Enhancement of nonvolatile polarization and pyroelectric sensitivity in lithium tantalate (LT)/poly(vinylidene fluoride) (PVDF) nanocomposite

We report the ferroelectric and pyroelectric properties of the composite films of lithium tantalate (LT) nanoparticle in poly(vinylidene fluoride) PVDF matrix at different volume fractions of LT (f(LT) = 0.047, 0.09 and 0.17). For an applied electric field of 150 kV cm(-1) the nonvolatile polarization of the composite was observed to increase from 0.014 mu C cm(-2) at f(LT) = 0 to 2.06 mu C cm(-2) at f(LT) = 0.17. For f(LT) = 0.17, the composite films exhibit a saturated ferroelectric hysteresis loop with a remanent polarization (2P(r) = 4.13 mu C cm(-2)). Compared with pure poled PVDF the composite films also showed a factor of about five enhancement in the pyroelectric coefficient at f(LT) = 0.17. When used in energy detection mode the pyroelectric voltage sensitivity of the composite films was found to increase from 3.93 to 18.5 VJ(-1) with an increase in f(LT) from 0.0 to 0.17.

Dielectric properties of Poly(vinylidene fluoride)/CaCu3Ti4O12 composites

The possibility of obtaining relatively high dielectric constant polymer-ceramic composite by incorporating the giant dielectric constant material, CaCu3Ti4O12 (CCTO) in a Poly(vinylidene fluoride) (PVDF) polymer matrix by melt mixing and hot pressing process was demonstrated. The structure, morphology and dielectric properties of the composites were characterized using X-ray diffraction, Thermal analysis. scanning electron microscope, and impedance analyzer. The effective dielectric constant a(epsilon(eff)) of the composite increased with increase in the volume fraction of CCTO at all the frequencies(100 Hz-1 MHz) under study. The dielectric loss did not show any variation up to 40% loading of CCTO, but showed an increasing trend beyond 40%. The room temperature dielectric constant as high as 95 at 100 Hz has been realized for the composite with 55 vol.% of CCTO, which has increased to about 190 at 150 degrees C. Theoretical models like Maxwell's, Clausius-Mossotti, Effective medium theory, logarithmic law and Yamada were employed to rationalize the dielectric behaviour of the composite and discussed. (C) 2010 Published by Elsevier Ltd.

Effect of annealing on phase transition in poly(vinylidene fluoride) films prepared using polar solvent

The gamma-phase poly (vinylidene fluoride) (PVDF) films are usually prepared using dimethyl sulfoxide (DMSO) solvent, regardless of preparation temperature. Here we report the crystallization of both alpha and gamma-phase PVDF films by varying preparation temperature using DMSO solvent. The gamma-phase PVDF films were annealed at 70, 90, 110, 130 and 160 degrees C for five hours. The changes in the phase contents in the PVDF at different annealing conditions have been described. When thin films were annealed at 90 degrees C for 5 h, maximum percentage of beta-phase appears in PVDF thin films. The gamma-phase PVDF films completely converted to alpha-phase when they were annealed at 160 degrees C for 5 h. From X-ray diffraction (XRD), Fourier transform infrared spectrum (FTIR), differential scanning calorimetry (DSC) and Raman studies, it is confirmed that the PVDF thin films, cast from solution and annealed at 90 degrees C for 5 h, have maximum percentage of beta-phase. The beta-phase PVDF shows a remnant polarization of 4.9 mu C/cm(2) at 1400 kV/cm at 1 Hz.

Size dependent structural relaxations and dielectric properties induced by surface functionalized MWNTs in poly(vinylidene fluoride)/poly(methyl methacrylate) blends

Structural dynamics, dielectric permittivity and ferroelectric properties in poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) (PVDF/PMMA) blends with respect to crystalline morphology was systematically investigated in presence of amine functionalized MWNTs (NH2-MWNTs) using dielectric spectroscopy. The crystalline morphology and the crystallization driven demixing in the blends was assessed by light microscopy (LM), wide angle X-ray diffraction (WXRD) and, in situ, by shear rheology. The crystal nucleation activity of PVDF was greatly induced by NH2-MWNTs, which also showed two distinct structural relaxations in dielectric loss owing to mobility confinement of PVDF chains and smaller cooperative lengths. The presence of crystal-amorphous interphase was supported by the presence of interfacial polarization at lower frequencies in the dielectric loss spectra. On contrary, the control blends showed a single broad relaxation at higher frequency due to defective crystal nuclei. This was further supported by monitoring the dielectric relaxations during isothermal crystallization of PVDF in the blends. These observations were addressed with respect to the spherulite sizes which were observed to be larger in case of blends with NH2-MWNTs. Higher dielectric permittivity with minimal losses was also observed in blends with NH2-MWNTs as compared to neat PVDF. Polarization obtained using P-E (polarization-electric field) hysteresis loops was higher in case of blends with NH2-MWNTs in contrast to control blends and PVDF. These observations were corroborated with the charge trapped at the crystal-amorphous interphase and larger crystal sizes in the blends with NH2-MWNTs. The microstructure and localization of MWNTs were assessed using SEM.

Poly(vinylidene fluoride)-Based Flexible and Lightweight Materials for Attenuating Microwave Radiations

Two unique materials were developed, like graphene oxide (GO) sheets covalently grafted on to barium titanate (BT) nanoparticles and cobalt nanowires (Co-NWs), to attenuate the electromagnetic (EM) radiations in poly(vinylidene fluoride) (PVDF)-based composites. The rationale behind using either a ferroelectric or a ferromagnetic material in combination with intrinsically conducting nanoparticles (multiwall carbon nanotubes, CNTs), is to induce both electrical and magnetic dipoles in the system. Two key properties, namely, enhanced dielectric constant and magnetic permeability, were determined. PVDF/BT-GO composites exhibited higher dielectric constant compared to PVDF/BT and PVDF/GO composites. Co-NWs, which were synthesized by electrodeposition, exhibited saturation magnetization (M-s) of 40 emu/g and coercivity (Hc) of 300 G. Three phase hybrid composites were prepared by mixing CNTs with either BT-GO or Co-NWs in PVDF by solution blending. These nanoparticles showed high electrical conductivity and significant attenuation of EM radiations both in the X-band and in the Ku-band frequency. In addition, BT-GO/CNT and Co-NWs/CNT particles also enhanced the thermal conductivity of PVDF by ca. 8.7- and 9.3-fold in striking contrast to neat PVDF. This study open new avenues to design flexible and lightweight electromagnetic interference shielding materials by careful selection of functional nanoparticles

Contrasting Effects of Graphene Oxide and Poly(ethylenimine) on the Polymorphism in Poly(vinylidene fluoride)

The nature of interaction between a heteronucleating agent (graphene oxide, GO) and a strongly polar macromolecule (poly(ethylenimine), PEI) with poly(vinylidene fluoride) (PVDF) influencing the crystalline structure and morphology has been systematically investigated in this work. PEI interacts with PVDF via ion-dipole interaction, which helps in lowering the free energy barrier for nucleation thereby promoting faster crystallization. In contrast, besides interacting with PVDF, GO also promotes heteronucleation in PVDF. We observed that both GO and PEI have very different effects on the overall crystalline morphology of PVDF. For instance, the neat PVDF showed a mixture of both alpha and beta phases when cooled from the melt. However, incorporation of 0.1 wt % GO resulted in phase transformation from the stable alpha-phase to polar beta-polymorph in PVDF. In contrast, PEI, which also resulted in faster crystallization in PVDF predominantly, resulted in the stable alpha- phase. Various techniques like Fourier transform infrared spectroscopy, X-ray diffraction, and differential scanning calorimetry were employed to confirm the phase transformations in PVDF. PEI was further grafted onto GO nanosheets to understand the combined effects of both GO and PEI on the polymorphism in PVDF. The PVDF/PEI-GO composite showed a mixture of phases, predominantly rich in a. These phenomenal effects were further analyzed and corroborated with the specific interaction between GO and PEI with PVDF using X-ray photon scattering (XPS) and NMR. In addition, the dielectric permittivity increased significantly in the presence of GO and PEI in the composites. For instance, PVDF/PEI-GO showed the highest permittivity of 39 at 100 Hz.

Dielectric properties of poly(vinylidene luoride)/CaCu3Ti4O12 nanocrystal composite thick films

The poly(vinylidene fluoride)/CaCu3Ti4O12 (CCTO) nanocrystal composite films (thickness approximate to 85 mu m) with relatively high dielectric permittivity (90 at 100 Hz) were prepared by the solution casting followed by spin coating technique. The structural, the microstructural and the dielectric properties of the composites were studied using X-ray diffraction, Scanning Electron Microscope, and Impedance analyzer respectively. The effective dielectric permittivity (e(eff)) of the composite increased with increase in the volume fraction of CCTO at all the frequencies (100 Hz to 1 MHz) under investigation. The room temperature dielectric permittivity which is around 90 at 100 Hz, has increased to about 290 at 125 degrees C (100 Hz). These results may be exploited in the development of high energy density capacitors.

Segmental relaxations and crystallization-induced phase separation in PVDF/PMMA blends in the presence of surface-functionalized multiwall carbon nanotubes

Crystallization-induced phase separation and segmental relaxations in poly(vinylidene fluoride)/poly(methyl methacrylate) (PVDF/PMMA) blends was systematically investigated by melt-rheology and broadband dielectric spectroscopy in the presence of multiwall carbon nanotubes (MWNTs). Different functionalized MWNTs (amine, -NH2; acid, -COOH) were incorporated in the blends by melt-mixing above the melting temperature of PVDF, where the blends are miscible, and the crystallization induced phase separation was probed in situ by shear rheology. Interestingly, only -NH2 functionalized MWNTs (a-MWNTs) aided in the formation of beta-phase (trans-trans) crystals in PVDF, whereas both the neat blends and the blends with -COOH functionalized MWNTs (c-MWNTs) showed only alpha-phase (trans-gauche-trans-gauche') crystals as inferred from wide-angle X-ray diffraction (WXRD) and Fourier transform infrared (FTIR). Furthermore, blends with only a-MWNTs facilitated in heterogeneous nucleation in the blends manifesting in an increase in the calorimetric crystallization temperature and hence, augmented the theologically determined crystallintion induced phase separation temperature. The dielectric relaxations associated with the crystalline phase of PVDF (alpha(c)) was completely absent in the blends with a-MWNTs in contrast to neat blends and the blends with c-MWNTs in the dielectric loss spectra. The relaxations in the blends investigated here appeared to follow Havriliak-Negami (HN) empirical equations, and, more interestingly, the dynamic heterogeneity in the system could be mapped by an extra relaxation at higher frequency at the crystallization-induced phase separation temperature. The mean relaxation time (tau(HN)) was evaluated and observed to be delayed in the presence of MWNTs in the blends, more prominently in the case of blends with a-MWNTs. The latter also showed a significant increase in the dielectric relaxation strength (Delta epsilon). Electron microscopy and selective etching was used to confirm the localization of MWNTs in the amorphous phases of the interspherulitic regions as observed from scanning electron microscopy (SEM). The evolved crystalline morphology, during crystallization-induced phase separation, was observed to have a strong influence on the charge transport processes in the blends. These observations were further supported by the specific interactions (like dipole induced dipole interaction) between a-MWNTs and PVDF, as inferred from FTIR, and the differences in the crystalline morphology as observed from WXRD and polarized optical microscopy (POM).

Process induced electroactive beta-polymorph in PVDF: effect on dielectric and ferroelectric properties

The effects of various processing conditions, like annealing, poling, mechanical rolling and their combinations, on the dielectric and ferroelectric properties of PVDF poly(vinylidene fluoride)] were systematically studied in this work. Further, the effect of processing sequence on the structure and properties was investigated. While all the processing conditions adopted here resulted in phase transformation of the alpha- to electroactive beta-polymorph in PVDF, the fraction of beta-phase developed was observed to be strongly contingent on the adopted process. The transformation of alpha- to electroactive beta-polymorph was determined by X-ray diffraction and FTIR. The neat PVDF showed only beta-phase, whereas mechanically rolled samples exhibited the highest ca. 85% beta-phase in PVDF. Both the permittivity and the loss tangent decreased in the samples which had undergone different processing conditions. The polarization-electric field (P-E) loops for all the samples were evaluated. Interestingly, the energy density, estimated from the electrical displacement-electric field (D-E) loops, was observed to be highest for the poled samples which were initially rolled. The results indicate that various processing conditions can influence the dielectric and the ferroelectric properties differently.

Unique nanoporous antibacterial membranes derived through crystallization induced phase separation in PVDF/PMMA blends

In this study, a unique method was adopted to design porous membranes through crystallization induced phase separation in PVDF/PMMA (poly(vinylidene fluoride)/poly(methyl methacrylate)) blends. By etching out PMMA, which segregates either in the interlamellar and/or in the interspherulitic regions of the blends, nanoporous hierarchical structures can be derived. Different nanoparticles like titanium dioxide (TiO2), silver nanoparticle (Ag) decorated carbon nanotubes (Ag-CNTs), TiO2 decorated CNTs (TiO2-CNTs), Ag decorated TiO2 (Ag-TiO2) and Ag-TiO2 decorated CNTs (Ag@TiO2-CNTs) were synthesized and melt mixed with 80/20 PVDF/PMMA blends to render antibacterial activity to the membranes. Scanning electron microscopy (SEM) was used to study the crystalline morphology of the membranes. A significant improvement in the trans-membrane flux was obtained in the blends with Ag@TiO2 decorated CNTs as compared to the membranes derived from the neat blends, which can be attributed to the interconnected pores in these membranes. Both qualitative and quantitative studies of antifouling and antibacterial activity (using E. coli as a model bacterium) were performed using the standard plate count method. SEM micrographs clearly showed that the antifouling activity of the membranes was improved with addition of Ag@TiO2-CNTs. In the quantitative standard plate count method, the bacterial colony significantly decreased with the addition of Ag@TiO2-CNTs as against neat blends. This study opens a new avenue in the fabrication of polymer blend based membranes for water filtration.

Unusual Fragility and Cooperativity in Glass-Forming and Crystalline PVDF/PMMA Blends in the Presence of Multiwall Carbon Nanotubes

Poly(vinylidene fluoride) (PVDF) and poly(methyl methacrylate) (PMMA) are completely miscible below 50 wt % PVDF in the blends. In this work, an attempt was made to understand the fragility/cooperativity relation in glass-forming and crystalline blends of PVDF/PMMA and in the presence of a heteronucleating agent, multiwall carbon nanotubes (CNTs). Hence, three representative blends were chosen: a completely amorphous (10/90 by wt, PVDF/PMMA), on the verge of amorphous miscibility (50/50 by wt, PVDF/PMMA), and crystalline (60/40 by wt, PVDF/PMMA) blends. The intermolecular cooperativity/coupling, fragility, and configurational entropy near the glass transition temperature (T-g) were studied using differential scanning calorimetry (DSC) and broadband dielectric relaxation spectroscopy (DRS). It was observed that the blends with higher concentration of PMMA were more fragile (fragility index m = 141) and those with higher concentration of PVDF were more strong (m = 78). Interestingly, the coupling was less in the glass-forming blends (10/90 by wt, PVDF/PMMA) than the crystalline blends as manifested from DRS. This observation was also supported by DSC measurements which reflected that the cooperative rearranging region (CRR) existed over a smaller length scales in fragile blends as compared to strong blends, possibly due to restricted amorphous mobility. This effect was more prominent in the presence of CNTs, in particular for 50/50 (by wt) and 60/40 (by wt) PVDF/PMMA blends. Further, the configurational entropy, as manifested from DRS, decreased significantly in the strong blends in striking contrast to the fragile blends, supported by DSC, which manifested in an increase in the volume of cooperativity in the strong blends. The higher coupling in the crystalline blends can be attributed to good packing of the amorphous regions. While this is understood for crystalline blends (60/40 by wt, PVDF/PMMA), it is envisaged that enhanced dynamic heterogeneity is accountable for increased coupling in the case of blends which are on the verge of amorphous miscibility (50/50 by wt, PVDF/PMMA). The latter is also supported by broad relaxations near the T-g in DRS. Interestingly, the intermolecular coupling in the blends in the presence of CNTs has reduced, though the potential energy barrier hindering the rearrangement of CRR is lower than the blends without CNTs. In addition, the amorphous packing is not as effective as the blends without CNTs. This is manifested from reduced volume of cooperativity in particular, for 50/50 (by wt) and 60/40 (by wt) blends.

New physical insights into the electromagnetic shielding efficiency in PVDF nanocomposites containing multiwall carbon nanotubes and magnetic nanoparticles

This work attempts to bring critical insights into the electromagnetic shielding efficiency in polymeric nanocomposites with respect to the particle size of magnetic nanoparticles added along with or without a conductive inclusion. To gain insight, various Ni-Fe (NixFe1-x; x = 10, 20, 40; Ni: nickel, Fe: iron) alloys were prepared by a vacuum arc melting process and different particle sizes were then achieved by a controlled grinding process for different time scales. Poly(vinylidene fluoride), PVDF based composites involving different particle sizes of the Ni-Fe alloy were prepared with or without multiwall carbon nanotubes (MWNTs) by a wet grinding approach. The Ni-Fe particles were thoroughly characterized with respect to their microstructure and magnetization; and the electromagnetic (EM) shielding efficiency (SE) of the resulting composites was obtained from the scattering parameters using a vector network analyzer in a broad range of frequencies. The saturation magnetization of Ni-Fe nanoparticles and the bulk electrical conductivity of PVDF/Ni-Fe composites scaled with increasing particle size of NiFe. Interestingly, the PVDF/Ni-Fe/MWNT composites showed a different trend where the bulk electrical conductivity and SE scaled with decreasing particle size of the Ni-Fe alloy. A total SE of similar to 35 dB was achieved with 50 wt% of Ni60Fe40 and 3 wt% MWNTs. More interestingly, the PVDF/Ni-Fe composites shielded the EM waves mostly by reflection whereas, the PVDF/Ni-Fe/MWNT shielded mostly by absorption. A minimum reflection loss of similar to 58 dB was achieved in the PVDF/Ni-Fe/MWNT composites in the X-band (8-12 GHz) for a particular size of Ni-Fe alloy nanoparticles. This study brings new insights into the EM shielding efficiency in PVDF/magnetic nanoparticle based composites in the presence and absence of conducting inclusion.

Attenuating microwave radiation by absorption through controlled nanoparticle localization in PC/PVDF blends

Nanoscale ordering in a polymer blend structure is indispensable to obtain materials with tailored properties. It was established here that controlling the arrangement of nanoparticles, with different characteristics, in co-continuous PC/PVDF (polycarbonate/poly(vinylidene fluoride)) blends can result in outstanding microwave absorption (ca. 90%). An excellent reflection loss (RL) of ca. -71 dB was obtained for a model blend structure wherein the conducting (multiwall carbon nanotubes, MWNTs) and the magnetic inclusions (Fe3O4) are localized in PVDF and the dielectric inclusion (barium titanate, BT) is in PC. The MWNTs were modified using polyaniline, which facilitates better charge transport in the blends. Furthermore, by introducing surface active groups on BT nanoparticles and changing the macroscopic processing conditions, the localization of BT nanoparticles can be tailored, otherwise BT nanoparticles would localize in the preferred phase (PVDF). In this study, we have shown that by ordered arrangement of nanoparticles, the incoming EM radiation can be attenuated. For instance, when PANI-MWNTs were localized in PVDF, the shielding was mainly through reflection. Now by localizing the conducting inclusion and the magnetic lossy materials in PVDF and the dielectric materials in PC, an outstanding shielding effectiveness of ca. -37 dB was achieved where shielding was mainly through absorption (ca. 90%). Thus, this study clearly demonstrates that lightweight microwave absorbers can be designed using polymer blends as a tool.

Tailor-Made Distribution of Nanoparticles in Blend Structure toward Outstanding Electromagnetic Interference Shielding

Engineering blend structure with tailor-made distribution of nanoparticles is the prime requisite to obtain materials with extraordinary properties. Herein, a unique strategy of distributing nanoparticles in different phases of a blend structure has resulted in >99% blocking of incoming electromagnetic (EM) radiation. This is accomplished by designing a ternary polymer blend structure using polycarbonate (PC), poly(vinylidene fluoride) (PVDF), and poly(methyl methacrylate) (PMMA) to simultaneously improve the structural, electrical, and electromagnetic interference shielding (EMI). The blend structure was made conducting by preferentially localizing the multi-wall nanotubes (MWNTs) in the PVDF phase. By taking advantage of pp stacking MWNTs was noncovalently modified with an imidazolium based ionic liquid (IL). Interestingly, the enhanced dispersion of IL-MWNTs in PVDF improved the electrical conductivity of the blends significantly. While one key requisite to attenuate EM radiation (i.e., electrical conductivity) was achieved using MWNTs, the magnetic properties of the blend structure was tuned by introducing barium ferrite (BaFe) nanoparticles, which can interact with the incoming EM radiation. By suitably modifying the surface of BaFe nanoparticles, we can tailor their localization under the macroscopic processing condition. The precise localization of BaFe nanoparticles in the PC phase, due to nucleophilic substitution reaction, and the MWNTs in the PVDF phase not only improved the conductivity but also facilitated in absorption of the incoming microwave radiation due to synergetic effect from MWNT and BaFe. The shielding effectiveness (SE) was measured in X and K-u band, and an enhanced SE of -37 dB was noted at 18 GHz frequency. PMMA, which acted as an interfacial modifier in PC/PVDF blends further, resulting in a significant enhancement in the mechanical properties besides retaining high SE. This study opens a new avenue in designing mechanically strong microwave absorbers with a suitable combination of materials.