectric property with nearly saturated high remnant polarization 2.8 µC.cm−2 owing to its large proportion of β PVDF, whereas, a nonpolar pure PVDF thin film shows unsaturated hysteresis loop with 0.6 µC.cm−2 remnant polarization. PVDF films with the nanofillers exhibit strong adhesive strength over different metallic substrates making them have edge over PVDF in various thin film applications. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 2401–2411

To meet the growing demand for rapid heat dissipation in electronic devices to ensure their reliable performance with a high level of safety, many polymer composites with thermally conductive but electrically insulating 2D boron nitride nanosheets (BNNSs) are being developed. Here we present an efficient way to enhance the thermal conductivity (TC) of a polymer composite by means of "grafting-from" polymerization of a poly(caprolactone) (PCL) onto BNNSs. The BNNSs, which were exfoliated from bulk BN by means of ultra-sonication, were prepared by means of radical oxidation. These oxidized BNNSs (oxi-BNNSs) were employed as initiators for subsequent ring-opening polymerization of PCL, which successfully resulted in PCL chemically grafted onto BNNSs (PCL-g-BNNSs). The excellent dispersion of PCL-g-BNNSs in common solvents allowed us to readily fabricate a polymer composite that contained PCL-g-BNNSs embedded in a PCL matrix, and the composite showed TC values that were five and nine times greater in the out-of-plane and in-plane mode, respectively, than those of pristine PCL.

Wrapping of reduced graphene oxide (RGO) over 2D layered transition metal oxide cathode material is very prevailing strategy to improve the capacity and cycling performance of cathode materials for sodium-batteries. However, poorly dispersed RGO in aqueous medium restricts the proper attachment of active-material with RGO resulting in non-uniform wrapping. Herein, graphene oxide is functionalized non-covalently through multifunctional agent dextran and reduced moderately to dextran functionalized-RGO (Dx-RGO). Further, it is attached chemically with Na[Ni0.60Mn0.35Co0.05]O2 (NMC) nano-sphere, which is synthesized by co-precipitation method. Strategically, hydrothermal-treatment is applied to empower reduction as well as attachment of Dx-RGO with NMC nano-sphere to prepare NMC-Dx-RGO composite. The successful attachment of Dx-RGO over NMC nano-sphere is confirmed by various experimental techniques and their resulting electrochemical performances are investigated. The surface-modified NMC-Dx-RGO cathode material exhibits high discharge capacity of 151 mAh g−1 at 0.1C and 55% capacity retention after 120 cycles at 0.2C. Dx-RGO layer acts as conducting network around NMC providing uniform state of charge distribution (SOC), which facilitates fast transport of electrons. The presence of protective Dx-RGO layer suppresses the growth of resistive layer at cathode-electrolyte interface (Rcei) and prevents the dissolution of transition metals cathode material to get high discharge capacity for sodium-batteries.

The composite cathode of sulfur-rich polymer and long cylindrical porous multiwalled carbon nanotubes (LCNT) is reported for high performance lithium-sulfur (Li–S) batteries through combining both chemical and physical binding strategies of sulfur, respectively. This technique efficiently exploits the synergistic effect of ability of stabilizing the polymeric sulfur. The role of uniform distribution of highly conductive LCNT network is optimized as a cathode host material by solution route. Annealed sulfur-co-polymer (S-co-poly) composites are homogeneously well attached via physisorption with LCNT submicron channel. The composite shows a high discharge capacity of 1040 mAh g−1 in the 1st cycle of galvanostatic charge-discharge at 0.5C. Whereas, the cell maintains a reversible capacity of 610 mAh g−1 after 200 cycles, showing good capacity rate. Therefore, solvent assisted both synthesis and further proper mixing enables high active material utilization whereas porous submicron channel of CNT network, which provides conducting pathway, adsorbs sulfur copolymer homogeneously for better electrochemical performance.

A nanohybrid has been synthesized by incorporating organically modified layered silicate in a poly(vinylidene fluoride) (PVDF) matrix. Molecular-level phenomena have been explored after exposing PVDF and its nanohybrid to an electron beam of varying doses. The electron beam interacts with polymer chains and thereby generates different free radicals, the number of which is quite high in nanohybrid as compared to pure PVDF. The stability of free radicals has been confirmed through density functional theory energy minimization, predicting stable β-phase free radicals in the nanohybrid. Quantitative analyses of chain scission, crosslinking and double bond formation are reported and compared after irradiation for both PVDF and its nanohybrid using UV-visible and Fourier transform infrared spectroscopies, sol–gel analyses and gel permeation chromatography, revealing both chain scission and crosslinking phenomena in irradiated PVDF and its nanohybrid, but at higher dose (>90 Mrad) crosslinking dominates in the nanohybrid due to more free radicals and proximity of radical chains on top of templated system in the nanohybrid as compared to pure PVDF. The enhanced crosslinking alters the nanostructure causing disappearance of the peak at 2θ ≈ 3°. Moreover, the electron beam induces significant piezoelectric β-phase in the nanohybrid against only α-phase in pure PVDF at a similar dose and raises the possibility for the use of electron-irradiated nanohybrid as an electromechanical device. β-Phase formation is also supported through solid-state NMR, scanning electron microscopy and differential scanning calorimetry studies. The thermal properties in terms of heat of fusion and degradation temperature have been verified indicating steady decrease of melting point and heat of fusion for pure PVDF while considerably less effect is observed for the nanohybrid. The combined effect of chain scission and crosslinking makes both PVDF and its nanohybrid brittle, but with greater stiffness with respect to unirradiated specimens. © 2014 Society of Chemical Industry

Process and nanoparticle induced piezoelectric super toughened poly(vinylidene fluoride) (PVDF) nanohybrids have been demonstrated. The nanohybrids have been prepared by incorporating organically modified nanoclay through melt extrusion and solution route. The solution processed nanohybrid exhibit 1100% improvement in toughness as well as adequate stiffness as compared to pure PVDF without any trade-off. The structural and morphological origins of super toughening phenomena have been worked out. The unique crystallization behavior of PVDF on top of the silicate layers (β-phase, planar zigzag chain conformation, and subsequent polar γ-phase and α-phase as layered type) has been revealed to create an island type of structure, which in turn is responsible for greater toughness. The extent of piezoelectric β-phase has been enhanced by controlled stretching of the nanohybrid at moderately high temperature for better disentanglement, and 90% of the piezoelectric phase has been stabilized. The structural change ...

Swift heavy ions (SHI) induced modification of biodegradable poly( e -caprolactone) (PCL) nanohybrids (NH) with organically modified nanoclay has been studied for structural, thermal, surface morphology and sol–gel analyses and its function to control biodegradation. Nanohybrids retain its structure and thermal stability even at higher irradiation fluence. Surface morphology of nanohybrid indicates insignificant changes in roughness after irradiation at high fluence vis-a-vis marked degradation in pristine PCL. Sol–gel analyses suggest that crosslinking is a major phenomenon in nanohybrid in presence of nanoclay against chain session in pure PCL. These induced properties in PCL/nanohybrid caused by SHI irradiation affect the biodegradation in a pure enzymatic medium. Before irradiation, nanohybrids show greater biodegradation as compared to pure PCL, whereas it exhibits less degradation after irradiation due to extensive crosslinked network in nanohybrid in presence of nanoclay raising SHI induced controlled biodegradation in polymer. Morphological studies confirm the regulated biodegradation after irradiation in pure PCL and its nanohybrids.

Poly(vinylidene fluoride-co-hexafluoropropylene) (HFP) nanocomposites with layered silicate have been synthesized via the melt extrusion route. The intriguing nanostructure, crystalline structure, morphology, and thermal and mechanical properties of the nanocomposites have been studied and compared critically with pristine polymer. HFP forms intercalated or partially exfoliated nanostructure (or both) in the presence of nanoclay, depending on its concentration. The bombardment of high-energy swift, heavy ions (SHI) on HFP and its nanocomposites has been explored in a wide range of fluence. The nanoclay induces the piezoelectric beta-phase in bulk HFP, and the structure remains intact upon SHI irradiation. SHI irradiation degrades pure polymer, but the degradation is suppressed radically in nanocomposites. The heat of fusion of pristine HFP has drastically been reduced upon SHI irradiation, whereas there are relatively minute changes in nanocomposites. The coarsening on the surface and bulk of HFP and its nanocomposite films upon SHI irradiation has been measured quantitatively by using atomic force microscopy. The degradation has been considerably suppressed in nanocomposites through cross-linking of polymer chains, providing a suitable high-energy, radiation-resistant polymeric material. A mechanism for this behavior originating from the swelling test and gel fraction (chemical cross-linking) as a result of SHI irradiation has been illustrated.

Poly(vinylidene fluoride) (PVDF) has been made radiation-resistant through a nanocomposite (NC) route. The bombardment of high-energy swift heavy ions (SHI) on PVDF and its NCs with layered silicate has been studied in a range of fluences. The degradation of PVDF after SHI irradiation is suppressed radically in NCs. PVDF forms an intercalated nanostructure in the presence of nanoclay and, further, the ion fluence raises the extent of intercalation. The crystallinity and the heat of fusion of pristine PVDF have drastically been reduced after SHI irradiation, while there are relatively small changes in NCs even at higher fluences. The metastable piezoelectric beta form of PVDF gets stabilized by the presence of layered silicate, and the structure is retained upon SHI irradiation. The clay platelets act as nucleating agents, and SHI irradiation causes two crystallization temperatures for the samples exposed to high fluences. The damages created on the surface and bulk of PVDF and its NC films upon SHI irradiation have been measured quantitatively by using atomic force microscopy. The pitting dimensions and degradation are enhanced significantly beyond 10(11) ions/cm(2) fluence for pristine PVDF, which limits the use of PVDF for any ion irradiation application. The degradation is considerably suppressed in NCs, providing a suitable high-energy radiation-resistant thermoplastic polymer.

A series of high molecular weight poly(N-isopropylacrylamide) (PNIPAM)s with low polydispersity (Mn = 7.0 × 104 to 10.2× 104 g mol–1, PDI = 1.23–1.35) having different isotacticity [meso diad (m) =...

We have developed multifunctional nanohybrids of poly(vinylidene fluoride-co-chlorotrifluoroethylene) (CTFE) with a small percentage of surface modified inorganic layered silicate showing dramatic improvement in toughness, radiation resistant and piezoelectric properties vis-à-vis pristine polymer. Massive intercalation (d(001) 1.8 → 3.9 nm) of polymer inside the nanoclay galleries and unique crystallization behavior of the fluoropolymer on the surface of individual silicate layer has been reported. Toughness in the nanohybrid increases more than three orders of magnitude as compared to pure CTFE. High energy radiation (80 MeV Si(+7)) causes chain session, amorphization and creates olefinic bonds in the pure polymer while the nanohybrids are radiation resistant at a similar dose. Nanoclay induces the metastable piezoelectric β-phase in CTFE, suitable for sensor and actuator application. Molecular level changes after irradiation and controlled morphology for smart membrane have been confirmed by using spectroscopy, sol-gel technique, surface morphology studies and in situ residual gas analysis.

Ion flux dependent swift heavy ions (SHI) induced structural changes have been reported for pristine poly(vinylidene fluoride) (PVDF). Ordering phenomena has been observed first followed by its transformation from α to β-form (polar metastable piezoelectric phase). The ordering of (020) plane become prominent at higher ion flux SHI irradiation and its further increase induces structural change from α to β phase as revealed by XRD and FTIR analyses. Structural changes are also supported by morphological evidence and thermal studies before and after SHI irradiation.