PVDF/poly(3-methylthiophene)/MWCNT nanocomposites for EMI shielding in the microwave range.

This work presents a new approach to enhance EMI shielding efficiency of nanocomposites of dielectric polymers, multiwalled carbon nanotubes (MWCNTs) and intrinsically conducting polymers for account of using core-shell morphology for conducting components. To realize this approach new ternary nanocomposites of poly(vinylidene fluoride) (PVDF), MWCNTs and poly(3-methylthiophene) doped by Cl- anions (P3MT) were prepared through synthesis of thermally stable core/shell nanocomposites PVDF/P3MT and MWCNT/P3MT. These binary nanocomposites were mixed with pure MWCNTs or PVDF followed by compression molding to prepare the ternary nanocomposites of different morphology to discriminate their EMI shielding properties in a wide frequency range (1-67 GHz). Values of the tangent of dielectric loss angle, the efficiency of transmission, reflection and absorption of microwave radiation, and shielding efficiency (SE) of the specified materials were found from analysis of spectral dependences of their complex dielectric constants. It was shown that while the melt mixing of the binary PVDF/P3MT nanocomposite with MWCNTs both in a pure state and in the binary nanocomposite (MWCNT/P3MT) expectedly strongly enhances SE of the former, this effect is non-linear and depends on presence/absence of the P3MT shell on the MWCNT core. The ternary nanocomposite PVDF/P3MT/MWCNT made of the binary polymer-polymer nanocomposite PVDF/P3MT and pure MWCNTs showed highest SE values at the frequencies above 4.5 GHz up to 68.4 dB at 67 GHz in the case of the 1 mm thickness sample. However, below 4.5 GHz the SE was higher in the case of the ternary nanocomposites containing core/shell MWCNT/P3MT nanocomposite instead of pure MWCNT.

Polyaniline Doping by α,α-Difluoro-ß-amino Acids.

Currently, polyaniline (PANI) is considered as a promising polymer that can be used in biosensors, drug delivery systems, bioelectronics, etc. Its biocompatibility can be strongly improved by using dopants with biofunctionality. This study reveals the protonation/doping of PANI by fluorinated analogs of natural amino acids, namely, α,α-difluoro-ß-amino acids (DFAAs) with alkyl and aromatic tails in N-methylpyrrolidone solutions. We find that these acids can dope PANI due to both the weakened basicity of their amino groups because of two fluorine atoms in α,α-positions and specific intermolecular interactions (π-π stacking, alkyl-π, F-π) of their tails with units of PANI chains. These interactions did not give the doped PANI salts with high conductivity but led to formation of stable PANI-DFAA complexes, which were confirmed both by clear changes in the UV-Vis and Fourier transform infrared spectra of the protonated/doped PANI and by their conductivity of ∼10-6 S/cm. Our results suggest an applicability of such PANI complexes as carriers of DFAA for their biomedical applications.

High effectiveness of pure polydopamine in extraction of uranium and plutonium from groundwater and seawater.

Sorption properties of polydopamine (PDA) for uranium and plutonium from an aqueous environment are reported at three different pH values (2, 4 and 6.5-7). In addition to deionized (DI) water, artificial groundwater (GW) and seawater (SW) were used with U uptake close to 100% in each case. PDA polymer has been identified as a material with extremely high sorption capacity Q max ∼500 mg g-1 of the polymer at pH 6.5 and high selectivity for uranium. Similar high sorption properties are revealed for plutonium uptake. PDA-uranyl and PDA-plutonium interactions responsible for the observed adsorption processes have been addressed with a set of experimental techniques including FTIR spectroscopy, electron microscopy and cyclic voltammetry.

Poly(vinylidene fluoride)/poly(3-methylthiophene) core-shell nanocomposites with improved structural and electronic properties of the conducting polymer component.

We report significant improvements in the structure and electronic properties of a poly(3-alkylthiophene) representative, namely poly(3-methylthiophene) (P3MT), when it is synthesized in the presence of submicron electroactive poly(vinylidene fluoride) (PVDF) particles. The applied template oxidative synthesis leads to the formation of the PVDF/P3MT composite consisting of core-shell particles. The shells are constituted with a monolayer of 20-40 nm nanoparticles of the doped P3MT (P3MT-Cl) precipitated at the surface of the spherical PVDF cores. This morphology differs strongly from the hierarchical one of the neat P3MT synthesized without PVDF particles. In the latter case, 20-60 nm P3MT nanoparticles form ∼200 nm aggregates, which, in turn, are arranged in a few micrometer agglomerates. Furthermore, we demonstrate that compared to the neat polymer, doped P3MT in the shells of the composite is characterized with higher effective conjugation length, regioregularity of the molecular structure, improved intrachain packing order and lower bipolaron/polaron ratio. These features of the PVDF/P3MT composite strongly suggest applicability of this material in various electronic devices. As a proof of concept, we report on an improved sensing performance of the PVDF/P3MT-Cl composite compared with the neat P3MT-Cl in detection of several volatile organic compounds known as markers for some diseases and toxic substances. We have discovered that the maximal improvement in the sensor response magnitude corresponds to the case when the values of the analyte electronegativity and polythiophene work function are close. We associate this behavior with a higher surface dipole component of the work function of the PVDF/P3MT-Cl composite compared to that of the neat conducting polymer.

Influence of Dispersed Nanoparticles on the Kinetics of Formation and Molecular Mass of Polyaniline.

Using a combination of the open circuit potential and pH profiles of aniline (An) polymerization and their mathematical treatment, we develop a new convenient semiquantitative approach to determine the influence of the dispersed nanoparticles (e.g., TiO2 nanoparticles) on the kinetic features of this process and molecular mass of the formed polyaniline (PANI). It is revealed that the reciprocal values of the polymerization stages, namely, the duration of the induction period, of homogeneous and heterogeneous pernigraniline (PN) accumulation, and of PN reduction with An, are linear functions of the weight fraction of the nanoparticles. We found that when nanoparticles are added the weight-averaged molecular weight of PANI initially increases from 56 000 to 79 000 and the polydispersity index drops from 3.9 to 1.7. However, at high TiO2 concentrations, the former dramatically decreases, whereas the latter increases. We use the relative proton concentration as a function of time and the different extents of acceleration of the consecutive stages of An polymerization to explain the changes in the molecular weight distribution of PANI with different contents of TiO2 nanoparticles in the polymerization medium.

Hybrid solar cell on a carbon fiber.

In this work, a method to assemble nanoscale hybrid solar cells in the form of a brush of radially oriented CdS nanowire crystals around a single carbon fiber is demonstrated for the first time. A solar cell was assembled on a carbon fiber with a diameter of ~5-10 µm which served as a core electrode; inorganic CdS nanowire crystals and organic dye or polymer layers were successively deposited on the carbon fiber as active components resulting in a core-shell photovoltaic structure. Polymer, dye-sensitized, and inverted solar cells have been prepared and compared with their analogues made on the flat indium-tin oxide electrode.

Effect of multiwalled carbon nanotubes on the kinetics of the aniline polymerization: the semi-quantitative OCP approach.

We demonstrate applicability of the open-circuit potential (OCP) method for kinetic analysis of the oxidative chemical polymerization of aniline both in clear solution and in dispersions of multiwalled carbon nanotubes (MWCNT). The characteristic points and the shape of the OCP profile are used to estimate the kinetic parameters of the main stages of the known two-step polymerization mechanism of aniline. We have found that the reciprocal values of the duration of the main polymerization stages namely the induction period, pernigraniline (PN) accumulation and reduction of PN with residual aniline are the linear functions of the weight fraction of MWCNT. To compare the kinetic data of the proposed OCP and known approaches the last two stages have been considered as a single heterogeneous stage of emeraldine (EM) formation. The kEM rate constant calculated by the OCP profiles for this EM stage in the solution and dispersion media is in a very good agreement with the known k2 values.

Deep impact of the template on molecular weight, structure, and oxidation state of the formed polyaniline.

In this work we find that polyaniline (PANI), synthesized by aniline chemical polymerization at a surface of template polycarbonate (PC) particles, is significantly different in molecular weight, structural order, oxidation state, and conductivity from a neat PANI. Molecular weight of the PANI phase in the composite (Mw = 158,000) is 1.6 times higher than that of the neat PANI synthesized in the absence of the template particles. Moreover, XRD analysis shows that crystallinity of the PANI phase in the composite is three times higher than that of the neat PANI. Raman spectroscopy indicates that the oxidation level of PANI in the PC/PANI composite is lower than that of the neat PANI. These noticeable changes of the PANI phase properties suggest specific interactions of reagents in the polymerization medium and formed PANI with the template phase as well as an orientation effect of the latter surface. FTIR spectroscopy reveals that hydrogen bonding in the neat doped PANI is weaker than one between -NH- of PANI and C═O of PC at their interface. The discovered differences are supported by the fact that conductivity of the PANI phase in the composite is more than three times higher than that of the neat PANI.

Evidence of the controlled interaction between PEDOT and PSS in the PEDOT:PSS complex via concentration changes of the complex solution.

Photoluminescence, electronic absorption, and pH studies of a poly(ethylene-3,4-dioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) dispersion as a function of the PEDOT:PSS concentration are shown to provide a better understanding of the effect of PSS on the intramolecular conductivity of PEDOT chains. Particularly, concentration changes of PEDOT:PSS were found to be accompanied with different extents of dissociation of protons in the solution and different charge states of PSS chains, respectively, which affect the electrostatic interaction between PSS and PEDOT and intramolecular conductivity in the PEDOT backbone.